NBS Special Publication 662

The National Bureau

of Standards Office of

Recycled Materials

1976-1982

U.S. Department of Commerce

National Bureau of Standards

QC

100

U57

662

1983
NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards1 was established by an act of Congress on March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation's science and technology

and facilitate their effective application for public benefit. To this end, the Bureau conducts

research and provides: (1) a basis for the Nation's physical measurement system, (2) scientific and technological services for industry and government, (3) a technical basis for equity in trade, and (4) technical services to promote public safety. The Bureau's technical work is per- formed by the National Measurement Laboratory, the National Engineering Laboratory, and

the Institute for Computer Sciences and Technology.

THE NATIONAL MEASUREMENT LABORATORY provides the national system of

physical and chemical and materials measurement; coordinates the system with measurement

systems of other nations and furnishes essential services leading to accurate and uniform

physical and chemical measurement throughout the Nation's scientific community, industry,

and commerce; conducts materials research leading to improved methods of measurement,

standards, and data on the properties of materials needed by industry, commerce, educational

institutions, and Government; provides advisory and research services to other Government

agencies; develops, produces, and distributes Standard Reference Materials; and provides

calibration services. The Laboratory consists of the following centers:

Absolute Physical Quantities2 — Radiation Research — Chemical Physics —

Analytical Chemistry — Materials Science

THE NATIONAL ENGINEERING LABORATORY provides technology and technical ser- vices to the public and private sectors to address national needs and to solve national problems; conducts research in engineering and applied science in support of these efforts; builds and maintains competence in the necessary disciplines required to carry out this research and technical service; develops engineering data and measurement capabilities;

provides engineering measurement traceability services; develops test methods and proposes

engineering standards and code changes; develops and proposes new engineering practices;

and develops and improves mechanisms to transfer results of its research to the ultimate user. The Laboratory consists of the following centers:

Applied Mathematics — Electronics and Electrical Engineering2 — Manufacturing

Engineering — Building Technology — Fire Research — Chemical Engineering2

THE INSTITUTE FOR COMPUTER SCIENCES AND TECHNOLOGY conducts

research and provides scientific and technical services to aid Federal agencies in the selection, acquisition, application, and use of computer technology to improve effectiveness and

economy in Government operations in accordance with Public Law 89-306 (40 U.S.C. 759), relevant Executive Orders, and other directives; carries out this mission by managing the Federal Information Processing Standards Program, developing Federal ADP standards

guidelines, and managing Federal participation in ADP voluntary standardization activities; provides scientific and technological advisory services and assistance to Federal agencies; and

provides the technical foundation for computer-related policies of the Federal Government. The Institute consists of the following centers:

Programming Science and Technology — Computer Systems Engineering.

'Headquarters and Laboratories at Gaithersburg, MD, unless otherwise noted; mailing address Washington, DC 20234. 'Some divisions within the center are located at Boulder, CO 80303.
NBS Special Publication 662

The National Bureau

of Standards Office of

Recycled Materials

1976-1982

U.S. Department of Commerce

National Bureau of Standards

The National Bureau

of Standards Office of

Recycled Materials

19761982

Harvey Yakowitz, Editor

Office of Recycled Materials

National Bureau of Standards

Washington, D.C. 20234

Final Report of Activities and Accomplishments

Pursuant to the Mandates of Section 383C of the Energy Policy Conservation Act and to the Mandates of Subtitle E of the Resource Conservation

and Recovery Act

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued Sept. 1983

Q
Library of Congress Catalog Card Number: 83-600573

National Bureau of Standards Special Publication 662

Natl. Bur. Stand. (U.S.), Spec. Publ. 662, 634 pages (Sept. 1983)

CODEN: XNBSAV

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1983

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, DC 20402

Price $11.00

(Add 25 percent for other than U.S. mailing)
Purpose of the Report

This Report summarizes the activities and accomplishments of

the Office of Recycled Materials of the National Bureau of Standards

(NBS/ORM) undertaken in response to legislative directives from

1976 through 1982 and provides a compilation of FY 1982 activities

of NBS/ORM.

During its six and one-half year lifetime, NBS/ORM fulfilled

virtually all of the legislative directives with which NBS was

charged. Waste oil and other materials destined for waste were the

subject of requirements for test method development, evaluation and

subsequent production of standards and guidelines for specifications.

More than 125 publications and reports remain as a tangible legacy

of NBS/ORM. In addition, the methods and standards developed under

the guidance of NBS/ORM have been adopted throughout the recycling

community. This report places major NBS/ORM activities in perspective

and provides a point of embarkation for anyone wishing to utilize

or adapt NBS/ORM results. In addition, the Report indicates that

NBS fulfilled the legislative requirements in a timely, accurate,

and efficient manner.

i i i
Acknowledgments

Literally hundreds of persons contributed to the results

produced by NBS/ORM. The prime movers of NBS/ORM were Donald A. Becker, Manager of the Recycled Oil Program of NBS/ORM, Joseph

Berke, Manager of the Recycled Materials Program from late 1977 to

mid-1981, Dr. Eugene S. Domalski, Manager of the Recycled Materials

Program from mid-1981 to October, 1982, and Mrs. R. T. Matthews,

Manager of the NBS/ORM Technical Advisory Center from its inception

to the end of FY 1982. The Administrative foundation on which

NBS/ORM rested was entrusted to Mrs. V. M. Davis and Mrs. A. Marinoff in the 80' s and to Mrs. R. D. Graham and Mrs. H. A. Hurd

in the 70' s. Mrs. A. Epstein served as Fiscal Aide from 1980-1982;

Mrs. M. DeWese carried out this function from April, 1982 to

December, 1982. Without the dedicated help of these key people,

NBS/ORM could not have functioned.

With respect to this Report, Section III was prepared by Mr.

Becker, Section IV.(3)b.l through IV.(3)b.3 was prepared by Dr.

Domalski, Section IV.(3)b.4 was prepared by Dr. A. Macek, Section

IV. (3)c by Drs. W. Tsang and W. Shaub, Sections IX. (3) through

IX. (5) by Mr. R. Chapman, Section IX.(8)a was prepared by Mr. T. Lettes of MBDA. Where appropriate, authors names are shown for the

various Appendices. The remainder of the Report was written and

compiled by Dr. Harvey Yakowitz, Chief NBS/ORM; he also edited the

entire Report.

Note that the entire text was typed by the Text- Editing

Facility of the NBS National Measurement Laboratory. The patience,

forbearance, and excellent performance of this group is gratefully

acknowledged.

iv
Table of Contents

Page

Purpose of the Report iii

Acknowledgments iv

Executive Summary xi

I. Introduction 1

II. Formation of the Office of Recycled Materials 1

III. The Recycled Oil Program 2

1. Introduction 2

2. Implementation of the NBS Recycled Oil Program.... 4

3. The NBS Role in Recycled Oil 4

4. Achieving Specific Objectives 6

5. Program Plan and Results 7

6. Proposed Test Procedures for "Substantial

Equivalency" 12

a. Performance Tests (Qualification

Procedures) 12

b. Provisional Tests for Re-Refined Basestock

Consistency 15

7. Discussion of a Potential Test Verification

Effort 18

8. Summary of Achievements 20

IV. Recycled Materials Program in Response to the

Resource Conservation and Recovery Act 23

1. Mandates and General Approach 23

a. Goal 24

b. Objectives 24

c. Technical Advisory Center 25

d. NBS/ORM Participation With the OECD 25

2. General Statement of the Challenges Posed by the

Need to Deal With Municipal Waste 26

3. Guidelines for Specifications for Recovered

Materials (Section 5002 of RCRA) 30

a. Provision of Guidelines 30

1. Municipal Solid Waste 31

1. The Aluminum Fraction 31

2. The Ferrous Fraction 32

3. The Glass Fraction 34

b. The Organic Fraction of MSW 42

1. Calorimetric Characterization of

Refuse Derived Fuels 45

2. Oxygen Flow Calorimetry of Solids 46

3. Oxygen Bomb Calorimetry of Solids 46

4. Combustion of Refuse Derived Fuels

in a Laboratory Scale Fluidized Bed

Furnace 49

v
1. Entrainment of RDF Particles 49

2. Combustion of Lignite Particles.... 50

3. Combustion of RDF Particles 50

4. Sub-scale Requirements 51

5. Documentation 52

c. Combustion Process Characterization.... 52

1. Development of Chemical and Kinetic

Techniques 53

2. The Dioxin Emission Issue 54

d. Corrosion Studies 56

4. Fibre and Wastepaper 56

V. Special Waste Categories 58

1. Used Tires 58

a. Retreading 58

b. Waste Tires as Fuel 59

c. Asphalt-Rubber 61

2. Large Volume Wastes 64

a. Fly Ash. . 65

b. Sludges, Slags and Mineral Wastes 66

3. Plastics 67

4. Landfill Gas 68

5. Compost 70

VI. Recycling of Industrial Wastes 73

VII. Procurement Practices Relating to Items Containing

Recovered Materials 75

1. Legislative Mandate 75

2. State Procurement Study 75

3. Bid Modifier 78

4. National Recycling Directory 79

VIII. Challenges Posed by the Need to Deal With Hazardous

Wastes 80

1. Background 81

2. Current Status in the U.S 87

3. Specific Challenges-Options and Impacts 90

a. Approaches to a Definition and

Classification 90

b. Identification of Possible Disposal

Options 91

c. Development of an Equitable Level of Control

System 91

d. Provision for a Valic Monitoring Scheme 91

e. Evaluate Potential Harm 92

f. Unified Means of Informing 92

4. Technical Approaches to Specific Challenges 92

5. Analytical Test Methods and Standards 104

6. Current Approaches - Degree of Hazard 106

7. Hazardous Materials Incineration 109

a. General 109

b. Incineration at Sea 110

8. Land Disposal 117

vi
9. Technical Issues Relating to Disposal Site

Evaluation and Rating - Degree of Hazard 118

10. NBS/ORM Efforts Concerning Recycling of

Potentially Hazardous Wastes 124

a. Pilot Study of Steel Industry Mill Scales 125

b. Characterization of Electric Furnace Dusts... 128

11. Economic Factors Affecting Recycling of

Potentially Hazardous Wastes 131

a. Econometric Methodology Development 132

12. Summary of Requirements 139

13. State Measurement Needs 140

14. NBS/ORM Participation in the OECD Study Concerning

Control of Hazardous Wastes 142

IX. Markets for Recovered Materials (Section 5003 of

RCRA) 145

1. Congressional Mandate 145

2. Market Survey for Waste Paper in Four Southeastern States 145

a. Survey Results 146

3. Resource Recovery Market Models 148

a. Evaluation Criteria for Mathematical

Models 148

1. Appropriateness 149

2. Validation 149

1. Technical Validity 149

2. Operational Validity 151

3. Dynamic Validity 151

3. Documentation 152

4. Two Computer Models for Assessing the Economics

of Resource Recovery 153

5. The Resource Recovery Planning Model (RRPLAN):

A New Decision Tool for Solid Waste Management.... 154

a. Examples of the Use of RRPLAN 157

1. New York City 157

2. Central Mississippi 161

6. General Assessment of RRPLAN-Error Propagation.... 169

7. General Market Related Activities of NBS/ORM 172

a. Fate of Fiber 172

b. Other Market Studies 172

8. Efforts to Encourage Development of New Uses for

Recovered Materials (Section 5003(3) of RCRA) 173

a. Technology Commercialization Program

(MBDA) 174

X. Evaluation of Commercial Feasibility of Resource

Recovery Facilities (Section 5004 of RCRA) 177

1. Congressional Mandate 177

2. Specific Activities 177

a. International Conference on Urban Development

Through Resource Recovery 177

b. U.S. Conference of Mayors Grant 179

c. Projects in Cooperation With the City of

New York 183

vi i
1. Feasibility Study Involving Conversion

of an Existing Incinerator to an Energy

Recovery Unit , 183

d. Conversion of the San Diego County, CA

Resource Recovery Facility to a Solid Waste

Research Center 188

e. Cooperative Efforts With the Government of

Japan 190

f. Advisory Activities Relating to Section 5004

of RCRA 192

XI. Pilot Program With the California State Solid Waste

Management Board 193

XII. Brief Synopses of Other NBS/ORM and DOC Activities.. 195

XIII. Amendments to RCRA (PL 96-482) 197

XIV. Contributions of ORM to the Institutional Health of

NBS 198

v i i i
Appendices

I. Direct Publications of the Office of Recycled Materials

II. Selected Abstracts from Conference on Measurements and

Standards for Recycled Oil -IV

III. Dioxin Formation in Incinerators

IV. Non-Concrete Uses of Fly Ash in Construction Materials

V. Interlaboratory Study of Organic Extraction Recoveries

VI. Hazardous Waste Characterization (Representative Activities

FY 1982)

1. Hazardous Waste Characterization Project

a. Synthetic Aqueous Leachate Extraction Recovery Study

b. Gas Chromatographic Analysis of Synthetic Aqueous

Leachate Extracts

c. GC/MS Analysis of Synthetic Aqueous Leachate Extracts

d. GC/MS Analysis of Vacuum Still Bottom Bulk Aqueous

Leachates

2. Organic Leachates - Statistical Analysis of Interlaboratory

Data

3. Leach Test Analysis on California Soil Test Material

4. Multielement Analysis of Oils and Hazardous Waste Leachates

Using the Inductively Coupled Plasma Technique

5. Polymer Modified Electrodes: Chemically Modified Electrode

Detectors for Halogenated Hydrocarbons

6. Combined Liquid Chromatography/Mass Spectrometry

7. Development of a Temperature Stabilization System for a D.C. Plasma/Echel le Spectrometer

8. Development of a Quality Assurance Sludge Material for

Hazardous Waste Analysis

VII. The Waste-Environment Technology Model: A Brief Evaluation

and Assessment

VIII. Surrogates as Substitutes for Principal Organic Hazardous

Constituents Validation of Incinerator Operation

IX. Research Approaches for Determining Compatibility of

Polymeric Liner Materials with Hazardous Wastes

X. Regulatory Control of Hazardous Waste Level

XI. Development and Use of a Simulation Model for the Economic

Analysis of Resource Recovery Options

XII. Overview of RRPLAN

XIII. Tentative Agreement for Joint Research: Japan-United States

XIV. A Simple Degree of Hazard System for Hazardous Wastes

ix
XV. Characterization of Mill Scale Steel Wastes

XVI. Evaluating the Risks of Solid Waste Programs: A Suggested

Approach

x
EXECUTIVE SUMMARY

During the Congressional deliberations which led to the

passage of the Resource Conservation and Recovery Act of 1976

(RCRA, Public Law 94-580), Congress perceived the need for a research and development effort which would be independent of

agencies given regulatory authority under the Act. Since the lead

agency was to be the Environmental Protection Agency (EPA), the

Congress sought another department of the U.S. government which

would have experience and credibility in the measurement methods

and techniques necessary to classify and characterize society's

discards.

Congress elected to insert into the Act a separate Subtitle E assigning to the Secretary of Commerce several duties with respect

to resource recovery. Specifically, the duties of the Secretary of

Commerce are as follows:

o provision of guidelines for specifications for recovered

material s

;

o market development stimulation for these materials;

o promotion of proven technology; and

o a forum for the exchange of both technical and economic data

relating to resource recovery faci 1 i ties—presumably hightechnology plants designed to recover materials and/or energy

from waste.

In order to implement all of these responsibilities, the Secretary

of Commerce delegated the necessary authority to accomplish the

task to the National Bureau of Standards (NBS). Indeed, Section

5002 of RCRA states that the Secretary act through NBS in order to

establish guidelines and specifications for materials which could

be recovered from waste originally destined for disposal. In

addition, NBS was directed to cooperate with voluntary consensus

standards organizations, such as ASTM, and to work with other

federal agencies in carrying out the mandates of the law.

FORMATION OF THE OFFICE OF RECYCLED MATERIALS

The NBS resource recovery program was formally established in

November 1976. In 1978, the program was expanded to encompass NBS

responsibilities under the Energy Policy and Conservation Act of

1975 (EPCA, Public Law 94-163), which requires NBS to determine the

substantial equivalency of used and virgin oils. The work on recycled materials in response to Subtitle E of RCRA and the

Recycled Oil Program was combined into the Office of Recycled

Materials. In late 1979, NBS added a Technical Advisory Center,

charged with the responsibility of determining the geographic location of markets for recycled materials and with developing an economic and technical database describing resource recovery

systems.

xi
The NBS Office of Recycled Materials staff recognized from the

outset that recovering any materials from a waste destined for

disposal was possible, but purposeless unless a market could be

found for the recovered material. Therefore, materials to be

recovered had to be marketable at a price which made recovery

economically useful. The Office of Recycled Materials (ORM)

examined the market for materials that could be recovered from

wastes.

RECYCLED OIL PROGRAM

The NBS Recycled Oil Program was established in 1976, in

direct response to passage of the Energy Policy and Conservation

Act of 1975 (EPCA, Public Law 94-163; 42 U.S.C. 6201 et seq.),

Section 383(3) of this law requires NBS to "...develop test procedures for the determination of substantial equivalency of re-refined

or otherwise processed used oil or blend of oil ... with new oil

for a particular end use."

The stated goal of the Recycled Oil Program was to provide the

measurement methods and standards required for effective utilization

of recycled petroleum products. This goal was achieved through:

o establishing the scientific and technical basis for characterization of recycled petroleum products;

o developing and evaluating test procedures for establishing the

substantial equivalency between recycled and virgin petroleum

products; and,

o providing technical information and support for the effective

utilization of recycled petroleum products.

These goals were implemented through research and development

activities both within NBS and at several outside institutions.

Details of accomplishments can be found in Section III.

RECYCLED MATERIALS PROGRAM

The NBS program was formally established in November 1976. In

1979, NBS added a Technical Advisory Center, charged with the

responsibility for assisting in the determination of the geographic

location of markets for recycled materials and with developing an economic and technical database describing resource recovery

systems.

With regard to municipal solid waste (MSW), the basic constituents are an organic fraction consisting of such items as newsprint,

other paper fibers, grass clippings, and other garbage (waste

food). By weight, this fraction comprises about 80 percent of MSW.

The remaining 20 percent consists of glass (12 percent) and metal

consisting of ferrous discards (7 percent) and aluminum, primarily

from beverage containers (1 percent). These percentages are based

on national averages developed under a study sponsored by the

xi i
Environmental Protection Agency. The United States produces

approximately 140 million tons per year of MSW; this figure has not

changed appreciably in the past five to seven years. In examining

the marketability of the various fractions of MSW, staff of ORM

found that aluminum marketed very well without governmental support.

Therefore, there was no need to utilize Federal research funds to

aid in the marketability of aluminum, and ORM has done no work

on the aluminum fraction. With regard to the ferrous fraction, the

most salient piece of research which concerned the effect of

impurities such as copper and tin on the marketability of ferrous

material, was carried out by the National Center for Resource

Recovery under a National Academy of Sciences grant at about the

time ORM was formed. We saw no need to duplicate this research,

and therefore have done little research on the ferrous fraction.

In most case, the marketability of the ferrous fraction has followed

the market fluctuation for No. 2 dealer scrap bundles.

The glass fraction usually appears as broken glass rather than

as separated bottles or other containers. Since glass is manufactured in three basic colors —amber , green, and flint (or clear)--col

mixture is of great importance to the manufacturers of glass

products. Furthermore, in the manufacture of glass, non-melting

components, such as ceramics, are of crucial importance since these

unwanted components can reduce the strength of the glass container

or seriously mar its appearance, or both. Thus, for very good

commercial reasons, manufacturers of glass products are extremely

careful about the raw materials they will allow in the glass

furnaces or tanks. Specifications for including post-consumer

waste glass in the glass container manufacturing process were

nearly exclusionary prior to research on the properties of the

glass fraction. Therefore, NBS carried out a research program

aimed at characterizing post-consumer waste glass for potential

introduction into a glass tank. As a result of NBS research, the

present ASTM specification is less restrictive than in the past.

The organic fraction is the most difficult to market, since at

first consideration, who wants to buy garbage? But, the organic

fraction will burn, and if the incinerator in which it is burned is

appropriately configured, energy can be recovered and the atmosphere

not polluted. Thus, the organic fraction can be destroyed, energy

from it recaptured, and the environment not damaged. Very little

was known in 1976 about the characteristics of MSW as a fuel or about processing the organic fraction of MSW to create what is

known as refuse-derived fuel. Therefore, a major portion of the

NBS research program relating to MSW was devoted to characterizing

the organic fraction. In addition, there was a second question:

If one separates fibers such as newsprint from the organic fraction,

will that action affect the economics of a resource recovery

facility or, the reverse, if the paper is taken to the incinerator,

will paper recyclers be driven out of business? Through the

efforts of the Bureau of Industrial Economics (DOC), we have

released a study of wastepaper markets in four States (Florida,

Georgia, and North and South Carolina). The survey indicates a

x i i i
growth in demand for waste newspaper and includes a directory of

waste newspaper markets, as well as cellulose insulation demand.

NBS research has addressed all of these issues and, many of

the research results on refuse-derived fuels have been transferred

to the public in conjunction with ASTM Committee E-38 on resource

recovery. Indeed, NBS/ORM research has contributed substantially

to fifteen standards published in the ASTM annual book of standards.

Examples of specific NBS research include the following:

1) Provision of consensus test methods for determining the

heating value of minimally processed refuse so that

engineers can evaluate the performance and design specifications of an incinerator or boiler.

o Finding: In aid of these goals, NBS has demonstrated

that one-kilogram-size samples of refuse can be burned in

flowing oxygen; the characteristics of this process have

been completely characterized.

2) Provision of test methods for determining the heating

value of refuse-derived-fuel so that it can be established

as an article of commerce.

o Finding: In cooperation with ASTM, heating values of

various refuse-derived-fuels have been determined; the

measurement method can be widely adopted.

3) Development of thermo-analytical test methods for charac-

• terizing refuse-dri ved-fuel s.

o Finding: Thermo-analytical test methods provide a fingerprint of a refuse-derived-fuel sample, and have

applications in quality control related to processing,

handling, and up-grading refuse-derived-fuels.

4) NBS is developing a definitive body of data on the

physical and chemical properties of fossil fuel residues

from a variety of combustion systems. The data, protocols,

and test methods which are being developed will aid in

the environmental management of waste streams from coal

combustion and other fossil energy conversion processes.

Note that this work is being carried out in cooperation

with the Department of Energy.

o Finding: An NBS Standard Reference Material representing

fly ash has been characterized.

5) Examination of the available physical and chemical

properties of selected hazardous waste components and

utilize these data to develop practical predictive

schemes for various properties.

xi v
o Finding: NBS has developed a procedure for estimating

the heats of formation of aromatic compounds, including

chlorinated benezenes, phenols, and dioxins.

6) Development of test methods for the determination of

trace metallic components in solid waste and recycled

material s.

o Finding: NBS was able to prepare a synthetic leachate

reference material containing known concentrations of

inorganic priority pollutants; this leachate is being

used throughout the U.S. in order to characterize hazardous waste extraction procedures.

7) Development of test methods for the quantitative analysis

of trace organic constituents in recycled materials.

o Finding: NBS has developed a method to analyze for the

presence of trace amounts of PCBs in an oil base; unless

it can be shown that PCBs are not present, such recycled

oils cannot be marketed.

These are only a few examples of NBS laboratory research on recycled

materials. Details are discussed in Sections III through VI and

VIII and in the publications listed in Appendix I.

As a further effort toward improving markets for recovered

materials, Subtitle F of RCRA mandates the Federal Government and

other governmental entities which utilize Federal funds to procure

the maximum practicable amount of recyclables in what they purchase.

ORM, in cooperation with seven States—Colorado, Florida, Michigan,

Minnesota, New Jersey, New York, and Washington—and, the National

Association of State Purchasing Officers, produced a multivolume

study entitled "Procurement of Products Containing Recovered

Material: A Summary of Activities in Seven States." These reports

deal with supply and demand problems associated with government

procurement of recyclables. Section VII contains details.

The Technical Advisory Center (TAC) of NBS/ORM was established

to provide a framework for fostering the advances required to

optimize both economic and environmental factors associated with

recovery and/or reuse of resources contained in solid wastes. The

TAC accomplished these goals by developing methodologies for the

economic assessment of current and potential technologies, market

potentials, as well as identifying institutional barriers to resource conservation and recovery; to assist public and private

sector to utilize the methodologies and information; and, by

identifying the potential for new business opportunities and

growth. TAC's primary function was to help to assure implementation of RCRA responsibilities for the Department, which are 1)

encouragement of the commercialization of proven technology; 2)

stimulation of the development of markets for recovered materials,

and 3) evaluation of the commercial feasibility of resource recovery

facilities as well as the development of an information base to

xv
assist communities and other entities in selection of a recovery

system.

NBS/ORM explored the feasibility of developing a Resource

Recovery Planning (RRPLAN) model design for economic evaluation of resource recovery systems on a regional or statewide basis. A

study sponsored by NBS/ORM concluded that a gross design of a mathematical model to serve the following purposes was possible:

1) Generation of a preferred regional plan for resource

recovery;

2) evaluation of a specified plan for resource recovery;

and,

3) provision for the inclusion of source separation as an option.

The criteria selected for generating a preferred regional plan for resource recovery were:

o Minimize lifetime cost of a selected plan; or

o minimize lifetime discounted cost; or

o maximize net energy balance; or,

o optimize a composite of weighted cost and/or energy considerations.

NBS/ORM staff cooperated with both State and local governmental

entities in development of case studies. See Section IX for

details. Section IX also provides an analysis of uncertainties

associated with the model and with the input data.

RRPLAN, if used properly, provides the foundation for planning.

But considerable additional assessment may well be necessary in

order to choose the proper strategy for a given region. This

assessment involves probabilistic estimation for the input variables

(discount rate, costs, etc.) followed by multiple RRPLAN evaluations

[The results will provide values for all terms in equations (IX-12)

and (IX-16).] Unless aJM of these steps are taken, RRPLAN results

need to be treated with extreme caution.

RRPLAN, as developed for and by NBS/ORM, represents an appropri

ate means to begin evaluation of specific resource recovery options

for a city, state or region. The input data requirements will tend

to require the prospective RRPLAN client to determine as accurately

as possible each item of data. If these data are not properly

obtained, the risks of adopting a resource recovery plan become

much greater; the U.S. has had several cases where resource recovery

options have not lived up to proponents expectations. Careful data

assessment, RRPLAN and solutions to equations (IX-12) and (IX-16)

should help to reduce the risk associated with resource recovery.

xvi
In turn, the data gathering process and the subsequent RRPLAN and

probabilistic analysis should clearly highlight potential or actual

institutional problems.

RRPLAN can be applied to recovery of hazardous or non-hazardous

industrial waste with some modifications. Thus, all waste classes

which were dealt with by RCRA can be taken into account. The

preceding general assessment is true for all classes of waste.

The Resource Recovery Committee of the Association of State

and Territorial Solid Waste Management Officials under terms of an NBS/ORM grant submitted the report States' Measurement Needs . The

report consists of the following sections:

o Part I: Final Report and Executive Summary: State summary

charts depicting definitions of hazardous waste,

measurement parameters, laboratory needs, and

available training programs; Conclusions and Recommendations.

o Part II: State Profiles (Texas, Louisiana, Oklahoma, Pennsylvania, New York, Mississippi, Virginia): Solid

waste, hazardous waste and resource recovery program

objectives; State agency organizational make-up; resources and manpower; selected regulations; data

from field visits on laboratory capability; other

appropriate documentation.

o Part III: Analytical Operations Procedure Manual Model: A

cohesive technical framework and outline of tools

necessary to augment States' hazardous waste program

based on experience and guidance of State of Louisiana.

In preparing this Final Report on Part 2, the Association's

Resource Recovery Committee considered the following questions:

1) Does the State have adequate laboratory support staff,

equipment, and resources or the services of a private

contractor to perform RCRA-related measurement activities?

2) What are State laboratory equipment holdings?

3) Are the laboratories certified? Do they have a quality assurance program?

4) Is there adequate laboratory and field protective equipment

and clothing?

5) What types of technical assistance do laboratory and

field personnel need and from which entities?

6) What are the overall prioritized needs in support of

implementing the technical requirements under RCRA?

xvi i
The Committee concluded that even though State programs vary

in stringency of regulatory requirements, State measurement needs

are similar in hazardous waste. However, Subtitle D resource recovery measurement needs, while identified, do not exhibit the same level of priority associated with the Subtitle C - Hazardous

waste program. Nevertheless, standard analytical methods, protocols,

and procedures specified in State regulations match those methods

cited in Federal criteria. Development of standard laboratory and

field methods for sampling and analyses as well as standard reference

data are required. The lack of availability for such measurement

tools is severely impeding national consistency on a State-to-State

basis, timely program implementation, and worker protection and

safety. Consequently, a formal operating procedures manual is

necessary to assure not only State-to-State programmatic and

enforcement consistency, but also in intra-State field and functional

laboratory activities. A standard laboratory certification quality

assurance program does not exist but would be helpful in attaining

State-to-State consistency. Lastly, training programs and technical

assistance for laboratory and field personnel are deficient at

State level. Section VIII contains details.

Throughout FY 1981, the Great Lakes Basin Commission conducted

a study to develop methodologies for estimating the economic

development effects of hazardous waste management and to assess the

potential for resource recovery of materials from selected waste

streams. The three industrial and manufacturing, activities

selected as case studies were: steel manufacturing, electroplating,

and paint manufacturing. This study commenced September 1980 and was scheduled for completion by May 1982. However, the Great Lakes

Basin Commission expired September 1981. After that date, the

Michigan Department of Commerce worked to complete this study and

to explore implementation options. The Michigan Department of

Commerce retained original project staff; consequently, the study was completed on schedule in 1982. The Michigan Department of

Natural Resources assisted as technical advisers to the project.

In the first phase of the study, an assessment was conducted

of the economic effects if efficient hazardous waste management

options are not available to generators. The analysis encompasses

the cost of on and off site management options, volume reduction

through process change, and resource recovery from hazardous waste

streams as well as current recovery practices. A methodology for

determining factors affecting the marketability of recovered

products was developed. Projections were made on current market

size, and impact of financial and institutional incentives on potential market size.

Criteria were divided into three general areas: 1) industry

background; 2) waste stream characterization; and, 3) those related

to impact of the Resource Conservation and Recovery Act of 1976, as amended, in the region. The first criteria group ensured that

industries chosen are vital to the region; the second group designated industries with significant waste management problems, and

xvi i i
lastly, the third group addressed those industries seriously

affected by implementation of RCRA in the region.

On basis of this two step approach three selections were made:

1) steel manufacturing; 2) electroplating; and, 3) paint manufacturing. Three other activities were considered but not selected:

textiles, organic chemicals, and wood preserving. Other industries

considered but scoring lower than the selected industries were:

leather tanning, pulp and paper, electric utilities, petroleum

refining, petroleum re-refining, pharmaceuticals, special machinery

manufacturing, electronic components, rubber, plastic, pesticides,

batteries, chemical wholesaling, drum reconditioning, agricultural

services, gas and service stations, soaps and detergents, and

glass.

Methodology for analyzing economic potential of recycling and resource recovery in the electroplating industry was developed. A

similar analysis for solvent recovery in paint manufacturing

industry was also completed. A computer model to select an optimal

treatment, disposal or recovery option given varying assumptions

concerning landfill costs, distance to disposal site and other

parameters was the final product. Further details and conclusions

can be found in Section VIII.

As part of its continuing commitment to working with State and

local government, NBS has a senior staff person working with the

State Solid Waste Management Board in California. The purpose of

this two-year Intergovernmental Personnel Agreement is to provide

an interface between perceived State measurement needs and NBS

expertise (Section XI.). In addition, a great deal of cooperative

work was performed with city of New York officials.

By the end of Fiscal Year 1982 most of the responsibilities

mandated directly to NBS by RCRA were completed and the results

transferred to interested parties. In addition to its directly

mandated responsibilities, ORM has cooperated with other mission

agencies within the Federal government who have other distinct

responsibility in recycling and solid waste management. For

example, in aid of the Department of Energy's activities under the

Energy Security Act of 1980 (Public Law 96-294), the NBS Office of

Recycled Materials carried out a program of research to characterize

ash created by the incineration of waste, sampling of power plant

ash in order to determine its potential for recycling, and developed

instrumentation in cooperation with DOE to measure the amount of

energy which could be produced via incineration of waste. (Sections

IV-VI.) In cooperation with EPA, NBS/ORM helped in the development

of methods meant to characterize whether or not a discard would be

classified as hazardous. (Section VIII.) The Department of

Defense was aided in characterizing materials problems associated

with the incineration of waste. (Section VIII.) The ORM provided

technical assistance and economic analysis to DOT and EPA in

incineration at sea projects. (Section VIII.)

xix
Section X describes a variety of evaluative activities pertaining to resource recovery which can be adapted by potential users in

the public or private sectors. In the case of hazardous wastes,

NBS/ORM has developed a proposed degree of hazard classification

system which is easy to understand, evaluate and administer.

(Section VIII.) This method is also ready for transfer to the

public and private sectors. Sections XII and XIV describe NBS/ORM

contributions to the institutional health of NBS. The Appendices

provide specific details of work completed in FY 1982.

NBS/ORM ceased operations at the end of FY 1982 having achieved

most of its objectives. The Congress concurred in this conclusion.

NBS/ORM produced well over 100 publications describing its activities

and results (Appendix I contains a listing); several workshops,

symposia and tutorial sessions were sponsored by NBS/ORM as well.

xx
I. INTRODUCTION

During the Congressional deliberations which led to the

passage of the Resource Conservation and Recovery Act of 1976

(RCRA, Public Law 94-580), Congress perceived the need for a research and development effort which would be independent of

agencies given regulatory authority under the Act. Since the lead

agency was to be the Environmental Protection Agency (EPA), the

Congress sought another department of the U.S. Government which

would have experience and credibility in the measurement methods

and techniques necessary to classify and characterize society's

discards.

Congress elected to insert into the Act a separate Subtitle E assigning to the Secretary of Commerce several duties with respect

to resource recovery. Specifically, the duties of the Secretary of

Commerce are as follows:

o provision of guidelines for specifications for recovered

material s

;

o market development stimulation for these materials;

o promotion of proven technology; and

o a forum for the exchange of both technical and economic data

relating to resource recovery facilities, e.g., facilities

designed to recover materials and/or energy from waste.

In order to implement all of these responsibilities, the

Secretary of Commerce delegated the necessary authority to accomplish

the task to the National Bureau of Standards (NBS). Indeed,

Section 5002 of RCRA directs "that the Secretary act through NBS in

order to establish guidelines and specifications for materials

which could be recovered from waste originally destined for disposal."

In addition, NBS was directed to cooperate with voluntary consensus

standards organizations, such as the American Society for Testing

Materials (ASTM), and to work with other federal agencies in

carrying out the mandates of the law.

II. FORMATION OF THE OFFICE OF RECYCLED MATERIALS

The NBS resource recovery program was formally established in

November, 1976. In 1978, the program was expanded to encompass NBS

responsibilities under the Energy Policy and Conservation Act of

1975 (EPCA, Public Law 94-163), section 383 of which requires NBS

to determine the substantial equivalency of used and virgin oils.

The work on recycled materials in response to Subtitle E of RCRA

and the Recycled Oil Program were combined into the NBS Office of

Recycled Materials (NBS/ORM). In late 1979, NBS added a Technical

Advisory Center, which was charged with the responsibility of

determining the geographic location of markets for recycled materials

and with developing an economic and technical database describing

resource recovery systems.

1
From 1976 through 1982, the NBS Office of Recycled Materials

(NBS/ORM) produced 123 articles and reports pertaining to the

mandates set forth under the laws to which its formation responded.

A list of these publications is reproduced as Appendix I. Since

this final report is a summary of NBS/ORM activities over seven years, details of the results will usually be referred back to this

publications list by number. Most of the publications listed are available from NBS. In addition to the written output, over 100

oral presentations were contributed to a wide variety of audiences.

Training seminars were held as were biannual symposia dealing with

recycled oil. Thus, NBS/ORM was careful to insure information and

technology transfer of its results to the appropriate clientele.

The NBS Office of Recycled Materials staff recognized from the

outset that recovering any materials from a waste destined for

disposal was possible, but purposeless unless a market could be

found for the recovered material. Therefore, materials to be

recovered had to be marketable at a price which made recovery

economically useful.

III. THE RECYCLED OIL PROGRAM

III. 1 . Introduction

The recycling of oil is not a new idea but, in fact, dates

back to about 1920. At that time lubricating oils had few or no additives, i.e., chemical compounds added to oils to improve

lubricating characteristics such as wear, oxidation, corrosion;

recycling these oils required only limited processing which included

heating (to remove volatile components), settling (to separate

water, dirt, and sludge), and finally centrifuging or filtering to remove most of the remaining insoluble contaminants. With this

limited processing, lubricating oils could be restored essentially

to original oil quality. Today, however, the types of lubricating

oils in the marketplace have expanded to include a wide variety of

different kinds and qualities of oils, many containing high levels

of additives which can make recycling the used oils a much more difficult problem.

In 1980, new lubricating oil sales in the U.S. were estimated

at 9.5 x 10 6 cubic meters (2.5 x 109 gallons) per year. Of this,

automotive lubricants represented 4.5 x 106 cubic meters (1.2 x 109

gallons), and industrial lubricants the remainder of approximately

5 x 106 cubic meters (1.3 x 109 gallons). The industrial lubricants

include hydraulic oils, quenching oils, cutting oils, metal working

oils, power generation lubricants, and oils used in industrial

process equipment (pumps, compressors, gears, etc.).

Of the 9.5 x 10 6 cubic meters of lubricating oils sold, about

one-half or approximately 4.8 x 106 cubic meters of collectible

used oil are generated annually in the U.S. Estimates suggest

that, of the used oil which is collected each year, about 7 percent

is re-refined into motor oil, 17 percent is reclaimed into industrial

oil, approximately 50 percent burned for fuel or used in road

oiling and dust control (often with little processing to remove

2
contaminants), and the fate of the remaining 25 percent (approximate

ly 1.2 x 106 cubic meters each year) is unknown.

At the present time there are a relatively small number of oil

recyclers in the U.S.; estimates range between 30 and 50. Of

these, only 10-20 are re-refiners, who produce a lubricating oil

basestock from the used oil. The individual companies involved in

oil recycling usually are small, averaging only 10-15 employees.

These recyclers fall into three categories: processors (who clean

up used oil for reuse as a fuel, often removing free-standing water

and heavy sludge or dirt); reclaimers (who usually apply a variety

of relatively simple chemical and/or physical processes to recondition the used oil for reuse as an industrial oil); and re-refiners

(who employ a number of different re-refining technologies, usually

with acid/clay or distillation/ finishing treatment, to remove most

of the impurities and contaminants, to yield clean, quality lubricat

ing base oils). In many cases an oil recycler may be involved with

more than one of these categories, and at times with all three.

In the past, there have been a number of regulatory obstacles

to increased recycling of used oils in the U.S. Two of the most

significant of these were: 1) a 1965 Federal Trade Commission (FTC)

trade regulation rule, and 2) the exclusionary clauses in various

Federal and military specifications. The first of these, the FTC

trade regulation rule, required that all recycled motor oils

contain the label "...made from previously used oils...". This

requirement was considered harmful to the image of re-refined oils,

and was recently modified by the Used Oil Recycling Act of 1980 (P.

L. 96-463). This law now removes the FTC requirement of labeling

as to origin until future labeling standards mandated by the Energy

Policy and Conservation Act (P. L. 94-163, Section 383) become

effective i.e., NBS test procedures as provided to the FTC.

The second obstacle to increased recycling of used oils had

been the specific prohibition of the use of recycled petroleum

products found in a number of Federal and military specifications,

e.g., burner fuels and engine oils, regardless of the quality of

the recycled products. In response to requirements in the Resource

Conservation and Recovery Act (P.L. 94-580), hereinafter called

RCRA, and after a substantial study, the Department of Defense

(D0D) has recently issued revised specifications for both burner

fuel oil (Federal specification VV-F-815d) and engine oils used in

administrative vehicles (passenger cars and light trucks; MIL-L461 52B). These revised D0D specifications now allow the use of

recycled oils in products submitted for D0D use, provided these

recycled products meet all requirements.

Technically, recycled lubricating oil products appear to be

potentially suitable for all end uses with proper clean-up and

additive treatment, since the basic hydrocarbon structure is not

significantly altered during use. While non-technical factors such

as economics and availability will determine whether some or even

all potential end uses for recycled oil can be realized on a

3
realistic basis, the national goals of energy conservation, resource conservation, pollution control, and balance of payments certainly

suggest that strong efforts should be made in pursuing the goal of

effective oil recycling in the U.S.

III. 2. Implementation of the NBS Recycled Oil Program

The NBS Recycled Oil Program was established in 1976, in

direct response to passage of the Energy Policy Conservation Act of

1975 (EPCA, Public Law 94-163; 42 U.S.C. 6201 et seq. ) Section

383(c) of this law requires NBS to " ... develop test procedures

for the determination of substantial equivalency of re-refined or otherwise processed used oil or blend of oil ... with new oil for a particular end use."

The goal of the Recycled Oil Program was: To provide the

measurement methods and standards required for effective utilization of recycled petroleum products. This goal was pursued by:

o establishing the scientific and technical basis for characterization of recycled petroleum products;

o developing and evaluating test procedures for establishing

substantial equivalency between recycled and virgin petroleum

products; and

o providing technical information and support for the effective

utilization of recycled petroleum products.

These goals were implemented through research and development

activities both within NBS and at several outside institutions.

The latest results were presented at the fourth NBS Conference on Measurements and Standards for Recycled Oil, held on September

14-16, 1982. Abstracts of papers by NBS or NBS funded research and

development are included in Appendix II. Full texts of these

papers will be published in the conference proceedings.

III. 3. The NBS Role in Recycled Oil

Three areas of legislation provided the framework for NBS

responsibilities in oil recycling. These include: 1) the National

Bureau of Standards (NBS) Organic Act and its amendments; 2) the

Energy Policy and Conservation Act; and 3) the Resource Conservation

and Recovery Act. The model "States Used Oil Recycling Act," while

not a specific article of legislation, also had an influence on the

NBS responsibilities, and will be discussed briefly.

The NBS Organic Act (particularly 15 U.S.C. 272) states that

NBS responsibilities include in part "... the development of

methods for testing materials ... cooperation with other governmental

agencies and with private organizations in the establishment of

standard practices ... the preparation and distribution of standard

samples ... the development of methods of chemical analysis ...."

While these functions do not specifically consider the subject of

4
recycled oil, they are consistent with the efforts required of the

Recycled Oil Program as described in Sections 111.(4) and 111.(5).

The Energy Policy and Conservation Act (EPCA, Public Law

94-163; 42 U.S.C. 6201 et seq. ) was the primary force in establishing the Recycled Oil Program at NBS in September 1976. Section

383(c) of this law requires NBS to "... develop test procedures for

the determination of substantial equivalency of re-refined or otherwise processed used oil or blend of oil ... with new oil for a particular end use." The stated purposes of this legislation were:

1) to encourage the recycling of used oil; 2) to promote the use of

recycled oil; 3) to reduce the consumption of new oil; and 4) to

reduce the environmental hazards associated with disposal of used

oils.

The Resource Conservation and Recovery Act, RCRA, 42 U.S.C.

3251), in section 6002, states that each Federal agency shall

procure items with the highest percentage of recovered materials

practicable. RCRA further states that any decision not to procure

such recycled material must be based on one or more of the following:

unavailability; unreasonable price; or failure to meet NBS performance

standards (when available). This act includes recycled oils as well as other recycled materials, and when taken in combination

with the EPCA, requires that NBS address the problem of performance

standards for recycled oils. In addition, this law requires that

exclusionary clauses in Federal and military specifications be

reviewed by the appropriate Federal agency, and revised to encourage

the use of recycled materials.

Finally, a model state "Used Oil Recycled Act" was sponsored

by the Federal Energy Administration in 1976 and published in the

Federal Register. This model act was designed to assist individual

states in establishing control over used oil disposal, and clearly

encourages recycling as a superior method of disposal. This model

act refers directly to section 383 of EPCA for the determination of

substantial equivalency for recycled petroleum products. Used oil

recycling laws have been passed by at least eight states to date,

and in many cases these laws are similar to the model act. Several

additional states have also introduced legislation based on this

model act.

The NBS role was reaffirmed by passage of the "Used Oil

Recycling Act of 1980" (P. L. 96-163). This act was passed late in

1980 to alleviate the problem oil recyclers were having as a result

of the FTC labeling requirements, but is to remain in effect only

until the NBS test procedures become available. The U.S. Congress

Committee report further states " ... the Committee believes that

the work of the Bureau (of Standards) should continue .... The

Committee expects the Bureau to give this work a high priority." 3

An important reason why recycled lubricating products have not

yet met with widespread consumer acceptance, both by the Federal

government as well as by the public, is the lack of reliable test

procedures and standards on which realistic performance criteria

5
can be based. In the aforementioned legislation, particularly

EPCA, NBS was directed to develop such test procedures and standards.

These procedures will provide the basis for industry-wide performance

standards and labeling requirements for recycled oil.

The resolution of this problem by NBS is particularly appropriate because it involves both the development and evaluation of

measurement methods and standards, and because it requires an independent third party role for acceptance by all concerned

parties (virgin oil refining industry, oil recycling industry, user industries, and government regulators). One alternative to increased

recycling of petroleum oils is continued contamination of the

environment and loss of a valuable resource. Recently published

data indicate that, of all crude petroleum and petroleum products

reaching the ocean, over 40 percent is due to used lubricating

oils.

III. 4. Achieving Special Objectives

The three basic objectives of the program were to:

1) Establish the scientific and technical basis for characterization of recycled petroleum products.

2) Develop and evaluate test procedures for establishing the

substantial equivalency between recycled and virgin

petroleum products.

3) Provide technical information and support for the effective

utilization of recycled petroleum products.

The first objective deals with the research required to

effectively utilize recycled lubricating oils. There is a concern

among some user industries, especially the automotive industry,

about the quality and batch-to-batch variability of re- refined

oils. In addition, the various impurities and contaminants which

can occur in a used or recycled petroleum product were of concern.

A sound scientific and technical data base was crucial for the test

procedures developed by NBS to be widely accepted by industry.

The second objective embodied the basic requirement for NBS

action as set forth in EPCA. Realizing this objective was complicated

by the current testing methods used. These tests called "engine

sequence tests," call for placement of automobile/truck engines

and/or special test engines onto laboratory dynamometer test

stands; the actual tests are then run in sequence with different

loads, speeds, temperatures, controlled blowby (gases bypassing the

piston rings), etc., usually requiring special fuels. A series of

controlled variables must fall within prescribed limits for the oil

being investigated to have "acceptable" test results reported. For

the American Petroleum Institute API SF classification, i.e., the

oil quality currently necessary to maintain 1981 automobile warranties, four different engine tests must be passed. For military

6
specifications for administrative vehicles (MIL-L-46152B, approximately equivalent to API classification SF/CC), five engine sequence

tests are needed. The minimum cost of a set of these tests for a single oil is at least $30,000 for four tests, and $38,000 for five

tests. Since there is no alternative set of commonly accepted test

procedures or specifications for physical and chemical laboratory

tests on oil basestocks or formulated oils, small re-refining

companies have had a difficult time entering the lubricating oil

market due to the high costs.

The third objective, to provide technical information and

support for the effective utilization of recycled petroleum products,

is important in accommodating recycled products for each end use. This objective includes providing technical support as required for

the NBS test procedures, as well as to disseminate the NBS research

and evaluation results and other technical information on used and

recycled petroleum products to the industry and the consumer

public. Both the EPCA and RCRA legislation contain sections which

emphasize the necessity for Federal agencies to encourage the

utilization of recycled products, and to educate the public with

respect to the proper reuse and disposal of these products.

III. 5. Program Plan and Results

The initial emphasis of the NBS Program from 1976 to 1978

concerned used oil recycled for use as fuel. This choice was made

for a number of reasons:

o The primary fate of used oil at present is through burning for

fuel, and is largely uncontrolled;

o There appear to be operational and environmental problems

arising from uncontrolled burning of used and minimally

processed recycled oils; and

o Use of waste oil as fuel could be addressed with the limited resources available at that time.

In November of 1978, the official report on Phase I of the

Recycled Oil Program, "Test Procedures for Recycled Oil Used as Burner Fuel," was transmitted to the Federal Trade Commission

(NBSIR 78-1453; later issued as NBS Technical Note 1130; see Publications List #7). This report contains test procedures for

the operational performance of recycled oils used as burner fuel

oils. Simultaneously, Phase II of the NBS Program, "Test Procedures

for Recycled Oil Used as Motor Oil," was initiated.

There has been sufficient engine testing on re-refined oils to

establish that: 1) a quality re-refined lubricating oil which has

been formulated with a high quality additive package can be

comparable to a virgin oil similarly formulated, and 2) both such

oils will provide satisfactory performance in automotive service.

The problem which existed was the lack of technical information and

data to determine which tests are necessary and how often they

should be applied in order to assure that the re-refined oil

7
basestock is consistent in between the engine testing. The user industries have made it clear that they are concerned about the

potential lack of consistency of re-refined oil products, and about

the potential effects of unusual or unknown contaminants in the

used oil feedstock to re-refineries. These potential problems are of particular concern when warranty questions are involved.

The most important requirement for assuring the quality of

re-refined motor oil was development of a set of test procedures

capable of monitoring the quality, consistency, and additive

response of the oil basestock in between engine qualifications.

These selected and evaluated test procedures are crucial in order

to allow accommodation of the re- refined oils within the existing

API-SAE-ASTM classification system. (Note: API = American

Petroleum Institute; SAE = Society of Automotive Engineers; ASTM = American Society for Testing and Materials.) Development and

evaluation of these tests by NBS was significantly more difficult

because no such set of test procedures exists for virgin lubricating

oils. Historically, virgin oil producers were instead required to

control the crude source and refining technology in order to assure

a constant lubricating oil basestock, particularly for the U.S.

military specifications. This option was not available to oil

recyclers.

The question of the consistency of re-refined oil was addressed

in a cooperative ASTM/NBS/ORM Basestock Consistency Study. In this

one-year study, four virgin oil producers and six re-refined oil

producers submitted monthly samples of their regular production

basestock for analysis by a group of 14 laboratories, including NBS

(table III.l). These laboratories analyzed the coded samples using over 40 different chemical, physical, and performance tests (tables

III. 2-4). This database hopefully will provide the information

necessary to indicate an appropriate set of test procedures to

monitor re-refined basestock consistency. In addition to the

consistency study, NBS/ORM evaluated the chemical and physical test

procedures used on lubricating oil basestocks, and also performed

research and development on bench-scale performance tests fcr

establishing basestock additive response. Development of effective

and economical test(s) for additive response was crucial to the success of our efforts.

Therefore, the strategy that NBS adopted (see fig. III.l) in

providing a methodology for establishing the substantial equivalency

of re-refined engine oils on a routine basis, first calls for the

formulated oil quality to be determined by means of all current

industry required performance tests. Further, after the quality of

the formulated re-refined oil has been established, the consistency

of the re-refined basestock can be monitored as a function of time

through use of NBS proposed consistency tests. The concept of

engine testing for quality, combined with consistency monitoring

with physical, chemical, and bench tests (if needed) has been

discussed previously and is included in the current military

specification for administrative vehicle engine crankcase oil

(MIL-L-46152 B) and is proposed for the tactical vehicle engine oil

8
Table III . 1. Laboratories cooperating in the ASTM/NBS

basestocks consistency study.

Bartlesville Energy Technology Center Chevron, USA

National Research Council of Canada Suntech, Inc.

Motor Oils Refining Co. SAVANT, Inc.

Mobil Oil Corporation Texaco

U.S. Army MERADCOM Lubrizol

National Bureau of Standards Gulf R&D

Shell Research/Thornton (U.K.) Filmite

Table III. 2. Physical property tests.

TEST Method

API Gravity ASTM D287

Aromatics HPLC; UV

Boiling Point Range ASTM D2287 (GC)

Brookfield Viscosities ASTM D2983

@ 0° to -40 °F

Carbon residue ASTM D524

Color ASTM D1500

Demulsibility ASTM D1401

Filterability (1)

Foam ASTM D892

Oxidation (1)

Pour Point ASTM D97

Refractive Index ASTM D1218

Sulfated Ash ASTM D874

Viscosities @ 40 °C and 100 °C ASTM D445

Viscosity Index ASTM D2270

(1) Proprietary

9

I
Table III. 3. Chemical property tests.

Test Method

Acid Number

Bromi ne Chlorine

Ethylene Glycol

Metals

Nitrogen

Oxygen

Potassium

Saponification Number

Sodium

Sul fur

Water

Carbon-13 NMR Analysis

Polycyclic Aromatics by DMSO

Extraction

Hydrocarbon Types by TLC/FID

High Resolution Mass

Spectrometry

Polychlorinated Biphenyls (some samples)

Chromatographic Separation of HC

Differential Infrared

ASTM D664

Neutron Activation

Neutron Activation

(1)

Emission Spectrograph

Chemi 1 umi nescent

Modified UOP

Neutron Activation

ASTM D94

Neutron Activation

ASTM D1551

ASTM D1744

IP 346

(1)

HPLC/GC

ASTM D2007; ASTM D2549

(1) Proprietary

Table III. 4. Bench tests.

Anti-Oxidant Response (1)

Cold Crank Simulator @ 0° to -40 °C ASTM D2602

Differential Scanning Calorimeter —

Ford Anti-Oxidant Capacity —

Load Wear Index ASTM D2783

Mini -Rotary Viscometry ASTM D3829

RBOT ASTM D2272

Rust Tendency ASTM D665

Sequence III Simulator (1)

Storage Stability —

TOST ' ASTM D943

LUBETOT

^^Proprietary

10
PROPOSED BASESTOCK

CHARACTERIZATION

TESTS

PROPOSED BENCH

TESTS FOR ADDITIVE

RESPONSE

\ r JL

INDUSTRY

PERFORMANCE

TESTS

YES

< f

"SUBSTANTIAL EQUIVALENCY"

(Qualified Re-refined Oil)

Figure III. 1 . Proposed Re-refined Engine Oil Qualification

Procedure.

11
specification (MIL-L-2104 D). This methodology is discussed in more detail in Section 111.(6) of this report.

III. 6. Proposed Test Procedures for "Substantial Equivalency

At the September, 1982 recycled oil conference, NBS proposed a re-refined oil testing system meant to be capable of establishing

the "substantial equivalency" of re-refined to virgin engine oil.

This system is composed of two parts, one being the proposed

re- refined oil qualification procedure and two being the proposed

re-refined oil consistency monitoring procedure. The latter can be

used to monitor the re-refined oil, once quality has been established

through appropriate engine testing.

III. 6. a. Performance Tests (Qualification Procedures)

The performance tests proposed for use with re-refined oil are identical to those necessary for the various API Engine Service

Classifications and the military specifications for engine oil, and

are listed in table III. 5. The primary performance criteria for

these tests are also found in SAE J-183 and SAE J-304, ASTM STP

315, ASTM STP 509 and Federal Test Method STD #79.

Re-refined oils to be engine tested and monitored for consistency under the proposed system described here usually will have been

fully formulated with an engine oil crankcase additive package, and

will have been found to provide acceptable performance with that

specific additive package and at that specific treat level. The

actual engine testing may be obtained through various means, e.g.

purchased at commercial test facilities; run by additive supplier

as a customer service.

Concurrent with the engine testing, in order to implement the

proposed system discussed here, a complete set of base oil characterization tests (as described in III. (6)b) must be made of that

same re-refined base oil (and formulated oil, to be used with the

bench test for additive response) in order to determine the baseline

data required to monitor the basestock consistency.

The proposed system of tests should be applicable to as many

categories as possible. They may apply to the CD category as well,

but that has not been evaluated. Thus, the API Service categories

include, in addition to the SF category, oils classified as SA, SB,

SC, SD, SE, CA, CB, and CC. These oils are described in table 5

along with their respective current engine test requirements as taken from SAE recommended practice J-183. Where such categories

are accepted by the lubricant industry, it could be expected that

re- refined oil would need to meet the same testing requirements as the virgin engine crankcase oils. However, for some of the API

Service categories, the engine tests are obsolete or no engine

tests are required. While these oils may represent only about 20

percent of the engine oil market, nevertheless some oils in these

categories are actively produced and marketed, and are at least

12
Table III. 5. General requirements

categories and U.S. military

API Engine

Servi ce Use

for API engine service

speci f i cations.

Current Engine

Test Requirements'

SA

SB

SC

SD

SE

SF

CA

Utility Gasoline or Diesel Engines

Minimum Duty

Gasoline Engines

1964-1967-Gasoline

Engine Warranty

Service

1968-1970 (some 1971)

Gasoline Engine

Warranty Service

1971-1979

Gasoline Engine Warranty

Service

1980 and newer-Gasoline

Engine Warranty Service

Light Duty Diesel Engine

Service

none

Sequence IV (obsolete); L-38

Sequences IIA, IIIA, IV, V

and L-l (all obsolete); L-38

Sequences I IB , II IB , IV, VB,

L-l or 1-H, Falcon (all obsolete); L-38

Sequences I ID , HID, VD; L-38

Sequences IID, HID, VD ; yc

L-38

L-l (obsolete); L-38

CB

CC

CD

MIL-L-46152B

Moderate Duty Diesel

Engine Service

Moderate Duty Diesel

and Gasol ine Engine

Service; (includes some current automotive

requi rements

Severe Duty Diesel

Engine Service

Military specification

for crankcase lubricants

for administrative vehicles (approximately

equivalent to SF/CC

1 ubricant)

L-l (obsolete); L-38

LTD (obsolete) ; L-38, IID,

1-H2

1-G2, L-38

IID, HID, VD, L-38, 1-H2

13
Table III. 5 (cont'd)

API Engine

Service Use

Current Engine

Test Requirements

MIL-L-2104Cyd Military specification

for crankcase lubricants

for heavy duty diesel

engines (approximately

equivalent to SC/CD

1 ubricant) IID, HID, VD, L-38, 1-G2

a0btained from the 1981 SAE Handbook.

^Old Engine Service categories; should not be used in any engine

unless specifically recommended by manufacturer.

c Sequence Tests for SF have different performance criteria then for

the SE categories.

"^While this test is listed as obsolete in J-183 (1981 SAE Handbook),

ASTM has provided special criteria to allow it to be used for

evaluating CC oils, if required.

e Not an API Service categories, but a separate military specification.

14
tolerated by the lubricant and automotive industries. For example,

in the API Service category SA, no engine tests or other tests are currently required for either virgin or re-refined oils. Therefore,

in the system proposed in figure 1 as well as in current industry

requirements, a re-refined oil would meet the requirements for

substantial equivalency to an SA virgin oil with no testing. This

unfortunate situation would exist until such time as testing

requirements are instituted by the API for their Service category

SA.

I I I . 6. b. Provisional tests for re-refined basestock consistency

For the past four years, the NBS Recycled Oil Program has

carried out an extensive research effort on lubricating base oil

characterization and testing. That research culminated in a series

of publications detailing the evaluation of existing test procedures

for use with re-refined oils, the development of new tests where it was felt that existing tests were not adequate, and the determination

of which characteristics of re-refined oil should be tested in

order to monitor consistency in a re-refined oil already shown to

be capable of producing a high quality crankcase oil.

These publications include many of the papers presented at the

1982 NBS Recycled Oil Conference, as well as a number of additional

papers already published or in the process of being presented and

published (Publications List #'s 16-37). In particular, the paper

entitled, "Re-refined Base Oil Characterization and Consistency

Monitoring," summarizes the data and findings of this research

effort (Publ. List #106). Subjects covered in this paper include:

lubricating base oil quality; re-refined base oil characterization;

comparison between re-refined and virgin base oils; physical

properties; chemical properties; hydrocarbon structures; effect of

viscosity grades on properties; contaminant isolation and analysis;

bench performance characterization of oxidation and wear; base oil

composition-oxidation performance correlation; and consistency of

re-refined base oils.

The data and results presented in these publications are far

too extensive to discuss in detail here, but in summary, the

results thus far show that some re-refined base oils, when compared

to a set of typical medium to low sulfur crude derived virgin base

oils in approximately the same viscosity grades, showed measurable

and real differences in some characteristics, e.g, oxyacids, VI

improvers, chlorine, additive/wear metals and in some test results,

e.g., total acid number (TAN), saponification number (SAP. NO.).

Since the effect of all such variations on performance is still not

well understood, a two level testing system is being proposed for

the measurement of re-refined oil consistency as shown in figure

III. 2. Initially, the re-refined base oil undergoing engine

testing would be characterized using the following physical/chemical

tests (table III. 6): API gravity, viscosity index, pour point,

flash point, sulfated ash, TAN, SAP NO., clay-gel chromatography,

chlorine, boiling point distribution by gas chromatography, infrared

spectroscopy, and metals analysis, e.g., by atomic absorption (AA) or emission spectroscopy (ES). Further, after formulation with the

15
PRIMARY

CONSISTENCY

TEST

PROCEDURES

\ t

SECONDARY

CONSISTENCY

TEST

PROCEDURES

YES

t

CONSISTENT

(Maintains Qualification) 1

'

YES

Y

CONSISTENT

(Maintains Qualification)

Figure III. 2. Proposed Re-refined Engine Oil Consistency

Monitoring Procedure.

16
Table III. 6. Proposed provisional test procedures.

Provi sional

Consistency Tests

Characterization Tests Reference Primary Secondary

API Gravity (Density) ASTM D287 X

Viscosity Index ASTM D2270 X

Pour Point ASTM D97 X

Flash Point ASTM D92 X

Sulfated Ash ASTM D874(M)ya X

Total Acid No. (TAN) ASTM D664 X

Saponification No. (SAP. NO) ASTM D94 X

Clay-gel Chromatography ASTM D2007 X

Chlorine Analysis Publ. List # X

Boiling Point Dist. by GC ASTM D2887 X

Infrared Spectroscopy b X

Metals Analysis AA, ES X

Thin Film Oxygen Uptake Publ. List # X Test (TFOUT)

Four ball Step Loading Publ. List #

Seizure Test (SLST)

Bearing Corrosion Test c X

aAs modified; see Publ. List #36

^See equipment manufacturers literature for determination of relative carbonyl absorption.

NBS research on this test is not complete; Fed. Test. Method Std.

79 appears to provide a test with appropriate correlation to the

L-38 engine test.

17
additive package, the following bench tests would be made: NBS

thin film oxygen uptake test (TFOUT), NBS four-ball step loading

seizure test (SLST), and a bearing corrosion test.

The resultant data would then be used to establish a set of

limits for each of the above tests. The actual procedure to be

used in developing these test limits probably should be developed

by joint government/ i ndustry/ASTM groups. Once established,

subsequent production samples of re-refined oils can be tested

without additives in seven tests (table III. 7): API gravity,

viscosity index, pour point, flash point, sulfated ash, TAN and

SAP. NO. If the base oil meets the preset limits, the oil is then

blended with the same additive package used to pass the engine

tests, and tested in the TFOUT test. If the TFOUT test result

meets the preset limit, the re-refined base oil could then be

declared consistent.

However, if the re- refined base oil fails to meet the limit(s)

in one or more parameters, then one or more additional tests are indicated. The additional ("secondary") tests needed to further

evaluate the characteristics for each of the primary tests are listed in table III. 7. Results from the additional tests should be

compared with the baseline characterization tests results of the

initial sample. If the results deviate significantly from the

preset limit(s), the sample under test should be rejected as inconsistent. The overall characterization scheme is shown in

figure III.l and table III. 6, and the consistency monitoring scheme

in figure III. 2 and table III. 7.

The success of this proposed consistency monitoring system

relies heavily on the reasonableness and technical soundness of the

limits derived from the initial characterization testing.

III. 7. Discussion of a Potential Test Procedure

Verification Effort

The engine oil testing system as proposed by NBS hopefully

will be capable of providing an adequate methodology for establishing and monitoring the substantial equivalency of re-refined

lubricating oil basestocks to be used as engine crankcase oil.

Performance tests, including particularly the engine tests, Part

One of the testing system, are fully accepted throughout the

lubricant industry as indicators of engine oil quality. Part Two

of the testing system, the set of provisional physical/chemical/additi

response tests to monitor consistency in the refined oil basestock,

provides a mechanism for possible quality control.

With respect to the set of provisional tests for consistency,

a period of verification of these tests would appear to be necessary

before full implementation should be attempted. That is, a controlled

18
Table III. 7. Provisional tests for consistency monitoring

Primary Test

API (Gravity)*

Viscosity index

Pour point

Flash point

Sulfated ash

TAN

Saponification number

NBS TFOUT test

Secondary Test (if the Oil Fails to

Meet the Limits of the Primary Test

ASTM D-2007 (saturates)

ASTM D-2007 (polars)

ASTM D-2007 (aromatics and saturates)

Boiling Point Distribution by GC

Metals analysis by AA/ES

Chlorine + bearing corrosion test

+ 4 ball wear test (SLST)

Chlorine + carbonyl by IR + 4 ball

wear test (SLST)

Reject

Equivalent to density/specific gravity.

19
application of these tests to re-refined oils over a period of time

is needed to insure that they are completely capable of fulfilling

the requirements of consistency monitoring. Upon successful

completion of such a verification process, the provisional re- refined engine oil testing system as described here, should be an acceptable procedure for establishing that a re-refined engine oil

product is substantially equivalent to a virgin engine oil.

At present, who will ultimately complete the verification

effort described above is not clear. Certainly, ASTM and/or SAE

would have the necessary technical expertise, but it is not obvious

at this time whether sufficient motivation exists in these organizations to move strongly into fulfilling these verification needs.

Several industry associations have made an effort to convince the

Congress to provide additional funding for NBS to continue to

characterize recycled oil in FY 1983. If funds are provided by

Congress, NBS has agreed to continue to study recycled oil, even though the NBS/ORM officially ceased to exist as of September 30,

1982.

If funded, the primary effort for NBS in FY 1983 will be to

initiate the requisite verification process. Another important

effort will be to initiate discussions on the proposed set of tests

with various industrial, technical and governmental organizations

to obtain their views on these tests. Under normal circumstances,

these discussions would have occurred prior to presentation of the

proposed tests at the NBS Recycled Oil Conference (September 14-16,

1982). But, due to the then imminent termination of the Program,

all available resources were concentrated on completing the research

necessary for presentation of the test procedure evaluation and

development; this work was only completed immediately prior to the

NBS Conference.

III. 8. Summary of Achievements

In the six years of its existence, the Recycled Oil Program of

NBS/ORM has effectively responded to the legislative mandates of

the Energy Policy and Conservation Act. During this time, the

Recycled Oil Program of NBS/ORM and the associated Tribochemi stry

Group (headed by Dr. Stephen M. Hsu) in the NBS Center for Materials

Science, have established a lubricating oil research center that

has rapidly advanced to the forefront of lubrication research in

the U.S. The efforts of this group have culminated in work that is

likely to substantially affect both re-refined and virgin lubricatin

oil standards and testing in the future. In addition, this team

has cooperated with many technical and trade organizations as well

as private companies and government agencies. Wide dissemination

of results and information to all interested parties has been

achieved.

Major highlights of these NBS/ORM efforts include the following

1) Organized and held four major Conferences on Measurements

and Standards for Recycled Oil (1976, 1977, 1979, 1982).

20
The widely disseminated Proceedings from these Conferences

have included virtually all of the significant activities

in oil recycling during this period.

2) Was instrumental in creating the new ASTM Technical

Division P, on Recycled Petroleum Products and Lubricants.

This Technical Division now has over 100 active members.

3) Established outstanding laboratory facilities, equipment,

and sample storage/blending facilities in support of the

state-of-the-art research activities in the Tribochemi stry

Group.

4) Obtained senior staff member from a major additive

company to head research efforts; obtained and trained

non-lubrication scientists into cohesive, productive

lubrication research group. Also obtained two Industrial

Research Associates during this period.

5) Completed an extensive ASTM/NBS re-refined oil basestock

consistency study. In this study, monthly oil samples

from six re-refiners and four virgin oils refiners, after

subsampling and coding by NBS, were analyzed for 47

characteristics by 14 laboratories in three countries.

These results are the most extensive ever compiled on a representative set of lubricating oils, and provided the

data necessary for the selection of the proposed NBS

tests for re-refined oil basestock consistency.

6) Provided cooperative efforts in support of four important

non-NBS recycled oil programs:

o U.S. Army MERADCOM's development of several Federal and

Military Specifications which now allow the use of

re-refined or recycled oil.

o Environment/Canada's fleet test evaluation of re-refined

oil in Royal Canadian Mounted Police vehicles.

o Department of Energy's continuing study on the fate and

effects of contaminants in used oil feedstocks provided

to re-refiners and recyclers.

o Conducted PCB analysis round robin in support of ASTM

efforts to develop an analytical procedure for PCBs in

used oils.

An independent confirmation of the effectiveness and quality of the

above efforts took place in October, 1982, at the annual Society

for Automotive Engineers Fuel and Lubricants Meeting in Toronto.

At a special symposium on base oils for automotive lubricants, NBS

lubrication research scientists associated with the Recycled Oil

Program provided three out of the total of eight invited papers.

21
In conclusion, the Recycled Oil Program of NBS/ORM provided

test procedures for recycled oil used as burner fuel [NBS Technical

Note 1130 (1980)], and proposed a system for the effective utilization of re-refined oil as automotive engine oil, including a proposed set of test procedures for re-refined basestock consistency.

These test procedures are expected to be effective in providing the

technical foundation for the efficient utilization of recycled oil

products. Some 49 papers and reports have been published (Publ.

List rs 1-38 and 99-109).

22
IV. RECYCLED MATERIALS PROGRAM IN RESPONSE TO RCRA

IV. 1. Mandates and General Approach

Specific legal mandates assigned to the Secretary of Commerce

and delegated ultimately to the NBS Office of Recycled Materials

are to be found in the Resource Conservation and Recovery Act of

1976 (P. L. 94-580), as amended (P. L. 96-482). (The following is

reproduced directly from P. L. 94-580)

"Subtitle E -- Duties of the Secretary of Commerce in Resource

Recovery

"FUNCTIONS

"SEC. 5001. The Secretary of Commerce shall encourage greater

commercialization of proven resource recovery technology by providing

"(1) accurate specifications for recovered materials;

"(2) stimulation of development of markets for recovered

materials;

"(3) promotion of proven technology; and

"(4) a forum for the exchange of technical and economic data

relating to resource recovery facilities.

"DEVELOPMENT OF SPECIFICATIONS FOR SECONDARY MATERIALS

"SEC. 5002. The Secretary of Commerce, acting through the

National Bureau of Standards, and in conjunction with national

standards-setting organizations in resource recovery, shall, after

public hearings, and not later than two years after the date of the

enactment of this Act, publish guidelines for the development of

specifications for the classification of materials recovered from

waste which were destined for disposal. The specifications shall

pertain to the physical and chemical properties and characteristics

of such materials with regard to their use in replacing virgin

materials in various industrial, commercial, and governmental uses.

In establishing such guidelines the Secretary shall also, to the

extent feasible, provide such information as may be necessary to

assist Federal agencies with procurement of items containing

recovered materials. The Secretary shall continue to cooperate

with national standards-setting organizations, as may be necessary,

to encourage the publication, promulgation and updating of standards

for recovered materials and for the use of recovered materials in

various industrial, commercial, and governmental uses.

"DEVELOPMENT OF MARKETS FOR RECOVERED MATERIALS

"SEC. 5003. The Secretary of Commerce shall within two years

after the enactment of this Act take such actions as may be necessary

to --

23
"(1) identify the geographical location of existing or potential markets for recovered materials;

"(2) identify the economic and technical barriers to the use

of recovered materials; and

"(3) encourage the development of new uses for recovered

material s.

"TECHNOLOGY PROMOTION

"SEC. 5004. The Secretary of Commerce is authorized to

evaluate the commercial feasibility of resource recovery facilities

and to publish the results of such evaluation, and to develop a data base for purposes of assisting persons in choosing such a system.

Other than oil, NBS involvement with recycled materials spans

several decades. However, the program described here dates from

1973 when data concerning reactions from incineration of municipal

solid waste were obtained by the Physical Chemistry Division. In

1976, the Congress via the Resource Conservation Recovery Act

(RCRA), assigned DOC and NBS direct responsibilities for research

concerning recycling. The Office of Recycled Materials within NBS was the Departmental focal point for fulfilling these legal mandates.

The goals and objectives of the RCRA program were as follows:

IV. 1. a. Goal

To improve the Nation's productivity and innovation by providing

a framework for fostering the advances required to optimize the mix

of economic and environmental factors associated with the disposal

and subsequent recovery and/or reuse of resources contained in

municipal, industrial, commercial and hazardous solid wastes.

IV.l.b. Objectives

1) To develop methodologies for the economic assessment of

current and potential technologies, market potentials, and institutional barriers relative to resource conservation and recovery, and

to assist public and private sectors to fully utilize both the

methodologies and information derived therefrom; 2) to evaluate

current and innovative technologies for the conservation of materials,

as well as the recovery, reuse, and recycling of waste materials

from all potential sources including industrial processes; 3) to

provide for the economic retention and development of businesses

and industries through mitigation of the impact of Federal regulatory policies, particularly environmental actions, and by utilizing

the potential of new business opportunities and growth.

The NBS efforts were divided into three main categories:

1. Direct laboratory-based research aimed at achieving the

goals of RCRA;

24
2. Examination of governmental policies with respect to

procurement of products containing recovered materials;

and

3. Identification and assessment of the need for uniform

physical and chemical measurements which derive from

laws, regulations and policies at the state and local

level

IV. I.e. Technical Advisory Center

A Technical Advisory Center (TAC) was established in late 1979

to provide a framework for fostering the advances required to

optimize both economic and environmental factors associated with

recovery and/or reuse of resources contained in solid wastes. The

TAC accomplished these goals by developing methodologies for the

economic assessment of current and potential technologies and

market potentials, as well as by identifying institutional barriers

to resource conservation and recovery; by assisting the public and

private sectors to utilize the methodologies and information; and,

by identifying the potential for new business opportunities and

growth. TAC's primary function was to assure implementation of

RCRA responsibilities of the Department, which were (i) encouragement of the commercialization of proven technology; (ii) stimulation

of the development of markets for recovered materials, and (iii)

evaluation of the commercial feasibility of resource recovery

facilities as well as the development of an information base to

assist communities and other entities in selection of a recovery

system.

IV.l.d. NBS/ORM Participation with the Waste Management Policy

of the Organization for Economic Cooperation and Development

The Waste Management Policy Group (WMPG) of the OECD has

eighteen active member nations representing virtually the entire

industrialized portion of the non-communist block. The mandate of

the WMPG is to:

o Identify and develop the essential elements of an overall

waste management policy to meet both economic and environmental objectives.

o Focus special emphasis on such issues as waste reduction,

encouragement of recycling and recovery of resources from

waste, hazardous waste challenges, and the promotion of energy

recovery from waste.

Since the mandates of Subtitle E of RCRA and the WMPG are quite

similar, participation in the endeavors of the WMPG provided

NBS/ORM a voice in international waste management policy. Such

activity enabled DoC to be aware of and to benefit from detailed

knowledge of international practices and experience. The Chief,

NBS/ORM served as a member of the U.S. Delegation to WMPG from 1979

through 1982.

25
IV. 2. General Statement of the Challenges Posed by the Need

To Deal with Municipal Waste

There is generated in the United States about 150 million tons

of post-consumer solid waste per year and well over 50 million tons

(dry basis) of potentially hazardous wastes, the disposal of which

involves methods that often preclude any future value to the

national economy and which indeed may be hazardous to the human

envi ronment.

Table IV. 1 taken from the National Recycling Directory (compiled

under the aegis of NBS/ORM, Publ. List #60) lists some uses for a variety of recovered materials. In cases where paper and other

wastes are mixed, energy can be reclaimed by burning such materials.

Chemical wastes, in a number of instances, can be recovered with

conventional technology and reused. This process can reduce the

burden of disposing of these potentially hazardous materials. Many

of the materials and substances found in waste destined for disposal

can be reclaimed in some potentially useful form. The generic term

for such activity is "resource recovery."

There are various methods of resource recovery that can be

employed, from source separation to mass burning, to the use of more advanced technology that can further enhance the value of the

recovered commodities. No matter which method is selected, however,

it must be designed to provide recovered commodities in an acceptable form and at acceptable prices to achieve full marketability.

Therefore, dealing with solid waste represents one part of a larger

waste management strategy involving environmental considerations,

health and safety aspects, transportation factors, labor and other

institutional factors. The foundation underlying any such strategy

is the "bottom line," i.e., economic efficiency.

In dealing with newer concepts and technologies for recovery

and reuse of resources destined for waste, several parties must of

necessity be involved. The parties involved in planning, and

implementing, resource recovery and reuse of materials from solid

wastes include:

1) The communities generating solid waste who are facing

solid waste management problems.

2) The state and local governmental bodies who have the

responsibility of ensuring that solid waste disposal

practices are environmentally sound.

3) The recycling and basic industries who are the potential

customers and users of materials recovered from solid

waste.

4) The potential users of energy recovered from solid waste.

5) The resource recovery industries that are the sources of

recovery technology, equipment and resource recovery

plant construction capabilities.

26
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27
6) The transportation industry that plays a most important

role in collecting and delivering solid waste as well as transporting the recovered products to their markets.

7) The innovative technology firms who will provide improvements to recovery processes, improvements to the products

recovered and the development of new uses or recovered

products.

8) The financial community who will be called on to provide

the capital for the construction of resource recovery

faci 1 i ties.

9) The Federal Government in its responsibilities under

RCRA.

Experience has shown that unless a partnership can be arranged

between all of these parties, resource recovery options are almost

certain to be discarded, delayed, or implemented inappropriately.

Because local or state governmental bodies are responsible for

solid waste management, in most instances, these bodies also are responsible for establishing the optimum partnership between all of

the parties involved.

A concept which is emerging and which should aid in establishing

the necessary partnership is that recovery of usable materials from

the waste stream is unique in the field of environmental control in

that it can be combined with or act as a spur to an area's economic

development. Resource recovery provides a new source of industrial

feedstocks. As a result of these new feedstocks becoming available,

new industrial operations often can be encouraged to locate in the

vicinity of the recovery operations. Alternatively, existing

companies may expand their operations. In addition, because resource recovery is one of the few environmentally acceptable

methods for managing municipal solid wastes and industrial residues,

it allows increased economic activity without the usual attendant

environmental effects. Thus, resource recovery offers an opportunity to not only attack disposal of solid wastes but to address

other issues simultaneously since proper development and management

of resource recovery programs can provide significant economic

development benefits to host communities and/or regions.

Economic development can be best stimulated by resource recovery programs when there are multiple opportunities for marketing

the materials and energy so desired. But ready markets do not

often exist for recovered components from mixed municipal solid

waste; in response, there have been efforts to develop market

strategies and product specifications. Whether from mixed waste

processing facilities or from source separation, there is the common requisite that a particular material be able to compete —

in quality and price ~ with the material to be substituted for.

In this sense, selling recovered materials and fuels is not different

from selling virgin materials and fuels.

28
In the challenge to market recovered products, there are two

important elements: 1) the ability to consistently separate

targetted materials in salable form, and 2) the availability of

customers for the recovered materials. In planning for a recoveryfrom-waste facility, it is that second element that determines the

technology to be selected, and markets must be identified for each

material as a first step in an economic analysis in the total

context of the solid waste-economic development strategy for a town, city, state or region. In every case, however, recovery

technology must be matched to existing markets or new technology

must be developed to create increased use and therefore market

demand for the recovered resources.

The first step in a general conceptual approach toward evaluating resource recovery in economic terms is to carry out market

surveys in terms of what recoverables might sell and in what

quantities as a function of time. In addition, the quality of the

recoverables must be ascertained via specifications. Specifications

can be defined as designations of the particulars or form and/or

composition of products and materials; they are a method of communicating an exact description of the material. Specifications are used in most forms of commerce, including the production and sale

of products recovered from mixed municipal solid waste. Specifications form the basis for acceptance or rejection of the products or materials, and may be used to determine price as well. Clearly,

needs for new materials as feedstocks for industrial processes,

energy production, soil conditioners, and others vary greatly from one area of the U.S. to another as do waste streams themselves.

Once a market survey indicates that resource recovery may be

economically and/or environmentally beneficial, commitments from

prospective purchasers of recoverables must be sought before final

technological details can be developed. A major step in this

direction has been the development of realistic, 1 etters of i ntent

to purchase. Such an instrument is negotiated between the resource recovery planner and the potential purchaser of recovered materials.

The letter of intent sets fundamental terms and conditions of an advance commitment such as the length of commitment, quantity of

material, quality (specifications), delivery schedule, termination

and price. It provides the necessary financial underpinning to the resource recovery project and is the precursor to the buyers

purchase orders.

At this point, the risks associated with potential demand as a function of time for the recoverables can be assessed. If commitments for all recoverables exist, a technology which will obtain

those recoverables at an acceptable cost is needed. If such

commitments are incomplete, then new demand for the recoverables

needs to be stimulated if possible. In either case, innovative

technology at an acceptable cost may be required.

29
IV. 3. Guidelines for Specifications for Recovered Materials

(Section 5002 of RCRA~T

There are three main sub-areas of responsibility set forth in

Section 5002. Each of these was dealt with by the Management and

Staff of the Office of Recycled Materials.

IV. 3. a. Provision of Guidelines for the Development of

Specifications for the Classification of Materials

Recovered from Waste. Physical, Chemical and Other

Characteristics of Such Materials Were to be Determined

From the inception of ORM in 1976, the requirement for

"provision of guidelines for the development of specifications" was interpreted to mean that the major recyclable constituents of waste

destined for disposal needed to be characterized as to various

material properties in order to state what parameters needed to be

taken into account in a set of specifications. No attempt was to

be made to set quantitative limits for individual specifications.

In this, ORM was adhering to the letter of P. L. 94-580 and to the

spirit of the following quotation from The Life and Work of Charles

Benjamin Dudley , STP 1, American Society for Testing and Materials

(P. 127):

"The special fault which characterizes many specifications is

the attempt on the part of the one who draws the specification

to make it a place to show how much he knows. We have seen specifications which were apparently drawn with no other

thought in mind than to embody all the knowledge the writer

had on the subject. No discussion is needed on this point.

The folly of it is apparent to all.

"Another fault is putting too many restrictions into the

specification. According to our views, the fewer possible

restrictions that a specification can contain, and at the same time afford the necessary protection in regard to the quality

of the materials, the better the specification is. In some of our specifications we have only one test; in others, perhaps

half a dozen; the effort, however, being always to have the

minimum number which will yield the product that is required.

"A third fault in specifications is in making the limits too severe. Some writers who draw specifications apparently put

themselves in a position of absolute antagonism to those who

are to make the material, and seem to have as a permanent

thought in their minds to tie them down to the extreme limit.

The maximum that a single test piece shows, the minimum of an objectionable constituent that may be obtained by analysis,

the extreme point in elongation that by chance some good and

exceptional sample gives, are made to represent the total

output of the works. It is, perhaps, needless to say that

such extreme figures are the worst possible mistake in making

speci fi cations.

30
While many waste streams, e.g., agriculture, nuclear, could

have been examined, ORM chose to deal with municipal solid waste,

certain large volume industrial wastes, ash, certain potentially

hazardous wastes and, as previously described, used oil.

IV.3.a.l. Municipal solid waste (MSW)

Post-consumer MSW consists of about 80 percent organic material,

1 percent aluminum, 8 percent ferrous materials and 11 percent

glass by weight. These are approximate national averages. The

organic fraction includes potentially recyclable fibers such as newsprint (8-12 percent by weight). Certain items - glass, metal,

newsprint - can be separated at the point of discard to provide a fairly uniform feedstock material for recycling. Note that "complete" source separation would account for 20 to 30 percent by

weight of MSW. The remainder would be largely the putrescible

organic fraction. Mixed MSW is simply MSW from which little or no separation has been previously effected.

IV. 3. a. 1. 1. a. The aluminum fraction

Recovery of aluminum is possible by mechanical separation from

mixed MSW. The generic implement used to obtain separation of Al

from other constituents is an eddy current device. This device can

be placed in the mechanical sorting train to examine the heavy

(primarily inorganic material) MSW fraction after ferrous materials

have been magnetically separated. Eddy current devices recover about 65 to 90 percent of the Al which passes through them. Some

aluminum loss is experienced during other prior mechanical sorting

of the mixed MSW.

Since the aluminum content of the waste is low and unevenly

distributed nationally, a careful survey is needed by proponents of

mechanical sorting prior to investing in recovery of Al from mixed

MSW:

1) Determine amount of Al in the waste which would come to

the sorting facility

2) Determine chemical composition of Al based mixture which

can be sorted;

3) Determine if a market exists for this composition.

ASTM, with a contribution from NBS/ORM, has developed a standard

specification for municipal aluminum scrap (MAS) designated ASTM-E753

including physical and chemical specifications for Al scrap.

Clearly, the prospective seller of Al material separated from mixed

MSW must be able to demonstrate that the output material meets

required specifications for each batch to be shipped. Thus, fairly

constant and elaborate quality control procedures need to be

planned and implemented. ASTM-E753 represents the current guidelines

for specification of MAS.

31
Consider a mechanical sorting operation in which the operator

estimates an input of 10 tons daily of Al material in a total input

of 1000 tons per day of mixed MSW. Approximately 6.5 tons of

saleable Al product might be obtained daily or 1950 tons annually.

With current capital costs for the eddy current devices ($2 million)

current interest rates, and operating and maintenance costs and a selling price of about $450 per ton for the mixed material, the

maximum net income to the operator is estimated as about $350,000

annually or about $1.17 per input ton of mixed MSW. If certain

shipments are rejected as being out of specification, these modest

gains could become losses.

Al in the MSW stream often comes from beverage containers.

Since source separated Al cans can be used directly to prepare

additional can bodies at a great savings of energy and raw material,

can manufacturers prefer this recycling route. Hence, these

manufacturers often survey a given area as a basis for an investment

decision to install major can return facilities and programs. If

enough Al cans are likely to be obtained, then the manufacturers

will buy the product, shred it and ship to appropriate smelters.

Manufacturers of Al beverage cans currently claim that 50 percent

of all Al used for this purpose is recycled.

The net result is that virtually no one is willing to risk

placing eddy current sorters in a plant meant to deal with mixed

MSW since the projected financial gains could easily become losses

and since much of the Al available as beverage cans might never arrive at the plant. Therefore, under present conditions, an "effective specification" for Al which might appear in MSW is that

of the typical Al beverage can. There is a ready market for all

such cans throughout the U.S.

IV.3.a.l.b. The ferrous fraction

Ferrous metal in mixed MSW usually results from discarded cans consisting of either tin free steel or tin plate. Often steel

beverage cans having aluminum "flip-tops" are found as well. As

early as 1975, ASTM Committee E-38 on Resource Recovery identified

several potential uses for steel cans: 1

o substitute for iron ore as a charge to blast furnaces;

o charge for steelmaking in the open hearth, B0F, Q-B0P 'furnaces

or electric furnaces;

o remelt in electric furnace for continuous casting detinning

o raw material for ferroalloy production

o precipitation iron

HSee EPA-670/2-75-034 for details-available from U.S. Environmental

Protection Agency).

32

L
o cast steel

This same report suggested a wide variety of target specifications for various uses of ferrous metal which could be recovered

from mixed MSW by means of ferromagnetic separation.

However, the most comprehensive set of guidelines for specifications for recyclable ferrous metals is promulgated by the Institute

of Scrap Iron and Steel (ISIS) on behalf of the Institute's Specifications Committee. According to the ISIS report subtitled Speci f

i

cations (available at nominal cost from ISIS):

"Inasmuch as scrap usually originates in used materials,

convering a wide range of sources, consumers generally exercise

some tolerance with regard to size, and recognize further that

some rust, scale, and dirt may adhere.

"These specifications cover basic open hearth, basic oxygen,

electric, and blast furnaces, plus foundry furnaces, including

cupola, electric, and air. Specifications for cast iron

grades are included, plus the specially processed grades and

certain special grades for chemical use.

"Railroad scrap specifications are included herein, as provided

by the Association of American Railroads, plus grades for

alloy scrap as promulgated by the Institute's Alloy committee.

"Off-grade material and scrap containing residual material are defined, and the degree of cleanliness is described. Provisions

are also made for deviations from the designated classifications.

"Consumers may vary the existing specifications to conform

with individual melting practices."

Well over 100 individual detailed specifications are included.

These specifications are continually reviewed and ammended or supplemented as deemed appropriate.

NBS/ORM as mandated by Section 5002, has cooperated with ASTM

(Committee E-38) in helping to develop and promulgate test protocols

for recovery of ferrous materials; Dr. James Early of NBS has

prepared a major review of ferrous scrap recycling in the U.S.

dealing with its history, current status and possible future

trends. (See publications list # 111 ) . According to Dr. Early:

"The secondary metals industry associated with the recycling

of ferrous scrap is tied to the development in the 1850 ' s of

the acid-Bessemer furnace, the first large capacity steelmaking

process. Within twenty-five years of this development, the

recycling of ferrous scrap became an established industry.

Changes in steelmaking technology since World War II, especially

since the 1960's, are impacting the traditional ferrous scrap

industry. The increased demand for old scrap is due to growth

33
in electric-arc furnace steelmaking capacity, reduced availability of home scrap and prompt industrial scrap, and larger

scrap exports. Ferrous scrap recovered from municipal solid

waste is one of the new sources of old scrap that may satisfy

these increased demands. Systems for the recovery of the

ferrous fraction from municipal solid waste have been developed,

although increased usage of municipal ferrous scrap has been

very slow due to institutional and technical barriers. The

technical barriers posed by the physical and chemical characteristics of municipal ferrous scrap strongly inhibit the

development of markets for this new material. The real and

potential markets for increased consumption of municipal

ferrous scrap are discussed in the review in terms of these

barriers together with the important role of standards for

municipal ferrous scrap in improving communications between

buyers and sel lers.

Present trends in steelmaking technology and ferrous scrap

supply could result in increased demand for scrap including municipal ferrous scrap. The reduced size of automobiles will eventually

reduce the supply of automotive scrap while changes in materials

used in automobiles may lower the resulting scrap quality. Anticipated growth in continuous casting capacity with its lower scrap

generation than ingot casting, and improved electric furnace

productivity will reduce the quality of home scrap. Efforts by some steel fabricators to recycle their in-house scrap will reduce

the availability of prompt industrial scrap. Finally, the continued

growth of scrap-based electric-arc furnace capacity, combined with

increasing overseas exports of scrap, will place added pressures on additional sources of scrap.

Table IV. 2. reproduced from ASTM Standard E702-79, indicates

currently accepted chemical and physical guidelines for specifications for municipal ferrous scrap.

IV. 3. a. I.e. The glass fraction

Glass manufacturers use cullet (broken glass) as a fraction of

the charge to their furnaces. This long established practice

promotes the melting of raw materials and permits the reduction of

furnace temperatures. Benefits of such practice translate into

energy savings, extension of furnace linings life, and greater

productivity. Most of the recycled cullet so far has been scrap

glass from the manufacturing plant itself.

A potential new source of cullet is the glass contained in the

municipal solid waste stream. Several large-scale reclamation

facilities have been built and others are planned. These facilities

will separate the glass fraction from the other components. The

glass so recovered must meet stringent standards for quality and

consistency (e.g., color, contamination, etc.). Targets for

reclaimed glass specifications and test methods have been set for reuse in container manufacture. Tentative standards applicable to

34
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TABLE IV. 2 (cont'd)

Physical Requirements

End-Use Bulk Density, lb/ft3 Form

(kg/m3

)

Copper Indus- 30 (480)

try (Precipi- max tation Process)

loose, shredded as agreed

upon between purchaser

and supplier, shall not

be bal led or baled

Iron and Steel

Foundries

Iron and Steel

Production

Detinning Industry

Ferroal loy

Production

50 (800)

min

75 (1200)

mi n

25 (400) max

50 (800)

mi n

loose, bal led, or baled

as agreed upon between

purchaser and supplier

c b loose or baled as agreed

upon between purchaser

and supplier

shredded, 95 weight % shall

be -6, +h in. (-152, +12.5

min); shall not be balled,

baled, burned, incinerated,

or pyrolyzed

loose, as agreed upon between

purchaser and supplier

a Various consumers may establish gage limitations on the material they

purchase.

^Industry practice is to specify a maximum bale size that may vary amo

users. Experience has shown that if the size range is 95 weight %, -2, +h in

(-50, +6.3 mm), the bulk density requirement can be met and the mater

will be loose and free flowing.

36
the manufacture of glass wool insulation are currently under

review.

NBS/ORM cooperated with ASTM Committee E-38 on Resource

Recovery, the glass industry, reclamation facilities, and the

National Center for Resource Recovery. These activities contributed

to the generation of two standards for recovered glass specifically

for reuse in container manufacturing. These standards are ASTM

E688, Standard Methods of Testing Waste Glass as a Raw Material for

Manufacture of Glass Containers and ASTM E708, Standard Specification

for Waste Glass as a Raw Material for the Manufacture of Glass

Containers. These standards constitute the present guidelines for

specification for reuse of glass destined for waste.

NBS/ORM also cooperated with ASTM and the glass industry on technological problems that might be encountered when using recovered

glass in manufacturing. The objective in this area was to assess potential limits on the use of reclaimed glass. Examples of such

barriers to recycling are the influence of color mixture and

refractory contamination in glass production.

Color mixed glass when added to a batch formulated for a particular glass color is a problem. Oxides of chromium and iron

are the main coloring agents used in container manufacture. For

example, concentrations of Cr2 0 3 by weight percent are 0.0015

(flint), 0.025 (amber), and 0.27 (green). Therefore, only minute

quantities of amber or green colored glass can be accepted in

flint.

Refractory contaminants (e.g,. pieces of ceramics, gravel,

concrete, spark plugs, etc) are especially troublesome in glass

manufacture. The particles, depending on their size, often do not

melt in the glass furnace. Such particles are the source of

"stones" in the glassware in which case the product must be rejected

for aesthetic reasons or structural weakness. The latter is

especially important in minimizing safety hazards, especially for

carbonated beverage containers.

NBS Testing Evaluations

NBS carried out testing of samples from initial glass recovery

operations from a mechanical sorting plant dealing with mixed MSW.

Test methods cover determinations of moisture content, organic

contamination, magnetic/non-magnetic contamination, color fraction,

particle size distribution, refractory content, and melt evaluations.

Results of these tests indicate that the overall quality of recovered

glass falls short of meeting ASTM E708 established acceptance

standards for waste glass as a raw material for the manufacture of

glass containers.

Data for these tests, performed in accordance with ASTM for

E688 are presented in tables IV. 3-6. Viscosity parameters, although

not listed in the ASTM specifications, are very important in the

forming processes for glass containers. All samples used in the

37
Table IV. 3. Source 1 (Flint, Color Sorted) (11.6 lbs,

material greater than 6 mm).

Moisture (%)

Non-Glass Contaminants:

Organics (%)

Magnetics (%)

+ 1/4" particles

Non-Magnetic (%)

+ 1/4 particles

+ 20 particles

Inorganics + 20 (%)

Refractories

+ 1/4" particles

+ 20 particles

- 20, + 40 particles

- 40, + 60 particles

Sampl

e

Dry

0.5

0.15

2

0.4

6

13

0.45

3

7/1 b

11/1 b

27/lb

ASTM Specs'

0.05 % wt

0.2 max

0. 05 max

0

not available

not available

1/40 lbs

0.1

1/40 lbs

2/lb

20/lb

ASTM specs have not been developed for this material. ASTM specs

listed are for recovered material 6 mm or less in size.

38
Table IV. 4. Source 1 - Color Distribution (2 kg, Color

Sorted Flint).

Samp!

e

ASTM Specs

Flint, % 92.6 95-100

Amber, % 4.1 0-5

Green, % 2.3 0-1

Other Colors, % 1 0-0.5

Melt Test

Poor quality glass, dark emerald green.

39
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CTi

CXI +

rH O M H f)

CD

ro

E

=3u

CM

CDu

S-o

on

>>

S- O eg +o ro to oo

CT

S-oo

CL

to

CL> U

i- tn -—

1- ro

ro +-> CO

CL. .a J3 aj 0J z:

"—

\ u /—

\

s—

s

10 o o u

a QJ to

-—

QJ r" +-> s_

QJ s_ + + QJ ro +-> CD tn !- o C CL to

s- u U -(-) CD OJ

=3 •i

OO u o o o ro o I—

-(-> ro CXI CXI s: CXI lO ro O S- -M CD <*- + 1 C + o s- l-H 0J o QJ o cc

40
Table IV. 6. Viscosity data (Source 4).

Log in Viscosity (poise) Temperature (°C)

3.50

3.0

2.75

2.50

2.25

1130

1220

1275

1335

1400

These data were fitted by a simple linear re- gression expression as log in Viscosity (poise) = 8.66 - 0.0046 T (°C)

iU

As a comparison for NBS-SRM 710, Soda-Lime Glass

log

10 Viscosity (poise) = 8.21 - 0.0044 T (°C)

(Range of validity of both expressions 1075 < T (°C) < 1425)

41
above tests were labeled as: source 1, source 2, etc., depending

upon specific source.

Cooperative Testing Activities

NBS cooperated with the National Center for Resource Recovery,

EG&G, and Owens-Illinois on modifications and testing plans for

Recovery I, a mechanical separation plant in New Orleans. For this

activity, data on Refractory Count for Recovery I samples obtained

by Owens-Illinois and NBS are presented in table IV. 7. All samples

submitted met the Refractory Specifications of ASTM E708. However,

the validity of the tested samples is in question since no sample

description and/or sampling procedures were provided.

IV. 3. b. The organic fraction of MSW

This fraction comprises about 80 percent of total MSW generated.

Table IV. 8 indicates the basic components of this fraction as well

as the percentage of each.

The organic fraction can be burned, either in the form as- received MSW, or as converted to various forms of refuse derived

fuels (RDF) in order to reclaim energy-from-waste. ASTM E-38

designations for various forms of RDF are:

RDF-1: Wastes used as a fuel in as-discarded form

RDF-2: Wastes processed to coarse particle size with or without

ferrous metal separation

RDF-3: A shredded fuel derived from municipal solid waste (MSW)

that has been processed to remove metal, glass, and other

inorganics. This material has a particle size such that

95 weight percent passes through a 2-in. (50-mm) square

mesh screen.

RDF-4: Combustible waste processed into powder form, 95 weight %

passing 10-mesh screening

RDF-5: Combustible waste densified (compressed) into the form of

pellets, slugs, cubettes, or briquettes.

RDF-6: Combustible waste processed into liquid fuel.

RDF-7: Combustible waste processed into gaseous fuel.

MSW - Unprocessed (or minimally processed) raw municipal solid

waste - equivalent to RDF-1.

A number of questions and challenges are posed in dealing with the

organic fraction. Among these are:

o Should certain fiber based materials, e.g., newsprint, boxboard,

be separated out and recycled back to fiber based products?

o Should raw MSW be fired on a mass basis as the most economical means to reclaim value from the waste?

o Is there a stable market for some or all forms of energy-from- waste (EFW)? If so, what forms?

42
^ v oj0

o >, 1—

«3-

l/> m

(J

+-> s_

IT3 I/) Q_ ai 0 1— UD

>, U +

i- rTM o +-> +_> 5_ q

U ro «3- rO n | S- 4— M—

a» O

Q£

s_ +j

1~) 0 CD £ «3"

• 1-5 3 + O 2; < 1 1_ 0

to

ro

i—i>> S1_a*>

0 Q_ <-—

\

CO • rv

C£L

CC, CNJ C_> +

>

aj .a

X3 ro

rO _1 t—

rO +J

ro 4- Q O

ai r- d) a. a) E 3

ro w 00

/11 OJ QJ

-J—

1

-7— •r" 'r- -Q

e Q »— j— ID rv. t S E E E E E E E 3 rz 3 C 3 3

-O a T3 T3 0 a O ~o T3 C c C c u c u c C 3 3 3 3 3 3

S- s_ S- S- S- J_ L. O 0 O O 0 O O

CJ C_) O <_> C_J C_5

CM CNJ CNJ CNJ O rH

O O OOO OOO O O

O O

CNJ CO O O

IDo

«3- o

«3- ro O O

< 00

00

CD

CNJ

co

COoCNJ

cc

CNJ

T3

Sro T3c

3

rcOJ

S-3

03

roC

O

-t->

<T3

Im

c

rjj 3- o

to

• '

S-o

+-> roi-O

ro

c

>-> ro

t_CDa

o

ooro

43
TABLE IV. 8.

Material Percent of Total

Paper

Plastics

Rubber

Leather

Texti les

Wood

Food wastes

Yard wastes

32.4

3.2

2.1

0.5

1.5

3.5

16.8

19.1

Source: U.S. EPA Publication SW-600 (1977) P. 18

o Is conversion to some form of RDF sensible from an economic,

technical and marketing viewpoint?

o How do local, state and federal statutes affect the flow and

usage of various forms of materials used to generate EFW?

o What "side effects", e.g., production of potentially dangerous

pollutants, corrosion of boilers, might result from use of

o What steps are necessary to characterize various forms of

materials which may be used to generate EFW?

o What are the trade-offs between direct recycling and burning

to create EFW?

While ORM examined many of these questions, the first to be

addressed was that of characterization. Our view was that until

appropriate sampling and characterization techniques were developed,

no solid basis of comparison would exist for dealing with most of

the other questions. Therefore, with aid, advice, and encouragement

from ASTM, ASME (American Society of Mechanical Engineers) and

other federal agencies, ORM began systemmatic efforts to develop

test methods, procedures, and standards to aid in characterization

of the various materials, combustion processes, emissions and other

effects relevant to EFW. (See Publications List #'s 39-45, 55,

57-59, 61-68, 71-73 for specific results.)

ORM staff, in cooperation with ASTM, have contributed significantly to no fewer than ten standards listed in the 1982 Annual

Book of ASTM Standards:

E711-81 Standard Test Method for Gross Calorific Value of

EFW?

Refuse-Derived Fuel by the Bomb Calorimeter

E775-81 Standard Test Methods for Total Sulfur in the

Analysis Sample of Refuse-Derived Fuel

44
E776-81 Standard Test Method for Forms of Chlorine in

Refuse-Derived Fuel

E777-81 Standard Test Method for Carbon and Hydrogen in the

Analysis Sample of Refuse-Derived Fuel

E778-81 Standard Test Methods for Nitrogen in the Analysis

Sample of Refuse-Derived Fuel

E790-81 Standard Test Method for Residual Moisture in a Refuse-Derived Fuel Analysis Sample

E791-81 Standard Method for Calculating Refuse-Derived Fuel

Analysis Data from As-Determined to Different Bases

E829-81 Standard Method of Preparing RDF-3 Laboratory

Samples for Analysis

E830-81 Standard Test Method for Ash in the Analysis Sample

of Refuse-Derived Fuel

E856-82 Standard Definitions of Terms Relating to Physical

Chemical Characteristics of Refuse-Derived Fuel.

IV.3.b.l. Calorimetirc characterization of refuse derived fuels

Recent NBS/ORM efforts have been devoted to development of a calorimeter in which to determine the calorific value of kilogramsize samples of minimally processed municipal solid waste (MSW). A

large scale calorimeter affords greater credibility because kilogramsize samples of MSW should represent the properties of the heterogeneous bulk material more reliably than the highly processed gram-size

samples currently used in bomb calorimetric determinations.

E 711, Test for Gross Calorific Value of Refuse-Derived Fuel

(RDF-3) by the Bomb Calorimeter, published in Part 41 of the 1982

Annual Book of ASTM Standards, is available to analysts throughout

the world. This method uses a one gram sample to determine the

gross calorific value of RDF-3. Many engineers feel that one cannot sample MSW or RDF accurately using one gram. Moreover, they

also feel that processing to 0.5 mm particle size--as directed in

the ASTM E829 Method for Preparing RDF-3 Laboratory Samples of

Analysis - could change the sample chemically so that if no longer

resembles the original MSW or RDF. The development of a flow

calorimeter by NBS/ORM which can accommodate a 2.5 kg sample

provides greater credibility with respect to representing the true

properties of the original refuse sample. The comparison of

calorimetric data derived from both the one gram capacity bomb

calorimeter and 2.5 kg capacity flow calorimeter should furnish

test laboratories with the kind of assurance they need regarding

the accuracy of determinations of calorific values.

In the past year, three lines of work have been emphasized:

a) Oxygen flow calorimetry of solids; b) Oxygen bomb calorimetry of

45
solids; and c) Laboratory scale fluidized bed combustion studies

comparing combustion characteristics of some coals with some RDF's.

IV.3.b.2. Oxygen flow calorimetry of solids

The 2.5 kg capacity flow calorimeter, shown in Figure IV. 1 has

been used to burn pellets of minimally processed waste (RDF-2).

The major components of the calorimeter (see A, B, E, F, and H of

figure) have been fabricated and installed in a new laboratory

facility in the Mechanics Building of NBS. Design of the auxiliary

parts of these major components and also the accessory components

of the calorimetric system have been completed. Fabrication,

assembly, and testing is in progress: A 2.2 kg RDF-2 sample was combusted in 30 minutes time which is well within the acceptable

limit of 18 minutes per kilogram. In the second trial experiment,

the controllers for the oxygen supply to the combustor and the

color video monitor for viewing the sample were tested. During the

last quarter of FY 1982, the calorimeter was put into operation and

four calorimetric runs completed—two calibrations with cellulose

and two heats of combustion of RDF-2. In FY 1983, a comparative

study will be done to determine if there are significant difference?

between the heating value of MSW obtained by using 2.5 kg processed

samples and 1 g processed samples.

IV.3.b.3. Oxygen bomb calorimetry of solids

Industry and test laboratories have expressed a need through

ASTM Committee E-38 on Resource Recovery for a secondary standard

for determining the heating value, ash and moisture content of RDF.

For this purpose, a synthetic RDF consisting of 80 percent cellulose

and 20 percent non-combusti le materials (15 percent silica and 5

percent alumina) was prepared by NBS/ORM in collaboration with ASTM

Subcommittee E-38. 01 on Energy. Two different formulations of this

material were submitted to eleven different laboratories for Round

Robin Testing. The essential difference between the formulations

was that the second contained non-combustible material having a more uniform particle size (about 50 micrometers). The participating labs in the two Round Robins (including NBS) provided NBS/ORM

with data on the heating value, moisture, and ash content of each

formulation. The interlab agreement of the results on the second

(i.e., final) formulation was improved (a factor of three in the

heating value and five in the ash content) and was comparable to

that obtained in a previous Round Robin with NBS SRM Bituminous

Coal 1632a. As a result of these findings, the NBS Office of

Standard Reference Materials has approved funds toward certification of this synthetic RDF as an SRM.

Objectives to be attained by using the 2.5 kilogram capacity

flow calorimeter in FY 19832

:

*FY 1983 funds from Department of Energy, Energy from Municipal

Waste Division.

46
ATIONAL BUREAU OF STANDARDS

Figure IV. 1. The 2.5 Kilogram Capacity Flow Calorimeter. A

denotes the combustor, B the combustor enclosure, C the exhaust cooling coils, D the exhaust condenser,

E the flow shield, F the calorimetric vessel, G the

stirrer and H the water wall enclosure.

47
Combustion data which characterizes refuse and is applicable

to the design and operation of incinerators and boilers.

Development of a fundamental scientific approach to the

operation of incinerator systems should replace the empirical

approach

A comparison of calorific values determined on highly-processed

samples of refuse in 2.5 kg capacity and 1 gram capacity

combustion calorimeters.

A comparison of calorific values of the both highly-processed

and minimally-processed refuse determined in the 2.5 kg

capacity calorimeter.

Determination of the variability of minimally-processed refuse over a two-week period and comparison of calorific values

determined in the 2.5 kg capacity and 1 gram capacity calorimeters.

Future Research Objectives

Perform combustion calorimetry on refuse samples under excess-ai

stoichiometric-air , and starved-air conditions.

Identify the threshold conditions for the formation of incomplete combustion products (CO, soot/carbon, hydrocarbons) and

volatile pollutants containing sulfur and/or chlorine (CO,

soot/carbon, hydrocabons) and volatile pollutants containing

sulfur and/or chlorine (S0 2 , HC1) in calorimetric measurements

using air rather than oxygen to support combustion.

Compare data on calorific value, composition of ash, volatile

combustion products, and temperature profile of the combustor

between combustion measurements carried out in oxygen and

varying amounts of air.

Perform combustion studies on synthetic hazardous wastes using

large (2.5 kg) samples so that detection of the kind and

amount of effluent can be carried out to high destruction

efficiencies. Determination of calorific value, temperature

profile of the combustor, composition of the waste and ash

residue would be included.

Perform combustion studies on coal-RDF mixtures. If oil and

natural gas supplies undergo shortages and/or increases in

price, coal and alternative fuel (i.e., RDF) will increase in

demand and usage. Power companies will again accept processed

refuse to be burned with coal in their boilers. No data-base

is available on the combustion characteristics of coal-RDF

mixtures.

48
IV.3.b.4. Combustion of refuse-derived fuels in a laboratory

scale fluidized bed furnace

Over the years a large amount of information has become

available on various aspects of coal combustion in small-scale

laboratory furnaces. This information forms a body of basic data

which a combustion engineer can draw upon as a rough but useful

guide for prediction of coal combustion characteristics in industrial boilers and furnaces. Among the most important data available

from laboratory experiments are fuel burning rates as a function of

both fuel properties and parameters of gas streams surrounding the

fuel particles. This information is required for estimation of key

boiler parameters: rate of heat release, furnace retention time,

completeness of combustion, and furnace outlet temperature.

The equivalent laboratory information does not exist for

refuse-derived fuels (RDF). The objective of the present project

was to fill some of the data gaps by laboratory-scale measurement

of air-entrainment and combustion of RDF. Most of the combustion

data were obtained in the entrained mode with the view of application

to pulverized fuel and semi-suspension boilers.

The project was accomplished in four tasks: 1) a laboratory

study of entrainment characterization of RDF; 2) a "baseline" study

of combustion of lignite particles in a laboratory furnace constructed at NBS for that purpose; 3) combustion of RDF in the same

furnace; and 4) a survey of capability, outside NBS, required for

pilot tests of RDF combustion. Brief summaries of these four tasks

are given in sections 1 through 4. Section 5 lists the documents,

existing or in preparation, on this project.

IV. 3. b. 4.1. Entrainment of RDF particles

The fact that even well prepared RDF samples (e.g., RDF-3)

consist of particles having a variety of shapes, sizes, and densities, introduces a serious problem of entrainment characterization.

Whereas pulverized coal particles can be considered quasi-spherical

(all three dimensions of the same order of magnitude for the

purpose of engineering estimates of settling velocities, burning

rates and furnace retention times), this is not true of RDF. To

address the entrainment problem, a cold-flow elutriation apparatus

(CFEA) was constructed and used to measure settling velocities for

particles of various shapes, sizes, and densities. Correlations

were then developed allowing prediction of entrainment velocities

and of maximum particle sizes entrainable under condition representation of boiler furnace gas streams.

For quasi-spherical particles some widely used correlations,

examined in the light of our experimental results, were found to

give erroneous predictions because of improper definition of flow

regimes. Composite correlations, based on four different regimes

(Stokes, intermediate I and II) and Newton's) were found adequate

for predictions in boiler furnace gases, e.g., the maximum diameter

49
of a solid piece of wood entrainable at 30 ft/sec and 1500 °F is

0.134 in, corresponding to sieve Mesh 6.

Extensive CFEA data were taken, and correlations for furnace

gases were developed, with particles of increasingly irregular

shapes: circular discs and oblong discs with decreasing thicknesses,

down to newsprint paper. In particular, it was found that in the

intermediate regimes many of these showed increased drag coefficients

with the Reynolds number, leading to high entrainabi 1 ity. This

trend is a departure from the conventional drag-coefficient curve,

but is in second with some recent data for thin platelets.

The CFEA was also used to measure the range of settling

velocities of sieved fractions of RDF-3. Of special interest to

this study was the -20 + 35 Mesh fraction, the settling velocities

of which, while covering a very wide range, are comparable to those

of pulverized coal (see Section 3).

IV. 3. b. 4. 2. Combustion of lignite particles

A laboratory furnace was constructed and used for combustion

of particles. The furnace has a rectangular cross-section, 5.5 x 4

inch, is 13 inches high, and has two glass walls for full view of

its interior. Furnace gas temperatures and velocities ranged up to

1650 °F and 5 ft/sec, with widely variable oxygen content. Burning

times of individual particles were determined photographically with

light chopping at 600/sec.

The fuel chosen for a baseline combustion study was a type A

lignite, 30.4 percent moisture, 7.9 percent ash, 7570 Btu/lb (as

received). Two samples -140 + 170 Mesh, and -200 +230 Mesh were

used for detailed particle burning-rate studies. The gas temperature was kept constant t 1610 ± 30 °F, while the oxygen content of

the furnace gas was varied. Particles were injected into furnace

gas horizontally from the sidewall through a small (1/8 inch) tube.

It was found that at high oxygen contents (oxygen-enriched air

to the gas burner), the experimental rates agreed with the established

correlations for rapid, diffusion-controlled combustion of coal

particles. This result indicates that the furnace is adequate for

quantitative particle-combustion studies. Transition to slow,

incomplete combustion was found to take place when the oxygen

content was decreased below 19 percent for the 140/170 Mesh sample

or below 14 percent for the 200/230 Mesh sample. While these

oxygen constants are still much higher than in actual boilers,

these results are not surprising, because our experimental

temperatures —chosen for RDF combustion studies —were lower than in

coal boilers.

IV. 3. b. 4. 3. Combustion of RDF particles

Two sets of experiments were performed: pure suspension

combustion of samples from a batch of Teledyne National RDF is,

pulverized and sieved, -20 + 35 Mesh; and combustion of larger

50
samples (between 6 and 14 Mesh) from the same batch burning partly

on a grate and partly in suspension.

The pulversized samples were burned under the same conditions

as the lignite samples (see Section 2), except that in some runs the gas temperature was even lower. The sieve fraction, -20 + 35

Mesh, was chosen because we found that most of this material

ignited before settling to the bottom of the furnace and then

burned entirely in suspension, just as the lignite samples. (It is

probable that some solid non-combustible particles--e. g. , dirt or glass pieces —settled to the bottom without affecting the combustion

of the bulk of entrainable material; see Section IV. (3)b. 4. 1. )

.

Combustion of pulverized RDF was found to be different from

combustion of lignite powder in at least three ways. First, RDF

particles, although larger than lignite samples, burned down to

lower gas oxygen contents than lignite: e.g., 11% 0 2 at 1550 °F was sufficient for ignition of many particles. Second, the average

burning times of particles were longer than for lignite sizes

reported in Section IV.(3)b.4.2. Third, the range of burning times was very wide.

It must be re-emphasized that these comparisons are not made

for particles of comparable sizes (RDF vs lignite), but of comparable

entrainabi 1 i ty. This type of comparison appears to be much more

useful, because it is more indicative of the tendency for carryover

of clear char from the furnace. Specifically, for the particle

size studied, it shows that even when given adequate temperature

for ignition and adequate oxygen for combustion, some constituents

of RDF will require longer time for complete combustion than

1 ignites.

To explore the question of carryover somewhat further, we made

a limited number of tests with RDF sizes large enough to drop onto

a grate (Ni chrome mesh) near the bottom of the furnace. Two

samples were used: -6+8 Mesh and -12 + 14 Mesh. Combustion was observed by high framing photography. As suspected, we observed

that some particles, after burning on the grate for a relatively

long time (0.1 to 1 sec), lifted and continued to burn in suspension

for a similar period of time. This result confirms that it is not

so much the original fuel particle size that matters, but the size

(and shape and density) at which the particle becomes entrainable.

IV. 3. b. 4. 4. Sub-scale pilot requirements

The two objectives of this task were:

1) Survey of industrial facilities suitable for sub-scale

combustion of RDF;

2) definition of a program plan for obtaining generic design

data applicable to suspension combustion of RDF in

boi lers.

51
Three industrial test facilities have been selected as being

applicable for generation of data for suspension combustion of RDF:

In addition, ancillary spreader-stoker data would be most desirable;

a model furnace at the University of Utah, Salt Lake City, Utah, is

uniquely suitable for supplying these data.

IV. 3. b. 4. 5. Documentation

1) S. R. Charagundla and A. Macek: "Entrainment Characteristics of Particles in Gas Streams." In preparation.

2) A. Macek and S. R. Charagundla: "A Laboratory Approach

to Obtain Suspension Combustion Data for Refuse-Derived

Fuels." DOE/ANL Workshop: Converting Waste to Energy,

ANL/CNSU-TM-96, Feb. 1982.

3) A Macek and S. R. Charagundla: "Burning Rates of Lignite

Particles". Submitted for presentation of Combustion

Institute Meeting, Eastern Section, Atlantic City, N.J.,

Dec. 1982.

4) A. Macek and S. R. Charagundla: "Burning Times of

Pulverized RDF." In preparation.

5) A. Macek: "Combustion Characteristics of RDF, Phase II."

Final Report submitted to DoE, Nov. 13, 1981.

As noted previously, details of NBS/ORM efforts to develop

test methods and standards for the characterization of MSW and

various forms of RDF can be found in the NBS/ORM Publications List

(Appendix I) through reference to the following numbers: 39-45,

55, 57-59, 61-68, 71-73.

In addition to these efforts, NBS/ORM and the Government of

Japan cooperated on a study dealing with the pyrolysis and subsequent

gasification of a large amount (40 tons) of commercially produced

U.S. refuse derived fuel. Details regarding this project are included in the Section dealing explicitly with the special cooperative venture with Japan. (Section X.(2)e).

IV. 3. c. Combustion process characterization

Combustion of MSW or any form of RDF results in off-gases

which have the potential to adversely affect air quality. In the case of one waste-to-energy facility, emission of low levels of

dioxin was detected. The end result was that the facility representing over $150 million in capital costs —was required to suspend

operations in late 1982. Fear of dioxin emissions led to

suspension of efforts to establish a waste-to-energy plant at the

Brooklyn Navy yard. Therefore, the thermodynamics and kinetics of

the combustion process need to be better understood in order to

minimize the probability that unsafe concentrations of pollutants

will be emitted by a waste burning facility.

52
IV.3.C.1. Development of chemical and kinetic techniques

Efforts were made to characterize both the combustion process

and the mechanisms underlying formation and possible escape of

resultant pollutants. (See ORM Publications List Numbers 118, 119

and Appendix III for detailed results). In the past year, work in

this area has been concerned with the demonstration of the applicability of thermal analytical techniques for the characterization of

the pyrolytic and oxidative properties of refuse derived fuels.

The important thrust of this program has been the application of

these methods (High Pressure Differential Thermal Analysis and

Thermal Gravimetric Analysis) and developmental work on an associated

technique, Evolved Gas Analysis. With respect to HPDSC and TGA, a broad quantitative data base on assorted RDF and coal samples has

been accumulated. Coal samples are indicative of the variations

that can be expected in commercial samples and the basis for

comparisons with coal established. The conditions for determining

accurate heats of formation have been derived.

In cooperation with the experimental program in the NBS

Chemical Engineering Center partially combusted RDF and coal

samples have been analyzed. It has proved to be possible to make

satisfactory thermal analytical measurements on samples with

combustible carbon samples having accuracy in the few percent

range. The thermograms have proved to be interesting in that

although the volatile peaks are gone, the char peaks remain, except

that they are in the lower temperature ranges. This is indicative

of great reactivity. An attempt is underway to relate these

observations with the parameters of the combustion experiments

[flame length, excess oxygen, feed rate, etc.] which produced the

partially combusted samples. With respect to the uncombusted

samples, it is clear that RDF samples will in general prove to be more readily igni table than coal samples. This is brought about by

the presence of plastics (polyethylene?) and may well pose a spontaneous ignition hazard. The thermograms that have been

obtained contain phenomonological kinetic information. Indeed the

presence of each distinct peak is indicative of a specific reaction

process. We are in the process of reducing the data on char

oxidation within such a context. In the case of the coal samples,

kinetic data obtained on the basis of other techniques exist; thus,

there is a basis for comparison. We are particularly interested in

comparing results from RDF and coal char samples, since one expects

that such information will be relatable to burn-off.

Our interest in Evolved Gas Analysis is due to the fact that

such studies yield more "chemical" type information as compared to

the heat and weight changes from DSC and TGA type experiments.

Furthermore, it should be possible to carry out heating experiments

at rates considerably faster than the 100°/min used in the former

systems. Two devices have now been set up and are being tested.

One of these involves coupling a gas chromatograph to the existing

TGA apparatus, so that at selected temperatures during a run, a gas

53
analysis can be carried out. The other couples infra-red cells

pyrolyzer where flash heating is effected on a platinum ribbon or

coil. The major problem has been the generation of reproducible

data. Up to the heating rates of the DSC and TGA apparatus, these

problems have now been surmounted. Results are in very good

agreement with those from the other techniques. Current work is

concentrated on making results more quantitative and moving on to more rapid heating times. With respect to the former, there is a need for internal calibration, and we have been carrying out

extensive studies with well characterized polymers.

IV.3.C.2. The dioxin emission issue

Dioxin which might arise from combustion sources is of major

concern to the U.S. incinerator community and to the public. This

problem caused the Research Committee on Industrial and Municipal

Wastes of the American Society of Mechanical Engineers to sponsor

an interdisciplinary "Study on State-of-the-Art of Dioxin from

Combustion Sources" (ASME-New York 1981). Therefore, processes

which may contribute to the formation of polychlorinated dibenzo-pdioxins (PCDDs) were investigated. A model mechanism was constructed

to investigate the possibility for homogeneous gas phase formation

of PCDDs from polychlorinated phenols in an incinerator environment.

Numerical calculations lead to the conclusion that the probability

for gas phase formation of PCDDs is likely to be very low at high

temperatures if mixing between fuel and air is efficient. Effects

of use of auxiliary hydrocarbon fuel and excess air as well as probable sources of non-idealities and the potential role of

non-gas phase effects were considered. The results indicate that

dioxin formation tends to occur in the incinerator as a result of

such processes as mixing inhomogeneities between fuel and air

and/or surface reactions. Perhaps, then, dioxin emissions can be

minimized either with or in a combination of optimized incineration

design, operation and maintenance. (Details of this work can be

found in Appendix III).

The propensity for the incinerator to produce chlorinated

emission products is very likely to depend in some fashion on the

chlorine content of the fuel. Tests for chlorine content and

sulfur content were carried out; samples were taken on consecutive

days from a commercial plant which produces fuel grade RDF-2. The

results are shown in table IV. 9. Clearly, incinerator and boiler

operators utilizing waste fuel sources should find it advantageous

to monitor chlorine content; emissions from the facility should

also be monitored carefully on days when high chlorine fuels are

fired.

54
Table IV. 9. Chlorine and sulfur contents of commercial samples of

RDF-2 (Winter 1980). Moisture free basis

Day % Chlorine % Sulfur

1 0.40 0.17

2 0.96 0.14

3 0.61 0.12

4 0.55 1.38

5 0.44 0.13

6 0.69 0.27

7 1.59 0.30

8 0.51 0.08

9 0.49 0.11

10 0.57 0.88

55
IV. 3. d. Corrosion Studies

Another characteristic of refuse based fuels which needs to be

well understood is the propensity for these fuels to cause boiler

material degradation. Therefore, NBS designed special corrosion

probes; two of these have been installed in boilers co-firing coal

and RDF. The first of these was installed March 11, 1982, at the

NASA/Langley facility. The other was installed August 24, 1982, at

Wright-Patterson Air Force Base in a similar boiler. Because of

the short time since insertion of these devices, only preliminary

data are available from the NASA facility; none are available from

the Air Force facility as yet.

With regard to the investigation at NASA/Langley, the probe

was constructed to expose four sets of five different alloys.

These alloys are three stainless steels designated as SA213-T11,

SA213-T22, and SA213-TP304, and two alloy steels designated as SA192, and SA178. These materials were exposed to a controlled

temperature range of from 100 °C to 388 °C when the incinerator is

at full heat and above 400 °C in the area of the probe. Prior to

the installation of the probe, a special trip was made to the NASA

incinerator facility to determine the final details of sources for

power, compressed air, and cooling water. Exact dimensions for the

"door" which holds the probe in place were also determined. The

corrosion probe and associated monitoring equipment were installed

on March 11, 1982. Since that time, temperature data have been

automatically measured at four points along the probe, recorded,

and sent to NBS/ORM for evaluation. These data indicated that over

the period of exposure the temperature fluctuated by hundreds of

degrees from a minimum of 100 °C to a controlled maximum of 387 °C.

This set of data does not include temperature changes during

periods when the incinerator was shut down which causes the measured

temperature to approach normal room temperature (25 °C).

On September 28, 1982, six months after initial exposure, the

probe was withdrawn from the incinerator and the specimens removed

for analysis. Initial visual examination revealed some pitting on the materials. New specimens were added in place of those removed

and the probe reinserted for a second period of exposure. Further

results will be obtained from this facility and from the Air Force

facility in FY 1983.

IV. 4. Fibre and Wastepaper

Recycling of waste fibre is carried out in many parts of the

United States. According to the American Paper Institute, about 18

million tons of newsprint, boxboard and other fibres are recycled

into new raw material each year. These fibres are always source separated from the remainder of the waste. The National Association

of Recycling Industries (NARI), as well as individual dealers and

jobbers have developed specifications for these goods. The NARI

specifications are updated periodically and serve as the basis for

many, if not most, market transactions (The most recent NARI

56
specifications are available from NARI headquarters in New York

City).

Some efforts have been made to reclaim useable fibre from

mixed wastes; these attempts have met with varying degrees of success —most notably for production of low grade tissue in Japan.

But these processes do not yet appear ready for wide scale commer- cialization on an economically sound basis.

Key issues affecting supply, demand, and market fluctuations

for waste fibres are only weakly dependent on specifications.

Therefore, NBS/ORM chose not to investigate technical aspects of

guidelines for specifications for waste fibres. Rather, ORM chose

to examine the trade-offs between various uses for the fibre and

resultant options for either recycling into paper products, burning

to claim energy or other recycling options, e.g., for cellulose

based insulations. The results of these investigations are discussed

in the Section dealing with NBS/ORM response to Section 5003 of P.

L. 96-482 dealing with markets. (See also Publ. List #78).

57
V. SPECIAL WASTE CATEGORIES

V. 1. Used Tires

NBS/ORM did not use empirical methods to characterize used

tires in its effort to develop guidelines for specifications for

various uses. The reason for this was that ORM personnel, in a survey made in 1978, ascertained that, to a reasonable first

approximation, a possible reuse-recycling protocol for discarded

tires is:

1) Retread and reuse to end of carcass life;

2) Render into crumbs for various uses—this process implies

shredding of the original tire.

3) Use shredded tries as supplemental fuel.

4) Pyrolize shredded tires.

(See ORM Publication List #75 for details)

V.l.a. Retreading

By far, the best possible course of action is to retread and reuse all eligible tire carcasses since this process "recovers"

considerable material which otherwise would be destined for waste.

Note that roughly 175 million new tires and 50 million retreads were sold in the replacement tire market in 1979. That means approximately 225 million worn tires were taken out of service and

replaced with either a new or retreaded tire. In addition, new

cars, trucks, and buses, were equipped with about 62 million new

tires in 1979--51 million passenger tires and 11 million truck-bus

tires were taken out of service on scrapped vehicles. In total,

approximately 260 million tires were potential candidates for

disposal as solid waste. Approximately 40 million to 50 million of

them were retreaded--15 percent to 19 percent. An additional 10 to

15 percent of the worn out tires were to be used for other productive

purposes such as reclaimed rubber for recycling into new rubber

products, fuel, breakwaters and artificial reefs, dock bumpers,

playground equipment, roadside impact absorbers, and construction

materials. The remaining 70 to 75 percent of the worn out tires,

about 180 million, were disposed of in non-productive ways—mainly

in landfills. Based on industry data one can estimate oil consumption at about 25 gallons per hundred weight of tires produced—about

20 gallons for the materials and five gallons in the manufacturing

of tires. The total weight of the 180 million tires which were

non-producti vely disposed of in 1979 was approximately 7 billion

pounds, representing the consumption of 1.75 billion gallons of

oi 1 --40 million barrels.

The 650 million plus pounds of tread rubber consumed in the

production of the 50 million retreads sold in 1979 provided the

equivalent service of 2.3 billion pounds of new tires. At 20

58
gallons per hundred weight of tires, the oil savings from raw materials production alone was 330 million gal 1 ons--more than 20

thousand barrels per day. Additional energy savings are realized

during the manufacture of retreads versus new tires. With the

current product mix of passenger, truck and other retreads, the

average oil savings in raw materials alone for a retread over a new tire is about seven gallons per tire--a 70 percent savings.

There exists a varying degree of acceptability of retreaded

tires, as is the case with most recycled products. One out of five

new replacement passenger car tires is a retread, while 90 percent

of the world's airlines use retreaded tires. A majority of trucks

drive on retreads (about 1.1 retreaded truck tires are sold for

every new truck tire installed). Nearly 60 million worn tire

casings that could be retreaded as discarded every year. The

American Society for Testing Materials has developed a recommended

practice for the inspection of these casings prior to retreading.

(See ASTM Book of Standards, Volume 38: F393-74 for details).

V.l.b. Waste Tires As Fuel

While 0RM Publication List Reference #75 lists many possible

uses for waste tires that cannot be retreaded, the easiest task

which might reclaim something useful from such tires is to use shredded tires as supplemental fuel in a waste-to-energy plant or appropriate industrial boiler. Table V.l taken from a report by R. H. Taggart (GMC, Warren, Michigan) lists pertinent data for rubber

to be used as a supplemental fuel. Taggart also measured air

emissions over a six month test burn involving a coal-10 percent

rubber mixture. Particulate emissions increased but SO actually

fell. The ZnO component played no significant role. Oclors were

not a problem.

Since approximately one tire for each person in the U.S. is

discarded annually, of which about 20 percent are retreaded, a population center containing 200,000 persons could be expected to

yield about 150,000 tires annually or about 1500 tons of combustible

chips. Allowing for energy to transport and shred these tires, as well as a boiler efficiency of 0.67, these tires, if burned, will

yield a net gain of over 25,000 MBTU annually; the net dollar gains

will be somewhere between $50,000 and $100,000 annually.

Shredders which will provide required chips are readily

avai lable.

In effect, guidelines for specifications of waste tires are dictated by the availability and handling costs of the tires. The

data in table V.l and the recommendations of ASTM F393-74 provide

reasonable guides as to the technical characteristics which must be

taken into account for retreading or use as fuel.

59
Table V.l. Characteristics of rubber for use as a supplemental fuel

A. BTU Content

1. Pure rubber—approximately 18,000 BTU/lb.

2. Shredded rubber ti res—approximately 15,000 BTU/lb.

B. Trace Element Concentrations

1. Sulfui—approximately 1 percent.

2. Zinc oxide— approximately 2 percent.

C. Materials Handling Characteristics

1. Shredded rubber has a tendency to bridge.

2. Stringers from reinforcing material can tie up rotating

equipment.

3. Rubber chips had a tendency to compress and become caught

in the stokers.

4. The size and purity of the shredded rubber was critical

to materials handling throughout the system.

a. The normal size required was l"xl"xl/4"

b. The shredded rubber must be substantially free of

metal s—bead , belting, etc.

a

R. H. Taggart, Jr., "Shredded Tires as an Auxiliary Fuel", available

from the Author, General Motors Corporation, Environmental Activities

Staff, Warren, Michigan.

60
V.l.c. Asphalt-Rubber

Another possible use is to combine crumb rubber from waste

tires with asphalt cement to create asphalt-rubber. This substance

is a relatively new product and can be used as a binder in road

building. Extended pavement life has been achieved by the use of

asphalt-rubber in chip seal applications. These applications act

as stress absorbing membranes which reduce the rate of crack

propagation from the old pavement surface to the new surfacing

material (reflection cracking). In addition to its engineering

advantages asphalt-rubber extends the use of asphalt cement. Some

forecasts indicate that after 1985, asphalt shortages are likely to occur.

After shredding, the vulcanized rubber crumb from typical

whole passenger tires will contain approximately the following

composition:

Whole Pass. Radial Pass.

Acetone Extractables , percent 19 18

Ash (from ZnOxide, etc.), percent 5 5

Carbon Black, percent 30 32

Rubber Hydrocarbon, percent 46 46

Natural Rubber, percent 18 22

Truck tires would use similar construction to that of a passenger tire but compounding would be quite different. A typical

whole truck tire compound is compared with the peel section of a truck tire shown below:

Whole T&B Peels (Tread)

Acetone Extractables, percent 12.5 16

Ash, percent 5.0 4

Carbon Black, percent 28.5 30

Rubber Hydrocarbon, percent 54.0 50

Natural Rubber, percent 33.0 27

Chemical composition of the rubber has only minimal effect on asphalt-rubber mixes where the rubber remains substantially undissolved in the asphalt but can have a marked effect on asphalt-rubber

mixes where it is solubalized to a greater extent.

Many of the primary uses of asphalt rubber have been in

pavement rehabilitation systems which act to reduce the occurrence

of reflection cracks. The most widely used systems are asphaltrubber chip seals (SAM—Stress Absorbing Membrane) and asphalt-rubber

interlayers (SAMI--Stress Absorbing Membrane Interlayer). At

present, design and construction of these two systems are nearly

identical

.

Asphalt-rubber binder systems have also been used in hot mixed

dense and open graded asphalt concrete and as a fog or flush coat

61
application on open graded mixtures. The use of asphalt-rubber for

crack pouring and joint sealing is gaining popularity. Asphalt-rubber

binders as membranes for bridge decks, for control of swelling

clays and for pond liners have been used on a trial basis. Asphaltrubber has been incorporated in more than 2000 lane-miles of

roadway in Arizona.

One company which produces asphalt-rubber binder uses a mix

containing 23 to 24 percent of scrap tire rubber, 70-72 percent of

asphalt cement and 4.5 to 6.5 percent. Kerosene type solvents are added to the reacted asphalt-rubber to control the viscosity

required for spraying. The asphalt-rubber is reacted between about

325 and 400 °F and applied at temperatures between about 290 to 325

°F. Specially designed asphalt distributors are utilized as reaction vessels. A diluted emulsified asphalt is applied to the

surface of the old pavement prior to the spraying of the asphaltrubber binder. Cover aggregate is applied immediately after

placement of the asphalt-rubber binder.

A second producer utilizes slightly lower percentages of

rubber. This rubber is a blend of 40 percent powdered reclaimed

(i.e. devul cani zed) and 60 percent ground vulcanized rubber scrap

selected to have a minimum of 30 percent natural rubber content.

Industrial scrap rubber is often used as a portion of this rubber.

The primary size of the rubber is between the No. 30 and No. 50

sieves. Rubber extender oils are mixed with the asphalt cement

prior to the introduction of the rubber into the asphalt. The

asphalt-rubber is reacted between about 350 and 425 °F and applied

within the same temperature range. Reaction vessels may be used

for preparation of the binder. Conventional asphalt distributors

are used to apply the binder. Tack coats are not used prior to

placement of the asphalt-rubber binder on the pavement surface.

So far as guidelines for specifications are concerned, performance cannot now be unambiguously related to physical properties in

a general fashion. Hence, very tight quality control on the

material is essential; one firm reportedly uses the following

procedure:

1. Sampling of Materials

a. Locally available asphalt cements (several sources and

grades)

b. Granulated crumb rubber

c. Cover aggregate (all Stress Absorbing Membrane and

selected Stress Absorbing Membrane Interlayer treatments)

2. Testing of Materials

a. Asphalt cements

(1) Absolute viscosity, 60 °C (140 °F)

62
(2) Penetration, 25 °C (77 °F) and 4 °C (39.2 °F)

(3) Rostler analysis

b. Granulated crumb rubber

(1) Sieve analysis

(2) Chemical analysis (portions of ASTM D297)

c. Cover aggregate

(1) Sieve analysis

(2) Asphalt-rubber stripping (Arizona DoT Test 217)

d. Asphalt-rubber mixture

(1) Torque-fork time-temperature-viscosity, 177 °C (350

°F)

(2) Modified absolute viscosity, 60 °C (140 °F)

(3) Elastic rebound, 25 °C (77 °F)

(4) Force ductility, 4 °C (39.2 °F) or lower temperatures

After completion of the above testing program, recommendations

-are made for each project relative to asphalt source and grade,

rubber material and percentage, asphalt-rubber reaction time, final

mixture viscosity, amount of diluent and spraying viscosity. In

developing the preceding recommendations, a number of factors are considered which include type of membrane (SAM or SAMI), project

climatic conditions and type and volume of traffic. On the project,

asphalt-rubber samples are obtained from each distributer truck

prior to spreading for viscosity determinations using a battery

operated rotational type viscometer. From these viscosities,

adjustments may be made when necessary to the asphalt-rubber

mixture, i.e., changes in reaction time and/or asphalt, rubber and

diluent content. Very detailed job records are now maintained for

future review and use in comparing material properties to project

performance.

Binder properties are dependent upon the type and quantity of

asphalt cement, type and quantity of rubber, type and quantity of

petroleum based additives, reaction temperatures and reaction time.

Considerable long-term research armed at developing theoretical

models and a better understanding of asphalt-rubber binder systems

(including laboratory-field performance correlations) has been

suggested by proponents of asphalt-rubber. This need arises since

asphalt-rubber is a new binder system which does not respond to

analysis by conventional tests associated with asphalt technology.

Furthermore, the binder and the binder-aggregate system are both

63
chemically and mechanically complex and far from being fully

understood.

Key economic considerations are 1) the price which must be

charged for the rubber to be used in the asphalt-rubber binder, and

2) the probable necessity for public entities, such as state roads

agencies, to procure asphalt-rubber based road materials at a higher first cost then conventional competitors. NBS/ORM sponsored

work on lid modifiers and the general results of an NBS/ORM state

procurement practices study provide some insight regarding the

second issue (see Publications List #'s 49-54 and 56). Rubber

price will vary, but a cost of 14<t to 16<t per pound (1982) is

1 i kely

.

The basic challenge for proponents of asphalt-rubber is to

show conclusively that reductions in life cycle costs can be

achieved by the development of materials, equipment, and/or techniques which provide a desired combination of first costs and

performance life. For example, a new product may have a higher

first cost while providing an extended performance life which

results in a lower life cycle cost as compared to a standard

product. Nevertheless, many state procurement codes require that

contracts be let to the lowest first-cost-bidder whose product will

meet the performance specifications.

Proponents point out that asphalt-rubber may provide an attractive economic alternative for construction, rehabilitation

and maintenance of our nation's roadway network. Economic advantages

stem from increased life and reduced thicknesses of pavement

sections. In addition the material is attractive from an energy

and resource recovery point of view. As of December, 1982 the U.S.

Congress was considering legislation provide supplemental grants to

states which would adopt and implement programs to require the use

of substances or materials based on rubber derived from waste tires

in projects for constructing, resurfacing, restoring, rehabilitating,

maintaining or reconstructing routes of the Federal interstate

highway system, including bridges, tunnels and overpasses.

V. 2. Large Volume Wastes

Large volume wastes include industrial by-products for which

large storage inventories exist. These wastes include such materials

as:

o Sludges

o Residual sulfates and sulfur bearing wastes

o Slags

o Mining wastes

o Organic wastes

64
o Incinerator reuse

o Fly ash

As an example, in the case of fly ash, such as that produced

by a coal-fired power plant, the U.S. produces about 75 million

tons per year of which 18 to 20 million tons is recycled or reused.

Hence, over 50 million tons goes into inventory annually. There

are estimates that 300 million to one billion tons represents

current total inventory.

Fossil-fuel fired energy generating facilities produce sludges,

slags, fly ash, bottom ash and sulfur bearing wastes. Some organic

wastes may also be produced. Studies carried out on behalf of the

U.S. Department of Energy concluded that, if these wastes--especi al ly

fly ash--were declared hazardous under Federal environmental

regulations, the cost of electricity to the consumer would increase

by 12 to 15 percent. The additional burdens would be unevenly

distributed geographically. Furthermore, insufficient hazardous

waste treatment capacity to deal with this "new hazardous waste"

existed. In addition, NBS/ORM realized that, if fly ash were to be

declared a hazardous waste, the amount of fly ash which is currently

recycled or reused—18 to 20 million tons annual ly--would probably

fall to nearly zero.

Fortune Magazine (November 20, 1978) put the problem in plain

terms:

"Fly-ash and sludge contain a rich variety of heavy metals and

assorted other chemicals, many of which are known to be

carcinogenic or otherwise toxic. These materials can leach

out and possibly endanger streams, flood-plains and sources of

drinking water such as aquifers. Under provisions of the 1976

Resource Conservation and Recovery Act, it is likely that the

U.S. Environmental Protection Agency will declare ash and

sludge to be hazardous waste, ineligible either for sale or for disposal by conventional open dumping. No one knows what

then is to become of them."

(As of March 1983, these wastes have not been declared hazardous;

they are designated "Special" and await further action.) NBS/ORM

initiated studies to characterize fly ash and other fossil fuel

technology wastes. [The U.S. Department of Energy/Laramie Energy

Technology Center (D0E/LETC) sponsored (and cooperated in) many of

these efforts.

]

V.2.a. Fly Ash

For this material NBS/ORM investigations fell into three main

categories:

1) Physical and mineralogical test method development,

characterization and production of standards. For

example, the NBS Office of Standard Reference Materials

65
(OSRM) has issued fly ash SRMs having certified composition

and characteristics. The NBS Center for Materials

Science, with ORM support, developed programs for quantitative X-ray powder diffraction for characterization of the

ash. (Details of NBS/ORM work in this area can be found

in Publications List #67).

2) Chemical test method development and evaluation. For

example, proposed extraction procedures for leaching

potentially toxic substances from ash were tested.

Sampling procedures and test samples were selected for a variety of ash (and other waste) sources. (See Appendix

VI).

3) Potential uses for fly ash in terms of physical and

chemical properties. Appendix IV provides these results.

Briefly, a wide variety of civil engineering applications

are possible, e.g., road base, grout, insulation, but

primary use is limited by compositional variability,

transport costs and lack of technical information regarding

its performance in construction materials.

Because of the extreme compositional variability and the

potential for regulatory prescription, individual guidelines for

specifications could not be developed. But the test methods,

standards and characterization carried out by NBS/ORM can certainly

serve as a foundation for individual decisions concerning recovery,

recycling and reuse of fly ash.

V.2.b. Sludges, Slags and Mineral Wastes

These materials, which are by-products of various industrial

processes, tend to be "large-volume" wastes. Many of these wastes

are classified as "Special" by the U.S. EPA for purposes of regulation under RCRA. Key issues for these materials are:

1) Possibility that these materials or some portion of them

will be declared to be hazardous waste;

2) Markets which would allow the materials to be utilized,

primarily in civil engineering applications, in an economically efficient manner.

Uses and markets for these materials are extremely diverse.

For example, steelmaking slags fall into two major categories,

viz., lime-silicate slags or phosphate slags. The former is used

extensively in roadbuilding in Europe; limits concerning volumetric

stability and guidelines for free calcium oxide and magnesium oxide

have been proposed. High phosphate slag demand is good; specifications are agreed by buyer and seller.

Mining wastes are used in concrete, cement, bricks and lightweight aggregates. In the case of cement manufacture, unburned

shale is used to supply the agrillaceous component of cement so

66
that the waste requires an alumina content of 25-29 percent and

non-oxide content of 5-10 percent for this use. On the other hand,

if base construction for roads is to be the application, the key is

durability under highly specific conditions, e.g., climate, construction method, traffic-patterns, etc. In brickmaking, the carbonaceous

material in the shale contributes an energy saving component in the

firing process. In one method (Surschiste) a 40 percent savings of

energy can be netted. Many other examples could be produced.

Sludges, slags and mining wastes are extremely heterogeneous

in composition, and physical properties of marketable products tend

to be achieved by special blending of virgin and waste materials.

Thus, NBS/ORM did not attempt to formulate a comprehensive research/

characterization effort for these materials. Indeed, such an effort would have required resources far beyond those available.

With regard to guidelines for specifications for these materials:

1) By-product must not be classified as a hazardous waste,

i.e., the entire lot must be sampled in a statistically

valid fashion and the lot must pass appropriate state

and/or federal requirements as set forth in appropriate

regulatory documents governing what shall be deemed a hazardous waste.

2) Appropriate physical and chemical tests to meet perfor- mance requirements have been formulated by many groups,

e.g., ANSI, ASTM, Portland Cement Association, for many

materials to be used in civil engineering. Thus, addition

or substitution of waste materials must still provide a product which meets these requirements.

3) The addition or substitution of the waste material must

in some way yield a product having better value for money

spent, i.e., better, more durable, cheaper, more energy

conserving, etc. In other words, the lifetime cost of

the final product must be as good or better than the

non-waste bearing product. In one case, ferro-alloy

waste (fume powder-mainly ferrosilicon by-product consisting of small Si0 2 spheres) was shown to provide better

stability and durability properties when added to certain

cements. The issue then becomes one of supply and demand

for this material such that the economics are acceptable

to buyers and sellers.

V. 3. Plastics

Recycling of plastics, which comprise about two to three

percent by weight, of the MSW stream can conserve energy. In fact, over 80 percent of the energy required for the preparation of

typical packaging products, including the energy of petroleum

feedstocks, can be saved. But economic and technical constraints

have prohibited recycling of plastics mixed within MSW.

67
In Europe and Japan, where the plastic content of the MSW

stream is two to three times in the U.S., some reclamation of

plastics from mixed MSW has been carried out. The most notable

success is in Italy where low density polyethylene is salvaged from

Roman MSW. This material is mixed with various quantities of

virgin resin and rendered into plastic bags which are then issued

to Roman householders for use as garbage sacks. In Japan, manual

sorting of the trash is carried out in order to reclaim plastics;

source separated plastics are also collected. These plastics are cleaned and separated (in a circulatory tank) into a light fraction,

e.g., polyethylene, polypropylene and a heavy fraction, e.g., PVC,

PVDC. These materials are then pelletized and used to make rods,

pipes and some decorative objects.

By far, the most advantageous use of waste plastic is recycling

(either in original form or another plastic form or even as feeds

for oils or waxes) back into the plastics production process.

Guidelines for specifications are quite clear in such cases. The

waste resin must meet virtually the same criteria as virgin resin.

Hence, closed system reclamation by procedures and primary users of

plastics is widely practiced. At present, there seems little

choice but to obtain source separated plastics if reclamation is to

be economically and technically feasible.

Research is being performed to determine if mixed plastics or plastics in mixed wastes can be separated conveniently and economically. Nevertheless, specifications for reinsertion as resin are unlikely to be substantially altered. Hence, NBS/ORM undertook no direct research in this area. Note that if plastics mixed in MSW

are burned to recovery energy, no special precautions are needed.

The material contains high energy content per unit weight, burns

cleanly and in view of the information contained in Appendix III is

unlikely to be a major source of potentially hazardous emissions.

V.4. Landfill Gas

In a sanitary landfill, each day's solid waste is covered with

dirt or clay. Natural processes then operate within the landfill;

the organic material decomposes. The result is gas--consi sti ng

primarily of methane and carbon dioxide but also usually containing

mercaptans. The generation of methane gas is considered a nuisance

and a potential problem. In fact, to prevent the gas from migrating

to nearby areas where it could form explosive mixtures, collection

systems have been installed. The gas collected from these systems

is often flared.

Two main options exist for the use of landfill gas. First, it can be used as it is collected at the landfill (low BTU)--about

half methane and half carbon dioxide, with only some compression

and removal of moisture. In this form it is presently being used

to generate electricity and fire boilers for space heating and

industrial processes. The other option is to remove carbon dioxide,

resulting in gas which is richer in methane (high BTU). In this

form, it can be injected directly into existing natural gas pipelines.

68
Landfill methane recovery systems now in operation employ both of

these options.

The applicability of high BTU landfill gas processing depends

on the size and configuration of the landfill, and the location and

capacity of a utility company pipeline, as compared with the

location and volume requirements of a potential low BTU customer.

In, order to optimize the efficiency and economics of a methane

recovery system, the maximum possible amount of gas must be withdrawn

from the landfill and sold to a customer who can accept the entire

output. The utility company pipelines usually provide greater

flexibility in this regard.

High BTU systems also provide the capability of shutting down

for maintenance repair or other reasons without incurring penalties

from the utility company, since their line capacity has the capability

of making up this lack of supply. On the other hand, a commercial

low BTU customer who has relinquished his normal natural gas supply

in favor of low BTU landfill gas may be severely impacted by even a short-term shutdown, unless he has a guaranteed supply of alternate

fuel.

Another advantage provided by high BTU facilities is the

potential for additional markets for carbon dioxide and liquid

condensate by-products, which can enhance the economics of such a faci 1 i ty.

Although both high BTU and low BTU facilities must deal with

the same general characteristics of landfill gas, a decision to go

to a high BTU system takes the processing step totally out of the

solid waste industry and places it firmly in the gas processing

industry, requiring thorough knowledge of all available processes

to handle a wider variety of landfill gas components and the

problems associated with removing them from the gas stream.

Slotted pipes, embedded in gravel and connected to vacuum

pumps or compressors, are used to collect methane from within a landfill. Processing facilities are on-site or nearby. Gas

collected from the central portions of the landfill is normally

rich in methane, usually about 50 percent. Gas withdrawn near the

perimeter, however, sometimes contains too much air to be processed

economically. If necessary, this gas is collected to prevent

migration into nearby areas, and is usually burned off wi.th a flare

system. Thus, a landfill project may have two separate gas collection systems, a central one for energy production, and a perimeter

system to prevent gas migration.

A number of factors enter into the decision of a community in

considering a gas recovery system for its sanitary landfill and

there are no hard and fast rules. The age, size, moisture, average

depth and tons in place are key factors. Equally important are the

potential end uses of the gas. Methane recovery probably is not

feasible if the landfill is less than 30 to 40 feet deep, on the

average. To obtain gas that can be used "as is", at least a

69
million tons of solid waste should be in place. For long-term

economical pipeline quality methane production, even more refuse

should be in place, probably two or three million tons.

Composition of landfill gas varies from site to site and

within individual sites. For those wishing to obtain and market

economical quantities of high BTU gas, the guideline for specification is quite simple: the product must be of the same purity and

energy content (1000 BTU/SCF) as that of nearly pure methane, i.e.,

pipeline quality.

In the case of low or medium BTU gas, specifications must be

agreed between individual buyers and sellers based on need and

economics. For example, the Ascon Landfill in Southern California

produces gas with an average higher heating value of 530 BTU/SCF.

A nearby oil refinery agreed to purchase this gas for daily use;

gas pressure, moisture and heat value were specified as well as types and maximum tolerable content of contaminants.

In view of the market requirements for specifications for

landfill gas and the highly site-specific nature of the gas,

NBS/ORM conducted no direct research on this gas. The guidelines

for specifications are either "pipeline quality" or set individually.

V. 5. Compost

Non-toxic wastes can be converted to compost products by

natural or accelerated processes. The problem in the U.S. has been

lack of a steady market for the material. One of the causes of concern is that using compost created from consumer wastes indeed

may inadvertently contain toxins. Thus, the use of this compost on food bearing cropland must be carefully monitored. Furthermore,

the U.S. has rarely required large steady applications of the

nutrients available in most composts based on consumer wastes.

NBS/ORM had virtually no involvement with any aspect of

composting. One activity which was undertaken consisted of review

of several proposals for EDA funding concerning methods to create

and characterize compost from various sources. The only other

activity was the analysis of some compost samples supplied by the

U.S. Department of Agriculture (USDA). The USDA wished to know if

a specific product of accelerated composting of municipal waste

through bacterial action was able to pass the EPA extraction

procedure test for toxicity.

This material was produced by means of the following process:

Shredded MSW was inoculated with a substance that expedites

the breakdown of all components in the waste. (Although toxic

and hazardous materials are not knowingly handled in the

system, small amounts of such materials supposedly can be

introduced into the process without materially affecting the

plant or end-product.) The shredded and inoculated waste was

then conveyed to the composting area where it was windrowed in

70
a closed building on a concrete floor where biological activity,

accelerated by the inoculant, breaks down the waste. The

bacterial action is aerobic, which prevents the formation of

odor forming gasses and generates great quantities of heat.

Temperatures in the composting piles were allowed to reach

approximately 170 °F long enough to destroy pathogenic bacteria.

Incidental to the aerobic breakdown is the resulting structural

change in glass (powdering), metal (oxidation), and plastic

and rubber (acid, bacterial and heat reaction).

Each of the composting piles was numbered and readings of

temperature and moisture content were taken at six-hour

intervals. After about three days the pile was "turned" and

repiled. The "turning" of the pile in this manner promotes

aeration and with controlled addition of moisture the bacterial

decomposition cycle is reactivated. After about four turning

cycles over a period of fourteen to twenty days, the material

reaches a black humus-like state and is stabilized.

The converted waste was then transferred from the piles by

conveyor to a grinder or hammermill where it was reground to

eliminate course material. The reground product was screened

to insure full elimination of all coarse particles and finally

fed into bulk storage or bagging equipment for marketing. The

screening process rejected about 15 percent of the material as too coarse, but the rejected material was conveyed to blend

with incoming material and reprocessed.

Samples of this material all passed the Ep toxicity test,

i.e., would not be classified as hazardous under provisions of

Subtitle C of RCRA. These results were conveyed to USDA.

Apparently, this compost is a satisfactory soil conditioner,

but NBS/ORM did no further tests on it.

Passage of an accepted toxicity test is the only guideline for

specification which can be applied generally to compost

created from waste. Markets for compost are highly localized,

nutrient requirements for various agricultural or botannical

cultivation processes vary considerably from place to place.

Thus, if the prospective purveyor of compost derived from

consumer waste can show that the material is not toxic,

conventional market economics will determine if composting is an efficient means to reclaim some value from the waste.

Some idea of the costs of producing compost from MSW can be

obtained using data quoted by J. Kass (Stock Market Magazine,

September 1980). According to Kass, a plant capable of

processing 76,500 tons per year of MSW would cost $4.5 million

and would produce 53,500 tons per year of over 15 years, and

if operating and maintenance costs were $17 per ton, then the

cost to treat one ton of MSW after its arrival at the facility

is about $20. If all 53,500 tons of product could be sold,

the break-even price would be about $29 per ton of copost FOB

the facility. These figures assume public ownership of the

71
plant, i.e., no taxes. Presumably, a statistically valid

sampling procedure would be combined with frequent testing to

prove that all batches of product pass an accepted toxicity

test and contain the mix and quantity of nutrients required by

the customer.

72
VI. NBS/ORM AND THE RECYCLING OF INDUSTRIAL WASTES

NBS/ORM was concerned with increasing the possibilities for

recovery, recycling and reuse of all materials which were destined

for waste. With regard to industrial wastes, e.g., scrap metals,

rubber, textiles, NBS/ORM attempted to develop methodologies which

could lead to increased recycling on an economically sound basis.

The work conducted by the State of Michigan on behalf of NBS/ORM by

Lehigh University on behalf of EDA and by NBS/ORM directly provides

some examples of these efforts. (See Sections V and VIII for

details of these projects).

The National Association of Recycling Industries (NARI) has

developed (and continually updates) guidelines for specifications

for such items as non-ferrous scrap metals, rubber and textiles; as noted, the Institute for Scrap Iron and Steel does the same for

ferrous metals. Therefore, NBS/ORM chose not to use its limited

resources to try to perform direct studies of these materials. In

effect, valid guidelines for specifications exist and are subject

to constant review and revision.

With respect to the mandates of section 5003 of RCRA regarding

market promotion and identification of barriers to recycling as applied to industrial discards, NBS/ORM worked directly with the

steel industry and the leather and tanning industry. In this

latter case, two recovery technologies were identified and an outline for cost effective research and development of these

technologies was provided. The methodology developed in the

Michigan/NBS/ORM study (see Section VIII) can be used to assess economic actions required to implement the options and to predict

the likely outcome of such actions.

This approach, provided by NBS/ORM, can be replicated with

other business and industry sectors. Small businesses would seem

to be excellent candidates. NBS/ORM developed a pilot program plan

which was meant to:

1) assist in reducing regional economic impact of federal

hazardous waste management regulations;

2) protect and enhance productivity in selected industrial

and manufacturing operations;

3) prevent unnecessary reinvestment of private capital; and

lastly,

4) create a public awareness of the economic development

potential in conservation or recovery of materials

destined for disposal.

This program could not be implemented prior to the close of FY

1982, however.

73
A suggestion was submitted by NBS/ORM to DoC to form a group

consisting of state officials, NARI, ISIS and NBS/ORM personnel to

create a "Clearinghouse" meant to provide appropriate bases for

dealing with supply and demand problems associated with recyclables

to be procured by governmental entities. The procurement studies

sponsored by NBS/ORM were to serve as the foundation for the

necessary negotiations.

With regard to barriers, NARI and ISIS have developed detailed

arguments concerning impediments to the economics of recycling.

These include differential freight rates, e.g., more costly for

secondary goods, tax policy, export policy and market fluctuations

exceeding "normal" cycles. As these impediments are directly

concerned with legislative and regulatory prerogatives. NBS/ORM

did not deal with these issues directly. However, NBS/ORM personnel

provided resource information to DoC policy decision makers on all

of these issues. NBS/ORM personnel maintained contact with the

major industrial recycling representatives, e.g., NARI, ISIS,

American Paper Institute, individual firms, throughout the lifetime

of NBS/ORM.

74
VII. PROCUREMENT PRACTICES RELATING TO ITEMS CONTAINING

RECOVERED MATERIALS

VII. 1. Legislative Mandate

Section 5002 states in part that:

"the Secretary shall also, to the extent feasible, provide

such information as may be necessary to assist Federal agencies

with procurement of items containing recovered materials."

VII. 2. State Procurement Study

In order to fulfill this requirement and also to encourage

greater commercialization of proven resource recovery technology as required by Section 5001, NBS/ORM initiated investigations of

federal and state level procurement practices relating to products

containing recovered materials. Clearly, increased procurement of

such products would increase markets for recovered materials.

Seven states, Colorado, Florida, Michigan, Minnesota, New Jersey,

New York and Washington as well as the National Association of

State Purchasing Officials (NASPO) cooperated with NBS/ORM by

agreeing to:

1) Survey and report on state statutes pertaining to the

procurement of products containing recovered materials.

2) Report on past, current or future programs and other

state activities related to the procurement of products

containing recovered materials.

3) Identify and report any legal, institutional, procedural,

economic, or technical barriers to the state procurement

of products with recovered materials.

4) Identify and report on any successful or unsuccessful

attempts to procure products with recovered materials.

This compilation to include those initiated by state

solicitation or offerings by suppliers and manufacturers.

5) Provide a listing of the state's top ten products purchased

based on volume and/or dollar value. This list was to

include an cooperative purchases for local governmental,

special districts or agencies.

6) Provide a listing, based on the best knowledge and

experience in the state, or products that are most

amenable to the inclusion of recovered materials.

7) For the list of products selected for item 6, provide all

pertinent specifications, test methods, performance

criteria and other information related to the procurement

of each product.

75
The results of this study can be found by reference to ORM

Publication List #'s 49-54 and 56. What follows was taken from the

summary of the results: Responses to the several components of the

project work statement were indictive of three important conclusions:

1) that the state purchasing offices appreciate the need to expand

purchases of recycled products and reduce solid waste; 2) that the

principal barriers to accomplishing this are lack of suitable

standards, specifications, and price/performance criteria for

individual materials; and 3) that there is need for a continuing

means of interstate communication to focus attention inspire

cooperation, and transmit experiences.

The validity and practicality of these conclusions could be

tested by experiments involving all states working in a few selected

product areas. Acceptability of recycling as a concept is likely

to be affected in a positive way by growing economic considerations.

This is already noticeable in the case of waste lubricating oils,

as evidenced by visits during March 1981, of more than 100 purchasing, energy, and other administrators and officials from 47 states

to the new re-refining plant being operated by the state of North

Carolina. Traditionally, the United States has recovered some 20

percent of its waste paper for production of additional paper. In

Germany, the figure exceeds 30 percent, and Japan imports certain

grades of waste paper for this purpose. Declining highway revenues

are spurring states to use more reclaimed materials in road construction and maintenance. These and other examples of the effect of

economic factors suggest that in terms of procurement, perhaps the

substantive aspects of recycling are only beginning to get underway.

Collectively, the purchasing programs of the fifty states have

extension capacity for new and progressive ideas. But unfortunately,

there is no mechanism or system available for stimulating, assembling, organizing, disseminating and exchanging these ideas. If the

problems pertaining to the purchase of recycled products were identified and articulated in a manner to challenge state purchasing programs, and if an effective information exchange could be

established, it could be expected that workable solutions would be

forthcoming to the extent they are available. This broad-based,

unique resource for innovation needs to be instituted and utilized

to its full advantage.

Finally, there are supplementary ways by which NASPO might

conduce to more buying and use of recycled products. An established

information exchange would strengthen the success potential or related endeavors in which NASPO engages with other professional

organizations, including current programs with ASTM (American

Society for Testing and Materials) and NIGP (National Institute for

Governmental Purchasing). And the Association could supply additional motivational support by institutional means such as consideration

by its Executive Committee of formal endorsement of the concept, or

a resolution to this purpose presented to the full membership for

adoption at its annual conference.

76
If the purchasing knowledge and resources of the states are to

be applied to the manifold questions inherent in the buying of

recycled products, NASPO recommends that it be done by means of a program under the aegis and direction of the Council of State

Governments.

One way in which such a program could test, and demonstrate,

its effectiveness would be by assigning selected product areas to

diffferent groups of states. Thus, one group could focus on the

policies and problems associated with the purchase of rebuilt and

remanufactured items. Another group could work in the field of

recovered papers. A third group could concentrate on the entire

spectrum of energy resource items, including the extended use or reclamation of oils. Among additional areas of examination could

be the recycling of highway construction materials, and the in-house

reconditioning of various kinds of equipment (office, transportation,

furniture, etc.).

The program would require experimentation, and as appropriate,

a trial and error approach. Test procurements would be made.

Experiences would be analyzed, summarized, and disseminated to all

of the states and to numerous interested parties. The Council of

State Governments would exercise coordination in providing a policy

or oversight component, and in securing the active participation of

the industrial sector, local governments, trade associations, and

of standards and specifications groups such as the American Society

for Testing and Materials and the American National Standards

Institute. The cooperation and assistance of a number of Federal

agencies would also be needed.

Benefits from such a program, properly managed, would be many

and varied, including gains which would be considered both short-term

and long-term, primary and secondary, practical and theoretical.

In addition to reduction of solid waste would be, for example, the

fostering or the achievement of:

o A deeper understanding of the need for recycling.

o More clearly defined and usable standards and specifications.

o More complete and reliable information from manufacturers.

o Increased realization of savings through use of recycled

i terns

.

o More serviceable product labeling.

o A greater commitment by purchasing to the acquisition of

recycled products.

o More explicit performance criteria for comparing recycled and

virgin products.

77
o A better ability to calculate "social" cost benefits in

evaluating bids.

o More artful drafting of Invitations for Bids.

o Added acceptability of recycled articles on the part of

program agencies.

o Improved testing and evaluation capabilities of the individual

states.

o A larger market for recycled products.

o More widely disseminated information among the purchasing

community as to availability of recycled commodities.

o A better identification of problems capable of solution; of

those not so amenable; and of alternatives.

o The inception of an ongoing public purchasing information

exchange system.

o Increased conservation of public funds.

NBS/ORM commissioned two follow-up activities once these

results were in hand:

VII. 3. Development and Test of a Mathematical Tool Meant

To Aid Purchasing Agents in the Analysis of Bids, i.e.r~a

Bid Modifier^ in Order that Recyclable Materials Might Be

Purchased More Often

With respect to the bid modifier, a method was sought which

would be designed to adjust bids received for a commodity to

incorporate the estimated disposal costs of the commodity. A

factor called the Purchasing Adjustment for Recycling (PAR) was developed based on the examination of the following factors: 1)

the two most common disposal systems (landf il 1 ing , and incineration),

2) the data from a literature search, 3) a simulation of the

bid/award process using prior purchasing records, and 4) discussions

with purchasing personnel about the problems and attitudes that

could affect the use of a PAR factor in bid evaluation.

While the PAR factor might well identify disposal costs, these

costs usually were not sufficiently large to change the buyer's

decision regarding the choice of which product to purchase. The

buyer neither expected to actually pay the true costs of disposal,

nor was he interested in revising the specifications (principally

the style of the product) in order to purchase a recycled or recyclable product.

The PAR function might find an application as an educational

tool for requisitioners and others in the logistics cycle who

prepare the original specification or requirements for goods. If

78
these originators of product purchases were better able to recogniztr

the economic, social, and inflationary values of non-recycl abl es

,

progress towards the purchase of recycled and recyclable materials

might be hastened. (See Publications List #74 for full details)

VI I. 4. Compilation and Issuance of a National Recycling Directory

The main purpose of the National Recycling Directory (Publications List #60) is to encourage recycling and the manufacturing of

products made from recycled or recovered materials. This directory

can be used to assist individuals, organizations, government,

businesses, and institutions in their recycling efforts by providing

information on markets for secondary materials. Federal, state and

local governments should find the directory useful in their efforts

to procure products made from recycled materials. Scrap processors

and dealers can use it to aid in locating the closest or most

suitable market for their materials. Community and other non-profit

recycling programs will be assisted in locating the best markets

for their recovered materials.

The companies listed in the directory manufacture products

which contain some recycled or recovered material. The directory

consists of separate sections for the types of materials used. The seven categories of materials are glass, ferrous metals, non-ferrous

metals, paper, plastic, rubber, and textiles. Within each section,

the states are listed in alphabetical order. The companies are listed in alphabetical order under the state in which they are

located.

The listings do not include those companies which are exclusively dealer/processors, tire retreaders, energy recovery facilities,

or are involved in the recovery of used oils, solvents, or chemical

wastes. The directory has become very popular with those engaged

in all forms of recycling. National publicity has resulted in a strong demand for the directory. An updated version was released

in early 1983.

79
VIII. CHALLENGES POSED BY THE NEED TO DEAL WITH HAZARDOUS WASTES

During the lifetime of NBS/ORM (1976-1982), issues associated

with the disposition of potentially hazardous wastes became a major

public policy focus in the U.S. Therefore, other Federal agencies

who were involved with measurement aspects of the hazardous waste

problem sought the aid of NBS. These agencies included EPA, DoD,

DoE and DoT. In addition, NBS/ORM had directly mandated responsibilities to investigate the possibilities, opportunities, and barriers

to recycling of hazardous wastes. Thus, NBS/ORM became involved

with many of the challenges posed by the need to deal with hazardous

wastes. This Section will summarize NBS/ORM activities and contributions concerning hazardous wastes. Hence, efforts associated with

Sections 5002, 5003, and 5004 of RCRA are included here in Section

VIII of this report.

Production and use of many commercial items in the U.S.

economy create a residual amount of material to be discarded.

Under current U.S. law, when these discards are reactive, corrosive,

igni table, infectious, radioactive or toxic, they are termed

"hazardous wastes." Under terms of the Resource Conservation and

Recovery Act, as amended (RCRA) (P.L. 94-580; P.L. 96-482), hazardous

wastes are to be monitored from creation through final disposal,

i.e., from cradle-to-grave. In addition, so-called "Superfund"

legislation provides for funding— largely through a tax on hazardous

waste generators —to remedy threatened or actual environmental

and/or health insults posed by abandoned hazardous waste sites.

A reasonable goal would be to achieve an economically and

environmentally acceptable approach to meeting the challenges posed

by existing, proposed and defunct facilities meant to deal with

hazardous wastes. The magnitude of the problem has been investigated

by the U.S. Environmental Protection Agency (EPA): Approximately

55-60 million metric tons of hazardous wastes are generated annually

or about two tons every second of every day. In addition, EPA

estimates that there are several thousand abandoned sites into

which hazardous wastes were placed at one time or another.

Hazardous wastes pose challenges in three major areas:

o Technical evaluation, i.e., definition and measurement of the

exposure of humans, ecosystems and livestock to potentially

harmful effects of hazardous wastes.

o Economic evaluation, i.e., definition and estimation of the

economic effects of various levels of control which might be

imposed on generators, disposers, and recyclers of hazardous

wastes. In addition, potential economic effects on other

societal elements affected by the existence of hazardous

wastes must be considered, e.g., the perceived value of a home

when a previously unknown abandoned dump is found in the

vici ni ty.

80
o Institutional responses, i.e., the reaction of a population

which is in the vicinity of an abandoned, existing or proposed

site. Here social and psychological factors may enter into

consideration—and usually do. Often legal interpretation is

sought. The question of who is liable for real or potential

or imagined insult becomes of key importance in such instances.

Next, the issue of what is the extent— in both dollars and

time--of such liability is then of paramount importance to the

parties of interest.

This section will deal primarily with technical approaches which

will lead to a firm foundation for economic and institutional

decisions. The goal will be to stimulate appropriate research and

development of test methods, specifications, and practices relating

to discarded materials destined for disposal. The object is to

outline an approach to a measurement foundation which will allow

for disposal of such discards in a technically, economically and

institutionally acceptable fashion. Within the resources available,

NBS/ORM attempted to develop a unified approach to fulfill the

mandates of sub-title E of RCRA as applicable to hazardous waste.

In order to arrive at such an approach, background information

on legislative and regulatory policy in the U.S. and other industrialized nations needs to be enumerated so that the parties of

interest and their respective roles can be defined. Then a brief

summary of conditions existing currently will be provided in order

to identify specific challenges. Next, a framework for dealing

with specific technical challenges can be postulated.

VIII. 1. Background

Almost all industrialized nations have exercised a degree of

control over hazardous wastes by means of national legislation

and/or regulation overseen by a national agency. There is no particular uniformity to legislation defining hazardous wastes, but

typically a set of substances is subjected to special rules. This

list takes into account the properties of the waste which may

produce specific effects. However, there is no uniform definition

as to what it is that the waste must have a negative effect upon in

order to be labelled "hazardous," i.e., the problem is not clearly

defined. Still, Belgium, Denmark, West Germany, France, the

Netherlands, Sweden and the United States have compiled lists of

presumably objectionable wastes. Of all countries, only the U.S.

deals with wastes which might pose a threat if improperly managed.

All of the laws and rules can be divided into two categories:

o Prescription of a certain conduct

o Prohibition of a certain conduct

For example, the West German statute of 1977 states that "waste

shall be disposed of in such a way that the well-being of the

81
community is not impaired." Next, a list of situations which must

be avoided is provided. The 1975 French law is similar.

In all cases, the duty to maintain records and, in certain

cases, to notify responsible authorities, plays a pivotal role in

the legal regime for hazardous waste management, where documentation

and information are essential for effective monitoring and control.

Indeed, the U.S. EPA flatly states that:

"Cradle-to-grave control via manifests and reporting is the

keystone of the program; only permitted sites may receive

hazardous wastes. EPA anticipates 25,000 permit applications

national ly. 11

A license or permit for waste treatment facilities is required

in all countries. Permit applications require information regarding

types and quantities of waste involved, technical capabilities,

safety precautions and methods and sites for disposal. In addition,

many states in the U.S. have separate laws and regulations governing

hazardous waste treatment; these must be at least as stringent as the Federal laws and regulations. Furthermore, state-to-state

"consistency" is required by Federal law.

In summary, the following similarities exist between the

various legal entities for the transport, treatment and disposal of

hazardous waste within industrialized countries:

o Hazardous waste must not be abandoned;

o Hazardous waste belongs to the generator;

o The generator is responsible for ensuring safe disposal of

hazardous waste;

o The "polluter pays" principle applies to all hazardous waste

generated, abandoned, transported, treated and/or disposed of;

o Detailed records concerning such things as quantities, types,

methods of treatment, and disposal sites must be maintained

during all phases of hazardous waste operations; reports must

be furnished where required;

o Hazardous waste must be handled separately from other waste;

o Whether hazardous waste is treated on-site or off, it must be

done under close supervision and by competent personnel

applying environmentally safe methods;

o Hazardous waste which is treated off-site must be treated

installations which are either licensed or operated by the

authorities.

82
Obviously, the industrialized world is concerned about the

challenges posed by the existence of hazardous or potentially

hazardous discards, but no one has yet defined the problem or a unified program to deal with all aspects of the situation arising

from the existence of such wastes. In an effort to do so, at least

two major cooperative studies have been undertaken in which the

U.S. was an official participant:

o NATO Committee on the Challenges of Modern Society study

entitled "Disposal of Hazardous Wastes" begun in September

1973 and completed in April 1981

o Organization for Economic Cooperation and Development (OECD)

study entitled "The Control of Hazardous Waste in Selected

Member Countries," begun in 1980 and still under way. NBS/ORM

participated directly through 1982. (See Section VIII (14)

for detai Is.)

The NATO study concluded that there are ten major priority topics

or challenges which needed attention:

o Approaches to the Definition and Classification of Hazardous

Wastes

;

o Control Mechanisms for Hazardous Waste Disposal;

o Siting of New Hazardous Waste Disposal Facilities;

o Transboundary Disposal of Hazardous Wastes;

o Improvement and Harmonization of Hazardous Waste Disposal

Quality in NATO Countries;

o Relationship between Hazardous Waste Disposal and Environmental

Protection in General;

o Problem of Abandoned Sites;

o Role of Recycling and Resource Recovery in the Area of Hazardous

Wastes

;

o Financial Responsibility and Liability for Hazardous Waste

Disposal Facilities;

o Need for Research and Technology Development.

The NATO project participants concluded that—from the point

of view of environmental amenity—the desired management options

ranked in order of desirability are:

o Reduce generation of hazardous waste;

o Separate out and concentrate the waste;

83
o Utilize the waste either directly or via recycling;

o Detoxify and neutralize the waste;

o Destroy in special incinerators;

o Dispose in "secure" landfill.

Indeed, this priority listing was one basis for current U.S.

regulations concerning hazardous waste disposal.

Central to all regulations is the so-called "polluter pays"

principle, i.e., the agency responsible for generating the waste

must pay for its eternal care to assure that no environmental

insult occurs. Thus, the liability aspects in theoretical legal

form are defined.

The NATO study states bluntly that:

"Liability requirements are necessary because of the potential

for damage to people and property from hazardous waste management operations, as indicated by actual damage cases and the

very nature of hazardous wastes. If the facility owner has

insufficient financial resources to pay for damages, private

parties or government may be forced to bear the costs.

Liability protection is necessary and should be provided for

both sudden occurrences, such as fires and explosions, and for

non-sudden occurrences, such as slow migration of toxic

constituents from hazardous waste landfills or surface impoundments. "

In the U.S., bonds and insurance provisions against the potential

for damage as a result of hazardous waste treatment facilities were

required through the regulatory mechanism. But as stated in the

NATO study, the lack of information and experience precludes a decision in favor of or against specific models for financial

responsibility and liability. Thus, most countries still try to

determine liability through traditional channels in the framework

of normal civil law.

The OECD study is focused on four major aspects of the control

of hazardous wastes:

o "Problem" or abandoned sites;

o The transfrontier transport of hazardous wastes;

o The private and public costs of complying with the provisions

of hazardous waste regulations, and of administering them;

o The insurance and assurance problems raised by such regulations.

The OECD study began recently (1980), and only the abandoned

site problem has been dealt with in any depth to date. A symposium

84
was held at which experts from the OECD countries reached the

following general conclusions:

o The awareness of, problem waste sites is relatively new in

most countries and scientific and government institutions are experiencing considerable difficulty in meeting the challenge.

o The location and discovery of many problem waste sites without

the institutional capability to deal with the resultant

problems has caused significant public anxiety.

o Actual and environmental and public health impacts resulting

from problem waste sites is in general either very poorly

understood or misunderstood. The scientific foundation on which particularly health impact assessments is based is weak.

As a result development of such health impact measurements

will probably be some time in development.

o Environmental and health impacts are complex and far reaching;

remedial and countermeasures are uncertain in the long term

and often exceedingly expensive. The most practical and

effective solution lies in avoidance of such problems before

they occur, by minimizing the placement of "problem wastes" in

the ground and by proper engineering and control of those land

disposal sites which are absolutely necessary.

The foregoing background material is meant to help define the

general legal, regulatory and institutional challenges posed by the

need to deal with hazardous wastes. In what follows, the situation

with respect to the U.S. generation of hazardous waste will be

outl i ned.

According to EPA, in 1979 seven industry sectors generated

28.1 million tons--or about half—of all U.S. hazardous wastes.

These sectors include:

o Primary metals--8.3 million tons per year.

o Organic chemicals —6.7 million tons per year.

o El ectropl ati ng--5. 3 million tons per year.

o Inorganic chemical s--3. 4 million tons per year.

o Petroleum ref i ni ng--l. 8 million tons per year.

o Texti 1 es--l. 8 million tons per year.

o Rubber and pi astics--0. 8 million tons per year.

Over 65 percent of hazardous wastes are generated in ten states:

Texas, Ohio, Pennsylvania, Louisiana, Michigan, Indiana, Illinois,

Tennessee, West Virginia and California.

85
The total number of generators of hazardous waste in the U.S.

is estimated by EPA to be 760,000. Of these:

o 695,000 generators produce less than 1000 kg per month for a total of 600,000 tons per year;

o 563,000 generators produce less than 100 kg per month for a total of 138,000 tons per year; and

o 40,000 generators produce more than 5000 kg per month for a total of 22 tons per year.

Obviously, the impact of hazardous waste management regulations

cannot be divided evenly among all of the disparate generators.

Some of the factors leading to differences in impact include:

o Nature of processes generating regulated wastes, including

correlations of the intensity of waste generation and relationships between relative value of product and the costs of waste

management;

o Economy of scale factors: Above the "small generator" threshold,

a number of regulatory parameters such as costs associated

with financial responsibility, recordkeeping, increased

storage, transportation, treatment, and disposal appear to

favor larger over smaller operations;

o For similar industrial operations, newer plant facilities are likely to have an economic impact advantage over older facilities based on, but not limited to, improved process technologies

and improved waste management technology available; and,

o Economic impact differentials between types and sizes of

industries are likely to appear as relationships to overall

market competitiveness, e.g., ability to pass on cost differentials of the hazardous waste regulations without significant

loss of market.

According to the Illinois Environmental Protection Agency, approximately 25 percent of businesses in the State are likely to be

adversely affected by Federal hazardous waste management regulations.

Those industries most seriously impacted are foundries, small

plating operations, and small plastic manufacturing companies. The

costs of hazardous waste disposal to small process industries such

as el ectropl aters preparing integrated circuit devices, and tanners,

can be exceedingly large as compared to gross sales from business.

To compound the uncertainties faced by generators and disposers

of hazardous wastes, some 30-35 states will probably obtain temporary

authorization to regulate hazardous wastes and operate the RCRA

programs independent of EPA. Note that EPA must operate the

program in any state not gaining such temporary authorization.

Ultimately, state programs must be equivalent—or more stringent--

with respect to the Federal program, consistent with other state

programs, and provide for "adequate enforcement."

86
Finally, local opposition to the establishment of waste

management facilities is a major obstacle not only for hazardous

waste management but for solid waste management in general. Such

opposition has often blocked environmentally and economically

sites.

Several states and a number of localities have imposed bans

and restrictions on the movement of waste into their jurisdictions.

Restrictions on the movement of hazardous waste have caused especially difficult problems—many of the specialized facilities equipped

to handle certain hazardous wastes must serve large areas in order

to be economically viable.

Assurance of improved management of waste and incorporation of

public education and participation measures may affect public

attitudes, but whether they will reduce opposition enough to permit

all the well- justified sitings that are needed is uncertain.

VIII. 2. Current Status in the U.S.

The situation within the United States today was created by

the EPA efforts to compile regulations governing hazardous wastes

from cradle-to-grave. A former Assistant Administrator of EPA

declared the initial fruits of these efforts to be the "most

complex set of regulations ever issued by any government at any

time in history." The regulatory program includes:

o Identification of hazardous waste;

o Standards for generators and transporters of hazardous waste;

o Performance, design and operating requirements for facilities

that treat, store or dispose of hazardous waste;

o A system for issuing permits to such . faci 1 i ties ; and

o Guidelines describing conditions under which state governments

can be authorized to carry out their own hazardous waste

management programs.

Each of these general areas is buttressed by extremely detailed

descriptions of characteristics, performance specifications, tests

and trigger concentrations of pollutants which can result in

a waste being classified as hazardous and the generator of that

waste being held responsible — in perpetuity—for any possible

damage the waste may cause.

Lists of proscribed substances were compiled by EPA using the

RCRA definition of hazardous waste, i.e., a solid waste which may

cause or significantly contribute to serious illness or death, or that poses a substantial threat to human health or the environment

when improperly managed. In addition, EPA defined proper management of such wastes and detailed specific tests for ignitability,

87
corrosivity, reactivity and toxicity. EPA also required all

generators of such wastes to register in 1980.

During the period 1976-1981, environmental insult due to

hazardous wastes occurred. The most notorious instance was at Love

Canal near Niagara Falls, New York. The news media dealt with real

and potential effects of hazardous wastes in great detail. Hence,

public awareness of the problem was heightened and public aversion

to risks due to exposure to hazardous wastes strongly increased.

Indeed, public opposition has closed at least one site which

formerly had valid state and Federal permits; this closing has been

upheld by the courts on the basis of the presumed possibility of

harm to the population which might be exposed to emanations from

the site.

The current situation, as a result of the legal and regulatory

actions since 1976, can be summarized for each of the three major

components of the problem, viz, technical, economic and institutional :

Technical : Much of the effort of the past five years has been in

reaction to EPA actions and proposals. For example, EPA proposed a test for hazardous waste based upon a model presuming a mixture of

industrial and municipal wastes leaching from a landfill. Literally,

thousands of hours of professional staff time have been spent

investigating this one aspect of the regulations. The physical

chemistry and kinetics of any leaching process are unknown to this

day. Yet, on this issue, ASTM took the unusual policy step of

testifying before Congress in opposition to this one test.

As another example, a waste substance was declared hazardous

if after leaching, the concentration of the resulting leachate was

100 or more times that allowed for drinking water. Yet nothing was

said about analytical uncertainty.

Economic : Great uncertainty exists in the minds of the generators

of wastes designated as hazardous by EPA tests. Liability for

actual or alleged damage is undefined; insurance is difficult or impossible to procure. Since EPA has claimed that about 90 percent

of hazardous wastes in the U.S. are disposed of by environmentally

unsound methods, the average cost and availability of disposal

facilities has skyrocketed. Rumors exist that illegal dumping

operations have occurred; the U.S. Congress held hearings on this

possibility in 1981.

Since most large generators have traditionally dealt with

hazardous wastes on-site, they are likely to continue to do so. In

addition, because of potential --and undefined--l iabil ity issues,

such generators are likely to resist having their disposal and

treatment facilities utilized as a communal site. Thus, small

generators will require permitted communal sites at an affordable

cost. The alternatives are reduced profits, illegal actions or maybe even closure of the business.

88
Finally, many industries which produce relatively large

volumes of waste which are not deemed hazardous under present law

have encountered steeply rising disposal costs simply because they

generate "industrial waste." Examples include foundry sands and

ferro-alloy wastes. A final example is fly ash produced by the

Nation's power industry. A Department of Energy study indicated

that the average electricity bill for consumers would increase 10

to 15 percent if that ash were found to be a hazardous waste.

Hence, literally billions of dollars and the fate of a number

of small businesses rest upon the need for technically accurate and

legally equitable administration of the RCRA and Superfund legislation.

Institutional : The key actors are local and state government, the

Federal establishment, generators, transporters, disposers, recyclers

and the general public. At issue is the possibility of siting new facilities, monitoring existing facilities, and remedial action

relating to abandoned sites. There appears to be no unified policy

in this area. Unless a policy can be brought forward which is

acceptable to the key actors, the courts are likely to make national

policy via qualitative concepts as developed on a case-by-case

basis under common law. In reaching decisions concerning risks

under common law, courts usually rely on concepts of reasonable

behavior, of duties and responsibilities to inform, of assumptions

of risk that are borne by various parties and of contributory

actions. Application of these concepts is constrained by common

law precedents, procedural rules and rules concerning the admissibility of so-called competent evidence. Quantitative considerations

of economic and technical data are likely to play a minor role in

such instances.

With regard to hazardous waste regulatory efforts in the

period 1976-1981, EPA apparently emphasized quantitative requirements

in reaching decisions, e.g., a statement that such-and-such waste

is hazardous if its concentration in a leachate exceeds "X" parts

per million where "X" is defined to two or three significant

figures. This emphasis on numbers to reach certain analytical

outcomes has produced an apparent lack of credibility or acceptance

with the public which wishes "no risk" and the regulated community

which must abide by some regulatory framework that is supposed to

be consistent while providing for a means of obtaining the desired

environmental amenity at lowest possible cost.

Thus, the current situation can be described as confused:

Technical efforts have been largely in reaction to regulatory

proposals. With regard to economic issues, great uncertainty

exists in the regulated community since liabilities are basically

undefined. The public is faced with loss of property values as well as other risks. Institutional issues concern legal definitions

and responses to regulatory actions at all levels of government.

The simple fact is the parties of interest feel that no unified or consistent policy exist.

89
VIII. 3. Specific Challenges—Options and Impacts

VIII. 3. a. Approaches to a Definition and Classification

of Hazardous Waste

During the past five years, the political and regulatory

discussion has, to a large extent, focused on the question of what

constitutes a hazardous waste. This discussion has not been

completely fruitful, to the extent that an international consensus

has not been achieved on this issue. The question has often been

posed without indicating clearly the legal requirements which the

definition and classification were required to satisfy. A frequent

oversight is that the definition of hazardous wastes has to meet

quite different criteria when one looks to the various elements of

the overall disposal system. Requirements for the classification

of hazardous wastes for transportation, disposal or treatment

controls are likely to be stringent.

There are three basic approaches which can be taken towards

the legal classification of hazardous waste: first, a pragmatic

solution is achieved by describing the waste in a qualitative way,

indicating type, origin and constituents of the waste; second, a more scientific approach defining hazardous wastes by certain

characteristics usually involving standard testing procedures; and,

thirdly, definition of the waste in association with concentration

limits of harmful substances. In the latter case, the presence of

certain listed hazardous components in a waste beyond a defined

concentration makes a waste a hazardous waste.

All three approaches can be justified. The first one has the

advantage that a legal system, based on that type of definition,

can more easily be administered and enforced without too much

bureaucratic difficulty. It also gives a certain flexibility to

the waste disposal authorities in making qualitative judgments on individual waste disposal situations and, thus, in meeting practical

needs. The effectiveness of this listing approach is essentially

dependent on the legal system of individual governmental entities,

in particular the flexibility to make case-by-case decisions by the

controlling authorities to incorporate problematic wastes into the

hazardous waste control system.

The other two approaches have the advantage of presenting a clear and accurate description of wastes, theoretically leaving no doubt for the waste generator and waste disposer about how to deal

with the waste. These precise definitions imply a tight control

and surveillance of the definitions and parameters which in practice

may pose problems with respect to limited manpower, both on the

part of waste generators and the controlling authorities.

* % Further evidence is required in order to decide which one or which combination of the three approaches is most appropriate to ensure proper hazardous waste disposal at minimum administrative

costs. This question must not be isolated from the overall

90
hazardous waste disposal system. The central objective of such

systems is to dispose of the waste correctly, and this is less a problem of the definition of the waste than of actually applying

disposal criteria and disposal opportunities. At present, there is no evidence in practice of a direct correlation between the quality

of disposal and a high degree of accuracy in the legal definition

of hazardous wastes expressed in terms of chemical composition, and

concentrations of toxic substances.

Hence, sustained efforts aimed at providing a "better" or more "accurate" definition of hazardous waste are not likely to succeed

on any objective basis. More important, such efforts are not

likely to be satisfactory to the interested parties. Perhaps the

only real-world definition of what constitutes a hazardous waste is

that waste which some segment of the populace views as potentially

harmful to themselves or to an ecosystem and about which they are willing to take action.

VIII. 3. b. Identification of Possible Disposal Options Available

at an Affordable Cost

Generators of potentially hazardous wastes have examined this

issue in some detail as have "blue-ribbon" committees of scientific

and technical personnel. For most wastes, disposal means thermal

degradation or burial, i.e., incineration or disposal in or on

land. Technologies to dispose of such wastes via other means are

not often available although technologies exist to reduce the

amount of such waste, e.g., wet air oxidation, simple neutralization

and others. Still, final disposal is virtually certain to require

"bury" or "burn" as the major means. There appears to be no way to

avoid this conclusion. Technical efforts must deal with potential

difficulties arising from land-based disposal methods and from

incinerator operations —both on land and at sea. Of course, all

abandoned hazardous waste sites are land based or landfills.

VIII. 3. c. Development of an Equitable Level of Control System

Here, agreement between Federal and state and local governmental entities is essential. Basically, what is required is to

evaluate--as quantitatively as possible—a regulatory stance

embodying hazardous discard disposal via incineration or some form

of landfill which embodies the concept of level of control. One

goal of such an effort is to provide the state-to-state consistency

required by law. Then agreement must be obtained from the regulated

community and the public. (Note that transport of wastes to

appropriate disposal sites is included here.)

VIII. 3. d. Provision for a Valid Monitoring Scheme to Assure That

Exposure to Potentially Harmful Constituents of the Waste

is Minimized

A monitoring system agreeable to all parties of interest needs

to be developed. Without such a system, no valid assessment of

potential harm is possible. Hence, the courts may prescribe

91
solutions which will be difficult to achieve using best available

technol ogy.

VIII. 3. e. A Means to Evaluate Potential Harm

This challenge requires a means to relate what can be measured

directly, e.g., chemical composition, chemical concentration to the

probability that some adverse effect will be observed.

VIII. 3. f. A Unified Means of Informing all Parti es- of- Interest

of Actions

Without some system of information transfer, the likelihood of

siting a proposed facility, expanding disposal capacity or providing

for rational remedial action in case of unanticipated potential

harm to the environment, e.g., discovery of an abandoned landfill

or a spill, is likely to be strongly diminished.

VIII. 4. Technical Approaches to Specific Challenges

The technical community must provide basic information concerning improved technologies for reducing the burden of hazardous

wastes via resource recovery, recycling and reuse of constituents

destined for disposal. But, there will always be a need for

disposal of potentially harmful substances. At present, incineration

and land disposal appear to be the only economically feasible means

to achieve final disposal. Indeed, any residues from an incinerator

dealing with solid waste will need to be disposed of in or on the

land. Naturally, if the oceans are re-opened to the disposal of

certain constituents of wastes deemed compatible with the ocean environment, e.g., chlorinated wastes, then other possibilities

will exist. However, under current international agreements and

existing U.S. law, the oceans are closed to any such disposal

options. Therefore, this section will deal only with land disposal

and incineration.

1) Land disposal

Assume that there is an existing or proposed land-based site

in which possibly hazardous discards have been (or will be) placed.

The site can be a pit, pond, lagoon, landfill or land spread,

deep-well injection, salt dome or encapsulated (fixed) deposit.

Note that abandoned sites can be taken into account as well. In

addition, airborne effluents and residuals from an incinerator can

be included. Almost certainly, general questions which follow will

have to be dealt with in some detail.

a) What is present?

This question requires that qualitative analysis for all

constituents be carried out. Generators and disposers can, of

course, check incoming shipments fairly accurately. In the case of

old sites, some means of accurate qualitative analysis sensitive to

very low levels of various constituents must be developed. Thus,

92
sampling protocols and relatively rapid identification procedures

are needed—which are affordable. Clearly, organizations such as ASTM will need to compare sampling protocols, develop and evaluate

various test methods and agree on standards of comparison.

b) How much material is present or planned for the site?

Total amounts of potentially hazardous substances will be of

interest to any local jurisdiction.

c) How long has the site been in its present location? Are

records available?

This information is need'ed if an appropriate monitoring scheme

for emanations from the site is to be developed.

d) What is in the vicinity of the site? Are its boundaries-- in

three dimensions--wel 1 defined?

Paths by which emanations from the site may migrate into

ecosystems, e.g., via ground water, surface water, air, soil, etc.,

must be determined. Population density and land use data are also

requi red.

e) Are constituents escaping from the site?

Soil characteristics need to be assessed, e.g., composition,

permeability to the constituents at various depths, conductivity,

pH and others. In the case of long-term or abandoned sites,

baseline data are needed. Rainfall, rain pH and rain analyses are needed as well. Perhaps the appropriate leaching medium for any

given site is the liquid which filters through a system of local

soil subjected to having local rainwater poured over it. In fact,

a total geological and hydrological study of the vicinity of the

site is likely to be necessary. Again, standard practices, tests

and data reporting protocols are required. In the absence of

consistent methods, conflicting results are likely to occur leading

to legal actions. Indeed, in one case, conflicting data due to

different methodological approaches dealing with possible sources

of contamination of groundwater lead to threats of litigation and

finally a consent decree whereby the presumed generator will pay

full costs of remedial actions and is subject to virtually constant

monitoring by public agencies.

f) Determination of potential for harm.

o Quantitative characterization must be carried out in order to

determine possibility of exposure of humans or ecosystems to

the constituents of the site. The development of a measurement

assurance program is required so that the results from complex

and expensive tests such as GC/mass spectrography can be

translated, on a controlled basis, to less complex and less

expensive tests having similar precision and accuracy. Of

course, a valid sampling technique is implied as well.

93
In this context, the question of guarding against or detecting concentrations above a certain datum becomes of

interest. The datum may be set by regulatory action or the

probability of adverse effects if the concentration exceeds

some datum which may have been determined empirically. In any

event, classical statistical considerations (nonparametric

tolerance limits) can be used to determine how many samples

must be investigated in order to determine some probability of

finding a proportion of the total population below the datum.

For example, for a probability of 99 percent that 99 percent

of all possible tests will be below the largest concentration

measured, some 459 separate analyses are required. Conversely

if four separate analyses (replicates) are performed, one can only be 70 percent certain that 70 percent of all possible

tests will fall below the largest of the four concentration

values measured.

Research is needed to determine the relationship of

easily measured parameters, e.g., pH, to the potential for

adverse effects. In any case, statistical uncertainties are likely to make "legally accurate" concentration determinations

difficult to achieve.

Kinetics of what is present in terms of local surroundings.

In this case, research is required to determine constituents and their concentrations, as they move in a specific

ecosystem, by a variety of paths, as a function of time. This

presents a monitoring problem, i.e., concentration as a function of distance and time to define increased exposure to

the contents of the site.

If all of the needs described to this point were met,

i.e., rapid, accurate qualitative and quantitative measurements of effluents from the site in a statistically valid

fashion, the net result would be a determination of exposure

to the contents of the site as well as a determination of who

and what are exposed at a given level. No mistake should be

made in thinking that obtaining these data is simple, straight

forward or inexpensive in terms of professional talent,

equipment and dollars. Yet, without these data, no valid

statement concerning exposure levels can be made. With such

data firmly in hand, the final technical challenge can be

enumerated:

Relationship between concentration of constituents and

cumulative probability for adverse consequences. In simpler

terms --effect.

This challenges requires that the exposure or dose

experienced as a result of the hazardous waste facility via

any path be related to observed instances of harm or the

possibility of harm at some undefined future date. In the

94
following discussion, assume that the exposure or dose occurs

as a result of a hazardous waste facility. Further, assume

that the exposure can be measured accurately and that the

sampling procedure is statistically valid.

Plots of incidence of adverse effects in animals and

humans as related to exposure or dosage always result in a sigmoidal or S-shaped dose-risk curve (see fig. VIII. 1).

Under the terms of the assumptions, zero dose means zero risk.

But, the cumulative probability of risk as a function of very

low doses or levels of exposure is nearly impossible to measure or to predict theoretically as indicated in figure

VIII. 1.

For example, the question of a dose threshold arises

immediately. If a threshold exists, then there are exposure

levels of certain substances, e.g., carcinogens, such that no matter how many animals are exposed, none will exhibit cancerous

tumors. Leading authorities have stated flatly that resolution

of the threshold question is not possible given the current

state of scientific knowledge—even in a large-scale experiment

involving several thousand animals per exposure level.

Next, if no threshold is assumed, i.e., one molecule of

the substance has some finite--even if vanishingly small--

probability of causing harm, the relationship of the exposure

to risk level must be correctly known as the exposure approaches

zero. Here two other uncertainties intervene: 1) What is the

minimum detectable limit of concentration of the emanations

from the site in the various paths and media via which the

emanations can travel? 2) is there any valid mathematical

statistical model for extrapolating from detectable levels to zero exposure?

Minimum detection limits in the so-called part-per-bi 1 1 ion

range, for certain organic and inorganic species have been

reported. Such determinations —especially in heterogeneous

mixtures and media--have wide ranges of uncertainty (large

confidence intervals) and are exceedingly difficult to perform.

(Note that one part-per-bi 11 ion corresponds to about 600

trillion molecules of the substance under test.) Accurate

measurements at low exposure levels are likely to be difficult

and very expensive.

Consider now models for extrapolating from measurable

exposure data to the risk at lower exposures. In one experiment, some 24,000 female mice were subjected to a known

bladder and liver carcinogen in order to study dose responses

down to a one-percent tumor incidence, i.e., the concentration

of the carcinogen which would cause one mouse in 100 to

develop liver or bladder tumors. Results of these tests were

95
D D D

Dose of test chemical

a Excess tumor incidence (percent) is defined as: tumors in exposed population _ tumors in control population x 100

number of exposed population number of exposed population

a sigmoid dose-response curve; infralinear between O and Pi

linear extrapolation

supralinear extrapolation

line projected to a threshold

SOURCE: Office of Technology Assessment.

Figure VIII-1. A Stylized Dose-Response Curve and Some

Extrapolated Curves.

96
not especially enlightening. For example, a linear extrapolation and a "Wei bull model" which is a statistical probability

distribution having a finite starting point for estimating

life distributions as a function of exposure, were applied to

the data.

For a one in a million risk (P = 10-6

) of liver cancer in

the mice, an 0.045 part-per-bi 1 1 ion dose of the carcinogen was predicted by the linear model; the Weibull model predicted a 4.5 part-per-bi 1 1 ion dose for P = 10 -6 or an exposure of 100

times greater for the same risk.

The EPA Carcinogen Assessment Group has stated that:

"There is no really solid scientific basis for any

mathematical extrapolation model which relates carcinogen

exposure to cancer risks at the extremely low level of

concentration that must be dealt with in evaluating the

environmental hazard."

With respect to the prediction of "time-to-tumor" data,

there is no agreement between available models. Results are different, and certainty of prediction appears impossible at

present.

As stated by the Congressional Office of Technology

Assessment:

"The accuracy of the relation between exposure and

incidence (of adverse effects) is always limited.

Practical restraints on the number of animals that can be

tested means that the data are always subject to significant experimental error; it also means that only relatively high incidences; almost always greater than 10 percent,

can be measured in the experiments. There is also no agreement about which mathematical models best extrapolate

from the exposure levels measured in studies to those

encountered in the environment. Linear models, which

assume that incidence is proportional to exposure at low

exposure levels, are used by Federal agencies."

Note that use of a linear model tends to be "conservative,"

i.e., it predicts a higher cumulative probability for harm at

lower exposure levels. As a practical matter, there is often

no alternative to the linear model. Figure VI 1 1-2 shows a comparison of four models.

Apparently, there is no valid means to directly relate the

probability for harm to a measured exposure level at low exposure

levels. This situation poses another challenge:

o Estimation of the potential population who might be exposed to

effects from the site and determination of the proportion of

this population who might suffer harm as a result of the

existence of the site.

97
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98
The proportion of the population in the exposure area who

would be unaffected if the site did not exist can be found via

application of the theory of competing risks. For example, a person in the exposure area may be ill for reasons entirely

separate from the existence of the site. The elements of the

problem may be stated as follows:

• Given :

y = population in exposure area now who are not ill

u = population in exposure area showing adverse effects which

might be attributed to chemical exposure via some path

z = population in exposure area who would be unaffected if

dump did not exist

Requi red :

"z" in terms of "y" and "u"

Steps :

Let dz be the decrement of "z" in a small time.

Let dy be the decrement of "y" in the same small time.

If "z" individuals were subject to adverse effects due to

chemicals, then

dz = - dy (VIII-1)

But: We must subtract from this value of dz the decrement

arising from suffering of adverse' effects caused from

exposure to chemicals via some path. We must make such a subtraction since the "z" individuals are—by hypothesis

of this problem—not liable. This decrement is

(z/y) du. (VIII-2)

Therefore:

dz = - dy + - du (VIII-3)

y y

[We utilize +(z/y) du and not -(z/y) du since "z" and "y"

decrease while "u" increases.]

Rearranging: —dz _ dy . du n, TTT = y

+ —, so (VIII-4)

log z = log y + J ^, and (VIII-5)

99
r dU

* = ye s r

(VIII-6)

At some time "x" incremented via dt, Equation (6) can be

rewritten as

z = y exp If* i ^ dt] (VIII-7)

The right-hand side of eq. (VIII-7) can--in pri ncipl e--be

estimated. But, in practice, obtaining the necessary data in

unambiguous form and over a period of time represents a formidable, if not impossible, problem in epidemiology.

Hence, there is likely to be great uncertainty in identifying

members of the exposed population who suffer harm as a result

of the hazardous waste site.

In fact, determining the exposed population, i.e., the

group subjected to higher than baseline concentrations of the

substances at the site, is no simple challenge. In principle,

the various paths by which substances might reach the group

can be identified. Monitoring, which relies on qualitative

and quantitative determinations, at various points away from

the site can be implemented. Thus, what—if anything— is

escaping and how much will be known as a function of distance

from the site. When the slope of the concentration against

distance curve changes upward, the boundary for a particular

path can be located. Wind, other climatic factors and water

flow patterns may well alter the results over a period of

time. Airborne or rain-based factors must be considered.

Concentrations of substances produced by other means than the

waste disposal site may intervene, e.g., from the plants

generating the waste or other sources. Thus, attempting

unambiguous identification of who is exposed to higher con- centrations of potentially harmful substances from a waste

disposal site is likely to be exceedingly difficult, timeconsuming, expensive and inaccurate.

Parenthetically, the uncertainties in identifying unambigu

ously who is exposed as a result of only the waste disposal

site and in identifying what portion of that population has

suffered harm from the site are likely to make it exceedingly

difficult to obtain appropriate insurance coverage since

liabilities are undefined for generators, and victims cannot

be associated with the site in any certain fashion.

At this point, the chief difficulty for the regulatory

process should be clear: How to implement mandates to control

possible risks associated with waste disposal in a fair,

objective and accountable manner by using rational approaches

such as scientific and technical data and cost-benefit analyses

These approaches tend to emphasize economic cost factors, but

the concerned portion of the public generally considers that

the health and environmental amenities at stake are unmeasurabl

in economic terms; in fact, most of the public probably wishes

"zero exposure" from waste disposal.

100
If the regulatory process utilizes quantitative targets

for defining a waste as

" hazardous " and if exceedingly low

concentrations of substances in the waste must be achieved,

costs of control rise rapidly. Obviously, the lower the

concentration, the higher the cost of control. Hence, some balance between these costs and exposure is needed. Once a risk is accepted as real, i.e., worthy of regulatory attention,

the stringency of the regulation needs to consider economic

and technical factors to be workable.

One proposed method for taking these factors into account

is to apply some means to classify wastes destined for disposal

into categories depending upon the substances, their concentrations and their propensity to move and/or to persist in the

environment by any path. Thus, high concentrations of a known

carcinogen which move rapidly and are persistent might require

a more stringent level of control than lower concentrations of

the same substances; a different substance which moved more

slowly or was not a known carcinogen might require less

control and so on.

In principle, this classification scheme is appealing

since only the most objectionable wastes would require the

most expensive monitoring and treatment. In practice immediate

difficulties present themselves in how to set the classifications and to administer control over them in a fashion acceptable to the public.

Some of the technical difficulties will be apparent from

an examination of table VIII. 1 containing data which two

objective and competent groups of scientists obtained in an attempt to assess cancer risk from drinking water containing

one part-per-bi 11 ion (one microgram per liter) of known

carcinogens. The table purports to indicate the number of

persons per million exposed who are likely to fall victim to cancer from drinking this water. Note that in several cases,

a tenfold to hundredfold difference exists between the two

estimates. While the possibility exists for arranging these

carcinogens by probability for causing harm, doing so is not

likely to be especially satisfying: The indication that

1,2-Dichloroethane may be twenty to one hundred times as to cause harm as Chlordane probably will not likely induce anyone

to ignore Chlordane—at any concentration— in his drinking

water. Furthermore, since proportionality between measured

concentration and probability of harm is essentially unknown,

and since the public is likely to insist on control at some point near the minimum detectable limit, additional study is

needed.

Consider the situation prior to regulation of certain

wastes. In many instances, these wastes went to pits, ponds,

lagoons or landfills. Certainly, nature regulated the escape

of certain substances into ecosystems. In addition, nature

arranges matters such that if, in a population, "N", exposed

101
Table VIII. 1. Concentration of Drinking Water Contaminants

and Calculated Excess Cancer Risk

NAS

a CAGb

10"6 IF*

ug/l

c ug/l

c

Arrvl nnitrilp 0 77 0 034

wn 0 004.

Ron? onp ND 3 0

ND ND

Rprv 111 urn ND 0 02

Ri phi nirnpt hvl ^P*t" hp** 0 83 NO

f a rhnn tPtrarhlni^iHp 9 09 0 086

Ph 1 n rria np 0 OSS

Chi nroform 0 59 0 48

DDT 0 083 ND

1 , 2~Di chl oroe thane 1 4 1 . 46

1 , 1-Di chl oroethyl ene , ND 0. 28

0.004 ND

Ethyl enedi bromide 0.11 0.0022

ETU 0.46 ND

Heptachlor 0.024 2.4

Hexachlorobutadiene ND 1.4

Hexachlorobenzene 0.034 ND

N-ni trosodimethyl amine ND 0.0052

0.023 ND

0.108 ND

PCB 0.32 ND

PCNB 7.14 ND

TCDD ND 5.0 x 10~ 6

Tetrachl oroethyl ene 0.71 0.82

Tri chl oroethyl ene 9.09 5.8

Vinyl chloride 2.13 106.0

Standardized to 10~8 risks from National Academy of Sciences Drinking Water and Health (266) for consumption of 1 1/water/day.

Recalculated to exclude aquatic food intake from Cancer Assessment

Group, Ambient Water Quality Criteria (104). Standardized to 1

1/water/day intake.

Average adult water consumption is 2 1/day.

^Not discussed.

SOURCE: Office of Technology Assessment.

102
to emanations from the waste site, "P", individuals are harmed, a statistical estimation of the probability that "Q"

individuals will actually be harmed is expressed by a Poisson

distribution. The product NP is called A, and tables of Q for

a given A can be found in most statistical texts.

If N is one million, and P is 10~6

, A = 1.0 and we may be

37 percent certain that no one will be harmed and 100 percent

certain that no more than five persons will be harmed. For

ingestion of water from a hypothetical well containing the

highest detected concentrations of commonly found contaminants,

P has been estimated at 7.5 x 10~ 4 or if N is 1300, then A =

1.0.

From the foregoing, the key to dealing with waste disposal

of potentially harmful substances is to try to assume that

these do not escape and to monitor carefully all sites—abandoned,

existing or proposed. Where concentrations of potentially

harmful substances have dropped to baseline levels, excess exposure does not exist. Hence, appropriate "on-line" monitoring

is needed.

But, the key question remains:

o What technically valid and economically equitable means can be

found to declare that a waste shall be deemed potentially

harmful if some population is exposed to concentrations above

basel ine?

NBS/0RM addressed this question through several technical

activities undertaken on behalf of other Federal agencies,

e.g., DoE and EPA. Hazardous waste recovery and recycling

activities as well as research involving test method development

were undertaken with funds appropriated on behalf of RCRA,

Subtitle E, mandates.

To implement the various sections of Subtitle C of RCRA, EPA

has issued the following sets of regulations in Title 40 of the

Code of Federal Regulations: (As of October 19, 1982)

Part 260:

Part 261:

Part 262:

Part 263:

Part 264:

Part 265:

Part 122:

124:

Hazardous Waste Management System: General

Hazardous Waste Management System: Identification

and Listing of Hazardous Wastes

Standards for Generators of Hazardous Wastes

Standards for Transporters of Hazardous Wastes

Standards for Owners and Operators and Hazardous

Waste Treatment, Storage, and Disposal Facilities

Interim Status Standards for Owners and Operators of

Hazardous Waste Land Disposal Facilities

Consolidated Permit Regulations (including permit

regulations for hazardous waste facilities and State

program authorization)

103
These regulations have been promulgated in several stages and

are contained chiefly in the following Federal Register publications

although there has been a continuing process of amendment.

1) 45 FR 33066, May 19, 1980: Parts 260-263 and 265, general

provisions of Part 264, and Parts 122-124.

2) 45 FR 47832, July 16, 1980: Listing of additional hazardous

wastes in Part 261.

3) 46 FR 2804, January 12, 1981: Parts 264 and 122, standards

for storage and treatment facilities; and Parts 264, 265, and 122,

standards for closure, post-closure care, and financial responsibility.

4) 46 FR 7666, January 23, 1981: Parts 264 and 122, standards

for incinerators.

5) 46 FR 12414, February 13, 1981: Part 267, interim permitting standards for four classes of new land disposal facilities.

VIII. 5. Analytical Test Methods and Standards

Certain wastes are listed under RCRA regulations as hazardous;

well over 100 substances are on these lists. Usually some limiting

value of concentration above which the material is deemed hazardous

provided and associated with each substance in various media, e.g.,

water, soil, air. Therefore, some valid sampling procedure for

each waste stream is needed as well as appropriate qualitative and

quantitative analytical procedures. Unhappily, the heterogeneity

of potentially hazardous wastes and the need to analyze for mixtures

of compounds at very low levels can introduce a large amount of

uncertainty into the sampling and analytical results.

Much of the NBS/0RM sponsored research dealt with sampling

analysis and development of standards for potentially toxic wastes.

(NBS/0RM Publication List #'s 80, 92, 94, 113, 114, 118, 119 and

Appendices V and VI give details of published results to date).

A major effort of the scientific and regulatory community has

been in developing a simple, relatively inexpensive, extraction

procedure (EP) protocol which will test whether potentially toxic

wastes can be leached from parent entities, e.g., solid waste

mixtures, liquids in soil. The regulatory community must decide on

an appropriate upper limit of concentration for each toxic constituent

in the leachate obtained via any EP; wastes failing the test are designated hazardous. Note that no "degree-of-hazard" is impliedeither the waste is or is not prescribed as a result of the EP

test.

Thus, development of an equitable, universal test whose

precision and accuracy are well documented is necessary. NBS/0RM

applied considerable effort to these tasks. A rotary shaker for

the extraction process was designed, developed and tested at NBS

104
(Publ. #118); this shaker design was incorporated into the existing

Federal regulations.

The question of reproducibility of various EP test results is

still unanswered. NBS has been actively concerned with statistical

analysis of analytical results from leached samples involving both

organic and inorganic species at trace levels. Appendix VI deals

with this question in some detail.

In view of the uncertainties, NBS/ORM decided to develop a synthetic leachate trial standard which would contain known amounts

of several compounds of interest and could be used for interlaboratory comparison purposes. Appendix V shows the results of one set of experiments. Clearly, the yield depends on both con- centration and time of storage for all compounds studied in the

experiment. As shown in Appendix V, yields vary with type of

compound as well. For example, in the case of quinoline, the

percentage yield, Y, is:

Y = 68.5 + 1.2C - 0.10

4

t (VIII-8)

where C is the concentration in PPB and t is the time in hours from

specimen preparation to analysis. (Result valid in range 5 < C < 25

PPB and 0 < t < 50 hours). But for benzo (1) anthracene, the

percentage yield is

Y = 116.3 - 0.15C - 0.67o t (VIII-9)

x 9

Because of the complexities, I have decided to include as Appendix VI fairly complete descriptions of the experimental

procedures, results and statistical evaluation of several of the

NBS experiments. Careful review and reflection of these results

yields some understanding of current difficulties in establishing

a suitable EP test procedure. A universally satisfactory and

scientifically acceptable protocol still remains to be developed.

The NBS/ORM investigations have provided an important foundation

for the development of such a protocol, but considerably more research is required. In this regard, NBS and DOE have collaborated,

under DOE sponsorship, to produce a major compendium of the development of analytical methods for the determination of organic compounds

in fossil fuel aqueous leachates (Publ. List #125.)

At present, the NBS developed synthetic leachates can be used

to test analytical procedures. Certain NBS SRM's can be used to

test the EP itself. Indeed, NBS used just such a procedure.

(Publ. list #113) Definitive sampling and test protocols do not

exist, however. There is considerable controversy concerning what

leaching medium to utilize, e.g. water, acetic acid buffered to a pH of 5, citric acid, etc. and how long the sample should be

exposed to the leaching agent. (See Publ. List #'s 113, 114, 119

and Appendix VI).

Some idea of the uncertainties which may arise can be obtained

from a simple example involving the hypothetical analysis of

105
quinoline in water. Assume four replicate analyses yielding

concentrations of 12 PPB, 19 PPB, 15 PPB and 14 PPB respectively.

The mean is 15 PPB while the measured standard deviation, s*. . is

2.94. If the analytical procedure was performed 24 hours after

sampling, the yield eq. (VI 1 1-8) can be used to correct the

measured values. The new mean value is 17.8 PPB. The total effect

of the variable yield is shown in figure VIII. 3 in which the

cumulative probability for the true mean as a function of con- centration is shown for the original data set and the set corrected

for yield. Effects which may arise when several organic constituents

are present in a leachate mix are likely to be extremely complex.

One prudent means of dealing with such complexities might be

imposition of some "safety factor" meant to encompass losses due to

yield effects or synergistic effects. (Note that the increase from

a mean of 15 PPB to 17.8 PPB in the hypothetical example represents

about a 19 percent relative increase in risk if risk is linear with

concentration in the range 10 to 20 PPB for quinoline.) However,

selecting an appropriate means to equitably set such a safety

factor would require considerable further research.

VIII. 6. Current Approaches—Degree of Hazard

Despite the difficulties and uncertainties associated with the

accurate measurement of the concentration of a potentially hazardous

constituent, some means of classifying various waste streams with a view towards selecting appropriate environmental treatment, storage,

recycling or disposal options at an affordable cost is needed.

There is considerable effort being expended to evaluate possible

options and to develop reasonable methods or models for the

selection of the "best" course of action with respect to a given

waste stream. Specifically, the Office of Technology Assessment of

the U.S. Congress is evaluating a degree-of-hazard approach while

the U.S. Environmental Protection Agency has commissioned the

development of a Waste-Environment-Technology (W-E-T) Matrix.

According to the developers of this model:

"The RCRA Risk/Cost Policy Model establishes a system

that allows users to investigate how trade-offs of costs and

risks can be made among wastes, environments, and technologies

(W-E-T)) in order to arrive at feasible regulatory alternatives.

"There are many components in the system. Eighty- three

hazardous waste streams are ranked on the basis of the inherent

hazard of the constituents they typically contain. The system

assesses these waste streams in terms of the likelihood and

severity of human exposure to their hazardous constituents and

models their behavior in three media--air, surface water, and

ground water. The system also incorporates the mechanisms by

which the constituents are affected by the environment, such

as hydrolysis, bi odegradati on , and adsorption.

"A second integral part of the system is the definition

of environments in which the hazardous components are

rel eased.

106
f£

1.0

crO 0.9

0.8

S 0.7

CDO

o: 0.6

Q_

UJ

> 0.5

0.4

=> 0.3

o

0.2

0.1

0.0

QUINOLINE

4 REPLICATES (TAKEN 24 HRS AFTER SAMPLING)

C,—- 12 PPB

C 2— 14 PPB

C 3-- 15 PPB

C4 — 19 PPB

s n -i= 2.94 ; MEAN =

YQ

= 68.5 + l.2C Q-0.l0t

t— t = 24 hrs

CORRECTED C VALUES

C, = 12/0.804 =14.9

• C2

= 14/0.828 = 16.9

C 3

= 15/0.840= 17.9

C4

= 19/0.888 = 21.4

s n _, =2.7l ; MEAN = 17.8

13 15 17 19 21

CONCENTRATION -PPB

23 25 27

Figure VIII. 3. Effect of analytical uncertainties on determination

of concentration traces of organics in water.

Hypothetical data for quinoline determination are shown for illustrative purposes.

107
Thirteen environments including a special category for deep ocean waters are defined on the basis of population density,

hydrology, and hydrogeol ogy. The system adjusts the exposure

scores of the waste streams' hazardous constituents to account

for their varying effects in the three media in each of the

envi ronments.

"The third component of the system consists of the

technologies commonly used to transport, treat, and dispose of

the hazardous waste streams. This includes three types of

transportation, 21 treatment technologies, and nine disposal

technologies. The system determines costs and release rates

for each of these technologies based on the model's existing

data base. It also incorporates estimates of capacities of

the technologies, the amount of waste to be disposed of, and

the proximity of the wastes to the available hazardous waste

management facilities.

"EPA's purpose in developing the RCRA Risk/Cost Policy

Model is to assist policymakers in identifying cost-effective

options that minimize risks to health and the environment.

The framework of the system is intended as a screen—to

identify situations that are of special concern because of the

risks they pose and to determine where additional controls may

not be warranted in light of the high costs involved. The

framework uses a data base that is too imprecise and general

to be the sole basis for regulations. The results of the

model will be used in more detailed Regulatory Impact Analysis

to determine whether some type of regulatory action is warranted.

NBS/ORM, in partial fulfillment of the mandates of sections

5002 and 5003 of RCRA, utilized some of the results of hazard

scoring used in the W-E-T model in order to suggest certain statistical inferences for assessing degree of hazard posed by certain

substances. This work is included as Appendix VII. As reported by

the model builders, scores in the range 0 through 12 provide an index of increasing hazard. The NBS/ORM evaluation suggests that

for scores up to 5 or 6, there is a "low" hazard band, for scores

of 6, 7 there is an intermediate band and for 8 and above, there is

a high band. Hence, one possible suggestion is that low band

materials may be candidates for lowest cost options, e.g., landfill.

High band materials may be candidates for destruction while specific

local details may indicate appropriate action with regard to

intermediate band materials. However, each decision needs to be

based upon a wide variety of data such as proximity of ground

water, cost, citizen attitudes, state and local requirements and

many others. Still, the basic options for dealing with potentially

hazardous waste are recycle or reuse if economically and technically

feasible, dispose either by burial or destruction if not. Note

that "destruction" may include transformation to innocous products

via thermal treatment and/or chemical treatment, e.g., wet air

oxidation or incineration. NBS/ORM examined the recycle, bury or burn options in some detail.

108
VIII. 7. Hazardous Materials Incineration

VIII. 7. a. General

Work was divided into three distinct areas: a) Acquainting

the Hazardous Materials Incineration community with the existing

technology base in combustion kinetics, b) Development of a better

understanding of the technical problems of the industry and thus

opening up new areas where chemical kinetics can make contributions,

c) Development of laboratory facilities with the aim of answering

specific fundamental questions.

In the first area 12 lectures were presented on the chemical

kinetics aspects of hazardous waste incineration. Aside from

purely technical meetings presentations have been given before

regulatory bodies such as the California Air Resources Board, EPA

headquarters and laboratories and field offices, and trade and

professional organizations such as the Chemical Manufacturer's

Association and the ASME Research Committees on Municipal and

Industrial Wastes. NBS personnel took a leading role organizing

meetings for JANNAF on Hazardous Waste and the role of remote

sensing; a second meeting dealing with DOD hazardous waste disposal

problems was held in October, 1982 in Redstone, Alabama.

The fundamental problems in this area arise from the fact that

although incineration is an old technology, it has always been used

as a volume reducer. The concepts and techniques for assuring

total destruction of organic compounds are often foreign to the

practitioner of this technology. The NBS role may be viewed in

terms of technology transfer thus facilitating the use of incineration as a hazardous waste disposal technique.

The foregoing was concerned with the destruction of listed

hazardous wastes and the factors that makes one substance more difficult to destroy then another. NBS has studied the formation

of toxic chemicals and the role of tracers during incineration.

With respect to the former, NBS has concentrated on dioxin formation. For this purpose chemical kinetic models have been set up

using a number of possible mechanisms. Although the experimental

data base is sketchy, it does provide a basis for making worst case estimates of the elementary rate processes. The results have

been surprisingly informative in terms of the relation between the

amount of dioxins that can be produced, the necessary type of

precursors and the possible mechanisms by which it may be produced.

These considerations also lead to the possibility that detection of

dioxins in incinerator effluents may simply be an indication that

they were present in the input stream. A paper has been prepared

and is included as Appendix III.

Present EPA regulations for hazardous waste incinerators

require a capability to destroy 99.99 percent of selected Principal

Organic Hazardous Components in a waste mixture. The analytical

requirements for demonstrating such a capability are quite severe

and rendered more difficult by the fact that each hazardous waste

109
mixture may have different POHCs. EPA contractors have in fact

reported difficulties in carrying out required procedures. The

total cost of such tests has been estimated to be of the order of

$50,000 by EPA and $100,000 to $200,000 by industry. Furthermore,

one notes that there is no way of assuring that regulations are

still being met for a previously qualified incinerator. Thus, it

is natural to consider the introduction of tracers or a number of

tracers is that span the range of chemical stabilities. This

method can simplify the analytical problems in permitting the

development of specific analytical techniques for a limited number

of related compounds and indeed it may be possible to exploit some particular property of the tracer. On this basis per-f 1 uori nated

hydrocarbons appear to be particularly suitable. In an incinerator

environment, radical attack will be slower than that of ordinary

hydrocarbons, and stability in the unimolecular sense decreases

with increasing molecular size (for per-f 1 uori nated alkanes). One

can thus scan the full range of chemical stabilities. Equally

important, per-f 1 uori nated hydrocarbons produce unique gas

chromatographs and have unique infa-red characteristics. Gross

simplifications of analytical procedures are possible; and, the

possibility of real-time monitoring becomes feasible. There are,

however, certain problems. These include the introduction of such

tracers and-perhaps most important-complications arising from

unburnt hazardous wastes that may be present in particulates. We

are currently considering the aspects of the problem; preliminary

results are shown in Appendix VIII.

An important aspect of the program is the direct experimental

verification of the predictions that have been made. We are in the

process of putting together a flow reactor which simulates the

incinerator environment. Particular attention has been paid to

minimize the effect of the reaction wall. The data acquisition

system and all the hardware have now been delivered. The first

system to be studied will be various chlorinated aromatic compounds

Succeeding studies will be directed towards checking our proposed

scale of i nci nerabi 1 i ty and the effectiveness of the perfluorinated compounds as tracers. It may also be possible to make

some estimates of rates and mechanisms of formation of various

Products of Incomplete Combustion (PICS).

Considerable work remains to be done. For example, EPA

contractors have apparently concluded that proposed i nci nerabi 1 i ty

ranking procedures are inappropriate and that i nci nerabi 1 ity

differences are both small and dependent on the specific system

chosen (EPA Contract 68-03-3113, November 16, 1982). Thus, despite

cessation of the formal NBS/0RM program, research in this area will

probably continue with other agency funding.

VIII. 7. b. Incineration at Sea

A special case for incineration of hazardous wastes involves

thermal destruction at sea. If this step is taken, then difficult!*

in siting may be removed since the destruction site is about 100

miles offshore. Furthermore, the most noxious wastes can be dealt

110
with. At present, several firms are interested in pursuing the

option of incinerating liquid wastes at sea.

The U.S. Maritime Administration (MARAD), which was a part of

the Department of Commerce until July 1, 1981 when it was transferred

to the Department of Transportation, took a strong interest in

incineration at sea. At the request of MARAD, and in partial

fulfillment of responsibilities under section 5003 of RCRA, NBS/ORM

participated as a member of the Interagency Review Board of the

Chemical Waste Incinerator Ship Program which coordinated all

Federal establishment activities related to developing an incineration at sea capability in the United States.

The Board concluded that:

1) A high priority effort is required to solve the nation's

hazardous waste disposal problem. A privately-owned

incinerator ship service could be available by 1985 or sooner and would make a significant contribution to

alleviating the current extreme shortage of viable waste

destruction facilities.

2) Adequate laws and conventions exist to regulate incinerator

ship design, construction, and operation.

3) Federal maritime assistance is currently available to

encourage private U.S. -flag incinerator ship construction.

Federal ship loan guarantees are obtainable based on standards of technical and economic soundness. In

addition, ships from the National Defense Reserve Fleet

may be sold for conversion to incinerator ships.

4) A U.S. -flag chemical waste incinerator ship capability is

not likely to develop without substantial federal assistance, e.g., coordinated certification and permitting,

federal waste destruction contracts, and additional

maritime aids.

5) Several new construction incinerator ship conceptual

designs were developed. A design with 7,560 metric tons

of hazardous waste capacity was selected as a potentially

viable dual-mission demonstration vessel for routjne

destruction of liquid wastes and for experimental incineration of solid wastes.

6) Conversion designs of existing National Defense Reserve

Fleet ships were evaluated and determined to be less

costly but inefficient investments compared to a new incinerator ship for the dual mission of destroying large

volumes of pumpable wastes and conducting experimental

solid waste incineration.

7) Waterfront integrated hazardous waste management facilities

are necessary to support U.S. incinerator ships. Such a

111
facility would include waterfront storage tanks; waste

receiving, processing, and handling equipment; a laboratory

for waste analysis; and a transfer terminal for loading

wastes aboard ship. (see Publications List #90, for full

details of the Board's program).

A major NBS/ORM activity on behalf of the Board was to determine

what technical issues underlay the development of efficient, safe,

and economical systems for the disposal of hazardous chemical

wastes at sea. This challenge poses conventional and unique

technical problems in materials handling as well as in incineration

process and its aftermath. Problems in materials handling encompass:

o materials handling and storage hazards;

o determination of the mechanisms and rates of degradation of

selected compounds in storage, handling, and under high

temperature conditions; and

o durability and reliability of construction materials (metals,

ceramics, and polymers such as liner materials).

The incineration process and its attendant health and environment

concerns pose questions concerning:

o thermodynamic properties of combustion products;

o development of standard reference materials and methods for

defining incinerator operating conditions;

o determination of nature and reactivity of combustion gases as well as measurement of gases, vapors, liquids, particles of

toxic metals, metallo-organics , carcinogenic and toxic compounds;

and

o characterization and monitoring of specific effluents and

effluent clean-up and systems control and mitigation of

specific emissions.

Each of these problems requires development of essential materials

data, test techniques and methodology for materials properties,

design and performance modeling including prediction of materials

properties and chemistry.

The NBS Center for Chemical Physics (CCP) has identified

technical areas of concern which are:

o Determination of the mechanisms and rates of degradation of

selected compounds under a wide variety of high temperature

conditions : Although specific hazardous compounds have not

been studied, the methodology is general and can lead to

determinations of the conditions necessary for 99.99 percent

destruction and the variety of reaction products to be expected.

The key to such studies is the determination of reaction

112
products and intermediates. For this purpose CCP has

state-of-the-art capabilities in all current methodologies

including chromatography, and mass spectroscopy as well as infa-red and optical spectroscopy under. Note that this range

of capabilities can also be applied to monitoring and

controlling incineration and in fact to the entire materials

handling process. Furthermore, the NBS capability extends to

the detection and identification of new species. This is

particularly important for the at sea incineration application

since most of the substances have not been previously studied.

Past experience has demonstrated that the behavior of

related compounds follows well-ordered patterns. Thus from a few well characterized systems, extrapolations of considerable

validity can be made. For example, if one considered pesticides

as typical hazardous materials, one would expect a variety of

the nitrogen and sulfur-based compounds to be more readily

destroyed than analogous hydrocarbons--whi le chlorinated

aromatic compounds are probably more stable. The Chemical

Kinetic Data Center has produced eval uated data in this area

and is responsible for the development of the kinetic data

base for stratospheric chemistry (ozone depletion problem).

This center is presently developing a similar information base

for combustion kinetics.

o Defining Incinerator Operating Conditions, Methods, and

Standard Reference Materials : For the case where one is asked

to deal with a material with no previous knowledge regarding

degradabi 1 i ty , it is reasonable to conduct preliminary

studies on bench scale units. This approach however leads to

problems in scale-up. A possible solution is to define a standard reactor and standard operating procedures. Coupling

a standard reactor and operating procedures with a well

characterized series of calibration compounds, spanning the

operating range of the incinerator, allows one to define the

behavior of the new samples in terms of the behavior of the

calibrants. From such data it should be possible to deduce

the proper operating points for incineration.

o Thermodynamic Properties of Combustion Productions : Probably

the most uncertain problem in hazardous waste disposal is the

nature of the combustion products. Determination of mechanisms

and rates are aided immensely by thermodynamic knowledge.

Evaluated data as well as estimates are required. The NBS

experimental facility, still under development, is similar to

small incinerators and is particularly well instrumented. One

suspects that at the very least the technology if not the

instrument itself can be adapted for the new application.

o Materials Handling and Storage Hazards : In the handling and

storage of chemicals the possibility of exothermic self-reaction

113
or auto-oxidation leading to spontaneous combustion must be

considered. State-of-the-art expertise and instrumentation

along with differential scanning calorimeters and an absolute

reaction calorimeter are available. Currently CCP is using a high pressure Differential Scanning Calorimeter to study the

auto-oxidation properties of recycled oils. There are marked

similarities between and with regard to approach and problems

in handling industrial wastes. The integrity of the containers

in the restricted confines of a ship must be of considerable

concern. A large array of real time monitoring instruments

will be a necessity. State-of-the-art laser based devices

with high sensitivity and high resolution may be applied to

this problem.

o Nature and Reactivity of Combustion Gases : This problem is

concerned with the major components in the combustion of

complex substances. The interest lies with their interactions

with each other and with incinerator surfaces. A fundamental

attack on corrosion problems that may arise during incineration operations will be required.

o Effluent Clean-Up : If the proposed incinerator must meet all

land-based environmental regulations, a variety of state-of-theart clean-up techniques must be employed. Therefore, the

possibility of ozonizing aqueous effluents may well be worth

investigating. Currently CCP is carrying out programs dealing

with the fundamentals of S0 2 scrubbing from power plant

effluents, and the fate of toxic chemicals, in aqueous media.

The Center for Materials Science (CMS) has identified the

following areas requiring investigation by class of material

(metals, ceramics, polymers, composites).

o Assessment of stress-corrosion fatigue cracking of containment

and transfer materials.

o Non-destructive inspection procedures for containment structural

alloys and their welds.

o Establishment of fracture control planning for containment and

transfer systems.

o Corrosion resistance and other compatibility properties of

containment and transfer materials (metals, ceramics and

polymers)

o Identification of significant corrosive combustion products

and their attack on system components.

o Development of methodology for monitoring specific compounds

(primarily metals in effluents).

o Modelling the effect of inorganic elements on combustion

efficiencies.

114
The Center for Analytical Chemistry has outlined a measurement

quality assurance program utilizing numerous chemical analyses to ensure the proper functioning of sea-based incineration system.

A measurement quality assurance program requires supporting

research program in the Center that would include, but not necessarily

be limited to, the following:

o multielement analysis for screening of wastes and residuals

such as ash;

o organic analysis focusing on screening techniques for criteria

pol 1 utants

;

o gas analysis for toxic effluents; and

o particle analysis including identification of organics and

toxic heavy metals which adhere to particles.

With respect to the development of criteria for measurement of the

ability of the vessel to adequately destroy specific and blended

wastes, the essential requirement for hazardous waste incineration

is destruction at the 99.99 percent level. In the case of mixtures,

the suggested procedure involves selection of the Principal Organic

Hazardous Component and the demonstration of the capability for

destruction. There is at present the controversy regarding the

methodology for the selection of POHCs. In view of this uncertainty

it is likely that a number of compounds will have to be tested.

Individual compounds require analytical methods of high

specificity. Gas chromatography is the method of choice, but

(considering the expense) a gc-ms set-up may not be necessary if

the proper choice of waste streams for the research burns is made.

The destruction limits imply that less than 0.01 percent of the

surviving compound can be detected. In view of the dilution upon

combustion, nitrogen of the air and the fact that the POHCs may be

present in small amounts, the need for detection limits at the

1-100 ppb level is essential. This is just about the limit of

sensitivity of current g.c. instrumentation equipped with flame

ionization or electron capture detectors. Thus it would probably

be necessary to pre-concentrate samples. The methodology for this

and the collection of gas samples exists but can be subject to

experimental artifacts and considerable thought must be given to

how experiments are to be carried out. These tests should probably

be carried out on shipboard since during the research burns one would presumably want to correlate destruction efficiency with the

various processes and control variables. A certain number of

samples should be preserved for subsequent analysis upon return to

port. The integrity of such samples is a problem to be considered.

Important decisions must be made regarding nature, siting and

contents of a shipboard laboratory. Measurement of total hydrocarbon emissions (T-H-E) should be made. T-H-E is a variable which

115
like the combustion efficiency may in the future provide a surrogate means of determining destruction efficiency. In both

cases however, the methods for making the measurement, the placing

of probes etc. should be carefully considered. In the future, the

possibility of non-intrusive optical probes in the incinerator

represent an important analytical direction. Finally provision

should also be made for additional thermocouples. Additional ports

must be available for making such measurements when the need

ari ses.

In addition to incinerator monitoring on ship, there are a host of equally important ancillary problems; for example, analysis

of input streams, heating values, compatibility of different

wastes, blending, stability etc.

In summary, NBS findings with respect to measurement protocols

for monitoring of the incineration process aboard ship were as

fol lows:

1) There must be some means on board the ship to accurately

monitor emissions from the stack and the combustion

process itself, in order to determine whether or not the

requirement for 99.99% destruction is satisfied. Since

we deem it, at best, impractical and, at worst,

impossible to measure "destruction" directly, it is

necessary to develop a protocol for determining a surrogate relationship between the measurement of the

combustion process (emissions) and the destruction ratio.

2) Such a protocol must be developed for each waste stream

to be incinerated. The protocol should be employed in a test burn after on-shore blending or ship-board blending

has occurred. An apparatus similar to the NBS 2.5 kg

calorimeter would be appropriate to conduct the test

burn. Determination of the characteristics of each waste

stream prior to commercial at sea incineration is

necessary since 1) operators must be cognizant of blended

waste's reaction in combustion process; 2) operators must

be able to verify achievement of destruction efficiency

on basis of monitoring data; and 3) operators must be

able to verify that the products of combustion will not

imperil either the crew or the environment.

3) A means to measure the heat value of the various waste

streams is also necessary; this method can be an apparatus equivalent to the NBS 2.5 kg calorimeter.

4) Further research is necessary to define the parameters of

the combustion process in order to determine the appropriate monitoring system and surrogate measurements which

will 1) assure that the tests will be definitive with

regard to the required destruction (see Appendix VIII),

116
and 2) will be economically supportable (i.e., least

costly)

.

Clearly, many of these same measurement protocols could be

adapted for use with land based incineration systems with little or

no change.

In any event, on April 16, 1982 the Federal Government, acting

under authority of Title XI of the Merchant Marine Act of 1936,

approved a guarantee of a loan to finance construction of two U.S.

flag ships intended to incinerate hazardous chemical wastes at sea. Subject to MARAD final approval of the applicant firm's financing

arrangements, the loan guarantee covers $55,875,000 or 75 percent

of total anticipated construction costs. The ships are currently

under construction and are expected to be launched in late 1983 or early 1984. Presumably, the measurement protocols suggested by NBS

will be implemented on these and other similar incinerator vessels.

Each of the two ships will accommodate 6200 tons of waste to be

destroyed with the aid of two liquid injection incinerators having

a combined processing rate of 20 tons per hour. These vessels will

conduct operations at Federally designated sites about 100 to 150

miles off-shore. Under these conditions, the two ships can deal

with a total of about 250,000 tons of waste annually.

VIII. 8. Land Disposal

With respect to land disposal of potentially hazardous waste,

NBS/0RM was concerned with the durability of polymeric liners which

might be used in an attempt to isolate the waste from its immediate

surroundings. Indeed, present regulations call for liners under a wide variety of conditions. Depending upon specific conditions,

either a single or double liner is required.

A successful polymeric liner must retain its mechanical and

barrier properties in the presence of permanent contact with water

containing diluted hydrophilic or suspended hydrophobic substances

or solid particles. The first two kinds of material may diffuse

into the polymer and eventually transform into a soft rubbery

material or even disintegrate it by chemical attack. Solid particl

may abrade the polymer surface and thus gradually degrade the

useful properties of the polymer.

Hence, a special study is needed to select the proper'

polymeric materials to be used as a liner for a given industrial or other effluent waste. Three types of action have to be considered:

1) diffusion with the ensuing lowering of the glass transition of

the swollen polymer; 2) oxidative or any other type of chemical

action which may lead to the disintegration or at least softening

of the polymer; and 3) mechanical stress or abrasion. The effects

are not independent. They may be strongly synergistic. As a polymer softens it becomes much less abrasion resistent. The

softened or disintegrated material as a rule permits a much faster

diffusion of penetrants than the unaffected material.

117
NBS/ORM determined the mass loss and sorption/desorption of

Acetic Acid (HAc) in polyethylene of different densities at various

temperatures. Mass loss studies for a mixture of HAc and H 2 0

(three concentrations) were also done at the highest temperature

used. Loss rate, diffusivity, solubility and permeability of HAc were measured. (See Publications List #119 for full details).

Appendix IX contains a brief overview of possible research approaches

meant to aid in determining the compatibility of polymeric liner

materials with hazardous wastes.

VIII. 9. Technical Issues Relating to Disposal Site

Evaluation and Rating

All of the work described in this category was undertaken in

response to Section 5003, Part (2) of RCRA dealing with identification of economic and technical barriers to the use of recovered

materials. Technical issues associated with estimating the

potential risk caused by certain waste substances were evaluated.

Then the technical and economic issues were melted together via

joint efforts with the States and the Organization for Economic

Cooperation and Development (OECD).

The W-E-T model approach or similar degree of hazard classification scheme is useful for rough-cut general policy, technical and

economic guidance. But, of practical necessity, a "general" model

must have very broad categories. A more precise approach is

desirable to deal with specific conditions at an existing, proposed

or even abandoned land disposal sites. Fortunately, such an approach has been developed by Dr. David H. Rosenblatt and co-workers

at the U.S. Army Medical Bioengineering Research and Development

Laboratory, Ft. Detrick, Maryland. This approach derives preliminary

pollutant limit values (PPLV's) for effects on human health, but

effects on other species or ecosystems can be obtained by using a similar methodology. After a brief discussion and explanation of

the PPLV method, the W-E-T and PPLV approaches will be shown to be

fully complementary.

The PPLV concept leads to an environmental fate model for

chemicals in soil and water in which the allowable levels are determined by the acceptable daily intake of humans. The PPLV is

based on existing data that relates primarily to human health

effects, e.g., Handbook of Chemical Property Estimation Methods (W.

J. Lyman, W. F. Reehl and D. H. Rosenblatt, McGraw-Hill, 1982).

The PPLV concept treats each pathway by which humans may be exposed

to potentially hazardous substances as a series of compartments.

Equilibria are assumed to exist between successive compartments

except between the next-to-last compartment and a human. Often the

final step depends upon dietary intake. For each path by which the

substance may reach the human, a single-path PPLV (SPPPLV) can be

calculated. The final PPLV is derived by normalizing all SPPLVs.

The developers of the concept state as follows:

118
"Common sense should always be exercised in the derivation

and use of PPLVs. These values should always be derived with

careful consideration of the site-specific conditions. The

PPLV model should be regarded as a frame-work that can be

modified to account for site-specific elements. The temptation

to develop and institutionalize PPLVs as standards should be

avoided. Each value should be given a mandatory date for

reconsideration, and the data base used in the formulation

should be continually updated and examined.

"An experimental approach to determining environmental

pollutant standards is certainly preferable to the extensive

reliance on assumptions that characterizes the PPLV procedure;

the principal merit of the PPLV is that it can be determined

even in the absence of complete data. Where data gaps are sufficient to warrant experimental research, available resources

can be properly allocated by specifying research only for key

parameters identified by the PPLV-determi nation process.

"The PPLV is determined in six steps:

o Pollutants and pathways are identified.

o An acceptable daily dose of toxicant (DT

) and partition

(intermedia transfer) coefficients are determined or estimated.

o Relevant data are gathered from the literature.

o SPPPLVs are calculated for all pathways (not sitespecific).

o Critical pathways for each pollutant are selected (often

site-specific).

o The PPLV is derived by normalization of SPPPLVs.

"Normalization adjusts the pollutant concentration where

pathways originate in the same medium or have a common point

of intersection. A simple calculation, similar to adding

electrical resistances in parallel DC circuits, is used, such

that SPPPLVs taken together provide the target organism, man,

with an exact D^. The following equation describes the

calculation of a PPLV from SPPPLVs via three pathways from

water:

PPLV = It [1/(SPPPLV)

1

+ 1/(SPPPLV)

2 + 1/(SPPPLV)3

]

"The approach used in calculating SPPPLVs assumes contaminants to be in stepwise equilibrium (steady state) from source to receptor."

For complete details of the PPLV concept, see J. C. Dacre,

H. Rosenblatt and D. R. Cogley, Environmental Science and

119
Technology 14, 778-784 (1980) and D. H. Rosenblatt, J. C. Dacre and

D. R. Cogley, "An Environmental Fate Model Leading to Preliminary

Pollutant Limit Values for Human Health Effects", Chapter 15 of

Environmental Risk Analysis for Chemicals (R. A. Conway, ed. ) van Nostrand Reinhold (1982).

A number of PPLVs have been developed for various sites. For

example, in one scenario-involving polybromi nated biphenyl (PBB)

which had been deposited in a landfill in Michigan—a PPLV for

water consumption by animals and humans from the groundwater

aquifer beneath the disposal site was calculated as 2.4 PPB.

(D. H. Rosenblatt and R. J. Kainz, U.S. Army MBRDL Technical Report

8204, 35pp, 1982).

This value of 2.4 PPB is extremely difficult to measure

accurately. Indeed, detection limits for many organic species in

water are on the order of 5 PPB. The yield uncertainties, as shown

in Appendix V, complicate the analysis challenge even further.

NBS/ORM personnel considered this situation with a view towards

suggesting a relationship between measurable quantities and PPLVs

in terms of probability of risk to a given exposed population.

If the value of 2.4 PPB of PBB in water is, in fact, a concen- tration for which the possibility of harm is nearly zero, then an appropriate means to deduce the probability for no individual in a population exposed to (ingesting) water derived from the aquifer

can be derived. The assumptions are as follows:

1) Risk is linear with concentration in the region of

interest; this relationship is presumed to have some positive slope, designated as "m";

2) Exposure at PPLV level leads to a risk of adverse effect

from the contaminant of one in ten million (10 7

) in the

exposed population;

3) The exposed population is "N";

4) A Poisson distribution will represent the risk of the

adverse effect in the population; and

5) Some value of concentration, C , of contami nant(s) can be

measured.

Under these conditions, the Poisson parameter, A, can be expressed

as:

A = mN (PPLV). (VIII-10)

The probability, P , that no individual in the exposed population

wi 1 1 be harmed i s

P Q = e"

A = exp - [mN PPLV)]. (VIII-11)

120
For P = 0.9999, i.e., a 99.99 percent chance that no individual in

the entire exposed population may be harmed, A = 10 4

. Thus,

mN = for P =

o 0.9999. (VIII-12)

Whatever the exposed population:

A =

10 Cx

PPLV (VIII-13)

P =

o exp -

(

10" 4

Cx

PPLV

) (VIII-14)

Figure VIII. 4 shows P as a function of the ratio of C to PPLV;

extrapolation much beyond the limits shown in figure ViII.4, i.e.,

C -r PPLV of 725 is probably not justified. Note, however, that

even if this ratio is as high as 100, then there is still a 99

percent chance that no individual in the exposed population is

likely to be harmed.

The value of the PPLV concept can be summarized as follows:

1) PPLV can be used as a datum, given specific conditions,

such that any site whose contamination level is equal to or exceeded by PPLV can be declared "clean", i.e.,

non-hazardous to health. Thus, the "How clean is clean?"

issue can be addressed with a valid target;

2) The PPLV concept is independent of exposed population;

and

3) A simple direct relationship exists between measured

concentration in some medium, e.g. ground water and the

probability that no individual will be harmed if PPLV can

be used to represent the concentration for which there is

a 99.99 percent probability of no harm. Thus, analytical

uncertainties can be taken into account via "worst case"

computations of P . For example, in the quinoline case discussed previously, the measured mean of 15 PPB corresponds to a probable "true" mean of 18 PPB. Assuming the

15 PPB was even 150 times greater than PPLV, P is 0.985.

If the true concentration were 18 PPB, then P °is 0.982.

o Analytical uncertainties become increasingly important,

in terms of probable risk to a population, when C exceeds

PPLV by a factor of 200 or more. (See Appendix x¥v for

Details).

The relative error in P can be estimated by differentiation of eq.

(VIII-14): 0

121
o

8

Q

ki

©

Q.

-I' —

X

LV

UJ

Q_

Q_

R

Al

ION

1 cr » o S" Q 3

CO O Q_

CD n O

z or CD Q_

o

o

If)

o

o

o

o

in

Q.

Q_\

xO

<

rr

in

a> "O E

gj O

in 3 o >+- r> o e X +>

0>

OJ ha

fO

ns >> o

xp

fO

»r~ (JC

3 >> 01 A -po

> ~o O,

0) a e (T3 c t- ha of o

c 0) J3 X

+->fO +J •r" c

o

>> •f- C 4

°l— o

•rTM +3 XI TO c u

fO r" o> • r~ .O D u E

O Q. £= O)

l- O o

a, Q. u u

01

i~3

C

CD0)

00 CD0)

if)

C7) 0)

0d'a3WaVH 39 ~I~IIM IvnOIAIONI ON 1VH1 Aini8V80dd

122
AP /

10* 4

C

o x

P \PPLV

o x

APPLV

PPLV

AC \ 2 x

0. 5

(VIII-15)

This relationship indicates that even if PPLV and the measured Cx

are. both in error by a factor of 5, i.e., relative errors of 500

percent, then

AP

-4

'10

H

C

) PPLV (V50) =

7.1 x 10~ 4

C

} PPLV (VIII-16)

For a 1 percent relative error in P , C /PPLV is 14 and for a 10

percent relative error in P , this ?atio is 140. A ratio of 1400

leads to a 100 percent uncertainty in P .

The PPLV concept and eq. (VIII-14) and (VIII-15) also serve to

reduce the efforts and expenses associated with the determination

of C since the need for many replicate analyses —to demonstrate

with a high degree of confidence that a high percentage of the

sample population is below the highest individual value of C

measured—is obviated. Some four replicate analyses are probably

sufficient to obtain a value of C having the required precision

for use with eq. (VIII-14) and (V?II-15). If PPLV is taken as an upper limit, however, four replicates only provide a 70 percent

certainty that 70 percent of all subsequent samples will fall below

the highest value of concentration measured.

4) Computation of a PPLV leads to a direct statement of

degree-of-hazard which depends on site specific criteria

and is independent of population exposed. The "index" is

simply the ratio of C to (PPLV) where (PPLV) is the

lowest PPLV for all chemicals at

xthe site.

One possible classification scheme is

No hazard (Index 0):

Minimal hazard (Index 1):

Minor hazard (Index 2):

Hazard (Index 3):

Major hazard (Index 4):

Extreme hazard (Index 5):

1 > C x/(PPLV)

x

1 < C x/(PPLV)

x

< 14

14 < Cx/(PPLV)

x <140

140 < Cx/(PPLV)

x

< 700

700 < C x/(PPLV)

x

< 1400

0.001

C x/(PPLV)

x

> 1400

For Index 0, P < 0.9999 with "worst case" AP /P of about

O 0 0

123
For Index 1, P < 0.999 with worst case AP /P of 0.01

0 0 0

For Index 2, P < 0.99 with worst case AP /P of 0.1

' o oo

For Index 3, P < 0.95 with worst case AP /P of 0.5

' o oo

For Index 4, P < 0.90 with worst case AP /P of near unity ' o oo

For Index 5, P < 0.87 and worst case AP /P is difficult to

. . 0 0 0

ascertai n.

Thus, the extreme importance of accurate data in deducing

PPLVs is made clear as are the requirements for accuracy in

determining concentrations. Under these conditions, appropriate

sampling methods, measurement methods, standard reference data and

measurement standards can provide the technical foundation for

dealing with the "cleanliness" questions associated with existing,

proposed and even abandoned disposal sites. The work performed by

NBS/ORM has contributed strongly to all of these requirements.

(See Appendices V-IX and Publications List #'s 80, 90, 94, 113,

114, 118, 119).

The PPLV method and the W-E-T model are complementary. The

W-E-T model or similar classification scheme can be used to suggest

what wastes might be dealt with and by what technology, e.g.,

landfill, chemical treatment, incineration on land or at sea. After this rough classification, the PPLV method can be applied to

the particular site in question in order to ascertain how cleanliness

can be maintained and how the site monitoring system is to operate.

The W-E-T model is primarily an economic tool having a crude hazard

classification scheme attached, while the PPLV method is capable of

providing good local estimates of hazard, once the W-E-T model has

suggested an appropriate technology and cost for a given waste

stream or coordination of waste streams. Taken together, the W-E-T

model or similar scheme and the PPLV method can provide a powerful

tool for dealing with many of the economic, scientific and technical

issues relating to risks associated with treatment, storage and

disposal of potentially hazardous wastes. But recovery, recycling

and reuse of potentially hazardous waste streams can provide a better alternative if such recycling is technically feasible and

can compete in an economic sense with other alternatives.

VIII. 10. NBS/ORM Efforts Concerning Recycling of Potentially

Hazardous Wastes

NBS/ORM initiated one pilot study involving the technical

issues associated with the deoiling and subsequent recycling of

steel industry mill-scale wastes. NBS/ORM personnel also served as technical reviewers for a DoC/EDA sponsored study dealing with

characterization and recycling of electric furnace dusts. In

addition, NBS/ORM examined some of the economic issues affecting

the recycling of hazardous discards; the goal of this work was to

provide a general model, which could be adopted on a state or regional basis, to indicate probable economic outcomes of

124
certain hazardous waste management options. These activities were accomplished in partial fulfillment of the mandates of Sections

5002, 5003 and 5004 of RCRA.

VIII. 10. a. Pilot Study of Steel Industry Mill-Scales

Representatives of the steel industry acting under the aegis

of the American Iron and Steel Institute (AISI) approached NBS/0RM

in early 1981 to propose that NBS/0RM and the steel industry

cooperate in a recycling project. Specifically, the recovery of

metal units and energy from oily general steel making wastes and/or

recovery regeneration of NN0 3 /HF pickling media from stainless

steel operations were the two areas suggested. NBS/0RM saw an opportunity to increase recycling of the metal units but also to

provide a use or market for waste or recycled solvents. Hence,

NBS/0RM agreed to undertake a cooperative pilot project concerning

deoiling of mill-scales and sludges providing that waste or recycled

solvents be used as the deoiling medium. The steel industry

representatives agreed to this condition and appointed a liaison

group to act through the AISI.

The goals of the pilot project were to:

1) Evaluate the technical feasibility of existing and new methods for removing hydrocarbons from oi 1 -containing

steel plant sludges to render an iron-containing material

suitable for recycling.

2) Determine the most suitable methods for recovering the

hydrocarbon values in the waste, either as fuel value or

as reel aimed oil.

These goals were selected because various iron containing solid

wastes are generated in steel which contain hydrocarbons. The iron

content of some of these substances is significant and could

readily be recycled directly into steel making operations:

Iron Hydrocarbon Water

Content Content Content

% % %

Mill Scale 60-75 0.01->1.0 2-5

Hot-Rolling-Mill Sludges 60-70 5-30 21-58

Cold-Mill Sludges 2-7 81-88

Waste-Water-Treatment Sludges 30-44 2-8 40-78

The "low- hydrocarbon" materials, such as mill scale, are normally recycled to the blast furnaces and sinter plant (if

available). At times, some plants have added the fine mill sludges

to the sinter-plant feed also. The use of the hydrocarbon-containing

solids in sintering, however, results in a large portion of the

hydrocarbons vaporizing in the sinter bed and reporting to the

off-gases. These vaporized hydrocarbons either cause noncompliance

125
with air-pollution opacity regulations, if electrostatic precipitators are used, or require the installation of expensive scrubbers

involving complex water-treatment systems.

At present, most of the "oily sludges" are disposed of in

landfill operations. Because of the physical nature of the sludges,

special methods must be used prior to or after landfilling—slurries

are disposed of in lagoons, which may require treatment of the

leachate; filter or centrifuge cakes require blending with solid

materials such as slag before above-ground disposal. Disposal

costs have risen in response to regulations imposed by Federal and

state authorities concerning land disposal of hazardous wastes.

Since the domestic steel industry produces about three million tons

per year of these hydrocarbon bearing materials, estimates of

marginal cost increases due to increased disposal fees range from

$50 million to $300 million annually. In addition, iron units

which could be recovered if the wastes were treated to remove the

objectionable consti tuents-- the hydrocarbons and in some cases,

residual metals —are being discarded.

Methods for treating oi 1 -contami nated wastes include

incineration, evaporation, and solvent washing. These techniques

are best applied to mill scale because of its normally large

particle size and comparatively low oil content. Because of the

high oil content and fine size-consist of the oily sludges, they

are difficult and expensive to deoil using incineration; and, at

this time, little work has been done on solvent washing of these

sludges. Therefore, testing of solvent-washing techniques is

required to determine whether it is feasible to treat these sludges

economical ly.

The NBS/ORM pilot project concentrated on the problems associated with the recycling of mill scale. Mill scale is the material

that flakes off steel during the rolling process in the manufacture

of shaped products (such as sheet steel or I-beams). The scale

would be valuable as a raw material to be reused in making more

steel but it is contaminated by lubricant used on the rollers. The

oily residue may comprise from 0.5 to 5 percent of the mass of the

mill scale and must be removed before it can be used for the

ore-preparing sintering process. Sintering is the high- temperature

process where ore, coal, lime, and possibly mill scale are combined

at dull red heat prior to firing in the blast furnace. Presently,

large quantities of mill scale can not be added because of explosions

of the volatilized lubricant residue in the high- temperature

process. Thus, it is important to find a suitable method for

de-oiling mill scale.

In order to characterize the lubricant residue in mill scale,

a Soxhlet extraction was done with a volatile solvent and the

extract, was evaporated down to an oily residue. Soxhlet extraction

provides the basis for a simple laboratory method to determine oil

content before and after cleanup. The system is cyclic, operates

in a virtually closed manner and the extracting solvent can be used

126
almost indefinitely. Secondly, any one of a number of readily

available solvents can be used for deoiling. Finally, the paper

thimble used to contain the sample in the Soxhlet extractor provides

a very convenient means for estimating completeness of extraction

and for determining weight loss.

A study was made of a Freon 113 extract of mill scale and of

the unused mill lubricant by gel-permeation chromatography (GPC).

This analytical technique provided information about the molecular

weight fractions of the samples. In this work, a polystyrene

column with a 100 pore size was used with toluene as the flowing

solvent. Molecules that are smaller than the pore size can diffuse

into the stagnant solvent of the gel; whereas larger molecules will

not, and thus will be carried more rapidly by the flowing solvent.

Large molecules will elute from the column first followed by

progressively smaller molecules. Although the separation mechanism

is based on molecular size, this mechanism is linearly related to

the molecular weight for similar materials.

Some general observations can be made about the chemical

properties of the lubricants and mill scale extracts based on the

GPC/RI data. The mill lubricants are characterized by very prominent

aromatic hydrocarbon fractions of high (>500 amu) and low (100-400

amu) molecular weight. There is also a large aliphatic hydrocarbon

fraction in the moderate (400-500 amu) molecular weight range. By

contrast, the mill scale extracts are characterized by a much

smaller amount of the high molecular weight aromatic fraction and

only a moderate amount of the low molecular weight aromatic compounds.

The amount of the moderate molecular weight aliphatic hydrocarbons

found in the mill scale is similar to the amount found in the

original lubricant.

The mill rolling process would be expected to produce some chemical and physical changes in the mill lubricants. The

combination of the high temperature (red heat) contact with the

possibly catalytic steel surface is likely to promote "cracking" of some of the high molecular weight compounds, and this effect is

evident in the mill scale extract. Some of the low molecular

weight compounds are evidently volatilized to the atmosphere or are carried off in the rolling water wash, and thus comprise a smaller

fraction in the extract, relative to the original lubricant. The

most predominant fraction of the extract is the aliphatic fraction

of molecular weight 400-500 amu. These groups of compounds seem to

be little changed by the rolling process. This knowledge should be

of benefit in choosing the most efficient type of solvent for

de-oiling mill scale. Recent work involved the comparison of

several solvents of differing polarity. Four solvents were

evaluated: hexane (least polar) < freon 113 (1,1,2-trichloro1,2 ,2-tri f 1 uoroethane) < methyl i sobutyl ketone < methyl ethyl ketone

(most polar). The weight loss of the mill scale was measured and a GPC/RI molecular weight characterization was made on each.

The basic conclusions of the pilot study are:

127
Oil Recovery Experiment:

o Solvents of moderate polarity (methyl isobutyl ketone) gave

the highest oil recovery efficiency.

Gel Permeation Liquid Chromatography:

o High molecular weight aromatics are probably not extracted

well by any of the solvents in the low temperature Soxhlet

extraction.

o All solvents gave good recovery of all aliphatics and moderate

molecular weight aromatics.

o Low molecular weight aromatics are proportionally depleted in

the extracts relative to the lubricants.

o Low molecular weight aliphatics are proportionally increased

in the extracts compared to the lubricants (complete details

are to be found in Publications List #115 - Appendix XV).

VIII. 10. b. Characterization of Electric Furnace Dusts

AISI indicated to representatives of the Department of Commerce

(DoC) that electric furnace dusts were also a major problem with

respect to increasing costs of disposal. These dusts had been

declared hazardous wastes. Thus, the steel industry faced huge

marginal cost increases for disposal. The Economic Development

Administration sponsored a study by Lehigh University which was meant to:

o Characterize the dust particles;

o Investigate chemical extraction and physical separation

methods for the dusts;

o Determine the mechanism of dust formation; and

o Increase recovery and recycling of the dusts.

The electric-furnace utilizes nearly 100 percent scrap for its

charge. Hence, any reduction in the output of electric furnace

steelmaking could seriously impair markets for scrap iron. Thus,

NBS/ORM had an interest in both the recycling possibilities for the

dusts and the potential adverse effect on the scrap iron market.

NBS/ORM personnel were associated with this DoC project as technical

advisors and reviewers.

The electric furnace process is comprised of three major

phases: the melting of metallic ferrous raw materials, the refining

of the melt to remove unwanted tramp elements, and the final

deoxidation and adjustment of composition. In many modern installations, the refining and deoxidation steps are completed in a

128
separate vessel such as a ladle, the electric furnace being used

only to melt the charge and preheat it to refining temperature.

The process may be either acid or basic depending on the

nature of the refractories that contact the bath and the slag. The

basic process, in which the basic oxides lime and magnesia predominate in the refractories and refining slag, is used in most large

furnaces. The acid process, in which silica is the predominant

oxide is found mostly in foundries. The nature of the wastes

depends on the slag.

An electric furnace heat is begun by filling the furnace with

scrap. The scrap comprises a complete array of factory trimmings

and obsolete or worn out steel products. The impurities to be

removed with the melt vary with the scrap. For example, galvanized

steel introduces zinc; terne plate-lead; tin-plate-tin, and porcelain

enamel may bring in antimony and several other elements. Rusty

structural steel from an industrial environment may be extra high

in sulfur while case iron is high in both sulfur and phosphorus.

Depending on the final destination of the steel heat, there may be

unwanted alloying elements such as copper, nickel, chromium,

molybdenum, titanium and others. The presence of moisture in any

form such as hydrated rust, is a source of detrimental hydrogen

which is unwanted and must be removed.

The object of the melter is to convert the scrap into a homogeneous liquid, remove the unwanted elements, and adjust the

composition to specified levels. The melt is then poured into

molds where it solidifies into a form for subsequent processing.

The impurities and a portion of the desirable elements removed

from the steel are supposed to be collected in the slag which has

been prepared for this purpose. However, portions of the steel and

the slag may form a cloud of dust and fume in the gases over the

melt and its slag cover. The dirty escaping gases must be cleaned

by one or a combination of processes including an electrostatic

cleaner, a high-energy scrubber or a baghouse.

During the initial meltdown period considerable particulate

matter is emitted. This material is most likely comprised of

oxides of iron and other metals, with some smoke from combustible

matter. As melting proceeds the slag begins to form and cover the

melt. The arcs become more stable and emission of particulate may

subside to some degree. Moreover, as the slag cover forms, the

nature of the particulate emission will change.

In cases where a large amount of the lower grades of scrap is

used, the initial particulate will probably contain a large amount

of zinc from galvanized steel. Several other changes in composition

may occur and these vary with the type of steel being melted and

the method by which the melt is refined. Approximately 30 pounds

of dust are created per ton of raw steel.

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Several problems are associated with electric furnace dusts

and sludges with respect to their potential for recycle or reuse.

A few of these problems are:

a) Zinc, lead, and alkali elements in the dust carry through

the sinter plant and into the blast furnace causing blast

furnace operating difficulties (e.g., scaffolding and

premature lining failure).

b) The very fine particulates create handling problems.

c) The iron content is highly variable and too low for

reprocessi ng.

d) The amount of dust generated in a single steelmaking

facility is usually too small to support a viable recovery

faci 1 i ty.

The main results of the DoC/EDA sponsored Lehigh work are as

fol lows:

The study of the mechanism of formation yielded several

concrete suggestions for the reduction of the amount of dust

produced with an attendant conservation of resources; namely

1) Take steps to minimize direct entrainment of additives

in the furnace atmosphere as fine particles.

2) Reduce the total rate of gas flow through the furnace

first by making the furnace more air-tight and, second, by keeping

the gas bubbling rate through the bath to an absolute minimum.

3) Minimize the overall temperature in the furnace throughout

a given heat combined with a slight increase in the duration of the

heat.

4) Apply some form of enrichment or separation scheme to the

particulates when the amount can no longer be reduced and, therefore,

must be discharged from a given electric arc furnace.

Arc furnace dusts from stainless and specialty steelmaking are being treated by recycling techniques such as in-plant greenballing

and recycling to the furnace, or are being sent to a centralized

processing plant to be converted to a master alloy of controlled

composition. Because of the use of a better grade of charge

materials in the manufacture of these highly alloyed products,

there is much less potential for recovering zinc, lead and cadmium.

The most likely outlets for the recovery of nonferrous values

from carbon and low-alloy steel dusts are the existing smelters.

The source of dust should be close to an existing smelter, and the

dust should have a high zinc content (over 20 percent). Recycling

130
processes will be needed to concentrate the zinc, lead, and cadmium

to a sufficient degree to make them attractive to a smelter.

VIII. 11. Economic Factors Affecting Recycling of Potentially

Hazardous Wastes

For any region, the following data are required in order to

determine the economic trade-offs associated with disposal and/or

recycling options for potentially hazardous discards:

1) Determine what chemicals or mixes of chemicals are

di scarded.

2) Determine present fate of such chemical discards.

3) Determine how to assess and characterize such discards

for potential hazards to humans and the environment (see,

for example, the California Characterization and Assessment

System for Hazardous and Extremely Hazardous Wastes)

4) Determine costs associated with disposal of chemical

discards.

5) Assess risks to humanity and the environment associated

with disposal of chemical discards.

6) Forecast trends associated with costs and risks of land

disposal or of rendering harmless chemical discards which

are judged as hazardous.

7) Determine what chemicals local industry, government and

schools are using as feedstocks or reagents.

8) Establish "live" data bank.

9) Establish liaison with chemical production factors in

order to attempt to classify discard stream in order to

provide optimum fractions for recycling.

10) Determine technology needs, if any, to provide optimum

fractions for recycling to meet local or regional markets

as well as environmental and/or economic constraints.

11) Interact with State and local officials to provide

optimal climate for collection, transport and recycling

of chemical discards.

12) Carry out economic forecasting and trade-off analysis of

recycling vs. disposal option in the region.

13) Attempt input-output analysis to check effects on individual

SIC coded industries.

14) Establish mechanism to maintain the system.

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VIII. 11. a. Econometric Methodology Development

In ord«r to deal with these 14 points NBS/ORM, in partial

fulfillment of the mandates of sections 5003(2) and 5004 of RCRA,

chose to examine opportunities for economic development and resource

recovery in terms of hazardous waste management in the Great Lakes

Region. Complying with regulations or guidelines for hazardous

waste management usually involves altering the process used, or directing the wastes through disposal routes which differ from

those which have been traditionally used. This imposes on the

industries concerned either high operating costs or higher capital

costs. They are typically direct costs to the enterprise concerned,

and are likely to be partly absorbed by the enterprise, and partly

passed on to the purchasers of the products. These costs will,

therefore, affect the profitability of the industry. Some companies,

operating on a small-scale, with obsolete plants and equipment, and

small operating profits, may find their existence threatened by

these regulations. Throughout FY 1981, the Great Lakes Basin

Commission (GLBC) conducted a study meant to develop methodologies

for projecting the economic development effects of hazardous waste

management and to assess the potential for resource recovery of

material from selected waste streams: steel manufacturing, electroplating, and paint manufacturing. This study commenced September

1980 and was scheduled for completion by May 1982. However, the

Great Lakes Basin Commission expired as of September, 1981. Since

then the Michigan Department of Commerce sought and received from

Office of Recycled Materials a new grant initiative to complete

this study and to explore implementation options. The Michigan

Department of Commerce retained original project staff; consequently,

the study was completed by 1982. The Michigan Department of

Natural Resources assisted as technical advisers to the project.

(See Publications List #95 for complete report).

This study had two major purposes. The first was to develop

methodologies that would assess the economic impacts associated

with hazardous waste management in the Great Lakes region. The

second was to develop methodologies that could evaluate the economic

potential for resource recovery in hazardous waste management. In

conducting the study these two purposes often were difficult to

separate.

The objective was to develop methodologies which could be

applied in future studies to any industries that generate hazardous

wastes. This is not to say that this study did not produce any

results other than a package of methodologies. To determine if the

methodologies would be feasible and efficient, they were tested by

applying them to three case study industries chosen at the outset

of the study. As a result of these tests, conclusions regarding

the economic impacts of hazardous waste management and the potential

for resource recovery were obtained, if only for these industries.

However, it must be emphasized that the primary purpose was the

development of methodologies.

132
The study was primarily economic in nature. The methodologies

were intended to analyze the economics of hazardous waste management,

and that intention was followed. However, economics is only as good as the data which it applies, and it became apparent at the

outset that any methodology must first examine the technical

parameters of the problem. Therefore, many of the methodologies

incorporate a great deal of technical information regarding hazardous

waste characteristics and the systems for management of the wastes.

The development of a methodology to assess the economic impact

associated with hazardous waste management involved several tasks.

Some of the tasks were intended to provide background data, and

others to develop major components of the methodology. For example,

before the economic impact on industries within the region could be

evaluated, the costs of managing hazardous wastes had to be determined.

Therefore, a methodology was developed to determine the least cost

options for managing wastes within particular industries. The

information from these models was then applied to a methodology

to determine the financial impact on individual companies. The

results of the financial impact model were then used to predict

impacts within a state or region, based on a regional impact

methodology that was developed. The results of the economic

methodology were also used to test a methodology which assesses whether firms are likely to relocate as a result of hazardous waste

management costs.

The methodology for assessing the potential for resource recovery proceeded in a similar way. After conducting tasks which

looked at the technical and marketing aspects of resource recovery,

a methodology was developed which determines all of the factors

that must be analyzed to evaluate the potential for resource

recovery. The actual economic potential was analyzed as part of

the economic impact methodology. To determine whether resource recovery would have even greater potential if various financial

incentives were provided, a methodology was developed and tested

using the results of the economic model.

The absence of good data is a chronic problem in economic

studies, and this study was no exception. The major deficiency of

data was for the steel industry, one of the case study industries

selected. There was very little economic information regarding

hazardous waste management in this industry, in part because the

costs had never been evaluated to the degree of precision needed

for this study, and in part because the required data were often

proprietary. As a result, the steel industry was only analyzed

where the data allowed.

There were also problems with the financial data required for

the financial impact methodology. The model that was developed

required some data that were not available through Dun and Bradstreet reports. The study was able to work around these problems,

but the results are not as robust as had been hoped. More problematic was the inability to acquire financial information for the

133
same firms for which technical data were available. This necessitated averaging, which is never as accurate as analyses based on individual data.

Another problem was regulatory in nature. One of the case

study industries selected was paint manufacturing. At the time the

industry was selected, many of its wastes were listed as hazardous.

Subseguently , the U.S. Environmetal Protection Agency delisted many

of the paint wastes, but the study was too far along to select

another industry. Instead, the study focused on solvents generated

by this industry, which are hazardous, and provided an excellent

case for the resource recovery methodology.

Since it was too costly to analyze all industries that generate

hazardous wastes, and because the study had a methodological focus,

a case study approach was taken. A methodology was developed which

would select three industries that best met a number of criteria

that reflected the objectives of the study. The criteria included

such factors as resource recovery potential in the industry and

likelihood of economic impact from hazardous waste regulations.

After reviewing information on 25 industries that generate hazardous

wastes and ranking them according to each criterion, the three

industries that ranked the highest were electroplating, paint

manufacturing, and the steel industry. A lack of information on hazardous waste management costs in the steel industry eventually

precluded a complete analysis of this industry, and a delisting of

many of the wastes in the paint industry narrowed the scope of this

industry's analysis to solvent recovery.

Once the case study industries had been selected, a technical

review of each industry was prepared. This review identified each

of the hazardous wastes generated and current practices to treat

and dispose of these wastes. In addition, a literature review and

contacts with engineers in the industries revealed alternative

treatment/disposal and recovery technologies that may be technically

and economically feasible. A summary of hazardous waste regulations

affecting each case study industry was also prepared.

The study reguired information on the cost of treating or disposing of hazardous wastes in the region. Therefore a survey of

all off-site landfills, treatment facilities, incinerators, and

deep-well injection sites was undertaken. It identified current

charges, and estimated increases that would result from compliance

with federal Resource Conservation and Recovery Act (RCRA) regulations. The charges varied widely for each type of facility,

depending on the hazardous waste being handled. Landfills were expected to incur the highest regulatory costs, but the greatest

increase in charges would occur at treatment facilities. Increasing

demand for treatment and disposal services is likely to result in

charges somewhat higher than the level necessary to recover compliance costs.

Once the reguisite background information had been collected,

models of the economics of hazardous waste management were developed.

134
Their purpose was to determine the most economically efficient

waste management alternative, given various technical constraints.

Two models were developed; one for the electroplating industry and

the other analyzing options for solvent recovery. Both models were

based on constrained economic optimization methodology.

The computer model for analyzing the electroplating industry

compared the cost of five alternative treatment and resource recovery technologies for 24 electroplating shops in the Great

Lakes region. The cost and selection of management options varied

significantly among firms depending on technical parameters such as water use and metal concentrations. The annual costs to a plating

shop were quite high, ranging from $10,000 per year for a very

small operation to $250,000 per year for the largest company.

Under the "most realistic" scenario only a few of the firms analyzed

found one of the resource recovery technologies to be their least

cost option.

A sensitivity analysis of the results of the electroplating

model was conducted to determine what kind of financial incentives

would induce greater adoption of resource recovery technologies.

The incentive with the greatest effect on increasing the use of resource recovery was an investment tax credit. An investment tax

credit for recovery equipment of 25 percent resulted in 25 percent

more firms choosing resource recovery as their least cost option.

Accelerated depreciation and a 10 percent tax credit on recovered

materials had very little effect. However, if the interest rate

charges for loans on resource recovery equipment was 10 percent

lower than the borrowing rate on conventional treatment equipment,

the number of firms opting for resource recovery increased 24

percent .

The model for analyzing the economics of solvent recovery

compared the cost of off-site disposal or incineration with off-site

recovery of waste solvents and with recovery at the plant site. In

all cases, off-site recovery of solvents resulted in substantial

savings over disposal or incineration unless a substantial energy

credit was paid for burning waste solvents. The cost of on-site

solvent recovery varied significantly between large and small

firms. In most cases, on-site recovery was justified for larger

firms, and in some cases on-site recovery was less costly than

off-site recovery for smaller firms.

In order to determine the economic impact of hazardous waste

management costs, a computer program for a financial impact model was developed. This model analyzed the effect that waste management

costs generated by the electroplating model would have on key

financial indicators of firms in the electroplating industry. The

model makes various assumptions regarding demand and supply elasticities, and then determines how the balance sheets and income statements

change as waste management costs are incurred. The model results

indicated that there are likely to be substantial economic impacts

on small-to medium-sized firms under all but the most optimistic

scenario.

135
The results of the financial impact model were the basis for

testing a regional impact methodology developed in this study.

This methodology is designed to predict the aggregate economic

impact on a state or region resulting from changes in employment

and income in an industry that is impacted by hazardous waste

management costs. Various income and employment multipliers

indicate how losses in one industry translate into greater impacts

throughout the regional economy. The methodology was applied to

the results of the financial impact model under the assumption that

15 percent of the electroplating shops in Michigan would be forced

to close as a result of hazardous waste management costs. Under

this scenario, income losses would be between 29 and 47 million

dollars, and between 1,000 and 2,000 jobs would be lost.

The study also developed a methodology to predict whether

companies that generate hazardous wastes would be likely to relocate

closer to treatment and disposal facilities to reduce transportation

and disposal costs. The methodology weighs the transportation and

disposal cost savings against changes in other locational costs

such as product transportation and labor costs. Sensitivity

analysis of the electroplating model increased the distance wastes

would be shipped to 500 miles and the cost of disposal to $3.00 per

gallon. These changes increased annual costs by an average of 30

percent. While these changes are significant, they are unlikely to

induce firms to relocate. A more likely effect of these cost

increases is that firms will adopt resource recovery technologies

that lower the volume of waste that must be disposed.

The final methodology developed for the study was a detailed

approach to evaluating the feasibility of resource recovery. It

examines each of the factors that must be evaluated if a hazardous

waste is to be successfully marketed or recycled. The methodology

begins with a complete analysis of a firm's hazardous waste stream

and p :eeds through an analysis of all of the technical, regulatory,

market, ng, and economic aspects that must be considered. Resource

recovery is under-utilized in many industries because of a lack of

information and resources to evaluate its potential.

Certain methodological conclusions can be made. At the same

time, the methodologies were tested by applying them to hazardous

waste management practices in three industries. Therefore, the

study generated conclusions regarding economic impacts and the

economic potential of resource recovery. Caution must be used if

the results from a sample of three industries are to be generalized,

but some conclusions would seem to be applicable to most industries

that generate hazardous wastes.

The most important methodological conclusion that can be drawn

is that the results depend quite heavily on precise specification

of the technical, regulatory, and financial parameters. This

outcome may seem obvious, but many studies rely on average values.

This study has demonstrated that the use of averages may lead to erroneous conclusions. The Hazardous Waste Treatment Alternative

136
Analysis Model developed in this study generated results which

varied greatly from firm to firm. Similarly, if the Financial

Impact Model had used the average financial position of electroplating firms, it would have obscured the financial strain that hazardous waste management costs impose on many firms. Therefore, if

these methodologies are to be applied to other industries, an effort should be made to secure the best data that are available.

The foregoing does not mean that the methodologies developed

in this study are difficult to apply, or that they require reams of

data. On the contrary, they are relatively straightforward and were designed to be used by private industry or government agencies

that need information on economic impacts or resource recovery.

Computer models were developed for the economic and financial

analyses, but the methodologies could be applied with a hand

calculator. This study computerized the models primarily because

of the amount of sensitivity analysis that needed to be performed.

The Financial Impact Model does require a great deal of financial

data that is often difficult to obtain for smaller firms. To avoid

the necessity of collecting all this data, two simpler models were developed that require much less data, with little reduction in

accuracy.

The results indicate that resource recovery is an economically

feasible alternative in many cases, and does have a great deal of

potential, at least in the industries studied. In fact, resource recovery is probably being under-utilized because of a lack of

information concerning markets for recovered products or its

economic feasibility for in-plant recycling. The methodology

developed to assess whether particular hazardous wastes can be

recovered found that many firms were not aware of the marketability

of particular wastestreams or how they could treat the wastes to

increase their value. The methodology pointed out that the ability

to determine whether a product can be recovered from hazardous

wastes is often beyond the capability of smaller firms. For this

reason, it is probably appropriate that industry trade associations

provide the necessary information regarding resource recovery

systems.

This study evaluated the private cost of resource recovery,

excluding the potential savings associated with the liability

issue. A few of the larger firms the study contacted had chosen to

install resource recovery systems because they were concerned that

off-site disposal might eventually lead to liability claims against

the company. In this respect, the study undervalued the true

savings associated with resource recovery.

No evaluation was made of the social costs of off-site disposal

vs. resource recovery. Since resource recovery reduces the volume

of hazardous materials that could potentially be exposed to the

environment, resource recovery may impose lower social costs than

other hazardous waste management techniques. Therefore, society

may want to provide incentives for hazardous waste generators to use resource recovery. This study considered several financial

137
incentives that could be used, and evaluated how they would increase

the use of resource recovery in the electroplating industry.

The incentive that would have the greatest effect on lowering

the cost of resource recovery was an investment tax credit applied

against the capital costs of the system. An investment tax credit

of 25 percent increased the number of firms choosing resource

recovery over conventional techniques by 25 percent. Currently,

the investment tax credit applies equally to resource recovery and

conventional systems. Very low interest rates also tend to favor

resource recovery, and a 10 percent difference in the interest rate

charged on loans for resource recovery and conventional systems had

a significant effect. Accelerated depreciation on recovery systems

was found to have a minor impact, as did a 10% tax credit for

recovered materials. Even though these incentives were applied to

the electroplating industry, the relative effect of the incentives

would be much the same in any industry.

The economic impact portion only focused on the case study

industries, so no general conclusions on total impact can be made.

However, if the results obtained from the case study industries are indicative, there may be fairly significant impacts on small firms

that generate hazardous wastes. The cost of treating and disposing

of hazardous wastes in the electroplating industry were found to be

a significant proportion of total costs for small and medium sized

firms. The Financial Impact Model showed a dramatic worsening in

the key financial ratios of many of these firms, and in several cases hazardous waste costs made the difference between a profit

and a loss. If as many as 15 percent of the electroplating shops

in Michigan were to close as a result of these costs, the loss of

income to the state would approach $50 million.

The other economic impact issue concerns the availability of

hazardous waste treatment and disposal facilities in the region.

Currently, many generators must ship their wastes out of state for

disposal, which is quite costly. The Hazardous Waste Treatment

Alternative Analysis Model demonstrated that the cost of hazardous

waste management increased by an average of 30 percent when the

transportation distance increased from 25 miles to 500 miles.

While the locational impact methodology suggested that this increase

would not be great enough to induce firms to relocate, it does a significant cost burden on hazardous waste generators. A scarcity

of hazardous waste facilities will also increase disposal charges.

Therefore, efforts by the states to overcome opposition to the

siting of new facilities should be increased to minimize the

already substantial economic cost imposed on firms that generate

hazardous wastes.

The methodologies developed and utilized in this study are transferable to other regions in the United States for industries

which are facing problems of dealing with hazardous wastes in the

most economically efficient manner. Hence, each of the required 14

points can be taken into account for whatever region is chosen.

138
VIII. 12. Summary of Requirements

The following four parameters are crucial to the technical

foundation for any program:

a) Qualitative analysis of potentially hazardous wastes:

organic and/or inorganic and, mixed or unmixed.

b) Measurement methods to determine the concentration of

potentially hazardous wastes. This requirement implies

development of a measurement assurance program so that

the results from complex and expensive tests can be

translated, on a controlled basis, to less complex and

less expensive tests having similar precision and accuracy.

c) Determination of the concentrations of potentially

hazardous wastes moving in a specific ecosystem as a function of time.

d) Estimation of the cumulative probability for harm associated

with specific substances (and possibly specific sites) at some point in time in relation to a given population

and/or ecosystem.

An approach to these issues and provisions for consistent

Federal and State regulatory stances are desperately needed.

Cooperation between all affected parties is needed in order to

achieve a fair and equitable means of dealing with the technical,

economic and institutional challenges posed by the need to dispose

of so-called hazardous wastes.

A framework of actions which might be undertaken on behalf of

all parties-of-interest includes the following:

o Review and analyze the various definitions of hazardous wastes

and procedures and methods for differentiating such wastes,

e.g., composition and characteristics, currently utilized by

Federal agencies, State and local government, and affected

industrial operators.

o Identify sources of data related to the generation, transport,

processing, recycling, disposal, and health-related affects of

potentially hazardous discards; critically evaluate these

data.

o Identify and evaluate the technical methods and procedures for

determining composition, characteristics, mobility, and

health-related effects of hazardous wastes via identification

and evaluation of test methods and procedures allowing for a statistically valid analysis of the data.

o Analyze current and proposed State and Federal legislation/

regulation with emphasis on similarities and differences

between State and Federal technical and economic requirements.

139
o Compare Federal and State insurance requirements for hazardous

waste disposal facilities, including actual relationships in

terms of applicable laws and appropriate measures and definitions

of liability.

o Compile and determine on a State-by-State basis, the estimated

costs associated with implementation of potential regulatory

strategies.

o Develop methods to estimate the economic burden placed upon

the regulator as well as the regulated community.

o Examine institutional considerations.

o Evaluate the cost-effectiveness of achieving an implementation

strategy which will assure equivalency with existing and

proposed Federal regulations and which provides for State-toState consistency with such regulations.

A number of parties, e.g., ASTM Committee D34 on Waste Disposal

and various Federal agencies, have addressed themselves to some of

these issues. The Office of Recycled Materials of the National

Bureau of Standards, U.S. Department of Commerce, studied the

possibility for correlating and collating existing information and

developing new information as well except that no health related

issues were to be examined. Some of these NBS/ORM activities have

already been discussed; others follow.

VIII. 13. State Measurement Neeas

In an effort to determine the ability of the states to provide

appropriate measurement technology and methodology, NBS/ORM issued

a grant to the Association of State and Territorial Solid Waste

Management Officials (ASTSWMO). This Association is comprised of

State officials responsible for the planning and implementation of

State resource recovery and hazardous waste management programs

under the Resource Conservation and Recovery Act of 1976, as amended. Forty-three States are represented by the organization.

The Association's Resource Recovery Committee considered the

following questions:

1) Does the State have adequate laboratory support staff,

equipment, and resources or the services of a private

contractor to perform RCRA-related measurement activities?

2) What are State laboratory equipment holdings?

3) Are the laboratories certified? Do they have a quality

assurance program?

4) Is there adequate laboratory and field protective equipment

and clothing?

140
5) What types of technical assistance do laboratory and

field personnel need and from which entities?

6) What are the overall prioritized needs in support of

implementing the technical requirements under RCRA?

The Association Committee prepared profiles of seven States'

individual responses to the above cited inquiries. Those States were Oklahoma, Texas, Louisiana, Mississippi, Virginia, New York

and Pennsylvania.

The Committee concluded that even though State programs vary

in stringency of regulatory requirements, State measurement needs are similar in hazardous waste. However, Subtitle D resource recovery measurement needs, while identified, do not exhibit the same level of priority associated with Subtitle C program. Nevertheless, standard analytical methods, protocols, and procedures

specified in State regulations match those methods cited in Federal

criteria. Development of standard laboratory and field methods for

sampling and analyses as well as standard reference data is required.

The lack of availability for such measurement tools is severely

impeding national consistency on a State-to-State basis, timely

program implementation, and worker protection and safety. Consequently, a formal operating procedures manual is necessary to assure not only State-to-State programmatic and enforcement consistency, but also in intra-State field and functional laboratory

activities. A standard laboratory certification quality assurance

program does not exist and will be helpful in attaining State-toState consistency. Lastly, training programs and technical assistance for laboratory and field personnel are inadequate at State

level

.

The Report itself runs to 9 volumes (Publications List #'s 82-89

and 121) and consists of the following sub-parts:

o Part I: Final Report and Executive Summary: State summary

charts containing definitions of hazardous waste,

measurement parameters, laboratory needs, and

available training programs; Conclusions and Recommendations

o Part II: State Profiles (Texas, Louisiana, Oklahoma, New

York, Pennsylvania, Mississippi, Virginia):' Solid

waste, hazardous waste and resource recovery program

objectives; State agency organizational make-up; resources and manpower; selected regulations; data

from field visits on laboratory capability; other

appropriate documentation.

o Part III: Analytical Operations Procedure Manual Model: A

cohesive technical framework and outline of tools

necessary to augment States' hazardous waste program

based on experience and guidance of State of Louisiana.

141
In addition, NBS/ORM prepared a summary of the present situation

in the several states with regard to control of hazardous wastes.

This survey is included as Appendix X. Based upon these findings

the immediate outlook is as follows:

Despite funding shortages and dilemmas, states will

continue to assume, administer, and expand their respective

hazardous wastes programs. Funding will be supported through

combination of fees and appropriations. By 1984, the majority

of states will have authorized hazardous waste programs in

place. Concurrently, a result of federal funding and staff

reductions and completion of state assumption process, the

direct involvement of federal regulatory agency can be anticipated to lessen. Implementation issues (e.g., state-to-state

consistency) will come to the fore. Resolution at the regional

level will be attempted. Technical difficulties will arise

should states measurements needs not be addressed. Debate on perpetual care and victim compensation will be aired in

Congressional and State legislative community as part of the

regulated community need be apprised of the legislative,

technical and economic issues.

VIII. 14. NBS/ORM Participation in the OECD Study Concerning

Control of Hazardous Wastes

The Waste Management Policy Group (WMPG) of the OECD came to

the conclusion in late 1980 that the economic dimensions of hazardous

waste management were not well understood. In fact, the international

aspects were essentially not understood at all. At that time, the

GLBC/State of Michigan study sponsored by NBS/ORM had just begun.

Since similar basic issues faced a community of industrial partners

as faced a group of industrialized states within the U.S. the WMPG

adapted certain portions of the NBS/ORM project to the needs of the

OECD. The WMPG also added new goals. The major issues are concerned

with the fact that the hazardous waste regulations that have been

implemented affect the cost of production of the companies concerned,

and may affect the technology that is used. A country may not have

the capacity to manage some wastes within its own boundaries, and

they may have to be transported across national frontiers. The

need to clean up and rectify sites where hazardous wastes have been

tipped imposes costs either on regional authorities or upon private

developers. Insurance and assurance for sites licensed to accept

hazardous wastes may impose high costs on those companies or local

authorities operating these sites.

The set of problems associated with hazardous waste management

is extensive. In the area of basic data, it is necessary to have

some general information regarding the regulatory environment, as well as the amount and nature of wastes generated and the expected

increase in these flows in the future. The current capacity of the

hazardous waste industry, the methods of treatment and disposal and

their costs are also important parameters for any assessment of the

i ssue.

142
The Waste Management Policy Group discussed these basic

information needs as well as specific problem areas within the

general topic of hazardous waste management, and arrived at a consensus on those areas which were to be included in the hazardous

waste work program of the Group. These are:

1) the transport of wastes across frontiers, the quantity,

the reasons for these flows, and the provisions made for

them;

2) the costs to industries of complying with regulations,

and the costs to the regulating agency of enforcing the

regulations; and

3) the insurance and assurance of operations involving the

storage, transport and disposal of hazardous wastes, and

the liability for damage caused by inappropriate management

at any stage.

For Item 1 above, the WMPG is compiling:

o the procedures that are followed to permit the transport of

these wastes across national frontiers;

o the costs of transporting hazardous wastes over long distances;

and

o the legal provisions covering liability for damage caused by

spills of wastes during the transport or storage of wastes

outside their country of origin.

The chief impact of the NBS/ORM results will be for Item 2 via

the use of the methodology developed in the GLBC/State of Michigan

study:

o to characterize the extra costs to be borne by enterprises

which modify their processes;

o to evaluate disposal or storage costs under the requirements

of specific regulations; and

o to identify particular industries where the burden of compliance

costs may radically affect the viability of a significant

proportion of the firms in the industry.

The OECD investigation will serve to indicate the usefulness

of the NBS/ORM methodology in the international arena. Clearly,

any problems in transferring the methods to cases other than the

U.S. Great Lakes states will be identified and can be taken into

account. Thus, the OECD efforts will provide a critical review and

a further application of the NBS/ORM work in this area.

With regard to Item 3, insurance, assurance and liability,

financial provisions to deal with costs of damages caused through

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accidents, occurring during any operation involving hazardous waste

transport, storage or disposal, and through malpractice relating to

any of these activities, are of concern primarily because traditional

insurance markets are not currently able to provide insurance

cover. There are three basic issues involved:

o the provision of liability insurance in case of accident;

o the determination of liability; and

o the provision of assurance to ensure proper hazardous waste

disposal site operation, decommissioning, and post-closure

maintenance.

NBS/ORM did a brief review of the technical issues associated

with potential insurer risk and the requirements for the size of a reserve fund to prevent insurer bankruptcy. While the computation

of probability for survival of such a fund is straightforward,

uncertainties with respect to liability of parties and the extent

of liability have not been resolved in the U.S. as of the fall of

1982. Therefore, insurance carriers are likely to move slowly and

to be extremely risk adverse regarding third party liability

i nsurance.

If the PPLV concept, with or without the extension according

to eq. (VIII-14), achieves a measure of public acceptance, then

some measurable basis for assessment of risk by the prospective

insurer will be available. Until there is such a basis, insurance

availability and rates if available are likely to remain in a state

of flux.

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IX. MARKETS FOR RECOVERED MATERIALS (SECTION 5003 OF RCRA)

IX. 1. Congressional Mandate

Section 5003 of RCRA (42 USC 6953) placed three responsibilities

on the Secretary of Commerce (See Section IV. (1) for exact wording).

1) Market surveys for recovered materials.

2) Identification of economic and technical--but not

institutional—barriers to the use of recovered materials.

3) Actions to encourage the development of new uses for

recovered materials.

These responsibilities were delegated to NBS/ORM in January,

1980 by means of an ammended Departmental Organization Order (10-1,

Amendment 5, rescinded in October, 1982). A number of NBS/ORM

activities in response to Subtitle E of RCRA served to partially

fulfill requirements under more than one section, e.g., most of the

activities concerned with potentially hazardous discards (See

Section VIII). But Section 5003 clearly required some specific new projects to be initiated by NBS/ORM.

With regard to market surveys, a broad survey, national in

scope, had been carried out in 1976 on behalf of the Congressional

Office of Technology Assessment; this survey dealt only with

recoverables from MSW (Materials and Energy from Municipal Solid

Waste, OTA, Washington, DC 20510, 1979, Vol. II). The general

conclusion was that markets were regional in nature, highly volatile

and thus subject to very high risk for participants. More specific

market surveys, e.g., state-wide tended to reproduce these results.

Hence, NBS/ORM was faced with the dilemma of devising a means

to deal with market fluctuations in a dynamic fashion. Any direct

market survey, whether national, regional or local was likely to be

subject to rapid change, i.e., might be obsolete before published.

But, valid techniques to sample markets needed to be developed.

NBS/ORM chose to commission one major regional market survey

dealing with just one recovered material --wastepaper. This study

was organized and carried through by the Bureau of Industrial

Economics of DOC (BIE).

IX. 2. Market Survey for Wastepaper in Four

Southeastern States

Waste newspapers are a source of fiber for the manufacture of numerous paper and board products, and the main ingredient in

cellulose insulation. Wastepaper dealers are the major suppliers,

often relying on individuals, volunteer groups, institutions, and

municipalities for collection. Because of the concentration of

paper and board mills in the South, especially North and South

Carolina, and Georgia, these states have a high demand for waste

newspapers.

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In the Fall of 1979, representatives of the industrial wastepaper

community expressed concern that the future supply of waste newspapers

(old news) may not increase sufficiently to prevent prices from

rising sharply in the Southeast Atlantic States. The sources of

this apprehension were the opening of a newsprint mill in Georgia

that will need 150,000 tons of old newspapers per year, the increase

in old news consumption by cellulose insulation mills in the

region, and an apparent increase in exports of old news. In

addition, concern was expressed regarding the possible adoption by some Florida counties of a "flow-control" ordinance. This would

assign collected municipal solid waste to resource recovery facilities which would convert solid waste, including the paper content,

to saleable energy, principally in the form of steam. The restrictive

ordinance could obstruct the free market for waste newspapers by

eliminating the potential for cooperative source separation programs

with municipalities, deprive the wastepaper recovery firms of the

waste newspapers they need to survive, and cut off the user mills

from a source of raw material.

The BIE Study provided data on the markets for waste newspapers

in North and South Carolina, Georgia, and Florida for the Office of

Recycled Materials, National Bureau of Standards. It was not

intended to promote one market over another or draw conclusions

regarding whether or not a specific resource recovery facility

should burn waste newspaper. The BIE report provides the best

publically available marketing data on the subject in the four-state

area.

IX. 2. a. Survey Results

Supply and Demand

Data gathered through field interviews with wastepaper dealers,

paper and board mills, and cellulose insulation manufacturers

indicate that nearly 52 percent of the recoverable newsprint

consumed in the survey states in 1980 was recycled to user mills or exported. This is far higher than the national recovery rate of

about 23 percent. The potential supply of recoverable newsprint

was 855,700 tons in the four-state region, of which 438,600 tons

was recycled in 1980. Paper and board mills consumed 337,200 tons

and cellulose insulation producers used 111,300 tons; exports

accounted for 3,700 tons. This region's reported receipts of waste

newspapers from outside the four states were about 10,000 tons.

Florida was the largest supplier of waste newspaper and accounted

for 60 percent of the potential supply. Georgia was the largest

consuming state, using 70 percent of the recycled newspapers in the

region, mainly in paper and board mills.

The survey data indicate strong growth in demand for waste

newspapers. Consumption of old news by user mills in the survey

region doubled between 1977 and 1980, reflecting the startup of a new paper mill. Projections made from survey interviews suggest an increase in consumption of 8.2 percent to 475,000 tons by 1982.

Exports are expected to recover to 11,000 tons in 1982 after a

146
sharp decline in 1980. The greatest area of uncertainty in future

demand was in the cellulose insulation industry, which has experienced

some disruption in recent years. The supply of waste newspapers

should be adequate to meet any increase in demand, especially if

prices increase.

With a recovery ratio of about 50 percent in 1980, the potential

supply should not cause limitations due to any depletion of the

volume of used newsprint available. Moreover, the survey data

indicate that the supply of recycled newspapers is highly sensitive

to prices; dealers believe they could get all the old news they

need at a price of $2.00 per ton, compared with the price of about

$1.50 per ton in 1980.

Dealers

o More than one-half of old news processed by wastepaper dealers

is purchased at the dealer's place of business. The remaining

volume comes almost equally from that purchased on contract

and that recovered by company initiatives.

o Dealers obtain the old news primarily in their local areas,

and sell it in a much larger area, often using rail transport

for shipments to user mills. Transportation costs for

dealers' receipts are carried by the seller, the user mills

pay transportation costs for dealers' shipments.

o Price variations imply that there are marketing opportunities

in developing special market arrangements and negotiating on price and specifications.

o Dealers must compete for sales with local groups and individuals

who deliver old news directly to the manufacturers.

Paper and Board Mills

o Paper mills reported that price is the major factor controlling

quantity supplied. A few firms reported purchases through

formal contract arrangements.

o Paper manufacturers stated that technological improvements in

wastepaper cleaning systems would encourage increased use of

old news.

Cellulose Insulation Mills

o Most of the waste news consumed by cellulose insulation

manufacturers in the survey region comes from Florida.

Florida leads the other states in expected growth of shipments

of cellulose insulation.

o Georgia was the largest producing state in the survey region.

Cellulose insulation producers consumed 78,200 tons of newspapers

in 1980, compared with 18,300 tons in the Carol inas and 14,700

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tons in Florida. Firms in Georgia covered the largest radius

to obtain supplies of old news.

(For complete details, see Publications List #91.)

NBS/ORM personnel maintained close contact with BIE while this

survey was taken. We concluded at an early moment that a comprehensive set of market surveys for even just the recoverables

from MSW would require about 44 studies comparable to the BIE

effort. When other recyclables, e.g., solvents or other industrial

materials were added, the requirements doubled. Not only was such

an effort beyond the resources of NBS/ORM, but there was a strong

possibility that many of the results might be obsolete by the time

the work was completed.

IX. 3. Resource Recovery Market Models

NBS/ORM chose to develop models which would aid decision

makers in selecting resource recovery options. Models were developed

for selecting appropriate municipal solid waste management and

recovery options and for comparing the economic outcomes of selecting

resource recovery for certain industrial wastes as opposed to other

options, e.g., various forms of disposal. (See also Section

VIII. 11. a)

The general goal of this exercise was to identify options

which would be economically efficient, Then the specific market

situation required to fulfill the efficiency criterion as a function

of time could be pinpointed. Thus, specific market effects on a specific plan could be deduced and the survey requirements would be

reduced to estimating whether a satisfactory market existed or would exist to meet the predetermi ned--nearly optimal—plan.

IX. 3. a. Evaluation Criteria for Mathematical Models

The question of how well a model might be used to represent

the real world thus became of great interest to NBS/ORM personnel.

For this reason, R. E. Chapman of the NBS Operations Research

Division was asked to prepare a brief statement concerning the

evaluation of models. According to Chapman, at the most basic

level, one can define three topics which should be addressed in any

model evaluation activity. The topics are:

1) appropriateness;

2) validation; and,

3) documentation.

In the discussion which follows, each of the terms will be

defined. A brief description of how one would assess whether or not a particular model adequately covered the issue under consideration will also be presented.

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IX.3.a.l. Appropriateness

Many modelers believe that the purpose of building models is

to gain insight into how a particular process operates or to

predict the future behavior of the system. In either case, the

logical first step is to hypothesize a theoretical model of the

process. At this stage, many simplifying assumptions are made

regarding what is important or unimportant or what is controlled or uncontrolled. These decisions should be documented and carefully

assessed because they govern the functional relationships which

form the basis of an operational model. The appropriateness issue

thus focuses on the structure of the abstract model which establishes

the foundation upon which the rest of the modeling effort is based.

If the abstract model is revealed to be seriously flawed, then the

entire exercise of constructing and validating an operational model

is likely to be of little use.

One way in which model appropriateness can be assessed is to

survey recent technical advances in the field to see if some systematic development of a particular aspect of the problem is

revealed. Agreement here should provide guidance regarding functional

forms and serve to warn against potential pitfalls which confronted

other researchers. In the absence of adequate technical documentation, it would seem advisable that some pooling of ideas, which

relies on recognized experts in the field, would be advisable.

This effort should aim at not only gaining consensus but also

revealing and exploring major differences in perspective.

IX. 3. a. 2. Validation

The validation of a complex model aims at demonstrating that

the model bears a close resemblance to the system being modeled.

The validation process is, in reality, three separate tasks: (1)

technical validity; (2) operational validity; and (3) dynamic

val idi ty.

IX. 3. a. 2.1. Technical validity

Technical validity requires the identification of all model

assumptions, including those dealing with data requirements and

sources. It is especially important to document any divergences

from perceived reality.

As a first step, one should identify all stated and implied

assumptions, all decision variables, and any hypothesized relationships between variables. This step attempts to shed light on the

correspondence between the model and the real world phenomena it

attempts to explain. Three types of assumptions may be readily

defined. First, the mathematical assumptions implicit in any large

model include its functional form and the continuity of its relationships. A second type, content assumptions, define all model terms

and variables. They should also define the scope and limitations

of the model. The final type, causal assumptions, are concerned

with the assumed or hypothesized relationships between terms and

149
variables. Since these assumptions define the direction of flow in

a model, they are capable of producing significant divergences from

the real world phenomena.

Ideally, one would like to build a model which would produce

true conclusions (predictions) whenever all of the assumptions were

true. This property is known as modus ponens among logicians.

Since most assumptions have their roots in a empirical argument,

statements enter in a probabilistic rather than an absolute sense. Unfortunately, the strength of modus ponens does not apply to

probabilistic statements, so that some other criteria must be used

to reveal whether or not a model has a logical flaw. At one level,

the axioms of Aristotle can be used to critique a model (e.g., the

model contains one or more circular arguments). At a second level,

logical formalism can be used to assess the adequacy of the translation of the model form into a numerical process that produces

solutions. This involves:

1) determining if the mathematical or numerical calculations

are correct and accurate;

2) analyzing if the logical flow of data and intermediate

results are correct and consistent with our causal

assumptions; and

3) ensuring that variables and relationships have not been

omitted.

A concept which may be called the "principle of model economy"

focuses on data validity. For example, an elegant model based on poor quality data may be o* considerably less use than a simple

mode" v th slightly better ,uality data. In many cases, models use

both raw data and transformed data in producing solutions. Since

raw da -1

. a are the basis for transformed data, their validity is

essential. Basically the problem is one of assessing if the raw

data are true in terms of accuracy, impartiality, and representativeness. If any of these characteristics are violated and the nature

of the violation can be isolated and bounded, then a transformation

may produce the desired data set. Data transformations can also

have a significant impact on the validity of data. For example,

aggregating time series data can force a system which is, in

reality, recursive to become simultaneous. Similarly, the pooling

of cross-sectional data may be inappropriate if two or more distinct

populations are involved.

Assessing the predictive performance of complex models is the

subject of a rapidly growing literature. The techniques used

range from simple graphical analysis to the use of information

theory. All techniques, whether highly qualitative or quantitative,

seek to analyze the relationship between actual outcomes and

predicted outcomes generated by the model. Predicted outcomes are

of two kinds:

1) the values of the parameters used in the internal computational process of the model, and

2) the values of decision variables.

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On the first level, one woul^ review the statistical or related techniques used to obtain estimates for the relevant

parameters. The main thrust here would be to demonstrate that the

deviation of the estimated parameter value is as small as possible.

The second level of analysis is more complicated, because it

attempts to both document any divergences of actual and predicted

values and identify what portions of the model appear to have

caused them. These error decomposition techniques are especially

difficult in models with a large number of interrelated equations.

IX. 3. a. 2. 2. Operational validity

Operational validity attempts to assess the importance of any errors or divergences encountered when the model's technical

validity is reviewed. Operational validity is concerned with

whether or not the model can produce bad answers for proper ranges

of parameter values, i.e., the model should be robust in that a user would find it difficult to make the model yield (in terms of

the decision maker) an ostensibly wrong answer.

Sensitivity analysis is related to, but distinct from, robustness. This technique seeks to systematically vary the values of

the model parameters to determine how much (i.e., how sensitive)

the solution changes. The literature on sensitivity analysis has

rapidly grown as more and more decision makers wish to know the answers to "what if" questions. The techniques for performing

sensitivity analyses ranges from "brute force" Monte Carlo experiments to highly structured parametric programming.

The last aspect of operational validity and the most difficult

is implementation validity. Implementation validity is concerned

with the extent to which the real world system being modeled will

respond in a manner indicated by the recommended solution. This

task is difficult because if a decision maker knew how the system

would respond to a given change in a parameter or decision variable,

there would be considerably less need for a model. Consequently,

even after the model is built and shown to predict historical

occurrences well, it may not produce a good or even useful prediction

of some future event. One possibility is that under some conditions

the system does not appear to respond as the model predicts,

whereas under others, it does. If one could determine under what

conditions the system does not respond as predicted by the model,

then some of the techniques used in assessing the accuracy of

predictions could be used to attempt to isolate the cause.

IX. 3. a. 2. 3. Dynamic validity

Dynamic validity is concerned with determining how the model

will be maintained during its life cycle so it will continue to be an acceptable representation of the real system. The two aspects

associated with dynamic validity are updating and review.

In updating, the evaluator needs to be satisfied that the

model developers have established a procedure by which information

151
is collected and analyzed to determine if and when model parameters

or model structure need to be changed. It is also important that a process exists by which such changes can be incorporated into the

model and disseminated to users.

A regular schedule for reviewing the success or failure of the

model during its life cycle is also necessary. These reviews

should be carried out regularly and should focus on documenting any

systematic divergences between the solution predicted and the

actual outcomes. The implications and means of accomplishing any

proposed model changes should also be commented on. Periodically

an extensive review should be conducted which produces a new evaluation of model validity that yields either a formal pronouncement that the model is still valid or that it should be substantially

reworked or scrapped.

IX. 3. a. 3. Documentation

From a model user's point of view, documentation (the written

description of the model) is essential if the model is to be

usable, useful, and used. Since the abstract model is a mathematical representation whereas the operational model frequently appears

as a computer code, it is necessary to verify that there exists a unique relationship between the abstract (mathematical) model and

the operational model. It is important to point out that a third

party assessment should be sufficient to verify this relationship.

This would spare each user from carrying out the in-depth analysis

that this task requires. An issue which each model builder should

address is whether or not the computer code which describes a complex model is machine independent. Portability requires not

only that the program can be run on a variety of machines, but that

it produces the intended result. This step again should be a part

of a third party assessment, although the provision of test cases which could be run and compared to a known solution would facilitate

a move from one system to another. The final point in the evaluation

of documentation is user friendliness. Complex models often

involve subtle techniques which, in the absence of a buffer between

the user and the model could cause frustration and lead to a highly

inefficient use of the model. Documentation and an executive code

should serve to shield the user from unnecessary detail without

withholding any information which is essential to confidently use

the model. One way in which the model developers can test their

model is, again, through the use of a third party assessment. A

second, and for this case perhaps more useful exercise, is to rely

on a group of "casual users." These people might be expected to

have some familiarity with the problem under study but would be

less likely to analyze the model as deeply as its developers or a third party assessment team. Casual users are thus likely to

represent better the intended user than a team of model builders or assessors

.

There are no hard and fast rules for evaluating complex models

because, to a certain extent, the type of model and its intended

152
use will govern how much time and effort should be expended in

carrying out the assessment.

IX. 4. Two Computer Models for Assessing the Economics of

Resource Recovery

Choosing among alternative solid waste management plans is a difficult problem requiring a careful accounting of all projectrelated costs. Computer models provide a convenient method for

both organizing a decision maker's thoughts and for keeping track

of all costs and their likely effects on different segments of the

population. To adequately capture the realities of the situation,

however, such computer models must be able to address the problem

not only from the perspective of a typical community but also from

that of a region representing a collection of communities. Although

it is possible to develop a hybrid model which incorporates both

perspectives, the differing objectives of decision makers and the

data needed to assess their economic consequences justify the

development of two complementary models.

The first efforts focused on the development of a communityoriented model with special emphasis on the economic tradeoff

between selling newsprint for its fiber content versus incineration

for its BTU value. This model was an extension of the results of

the BIE wastepaper survey and the findings of NBS/ORM concerning

this tradeoff (see Publications List 91 and 93). The model was developed by the Bureau of Industrial Economics at the Department

of Commerce and is here after referred to as the BIE model. The

second model focuses on the identification of a preferred regional

plan for solid waste management. The Resource Recovery Planning

(RRPLAN) model identifies the best combination of sites and sizes

for all solid waste management facilities as well as the most

cost-effective allocation of wastes to and among these processing

facilities. The model also gives explicit instructions regarding

which materials or forms of energy can be recovered from the waste

stream and their allocation among competing markets. RRPLAN was developed by Edward B. Berman Associates, Inc.; a number of improvements were incorporated by the Operations Research Division at the

National Bureau of Standards.

Perhaps the greatest difference between the two models is one

of perspective. Whereas RRPLAN seeks to identify an optimal plan

for solid waste management, the BIE model compares the costs of a fixed set of five waste management options. This distinction is

necessary when sensitivity analyses are to be performed. Although

both models can efficiently access the impacts of changing assumptions, the interpretation of the results may require greater

qualification if the BIE model is used. This is due to the fact

that sensitivity analysis in the RRPLAN model is based on perturbations about a solution which is preferred to a very large number of

alternatives. Thus by fixing the set of waste management options

at five, the BIE model user may not be able to see how the "structure"

of the problem changes when one or more of the assumptions changes.

153
The degree of regional detail is another important difference.

For example, if the case under study is for a single community then

the BIE model should be used to determine if resource recovery is

cost effective. Similarly, if several communities were to be

studied in isolation then one should opt for the BIE model. If the case under study involves several communities, each of which must

contribute to the construction and operation of a resource recovery

facility, then the more complex RRPLAN model should be used.

Similarly, if a potential for economies of scale in the construction

and operation of solid waste management facilities exists, then the

RRPLAN model should be used. This recommendation may be better

understood when one recognizes that each community may be able to

reduce its processing costs through centralization. An analysis of

a single community would not be able to capture the effects that

the processing of other communities wastes would have on its own costs. Finally, it is worth noting that both models can be used to assess a no resource recovery option.

A third major difference between the models has to do with the

size of the model itself. Whereas the BIE model is quite small and

could conceivably be executed on a programmable calculator, the

RRPLAN model requires access to a computer system which satisfies

certain software standards for the FORTRAN programming language.

If access to a computer system is a problem or the intended user

has a very limited computing budget, then the BIE model will have

to suffice. Both models have documentation reports which give

explicit guidelines for exercising them. The manual for the BIE

model is entitled An_ Economi c Analysis of Resource Recovery Facil ities

and Waste Newspaper Recycling and is included as Appendix XI.

Since the RRPLAN model requires more effort to set up and execute,

it was necessary to prepare both a general purpose User's Manual

and a Programmer's Manual describing how to set up and test the

model on a particular computing system. (See Publications List 96

and 98.) The RRPLAN model is readily available to users on either

magnetic tape or punched cards. The BIE model is available only as

a listing within its documentation report (Appendix XI).

IX. 5. The Resource Recovery Planning Model: A New

Decision Tool for Solid Waste Management

The problem of identifying cost-effective methods for processing

a region's solid waste stream goes beyond the identification of

sites which are politically feasible. As fiscal pressures on communities increase, the economics of waste disposal becomes an ever more important issue. Resource recovery is thus an attractive

alternative, providing planners with the potential for reducing the

costs of processing the region's waste stream while conserving

valuable land, material and energy resources. The economics of resource recovery are significantly more complicated than other

approaches however, requiring an in-depth analysis of facility

design and cost as well as market size, structure and location.

The Resource Recovery Planning (RRPLAN) model was especially

designed to address the complicating factors mentioned above. On

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the one hand, RRPLAN explicitly incorporates potential economies of

scale in the construction and operation of a solid waste processing

facility. The model is thus able to support the basic tradeoff of

savings from centralized processing versus the costs of additional

haul required to bring it about. On the other hand, RRPLAN uses a detailed cost accounting system to attack the economic issues,

carefully measuring the effects on overall program costs due to

decisions affecting siting, routing, marketing, and financing. By

integrating the technical issues of processing with these four

major decision points, RRPLAN permits a wide variety of questions

to be examined carefully.

The model consists of a set of equations relating sources of

solid wastes, sites where the wastes can be processed and markets

for energy or materials recovery. The model begins with a source

of solid waste (e.g., a community in a region or a district in a metropolitan area). Each source has associated with it a location,

an estimated waste generation figure, a series of options for

preseparati ng paper, glass and cans, and a set of transportation

linkages to sites where the waste is processed. Sites, as used in

RRPLAN, may represent a landfill, a transfer station, an incinerator without heat recovery, or a resource recovery facility.

Each site has associated with it a location, the type of wastes it can process, the operating and capital costs required to process

the wastes, capacity considerations, outputs of wastes and

marketable items and transportation linkages. The model can handle

markets with downward sloping demand curves, constraints on capacity, and ones which can receive unlimited quantities of

recoverables. Each market has associated with it a location a revenue schedule and transportation linkages (See fig. IX. 1).

Appendix XII provides a more detailed description of RRPLAN as well

as a definition of terms. See Publications Lists 96 and 98 for

full details. The model approaches the problem of siting and

sizing solid waste processing facilities by approximating

non-linearities in the capital and operating cost functions with up

to three linear segments. Each segment has an intercept, a fixed

charge, and a slope, an incremental cost associated with increased

processing activities. The introduction of fixed charges causes

the solution domain to take on a lumpy appearance. Unfortunately,

this requires a specially designed optimization technique to

generate meaningful solutions. The technique used in RRPLAN

involves a fixed-charge linear programming algorithm with a forcing

procedure to insure that the model can pass over an area of

temporarily increasing cost in the solution domain to find the true

optimum. The RRPLAN method of forcing represents a significant

improvement over methods used in other models because each site

which was in the solution is forced out of the solution and vice

versa. This approach permits the solution domain to be searched in

a more coordinated way by operating on all activities (e.g.,

transportation, processing, marketing) associated with a particular

site. RRPLAN was originally developed by Edward B. Berman

Associates, Inc. The Operations Research Division at the National

Bureau of Standards incorporated numerous enhancements which should

make the model easier to use.

155

RRPLAN has been tested extensively through application to data

from up-state New York, central Mississippi and New York City.

Members of the NBS team met with representatives of each region

studied to discuss the implications that the use of the model would

have on project planning and implementation. The clarity with

which the implications of various assumptions could be measured

stimulated numerous discussions, indicating that the model may be

used extensively by solid waste management officials. A series of

mini-tutorials on the model were presented to officials from

Mississippi, New York and California. A two-day workshop for a broad cross-section of solid waste management officials was presented

at NBS in September, 1982. The workshop was sponsored by NBS, the

Association of State and Territorial Solid Waste Management Officials,

the Government Refuse Collection and Disposal Association, Inc.,

and the U.S. Conference of Mayors.

A complete set of documentation for the enhanced version of

the RRPLAN model was developed by the Operations Research Division

at NBS. The documentation consists of two reports. The first is a User's Manual which describes the input data requirements, the

logic and data flow of the model, its major assumptions and limitations, and guidelines for interpreting the output. Step-by-step

instructions on how to set up a test case as well as techniques for

controlling the structure of the solution and for handling large or unusually complex cases are included in the report (See Publications

List 98). The second report is a Programmer's Manual. It includes

a functional description of the model which should facilitate the

task of setting up the model on a different computer system. A

series of tests are outlined which will permit programmers to

verify if the model produces correct solutions (Publications List

96).

IX. 5. a. Examples of the Use of RRPLAN

IX.5.a.l. New York City

The municipal solid waste problem facing New York City involves

the interacting aspects of landfilling versus resource recovery.

Landfilling has been the basic reliance for disposing of most of

the City's refuse, but dwindling available space makes this a very

short-term solution. In the past, incineration was utilized to

prolong landfill space, but the increasing costs of non-energy

recovering incineration, as pollution control requirements become

more stringent, eliminated this method from consideration. City

officials realized that new refuse processing plants which incorporate energy and material recovery to help offset capital and

operating costs would be required to avoid the waste of former

times.

Rising energy costs also threaten the economic viability of

New York City and the quality of life of its residents. The city

is 62 percent more dependent on oil for its energy supply than the

rest of the Nation, and therefore is disproportionately vulnerable

157
to the problems associated with the Country's reliance on oil. New

York City energy consumers now pay over twice the national average

for electricity.

Over the next fifteen years, the City of New York plans to

build seven to ten waste-to-energy facilities throughout the five

boroughs and to convert existing incinerators to resource recovery

plants. These energy and materials recovery systems will significantly reduce the volume of solid waste that will have to be disposed

of in the City's remaining landfills, while at the same time

producing usable energy.

In support of this effort, the National Bureau of Standards

has provided technical assistance to New York City in determining

the economic and technical feasibility of resource recovery strategies

in the application of the Resource Recovery Planning (RRPLAN)

model. The Technical Advisory Center, Office of Recycled Materials,

worked closely with the New York City Department of Sanitation

(Office of the Deputy Commissioner for Resource Recovery and Waste

Disposal Planning) and the New York City Energy Office in the

collection of input data addressed to defining the essential

characteristics of the municipal solid waste stream, transportation,

waste disposal and processing sites, markets, and economic data.

The goal was to utilize these data to assist the City generate a preferred plan for disposal of municipal waste among planned or existing processing facilities.

The numerical results which will be summarized here must be

considered as only a rough first approximation to achieving this

goal. Development of a valid "preferred plan" depends upon considerable amplification and refinement of the input data. Nevertheless,

these first results certainly provide an indication of the general

nature of a feasible plan. Thus, the RRPLAN model was capable of

dealing with the data supplied in order to derive the basis for a least cost means to deal with the problem of residential waste in

New York City.

The modelling support effort required to analyze the New York

City data was shared between ORM, the Center for Applied Mathematics

at NBS, and Dr. Edward B. Berman, Edward B. Berman Associates, who

was under contract to NBS. The data received from New York City,

when put into a form readable by the RRPLAN model, exceeded the

capacity limitations of the optimization algorithm. The optimization algorithm used in RRPLAN consists of certain subroutines from

the Waste Resource Allocation Program (WRAP). This algorithm is

currently limited to 90 constraints (rows) and 360 activities

(columns). Since each source and each site which is capacitated

requires at least one row, it was decided to view New York City as having two parts. The first part consisted of Brooklyn and Queens,

and contained 32 major sanitation department districts and 15 sites

where municipal solid waste was processed. The second part consisted

of the Bronx, Manhattan, and Staten Island. It contained 27

districts and 16 sites.

158
In performing the two sets of computer runs, a number of

questions arose. First, the use of marine transfer stations

required an analysis of both the barge hauling capability of each

marine transfer station and whether or not a particular site could

be barge-fed. This was especially important for the Brooklyn Navy

Yard site where process steam was piped into the Con-Edison network

Second, since all of the marine transfer stations were not linked

to the Arthur Kill site on Staten Island where ultimate disposal

could be accomplished, it was necessary to set parametric limits on certain components of the marine transfer station's cost function.

This parametric analysis served two purposes. First, it prevented

certain capacity limitations in one part of the study from being

exceeded by shipments indicated in the other part. The parametric

analysis thus provided an overlay through which some degree of

interdependence among the two parts of the study could be captured.

Second, it permitted a limited analysis of how real flows (i.e.,

quantities processed) were affected by nominal values (i.e.,

process costs). This analytical capability was especially useful

in performing the aggregation of sources necessary for simultaneous

ly analyzing the entire city. The basic steps in the aggregation

were as follows:

1) Districts which were always linked to the same site were combined and "locked" into that site;

2) Districts which were not locked into a site were only

linked up to those sites which appeared to be efficient;

3) Sites which were not utilized were dropped from considera

tion; and,

4) The scale of processing activity was limited to what were perceived to be efficient levels.

The aggregated run consisted of 31 waste sources and 17 sites for

processing. (One site and its associated waste sources were eliminated from the study at Dr. Berman's request.) Of the 17

sites, all but five were transshipment points. The five resource recovery facilities consisted of two water-wall incinerators for

direct production of electricity, two water-wall incinerators for

steam generation, and a refuse-derived fuel plant. The site which

was omitted from the study was a water-wall incinerator for direct

production of electricity. (It is included in the discussion which

follows, however.)

The results of the run may be broken into two parts. The

first part shows all direct shipments from the waste sources to a marine transfer station or to one of the six processing facilities.

Results in table 1 suggest that over 30 percent of all wastes are first to be sent to a marine transfer station from which they need

to be sent via barge to another facility for ultimate disposal.

(Dr. Berman did not feel it necessary to handle process residue in

the run since it would occupy only a relatively small volume of

landfill space.) All wastes received at the marine transfer

159
stations can be sent to either the Arthur Kill processor on Staten

Island or to the Brooklyn Navy Yard. Table 2 shows that once these

shipments are taken into account a significantly different picture

emerges. Of the approximately 880 kilotons per year of wastes

going to the marine transfer stations, about 750 goes to the Arthur

Kill processor; the remaining 130 goes to the Brooklyn Navy Yard.

Thus Arthur Kill's portion of the total waste stream rises from 6.3

percent to 32.1 percent whereas the Brooklyn Navy Yard's only rises

from 10.6 percent to 15.1 percent.

Table IX. 1. Process Activity Levels: Direct Shipments Only.

Faci 1 i ty MSW Processed9

Percent of Total

(in ki 1 otons per year)

Arthur Kill 182 6.3

South Shore 930 32.1

West 215th Street 248 8.6

Canal Street 93 3.3

Brooklyn Navy Yard 309 10.6

Barretto Point 254 8.8

Marine Transfer Stations 878 30.3

As reported by computer printout.

Perhaps the most significant point which can be observed from

the results of the study is the model's preference for direct

production of electricity. The three sites which generate electricity al

are operating at 100 percent of their rated capacity (see

table 2). All other sites where resource recovery takes place are operating at less than 50 percent of their rated capacity.

Table IX. 2. Process Activity Levels: After Transshipment

Facil i ty and Type MSW Percent of Rated Percent of

Processed3 Capacity3

Total

Arthur Kill (Electricity) 930 100.0 32.1

South Shore (Electricity) 930 100.0 32.1

West 215th Street (Elec.) 248 100.0 8.6

Canal Street (Steam) 93 20.0 3.3

Brooklyn Navy Yard (Steam) 437 47.0 15.1

Barretto Point (RDF) 254 41.1 8.8

As reported by computer printout.

160
There are several problem areas which might reduce the usefulness of the results produced by RRPLAN, all of which stem from

difficulties in obtaining the data necessary to exercise the model.

First, the operating and capital costs figures used in the study were based primarily on data from the Louisiana case study. It is

unclear whether these figures are appropriate for the New York City

area. Second, the estimates for revenues from the sale of steam

and electricity to Con-Edison were very soft. As a result, both

recovery processes were assumed to generate the same revenue per

unit of input. It would therefore have seemed advisable to perform

a parametric analysis of the revenue function for each process.

Finally, the study excluded at least one recovery facility which is

currently under serious consideration.

IX. 3. a. 2. Central Mississippi

After the preliminary testing of the RRPLAN model with New

York City, the model was applied to data from the Jackson area of

central Mississippi. The object was to determine how RRPLAN could

be used as the basis for developing the economic requirements for a variety of municipal solid waste options which might be exercised

in the Jackson area.

Data on costs, markets, amount of MSW, inflation rates, and

sites in the Jackson area were provided by the Bureau of Pollution

Control of the Mississippi Department of Natural Resources. In

summary, approximately 360,000 tons per year of MSW were calculated

to be generated in the area. Steam and/or electricity from a potential waste-to-energy facility could be marketed--steam to the

packing industry and electricity to the local utility. Source

separation was not to be implemented regionally; there was little

or no market for recovered materials except aluminum. Landfill

could be used if necessary, i.e., siting could be accomplished.

Financing for a waste-to-energy facility could probably be obtained

at a 10 percent rate for a 15 year term; the facility lifetime was

to be 20 years.

The first task for RRPLAN was to estimate the cost of an all

landfill-no recovery option given collection costs, disposal costs,

land costs and labor and transport costs in the Jackson area. This

computation was meant to provide a datum against which all other

options could be compared. RRPLAN computed the discounted cost of

this option as $21.20 per ton for the 20 year period beginning

January 1, 1985 and ending December 31, 2004. This cost can be

interpreted to mean that it would take $21.20 of money at January

1, 1985 value to collect, transport, and dispose of one ton of

Jackson area MSW and that all MSW for 20 years could be disposed at

this discounted costs. All subsequent RRPLAN calculations were

discounted on the same basis. Hence, in what follows, all costs

are on the same basis, i.e., discounted to a value present as of

January 1, 1985. A cost difference between two options of $1 per

ton on this basis results in a $7.2 million cost difference for the

total of 20 years since 20 years times 360,000 tons per year is 7.2

mi 11 ion tons of MSW.

161
RRPLAN was then instructed to "site" a waste-to-energy facility

in the city of Jackson. In the absence of such a plant, eight

landfills ranged around Jackson would continue to receive 360,000

tons per year of MSW at a discounted cost of $21.20 per ton. Once

the new facility was in place, RRPLAN predicted that about 300,000

tons per year of waste could be processed there. Several landfills

would cease operations; the remainder of the MSW would go to the

rest. RRPLAN never predicted that siting, construction and use of

transfer stations would be economically advantageous for Jackson.

Note that RRPLAN selects the optimum activity level for each site,

i.e., waste tonnage and most economical transport links to utilize

these sites. For an input of 300,000 tons per year, facility

capacity needs to be about 1150 tons per day.

Next, RRPLAN was instructed to arrive at solutions for the

discounted cost per input ton as a function of steam and/or electricity revenues for various capital costs of the facility. Figures

IX. 2 and IX. 3 show the results. Note that each ton of MSW was assumed to yield six MBTU of steam or 625 kwh of electricity

delivered for use. (Assumes incinerator efficiency of 67 percent

for steam conversion and turbine efficiency of 35.6 percent.)

If Gj is designated as the savings per ton of MSW handled as compared to the all landfill -no recovery datum, then

Gj = $21.20 - D

c (IX-1)

where is the discounted cost per ton in the case of the waste-toenergy plant. If Gj is positive, then the recovery option is more economical than landfill, if Gj is zero, the two are equal and

if Gj is negative, landfill is more economical.

S

From figure IX. 2 the value of Dp for steam, Dp sales can be

deduced as:

Dq = $ 21.78 - 2.7 S MBTU

+ 1.07 x 10" 7

C

p (IX-2)

where ^wor^ 15 the sale price of steam per MBTU delivered at some temperature and pressure and Cp is the capital cost of the facility

in dollars.

For break-even, i.e., Gj = 0, then:

S

MBTU

= $ 4 X 10

" 8

C

F + °- 216 '

Figure IX. 4 shows S^gjy vs. Cp for this case. In general,

G

T

2 ' 7 S

MBTU

0.58 - 1.07 x 10

(IX-3)

(IX-4)

r Similarly, from figure IX. 3, the value of Dp for electricity.

D^, sales can be deduced as

D^ = 24.28 - 3.01 E

p + 1.12 x 10" 7

C

p (IX-5)

where E

p is the electricity sale price (cents per kwh)

162
65 70 75 80 85 90 95 100 105 110 115 120

FACILITY COSKMILLIONS OF DOLLARS)

Figure IX. 2. Relationship of steam revenues, facility cost

and final discounted cost per input ton as compared to no recovery-all landfill datum.

163
28

27

26

25

Z 24

h-^ 23

Q_

15

14

13

JACKSON ,MSAREA

RRPLAN, 1982

Ac*

NO RECOVERY

DATUM

J L I I I L

70 75 80 85 90 95 100 105 110 115 120

FACILITY COST (MILLIONS OFDOLLARS)

Figure IX. 3. Relationship of electricity revenues, facility

cost and final discounted cost per input ton as compared to no recovery-all landfill datum.

164
o

<

UJ

or< CO

co oo 5 cr>

CO <

—

I

o Q-

< or -3 or

I I I I

o

O

lO

o

OCD - o

x

OJ

^

O O

o <

o o

05

hC7) O O

00 O

o

o

CD

O

o

s

LU

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LU

<

LU

or

CD

o o o o o o o o O o

in o in q m q in o in q

CD CD in in ^* <3- ro ro cvi OJ

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in

o

o

o

4- ro O -t-> <d a

4-> > OJ

1/1 <D i

O •<- U -£=U

03 3

> -t-> •i- ro 3 "a

O"

ro - OJ

zj . £= -r- 0J>

OJ =

J- c

ai E >

ro O)

CU I +-> tn ro

<4— 5- O -Q CL~

•i- O

.£=

(/I C >> o +-> •f" *r~

+-> r—

ro T- i— U

a; ro

c -i- o 4-

-t-> T3c

-t-> ro 3 i

CLC r—

S- I ai >,

CL s_cv

COoU CU

s-o . oQj CSJ C

O J= . U -(-> rH

LO CM

•f- O V?-

X

CU

SQ3d3AH3a niQIAl U3d 30ldd 31VS WV31S
For break-even, i.e., Gj = 0 , then:

E

p

= 1.02

3 + 3.70 x 10

8

C

p (IX-6)

Figure IX. 5 shows E p vs. Cp for this case. Finally,

G

T

= 3.01 E p- 3.08 - 1.12 x 10" 7 C

p

. ( IX-7

)

In general, the return on investment, Rj , for the citizens if

the Jackson area is:

20 G

T

T

y /C

F

= Rj (IX-8)

where Ty is the number of tons of MSW actually converted to energy

per year of operation.

Equation (IX. 8) shows that if Cp is $100 million and T

Y is

300,000, the R. is 0.06 G-. or six percent per dollar saved over the

lifetime of the facility. Thus, G,- needs to be in the neighborhood

of $3 to $4 to fully justify the risk of investing $100 million now

in the recovery facility.

The cost of a facility to generate electricity is likely to be

higher than that of a facility to generate steam. The turbine

represents a considerable additional first cost . Thus, the value

E S of - is of interest in order to evaluate the additional

initial risk:

- = 2.5 - 3.01 E p + 2.7 S

MBTU

+ 1.1 x 10' 7

[cj: - Cp

5 ] (IX-9)

Equation (IX-9) enables one to calculate the affordable extra

E S turbine costs for any value of (D

c

- Dp) which is deemed to make

the risk acceptable. Figure IX. 6 shows S^y^ vs. E

p if this

difference is set at

$3.00, i.e., - = -$3.

In general, if a firm value of E p is available, then the sale

price for steam to be equivalent is:

S MBT[J

= 1.12 Ep - 0.372 [D^-D^-4.1 x 10"8

[Cp-Cp]-0.931 (IX-10)

On the other hand, if a firm price of SMRy.. is available, the

trade-off for electricity is:

E p

= 0.892 SMBTU

+ 0.332[D^] +

3.65 x 10" 8

[Cp-Cp] + 0.831. (IX-11)

Thus, complete risk analysis for virtually any reasonable scenario

can be performed in terms of market, price for steam or electricity

and capital cost of the recovery facility. Note that all of these

calculations assume that about 300,000 tons per year will actually

166
<4- O o 1LO c

QJ "O -C o +J u 03 o

"O CD>

ft) CD +J o

£Z OJ -C QJ o

U

c ID ro X > H

> **

re

<D E

>•

C 3

* o +J u

~C

+J da

S- CD +-> _J +-> > 3 u CD Q. O 1 C

< m

df

s- c

QJ ft) o -Q CL o Q. p

O in ST nsh

-<-> CO

it)

1>1 o o P a S_ QJ cu o +j +J >

(T3 C o o u

CD <t) O QJ LU cr 4- u i— >

LU

Ln < Xi—

i

LU

or re CD 3

(*) JM*>1 d3d 30ldd All0ldl03n3
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5

ELECTRICITY PRICE { / kw hr

Figure IX. 6. Risk of higher capital cost (for the turbine) to

generate electricity for turbine, costs ranging

from zero to $30 million: required electricity

revenue as compared to steam to yield an (arbitrary) improvement of $3.00 per input ton for

electricity sales.

168
be processed at the facility, and that all of the energy recovered

from this MSW can and will be sold at some price. What remains is

to consider the possibility that this value of Ty will vary.

In order to compute the dependence of D on the number of tons

peryear, Ty, which must actually be processeS, the general form of

the relationship for D

c may be written as:

D

c

= a(C

F /Ty

) + b + c R T (IX-12)

where RT

is the income or revenue for each input ton of MSW processed

through the facility. Note that if a tipping fee is charged per

input ton of MSW, its value is part (or all) of Rj. The coefficients

a, b, and c depend on the discount rate, terms of loan, lifetime of

the plant, transport costs and so on, i.e., all of the input data

for RRPLAN.

The results presented for Jackson as Equations ( I X -2 ) through

( I X -1 1 ) can be used to deduce a set of normal (most statistically

valid) equations in order to derive a, b, and c for this case:

D

c

= 0.033 (C

F /T

Y

) + 21.20 - 0.407 Ry

(IX-13)

Equations (IX-12) and (IX-13) are entirely analogous to the one suggested by Yakowitz (Publication List 78) for the approximate

break-even cost for any resource recovery facility. The difference

is that Equations (IX-12) and (IX-13) represents fully discounted

dollars for the lifetime of this facility while the relation given

by Yakowitz is in current dollars for the first year of a publically

owned facility.

If only T

y is allowed to vary in Eqn (IX-12) then differentiation yields:

= (aCp/Ty) ( -ATy/Ty

)

If C

F is $100 million, and T

y is 300,000, then

= 11.0 ("ATy/Ty)

(IX-14)

(IX-15)

Each one percent that Ty varies from 300,000 changes Dp by eleven

cents. The minus sign means that a decrease in tonnage will raise

Dp and vice-versa. Thus, if for some reason tonnage falls by about

ten percent, Dp will increase by $1.00. Therefore, in the Jackson

case, the amount of waste available for processing and the efficiency

of processing are crucial. Further details for the Jackson, MS case are in Publication List 112.

IX. 6. General Assessment of RRPLAN

The relationship given in eq. (IX-12) is the general economic

expression governing resource recovery or most other businesses

where a product is produced via the use of capital equipment and

sold on a per unit basis. For the case of resource recovery, one

169
wishes to minimize the values of a, b, and c. In effect, the

optimizer section of RRPLAN uses advanced techniques of operation

research to select values for a, b, and c, given the input data

supplied so as to minimize D^. However, uncertainties in a, b, and

c depend upon:

1) Formulation of the model mathematically.

2) The operations research algorithm used to optimize the

mix of a , b, and c.

3) The data from which the numerical values of a , b and c are derived, e.g., discount rate, life of capital stock,

inflation rate, market stability, labor costs, insurance

costs, transport networks and costs, etc.

4) The statistical estimate of error in the normal equations

used to obtain a, b and c as specific numerical results.

Differentiation of eq. (IX-12), assuming that all of the

variables can have uncertainty and are independent of one another

yields:

AD

C

= aC

p /T

Y (Aa/a + AC

p/CF

- AT

y /Tv

) +

b(Ab/b) + cR

t

(ac/c + AR

T

/R

T

). (IX-16)

Items (1) through (4) on the foregoing list are responsible for the

uncertainty terms for a, b, and c. The other uncertainty terms

represent cost variations, e.g., overruns for the capital stock,

variations in tonnage processed annually, and cost variations for

the revenue per ton actually processed.

Equations (IX-12) and (IX-16) represent the economic and

technical challenges facing planners and decision makers in

selecting an optimum scenario for resource recovery. (If other

factors, such as using the outputs of resource recovery to fuel

other industries, enter, the process becomes even more complex.)

In the case of resource recovery, RRPLAN, in effect, provides the

best estimates for a, b, and c that are likely to be obtained from

any given set of input data.

Nevertheless, a method to evaluate the functionality of a, b,

and c with respect to variations in input data would be extremely

useful. Then, local planners could be in a position to assess the

effect of specific uncertainties on the economics of any resource

recovery scenario. For example, in the case of the data for

Jackson, if C

F

= $100 million, Tv

= 300,000, RT= $30, then eq.

(IX-16) becomes: Y 1

AD

C

= 11 (Aa/a + AC

F /C

F

- aTy /Tv

) +

21.20(Ab/b) + 12.21(Ac/c + AR

T

/R

y

). (IX-17)

170
Assuming that Cr, TY and fU are known to within one percent, but

that a, b, and c are known to within five percent, eq. ( I X -17

)

yields a ADp of $2.56 while eq. (IX-12) yields a Dp of $20.00, or a relative uncertainty of about 13 percent in Dp, Hence, for purposes of planning in Jackson, the uncertainty of the "real world"

can perhaps, be guessed as about 20 percent. Still, if a com- bination of costs, tonnages and income can be obtained such that

RRPLAN predicts a reduction in Dp of $3.00 to $4.00 with respect to

the all landfill-no recovery case (which is also subject to similar

uncertainty computations), then the risk may be associated with

investing in the resource recovery facility is probably worth

serious consideration.

The role of RRPLAN in assessing resource recovery options can be summarized as follows:

1) RRPLAN selects a minimum cost plan by comparing the

various D^ values for each option.

2) In every case, the optimizer minimizes individual Dp

values as a function of the specific input data offered

by the user.

3) RRPLAN does not compute unique values for the variables

a , b , and c in eq. ( IX-12)

.

4) By varying the input data to RRPLAN, specific estimates

for a, b, and c can be obtained as well as preliminary

estimates for the uncertainties in these variables.

RRPLAN probably provides the best available means to

predict a, b, and c accurately.

5) Equation (IX-16) represents the "risk evaluator" for a specific set of data and the uncertainties in these data.

6) Until all terms in eq. (IX-12) and (IX-16) are evaluated

numerically for various options, a planning basis for a waste management strategy is incomplete.

Thus, RRPLAN, if used properly, provides the foundation for

planning. But considerable additional assessment may well be

necessary in order to choose the proper strategy for a given

region. This assessment involves probabal istic estimation for the

input variables (discount rate, costs, etc.) followed by multiple

RRPLAN evaluations. The results will provide values for all terms

in eq. (IX-12) and (IX-16). Unless all of these steps are taken,

RRPLAN results need to be treated with extreme caution.

RRPLAN, as developed for and by NBS/0RM, represents an appropriate means to begin evaluation of specific resource recovery options

for a city, state, or region. The input data requirements will

tend to require the prospective RRPLAN client to determine as accurately as possible each item of data. If these data are not

properly obtained, the risks of adopting a resource recovery plan

171
become much greater; the U.S. has had several cases where resource

recovery options have not lived up to proponents expectations.

Careful data assessment, RRPLAN and solutions to eq. (IX-12) and

( I X - 16 ) should help to reduce the risk associated with resource

recovery. In turn, the data gathering process and the subsequent

RRPLAN and probablistic analysis should clearly highlight potential

or actual institutional problems. (See Appendix XVI for further

details.

)

RRPLAN can be applied to recovery of hazardous or non-hazardous

industrial waste with some modifications. Thus, all waste classes

which were dealt with by RCRA can be taken into account. The

preceding general assessment is appropriate for all classes of

waste.

IX. 7. General Market-Related Activities of NBS/ORM

IX. 7. a. Fate of Fiber

One general market area which NBS/ORM chose to consider

directly concerned the burn, recycle or bury issue for wastepaper.

Established wastepaper collectors, recyclers and dealers became

concerned that waste-to-energy facilities might reduce supply of

waste paper and/or bid up the price to a point where recycling was

no longer economically feasible. NBS/ORM analyzed the situation

and reported on the economics of several possible options for

wastepaper (See Publications List 78 for details). In addition,

both the BIE and RRPLAN models allow for detailed consideration of

the optimum uses for waste paper in a given region.

NBS/ORM concluded that a universal solution for the "best" use for wastepaper does not exist. Nevertheless, for most situations,

source separation of the newsprint fraction office paper including

computer materials, and corrugated stock will not seriously harm

the economics of a waste-to-energy facility. On the other hand, as shown in NBS/ORM Publication #78, certain situations could occur in

which the waste-to-energy facility's requirements could adversely

affect businesses engaged in recycling of wastepaper.

IX. 7. b. Other Market Studies

Many other NBS/ORM activities, which have already been described,

contributed directly to fulfilling the mandates of Section 5003(1)

and 5003(2) of RCRA concerning markets. These include the procurement analysis with state agencies (Publications List 56), the bid

modifier development (Publication List 74), the GLBC/Michigan

results (Publication List 95), and the waste solvent based recovery

of metal from steel making wastes (Publication List 115). The

entire thrust of the recycled oil program was aimed at showing that

such oil could be equivalent to virgin oils. Thus, used oil could

gain general market acceptance. The U.S. Conference of Mayors

developed, under a DOC grant, a critical issue report on energy

markets for recovery from MSW.

172
In addition, NBS/ORM participation with the Waste Management

Policy Group (WMPG) of the OECD, provided many useful insights into

the market issues associated with recovered materials destined for

waste. Other industrialized nations have been applying resource recovery methods longer than the U.S. Experience concerning wasteto-energy technology and economics, tire recycling, source- separation techniques and results, conditional effluent taxes and

other waste management issues was shared within the WMPG. Several

OECD publications, e.g., Waste Tyres, Source Separation, Energy

from Municipal Waste are available or in press. NBS/ORM contributed

to these efforts; the results provide a useful summary of economic

and technical issues associated with recovery and marketing of

materials destined for waste.

IX. 8. Efforts to Encourage Development of New Uses for Recovered

Materials (Section 5003(3) of RCRAT

An example of innovative technology which reduced barriers to

the use of reclaimed newsprint was the development of a quick,

economically and environmentally valid de-inking process for

newspapers. This process is crucial to the reclamation of many

thousands of tons of old newsprint for recycling as usable newsprint. While this de-inking process is a success story, many

technical, institutional and economic barriers continue to exist

with respect to new uses for recovered materials.

One case which NBS/ORM dealt with directly concerned problems

associated with recycling of bi-metal beverage cans, i.e., cans with ferrous metal bodies and aluminum tops. These tops seriously

degrade the processing of detinning ferrous cans to reclaim steel

and pure tin by consuming the chemicals needed. Thus, the return

on investment to the detinner may be inadequate, and a potential

market for waste cans may be lost. NBS/ORM realized that if some form of existing or innovative technology—either providing an all

steel can with easy to open yet safe top, or removing the existing

difficulty in the detinning process—the potential market barrier

might be reduced or even eliminated.

Developing new technology for can tops was clearly the purview

of the private sector. Therefore, in cooperation with representatives of the ferrous scrap and detinning industry, NBS/ORM sponsored

efforts to reduce the difficulties created by the presence of the

aluminum tops in the detinning process.

Several tons of can scrap were subjected to special shredding

and grinding operations. The object was to use the difference in

hardness between the ferrous (hard) and aluminum (soft) to provide

chips of the ferrous and almost an aluminum powder. This material

could then be spread out and subjected to a magnetic separation.

Thus, the two metals were separated into aluminum scrap and nearly

aluminum free ferrous for the detinner. As a bonus, detinning

efficiency was enhanced since the chips of ferrous offered higher

surface area to the chemical bath. In times of strong demand for

ferrous scrap, this process is economical. When the demand for

173
ferrous scrap is weak, this process is economically marginal

Publications List 117 for details).

(See

Other major direct NBS/ORM efforts to encourage new uses for

recovered materials include the GLBC/State of Michigan work,

procurement efforts, work on ash and the solvent based recovery of

metal from steel mill scale and sludge, all of which have been

described previously.

IX. 8. a. Technology Commercialization Program (MBDA)

Within the Department of Commerce, the Minority Business

Development Administration (MBDA) developed a technology commercialization program meant to assist minority firms to enter and compete

in the rapidly growing areas of the economy (industries), which are technology-based, and to enter these new industries at the earliest

practicable stage so that they can compete as the industry grows

rather than entering after the initial growth has taken place and

the opportunities have been diminished.

The program has established the first nationwide network of

resources, in both government and industry, specifically designed

to provide the sophisticated level of services required for technologybased minority firm opportunities.

The MBDA program, with its government/industry partnership,

has begun to define and attack those problems which inhibit technological growth as they relate to minority business.

From the beginning, the focus of program activity has been to

coordinate government and industrial resources (i.e., create a public/private sector partnership) in support of minority enterprise.

The program operates on the following four assumptions:

o The process must be profit-oriented.

o It must be set primarily in the private sector with the

government role one of continuing coordination and resources

development.

o The system must utilize the normal business process of the

participants to the greatest extent possible.

o The cost to the minority firm in determining product potential

must be kept at the absolute minimum.

How it operates — The program provides a much needed brokering

function for the development of new products and services, providing

a coordinated process for gaining access to and matching information

regarding: available technologies with commercial potential:

markets looking for new products; and sources of financing available

for new product devel opment--al 1 to be matched with interested and

qualified minority firms.

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One of the program's principal functions is to provide, where

possible, such direct services as evaluations of a new product

regarding its technical soundness and potential market. This

process helps to facilitate a match with an appropriate potential

source of financing.

o The Technology Information System keeps program participants

updated on the status of all of the projects that TCCs and the

Sectoral Development Unit are developing, and is beginning to

build a pool of information on technologies, markets, adaptive

processes, source of financing, and the MBE by specialty.

o The Sectoral Development Unit, in its initial year of operation,

will concentrate on identifying and ranking sectors of the

economy with growth potential. This effort will be compatible

with the commercialization process being carried out through

the TCCs.

Who benefits? —The primary beneficiary is the minority firm who

commercializes the technology and is provided with the opportunity

to enter developing markets. Additionally, developers of technology,

both in government and industry, sources of financing, markets

seeking new products and services benefit by participation in the

program.

What are the important features? --The brokering and evaluation

functions described above and the public/private sector partnership

which has resulted in a unique commercialization process, as opposed to the previously disaggregated approach to technology

transfer of utilization, are the most important features of the

program.

Number of benef iciaries --The generic process of technology commer- cialization is long term in nature. Recognizing this, we have

specifically designed our program to be flexible in nature and to

respond to the need of the individual project under development.

It is not an assembly line process. We are providing assistance in areas which were formerly closed to minorities and in areas of the

economy which offer the greatest opportunities for growth.

Types of businesses benef ited--The program is designed to assist

minority firms which are or have the capability of becoming second

or third tier firms. This would include manufacturers,

distributors, and retailers in growth areas of the economy.

One of the firms aided by this program developed a thermal

method to recycle iron units from oily mill scale and sludges. The

oil helped provide energy for the process. The iron units produced

can be sent directly to the blast furnace. (This process was so successful that its inventor was named Small Business Man of the

Year in 1981.) The innovative technology thus reclaims energy,

reduces hazardous waste and provides iron for the blast furnace

which otherwise would have been destined for waste.

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Another firm has developed methods to recycle solvents and

other useful substances from liquid hazardous waste. In addition,

this firm's treatment technology also reduces the volume of such

waste which must be disposed. A third effort dealt with zinc

recovery from a smelter in New Mexico.

The Economic Development Administration (EDA) also supported

efforts to develop new uses for recovered materials. Results

relating to electric furnace dusts have already been discussed. In

addition, a wood waste-to-alcohol facility in Maine received EDA

aid. The experimental pyrolysis unit for converting waste-to-energy

in the City of Baltimore also received partial support from EDA.

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X. EVALUATION OF COMMERCIAL FEASIBILITY OF RESOURCE RECOVERY

FACILITIES (SECTION 5004 OF RCRA)

X. 1. Congressional Mandate

Section 5004 of RCRA (42 USC 6954) authorizes the Secretary of

Commerce to evaluate the commercial feasibility of resource recovery

facilities, to publish the results of this evaluation and to

develop a database for purposes of assisting persons to select such

a system. Department of Commerce Organization Order 10-1, Amendment

5 caused activities under Section 5004 to be placed under the

purview of NBS/0RM in January 1980.

X. 2. Specific Activities

Prior to 1980, the Office of Environmental Affairs (0EA) of

DOC had initiated two important activities relating to Section

5004. (Note that 0EA ceased operations in 1981.) These activities

were:

1) Organization and sponsorship of an International Conference

on Urban Industrial Development through Resource Recovery

(Held April 17-18, 1980 in Detroit, MI); and

2) Development of a project whereby the U.S. Conference of

Mayors (USCM) evaluated possibilities for urban-industrial

development through resource recovery (this project was funded by EDA).

X.2.a. International Conference on Urban Development Through

Resource Recovery

The Detroit Conference was meant to inform persons such as Mayors, county, and state officials as well as representatives of

private enterprise and the general public of the DOC concept of resource recovery as an integrated industrial strategy to promote

urban economic development. Topics covered included:

o Economic impact of resource recovery and related industries

Effect on employment, the tax base, and other economic considerations, both directly and through the industries resource recovery

attracts.

o Policy concerns

What is holding up further economic development through resource

recovery, and how can some institutional barriers be overcome?

o Resource recovery industrial parks

Can this concept work in any but the largest of cities? What

variations on this siting concept are viable? What has been tried

thus far?

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o Attracting industry

How resource recovery fits into an industrial development strategy,

by attracting or keeping related user industries.

o Lessons from the Europeans

How various Western European communities solved some of the industrial

barriers facing U.S. projects through government/industry cooperation.

Some 300 persons attended this Conference. A number of

attendees contacted the NBS/ORM Technical Advisory Center after the

Conference for specific follow-up assistance. Most of these

requests concerned the need for technical and economic data to

evaluate the commercial feasibility of various resource recovery

options. The Technical Advisory Center provided these data along

with a very brief analysis of the specific problem raised in the

request. For example, a state prison official was provided data on

small waste-to-energy units as well as a calculation method by

which he could determine if such a unit could economically and

reliably provide supplemental energy to the prison. Several dozen

such requests were answered.

The Conference placed special emphasis on the feasibility of resource recovery options in terms of the broad range of questions

and concerns facing city, county, and state administrators. In

summary, the major concepts which the Conference dealt with included:

1) Resource recovery programs can be used as an urban

economic development tool when the benefits derived from

purchasing energy and materials from resource recovery

are concentrated in urban commerce and industry, and

where there are multiple opportunities for marketing the

recovered energy and materials.

2) Energy produced through resource recovery facilities can

be sold to specific industrial or commercial clients,

targeting energy benefits to particular users. Additional

economic development benefits can be derived by developing

industries which utilize recovered resources. If fully

developed, a total economic development/resource recovery

effort could close the cycle of manufacturing, consumption,

and disposal in a given geographic area.

3) Resource recovery can be viewed by economic development

agencies and project developers as another tool to be

added to their list of incentives which can attract or retain industries in their cities. This interaction

between resource recovery and economic development

activities may result in decreasing the overall costs

while streamlining the development of resource recovery

programs.

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4) Approaching resource recovery from an economic development

perspective may also provide additional opportunities to

organize public and private sector interests so as to

realize additional energy, economic, and environmental

benefits from a resource recovery effort. (See Publication List #77.

)

X.2.b. U.S. Conference of Mayors Grant

In order to evaluate the feasibility of applying these concepts

in the real world, DOC acting through OEA and EDA provided a grant

to the U.S. Conference of Mayors to perform this evaluation by means of a series of case studies of cities which had or were then

developing resource recovery programs. The initial USCM survey

found that:

o The majority of practices appear to be directed toward waste

disposal rather than conservation objectives.

o Many of the planning processes used by communities to develop

Resource Recovery Systems do not assure that the best technology

available will be selected for that particular site.

o The process of Resource Recovery development requires the

coordination of a variety of institutions and political

entities. This in turn requires the development of local

political expertise and local leadership that is notably

missing in the current planning and implementation activities.

o The sciences most frequently considered in the area of ResourceRecovery-from-waste, do not systematically consider the

alternatives beyond the energy recoverable; those being

extracted materials and new raw materials for industrial use.

o In assessing the economics of Resource Recovery, communities

do not appear to adequately take into account such economic

benefits as job creation, conservation, overall community

economic benefits, or the potential to obtain from a coordinated

resource recovery effort benefits which can be secured for

target populations within a community.

o The current methodology by which many communities currently

approach the development of resource recovery options and

programs is expensive, and often unproductive. This is a significant national problem in that it involves expenditures

of considerable size for planning, feasibility study, and

capital investment.

o The concept of Economic Development through Resource Recovery

appears to be a concept around which many of these issues can

be focused and resolved.

Specific case studies were carried out in order to:

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o develop a database including the technical, financial, and

political aspects of resource recovery, past and present;

o assess the role of the political leader and the various

institutions (private and public) in the project dynamics;

o determine how local decisions regarding waste disposal have

been made in the past - and what informational resources necessitate sound future decisions;

o examine the potential for the Urban Resource Recovery Industrial Park concept as an economic development tool;

o examine the acceptance of resource conservation - energy and

materials recovery; and

o increase the awareness of the local officials regarding

resource recovery as a potential economic development tool.

The issues addressed in the case study data gathering process

were represented by the following general categories:

o Background of Project

Motivation

History (Key Actors, Key Events)

Alternatives Considered

Technology Employed (How was it procured?)

Markets Used (Energy & Materials)

Costs (Planning, Construction, Operating)

Financing Approach (Alternatives Considered)

Siting Approach

Decision-Making Process (Type of Government Structure)

Public Participation (Project Team)

Institutional Barriers Overcome (Especially Waste Stream)

Socio-Pol i tical Impacts

* Support for Project (Constituency)

* Political Debate? Liability or Asset?

* Impact on Community (Pollution, Traffic, Image)

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o Economic Development Issues

Benefits to Municipality of Resource Recovery Facility

* Jobs

* Ratables

* Taxes

* Host Community Fees

* Improved City/County Relations

* Energy & Materials Produced

* Industries Supported (Markets)

* Reduction in Environmental Costs (Landfills)

* Reduction in Collection Turnaround/Maintenance

* Reduction in Transportation Costs for Products

Manufactured

Regional and National Benefits of Resource Recovery

Faci 1 i ty

Reduced Landfill Volume Required & Number of Facilities

* Energy Conserved

* Energy Produced

* Balance of Trade Improvement

* Reduced Welfare Costs (Due to Unemployment)

* Regional Reinvestment of Capital

* Minority and Women Employment

* Small Business Participation

* Open Space Preserved

o Current Problems

Facility Operating Technically?

Facility Economically Viable?

Waste Stream Problems?

181
Market Problems?

Eleven critical issues were identified:

1) Utility vs. industrial markets.

2) Development of new marketing strategies (including the

desire for multiplicity of these markets).

3) Public vs. private cooperation in project development.

4) Priorities and goals among state and federal energy,

environmental, and economic development agencies and

their interrelationship or lack of it.

5) Recycling as an economic development tool/what industry

can do to reuse/recover its own waste(s).

6) Life cycle costing with consideration of problems due to

duration of time for project implementation.

7) Financing/tax incentives.

8) Large scale vs. small scale regional ization.

9) Role of the consultant.

10) A champion with strong leadership qualities able to

coordinate a team effort is paramount in providing

continuity and minimizing the time for project completion.

11) The lack of technical expertise at the local level

warrants an educational program so that key actors can make reasonable decisions and, if necessary, choose

technically adequate consultants.

The USCM produced a series of 12 community case studies plus

two critical issue panel reports. The latest version was updated

in March, 1982. The case studies include the cities of:

o Akron, Ohio

o Baltimore, Maryland

o Berkeley, California

o Bridgeport, Connecticut

o Dayton, Ohio

o Fresno, California

o Nashville, Tennessee

182
o Newark, New Jersey

o North Little Rock, Arkansas

o Port Authority of New York

o Saugus, Massachusetts

'o Seattle, Washington

The critical issue reports are:

o Recycling

o Resource Recovery Energy Markets

The case studies provide a detailed analysis and report on the

issues affecting the commercial feasibility and performance of the resource recovery options selected by the respective cities. Each

contains a summary data page giving salient facts concerning costs,

output, general performance, etc. Thus, the complete set provides

a good overview of the feasibility requirements for a wide variety

of resource recovery systems as well as the underlying data.

X.2.C. Projects in cooperation with the city of New York

X.2.C.I. Feasibility study involving conversion of an existing

incinerator to an energy recovery unit

The Department of Energy and DOC decided in 1980 to work with

the City of New York to develop a joint project which would enhance

economic development by more efficient use of energy. Energy from

municipal waste was one of the prime "new" sources of alternate

fuel to be considered. NBS/ORM became the technical representative

for the entire effort; these responsibilities were assigned by the

Associate Deputy Secretary of Commerce with the assent of DOE and

NBS management. The basic goal of the project was to develop

practical methods to use waste to provide energy to industrial

enclaves, e.g., Brooklyn Navy Yard site or Bronx market, and/or to

provide supplemental energy for residential district heating.

NBS/ORM personnel worked closely with New York City personnel from

both the city's Energy Office and from the Department of Sanitation

on this project. (The application of RRPLAN to New York. City was part of this project as well; see Section IX. 4 of this report.)

New York, in company with many large population centers, used

incineration—without energy recovery—as a major means to dispose

of MSW prior to 1970. But the requirements of regulations associated

with the Federal Clean Air Act and companion state statutes forced

many of these incinerators to cease operations. However, better

air pollution control devices are available now. Furthermore, if

these abandoned incinerators could be retrofitted to reclaim energy

in a technically and economically sound manner, many community

183
benefits would accrue, e.g., more energy, use of the abandoned

facility, more waste disposal capacity, approved site.

Therefore, NBS/ORM and New York City officials agreed that the

joint project should thoroughly investigate the feasibility of

refurbishing such abandoned incinerators. The Southwest Brooklyn

Incinerator was selected by city officials as having the highest

priority in terms of need. On September 23, 1982, a detailed

report on this feasibility study was submitted to NBS/ORM on behalf

of the Department of Sanitation of New York City (for complete

citation, see Publications List #99). The findings of this report

are summarized in the paragraphs which follow.

The Southwest Brooklyn Incinerator is one of six 1,000 ton per

day (tpd) incinerators built by the City of New York in the 1950s.

Of these six, only three are presently operating: Betts Avenue,

Greenpoint, and Southwest Brooklyn. Each incinerator is equipped

with four furnace trains, each designed to process 250 tpd of

municipal refuse. The inoperative incinerators include: Hamilton

Avenue, South Shore, and Gansevoort.

Both the heating value contained in municipal refuse, which

can be converted into useful energy, and the material value of the

refuse ash, which can be recovered and recycled into a useful

product, offer an opportunity to convert the solid waste into a useful resource and product. The primary purpose of this investigation was to examine both the technical and economic feasibility of

exploiting the heating value of the refuse and the material value

of the incinerator ash processed at the Southwest Brooklyn incinerator.

Based on the results of field testing, the combustion of

municipal refuse at Southwest Brooklyn would be capable of generating 2.2 trillion Btu of energy annually. Enough of this energy

could be recovered to produce 93.8 million kWh of electricity,

which could supply the annual needs of almost 17,000 homes, or produce 1.2 billion pounds of steam to satisfy the annual heating

requirements of approximately 10,000 homes during the heating

season

Quenched incinerator residue is currently transported by barge

to New York City's Fresh Kills sanitary landfill on Staten Island.

On the basis of a review of market conditions for ferrous recovery

and the utilization of incinerator residue as asphalt aggregate,

the residue has a potential economic value capable of generating

revenues of $1 ,000-$3 ,000/day . Materials recovery could offer the

additional economic and environmental benefits associated with the

reduction or elimination of barging the residue to Fresh Kills.

On the basis of the examination of both the technical requirements and the economics of recovering energy and materials from

processed waste, the following conclusions were drawn:

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1) The recovery of energy for electricity generation and/or

electricity generation with steam production for district

heating during the winter months is both technically and

economically feasible, and appropriate action should be

taken as soon as practical to plan for the preparation of

construction contract documents for such an undertaking.

2) There exists an opportunity in the City of New York for

the recovery of incinerator ash for use as asphalt

aggregate in City-owned asphalt production facilities in

Brooklyn. Further testing is required to verify the full

potential of ash utilization. Plans for verification

should also proceed as soon as practical.

Plans for energy and/or material recovery at the Southwest Brooklyn

Incinerator are especially attractive because:

1) The existing furnaces and structures represent a significant portion of the processing systems required for a new refuse-to-energy facility. It is estimated that energy

recovery at a new refuse-to-energy facility would require

a capital investment greater than twice that of the

equivalent energy recovery facility at Southwest Brooklyn.

2) The existing facility eliminates the necessity for

comprehensive siting investigations.

3) Local trucking routes have already been established.

4) Additional environmental impacts and licensing requirements

are mi nimal

5) Energy and material recovery feasibility demonstrated at

Southwest Brooklyn can be directly applied to the other

operating incinerators at Betts Avenue and Greenpoint,

and may be applicable to those incinerators that are presently inoperative.

The technical feasibility associated with energy recovery from

Southwest Brooklyn was evaluated by determining the following:

1) Heat content of the refuse, and the energy available for

steam generation.

2) Requirements for the control of waste heat boiler corrosion

problems.

3) Requirements for the integrated control of boiler/turbine

operation for electricity generation.

4) Available district heating market.

5) Total energy output.

185
A field testing program was undertaken in which flue gas

quantities and temperatures were monitored to determine the heat

available for steam generation. This eliminated the need to rely

on literature values for the heat content of refuse to determine

the energy available for steam generation.

A detailed review of potential corrosion problems, and mitigating measures, as well as the expected waste heat boiler operational

life, was undertaken to determine process modifications and equipment

requirements to minimize the impact of corrosion on heat recovery

operation. This evaluation was undertaken by reviewing the literature for corrosion problems associated with municipal refuse

combustion, site visits to facilities with dirty gas waste heat

recovery applications, and discussions with both European and U.S.

waste heat boiler manufacturers concerning operating experiences

and recommended operating and design practices.

A comprehensive review of boiler/turbine operation utilizing a fuel with the fluctuating heating value characteristics of municipal

refuse was undertaken to ensure that compatible boiler/turbine

operation could be effected. This review was integrated into the

control systems for the boiler/ turbine operation.

A market survey of potential energy users within a three-quarter

mile radius of the incinerator was implemented to determine the

available steam market.

An energy availability model was constructed on the basis of

energy and equipment availability, and the effect of wet refuse on energy output. On the basis of this analysis, the efficiency of

the waste heat boiler and turbine output was projected.

The economic feasibility of energy recovery was addressed by

comparing projected revenues against projected costs using revenue projections from New York State Power Pool projected electricity

rate schedules and Power Authority (PASNY) projections of oil

replacement costs for the steam rate schedule.

Three energy recovery options were evaluated:

1) Generation of electricity only.

2) Cogeneration of electricity with steam distribution to

all users within a three-quarter mile radius of the

incinerator (full steam loop).

3) Cogeneration of electricity with steam distribution to

selected users (partial steam loop).

The installed equipment (capital) cost in 1981 dollars, for each

alternative is as follows:

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1) Electricity only $26,972,000

2) Cogeneration with steam distribution to

all users $53,082,000

3) Cogeneration with steam distribution to

selected users $32,309,000

Potential revenues associated with the electricity-only alternative,

although less than either cogeneration option, yields the most

favorable cash flow forecast. Three deficit years are projected

utilizing a rate structure that provides for electrical revenue

rates at $0.0770 per kWh in 1986, and escalating thereafter in

accordance with New York State Power Pool projections.

The cogeneration-to-selected-user alternative, using Power

Authority revenue projections of $10.31 per 1,000 lbs in 1986, is

the second most favorable option with only four years of deficit

cash flow. This alternative will become more favorable as the area

in the vicinity of the incinerator develops and the demand for

district heating increases.

On the basis of a review of costs, revenues, and implementation requirements, the electricity-only alternative was recommended

for immediate consideration. It was also recommended that this

system be designed with the flexibility to incorporate steam or hot

water generation for future district heating purposes.

The recovery of ferrous metals from incinerator residue and

the utilization of processed residue as aggregate material for

bituminous paving mixtures were judged to be the two areas with the

greatest potential for market penetration.

Market interest for recovered ferrous material has been

expressed by members of the Institute of Scrap Iron and Steel in

New York, as well as other ferrous metal dealers.

The New York City-owned Hamilton Avenue Asphalt Plant could

provide a reliable market for asphalt aggregate. This plant has a design capacity of 7,200 tpd, as compared to the incinerator's

residue generation rate of 200-300 tpd. Residue aggregate processed

to specifications could be blended with natural materials for use

in asphalt mixtures.

Both ferrous metal and residue aggregate could be recovered

with little interference with existing operations. The incinerator

residue could be diverted from the existing barge conveyors through

rotating screens and magnetic separators to classify residue sizes

and separate ferrous materials.

Two recovery concepts were investigated: partial recovery and

total recovery.

The installed equipment (capital) cost in 1981 dollars for

each option are as follows:

187
Partial recovery $796,500

Total recovery $945,500

On the basis of projections of aggregate replacement costs

and/or ferrous resale the partial recovery of ferrous and aggregate

from incinerator residue was recommended for further investigation.

This alternative could also be modified to provide for total

recovery of residue at some future date.

Given the present district heating market at Southwest Brooklyn,

generating electricity is the most promising economic alternative.

It also is the simplest to implement since it does not require the

construction of a distribution system, or negotiations with potential

steam customers. In addition, it has the flexibility to incorporate

steam or hot water distribution in the future.

With increased development in the vicinity of Southwest

Brooklyn, the economics of district heating, with its more efficient

utilization of the heat value of the refuse, are likely to become

more favorable.

A fourth air pollution control train for furnace No. 1 could

be installed at Southwest Brooklyn to meet present air pollution

control requirements and to provide the flexibility to operate the

incinerator and the waste heat boilers independently.

X.2.d. Conversion of the San Diego County, CA Resource Recovery

Recovery Facility to a Solid Waste Research Center

In September 1972, the County of San Diego, California,

accepted a $3.8 million grant from the U.S. Environmental Protection

Agency (EPA) to demonstrate a flash pyrolysis process developed by

a private firm. This firm had previously and successfully conducted

bench scale and pilot plant studies of the flash pyrolysis process

on municipal solid wastes at their La Verne, California, Laboratory

facil i ty.

The demonstration facility, known as the San Diego Resource

Recovery Demonstration Facility, was designed to produce a liquid

fuel, called "Pyro-fuel ," through the process of extracting and

pyrolyzing the organic fraction of municipal solid waste, and was also designed to recover substantial quantities of glass, aluminum

and ferrous metals for resale to help offset plant operating costs.

The facility was complete with electronic truck weight scales,

receiving area, shredding area, drying and separating facilities,

pyrolysis unit, fuel oil storage tanks, buildings, control room,

pollution abatement and associated equipment.

Construction of the demonstration plant at the El Cajon site

» began early in 1976 and was completed in December of 1976. For the

following eight months, the plant underwent "shakedown" procedures

to bring all process systems and sub-systems on line into proper

operational condition. Demonstration testing commenced on August

16, 1977 and terminated on March 13, 1978.

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The San Diego County Resource Recovery plant was designed to

process 200 tons/day (181.5 Mg/Day) of municipal solid waste by a flash pyrolysis system to produce 200 barrels of synthetic oil

(pyrofuel), 15 tons (13.6 Mg) of ferrous metals, 10.7 tons (9.71

Mg) of mixed colored glass, and 1.2 tons (1.09 Mg) of nonferrous

metals (primarily aluminum), all in the same time period. The San

Diego Gas and Electric Company contracted with the County of San

Diego to purchase the pyrofuel as a supppl emental fuel for one of

their existing steam-generating boilers.

Unfortunately, certain difficulties arose during the seven month trial period. Most important was that the flash pyrolysis

system did not perform well enough to warrant further commercialization efforts, i.e., technical and economic problems were uncovered.

In addition, local markets for the recovered materials were not

strong enough to justify further development of these systems.

By 1980 the owner, San Diego County, was prepared to either

find some use for the facility or scrap it. NBS/0RM personnel

realized that the defunct facility might be made to serve as a research test bed for investigating the commercial feasibility of

various resource recovery equipment. Therefore, in partial fulfillment of the mandate of Section 5004 of RCRA, arrangements were

made by NBS/0RM to determine if the facility could indeed be used

for research purposes.

NBS/0RM, acting under the provisions of the Intergovernmental

Personnel Act of 1970 (IPA), arranged for San Diego State University

(SDSU) to appoint a Technology Advisor to explore, for a six month

period, potential uses for the defunct facility. SDSU appointed

Professor Robert Bedore, Chairman of the Mechanical Engineering

Department to this position.

Professor Bedore concluded that the San Diego County Resource

Recovery Facility could be converted to a research center in six

months at an estimated cost of $361,000 plus the cost of new equipment. (San Diego County is willing to lease the facility for use

as a research center. The San Diego State University foundation is

willing to manage the facility and related research programs.)

Appropriate programs would be combustion research, methanol production research, and glass insulation production research.

Publications List #123 gives complete details of this effort and

summarizes how the various research programs could be used to assess commercial feasibility of resource recovery technology.

If the research center were to be fully developed, there would

exist a facility to allow potential buyers and sellers of resource

recovery technology to perform full scale pilot plant studies at

relatively low cost.

Many of the problems with full-scale solid waste plants are caused by use of unproven technology. The technology is unproven

because of the financial, legal, and time constraints which make

plant operations unfeasible.

189
Hence, such a facility would tend to promote proven technology

for resource recovery and to perhaps accelerate the process of

implementing proven resource recovery projects.

X.2.e. Cooperative efforts with the government of Japan

As part of the scientific interchange program initiated by the

United States Government and the Government of Japan, the Department

of Commerce was selected by the White House to be the pilot agency

for a project concerned with resource recovery from discards originally destined for waste. Such discards include municipal waste

and industrial waste. Under terms of the agreement signed by the

President and the Prime Minister on May 2, 1980, the United States

and Japan will exchange small teams of government scientists in

order to examine resource recovery in the respective countries and

to formulate possible joint research ventures.

NBS/ORM was designated as the U.S. contact point for this

project. The Japanese team visited the U.S. in December, 1981;

NBS/ORM arranged the itinerary and provided technical briefings and

an overview of resource recovery activities. At that time, NBS/ORM

and Japanese representatives concluded an agreement for joint

research to be performed as part of the project. Two items were agreed upon:

1) Japan would perform pyrolysis experiments on U.S. supplied

refuse derived fuels.

2) U.S. would perform RRPLAN analyses utilizing Japanese

technology as the basis for resource recovery. (Appendix

XIII contains the complete text of the agreement.)

NBS/ORM arranged to ship to Japan about 35 tons of fluff RDF

produced at the Baltimore County, MD resource recovery facility.

This material arrived in Japan in early November, 1982. This RDF

will be gasified in a paired-bed pyrolysis unit, e.g., a fluidizing

mechanism (sand) will be circulated between a pyrolysis reactor and

a combustion reactor. Thus, these two reactions occur separately,

hence the name "paired-bed."

The gas refining equipment consists of two chains, one for

pyrolysis gas and the other for combustion exhaust gas:

1) A cyclone separates char from the gas coming from the

pyrolysis reactor. This char is fed to the combustion

reactor for burning. After the gas passes through a heat

exchanger and is quenched in a carbon deposit protector,

a tar-separator removes oil mist and the gas is cleaned

in a scrubber. A small portion of this clean gas is

pressurized by a blower, preheated in a heat exchanger

and used to fluidize the pyrolysis reactor bed; the

remaining gas steam is sent to a gas tank for storage.

190
2) The exhaust gas generated by the combustion reactor is

discharged into the atmosphere after being treated by means of a two-stage cyclone and electric dust precipitator. The non-combustible substances contained in the

feed stock are discharged from the bottom of the combustion

tower periodical ly

.

The RDF will be fed into the system at a rate of 0.6 to 1.0

tons per hour. The pyrolysis reaction temperature is about 650 °C.

The following ultimate analyses will be performed:

1) Feedstock

a. Main components

C, H, N , CI , 0, Na, K, Ca, Ash.

b. Harmful components

Cu, Pb, Cd, T-Hg, As, T-Cr, Al , PCE.

c. Heat value

2) Pyrolysis gas components

a. Main components

H

2

, 0

2

, N

2

, CH

4

, CO, C0

2

, CmHn.

b. Harmful gas components

HC1, H

2 S, NH

4

, HCN, S0

x

, N0

x

.

c. Heat value

3) Flue gas

a. Main gas components

0

2

, N

2

, CO, C0

2

.

b. Harmful components

SO. NO. HC1 , dust.

X X

4) Ash

a. Main components

C, H, N, S, CI, Na, K, Ca.

b. Heavy metals

Cu, Pb, Cd, T-Hg, As, T-Cr, Al , etc.

191
5) Waste water

a. Main components

pH, EOD , COD, SS, n-Hex, Phenol, NH*, CI", CN", etc.

Results of the experiment will include:

o Heat and material balance,

o Gas and energy recovery rate.

o Evaluation of the data from public nuisance standpoint.

o Cost estimation.

o Final economics.

From these results, the total process flowsheet for a commercial

plant, including pretreatment system, will be deduced. Thus, the

final output will assess the commercial feasibility of the paired

fluidized bed pyrolysis unit under pilot plant conditions. (See

Appendix XIII. for details.)

X.2.f. Advisory activities relating to Section 5004 of RCRA

X.2.f.l NBS/ORM personnel were requested to cooperate with the

Department of Energy in selecting projects which would have a high

probability of rapid commercialization. The Chief, NBS/ORM and the

Manager of TAC personally reviewed well over 100 proposed projects

under this program. About seven such proposals were recommended

for further DOE consideration.

X..2.f.2 The Chief, NBS/ORM served as a technical advisor to a National Academy of Sciences/National Research Council effort

concerned with evaluation of technology meant to deal with hazardous

wastes. The report of this work was released in early 1983.

(Publication NMAB-398, 76 pp, 1983)

X.2.f.3 The Chief, NBS/ORM provided technical input to a NATO/CCMS

study concerning co-disposal of urban waste and sewage sludge. The

objective was to compare mass-burning methods, widely used in

Europe, with a U.S. technology embodying RDF as the fuel source. Mass burning was more efficient.

192
XI. PILOT PROGRAM WITH THE CALIFORNIA STATE SOLID WASTE

MANAGEMENT BOARD

The NBS/ORM cooperative efforts with the Association of State

and Territorial Solid Waste Management Officials were in part

concerned with state measurement needs. Results indicate that even though state programs vary with regard to stringency of regulatory

requirements, state measurement needs are similar in hazardous

waste. Resource recovery measurement needs identified in Subtitle

D do not exhibit the same level of priority as those under Subtitle

C —Hazardous waste program. Nevertheless, standard analytical

methods, protocols, and procedures specified in state regulations

match those methods cited in Federal criteria. Development of

standard laboratory and field methods for sampling and analyses as well as standard reference data are required. The lack of availability for such measurement tools is severely impeding national

consistency on a State-to-State basis, timely program implementation, and worker protection and safety. Consequently, a formal

manual of operating procedures is necessary to assure not only

State-to-State programmatic and enforcement consistency, but also

intra-state field and functional laboratory activities. Standard

laboratory certification and quality assurance programs do not

exist and would be helpful in attaining State-to-State consistency.

Lastly, training programs and technical assistance for laboratory

and field personnel may be inadequate at state level. As part of

its continuing commitment to working with State and local government,

NBS assigned a senior staff member to work with the State Solid

Waste Management Board (SSWMB) in California. The purpose of this

Intergovernmental Personnel Agreement was to provide an interface

between perceived State measurement needs and NBS expertise.

The SSWMB is required under California law to deal with all

aspects of solid waste management and to strongly emphasize resource

recovery, recycling and reuse of materials destined for waste.

Conservation and waste reduction are also under the purview of the

SSWMB. Since a number of SSWMB 's programs were similar to NBS/ORM

mandates, mutual efforts were decided upon.

The following general project areas were chosen for cooperative

work:

1) Procurement of recyclables and markets for such products

in California.

2) Technology transfer of RRPLAN to selected regions of

California, e.g., Fresno and Ventura Counties; Fresno was provided with a comprehensive analysis via RRPLAN in

April , 1983.

3) Measurement requirements to characterize potentially

hazardous wastes.

4) Technical advice regarding waste-to-energy systems, e.g.,

San Diego County.

193
5) Markets and use for fly ash.

6) Specifications for recovered materials.

A series of reports describing progress in each of these areas

was prepared by the NBS/ORM representative. These reports are available; see Publications List #122. Basically, the results

enabled NBS to better focus its efforts to provide test methods,

standards, and other measurement services to the States. Hence,

the State received the direct benefit of the NBS/ORM representative

while NBS was able to increase the efficiency of its services with

respect to waste management and other environmental measurements.

194
XII. BRIEF SYNOPSES OF OTHER ACTIVITIES

The Chief, NBS/ORM organized and chaired the DOC Intragency

Group on RCRA Related Activities. Virtually every agency and

bureau within DOC was represented. This Group coordinated all DOC

activities relating to RCRA; NBS/ORM provided technical assistance

to every area of DOC having projects concerned with resource

recovery, recycling and reuse of materials. The Group functioned

from February 1980 to mid-1982.

NBS/ORM co-sponsored two resource recovery research needs

seminars with the National Center for Resource Recovery. The

object was to bring together groups of scientists who could suggest

new research tools for resource recovery.

The Chief, NBS/ORM served as advisor to the Intergovernmental

Science, Engineering and Technology Applications Panel of the White

House Office of Science and Technology Policy. This panel sponsored

intensive research needs development meetings concerned with urban

waste and hazardous waste.

Departmental testimony before the U.S. Congress was required

on eight occasions; both EPCA and RCRA responses were required.

NBS/ORM personnel prepared the basic written statement of Departmental witnesses on all of these occasions. NBS/ORM staff also

testified directly on four occasions.

Subtitle H of RCRA created a Cabinet level Resource Conservation

Committee charged primarily with examining, (1) beverage container

deposit legislation and (2) product charges meant to fully internalize

waste costs for the discarding person or firm (polluter pays equity

principle). The Chief, NBS/ORM provided review, advice, and

technical analysis to the DOC representative on the Committee.

Analysis indicated that, on the Federal level, neither of the two

proposals before the Committee were appropriate. Other Committee

members agreed.

Subtitle D of RCRA required the Bureau of the Census of DOC to

aid in a survey of open dumps in the U.S. Specifically, Section

4005(b) of the Resource Conservation and Recovery Act of 1976

requires that the Administrator of the Environmental Protection

Agency (EPA) "with the cooperation of the Bureau of the Census'

publish an inventory of "all disposal facilities or sites in the

United States which are open dumps within the meaning of" the Act.

Under the provisions of the Act, regulations prescribing the

criteria for classifying facilities as open dumps were to have been

promulgated not later than October 1977, with publication of the

inventory not later than October 1978. However, the technical

complexity of solid waste disposal and its effect on the

environment, as well as legal requirements for consulting with the

States and conducting public hearings, prevented promulgation of

regulations within the time period prescribed by the Act. In the course of ensuing legal action by the State of Illinois and three

environmental groups, EPA negotiated revised dates for all deadlines

195
established by the Act. Final regulations under Section 4004

covering solid waste disposal were promulgated on September 13,

1979, in the Federal Regi ster .

The development of the inventory did not involve data

collection activity by the Bureau. The inventory was derived from

information submitted by State officials including facility

identification, code, name, location, ownership, and type, plus an indication of the criteria used to classify the facility as an open

dump. The Census Bureau, under an interagency agreement, was responsible for processing the data submitted by the States and for

preparing the inventory list for publication. The Bureau assisted

EPA in the development of the form used by the States in reporting

open dumps, the facility identification code system, geographic

reference materials, and publication formats for the inventory list

and attendant tabulations. The Open Dump Inventory was published

in 1981.

196
XIII. AMENDMENTS TO RCRA (PL 96-482)

In 1980, the Congress amended RCRA considerably. The bill

that Congress passed was signed into law on October 21, 1980 by the

President as PL 96-482. There were no substantive changes in

Sections 5001, 5002, 5003, and 5004 of Subtitle E. However,

Subtitle E was amended by inserting the following new section after

Section 5004:

"SEC. 5005. In establishing any policies which may affect the

development of new markets for recovered materials and in

making any determination concerning whether or not to impose

monitoring or other controls on any marketing or transfer of

recovered materials, the Secretary of Commerce may consider

whether to establish the same or similar policies or impose

the same or similar monitoring or other controls on virgin

material s.

(2) The table of contents for such Act is amended by

inserting the following new item after the item relating to

section 5004:

"Sec. 5005. Nondiscrimination requirement.". (42 USC

6955)

Responsibility for implementation of Section 5005 was not

delegated to NBS/0RM. Therefore, NBS/0RM did not deal with any

activities pursuant to Section 5005 at any time.

197
XIV. CONTRIBUTIONS OF ORM TO THE INSTITUTIONAL HEALTH OF NBS

Any programmatic effort at NBS should contribute strongly to

the basic competence of the Bureau. Thus, scientific and technical

contribution was always a goal of the managers of ORM as they

decided on specific aspects of the technical research projects. A

brief listing of new NBS competences developed as a direct result

of the ORM programs includes, but is not limited to, the following:

o Macrocalorimetric capabilities and equipment unsurpassed in

the world;

o A mature tribochemistry competence;

o A new algorithm for operations research models;

o Improved combustion chemistry competence;

o New contributions to trace inorganic and organic chemicals

analysis, e.g., PCBs in oil; and

o New SRMs, e.g., synthetic leachate, PCBs in oil.

Thus, while ORM formally ceased operations on September 30,

1982, these and other competences developed during its lifetime

will continue to contribute to the strength of NBS.

198
APPENDIX I

DIRECT PUBLICATIONS OF THE OFFICE OF RECYCLED MATERIALS (ORM)

ORM PUBLICATIONS IN THE OPEN LITERATURE

(Listing is Current to August 8, 1983)

1. Becker, D. A. , ed. , Measurements and Standards for Recycled

Oil, Proceedings of Workshop on Measurements and Standards for

Recycled Oil, August 1977 (NBS SP 488) [Out of Print].

2. Becker, D. A. and H. A. Hurd, eds. , Measurements and Standards

for Recycled Oil - II, Proceedings of Workshop on Measurements

and Standards for Recycled Oil, November 1977 (NBS SP 556).

3. Becker, D. A. , ed. , Joint Conference on Measurements and

Standards for Recycled Oil /Systems Performance and Durability,

Proceedings, October 1979 (NBS SP 584).

4. Becker, D. A., New Developments in Oil Recycling in the

U.S.A., Proceedings of the All India Conference on Acceptability

of Re-refined Oils, February 15-16, 1980.

5. Becker, D. A., Re-refined Lubricating Base Oils: Establishing

Consistency and Quality, Proceedings of the 45th Midyear

Meeting of the Refining Department, American Petroleum Institute,

May 12-15, 1980.

6. Braun, J. M. , Wise, S. A. , and May, W. E. , Determination of

Benzo (a) Pyrene in Recycled Oils by a Sequential HPLC Method,

Journal of Environmental Science and Health, June 20, 1980.

7. Becker, D. A. and Comeford, J. J., Recycled Oil Program:

Phase I--Test Procedures for Recycled Oil Used as Burner Fuel,

August 1980 (NBS Technical Note 1130 (supersedes NBSIR

78-1453)).

8. Becker, D. A., Re-Refined Lube Oil Consistency and Quality:

The Ultimate Question, Proceedings of the Second European

Congress on the Recycling of Used Oils, September 30th through

October 2nd, 1980.

9. Hsu, S. M. and Becker, D. A. , Status Report on the Characterization of Re-refined Lubricating Base Oils, October 1980 (SAE

Technical Paper Series 801382).

10. Becker, D. A., Research Methodology in Used Oil Recycling,

Proceedings of Conference on Atomic and Nuclear Methods in

Fossil Energy Research, December 1-4, 1980.

11. Chesler, S. N. , White, P. A., May, W. E. , and Parris, R. M.

,

Analysis of Polychl ori nated Biphenyls in Waste and Lubricating

Oils, The Pittsburgh Conference, 1981.

I-l
12. Becker, E. A., Alternative Utilization: Recycled Oil as Fuel,

Proceedings of the Fourth International Conference on Used Oil

Recovery and Reuse, September 1981.

13. Becker, D. A., NBS Research on Re-Refined Engine Oil Tests,

Proceedings of the Fourth International Conference on Used Oil

Tests, Proceedings of the Fourth International Conference on Used Oil Recovery and Reuse, September 1981.

14. Becker, D. A., Used Lube Oil: Hazardous Waste vs. Valuable

Resource, Proceedings of 16th Annual Conference on Trace

Substances in Environmental Health, 1982 (to be published).

15. Chesler, S. N. , Guenther, F. R. , May, W. E. , and Parris, R. M. , SRM's for Accurate Analysis of PCBs in Oil, ASTM Journal

(to be published).

16. Frame, E. , and Kohl, K. , SURI, Development of Methodology for

Engine Oil Deposit Characterization, Fourth Conference on Measurement and Standards for Recycled Oil, September 14-16,

1982.

17. Health, D. , Franklin Institute, Development of a Bench Engine

Screening Test for Motor Oil, Fourth Conference on Measurement

and Standards for Recycled Oils, September 14-16, 1982.

18. Becker, Donald A., and Hsu, Stephen, NBS Provisional Tests for

Re-refined Engine Oil, Fourth Conference on Measurement &

Standards for Recycled Oil, September 14-16, 1982.

19. Klaus, E. , Shah, P., and Kri shnamachar , V., Pennsylvania State

University, Development and Use of the Micro-Oxidation Test

with Crankcase Oils, Fourth Conference on Measurement and

Standards for Recycled Oil, September 14-16, 1982.

20. Parris, R. , Guenther, F. , May, W. , and Chesler, S. , Analysis

of PCBs in Oil: Technique and SRM Development, Fourth Conference on Measurement and Standards for Recycled Oil, September

14-16, 1982.

21. Becker, D. , Analysis for PCBs in Oil: The ASTM/NBS Round

Robin, Fourth Conference on Measurement & Standards or Recycled

Oil, September 14-16, 1982.

22. Weeks, S. J., Becker, D. A., and Hsu, S. M. , "ASTM/NBS

Basestock Consistency Study Data", NBS Spec. Publ. 661 (1983).

23. Becker, D. , Report on the ASTM/NBS Basestock Consistency

Study, Fourth Conference on Measurement and Standards for

Recycled Oil, September 14-16, 1982.

24. Weeks, S. , and Hsu, S. , Multiple Regression Analysis: A Look

Inside ASTM/NBS BCS Data, Fourth Conference on Measurement and

Standards for Recycled Oil, September 14-16, 1982.

1-2
25. Weeks, S. , and Hsu, S. , Comments on Test Methods for Physical

Properties of Re-refined Lubricating Basestocks, Fourth

Conference on Measurement and Standards for Recycled Oil,

September 14-16, 1982.

26. Cummings, A., Pei , P., and Hsu, S. , Comments on Test Methods

for Chemical Characterization of Re-refined Base Oil, Fourth

Conference on Measurement and Standards for Recycled Oil,

September 14-16, 1982.

27. Comeford, J., and Hsu, S. , Evaluation of Asking Methods for

Determination of Total Metal Content of Lubricating Oil Base

Stocks, Fourth Conference on Measurement and Standards for

Recycled Oil, September 14-16, 1982.

28. Ives, L. , Boyer, P., and Ruff, W. , Evaluation of Wear Behavior

Using a Modified Timkin Test, Fourth Conference on Measurement

and Standards for Recycled Oil, September 14-16, 1982.

29. Gates, R. , and Hsu, S. , Development of a Step-Loading Seizure

Test for Engine Oil Additive Response, Fourth Conference on Measurement and Standards for Recycled Oil, September 14-16,

1982.

30. Cummings, A., and Hsu, S. , Differential Scanning Calorimetry

Test Method for Oxidation Stability of Engine Oil, Fourth

Conference on Measurement and Standards for Recycled Oil,

September 14-16, 1982.

31. Walker, J., Tsang, W. , and Szegvary, S. , Comparative Response

of Re-refined and Virgin Lube Oils to Additives by DSC, Fourth

Conference on Measurement and Standards for Recycled Oil,

September 14-16, 1982.

32. Pei, P., and Hsu, S. , Lube Base Oil Characterization Using

Liquid Chromatographic Techniques, Fourth Conference on Measurement and Standards for Recycled Oil, September 14-16,

1982.

33. Ku, C. , Pei, P., and Hsu, S. , Evaluation of the ASTM D-2007

Method for Determination of Lube Base Oil Composition, Fourth

Conference on Measurement and Standards for Recycled Oil,

September 14-16, 1982.

34. Pei, P., Fleming, R. , and Hsu, S. , Test Methods for Total

Chlorine in Lubricating Base Oils, Fourth Conference on Measurement and Standards for Recycled Oil, September 14-16,

1982.

35. Ku, C. , and Hsu, S. , A Thin-Film Oxidation Uptake Test for the

Evaluation of Automotive Lubricants, Fourth Conference on Measurement and Standards for Recycled Oil, September 14-16,

1982.

1-3
36. Ku, C. , and Hsu, S. , Thin-Film Oxidation Test: Relationship

Between Chemical Composition and Additive Response for Re-refined

Oils, Fourth Conference on Measurement and Standards for

Recycled Oil, September 14-16, 1982.

37. Becker, D. , and Hsu, S. , NBS Provisional Tests for Re-refined

Engine Oil, Fourth Conference on Measurement and Standards for

Recycled Oil, September 14-16, 1982.

38. Becker, D. , Recycling Oil, Encyclopedia of Chemical

Technology, Third Edition, Volume 19, 1982.

39. Kirklin, D. R. , Mitchell, D. J., Cohen, J., Domalski, E. S.

,

and Abramowitz, S. , Test Procedures for the Determination of

the Gross Calorific Value of Refuse and Refuse-Derived-Fuels

by Oxygen Bomb Calorimetry. Summary of the 1977 Fiscal Year

Results, Proceedings of the Sixth Mineral Waste Utilization

Symposium, May 2-3, 1978.

40. Domalski, E. S. , Evans, W. H. , and Jobe, Jr., T. L. , Thermodynamic Data for Waste Incineration, August 1978 (NBSIR 78-1479).

41. Kirklin, D. R. , Mitchell, D. J., Cohen, J., Domalski, E. S.

,

and Abramowitz, S. , Test Procedures for the Determination of

the Gross Calorific Value of Refuse and Refuse-Derived-Fuels

by Oxygen Bomb Calorimetry. Summary of the 1977 Fiscal Year

Results, December 1978 (NBSIR 78-1494).

42. Domalski, E. S. , Evans, W. H. , and Jobe, Jr., T. L. , Thermodynamic Data for Waste Incineration, American Society of Mechanical

Engineers (ASME), 1979.

43. Kirklin, D. R. , Domalski, E. S. , and Mitchell, D. J., Calorific

Value Determination of Refuse-Derived-Fuels by Large-Bomb

Calorimetry, Proceedings of the Fifth Annual Research Symposium

on Municipal Solid Waste: Land Disposal and Resource Recovery,

March 26-28, 1979.

44. Kirklin, D. R. , Domalski, E. S. , and Mitchell, D. J., Determination of the Calorific Value of Refuse and Refuse-Derived-Fuels

by Large Bomb Calorimetry. Summary of the 1978 Fiscal Year

Results, January 1980 (NBSIR 80-1968).

45. Domalski, E. S. and Abramowitz, S. , Evaluation of Data on Higher Heating Values Determined During ASTM Round Robin

Testing of RDF-3, Proceedings of the 7th Mineral Waste Utilization Symposium, October 20-21, 1980.

46. Division of Purchasing, Department of Administration, State of

Colorado, Procurement of Products Containing Recycled/Recovered

Materials in State of Colorado, March 1981 (NBS-GCR 81-308).

1-4
47. Energy Enterprises Northwest on behalf of State Purchasing

Division, State of Washington: A Study of Procurement of

Products Containing Recycled Materials, March 1981 (NBS-GCR

81-314).

48. Frohnsdorff, G. and Clifton, J. R. , Fly Ashes in Cements and

Concretes: Technical Needs and Opportunities, March 1981

(NBSIR 81-2239).

49. Michigan Energy and Resource Research Association, Procurement

of Products Containing Recovered Materials: A Study of State

of Michigan Practices, March 1981 (NBS-GCR 81-310).

50. New York State Office of General Services, Procurement Practices

in New York State of Products Containing Recycled Materials,

March 1981 (NBS-GCR<t81-313).

51. Resource Conservation and Recovery Office, Minnesota Department

of Administration, A Study of Resource and Energy Conservation

Practices in the Procurement and Management of Commodities,

March 1981 (NBS-GCR 81-311).

52. Resource Recovery Section, Department of Environmental Regulation, State of Florida: The Procurement of Products Containing

Recovered Materials, March 1981 (N3S-GCRS81-309)

.

53. Trenton State College, and the Division of Purchase and

Property, Purchase Bureau, Department of Treasury, Procurement

of Products Containing Recycled Materials in State of New

Jersey, March 1981 (NBS-GCR 81-312).

54. Resource Recovery Section, Department of Environmental Regulation, An Analysis of the Procurement Policies of: Dade

County, The City of Miami, The Dade County School System,

Miami Dade Community College, May 1981 (NBS-GCR 81-309,

Supplement 1).

55. Kirklin, D. R. , Colbert, J., Decker, P., Abramowitz, S. , and

Domalski, E. S. , Test Procedures for the Determination of

Gross Calorific Value of Refuse and Refuse-Derived-Fuel by

Conventional and Large Bomb Calorimetry. Summary of 1979

Fiscal Year Results, June 1981 (NBSIR 81-2278).

56. Berke, J. G. and Hudson, C. H. , Procurement of Products

Containing Recovered Material: A Summary of Activities in

Seven States, July 1981 (NBSIR 81-2316).

57. Churney, K. C. , Reilly, M. L. , Ledford, A. E. , Ryan, R. V.,

and Domalski, E. S. , An Oxygen Flow Calorimeter for Determining

the Heating Value of Kilogram-size Samples of Municipal Solid

Waste, Proceedings of the Second International Conference on Materials and Energy from Refuse, October 20-22, 1981, pp.

6.31-6.38.

1-5
58. Mandel , J. and Paule, R. C. , Statistical Analysis of Sampling

and Measurement Errors in the Characterization of Refuse-Derived

Fuel, Proceedings of the Second International Conference on Materials and Energy from Refuse, October 20-22, 1981, pp.

6.25-6.30.

59. Domalski, E. S. , Churney, K. L. , Ledford, A. E. , Ryan, R. V.,

and Reilly, M. L. , An Oxygen Flow Calorimeter for Determining

the Heating Value of Ki 1 ogram-si ze Samples of Municipal Solid

Waste, Proceedings of the DOE/ANL Contractors Waste-to-Energy

Research and Development Briefing Workshop, December 1-4,

1981.

60. Resource Recovery Section, Florida Department of Environmental

Regulation, National Recycling Directory, January 1982 (NBS-GCR

82-366); Also National Directory of Manufacturers Utilizing

Recycled Materials (NBS-GCR-83-424)

.

61. Domalski, E. S. , Churney, K. L. , Reilly, M. L. , Kirklin, D.

R. , Ledford, A. E. , and Thornton, D. D. , 25 Gram Capacity

Combustion Flow Calorimeter, March 1982 (NBSIR 82-2457).

62. Kirklin, D. R. , Colbert, J. C. , Churney, K. L. , Reilly, M. L.

,

Ryan, R. V., Ledford, A. E. , and Domalski, E. S. , Test Procedures

for the Determination of the Gross Calorific Value of Refuse

and Refuse-Derived Fuel of Kilogram-size Samples Using Constant

Pressure Flow Calorimetry. Summary of the 1980 Fiscal Year

Results, June 1982 (NBSIR 82-2491).

63. Kirklin, D. R. and Domalski, E. S. , A 25 Gram-Capacity Oxygen

Bomb Calorimeter, Resources and Conservation, 1983 in press.

64. Kirklin, D. R. , Colbert, J. C. , Decker, P. H. , Ledford, A. E.

,

Ryan, R. V., and Domalski, E. S. , The Variability of Municipal

Solid Waste and Its Impact on the Development of Test Procedures

for the Determination of the High Heating Value of Refuse-DerivedFuels, Resources and Conservation, 9, 281-300 (1982).

65. Abramowitz, S. , Domalski, E. S. , Churney, K. L. , Ledford, A.

E. , Ryan, R. V., and Reilly, M. L. , Proceedings of the NATO

Conference-- Advanced Study Institute on Thermochemistry,

Reidel Publishing Co. (1983) - in press.

66. Domalski, E. S. , Churney, K. L. , Ledford, A. E. , Reilly, M.

L. , and Ryan, R. V., ASTM Standardization News, June 1982.

67. Kirklin, D. R. , Domalski, E. S. , Kelly, R. V., and Robbins, C.

R. , Ash Content and X-ray Analysis of Selected RDF and Coal

Samples as a Function of Temperature, Resources and Conservation, 9, 243-257 (1982).

68. Kirklin, D. R. , Colbert, J. C. , Kelly, R. V., Robbins, C. R.

,

and Domalski, E. S. , Test Procedures for the Determination of

the Gross Calorific Value of Refuse and Refuse-Derived-Fuel

1-6
Using Oxygen Bomb Calorimetry. Summary of the 1981 Fiscal

Year Results, 1982 (NBSIR number to be assigned).

69. Clifton, J. and Godette, M. , Identified Uses of Fly Ash in

Construction Materials NBSIR - in press (See Appendix IV).

70. Ledford, A. E. , Ryan, R. V., Reilly, M. L. , Domalski, E. S. , and Churney, K. L. , An Oxygen Flow Calorimeter for Kilogram-size

Samples of Municipal Solid Waste. Part II. Trial Combustions

of Kilogram-size Samples of Municipal Solid Waste, Resources

and Conservation, 8, 159-165 1982 (Also NBSIR 83-1711).

71. Reilly, M. L. , Churney, K. L. , Kirklin, D. R. , Ledford, A. E.

,

and Domalski, E. S. , An Oxygen Flow Calorimeter for Kilogram-size

Samples of Municipal Solid Waste. Part I. A 25 Gram Capacity

Combustion Flow Calorimeter for Determining the Calorific

Value of Refuse-Derived-Fuels, Resources and Conservation, 8,

147-157 1982.

72. Colbert, J. C. , Kirklin, D. R. , and Domalski, E. S. , The

Effect of Finely-Divided Aluminum and Iron Metal on Measured

Heating Values of Synthetic Refuse-Derived-Fuel, Resources and

Conservation, 1983 (to be published).

73. Domalski, E. S. and Abramowitz, S. , Evaluation of Data on Calorific Content Values Determined during ASTM Round Robin

Testing of RDF-3, Resources and Conservation, 8, 233-255

(1983).

74. Division of Purchasing, Department of Administration, State of

Colorado, The Bid Modifier as an Aid to Recycling, August 1982

(NBS-GCR-82-400).

75. Yakowitz, H. , The Interaction of P.L. 94-580 with Uses for

Discarded Tires, Annual Report 1978: Office of Recycled

Materials (1978).

76. Yakowitz, H. , Use of Wastes and By-Products in Building and

Construction Materials Industry, Proceedings of International

Conference on the Use of By-Products and Waste in Civil

Engineering, Volume III, p. 145-147, 1980.

77. Yakowitz, H. , "Emerging Concepts and Technologies for the

Recovery and Reuse of Materials", International Conference on Urban-Industrial Development through Resource Recovery,

Detroit, Michigan, April, 1980.

78. Yakowitz, H. , Recent Federal Actions Which Will Affect Prices

and Demands for Discarded Fibers, Technical Activities 1981:

Office of Recycled Materials, 1981 (NBSIR 81-2417).

79. Yakowitz, H. , Federal Policies with Respect to Resource

Recovery 1982 and Beyond, Proceedings of the 3rd International

Recycling Congress, Berlin, April 19-21, 1982, Recycl ing

International (K. J. Thome Kozmiensky, ed. ) p. 59-63.

1-7
80. Yakowitz, H. , The Waste-Environment-Technology Model: A Brief

Evaluation and Assessment, Presented at the Department of

Defense JANNAF Safety & Environmental Protection Subcommittee

Workshop on Hazardous Waste Management, Redstone Arsenal, AL,

1982. (See Appendix VII)

81. U.S. Environmental Protection Agency; U.S. Department of

Transportation, Coast Guard; U.S. Department of Commerce,

National Bureau of Standards, Report of the Interagency Ad Hoc

Work Group for the Chemical Waste Incinerator Ship Program,

September 1980.

82. Association of State and Territorial Solid Waste Management

Officials, States' Measurement Needs: Final Report (Executive

Summary), September 1981 (NBS-GCR 81-348).

83. Association of State and Territorial Solid Waste Management

Officials, States' Measurement Needs: Part II. State Profile

(Louisiana), September 1981 (NBS-GCR 81-349).

84. Association of State and Territorial Solid Waste Management

Officials, States' Measurement Needs: Part II. State Profile

(Mississippi), September 1981 (NBS-GCR 81-353).

85. Association of State and Territorial Solid Waste Management

Officials, States' Measurement Needs: Part II. State Profile

(Oklahoma), September 1981 (NBS-GCR 81-350).

86. Association of State and Territorial Solid Waste Management

Officials, States' Measurement Needs: Part II. State Profile

(Pennsylvania), September 1981 (NBS-GCR 81-351).

87. Association of State and Territorial Solid Waste Management

Officials, States' Measurement Needs: Part II. State Profile

(Texas), September 1981 (NBS-GCR 81-352).

88. Association of State and Territorial Solid Waste Management

Officials, States' Measurement Needs: Part II. State Profile

(Virginia), September 1981 (NBS-GCR 81-354).

89. Association of State and Territorial Solid Waste Management

Officials, States' Measurement Needs: Part III. Analytical

Operations Procedure Manual Model, September 1981 (NBS-GCR

81-355).

90. Chapman, G.O., Leubecker, D. W. , Martinez, L. A., Matthews, R.

R. , Oberacker, D. A., and Wybenga, F. , Chemical Waste Incinerator

Ships - The Interagency Program to Develop a Capability in the

United States, presented to the Chesapeake Section of the

Society of Naval Architects and Marine Engineers, September 1981.

91. Barton, David R. , Freedman, D. , Post, H. A., and Williams, F.

E. , Bureau of Industrial Economics, U.S. Department of Commerce,

Marketing Information Report: Waste Newspapers in Four South

Atlantic States 1980, October 1981 (NBS-GCR 82-371).

1-8
92. Yakowitz, H. , Economic Opportunities for Recovery of Hazardous

Wastes, Hazardous Waste Management, Harvard School of Public

Health, July 12-16, 1982.

93. Barton, David R. and McAuley, P., Bureau of Industrial Economics,

U.S. Department of Commerce, An Economic Analysis of Resource

Recovery Facilities and Waste Newspaper Recycling, August 1982

(NBS GCR to be assigned; See Appendix XI)

94. W. Tsang and W. M. Shaub, "Chemical Processes in the Incineration of Hazardous Materials," to appear in a Symposium Series

publication of the American Chemical Society - Environmental

Chemistry Division.

95. Michigan Department of Commerce, "Hazardous Waste Management

in the Great Lakes Region: Opportunities for Economic Development and Resource Recovery," September, 1982, NBS-GCR 82-405,

428 pp (NTIS-PB 83-119909).

96. Berman, E. , Chapman, R. and Hung, H. , Program Documentation

for Resource Recovery Planning Model, August, 1983, NBSIR

83-2745, 133 pp.

97. New York City, Department of Sanitation, Study of the Potential

and Proposed Implementation of Energy Recovery Projects from

Existing Municipal Incinerators in New York City, Parts I and

II, September 1982, NBS-GCR 82-409, 305 pp (NTIS-PB

83-119503).

98. Chapman, R. , and Berman, E. , "The Resource Recovery Planning

Model: A New Tool for Solid Waste Management", NBS Spec.

Publ. 657, 188 pp (1983).

99. Hsu, S. M. , Ku, C. S. , and Lin, R. S. , "Effects of Base Oil

Composition on Additive Response in 'Oxidation Stability," NBS

special publication, will be issued in 1983.

100. Ku, C. S. , Pei, P., and Hsu, S. M. , "Evaluation of ASTM D2007

Method for the Determination of Lubricating Oil Composition,"

Presented at the Fourth Conference on Measurements and Standards

for Recycled Oil, Sept. 14-16, 1982, National Bureau of

Standards, Washington, DC 20234.

101. Pei, P., Britton, Jr., J., and Hsu, S. M. , "Hydrogen Type

Separation of Lubricating Base Oil in Multigram Quantity by

Preparative HPLC," accepted for publication in J. of

Chromatographic Science.

102. Pei, P., and Hsu, S. M. , "Re-refined Base Oil Characterization

Using Liquid Chromatographic Techniques," Presented at the

Fourth Conference on Measurements and Standards for Recycled

Oil, Sept. 14-16, 1982, National Bureau of Standards,

Washington, DC 20234.

103. Hsu, S. M. , "Review of Laboratory Bench Tests in Assessing the

Performance of Automotive Crankcase Oils," Lubrication

Engineering 37, 12, 722 (1981).

1-9
104. Gates, R. S. , and Hsu, S. M. , "Development of a Four-Ball Wear

Test Procedure to Evaluate Automotive Lubricating Oils," ASLE

preprint 82-AM-6A-4, Cincinnati, Ohio, May 10-13, 1982.

105. Ku, C. S. , and Hsu, S. M. , "A Thin-Film Oxygen Uptake Test for

the Evaluation of Automotive Crankcase Lubricants," ASLE

preprint 82-LC-1D-1, Washington, DC, Oct. 5-7, 1982.

106. Hsu, S. M. , Ku, C. S. , and Becker, D. A., "Re-refined Base Oil

Characterization and Consistency Monitoring," Paper in Base

Oils for Automotive Lubricants, SP-526, pp. 87-104 (Society of

Automotive Engineers, 400 Commonwealth Drive, Warrendale, PA

15096, 1982).

107. Hsu, S. M. , and Becker, D. A. , "Status Report on the

Characterization of Re-refined Lubricating Base Oil," SAE

paper 801382, 1980.

108. Hsu, S. M. , et. al . , "Physical and Chemical Test Methods for

Re-refined Base Oils," NBS special publication, will be issued

in 1983.

109. Hsu, S. M. , Ku, C. S. , and Lin, R. S. , "Relationship Between

Lubricating Basestock Composition and the Effects of Additives

on Oxidation Stability, Paper in Base Oils for Automotive

Lubricants, SP-526, pp. 29-56 (Society of Automotive

Engineers, 400 Commonwealth Drive, Warrendale, PA 15096,

1982).

110. Early, J. G. , Recycling (Ferrous Metals), Encycl. Chemical

Technology, 19, 952-962 (1982) Wiley (3rd Edition).

111. Early, J. G. , Recycling Municipal Ferrous Scrap, NBSIR

82-2571, 35 pp (NTIS-PB 83-156968).

112. Chapman, R. and Yakowitz, H. , Application of RRPLAN to the

Jackson, MS Area, in press; See Appendix XV.

113. Paule, R. C. , Analysis and Modeling of the Leaching Process,"

Hazardous Solid Waste Testing , ASTM-STP 760, 112-135 (1981).

114. Paule, R. C. , An Interlaboratory Comparison of the Standard

and Modified ASTM Method A, Hazardous Solid Waste Testing , ASTM-STP, 13-36 (1982).

115. Domalski, E. S. , MacCrehan, W. A., Moody, J. R. , Tewari , Y.

,

and Walker, J. A., Characterization of Mill-Scale Wastes,

NBSIR (in press; See Appendix XIV).

116. Annual Report of 0RM, 1978.

117. Annual Report of 0RM, 1979.

118. Technical Activities 1980, Office of Recycled Materials,

(NBSIR 80-2178).

1-10
119. Technical Activities 1981, Office of Recycled Materials,

(NBSIR 81-2417).

120. Walker, J. A., and Tsang, W. , "Application of Differential

Scanning Calorimetry to the Characterization of Lubricating

Oils", Proc. Joint Conf. on Meas. and Stds. for Recycled

Oil/Systems Performance and Durability, October 23-26, 1979,

NBS SP 584, U.S. Department of Commerce, Washington, DC 20234

(1980).

121. Association of State and Territorial Solid Waste Management

Officials, States' Measurement Needs: Part II. State Profile

(New York), September 1982 (NBS-GCR to be assigned).

122. Berke, J., Report on IPA (NBS/ORM).

123. Bedore, R. , Conversion of the San Diego County Resource

Recovery Facility to a Solid Waste Research Center" (NBS/ORM).

124. Office of Environmental Affairs, U.S. Department of Commerce,

"Marketing and Financing Aspects of Resonance Recovery" 63pp

(1980).

125. Suzuki, S. , and Yakowitz, H. , "Gasification of Refuse Derived

Fuel in a Paired Fluidized Bed Pyrolysis Unit", NBS Special

Publication (1983) - in press.

126. Yakowitz, H. (ed. ) The NBS Office of Recycled Materials

1976-1982--Final Report NBS Special Publication (1983) - in

press.

127. Frohnsdorff, G. , Dise, J. R. , Clifton, J. R. , "A Reference

Sample Program for Fly Ashes as a Stimulus to technological

progress, Proc. Workshop Res. Develop. Needs for Use of Fly

Ash in Cement Concrete, Subsec. 5.4, 5-14--5-21 (Electric

Power Research Institute, 3412 Hillview Avenue, Palo Alto, CA

94304, Sept. 1982).

128. Tsang, W. , Walker, J. A., and Braun, W. , "Thermal,

Unsensitized Infrared Laser and Laser SiF 4 Sensitized

Decomposition of 1,2 Dichloropropane" , submitted to J. Phys.

Soc.

129. Walker, J. A., and Tsang, W. , "Characterization of Lubricating

Oils by Differential Scanning Calorimetry," Proc. Fuel and

Lubricants meeting (SAE), Oxt. 20-24, 1980, Baltimore, MD.

130. Walker, J. A., and Tsang, W. , "The Application of High

Pressure Scanning Calorimetry for Lubricating Oil

Characterization", Proc. Tenth NATAS Conference, Oct. 26-29,

1980, Boston, MA.

131. Brown, R. L. , Walker, J. A., and Tsang, W. , "The Modeling of

High Pressure Scanning Calorimetric Profiles for Autoxidation

Reactions," Proceedings 11th NATAS Conference.

I-ll
132. Tsang, W. , and Walker, J. A., "High Pressure DSC Study of

Refused Derived Fuels", Proc. Eleventh NATAS Conference, Oct.

18-21, 1981, New Orleans, Louisiana.

133. Walker, J. A., and Tsang, W. , "Autoxidati ve Properties of

Automotive Lubricating Oil by High Pressure Differential

Scanning Calorimetry", Proc. Eleventh NATAS Conference, Oct.

18-21, 1981, New Orleans, Louisiana.

134. Tsang, W. , and Walker, J. A., "Characterization of RDF

Properties Through High Pressure Differential Scanning

Calorimetry", Resource and Conservation, 9 (1982) 355-365.

135. Walker, J. A., Tsang, W. , and Szegvary, L. , "Comparative

Response of Re-refined and Virgin Lube Oils to Additives by

DSC", Conference on Measurements and Standards for Recycled

Oil -IV, Sept. 14-16, 1982 NBS SP, in preparation.

136. Tsang, W. , Domalski, W. , Macek, A., and Walker, J. A.,

"Combustion Characteristics of Refuse Derived Fuels", in

preparation.

137. Shaub, W. M. , "Estimated Thermodynamic Functions for Some

Chlorinated Benzenes, Phenols and Dioxins," Thermochima Acta

50, 11 (1982).

138. Shaub, W. M. , "Procedure for Estimating the Heats of Formatio

of Aromatic Compounds: Chlorinated Benzenes, Phenols and

Dioxins," Thermochimica Acta., 55, No. 1 (1982).

139. Shaub, W. M. , and Tsang, W. , "Physical and Chemical Properties

of Dioxins in Relation to their Disposal", entitled

Laboratory Safety and Waste Management , A. Young, Ed. , Plenum

Press, pp. 731-748 (1983).

140. Tsang, W. , and Shaub, W. , "Environmental Consequences Arising

from the Combustion of Municipal Solid Waste", In: Resource

Recovery from Solid Wastes , S. Sengupta and K. F. V. Wong,

Eds., Pergamon Press, N.Y., N.Y. , p. 219 (1982).

141. Shaub, W. M. , "Procedure for Estimating the Heats of Formation

of Aromatic Compounds (II): Chlorinated Phenols, Biphenyls,

Diphenyl Ethers and Dibenzofurans" , Thermochima Acta 62, 315

(1983).

142. Tsang, W. , Final Tech Report- Tyndale AFB, "Energy Recovery

from Air Force Industrial Process Wastes".

1-12
ADDENDUM TO APPENDIX I . NBS RESEARCH REVIEW ON THE

CHARACTERIZATION OF MUNICIPAL SOLID WASTE

(September 13, 1983)

National Bureau of Standards

Gaithersburg, Maryland

Cochairmen: Eugene S. Domalski, Chemical Thermodynamics Division

National Bureau of Standards

Christopher A. Kouts, Energy from Municipal Waste

Division

Department of Energy

The purpose of the one day research review was to report the

results of characterization studies on municipal solid waste (MSW)

and refuse-derived fuels (RDF) carried out at NBS under the sponsorship of the U.S. Department of Energy, Office of Renewable Technology

Energy from Municipal Waste Division.

The significance and impact of sample processing, particle

size distribution, sample variability, representativeness of

gram-size and kilogram-size samples, and the thermal characteristics

of such samples was discussed. In addition, quantitative measurements and methodologies characterizing MSW and RDF for the more efficient thermal conversion of such feedstocks to energy and/or

useful products were presented. Papers were presented on potential

mechanisms of formation and the subsequent destruction of trace

organic pollutants in the MSW combustion process.

The research review included a tour of the large sample (2.5

kilogram) calorimeter used by NBS in MSW research.

1-13
Review Agenda

Program

Entrainment Flow Combustion of RDF Particles

A Macek and S. R. Charagundla

Corrosion Studies in MSW-Fired and Coal -Fired Boiler Systems

E. Escalante

Development of a Synthetic RDF as a Standard Reference Material

J. C. Colbert and E. S. Domalski

Significance of Experimental Data from a 2.5 Kilogram Capacity Flow

Calorimeter

K. L. Churney, A. E. Ledford, Jr., M. L. Reilly, S. J. Skidmore, and E. S. Domalski

Variability of Sulfur and Chlorine Content in MSW and RDF

S. Abramowitz, J. C. Colbert, D. R. Kirklin, and

E. S. Domalski

Characterization of RDF During Various Stages of Processing

D. R. Kirklin, P. H. Decker, and E. S. Domalski

Enhancement of the Calorific Value of RDF by Aluminum and Iron

J. C. Colbert, D. R. Kirklin, and E. S. Domalski

RDF Characterization Using Thermal Methods of Analysis

J. A. Walker and W. Tsang

Hazardous Waste Aspects of Municipal Solid Waste Incineration

W. Shaub and W. Tsang

Tracers for Quality Assurance in Municipal Solid Waste Incineration

W. Tsang and W. Shaub

>

1-14
APPENDIX II . SELECTED ABSTRACTS FROM CONFERENCE ON

MEASUREMENTS AND STANDARDS FOR RECYCLED OIL-IV

Held

September 14-16, 1982

National Bureau of Standards

Gai thersburg , Maryland

Sponsored by:

Recycled Oil Program

National Bureau of Standards

U.S. Department of Commerce

ASTM Technical Division P, on Recycled Petroleum Products

Association of Petroleum Re-Refiners

II-l
ANALYSIS FOR PCBs IN OIL: TECHNIQUE AND SRM DEVELOPMENT

R. M. Parris, F. R. Guenther, W. E. May, and S. N. Chesler

Organic Analytical Research Division

Center for Analytical Chemistry

National Bureau of Standards

Washington, DC 20234

Polychlorinated biphenyl (PCB) mixtures (Aroclors) are toxic

global contaminants that have been extensively used as electrical

transformer fluids in this country. A hybrid technique utilizing

high-performance liquid chromatography (HPLC) and capillary column

gas chromatography (GC) has been developed for the determination of

polychlorinated biphenyl s in hydrocarbon matrices, such as transformer and motor oils. This method first employs preparative-scale

HPLC to remove the major portion of analytical interferences from

the oil sample. The "clean" sample is then analyzed using a nonpolar wall-coated open-tubular GC column and electron capture

detection for identification and quantitation of any PCB contaminants. Quantitative data are obtained by relating peak areas of

internal standards(s) (here, PCB congeners not detected in the

Aroclor of interest) to the areas of the PCB peaks of samples and

of calibration standards.

Samples of used motor oils containing a wide range of concentration and type of PCB contamination have been analyzed using this

method. This procedure has also been used to certify a Standard

Reference Material (SRM 1581) entitled "Polychlorinated Biphenyls

in Oil" that consists of separate solutions of Aroclor 1242 and

Aroclor 1260, each in a transformer oil and a motor oil base at the

100 ppm (wt./wt.) level. The SRM is designed to be used as an external standard for analytical calibrations as well as a benchmark

for interlaboratory comparisons. The method used should be easily

adaptable to other laboratories as it employes the use of conventional , commercially available instrumentation, columns, and

detectors. We have found it to give accurate analysis of samples

containing as little as 1 ppm total PCB concentration.

II-2
ANALYSIS FOR PCBs IN OIL: THE ASTM/NBS ROUND ROBIN

Donald A. Becker

Recycled Oil Program

National Bureau of Standards

Washington, DC 20234

Early in 1982, a cooperative effort on the analysis of polychlorinated biphenyls (PCBs) in oil was initiated by the National

Bureau of Standards (NBS) Recycled Oil Program and the American

Society for Testing and Materials (ASTM), Section II (Used Oils and

Basestocks) of Technical Division P (Recycled Petroleum Products).

The primary purpose of this cooperative effort was to help provide

the necessary information and data to identify an accurate,

relatively simple method for the analysis of PCBs in oil, with

subsequent consideration for development into an ASTM Standard

Method. A secondary purpose was to help oil recyclers identify an analytical methodology which could be utilized to obtain reliable

PCB analyses.

The round robin consisted of eleven (11) samples of oil in

sealed glass ampoules which contained one or more of the Aroclors

at known (by NBS) concentrations. Seven of these samples (A - G) were made with known quantities of Aroclor(s) dissolved in a virgin

lubricating base oil (i.e., gravimetric values), including two

duplicates. The remaining four samples were a re-refined base oil

with known PCB content (H), two used engine oils with PCBs added

(I, J), and a re-refined base oil with an additive package suspected

of causing interferences with some PCB analytical methods.

A total of eighteen (18) laboratories cooperated by supplying

analyses of the samples using their own procedures. Since our laboratory analyzed the samples by two methods, a total of nineteen

(19) sets of results were obtained. In addition, all laboratories

were requested to provide a copy of their procedure( s) , and most

complied although there was a wide discrepancy between the com- pleteness of the various procedures supplied.

The results of the interl aboratory round robin will be presented

along with statistical analyses of the data in an attempt to

identify the method(s) providing the most accurate results. As an example of the kind of results that were obtained, sample C (known

concentration of 148.3 yg/g of Aroclor 1260) had results averaging

121 ± 96 ug/g (± value is 95 percent Confidence Interval; n = 1 with a range of 31 ug/g to a high of 243 yg/g.

II-3
DEVELOPMENT OF METHODOLOGY FOR ENGINE DEPOSIT CHARACTERIZATION

E. Frame and K. Kohl

Southwest Research Institute

A method was needed for comparison of engine deposits formed

under varied conditions and/or with different oils. The method

developed involves removal of deposits from three distinct areas of

a piston: (1) the skirt, oil ring, and groove area; (2) the crown

and the compression rings, grooves, and lands area; and (3) the

undercrown area. Deposits were removed with a mixture of tolueneacetone-methanol (TAM) and dimethyl formamide (DMF) which allows

simultaneous removal of both oily deposits and high molecular

weight polar residues. Deposits were recovered by evaporation of

solvent, then extracted sequentially with increasingly polar

solvents and filtered to remove insoluble residue. Heptane,

toluene, TAM, and DMF soluble fractions and insoluble materials

were concentrated and recovered by solvent removal. The recovered

deposit fractions were then analyzed for each of the three areas of

the piston. Any analyses desired could be performed on recovered

fractions for comparison purposes. AFLRL analyses included infrared

spectroscopy, carbon, hydrogen, nitrogen, and sulfur content, and

molecular weight determination. Qualitative X-ray fluorescence

analysis for other elements was performed on soluble fractions.

Insoluble fractions were analyzed quantitatively.

*Work sponsored by ROP-NBS/ORM

II-4
THE ASTM/NBS BASESTOCK CONSISTENCY STUDY

Donald A. Becker

Recycled Oil Program

National Bureau of Standards

Washington, DC 20234

Early in the National Bureau of Standards (NBS) work on recycled oil, it became clear that the most important requirement

for assuring the quality of re-refined engine oil was the development of a set of test procedures capable of monitoring the consistency and additive response of a re-refined oil basestock, inbetween

qualifications of the formulated oil through use of the ASTM engine

sequence tests.

In 1979, NBS proposed to ASTM Technical Division P that a cooperative basestock consistency study be initiated, in which as many tests as possible are used to characterize monthly production

samples from both re-refining companies as well as virgin refiners.

This effort was approved by ASTM in June of 1979.

The ASTM/NBS Basestock Consistency Study (BCS) was initiated

in early 1980, when four virgin oil producers and six re-refined

oil producers submitted monthly samples of their regular production

basestock for analysis by a group of 14 laboratories. The production samples were provided to NBS, then subdivided and coded before

transfer in groups (including a control sample) to the analyzing

laboratories. These laboratories analyzed the samples using over

40 different chemical, physical, and performance tests.

The data contained in the report of this study is a compilation

of the results from these tests, on 13 monthly production samples

from each oil. The data has been statistically evaluated, and for

many tests the results have been graphed using one or more techniques,

in order to better visualize the relative consistency of the oils

and/or test data.

The data generated in this study is thought to be the most

comprehensive ever obtained on re-refined lubricating basestocks,

and has been used extensively by NBS in the evaluation of tests for

re-refined oil basestock consistency.

Grateful acknowledgment is also made to all of the manufacturers,

analyzing laboratories, and coordinators who have contributed so much to this study. It is hoped that all of the tremendous effort

represented here will be useful to many people, for multiple

purposes, for many years to come.

1 1-5
MULTIPLE REGRESSION ANALYSIS: A LOOK INSIDE ASTM/NBS BCS DATA

S. Weeks and S. M. Hsu

Tribochemi stry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

The selection of basestocks to be refined into finished

product lubricating oils has been historically determined using a variety of standardized bench, pump and engine tests. The first

phase of the ASTM/NBS Basestock Consistency Study (BCS) evaluated

test procedures with regards to the consistency of the feed stock

question. This second phase of the program is an attempt to

correlate the physical and chemical properties with the performance

bench tests.

Beginning with the fundamental axion: the data analyst knows more than the computer; performance tests were selected as the

responses and a subset of physical and chemical properties as the

candidate regression variables, and interactive computing and

exploratory methods were used to look for features in the data.

The results obtained show the 'best' correlations for the

examples chosen. Depending on the known relationship of the

selected performance test in predicting the results of the fullscale engine and tests, the physical and chemical property tests

determined to give the most predictive powers in determining the

performance test results can then be used as quideposts in selecting

high quality basestocks.

II-6
COMMENTS ON TEST METHODS FOR PHYSICAL PROPERTIES OF

RE-REFINED LUBRICATING BASESTOCKS

S. J. Weeks and S. M. Hsu

Tribochemistry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

Physical property measurements are routinely performed on lubricating basestocks to assure quality control. In the past,

refiners could control the feedstock source as well as the refining

process to ensure product quality. Re-refiners need to establish

(1) the applicability of available test methods to re-refined base

oils and, (2) the range limits of physical properties for their

products.

Re-refined base oils from various re-refining processes in the

U.S. were selected. Existing test methods were evaluated and

modified when necessary. The following tests were established as being applicable to re-refined base oils: Boiling point distribution

by GC, kinematic viscosity, density, refractive index, flash point,

pour point, API gravity, and color. In addition, derived properties,

such as viscosity index and hydrocarbon type distribution by n-d-m, were calculated.

II-7
COMMENTS ON TEST METHODS FOR CHEMICAL CHARACTERIZATION OF

RE-REFINED BASE OILS

A. L. Cummings, P. Pei , and S. M. Hsu

Tribochemi stry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

Standard test methods used to determine several characteristics

of lubricants were applied to re-refined lubricant basestocks, and

the results evaluated. Modifications in some test procedures were necessary in order to make the methods suitable for these oils.

The characteristics that were measured included total acid number

(TAN), total base number (TBN), total nitrogen, basic nitrogen,

saponification number, and water. The modified procedures were applied to a variety of commercially available re-refined oils and

the values tabulated.

* Present address: American Sterilizer Company, Erie, PA 16512
EVALUATION OF ASHING METHODS FOR DETERMINATION OF

TOTAL METAL CONTENT OF LUBRICATING OIL BASESTOCKS

J. J. Comeford and S. M. Hsu

Tribochemi stry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

Ash for a petroleum oil may be defined as the residue, free of

carbonaceous material, remaining after burning and ignition in air

at a specified high temperature. In the case of re-refined base

oils, ash content provides a simple method for the determination of

total metal content resulting from wear or additive metals remaining

after re-refining.

Three ashing methods were evaluated for volatile metal retention.

The sulfated ash method was found to have good metal retention

properties, and was modified to improve its precision in the low

ash range.

The sulfated ash contents of ten re-refined stocks, representing

all major U.S. re-refiners, ranged from 0.005 percent to 0.017

percent. The majority of the virgin stocks had ash values below

0.005 percent.

II-9
DEVELOPMENT OF A STEP LOADING SEIZURE TEST FOR

ENGINE OIL ADDITIVE RESPONSE

R. S. Gates and S. M. Hsu

Tribochemi stry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

Additive response measures the effect of base oils on the

performance of an additive or combination of additives. This study

is concerned with measuring the effect of basestock composition on the antiwear performance of an engine oil additive package.

Two step loading seizure four-ball wear test procedures were

investigated for measuring additive response using an engine oil

additive package and a set of seventeen base oils. The procedures

examined were a conventional step loading seizure test which uses

10 ml sample, a microsample step loading seizure test which uses only six microliters sample and combines oxidation and wear in a single test. Both tests have been shown to correlate with engine

wear experience. The conventional step loading seizure test was

not suitable for additive response determinations at high (8.0

percent) additive package concentrations. The microsample step

loading seizure test was able to measure a difference in additive

response among the base oils at 8.0 percent additive package.

This microsample step loading seizure test affords an opportunity to measure the additive response of a larger set of base

oils in an attempt to determine the individual components within

the basestock which affect the antiwear performance of the

lubricant.

11-10
DIFFERENT SCANNING CALORIMETRY TEST METHOD FOR OXIDATION

STABILITY OF ENGINE OILS

A. L. Cummings and S. M. Hsu

Tribochemi stry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

A laboratory bench oxidation test has been developed which

measures oxidation stability of automotive crankcase lubricants

under simulated engine conditions. The test employs a highpressure, differential scanning calorimeter (DSC) to measure

oxidation induction times in thin-film oil samples at 175 °C in 3.6

MPa oxygen. Engine chemistry is simulated by mixing the oil sample

with oil-soluble metal naphthanates and oxidized nitrated gasoline.

The DSC test ranks the relative oxidation stability of seven ASTM

engine sequence HID reference oils in the same order as the engine

test does. The bench test requires less than an hour's time to

perform, uses only 1 mg of sample, with an average 6 percent

repeatability. Details of method development are discussed.

11-11
COMPARATIVE RESPONSE OF RE-REFINED AND VIRGIN LUBE OILS TO

ADDITIVES BY DSC

J. Walker, W. Tsang, and L. Szegvary

National Bureau of Standards

Chemical Kinetics Division

Washington, DC 20234

Earlier studies have demonstrated the capability of high

pressure differential scanning calorimetry (HPDSC) in determining

the propensity towards autoxidation of lubricating oils. This

report is an extension of previous work and is focused on the

following issues:

(a) The consistency of basestocks produced over the course of

a year, with special reference to the similarities and

differences between recycled and virgin bases.

(b) The effect of the various components in the additive

mixture on the intensity and time for response.

(c) The response of various components of the base oil stock

towards a particular additive.

(d) The response of basestocks to different additive packages

Our results are consistent with the assumption that differences

between virgin and re-refined basestocks are no larger than that

between virgin bases. Appropriate additives can ameliorate such

differences. The variation in oxidative properties for samples of

virgin and re-refined basestocks prepared over a period of time were similar. The polar and aromatic fractions in basestocks

contain the active ingredient that interact with the antioxidant.

With respect to the additive, both detergent and dispersants have

effects on autoxidation properties. Addition of calcium phenate

result in dramatic increase in heat effects and serves to increase

the sensitivity of the method.

11-12
LUBE BASE OIL CHARACTERIZATION USING LIQUID

CHROMATOGRAPHIC TECHNIQUES

P. Pei and S. Hsu

Tribochemistry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

A separation scheme for lubricating base oils into molecular

compound classes has been developed. The isolated compound classes were tested for new insight and information linking basic hydrocarbon molecular structures to oxidation stability could be gained.

The separation scheme separates the oil into three major

fractions; saturates, aromatics and polars using clay-gel liquid

chromatography. The saturate fraction consists mainly of paraffinic

anc cyclic paraffinic hydrocarbons. The aromatic fraction comprises

of mono- and poly-aromatic compounds. Both poly-nuclear aromatic

compounds and hydrocarbons with hetro atoms such as sulfur, halogens,

and oxygen are present in the polar fraction. The polar fraction

is further separated into compound classes of different polarities

and functional structures. Spectroscopic methods such as infrared

and mass spectroscopy were used to elucidate the functional structures of each compound class.

The oxidation stability of each major fractions and compound

classes are tested with the micro-oxidation test. Of the three

major fractions of the lubricating base oils, only polar fraction

has the highest anti-oxidant capacity values in comparison to

saturate and aromatic fractions. Among, the compound classes in

the polar fraction, the amine and phenol fractions have high

anti-oxidant capacity value in comparison to other classes.

11-13
EVALUATION OF ASTM D-2007 METHOD FOR DETERMINATION OF

LUBE BASE OIL COMPOSITION

C. S. Ku, P. Pei and S. M. Hsu

Tribochemi stry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

ASTM D-2007, "Characteristic Groups in Rubber Extender Oil by

Clay-Gel Adsorption Chromatography," and its variations were evaluated for lubricating base oils, both virgin and re-refined.

Results from D-2007 are compared with those obtained from the n-d-m

method and low resolution mass spectroscopy. D-2007 is found to be

applicable to lubricating base oils and offers a rapid analytical

procedure for hydrocarbon type analysis for both virgin and re- refined base oils of various viscosity grades. Hydrocarbon types

such as polar compounds, aromatics, and saturates from various base

oils are separated using D-2007 and the fractions are characterized

using infrared spectroscopy, refractive index, etc.

11-14
TEST METHODS FOR TOTAL CHLORINE IN LUBRICATING BASE OILS

P. Pei , R. Fleming and S. Hsu

Tri bochemistry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

Chlorine is usually absent in virgin lubricating base oils

(usually less than 2 ppm). However, in re-refined lubricating

oils, chlorine usually is present at 5 to 10 ppm, a few base oils

have chlorine content as high as 1000 ppm. The effects of the

chlorine on performance are not clear. However, for consistency

monitoring of re-refined base oils, an accurate method to determine

the chlorine content is desired.

Five analytical methods were studied. They are ASTM D-808

method; Chlorine in New and Used Petroleum Products (bomb method),

ASTM D-1317 method; Chlorine in New and Used Petroleum Products

(sodium alcoholate method), X-ray Fluorescence Method (XRF),

Neutron Activation Analysis (NAA), and micro coulometric titration

method.

Both ASTM methods have a low applicability limit of 100 ppm

which is higher than the usual chlorine concentration in re-refined

base oils. Thus they are not applicable. Modifications of these

two methods to lower limits were unsuccessful.

XRF method has a low applicability of 5 ppm which is above the

chlorine content in virgin base oils. The remaining two methods,

NAA and microcoulometric titration method are suitable for the

determination of chlorine content in the base oils. The applicability

range of NAA is from 1 ppb to 100 percent and of the microcoulometric

titration method, the range is 1 ppm to 1 percent. The precision

of NAA is ± 0.2 percent and microcoulometric titration method, ± 10

percent.

11-15
A THIN-FILM OXYGEN UPTAKE TEST FOR THE EVALUATION OF

AUTOMOTIVE LUBRICANTS

C. S. Ku and S. M. Hsu

Tribochemi stry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

A thin-film, oxygen absorption test has been developed for the

evaluation of automotive lubricants using a standard Rotary Bomb

Oxidation Test apparatus (RBOT) with simple modifications. The

test measures the induction time of the lubricant under test

conditions which simulate high temperature oxidation processes in

automotive engines. Effects of oxidized fuel components and metal

catalyses as well as the effect of hydrolysis on oil oxidation were

considered. Test results on the ASTM engine sequence HID

reference oils suggested qualitative correlation with engine

viscosity increase data. Additional commercial oils were also

tested and the results fell within the reference oil ranges.

11-16
THIN-FILM OXIDATION TEST: RELATIONSHIP BETWEEN CHEMICAL

COMPOSITION AND ADDITIVE RESPONSE FOR RE-REFINED OILS

C. S. Ku and S. M. Hsu

Tribochemistry Group

Materials Chemistry Division

National Bureau of Standards

Washington, DC 20234

Sixteen re-refined lubricating base oils from different

manufacturing processes were examined for oxidation stability with

an NBS developed thin film oxygen uptake test. The oils were

tested with a commercial SE/CC DI additive package. Possible

correlation between oxidation stability and chemical composition

parameter such as saturates, aromatics, polars sulfurs, and total

nitrogen contents were investigated. Key composition parameters to

oxidation stability are identified.

11-17
NBS PROVISIONAL TESTS FOR RE-REFINED ENGINE OIL

D. Becker and S. Hsu

Recycled Oil Program

National Bureau of Standards

Washington, DC 20234

This paper describes results which complete the second and

final phase of the NBS efforts on recycled oil. Test procedures

are described which NBS is recommending for establishing the

substantial equivalency of re-refined engine oil to virgin engine

oil. The strategy that NBS has adopted first calls for the

formulated oil quality to be determined by means of all currently

required industry tests. After the quality of the formulated

re-refined oil has been established through use of these tests, the

consistency of the re-refined oil basestock is to be monitored as a function of time through use of the tests described in this paper.

Re-refined oils designed to meet the various industry-accepted

performance levels would require testing levels concomitant with

those required for virgin oils. The NBS provisional tests for

re-refined basestock consistency include a number of test procedures

for chemical and physical characteristics, plus a bench test for

oxidation stability.

With respect to the provisional testing system described in

this paper, a period of validation of these tests is necessary

before full implementation. That is, a controlled application of

these tests to re-refined oils over a period of time is needed to ensure that they are completely capable of fulfilling the requirements of consistency monitoring. Upon completion of such a validation process, the provisional re-refined engine oil testing system

as described can be accepted for indicating that a re-refined

engine oil product is substantially equivalent to virgin engine

oil.

>

11-18
APPENDIX III. DIOXIN FORMATION IN INCINERATORS

W. M. Shaub and W. Tsang

Chemical Kinetics Division

National Bureau of Standards

Washington, DC 20234

Abstract

Processes which may contribute to the formation of polychlorinated dibenzo-p-dioxins (PCDDs) in incinerators are examined. A

model mechanism has been constructed to investigate the possibility

of homogeneous gas phase formation of PCDDs from polychlori nated

phenols in an incinerator environment. Numerical calculations have

been made. The results lead to the conclusion that the probability

of gas phase formation of PCDDs is likely to be very low at high

temperatures if mixing between fuel and air is efficient. Probable

sources of non- i deal i ties in practical incinerators are examined.

Effects of use of auxiliary hydrocarbon fuel and excess air are

examined. The potential role of non-gas phase effects is considered.

A discussion of some of the significant problems which complicate a further understanding of PCDD formation processes in incinerators

has been presented in a manner that highlights future research

needs.

Introduction

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated

dibenzofurans (PCDFs) have been reported to have been found in

incinerator emissions and other combustion sources r.1,2]

1

. It has

been suggested that these chemicals may be ubiquitous as a conse- quence of trace chemical processes that occur during combustion

[3]. This is a controversial question (4a, b). With respect to

their formation in municipal incinerators, it has been suggested

that likely major routes of formation are from chemically related

compounds such as chlorinated benzenes, chlorinated phenols and

PCBs [5]. There appears to be uncertainty as to the relative

importance of formation from non-chlorinated precursors and inorganic forms of chlorine or from chemically unrelated chloro-organic

compounds such as polyvinyl chlorides [5]. Laboratory experiments

which deal with the formation of PCDDs and PCDFs from polychlorinated phenols, polychlorophenates , polychlorobenzenes and PCBs have

been reported [1 ,2, 4b, 6, 7]. Most observations concerning the

formation of hazardous waste compounds such as PCDDs during thermal

incineration are fundamentally qualitative in nature in the sense that they do not provide detailed answers which can lead to process

modifications that may minimize the formation of PCDDs. None of

the experiments [1,2,6,7] which have been reported to date can be

considered to be adequate to demonstrate that the compounds (PCDDs,

PCDFs, etc.) which have been observed to form are attributable to

gas phase processes [8,9]. In addition, we have previously suggested

1 Figures in brackets indicate the literature references at the end

of this paper.

III-l
that in some instances there seems to be evidence that formations

reported in some laboratory experiments may in fact be due at least

in part to surface reactions [10,11]. There is a substantial body

of literature in which it has been explicitly demonstrated that

reactions involving chlorinated species are frequently affected or controlled in whole or in part by the presence of reactive surfaces

[8,12-27].

In the following discussion we will examine some aspects of

these problems by first considering the potential for gas phase

formation under strictly homogeneous conditions in order to establish

a frame of reference. We draw upon existing information about gas

phase reaction processes to develop a reasonable mechanism for gas

phase formation of PCDDs from a suggested precursor, polychlorinated

phenols [2]. Next, we examine some possible gas phase non-idealities

which may develop during thermal incineration. This will be

followed by a consideration of potential non-gas phase contributions.

Some general conclusions will be drawn regarding the problem of

understanding PCDD formation in incinerators.

Mechanism Construction

The reaction steps which make up the proposed gas phase

mechanism, discussed below, are shown in table 1. The species

denoted P, P«, PD and D respectively represent polychlorinated

phenols, polychlorinated phenoxy radicals, polychlorinated 2-

phenoxyphenol s (dioxin precursor [2]) and PCDDs. These compounds

are shown in figure 1, where CI and CI denote the varying extent

of chlorination of the compounds. In tXble 1, the species denoted

by the symbol, R, represent any other organic fuel compounds in the

gas phase mixture. R* and Pr respectively denote a fuel molecule

from which a hydrogen atom has been abstracted and unspecified

products. In Figure 2, the pathways of the proposed mechanism are shown schematically.

The rate constants assigned to the steps in the mechanism have

been given values similar to rate constants which have been reported

in the literature for analogous reactions. However, where there

are uncertainties, the numerical values have been adjusted somewhat

to bias the mechanism in favor of PCDD formation i.e., worse case

model i ng .

Each of the reaction steps as given in table 1 is discussed

below. The assigned rate constants have been biased to favor PCDD

formation. Therefore the reader is strongly cautioned not to use these estimates out of the context of this paper, as actual values

for these rates will be quite different in some cases. The reaction,

P - P- + H (Rl)

represents the simple unimolecular bond rupture of the weakest bond

in a polychlorinated phenol. The activation energy for this step

is taken as the 0-H bond energy in phenol, which has been determined

experimentally [28]. Chlorine substitution is not expected to

affect substantially this value [10]. The pre-exponential factor

III-2
is assigned a value comparable to that associated with the formation

of benzyl radical from dissociation of toluene [29] as a reasonable

estimate. Thus, k(Rl)^10 155 exp(-86000/RT) s" 1

.

The reaction,

OH + P -» P- H

£

0 (R2)

represents the process of hydrogen atom abstraction by hydroxy 1 radicals. In high temperature combustion such as incineration, the

hydroxyl radical is the most important small inorganic radical

present under typical incinerator operating conditions [10,11,

30-34]. Furthermore, there is evidence that a local thermodynamic

equilibrium between small inorganic radicals rapidly develops in

the combustion flame zone [10,11,34]. A temperature dependent

hydroxyl radical concentration can therefore be estimated from the

local equilibrium assumption. In addition, we have previously

estimated a bimolecular rate constant of ~109 L'mol'^s" 1 for

hydroxyl radical attack on PCDDs [10]. The mechanism uses the

value of ~109 L*mol

1 *s" 1 for this reaction, and is biased in

favor of PCDD formation by ignoring the addition reaction of OH to

polychlorinated phenols, even though OH addition to aromatic

compounds is known to occur [30,36-38]. The adduct from OH addition

may simply decompose back to the original reactants, or undergo

further reaction with molecular oxygen or other species present in

the combustion system, leading eventually to ring opening [10,28,

35,36], a process which would not be expected to favor PCDD formation. Note also that the electrophi 1 ic nature of OH attack in

addition reactions leads to a drastic lowering of the rates with

increasing halogenation and that addition reactions usually decrease

in rate as the temperature is increased [30].

The reaction,

P- -> Pr (R3)

represents the decomposition of the phenoxy radical, resulting in

elimination of CO, which has been observed to occur [28,39]. The

assigned rate constant, k(R3) wlO 13,6 exp(-57654/RT) L-mol _1 'S" 1 follows from analogy to the results of Colussi, Zabel and Benson

[28].

The reaction,

P + P- * PD + CI (R4)

represents the formation of a PCDD precursor, a polychlorinated

2-phenoxyphenol . In order to bias the mechanism in favor of PCDD

formation, the possibility of reaction at other than the 2 position

is ignored. Reaction at other than the 2 position has been reported,

although not explicitly for the gas phase [40,41] and may

ultimately lead to polymerization in some instances. The rate of

this bimolecular reaction, (R4), is probably very slow with a very

small steric factor and possibly a negative temperature dependence

III-3
[10,42]. It is probably slower than the hydrogen abstraction

reaction, (R7),

P- + R -* P + R- (R7)

Mulcahy and co-workers [43] have reported (for the unsubsti tuted

phenol) that the reaction

CH 3 + P -> CH 4 + Phas an activation energy barrier of E. ~ 8±2 kcal • mol

1

- Since

AH°298 = 17.8 kcal -mol 1 for the reverse of this reaction [10,44,

45], the activation energy for the reverse of this reaction may be

estimated to be about 26 kcal •mol 1

. Therefore, by analogy, to

bias the mechanism in favor of PCDD formation, we assign to the

rate constant for reaction (R7), a value of k(R7) « 10 8 exp(-26000/

RT) L«mol" 1 *s" 1

. (In all rate equations that appear in this paper

the gas constant, R, has the value 1.987 cal •mol" 1 *K" 1 ), and we assign a rate constant for the reaction, (R4), a value of k(R4)«

10xk(R7).

Reaction, (R5),

PD * D + HC1 (R5)

is a molecular elimination reaction leading to PCDD formation.

Rate expressions for the molecular elimination of HC1 from alkyl

chlorides have been reported [29,46], with pre-exponential factors

in the range typically «io 13 - 510 - 5 and activation energies of

typically « 50 ± 5 kcal mol" 1. Reaction rates for gas phase

molecular elimination of HC1 from aromatics are not reported in the

literature. However, the reaction is not likely to be faster than

above, due to geometric requirements on the orientation of the

hydrogen and chlorine atoms on the two rings and the strengths of

the bonds involved [10,20]. The closest analogue for reaction (R5)

which we have been able to find in the literature [47a, b] is the

unimolecular elimination of HC1 from l-(l-chloroethly)-2-

methylbenzene for which a rate constant of k = 3.55 x 10 13 exp(-44,

830/RT) s1 is reported [47a]. We assign the value k(R5) * 10 14

exp(-45000/RT) s" 1 to the rate constant for reaction, (R5) in order

to bias the mechanism in favor of PCDD formation. In fact, by

analogy to other aromatic systems [48,49] there is reason to

suspect a substantially higher activation energy as well as possible competition between this molecular elimination channel and

other simple unimolecular bond fission reactions. It is also

likely that there is a small steric factor to be associated with

reaction, (R5) [10].

Reaction (R6),

PD + OH -» D + H

2

0 (R6)

is similar to reaction (R2), for which we have previously estimated

a bimolecular rate constant of k(R2) « 109 L-mol" 1 ^"1

. Here we

III-4
assume reaction, R(6), is actually a combination of a rate limiting

abstraction reaction

PD + OH -> PD- + H

2 0 (R6)'

leading to production of a polychl ori nated 2-phenoxyphenoxy radical

which then rapidly reacts unimolecularly to form a PCDD

PD- -> D (fast)

and ignore the possibility of decomposition, in order to bias the

mechanism in favor of PCDD formation. For the same reason, we ignore the addition reaction of OH.

Reaction (R8),

P- + OH -> Pr (R8)

is expected to be faster than reaction (R2), since both reactants

are radicals. However, to bias the mechanism in favor of PCDD

formation, we will assume the rates are comparable and set k(R8)=

k(R2).

. Reaction (R9),

D -> Pr (R9)

represents the unimolecular dissociation of a PCDD to form products

which will, at the temperatures where reaction (R9) becomes important,

subsequently undergo further decomposition. We have previously

estimated a rate constant of k(R9) ^10 15 - 5 exp(-80000/RT) s' 1 [10]

for this reaction.

Reaction (RIO),

OH + D -> Pr (RIO)

is the bimolecular reaction of a PCDD with a hydroxy 1 radical. We

have previously estimated a value k(R10) ~ 10 9 L-moW-s" 1 for this

reaction [10,11]. We bias the mechanism in favor of PCDD accumulation

by reducing this value to k(R10) ~ 10 8 L-mol

1

• s

1

.

Reaction (Rll),

0

2 + P- -> Pr (Rll)

is the bimolecular reaction of a polychl ori nated phenoxy radical

with molecular oxygen. The reaction of the unsubsti tuted phenoxy

radical with molecular oxygen has been estimated to have a rate

constant of ~108 L-moW-s' 1 [48-51], and we assign this value

here.

Reaction (R12),

R + OH - R- + H

2 0 (R12)

1 1 1-5
is expected to be slower in general than reaction (R8). However,

to bias the mechanism in favor of PCDD formation, we will set

k(R12) ~ 109 L*mol _

1

'S -1

, since the availability of the species, R,

will decrease the concentration of P* through reaction (R7). The reverse of reaction (R12), is neglected since in combustion typical

of incineration, the radical R«, resulting from hydrogen atom

abstraction is highly labile and can react further with molecular

oxygen, other fuel molecules and hydroxy! radicals, which will be

present at substantially higher concentrations than the phenoxy

radical [8-10,30].

Reaction (R13),

R -> Pr (R13)

like reaction (R12), actually represents a broad spectrum of

reactions, and we assign a typical value of k(R13) 10 16

exp(-90000/RT) s _1 [29,46]. These reactions are strongly temperature dependent, and will tend to become important at temperatures

at which PCDD destruction, as opposed to formation is already

strongly favored.

Computer Simulation

The mechanism, as given in Table I has been used to study the

possibility of PCDD formation under typical incinerator combustion

conditions through computer simulation via a standard Gear type

[52] ordinary differential equation system solver. Various initial

conditions as described below were tested. We considered a typical

trichlorinated phenol, although this choice is arbitrary in view of

the generalities of the mechanism. Initial mole fractions of fuel

reactant and oxygen are assigned based upon assumption of stoichiometric combustion (equivalence ratio equal to one) and conversion

to carbon dioxide, water and HC1 as major products. Atmospheric

pressure was assumed and reaction at a range of temperatures from

500 K to 1500 K was investigated. Four cases (i-iv) were examined,

for which initial mole fractions are as given in table 2. In all

cases, the concentration of hydroxyl radical was defined through

the assumption of local equilibrium to be (0H)rn « 10' 1 - 7 exp(-35000/RT) mol-L' 1 [10,30].

t4

Case (i) is used as a base against which to test the role of

molecular oxygen and auxilliary hydrocarbon fuel in the destruction

of polychlorinated phenols and in the possible formation of PCDDs.

In actual stoichiometric or fuel lean combustion, there are (except

in the case of mixing inhomogenei ties between fuel and air) consider

able molecular oxygen available up to the point of substantial fuel

conversion. Therefore, this case is actually worse than the true

situation and probably greatly exaggerates gas phase PCDD formation

beyond what is realistically to be expected in ordinary combustion

in the absence of significant mixing inhomogeneities between fuel

and air. It is also not representative of a pyrolysis process,

where [OH] << [OH]^. In fact, for pyrolysis the mechanism would

have to be developed differently, with inclusion of unimolecular

initiation reactions such as reaction, (Rl), and exclusion of

III-6
emphasis on reactions involving hydroxyl radical attack. Note,

however, that in the gas phase these reactions are likely to be

characterized by large activation energies. Thus gas phase pyrolysis may not necessarily be expected to produce substantial amounts

of PCDDs, as initiation reactions may have rate constants comparable

to those for decomposition of PCDDs etc. In addition, it is

possible that polymerization reactions would have to be included as part of the pyrolysis process [40,41]. With great care, since the

mechanism is biased in favor of PCDD formation, this case may

possibly be regarded as suggestive of the situation in which an unburned fuel pocket, due to mixing inhomogeneities , passes into a post combustion zone where oxygen has already been depleted, but

the [OH] radical concentration still tracks the local temperature

in the incinerator. However, to determine fully the importance of

this case one would have to analyze carefully the statistical

character of variations of fuel/air inhomogeneities throughout a combustor and in addition develop refined estimates of the rate

constants to eliminate the bias. In the case of a well designed

incinerator we suspect the importance of fuel/air inhomogeneities

is probably small relative to the bulk combustion process. This

case in which the fuel is a pure phenol in no way corresponds to

municipal incineration where such a chlorinated compound would only

be present as a trace substituent in the input feed stream and not

as a major component. In any event, note that in fact, if the

phenol were present as a nearly pure compound in a waste stream, it

would be most likely recovered for further use rather than destroyed

thermal ly.

Case (ii) is more suggestive of combustion of a chlorophenol

under hazardous waste incinerator conditions. Normally, most

incinerators are run under stoichiometric or excess air conditions.

However, to bias the mechanism in favor of PCDD formation we have

adjusted the initial mole fraction of molecular oxygen to a level

of about 60 percent of its value in stoichiometric combustion.

This has the effect of de-emphasizing the rate of loss of the

phenoxy radical, P-, via reaction Rll.

Case (iii) corresponds to a fuel rich pocket in a post combustion zone environment in the combustion of a mixture of a phenol

and an excess of an auxiliary hydrocarbon fuel. This case is

intermediate between combustion in a liquid hazardous waste incinerator where the percent of chloro-organic could be higher and the case of municipal incineration where the chloro-organic ^content

would be lower. Again, molecular oxygen is treated as though it were unavailable.

Case (iv) is similar to case (iii) but has molecular oxygen

present during the combustion stage. Case (iv) is to be compared

to case (iii) as case (ii) is to case (i).

Discussion

The results of modeling these four cases for combustion during

an elapsed time period of one second, which is a residence time

typical of incineration are presented in table 3. The symbols P,

P-, D, R and PD used in table 3 are defined in figure 1. Below,

III-7
the results are analyzed. Concentrations for all four cases were computed for a wide range of reaction times other than t = 1 second

but are not presented here to save page space.

Under the conditions of case (i) - i.e. post-combustion mixing

and reaction of unburned phenol with hydroxyl radicals, some substantial PCDD formation is indicated at intermediate temperatures.

This is the only case where that is true. However, this case is

not realistic. It assumes the entire initial mole fraction of

phenol makes it into the post combustion zone of an incinerator.

This is not likely to happen. In fact under normal operating

conditions in a well designed incinerator, only a very small amount

of unburned fuel would be likely to enter the combustion zone. Therefore, realistically, these mole fractions of PCDD produced

under case (i) would have to be weighted by the fraction of fuel

which actually makes it to the post combustion zone. On the basis

of such a weighting process, one would expect a much lower PCDD

formation than indicated in case (i).

In all the other cases it is quite clear that PCDD production

is very low. The use of auxiliary fuel, stoichiometric or excess

air and high temperatures (all of which are common operating

conditions) promote phenol destruction to products other than

PCDDs. At flame temperatures, gas phase PCDD formation would be

below detection limits. Note also from Table III that in all cases

the level of 2-phenoxyphenol formation is predicted by the mechanism

which has been utilized, to be much lower than PCDD formation. In

part this may possibly explain why phenoxyphenol s are not commonly

reported as products of combustion.

In actual practice, it is found that PCDD emissions sometimes

exceed the levels predicted by the above results. This requires

consideration in some detail as to the nature of these circumstances. Some additional possibilities may be:

a) PCDDs were originally present in the input feed streams

and survive thermal destruction in significant amounts.

b) Due to mixing i nhomogenei ties some unburned chloroorganics

survive the main combustion environment and make it into

the post-combustion zone.

c) Temperature fluctuations (thermal transients) result in

incomplete thermal stressing due to gas entrapment in

cold pockets, promoting PCDD production at above ambient

but below flame temperature conditions.

d) Molecules other than polychlori nated phenols are being

converted to PCDDs in the gas phase.

e) Inorganic chlorine sources in municipal waste input feed

streams lead to chlori nation of organics and ultimate

formation of PCDDs in the gas phase.

f) Non-gas phase, or a combination of gas and non-gas phase

reactions are contributing to the production of PCDDs

during the combustion process.
With regard to (a), it has been stated that at least for

municipal waste streams, PCDDs are not initially present in input

feedstreams in significant amounts [5], to the extent that would be

required to account for observed levels of emissions. In the case

of hazardous waste incineration streams, the situation would depend

on the feedstock. By way of a hypothetical example, note that if

it were the case that a municipal waste stream contained 1 part per

thousand of polychlorinated phenols which in turn contained 100 ppm

of a PCDD impurity, then the expected PCDD level in the effluent

stream (gas plus fly ash combined) would be on the order of tens of

ppb if the PCDD destruction efficiency were zero (due to dilution)

and would readily fall to a few parts per trillion once the destruction efficiency exceeds 99 percent for the PCDDs. We have previously

described an estimation procedure for calculating the expected

destruction efficiencies if homogeneous mixing is developed in the

gas phase of an incinerator [10,11]. This procedure was applied to

the case of PCDD destruction. We could conclude from these estimates

that the gas phase thermal destruction efficiency for PCDDs is

extremely high at flame temperatures typically achieved in an incinerator [10,11].

With regard to (b), further investigation is warranted as there is not much data presently available about statistically

representative temporal or spatial frequencies of unburned fuel

pockets of varying fuel /air composition in practical incinerators.

Mixing inhomogeneities may develop for various reasons, e.g., poor

atomization may sometimes be a problem in liquid hazardous waste

incinerators. Samuelsen [53] has discussed the formation of eddies

or pockets of varying fuel air mixtures in non-premixed flames.

Breen [54] has estimated that eddy lifetimes may range anywhere

from 10 to 50 milliseconds. Whether or not these eddies will

ignite depends significantly upon the fuel/air ratio in an eddy and

upon the extent to which an eddy may mix together with other eddies

[53]. Appelton and Heywood [55] have discussed how inhomogeneities

due to eddies or pockets of varying fuel/air mixtures may affect

pollutant formation in continuous flow combustors burning atomized

liquid fuels.

In addition, in the case of liquid injection, peculiarities of

the liquid mixture being injected may sometimes present problems.

Wood and others [56] have demonstrated that during the combustion

of a multi-component fuel drop, the composition of the drop and its

surrounding vapor change by a process of simple batch distillation.

The inference here is that one must sometimes be careful as to

which fuels are to be mixed together if fuel properties are such

that substantial distillation may be likely to occur. As an example, consider the injection of a mixture consisting of small

amounts of chloroform and chlorophenol diluted in an auxilliary

hydrocarbon fuel such as n-octane. To begin with, if atomization

and/or mixing are poor, the maximum temperature will occur, not at

the stoichiometric equivalence point, but at a somewhat lower

equivalence ratio (leaner fuel mix than theoretical stoichiometric

composition) corresponding to introduction of a substantial amount

of excess air [57]. At this maximum temperature point, the mixture

will be efficiently thermally decomposed. On movement into the

III-9
fuel lean and fuel rich sides of this maximum temperature point,

temperatures may be increasingly substantially lower and destruction

efficiencies may be component specific. In apparent contradiction

to expectations based upon a kinetic scale of incinerability [30], one would observe in some off maximum temperature circumstances,

due to the batch distillation process, that much more chloroform

than chlorophenol could persist through the combustion zone. This

is because the selective evaporation of chloroform into the vapor

phase rapidly enriches the vapor phase in this component as the

droplet begins to evaporate [58]. Depending on the amount of

enrichment this can significantly reduce the extent of reaction in

the chloroform enriched vapor phase due to the flame inhibiting

characteristics of the resulting mixture [59,60]. If the combustion zone is small, subsequent fluid hydro dynamic processes may

remove some of this self inhibiting mixture from the region of the

combustion zone before more substantial mixing and enhanced combustion can occur. At the same time, the liquid droplet is becoming

enriched in chlorophenol and auxilliary hydrocarbon fuel (increasing

mole fraction) by the distillation process. This mixture may have

less flame inhibiting character (due to chloroform removal) and as such will subsequently burn more completely on evaporation. Thus more chlorophenol than chloroform is destroyed in these circumstances.

It may be the case that as the chlorophenol is mostly contained in

a droplet which is burning at or near its boiling point [61], some conversion to secondary products of formation may occur within the

droplet prior to complete evaporation. However, this in itself

(and similarly for the case of secondary product formation due to

pyrolysis reactions which might occur during the short period of

warmup of the escaping vapor to its ignition point [62]) would not

necessarily create a hazardous secondary product emission problem

if the chlorophenol enriched droplet subsequently totally evaporates

within the high temperature combustion zone and providing the

off-maximum temperature is still substantially high enough to

thermally decompose the resulting gas phase mixture. Similar

arguments would apply to the small amounts of chlorophenol lost to

the chloroform enriched vapor phase. A complication could arise if

flame inhibition occurs to such a substantial extent that it

results in flame extinguishment in the region of the chlorophenol

enriched drops. This problem could possibly be solved by allowing

for a large enough combustion zone such that the droplet could

subsequently be re-ignited. In most cases, some approaches to

these problems would be to improve atomization, improve mixing,

adjust the initial fuel mixture composition to avoid undesirable

distillations, provide for a high temperature combustion zone transit time which significantly exceeds the droplet burnout and

mixing times, or to employ afterburners (staged combustion).

In any event, predictions of incinerability based upon chemical

kinetics [30] are still possible. The problem of the apparent

breakdown of a kinetic scale of incinerability is solved by recognizing that the incinerability scale is designed to be applied to

homogeneous gas phase mixtures . Thus, once a distillation process

occurs the kinetic scale of incinerability must be applied separately

to enriched and depleted vapor mixtures and their local environment

temperatures. In this case a weighting must be employed to account

111-10
for these physical mass transfer effects resulting from the distillation process.

It is possible to design experiments for measuring directly

fast transient fuel burning fluctuations [63,64], but these methods

have not been commonly applied to the process of incineration.

Note that if in fact mixing inhomogeneities are a problem, it is

not a problem without possible practical solution for reasons mentioned previously.

The possibility (c), is to an extent, related to the degree of

mixing, although other parameters are also operative in controlling

thermal fluctuations [65-67]. Detection of fast (100 Hz and

higher) thermal fluctuations at a point in space in turbocombustors

has been made optically [63] and via physical measurement with fast

time constant thermocouples [68-70]. Application of optical

detection to an incinerator environment will require correction for

substantial particulate entrainment in the flow stream. The

application of fast time constant thermal measuring devices will

require innovative technology such as R. R. Dils new high temperature optical fiber thermometer [71] to avoid large error measurements,

since at flow speeds and temperatures typical of an incinerator,

convective transport is greatly diminished relative to the

situation in a turbocombustor [68-71]. Under incinerator

conditions of low flow rates, thermocouple fast transient

temperature measurements are substantially based upon radiative

transport, and this dependence is the source of the large errors in

these thermal measurements when thermal fluctuations are rapid.

Numerical simulations of scales of incinerabi 1 ity or formation in

the presence of temperature fluctuations are possible

[10,11,30,65-67]. It is important to stress that in numerical

simulations of destruction or formation of toxics in non ideally

mixed reactive flows with temperature fluctuations, one must as a minimum, account for not only the effects of unimolecular but also

of bimolecular processes such as those involving hydroxyl radicals

[10,11]. If this is not done, results can be misleading. The

extent to which a typical thermal destruction process as characterized by the rate constant expression

k = k T0H] + k destruction biomolecular L J unimolecular

becomes dominated by the unimolecular character may possibly

provide useful information about deviations from the ideal case of

well mixed fuel/air combustion at flame temperatures. Another

important question for case (c) that will have to be addressed is

the question as to what extent or not unburned or partially combusted

fuel trapped in a relatively cool pocket can be easily transported

to the post combustion zone where PCDD formation might possibly

take place. While it is known that transport of unburned or partially combusted fuel does occur in some specific instances, for

example in a diffusion flame [53-55], a detailed and quantitative

assessment of this problem in practical incinerators has not yet

been developed. More work needs to be done in this respect, since

at least in the case of turbopropul sion , thermal fluctuations can

be enormous [68] and fluctuations in turbulent flames in general

III-ll
have been known sometimes to be substantial [53-55,67,71]. We

suspect based on observed combustion efficiencies that the statistical probability for transport of unburned fuel in a cold pocket to

the post combustion zone is probably low in a well designed incinerator [10].

The possibility (d), that molecules other than polycholorinated

phenols lead to gas phase formation of PCODs under typical incinerator conditions is amenable to the same type of numerical analysis

as we have presented in this paper. It is reasonable to expect

that the fewer the features a precursor molecule has in common with

PCDDs or PCDFs (e.g. aromatic character chlorine or hydroxyl

functional groups), the more complex the mechanism one would have

to propose for PCDD or PCDF formation. Under these circumstances,

at high temperatures, there will probably be more competitive

destruction pathways (vs. formation pathways) than in the mechanism

we have proposed for PCDD formation from polychlorinated phenols

(or polychlorinated 2-phenoxyphenols). Thus, the probability for

formation of PCDDs or PCDFs would be expected to decrease under

these circumstances. We plan to investigate this further. As

mentioned previously, we feel there have been no experiments made

to date which unambiguously demonstrate that gas phase formation of

PCDDs and PCDFs occurs under typical combustion conditions. We do,

however, feel confident that such experiments can be designed and

used to test for non gas phase and inhomogeneous mixing effects

[8,9,63-71].

The possibility, (e), that of de novo synthesis from inorganic

sources of chlorine in the gas phase has not been extensively

examined [1,2]. We have investigated briefly the presence of

FeCl 2 , FeCl 3 and NaCl in the gas phase through numerical equilibrium

modeling under conditions typical of incineration, for example, as outlined in this paper. This modeling indicates that in incineration, temperatures in excess of 1000 K are required for low levels

of NaCl to build up in the gas phase and that temperatures in excess of about 1200 K are required for low levels of iron chlorides

to develop in the gas phase. Equilibrium conditions at lower

temperatures overwhelmingly favor distribution of these metals

among non gas phase species.

The quantitative reactivity of NaCl or iron chlorides as a source of chlorine for gas phase chlorination of organics at high

temperatures has not been reported. In addition the time required

for these inorganic chloride species to develop to equilibrium

concentrations is not reported under typical incinerator combustion

conditions. In the event that aluminum recycling is not practiced,

aluminum chlorides would also have to be considered in a similar

manner. Heavy metal chlorides, e.g. ZnCl 2 , CdCl 2 and PbCl 2 are much more volatile at these temperatures [72], but except for

fairly specific waste streams the amounts of these metals initially

present is usually low.

The above discussion implies that even if these materials are present and reactive in the gas phase at incinerator conditions,

there are not likely to be any simple mechanisms in which through

111-12
only - few steps, the production of PCDDs would occur to any

sign. i icant extent. This is because the bimolecular rates associated

with the reaction steps of any proposed mechanism would be low as a consequence of the low gas phase concentrations of these species at

incinerator operating temperatures. As seen from our modeling of

polychlorinated phenol combustion, at high temperatures PCDD

formation involving multistep processes consisting of several

reaction steps where reactant concentrations are low to begin with

cannot easily compete with other routes which lead to destruction

during the combustion process. For these reasons we strongly

suspect de novo synthesis from inorganic precursors is unimportant

in the gas phase. This discussion does not imply, however, that

de novo synthesis from inorganic sources of chlorine via non gas

phase processes is to be discounted. Quite the contrary, multiphase

reactions involving inorganic chlorides have been reported, including

those which produce HC1 and C1 2 from metal chlorides [73] and those

which result in the production of PCDDs [74] and other chlorinated

organics [75].

The last and most intriguing possibility, (f), is the assumption

that non gas phase or a combination of gas and non gas phase

reactions may be contributing to the production of PCDDs during the

combustion process. We have previously alluded in this paper to the

extensive literature which reports the enhanced reaction sensitivity

of organic species to the presence of reactive surfaces. Fly ash

itself is principally a mixture of silica and metal oxides [10] and

should have many reactive Lewis and Bronsted acid and base sites

which could presumably promote reactions [23-25] at temperatures

considerably below those at which the previously discussed destruction processes dominate. In fact, chloro-organics formed from

reactions in the presence of chlorine and fly ash have recently

been reported [21]. We have also indicated that there is other

research which appears to suggest oxygenation of chloro-organics to

form PCDFs may be due to surface reactions [10]. One must also

consider the work of Nestrick and co-workers [27] in synthesizing

PCDDs from chlorophenates which must be due to surface reactions in

view of the low temperatures in which reactions were carried out.

The highly polar nature of the metal to oxygen bond in the chlorophenates that were used and the surface reactivity of the silica

support they used probably favor ionic reactions on the surface

[23-25], possibly involving surface bound hydroxyl groups and other

reactive sites. At these temperatures [27] radical reactions in

the gas phase cannot compete. Surface reactions and/or reactions

inside solids (such as fly ash and other materials) therefore seem

to be strong candidates as potential sources for PCDD and PCDF

formation. Transport of these compounds into effluent emissions

could then possibly be due to insulation inside particles that have

not been sufficiently heated to the core. Presumably, vapor

emissions of toxics would in part then be associated with particle

outgassing in the post combustion zone [10]. In addition, particles,

111-13
of PCDD emissions with particle size may be informative in

understanding the relative importance of the above possibilities

although care in interpreting results may have to be exercised if

data is taken from units equipped with electrostatic precipitators

due to differences in the ease of ionization of particles of

varying material composition.

Other complicating effects associated with particle emissions

may at times potentially be encountered. For example: With respect

to fly ash particle size as a function of distance measured movi ng

away from an incinerator point source, fly ash particle size

distributions taken from soil samples (surrounding the incinerator

point source) may shift to deposition of particles of smaller sizes

onto the soil. This is anticipated from differences in the terminal

gravitational settling velocity between particles of different

sizes [76,77]. If the smaller particles have been more thermally

stressed in the incinerator due to the strong dependence of particle

heat up times with particle diameter [10,78], then isomer distribution

ratios of PCDDs/octachl oro-DD (e.g. heptachloro-DD/octachloro-DD)

formed on the fly ash particles should be observed to asymptotically

shift towards lower ratios as one moves away from the incinerator

point source, i.e., particle size and PCDD/octachloro-DD ratios

reflect their thermal history inside the incinerator and should

track each other. That the shift should occur in the direction of

lower ratios on moving away from the incinerator point source is a reflection of the increasing thermal [30,79] and kinetic [10,11]

stability of PCDDs with increasing degree of chlorination, i.e., on the more thermally stressed particles the more kinetically and

thermally stable PCDDs should predominate. The asymptotic nature

of the shift reflects the fact that below a certain particle size,

essentially complete (to the core) thermal heating of all fly ash

particles which have been exposed to high temperatures inside the

incinerator has occurred. Whether or not this trend could be

interpreted to demonstrate that volumetric as opposed to surface

formation (or deposits) of PCDDs are occurring in the incinerator

requires further analysis, particularly with respect to heat

sinking and particle porosity during the lifetime of the fly ash

particle's tranversal through the incinerator. This analysis

probably applies to municipal waste incineration where there are

not likely to be any significant amounts of PCDDs to begin with.

In the case of hazardous waste incinerators the analysis may be more complicated depending upon which if any PCDDs are initially

present in the input feedstream.

In addition to reactions inside of or on the surfaces of

particles, the possibility for liquid phase transformations may

have to be considered in some instances. The literature is replete

with reports of organic synthesis of PCDDs in various solutions

with and without catalysts (see reference [2] and references

contained therein). Liquid phase reactions may possibly occur,

e.g., in liquid injection hazardous waste incinerators where

atomization is poor and droplet evaporation times approach or exceed combustion zone transit times. In these instances it may be

worthwhile to investigate alteration of droplet evaporation times,

improving atomization, use of afterburners (staging), etc., as mentioned previously.

111-14
A further source of precursors may be from compounds entrained

in the input combustion air feedstream itself. For example, Junk

and co-workers [80-83] have discussed in careful detail the presence

of PCBs in combustion air. Therefore, in addition to waste feedstream

sources [1-5, 84] additional consideration may have to be given to

the history of combustion air as it passes through an incinerator.

However, with respect to gas phase formation processes, arguments

similar to those presented in this paper probably apply, and PCDD

formation from trace organics in input combustion air is therefore

probably unimportant at the same conditions and high temperatures

that would ordinarily promote PCDD destruction.

Concl usions

Clearly, to more fully understand details of the processes for

formation and destruction of toxics such as PCDDs and PCDFs during

the process of high temperature combustion, more research is

required for reasons and in directions we have indicated above. On

the other hand, it is important to recognize that there is no unique thermal or kinetic stability attributable to these compounds

[30] that would prohibit their efficient destruction at high

temperatures.

We recommend that several research objectives should be set as enumerated below. This listing is not all inclusive but does serve

to highlight what we feel are some current research needs with

respect to understanding the processes by which PCDDs, PCDFs and

similar toxic compounds may be formed and destroyed during practical

thermal incineration:

a) Analytical methods should be further developed and applied

to quantify types and amounts of specific organic compounds and

classes of organic compounds not only as a function of fly ash (or

bottom ash, ESP ash, etc.) particle size but also as a function of

their distribution on the surface of or inside (volumetric and

internal surface due to pores) particles. The same comments should

be understood to apply to inorganic species associated with fly ash

emissions (or bottom ash, ESP ash, etc.). In addition the distribution of species among the various phases (solid/fly ash, soot;

liquid/water aerosol, organic aerosol, gas/evolved gas) needs to be

characterized.

b) Efforts should be made to study and understand fast

transient phenomena in incinerators, e.g. cold pockets, preignition pyrolysis, mixing inhomogeneities , etc.

c) Much more effort should be directed toward understanding

the nature of condensed phase reactions (catalyzed and

uncatalyzed) , e.g., surface reactions, reactions in solids, etc.

This applies not only to incineration but also to land filling .

d) Predictive, reactive flow multidimensional fluid

hydrodynamic numerical simulations should be performed to study the

dynamic character of the incineration process.

111-15
e) Laboratory scale experiments need to be performed as an aid to refining rate constants associated with reaction steps in

any proposed mechanisms. These should include both gas phase and

condensed phase kinetics. With more refined mechanisms sensitivity

analysis should be undertaken. Similarly more thermodynamic data

is needed for species such as chl orophenol s , PCDDs, PCDFs, etc.,

which is more reliable than what is currently reported, if predictions of equilibrium isomer distributions are to be made with

greater accuracy.

f) Complicating effects, e.g. selective compound distillations, particle size separations, etc., should be examined in more

detai 1

.

g) Optical methods should be applied to real time detection

of transients species in incinerator environments; especially

hydroxyl radical due to its importance in the combustion process.

Continuous rather than intermittent (e.g. as with a 10 Hz pulsed

laser) measurements would be desirable in order to understand

perturbations in concentration measurements due to effects such as vortex shedding.

h) Interferences in analysis, e.g. of organic compounds in

fly ash due to naturally occurring particulates, e.g., [85], should

be very carefully assessed.

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Stephenson, B. , and Banjoko, 0., J. Chem. Soc. (B), 805-808,

(1968).

[48] Ladachi, M. and Swarc, M. , Proc. Roy. Soc. (Lond.) A219 , 341-352 (1953); 353-366 (1953).

[49a] Asaba, T. and Fujii, N. , "High Temperature Oxidation of

Benzene," paper No. 46 In: Stollery, J. L. , Gaydon, A.G.

,

and Owen, P.R., Eds. Shock Tube Research , Chapman and Hall,

London, 1971

.

[49b] Fujii, N. and Asaba, T. J., Fac. Eng. Univ. Tokyo (B) 34,

189-224 (1977).

[50] Russell, G. A. and Bridger, R. F. , J. Amer. Chem. Soc. 85,

3765-3766 (1963).

[51] Tokumaru, K. , Horie, K. and Simamura, 0., Tetrahedron 21_,

867-870 (1965).

111-19
[52] Hindmarsh, A. C. , GEAR: Ordinary Differential Equation

System Solver , Rpt. No. UCID-30001 , Rev. 1, Lawrence Liver- more Laboratory, Livermore, CA, Aug. 20, 1972.

[53] Samuelsen, G. S. , "The Combustion Aspects of Air Pollution,"

in Pitts, J. N. , Jr., and Metcalf, R. L. , Eds. Advances in

Environmental Science and Technology, Vol. 5 , John Wiley and

Sons, Inc., N.Y., N.Y. , p. 219-323 (1975).

[54] Breen, B. P., in Cornelius, W. and Agnew, W. G. , Eds.

Emissions from Continuous Combustion Systems , Plenum Press,

N.Y. , N. Y. , p. 325-333 (1972).

[55] Appleton, J. P. and Heywood, J. B. , 14th Symposium (International) on Combustion, The Combustion Institute, Pittsburgh,

PA, p. 777-786 (1973).

[56a] Wood, B. J., Wise, H. and Inami , S. H. , Combustion and Flame

4, 235-242 (1960).

[56b] Law, C. K. , Prog. Energy Combust. Sci. 8, 171-201 (1982).

[57] Bonner, R. , Desai , B. , Fullencamp, J., Hughes, T. , Kennedy,

E. , McCormick, R. , Peters, J., and Zanders, D. , Engi neeri ng

Handbook for Hazardous Waste Incineration , EPA Contract No.

68-03-2550, U.S. EPA, Washington, D.C., November (1980).

[58] Canada, G. S. and Faeth, G. M. , 15th Symposium (International)

on Combustion, The Combustion Institute, Pittsburgh, PA,

p. 248 (1975).

[59] Fristrom, R. M. and Van Tiggelen, P. J., 17th Symposium

International on Combustion, The Combustion Institute,

Pittsburgh, PA, p. 773-779 (1979).

[60] Fristrom, R. M. and Sawyer, R. F. , "Flame Inhibition

Chemistry," AGARD Conference Proceedings #84, Aircraft

Fuels, Lubricants and Fire Safety , AGARD-CP-84-71 , Section

12 (1971).

[61] Khudyakov, L. , Chem. Abstr. 46, 10844e (1955).

[62] Bittner, J. D. and Howard, J. B. , "Pre-particle Chemistry in

Soot Formation," in Siegla, D. C. and Smith, G. C. , Eds.

Particulate Carbon Formation During Combustion , Plenum

Press, N.Y., N.Y., p 109-142 (1981).

[63] Crosley, D. W. , Ed. , Laser Probes for Combustion Chemistry , Am. Chem. Society, Wash., DC (1980).

[64] Schoenung, S. M. and Hanson, R. K. , Appl. Optics 21_,

1767-1771 (1982).

[65] Oran, E. S. and Boris, J. P., "Detailed Modelling of

Combustion Systems", NRL Memorandum Report 4371, U.S. Naval

Research Lab., Wash. DC, 1980.

111-20
[66] Fritts, M. J., Fyfe, D. E. , and Oran, E. S. , "Numerical

Simulations of Droplet Flows With Surface Tension," ASME

Rpt. No. 82-WA/HT-17, ASME , N.Y., N.Y. (1982).

[67] Boris, J. P. and Oran, E. S.

, "Modeling Turbulence: Physics

or Curve Fitting," in Bowen, R. , Manson, N. , Oppenheim, A.

K. and Soloukin, R. I. , Eds. , Combustion in Reactive

Systems ; Progress in Astronautics and Aeronautics 76,

187-210 (1981).

[68] Dils, R. R. , J. Eng. for Power, p. 265-277 (1973).

[69] Hayhurst, A. N. and Kittelson, D. B. , Comb, and Flame 28,

301-317 (1977).

[70] Dils, R. R. and Follansbee, P. S. , "Use of Thermocouples for

Gas Temperature Measurements in Gas Turbine engines," in

Hastie, J. W. , Ed., Characterization of High Temperature

Vapors and Gases , NBS Special Publication 561, Wash., DC,

pp. 1027-1070, October 1979.

[71] Dils, R. R. , "NBS Develops High Temperature Optical Fiber

Thermometer," NBS Press Release TN-5387, National Bureau of

Standards, Washington, DC, 21 September 1983; also to appear

in the Journal of Applied Physics.

[72] Kox, W. M. A. and Van Der Vlist, E. , Conservation and

Recycling 4, 29-38 (1981).

[73] Clews, F. H. and Thompson, H. V., J. Chem. Soc. 121 , 1442-1448 (1922).

[74 Mahle, N. H. and Whiting, L. F. , Chemosphere 9, 693-698

(1980) .

[75] Chapra, N. M. and Sherman, L. R. , Anal. Chem. 44, 1036-1039

(1972).

[76] Ermak, D. L. , Atmos. Environ. V[, 231-237 (1977).

[77] Chamberlain, A. C. , "Aspects of Travel and Deposition of

Aerosal and Vapor Clouds", A.E.R.E. Rpt. HP/R 1261, Atomic

Energy Research, Harwell, Gt. Britain (1953).

[78] Russel, W. B. , Saville, D. A. and Greene, M. I., AIChE 25,

65-80 (1979).

[79] Shaub, W. M. , Thermochimica Acta 58, 11-44 (1982).

[80] Junk, G. A. and Ford, C. S. , Chemosphere 9, 187-191 (1980).

[81] Junk, G. A. and Richard, J. I., Chemosphere 10, 1237-1241

(1981) .

111-21
[82] Richard, J. J. and Junk, G. A. Envir. Sci and Tech. 1_5,

1095-1100 (1981).

[83] Vick, R. , Junk, G. A., Avery, M. and Svec, H. , Chemosphere

7, 893-902 (1978).

[84] Buckley, E. H. Science 216, 520-522 (1982).

[85] Wils, E. R. J., Hulst, A. G. and den Hartog, J. C. , Chemosphere n, 1087-1096 (1982).

111-22
Table 1. Proposed Biased PCDD Gas Phase Formation Mechanism

# Reaction Step

Rl pr P- + H

R2 r T un P- + H

2

0

R3 P • r Pr

R4 P + P

.

f T y • PD + CI

R5 pnru D + HC1

R6 ru + Un D + H

2

0

R7 p . + p r ^ K P + R

R8 Pr

R9 D Pr

RIO D + OH -» Pr

Rll p- + o

2 » Pr

R12 R + OH -> R- + H

2

0

R13 R -> Pr

111-23
(a) Table 2. Initial Mole Fractions v '

CASE (i) CASE (ii) CASE (iii) CASE (iv)

0. 0.1 0. 0.1

X

R

0. 0. 99X

p 99X

p

X

p 3.16 x 10" 2 3.16 x 10" 2

3.16 x 10~ 43.16 x 10

_4

(a) (OH) ~ (0H)

EQ ~ 10 17 exp(35000/RT) [30]. Total pressure = one atmosphere (760 torr). Other species, e.g. N 2 , H 2 0, HC1

,

Pr, etc. , which do not participate as reactants in the

mechanism shown in Table I make up the balance of the mole

fractions not explicitly detailed in Table II.

(b) In cases (ii) and (iv), the mole fraction of molecular oxygen

has been set to a level of about 60 percent of the stoichiometric combustion value as follows from the discussion

presented in the body of this paper.

111-24
Table 3a. Concentration^ ' of species after 1 second: case(i)

T(k) P P- D R PD

500 7. 70-4 2. 31-16 6. 58-28 1. 00-20 7. 10-22

600- 6. 42-4 2. 03-9 2. 34-16 1. 00-20 2.01-13

700 5. 50-4 1. 20-7 5. 31-11 1. 00-20 1.86-10

800 4. 79-4 2. 41-6 4. 21-8 9. 95-21 1.83-9

900 4. 01-4 1. 85-5 1. 97-6 9. 42-21 3. 16-9

1000 2. 46-4 1. 09-5 7. 18-6 1. 20-21 1.73-12

1100 4. 11-5 6. 83-7 1. 91-6 1. 20-21 1.73-12

1200 6. 21-8 4. 57-10 3. 43-10 2. 22-24 8.42-19

1300 9. 34-19 4. 12-21 5. 43-32 1. 45-34 1.49-36

1400 5. 26-70 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70

1500 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70

(a) e.g.: The number: 1.53-12 is 1 . 53 x 10"12 moles/liter. The

symbols P, P*, D, R and PD are defined in Figure 1.

111-25
Table 3b. Concentration of species after 1 second: case(i i

)

T(k) P P- D R PD

500 7. 70-4 2. 79-17 7.95-29 1. 00-20 8.58-23

600 6. 42-4 1, 01-14 3.69-21 1 00-20 2.05-18

700 5. 50-4 6. 80-13 8.43-16 1 00-20 1.85-15

800 4. 79-4 1

,

59-11 5.64-13 9 95-21 1.23-14

900 4. 03-4 1

.

75-10 3.48-11 9 42-21 3.02-14

1000 2. 53-4 8. 71-10 6.68-10 6 56-21 3.23-14

1100 4. 04-5 7. 69-10 2.29-9 1 16-21 1.91-15

1200 5. 74-8 4. 75-12 3.61-12 2. 05-24 8. 10-21

1300 2. 07-18 6. 76-22 7.97-33 3. 10-34 2.19-37

1400 3. 11-70 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70

1500 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70

111-26
Table 3c. Concentration of Species After 1 Second: Case(iii)

1 k KJ pr r un pnr u

son 7 70-6 / <J VJ 2 31-18 u Rft-^2 7 7 11 0-2fi VJ i_ u

600 6 42-6 7 L_ VJ 2 08-1

1

\J\J II 2 55-20 ^5-4 ? 12-17 \ C if

700 5. 50-6 Jv VJ 1

,

20-9 5sJ 1 31-15 •J I 1 <J

c. 45-4 ^<J *T 1

1 . 86-14

800 <—>\J \J 4. 79-6 2 45-8 I xJ *J 4. 26-12 £- VJ 1 s_ 4 74-4 1 86-1 3

900 —' VJ w 4 03-6 \J «J \j 2 00-7 v/ VJ / 2 09-10 <J J 1 VJ 99-4 -5

.j • *t«J 1 o

1 000 2 52-6 <J C U 1 17-7 7 73-10 1 sJ 1 VJ 9 49-4 A*T . 3 A- 1 A *j*t I *t

111 1 00\J \J 4 12-7 6 85-9 \J*J -J 1 95-10 4 11 0-5 VJ *J 1 73-16

1200 6. 52-10 4. 80-12 3. 61-14 7. 38-8 9. 29-23

1300 9. 92-21 4. 38-23 2. 82-36 4. 51-36 7. 73-41

1400 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70

1500 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70

111-27
Table 3d. Concentration of Species After 1 Second: Case(iv)

T(k) P p* D R PD

500 7. 70-6 2. *7n 1 <1 79- 1

9

7. A 1 OA 93-33 7.

/"A >1 63-4 8.

r -7 a~7 57-27

/~ A a 600 £ A O £

6. 42~6 1

.

n i i c 01-16 -> J."7n oc /0~2b 0. 34_ 4 2.

A/" A A 06-22

"T A A 700 5. 50~6 c0. on i c 80- 1 b

o

8. /icon 4b"20 c

b. 4b 4

i

1

.

Of T A 86- 1

9

QAA 800 VI "7Q_ c 4. /9-6 1 . CO- 1 o r.D

.

04 1 / 4. "7/1 — A /4 4 1 . 0 0 _ 1

0

c6 18

AAA 900 4. 03"6 i

1 . jr. i o /b 1

2

o3 . 4y i b j

.

yy-4 3. no_ l 0 Uc 18

1 AAA 1000 O CO c

2. 52"6 o

8. CO. 1 1 68" 1

2

b

.

"7 1 _ 1 /I / 1 14 2

.

4y-4 /in /1 3. 0 i i 0

2 1 - 18

1 100 4. 1 6-7 -J no l o 92- 1

2

o

2. O 1 _ 1 O 31-13 4. 1 A C 14~b 2

.

no i n 02" 1 9

1200 6.29-10 5. 21-14 3. 95-16 7. 13-8 9, 74-25

1300 9.03-21 2. 96-24 1. 57-37 4, 12-18 4 31-42

1400 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70 <1 00-70

1500 <1. 00-70 <1. 00-70 <1. 00-70 <1. 00-70 <1 00-70

111-28
Figure 1. Species contained in the model mechanism.

111-29
111-30
APPENDIX IV. NON-CONCRETE USES OF FLY ASH IN CONSTRUCTION MATERIALS

McClure Godette

and

James Clifton

Center for Building Technology

National Engineering Laboratory

National Bureau of Standards

Washington, DC 20234

IV-1
TABLE OF CONTENTS

Page

ABSTRACT IV-3

LIST OF TABLES IV-4

SI CONVERSION

1. INTRODUCTION IV-5

2. PHYSICAL AND CHEMICAL PROPERTIES IV-7

3. OVERVIEW OF FLY ASH COLLECTION AND UTILIZATION iv-9

4. IDENTIFIED USES IV-9

4.1 Current Use IV-9

4.1.1 Aggregate for the Stabilization of Highway Subgrades IV-11

4.1.2 Intermediate Cover in Sanitary Landfills IV-14

4.1.3 Aggregate and Plzzolan for Road and Airport Pavement IV-14

Base Material

4.1.4 Construction of Structural Landfills and Backfills IV-15

4.1.5 Raw Material to Manufacture Light Aggregate IV-16

4.1.6 Aggregate in Cold Mixed Asphalt IV-16

4.1.7 Raw Material for Brick Manufacture IV-16

4.2 Potential Uses IV-19

4.2.1 Cenoshperes IV-19

4.2.2 Sanitary Landfill Liner IV-20

4.2.3 Raw Material for Making Mineral Wool Insulation IV-20

4.2.4 Prefabricated Exterior Walls IV-21

4.2.5 Mineral /Element Recovery IV-22

5. USE LIMITATIONS IV-23

5.1 Fly Ash Variability IV-23

5.2 Transportation Costs IV-23

5.3 Existing Source of Raw Material IV-24

5.4 Technical Limitations IV-24

6. USE BENEFITS IV-24

7. SUMMARY TV-27

8. REFERENCES IV-28
ABSTRACT

Current and potential non-concrete uses for fly ash in construction

materials are identified. Benefits and limitations of fly ash utilization

in its applications are described. Fly ash production, and physical and

chemical properties are reviewed. Current uses include structural fill,

road base, asphalt filler, grout, mine reclamation, aggregate, landfill

liner, brick manufacture, and concrete block. Potential applications

include use in prefabricated walls and mineral element recovery. The

cenosphere fraction of fly ash has potential uses in plastic extenders,

foams, coatings, paints, rubber compounds, tapes, sprays, sands, fire

proofing, and insulation. Primary use limitations are fly ash compositional

variability, transportation costs, and lack of material technical

specifications.

Key words: aggregate, brick, building materials, cenospheres, cost

effectiveness, fly ash, non-concrete, landfill liner, limitations,

pavement, prefabricated walls, specifications, utilization.

IV-3
LIST OF TABLES

Table 1 Chemical Properties of Fly Ashes

Table 2a. 1980 Fly Ash Production and Utilization in the United States

Table 2b. Fly Ash Utilization Trends from 1966-80

Table 3. World Use of Coal Ash in 1977

Table 4. Costs of Common Road Pavement Construction Operations (1978)

Table 5a. Properties of Fly Ash Brick

Table 5b. Properties of Clay Brick

Table 6. Mineral Resource Potential of Power Plant Ash

Table 7. Regional Distribution of Coal Burned in the U.S. and New

Coal-Fired Units Planned Through 1966

IV- 4
1. INTRODUCTION

Fly ash is the non-volatilized inorganic matter and unburned organic

material collected from the exhaust gasses of furnaces which burn

pulverized coal. Fly ash can be collected in various antipollution

devices, including mechanical cyclones, electrostatic precipitators,

baghouses, and/or scrubbers on the stack of the coal combustion unit.

Until recently, fly ash had been considered a liability to the operators of

coal fired utilities. The Department of Energy (DOE) is studing the use

of fly ash as a resource material for use in construction and other

industries. As a part of this effort, DOE has asked the Bureau of

Standards to investigate non-concrete uses of fly ash in construction

materials. This report shows that fly ash is a cost effective component of

numerous construction materials including aggregates, landfill liners,

brick raw material, and road pavement admixture.

The predominant construction application of fly ash is as a partial

replacement for cement in concrete. As this use has been addressed

previously (1), this discussion will focus upon construction applications

of fly ash other than in concrete. Both currently established and

potential construction uses for fly ash will be discussed in this paper.

Approximately 57.5 million tons (52 million tonnes) of fly ash was

generated from the combustion of 500 million tons (454 tonnes) of coal in

1979. Only 10 million tons (9 million tonnes) (17.4 percent) of this

material was utilized that year. The bulk of the unused fly ash was either

disposed of in lagoons and dumps (2) or stored in stockpiles (1). As of

IV-5
1980, over 300 million tons (272.13 million tonnes) of fly ash were stored

in stockpiles. Projected U.S. coal consumption and fly ash generation

figures for the late 1980s are 900 and 120 million tons (816 and 132

million tonnes) per year, respectively. Data for 1979 indicate that unused

fly ash will reach 90 million tons (82 million tonnes) per year by the

early 1990's if this level of increase is maintained (3). Disposal of this

unused fly ash is an escalating problem, in terms of both economy and

environment.

Energy concerns in recent years have brought about the practice of

considering the energy demands in the cost of a project. The use of

alternative construction materials, such as those incorporating fly ash,

will in some cases require less energy input in their production, handling,

and placement than traditional materials (5).

Clearly, there is a need to expand current applications and to explore and

implement innovative means of recovery and reuse of this abundant resource.

To further this effort, this paper reviews the physical and chemical

properties of fly ash (section 2), worldwide fly ash collection and

utilization (section 3), current and potential uses for fly ash (section

4), use limitations and research requirements (section 5).

IV-6
2. PHYSICAL AND CHEMICAL PROPERTIES

The average ash content for all coals is approximately 12.5 percent. Total

ash contents by weight of coal utilized range from 3 to 30 percent (4). Of

the total ash generated through coal combustion, 15 to 85 percent is fly

ash (5). The remaining portions are bottom ash and boiler slag.

Variability in the distribution of these ash fractions is due to the type

of coal and/or boiler used. For example, cyclone/furnace boilers generate

a high proportion of bottom ash (up to 85 percent of total ash), due to

high operating temperatures and ash fusion in the furnace (4).

The physical and chemical variability of fly ash, due to its production

source (e.g., composition of coal, combustion conditions, fly ash collector

utilized), is a significant limitation to its widespread acceptance for use

1n construction materials (see section 5). The properties of various fly

ashes are compared in table 1. Typical fly ash constituents include glassy

mineral particles (50-90%), crystalline mineral particles (10-50%), carbon

(0-12%), low volatility organic matter (0-1%), and additives used to aid

ash collection by electrostatic precipitation (0-0.1%). Fly ash particles

are typically tan to gray solid spheres measuring 0.5-100 microns in

diameter (6). Inefficient burning processes result in darker particles

resulting from excess carbon.

Desirable properties of fly ash useful for construction applications

include fineness and pozzolanic qualities (having the property of

cementation in the presence of lime and water without itself being a

cement) (6).

IV-7
1 C

O")O

CO •!— -f—

O CO

CO 4-> O C t- CM

O

_l

O

C

CO

(Ll

O ••— CM i— <o CM CO

r-- CM i— CO O

UO CO o i-H CM

CO

CO

CO o • • Oi «—1

un

CO

O) -C

co

<o>> CM CO r— C O • • <+- 0> <T3 CO

(J C_> CM

<*- J- o <U

O CO ' <T3 O CO

•<-> ? 01 CM

&_ co Ol • • 01 >> i- CM o Cu Li_ O

S>- £Z t

<o Ll.

<-) o 4-> + r~» CO

"V" o < E E 1— + CO u©

O* 01

—-co CO un

.c ^ o. i-H

01 CO * o uo CO

!o

—» CM • I CO CO *— Li_ «—t

CO * o o CO CM • < i— 1—< *—' < «—* * CM •—1

r—< —» O « CO i-CO co

cv- (L> o +J

«i- E

Ol r— c

4->

u cn ° o •t— CQ c J3 l

CO CM CM o o i—i {— CO UD un o CO co o o O «—i

(f. CO CO • * « o CO o CO

CO T—i—I • • • • CM QU

1—1

o»o

CO o CO CO • * • • 3

CM o CO o

CM CO 1—1 1—1 EE3

CM «—( o O CM o Sc

<o

ifil ; • • o +J CO CO i—t

'WD •r— uo un 00 c

O)

T—1

CO U0 —-0 o Ol 3 > • » 3

LO CM

m

CO 3 o -V* CM i—

o> jQ

y_ o CM >-< (*- • • • • ii ©

un o .—<

CM CM u. CO

gj • aCO CL o e

CM .a CM CO 30 • • <ay> r-. GO i—l ii >

co CM in CO ^=

4-» <0 • «

+-> CM C 1 i O O) E E i— co 3 3 co 0* +j +J +-> l_

•»— co in o. e -O JD 3 c o> O* © .O O Ol CO 3 e 3 C

TMl CO CO -r- _j +

IV-8
3. OVERVIEW OF FLY ASH COLLECTION AND UTILIZATION

Six and one-half million tons (5.9 million tonnes) (13.3 percent) of the

fly ash collected in the U.S. in 1980 was used rather than discarded. This

reversed a trend in which fly ash utilization climbed from 7.9% in 1966 to

over 17% in 1979 (5). The National Ash Association attributed the 1980 ash

utilization decrease to the economic downturn (7). A decrease in the

amount of fly ash generated in 1980 reflects a utility industry trend to

utilize low ash producing coals in order to Increase the reliability of

generating units (7). Table 2 summarizes fly ash collection and

utilization in 1980 and compares this data with previous years. The table

indicates that cement and concrete products comprise the greatest use of

fly ash in the U.S. Other significant uses include structural fills, road

base, filler in asphalt, grouting, and coal mine reclamation.

Several nations currently use fly ash to a far greater extent than the U.S.

(1). Poland, uses 37% of the 18 million tons (16.3 million tonnes) of fly

ash it generates for fill material, cement replacement, and aerated

concrete blocks. Other leaders in fly ash utilization include England (39%

utilization), West Germany (23%), France (42%), Canada (27%), Scotland

(30%), and Japan (23%).

4. IDENTIFIED USES

4.1 CURRENT USE

The predominate construction application for fly ash is in the manufacture

IV-9
TABLE 2a. 1980 Fly Ash Production and Utilization in the United States

(5)

Million Tons (tonnes)

1. Total Ash Produced 48.31 (43.8)

2. Ash Utilized 6.42 (5.82)

A. Commercial Utilization

1. Cement & concrete products 2.67 (2.42)

2. Structural fills 0.37 (0.34)

3. Road base 0.13 (0.12)

4. Filler in asphalt mix 0.09 (0.08)

5. Snow & ice control, blasting grit,

roofing granules -0-

6. Grouting 0.36 (0.33)

7. Coal mining application 0.12 (0.11)

8. Miscellaneous 0.39 (0.35)

Total Commercial Utilization 4.13 (3.75)

B. Ash Used Internally

1. Structual fills 0.63 (0.57)

2. Road base 0.15 (0.13)

3. Miscellaneous 0.27 (0.24)

Total Ash Used Internally 1.05 (0.95)

C. Ash Removed from Plant Sites at no Cost to Utility 0.07 (0.06)

TABLE 2b. United States Fly Ash Utilization Trends from 1966-1980 (million

short tons*) (5)

1966 1976 1977 1978 1979 1980

Fly Ash Produced 17.1 42.8 48.5 48.3 57.5 48.31

Fly Ash Utilized 1.4 5.7 6.3 8.4 10.0 6.42

% of Fly Ash Utilized 7.9 13.3 13.0 17.4 17.4 13.3

*1 short ton = 0.907 tonnes

IV- 10
of concrete. Other fly ash applications either take advantage of its

pozzolanic properties and/or use it as a fill material. Pozzolanic

applications include uses as an aggregate, landfill intermediate liner,

brick raw material, and paving admixture. Fill related uses include

applications as structural and construction related backfills and

embankments. Ten of the largest worldwide construction applications for

coal ash in 1977 are shown in Table 3. Current non-concrete construction

applications of fly ash are detailed in the following.

4.1.1 Aggregate for the Stabilization of Highway Subgrades

A highway subgrades is the surface base of earthen material which is

leveled off to receive a road foundation. Fly ash has been used throughout

the U.S. as a stabilizer of poor subgrades during road construction since

1950 (5). Soil stabilization uses have been successfully field tested at

projects in Kansas City, South Dakota, West Virginia, and other sites

(4,7,9). To improve subgrades, fly ashes are normally used to act as

either pozzolans or fillers to reduce air voids in naturally occurring or

blended aggregate systems. In fine grade soils, use of fly ash as a filler

is not suitable since the particle size of fly ash would be larger than the

voids in fine soils. But fly ash is of value in fine grade soils as a

pozzolan. Many clays are themselves pozzolanic in nature and therefore

have no need for additional pozzolanic stabilization. Therefore, the

Federal Highway Administration considers silts as the most suitable soil

type for stabilization with fly ash-lime or fly ash-cement mixtures (9).

Field tests by Kansas City Power and Light (6) showed that addition of

15-20 percent fly ash could be used to improve the properties of highly

plastic (easily deformed) clay subgrades with excellent results. Fly ash

IV- 11
TABLE 3. World Use of Coal Ash 1n 1977 (3)

Use 10

6

tonnes/yr

a Leading Users

F111 material

Cement replacement

Addition to cement

Road stabilizer

Aerated concrete blocks

Blast grit and roofing

Asphalt filler

Pozzolanic material

Lightweight aggregate

Bricks and ceramics

Other

Total

5.8

5.6

4.1

3.1

1.8

1.6

1.2

1.0

0.8

0.6

9.6

35.

2

C

England, USA, Canada

USA, England, E. Germany

France, Spain, W. Germany

Poland, Austria, USA

Poland, England, USA

Poland, England

USA, W. Germany

W. Germany, USA

USA, France

England, USA, E. Germany

W. Germany, Ukraine,

E. Germany

USA, Poland, E. Germany

W. Germany

a

l tonne = 1000 kg = 1.1024 short tons

^In order of decreasing quantity used.

cTotal ash production is 278 x 10

production.

tonnes/yr, 12.7% of world fly ash

IV-12
improved clays at the test site had increased strength and decreased

plasticity. Comparing the costs of various road paving operations, Table 4

indicates that lime-fly ash aggregate base construction is cost competitive

with cenemt and asphalt treated highway bases (10).

IV-13
Table 4. Costs of Common Road Pavement Construction Operations

(1978) (10)

Costs $/sq ?yd/in.

(S/0.836 nT/2.54 cm)

CtU'l nnctj L rurt i U L Ut

1 nnUN flnor^t upc f a l1 nnUll Average Range

Crushed Stone Base 0. 50 0.30 -0.60

Gravel Base 0. 40 0.20 -0.60

Lime Stabilized Subgrade 0. 25 0.15 -0.35

Cement Stabilized Subgrade 0. 30 0.20 -0.40

Cement Treated Base 0. 80 0.60 -1.10

Asphalt Treated Base 0. 80 0.60 -1.00

Lime-Fly ash Aggregate Base 0. 70 0.60--0.80

Chip Seal 0. 35 0.20--0.45

Asphalt Concrete 1. 00 0.70--1.20

Portland Cement Concrete 1. 40 1.00--2.00

4.1.2 Intermediate Cover in Sanitary Landfills

Fly ash has been used successfully as an intermediate cover in

sanitary landfills (11). Projects reporting success in using fly ash as

an intermediate cover include landfills at the Orange and Rockland

Utilities, the Columbus, Ohio Municipal Light Company, and the City of

Fairbanks, Alaska. West Virginia University has conducted additional

research in this area regarding the use of injected ash as a stabilizing

agent in landfills.

4.1.3 Aggregate and Pozzolan for Road and Airport Pavement Base Material

According to the National Ash Association (11), a 30 Inch (76.2 cm)

thick 1 ime-cement-fly ash airport runway base has a load performance

equivalent to 16 inches (40.6 cm) of portland cement concrete or 60 incnes

(152.4 cm) of aggregate base asphaltic concrete. The New York Port

Authority is utilizing over a quarter million tons of this fly ash mixture

IV- 14
for various paving projects at the Newark and Kennedy airports. Cost

estimates for this alternative construction material were reported to

result in savings of up to 60 percent compared to portland cement and

aggregate base asphaltic concrete (11).

Fly ash-lime sulfate sludge compositions are reported to produce a useful

paving and stabilization material having strength properties resembling

concrete while realizing substantial energy savings (10, 12). Fly ash, as

a component of highway base course materials, has been reported to perform

satisfactorily in the areas of soundness, abrasion, and percent of fines

(13). Initial gradation deficiencies that were experienced in the use of

fly ash in highway base course were overcome by the addition of other

aggregates such as gravel, limestone, or blast furnace slag.

4.1.4 Construction of Structural Landfills and Backfills

Compacted fly ash embankments are used extensively in Great Britain where

its characteristic light weight makes it attractive when embankments are

constructed over poor ground (13). Low weight, good shear strength, high

load bearing characteristics, and high cohesion give fly ash a better slip

circle safety than other embankment materials such as clay or stone. Fly

ash has been used as a structural fill in France, West Germany, Finland,

Poland, and the USSR. Reported uses of fly ash as a structural fill in

the U.S. include a housing project in West Virginia, approach embankments

to a railroad overpass in Minnesota, and an embankment for a 1.5 mile (2.41

kilometer) section of the Amstutz Expressway in Illinois (3).

IV- 15
4.1.5 Raw Material to Manufacture Light Aggregate

Fly ash pelletizing and sintering techniques for the manufacture of

lightweight aggregate have proven successful. Useful characteristics of

the aggregate include pozzolanic properties and resistance to freezing and

thawing (15). In the United Kingdom, "LYTAG, " a lightweight fly ash

aggregate product, has been used in the manufacture of block and concrete

(16).

4.1.6 Aggregate in Cold Mixed Asphalt

The State of Texas recently completed a 10,000 mile (16,090 kilometer)

highway project which used a non-skid asphaltic material containing

lightweight fly ash aggregate. An asphalt mixture (Gussaphalt) containing

fly ash which had been used in Germany was recently tested on the

Pennsylvania Turnpike near Bedford (16).

4.1.7 Raw Material for Brick Manufacture

Fly ash brick was first manufactured in the U.S. on a trial basis in 1949

(10). It has been found to have favorable characteristics compared to clay

brick, while its manufacture utilizes 20-50 percent less energy than that

of clay brick (18). Energy savings are attained due to the different

manufacturing processing methods of the two brick types. Clay must be

mined and crushed, while fly ash brick is composed of fly ash and bottom

slag without any preprocessing before use. Clay must be crushed and

extrusion formed with 20-25 percent added water, while fly ash needs no

crushing and only 6-8% added water for dry pressing. Clay brick must be

IV-16
kiln fired for 30 to 40 hours while fly ash brick requires only 3 to 18

hour firing. Finally, transportation savings can be realized with fly ash

brick due to its 10 to 20 percent weight advantage. Cost data for this

material has not been reported.

A large commercial fly ash brick manufacturing facility began operations in

Canada in the early 1970' s (11). This facility initially produced over 6

million bricks composed of 3 parts fly ash to 1 part slag and a small

amount of sodium silicate. The brick produced are light, strong, and

amenable to coloring. As shown in tables 5a and 5b, fly ash brick is more

porous and absorbs slightly more water absorbant than clay brick. Fly ash

brick, however, has a significantly greater compressive strength than its

clay counterpart.

Fly ash thermal insulation bricks, manufactured in combination with lime,

gypsum, and aluminum powder, are reported to cost only about 50 percent

that of conventional diatomite and mica insulation bricks. In India, these

bricks have been used successfully up to a hot face temperature of 800° C

(19).

According to the Resource Recovery and Utilization Technical Committee

and Envirosphere Company, the best market for fly ash utilization in the

immediate future is in highway construction, due to price increases in

asphalt and portland cement (4).

Other current non-concrete uses for fly ash include (3,11,17,19-22):

o Filler for paint, putty, and wall plaster

IV-17
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IV- 18
o Lightweight aggregate block

o Ingredient in the manufacture of roofing felt

o Ingredient in bituminous stabilized bases for highways

o Revegetation of surface mine spoil sites and coal refuse piles

o Ingredient in lime-cement-fly ash composite in the manufacture of paving

mix

o Ingredient in grout

o Pipe mix (as a replacement for cement)

o Mineral filler in asphaltic concrete

o Correction and deterrence of underground subsidence

4.2 Potential Uses

Although the use of fly ash has increased over the years, as discussed

in Section III, there is clearly potential for considerable expansion - not

only in the many already established markets for fly ash applications, but

in innovative uses. These potential uses for fly ash are discussed in the

following.

4.2.1 Cenospheres

Cenospheres, or "floaters," are minute silicate glass spheres,

constituting up to 5 percent by weight (20 percent by volume) of fly ash

produced. Among their potentially useful physical qualities are Included

excellent compressive strength, chemical Inertness, high temperature

resistance, and low thermal conductivity. It has been predicted that

properly graded cenospheres can could command a price approaching $500 per

ton (0.907 tonne) (5,19). Cenosphere applications currently under

IV- 19
investigation include:

o plastic extenders o foams

o aluminum o coatings

o paints o rubber compounds

o tapes o sprays

o sands o fire proofing

o insulation

4.2.2 Sanitary Landfill Liner

Fly ash may be used to improve the properties of the soils used to line

sanitary landfills. Tennessee Valley Authority studies indicate that a 1:1

or a 1:3 mixture of soil to dry fly ash reduced soil moisture absorption

rates to "slow." A 1:1 mixture of soil to wet fly ash produced similar

results (4).

4.2.3 Raw Material for Making Mineral Wool Insulation

The Coal Research Bureau at West Virginia University has shown that it is

both technically and economically possible to produce mineral wool

insulation from fly ash, limestone modified fly ash, and other coal ashes

(17). The insulation produced has a smaller fiber diameter than commercial

mineral wool but its insulating properties are reported to be superior to

its commercial counterpart. Advantages of the use of fly ash mineral wool

include:

IV-20
o elimination of mining costs required for acquisition of wool rock,

o reduced raw material preparation,

o elimination of the need for fluxing agents,

o availability of raw materials near most major markets,

o potential for reduced piping maintenance due to anti-corrosion

characteristics of fly ash mineral wool,

o and improved insulating and heat duty characteristics due to its high

silica and alumina content. Disadvantages of fly ash mineral wool

development include the requirement for reverberatory furnaces for which

melting must take place on a batch or semi-batch basis (rather than

continuous cupolas used in current commercial processes), and, due to its

color, finished mineral wool from bituminous or anthracite ash is not

suitable for use in exposed surfaces. Lignite and sub-bituminous ashes

are, however, suitable (5).

4.2.4 Prefabricated Exterior Residential Walls

A potentially large construction application of fly ash is the manufacture

of full length residential walls. This application has been successful in

Yugoslavia, by casting a composite of 80 percent fly ash with cement or

limestone (19). The cost estimates for this process are as low as

one-tenth the cost of conventional brick or frame construction exterior

residential walls. The final product is lightweight, termite and decay

free, fire resistant, dimensional ly stable, requires no special

construction tools, and has better insulating qualities than conventional

IV-21
residential walls.

4.2.5. Mineral /Element Recovery

Potential U.S. markets exist for fly ash in the area of mineral and element

recovery. Various processes are being explored to determine the

feasibility of extracting alumina, titanium, magnetite, silica, lime,

vanadium, uranium, and germanium from fly ash (3, 5, 19). Extraction of

alumina has been successfully achieved in Poland and Hungary. Table 6

lists the percentages of mineral constituents of power plant ash.

TABLE 6. Mineral Resource Potential of Power Plant Ash (14)

Constituent Percent

Silicon dioxide 45.7

Aluminum oxide 26.0

Ferric oxide 17.1

Calcium oxide 3.8

Sulfur tri oxide 2.6

Potassium oxide 1.5

Titanium oxide 1.2

Magnesium oxide 1.2

Sodium oxide 0.6

Phosphorus oxide 0.3

Total 100. b

Limitations of the future marketability of mineral and element

recovery from fly ash include the cost effectiveness of extraction and

reprocessing techniques, and domestic production and import supplies of

these materials. However, recognition of the following items may make fly

ash mineral /element recovery more feasible in the future (5):

o increasing costs of mining, extraction, and transportation of primary

IV-22
metals,

o need to reduce the volume of by-products requiring disposal, and

o concern over foreign control of these minerals.

5. USE LIMITATIONS

Although the use of fly ash in construction applications has become

generally accepted, in 1981 only about 13 percent of the total ash produced

in the U.S. was utilized (4). The following sections delineate some of the

limitations to the increased use of fly ash in construction materials.

5.1 FLY ASH VARIABILITY

The physical and chemical variability of fly ash, as described in

section 2, is a significant market constraint to its use in construction

materials. The physical and chemical characteristics of the ash cannot be

predicted; therefore, to achieve an ash with uniform characteristics

acceptable to commercial users, frequent on-line analyses at the power

plant are required (5). Factors influencing the characteristics of the ash

include type of coal, method of coal grinding, boiler load, and

precipitator efficiency (14).

5.2 TRANSPORTATION COSTS

The second constraint that could impede the marketing of fly ash in

construction material applications is transportation costs. Increased use

of fly ash in construction materials would require that fly ash sources be

located near large, populated areas in order to be economically transported

IV-23
to commercial users. Table 7 shows regional distribution of coal burned in

the U.S. and the location and numbers of new coal fired units.

5.3 Existing Source of Raw Materials

A further possible market limitation for the expansion of fly ash

utilization in construction materials is the existence of "own source

materials" by the manufacturer (6). A manufacturer owning a quarry or mine

to provide the raw materials for production would not be likely to purchase

fly ash as a substitute for those raw materials.

5.4 Technical Limitations

Another major constraint to the widespread use of fly ash in

construction materials is the lack of technical information on its

performance in construction materials. Current performance tests and

specifications apply for the most part to fly ash as a component of cement,

and even these are either unduly restrictive or inadequate (1). This lack

of technical data hampers the general acceptance of fly ash as a substitute

raw material in construction materials, as potential users have no method

for evaluating fly ash performance. The development of such tests is

prerequisite to widespread acceptance of fly ash utilization.

6. USE BENEFITS

The use of fly ash as a raw material as opposed to mining and process^?

primary materials 1s attractive from the standpoint of energy consumption.

IV- 24
Table 7. Regional Distribution of Coal Burned in the U.S. and New

Coal-Fired Units Planned Through 1986 (1, 24)

Geographic

Area

New England

States

(ME, NH, VI, MA, RI,

Coal Burned Planned

tons ^tonnes) Units

x 10 /year

CT) 8206 (7449) 1

Middle Atlantic (NY, NJ, PA) 40553 (36786) 7

East North Central (OH, IN, IL, MI, WI) 83570 (75806) 50

west Nortn uen era

i

( MM T A SD, ND)MD NO , fit , 13749 (12471) 40

South Atlantic (MD, DE,

SC, GA,

VA,

FL)

wv, NC,

39502 (35832) 31

East South Central (MS, AL, TN, KY) 33902 (30752) 30

West South Central (MS, AL, TN, KY) 10 (9.07) 59

Mountain (NM, AZ,

WY, MT,

NV,

ID)

CO, UT,

6644 (6027) 36

Pacific (CA, OR, WA) 5 (4.54) Non<

One short ton is equivalent to approximately 0.9071 tonnes

IV-25
as it is in most cases more energy efficient. This is Illustrated by the

energy savings realized in the manufacture of fly ash brick instead of clay

brick. The largest factor contributing to energy savings is that fly ash

is a pre-fired material; little additional heat work is required to form

the ceramic bonds to produce a brick. Energy savings are estimated to be

from 20 to 50 percent compared to clay brick.

Fly ash utilization is also attractive from the environmental viewpoint.

Its assets in this area include:

o The recovery or reuse of a material that was historically

considered a "waste product" can now be viewed as a useful

by-product of coal combustion,

o Disposal of "waste products" by a utility can be extremely

costly, and disposal sites are under increasingly negative

scrutiny. Fly ash recovery can reduce the burden on solid waste

disposal facilities.

Fly ash is generated in large quantities as small, ready-to-use particles

with little or no processing required prior to its reuse as a raw material

(14). Utilities should be able to profit economically by selling fly ash

as a raw material to commercial users because costs associated with its

disposal can be replaced with sales revenues.

IV-26
8. SUMMARY

Fly ash utilization in construction materials would reduce the current

fly ash burden on waste disposal facilities. Other benefits of increased

fly ash utilization include energy savings acquired through the utilization

of waste materials as a construction component as opposed to the mining and

processing of primary materials. Energy savings for fly ash brick, for

example, are estimated to range from 20 to 50 percent.

Construction applications may make use of fly ash's pozzolanic

characteristics, its bulk characteristics, or its cenosphere fraction.

Pozzolanic applications include use as an aggregate, landfill liner, brick

raw material, and road pavement admix. Potential cenosphere applications

include uses in plastic extenders, foams, coatings, paint, tapes, fire

proofing materials, and insulation. Bulk applications include uses in

construction backfills and embankments.

The primary limitations of fly ash utilization in construction

materials include the variability of its physical and chemical properties.

This variability plus a lack of technical Information regarding its

performance 1n construction materials have become a roadblock to

development of technical standards for uses of fly ash 1n construction

materials. Greater fly ash utilization in construction materials could be

realized if technical specifications and engineering performance standards

were developed for these materials. Transportation costs may also be a

limitation to increased fly ash utilization.

IV-27
9. REFERENCES

1. Frohnsdorff, G. and Clifton, D.R., Fly Ashes in Cements and Concretes:

Technical Needs and Opportunities.

2. Martens, D.C., Availability of Plant Nutrients in Fly Ash, Compost

Science, November-December 1971.

3. Fly Ashes in Cements and Concretes: Technical Needs and

Opportunities, Office of Recycled Materials, National Bureau of

Standards, U.S. Dept. of Commerce, March 1981.

4. Resource Utilization Technical Committee and Envirosphere Co.,

Electric Utility Coal Combustion By-Products: A Resource for Recovery

and Utilization, Envi roshpere , September 1981.

5. Church, R.L., et. al., Coal Fired Power Plant Ash Utilization in the

TVA Region, Tennessee Valley Authority and Environmental Protection

Agency, October 1980. EPA 600/7-80-172.

6. Ash Production and Utilization 1980, National Ash Association,

Washington, DC, 1982.

7. Joshi, R.C. et. al., New and Conventional Engineering Uses of Fly Ash,

Presented at the ASCE Annual and National Engineering Convention,

October 1974. Meeting Preprint 2406.

8. Memo to NAA Members and Survey Respondents, National Ash Association,

1980.

9. Greenwell , H.F. and J.R. Pizzella, Lime Fly Ash Stabilization, in Ash

Utilization, Proceedings of the Fourth International Ash Symposium,

March 1976.

10. Terrel , R.L. et. al .

, Soil Stabilization in Pavement Structures: A

User's Manual, Federal Highway Administration, U.S. Dept. of

Transportation, Oct. 1979. FHWA-IP-80-2.

11. Convey, J.N. and J.H. Faber, Ash Utilization- Views on a Growth

Industry, in Proceedings of the Third Mineral Waste Utilization

Symposium, "CTTi cago, IL, March 1972.

12. Yang, N.C., Fly Ash Captures New Market, Power, Sept. 1978, p. 78.

13. Pavement Durability Test Track in Operation at Penn State University;

Ash Being Studied, Ash at Work V(3):3, 1973.

14. Babcock, A.W. and J.H. Farber, Power Plant Aggregates for Highways of

the Future, Presented at the First FCP Research Progress Review,

Federal Highway Administration, U.S. Dept. of Transportation.

15. Klotten, R., Lightweight Aggregate From Sintered Ash, i_n Ash

Utilization, Proceedings of the Fourth International Ash Symposium,

March 1976.

IV-28
16. Moss, D.W. Lightweight Aggregate Production form Fly Ash 1n the United

Kingdom, _1p_ Ash Utilization, Proceedings of the Fourth International

Ash Symposium, March 1976.

17. Gussaphalt Paving, Ash At Work V(3):2, National Ash Association, 1973.

18. Slonaker, J.F., The Role of Fly Ash Brick Manufacturing in Energy

Conservation, Coal Research Bureau, West Virginia University (date

unknown).

19. Arthanoor, V.A. and M. Shanmugasundaram, Utilization of Lignite Fly

Ash from the 600 MW Neyveli Thermal Power Station, j_n Ash Utilization,

Proceedings of the Fourth International Ash Symposium, March 1976.

20. Reldlebach, J. A., Jr., Ash Management Can Do this for You: Conversion

of a Liability to an Asses, National Ash Association, March 1976.

21. Rowen, A., Utilization Experience 1n Detroit, presented at the

National Ash Association Fourth Annual Technical Meeting, Toronto,

November 1973.

22. Ash Solves Problem for King Knob Coal Company, Ash At Work IX(6):3-4,

1977.

23. F.H.W.A., F.A.A. Adopt Use of Fly Ash in Construction, Ash at Work

VI(2):1, 1974.

24. Raask, E. and C.J. Schilling, Research Findings on the Toxicity of

Quartz Particles Relevant to Pulverized Fuel Ash, Ann. Occup. Hyg.

Vol. 23, p. 147-157, 1980.

25. Ash Importance to Increase 1n Coming Months, Ash at Work IX(6):1,

National Ash Association, 1977.

IV-29
ii
APPENDIX V. INTERLABORATORY STUDY OF ORGANIC EXTRACTION RECOVERIES

A statistical analysis was made on the organic extractionrecovery data obtained from interlaboratory experiments involving

four laboratories. The percent recovery of 13 organic compounds

was measured at 0 and 48 hours. Each laboratory was supposed to

make duplicate percent recovery measurements at each condition, but

this was not fully realized (see attached data sheets, tables 1-4).

Our statistical analysis of the laboratory measurements for each

compound and condition therefore consisted of a within-between

analysis of variance for unbalanced data (1). The results of the

analyses for each compound and condition are presented in tables

5-8, and give the weighted mean values, the standard errors of the

weighted mean values, the components of standard deviation for the

within laboratory replication variability, and the components of

standard deviation for the between laboratory variability, respectively. (The components of standard deviation are the square roots

of the components of variance.)

An examination of table 5 shows that generally similar recoveries were obtained for all compounds except acenaphthylene and

1-naphthylamine. The column averages listed at the bottom of the

table therefore exclude these two compounds. A comparison of the

column averages as well as of the individually listed values show

that the 0 hour extractions allow about 90 percent recovery and

tend to be about 3-10 percentage recovery units higher than those

observed at 48 hours.

Table 6 shows that the standard errors are similar for all

compounds. The table suggests no trends relative to the four

experimental conditions. Average values were therefore taken for

the standard errors for each compound and the results are given in

the last column of the table. In general the standard error of the

weighted mean for any given extraction condition is about 16

percentage recovery units.

Tables 7 and 8 list components of standard deviation that show

no general or meaningful trends relative to the four experimental

conditions. Average values were therefore taken for the components

of standard deviation for each compound and the results are listed

in the last column of the tables. The within and between laboratory

component averages (17 and 22 percent, respectively) taken over all

compounds except acenaphthylene and 1-naphthylamine, are given in

the lower right-hand corner of the tables. As is frequently the case in interlaboratory studies, there exists a component for

between laboratory variability above and beyond the variability

within laboratories.

The overall average components of standard deviation listed in

tables 7 and 8 can be used to obtain an estimate of the standard

deviation of a single laboratory measurement.

s = (172 + 222)^ = 28%

(1) J. Mandel and R. C. Paule, "Interlaboratory Evaluation of a Material with Unequal Numbers of Replicates," Anal. Chem. , Vol. 42,

1194 (1970).

V-l
Table 1. Synthetic Leachate Extraction Recovery Study

Spike Concentration: 10 ppb

Time: 0 hr

% Recovery

Laboratory

Analyte NBS A B C

Phenol 46% 41% 125% 146% 87% 75% 86%

o-Cresol 84 73 73 69 67 75 92

Naphthylene 93 80 70 70 68 71 103

Qui nol i ne 93 86 70 66 93 72 72

Acenaphthylene 93 83

a _ _ _ 81 ND

b

ND

1-Naphthyl amine 19 37 18 ND ND

2-NaDhthol 91 76 105 60 108 62 41

Dibenzothiophene 90 84 92 68 101 62 51

Phenanthrene 90 84 95 77 100 72 52

Carbazole 84 86 132 79 108 88 62

Fl uoranthene 82 82 122 74 86 110 70

Benzo(a)anthracene 79 92 125 70 189 84 96

Benzo(a)pyrene 75 90 ND ND 186 ND ND — = not detected in extract

ND = not determined

V-2
Table 2. Synthetic Leachate Extraction Recovery Study

Spike Concentration: 10 ppb

Time: 48 hr @ 4 °C

% Recovery

Laboratory

Analyte NBS A B C

Phenol 46% 48% 31% 106% 75% 75%

o-Cresol / *j 79 33 55 83 100

Naphthylene J C- 61 49 63 79

Qui no 1 ine 71 J u 69 86 82 82

Acenaphthylene J Z7 a 65 ND

b

ND

1-Naphthyl amine — 37 ND ND

2-Naphthol 56 66 — 81 93 72

Dibenzothiophene O A7o / 99 80 72 72

Phenanthrene 89 87 146 86 93 82

Carbazole 32 45 159 84 100 88

Fl uoranthene 87 86 81 50 80

Benzo( a) anthracene 83 81 172 96 72

Benzo(a)pyrene 72 75 ND 167 ND ND

a — = not detected in extract

ND = not determined

V-3
Table 3. Synthetic Leachate Extraction Recovery Study

Spike Concentration: 20 ppb

Time: 0 hr

% Recovery

Laboratory--

Analyte NBS A B C

Phenol 33% 38% 94% 100% 56% 81% 75%

o-Cresol 62 69 112 68 66 62 88

Naphthyl ene 75 80 114 82 56 63 119

Qui no! i ne 68 73 108 83 98 77 134

Acenaphthyl ene 68 74

a 54 NDb

ND

1-Naphthyl ami ne 35 37 ... ... 30 ND ND

0_ Klanht hnl c. napn tno i 72 88 31 11 fi

Dibenzothiophene 79 86 121 68 100 57 170

Phenanthrene 80 87 109 73 105 98 186

Carbazole 86 95 121 61 84 56 69

Fl uoranthene 87 94 88 65 79 90 145

Benzo(a)anthracene 87 93 51 184 125 84 181

Benzo(a)pyrene 87 88 ND ND 73 ND ND

a — = not detected in extract

b

ND = not determined

V-4
Table 4. Synthetic Leachate Extraction Recovery Study

Spike Concentration: 20 ppb

Time: 48 hr @ 4 °C

% Recovery

Laboratory

Analyte NBS A B C

Phenol 43% 46% 72% 116% 57% 38% 54%

o-Cresol 80 81 67 81 45 75 54

Naphthylene 100 106 71 84 41 103 103

Qui no 1 ine 100 94 66 92 61 119 103

Acenaphthylene 56 97

a — 49 ND

b

ND

1-Naphthyl amine 22 17 — — 24 ND ND

2-Naphthol 58 83 64 52 67 98 98

Dibenzothiophene 92 93 114 78 57 216 170

Phenanthrene 89 92 108 85 56 196 155

Carbazole 26 85 140 53 194 181

Fl uoranthene 90 87 159 44 130 155

Benzo(a)anthracene 95 85 80 139 157

Benzo(a)pyrene 98 86 ND ND 62 ND ND

a — = not detected in extract

b

ND = not determined

V-5
Table 5. Weighted Means

Experimental ConditionAnalyte

10 ppb

0 Hrs

10 ppb

48 Hrs

20 ppb

0 Hrs

20 ppb

48 Hrs

Row

Averages

Phenol 87 65 67 61 70

o-Cresol 75 65 75 67 71

Naphthylene 79 69 84 81 78

Qui no 1 ine 81 75 92 88 84

Acenaphthylene 56 40 42 42 45

1-Naphthyl amine 15 15 22 14 17

2-Naphthol 79 56 78 74 72

Dibenzothiophene 80 85 97 111 93

Phenanthrene 83 102 105 105 99

Carbazole 91 94 82 95 91

Fl uoranthene 89 59 92 95 84

Benzo(a)anthracene 113 84 115 79 98

Benzo(a)pyrene 134 120 80 78 103

Average excluding

acenaphthylene &

1-naphthylami ne

val ues.

90 80 88 85 86

V-6
Table 6. Standard Errors of the Weighted Means

Experimental Condition

Analyte

10 ppb

0 Hrs

10 ppb

48 Hrs

20 ppb

0 Hrs

20 ppb

48 Hrs

Row

Averages

Phenol 19 16 13 12 15

o-Cresol 4 13 7 7 8

Naphthylene 5 9 9 15 10

Quinol ine 6 5 9 11 8

Acenaphthylene 28 20 21 23 23

1-Naphthyl amine 8 11 11 7 9

2-Naphthol 11 19 10 9 12

Dibenzothiophene 9 6 14 29 15

Phenanthrene 8 15 14 25 16

Carbazole 9 25 8 33 19

Fl uoranthene 7 20 10 22 15

Benzo(a)anthracene 24 3o 1 Q19 30 1

Benzo(a)pyrene 52 47 7 15 30

Average excluding

acenaphthylene &

1-naphthyl amine

val ues.

16

V-7
Table 7. Components of Standard Deviation for Within Laboratory

Replication Variability

Experimental Condition

Analyte

10 ppb

0 Hrs

10 ppb

AO 1 J _ 48 Hrs

20 ppb

0 Hrs

20 ppb

48 Hrs

Row

Averages

Pheno

1

1 ft 10 i 4 19 9

o-Cresol o8 9 18 10 11

Naphthylene 1 A 14 o8

O A 24 6 13

Qui no 1 ine 3 7 23 13 12

Acenaphthylene 5 7 3 20 9

1-Naphthyl amine 9 5 1 2 4

2-Naphthol 21 12 27 11 18

Dibenzothiophene 11 1 38 24 19

Phenanthrene 11 b

-3 Q JO iy 1 0 iy

Carbazole 22 9 22 62 29

Fl uoranthene 19 15 25 59 30

Benzo(a)anthracene 22 12 51 8 24

Benzo(a)pyrene 11 2 1 8 6

Average excluding

acenaphthylene &

1-naphthyl amine

values.

17

V-8
Table 8. Components of Standard Deviation for Between

Laboratory Variability

Experimental Condi ti on

Analyte

10 ppb

0 Hrs

10 ppb

48 Hrs

20 ppb

0 Hrs

20 ppb

48 Hrs

Row

Averages

Phenol 37 33 27 19 29

o-Cresol 3 24 0 12 10

Naphthylene 0 17 0 29 12

Quinol ine 12 9 0 19 1 r\ 10

Acenaphthylene 49 34 37 36 39

1-Naphthyl amine 13 19 19 13 16

2-Naphthol 15 37 0 15 17

Dibenzothiophene 16 11 0 55 21

Phenanthrene 13 29 0 48 23

Carbazole 0 49 0

A C 45 24

Fl uoranthene 0 37 5 0 11

Benzo(a)anthracene 44 69 0 61 44

Benzo(a)pyrene 73 66 10 20 42

Average excluding

acenaphthylene &

1-naphthyl amine

val ues.

22

V-9
Table 9. Yield Equations Derived from Data of Table 5

(C in PPB; t in hours)

Analyte Yield (%) Std. Error of

Phenol (95. 0-1. 2C

x

~0. 29t) 8. 0

o-Cresol f 1 A n i r\ ACT A OA! A (74. 8+0. ObC^-0. 20t) 1. 5

Naphthy 1 ene (68. 8+0. 850^-0. 14 1) 3. 5

Qui no 1 ine (68. 5+1. 2C

x

~0. lOt) 1. 0

1-Naphthol (65. 8+0. 850^-0. 28t) 9. 5

Dibenzothiophene (56. 2+2.

l

5 C x

+0. 20t) 4 5

Phenanthrene (75. 2+1. 25C

x

+0. 20t) 9 5

Carbazole (92. 5-0. 4C

x

+0. 17t) 5 0

Fl uoranthene (61. 3+1.9

5 Cx-0.28t) 16 5

Benzo( a) anthracene (116-0. 15C -0.68t) 3 5

Benzo(a)pyrene '(179-4. 8C -0.17t) 6 0

Valid for 10<C <20

0<t<48

V-10
APPENDIX VI. HAZARDOUS WASTE CHARACTERIZATION

(Representative Activities FY 1982)

Synthetic Aqueous Leachate Extraction Recovery Study

The initial phase of the Waste Characterization Project

involved determining the extraction recovery of selected organic

compounds from a synthetic aqueous leachate at the ppb level. The

synthetic aqueous leachates were prepared by adding aliquots (1 or

2 mL) of a methanol ic solution of 14 organic compounds to one liter

of high-purity HPLC water in clean teflon jars to produce solutions

at the 10 and 20 ppb levels. These samples were extracted and

analyzed according to the procedure developed at PETC on January

21-23, 1981. Four laboratories — NBS, Pittsburgh Energy Technology

Center, Argonne National Laboratory, and Oak Ridge National Laboratory -- participated in an interlaboratory study to assess the

analytical variability in determining the target compounds in the

synthetic leachates. The results of this limited round robin study

presented enough analytical difficulties that repetition of the

extraction and analysis of a synthetic aqueous leachate with

tightening of the analytical protocol was desired. A second

synthetic aqueous leachate solution, containing 16 compounds, was prepared and analyzed according to the revised "Agreed Upon

Analytical Method" as follows:

Approximately 10 mg of each compound was weighed on a Cahn electrobalance and transferred to a clean 1 L volumetric

flask partially filled with methanol. The concentration of

each compound added is given in table 1. The solution was brought to volume with methanol and sonicated for 15 minutes

to ensure complete dissolution of all compounds. The flask

was covered with aluminum foil to protect the contents from

exposure to light and stored at 4 °C until used. Synthetic

aqueous leachates were prepared by adding 1.0 mL of the

methanol ic solution to 1 L of Baker InstraAnalyzed water,

giving a solution of approximately 10 ppb of each analyte.

The synthetic leachates were prepared, extracted, and analyzed

in triplicate by gas chromatography and gas chromatography/

mass spectrometry according to the revised analytical method.

Gas Chromatographic Analysis of Synthetic Aqueous Leachate Extracts

One to two uL aliquots of the synthetic aqueous leachate

extracts were analyzed by gas chromatography with flame ionization

detection. Chromatographic separations were carried out on a 30

m x 0.25 mm i.d. SE-52 fused silica capillary column. Hydrogen was used as a carrier gas at an inlet pressure of 27 psig. The column

was temperature programmed from 60 °C to 300 °C at a rate of

4 °C/minute. Under these conditions, all of the analytes were

resolved from each other except for the dibenzothiophene and

VI-1
4-aminobiphenyl , which co-elute, and the 2,3,4,5-tetrachlorobiphenyl (internal standard) and fluoranthene which are only

partially resolved.

Table 1. Concentrations of Compounds in Second Synthetic

Methanol ic Leachate Solution.

Compound Concentration (mq/L)

9- ni ml i no i n 11

nhonn

1

U 1 1 C 1 IU 1 i n 79

nU

— cLIv*oC9Ucnl

•\- 1 9 77

nanhtha 1 1 a1 one p 1 1 '_• 1 1 a 1 c 1 Ic Q QQ

niU1 1

1 nn1 IU 11 i

1 no1 ic 11

.

Qfi 3D

n-tptrsrlpc^np II IC LI aUCUQIIC i n

± , h riapn uiiucju l none i nIU

.

3U

darflnanhth\/l (_ c 1 1 a \J 1 1 L 1 1 ono y 1 c 1 lc Q Do

2-naphthol 9 48

1-naphthyl ami ne 10. 17

4-aminobiphenyl 8. 94

dibenzothiophene 10. 56

phenanthrene 10. 12

carbazole 10. 59

f 1 uoranthene 11. 09

benz[a]anthracene 10. 40

Response factors for each of the analytes compared to the

2,3,4,5-tetrachlorobiphenyl internal standard were determined from

a gravimetric solution of the analytes and the tetrachlorobiphenyl

(see table 2). Concentrations of the analytes in the extracts and

the percent recoveries were determined from the integrated analyte

peak areas, the integrated internal standard peak area, and the

experimentally determined response factors. These values are presented in table 3. The 2-picoline was not determined by GC-FID

due to numerous interfering peaks in the early portion of the

chromatogram. The 2-picoline recovery was determined in later

VI-2
Table 2. Gas Chromatographic Determination of Analytes in a

Synthetic Aqueous Leachate at the 10 ppb Level.

Average Peak Retention

Analyte Time (min.

)

a Response Factor

2-picoline — —

phenol 9. 34 ± 0. 006 (n = 3) 2. 146

o-cresol 12. 24 ± 0. 000 1. 675

naphthal ene 16. 43 + 0. 006 2.469

qui no 1 ine 19. 50 ± 0. 006 1.484

n-tetradecane 25. 23 + 0. 000 2.398

1,4- naphthoquinone 25. 71 ± 0. 000 1. 106

acenaphthylene 27. 04 ± 0. 000 2.433

2-naphthol 29. 20 ± 0. 000 1.399

1-naphthyl amine 29. 81 + 0. 000 1. 086

4-aminobipheny

co-el ute 36. 45 ± 0 000 1.330

dibenzothiophene

phenanthrene 37 22 ± 0 006 2.500

carbazole 38 74 ± 0 000 1.424

2 ,3 ,4,5-tetrachlorobiphenyl 44 59 ± 0 006 1.000

f 1 uoranthene 44 69 ± 0 000 2.421

benz[a]anthracene 53 71 ± 0 012 1.724

aColumn: 30 m x 0.25 mm SE-52 fused silica capillary column

T program: 60° initial for 4 minutes, program @ 4°/minute

at 300 °C

Carrier gas: hL @ 27 psig

Response Factor:

analyte peak area/weight of analyte

2,3,4,5-tetrachlorobiphenyl peak area/weight of 2,3,4,5-tetrachlorobiphe-

.

VI-3
CD cr 53 CL P» ro Cu i—1 3 -LJ 3 cu1 "CT ro

-=5 fD CU ZT 1 1 1 n 1 £Z Qj 1 <V 1 3 C -5 fD CT Cu 3 3 fD -C» r+ -Q pj

fD Cu T3 Cu M O CT 3 fD 3 Ol Cu 3 1 fD 3 CT 1 3

-5 3 1 1 -5 Cu QJ 3 —1. CT CT Cu 3 r+ 0 r-t- fD

O

n Oc

fD QJ Cu 3 N 3 CT ZT CT QJ -5 3" cn 0 ct- cn 3 l_l 3 O ft" O O d" r+ CT CT Cu Cu O fD

re 0 Ol r+ ZT r+ . CT << CT r+ CT Q. 3

CT 3 3- fD -5 ZT

O CT f+ fD fD fD 3

r-t- fD fD CT Cu

—1

<< ZT

n 3 fD

a ZT 3 3 O ZT 3 O Cu fD

—1

Cu he S

Cu

fD fD pinh1

en

—!• 3

en nb ne ab 3 3 n fD -< fD fD

ro << fD 3 3 fD

QJ 3 fD 0 3

Cu fD

ne OJ

-hO CL

-5 Q. Ga

CT _l 1 cn O CT

c+ fDO

O

ZT nz -5 nf u1

ZT

-J

n 0 CD

O 0 c+ 3> 3 3 ZT 3 3 Cu -a CU Cu r+ 0 O 0 c CT «< CQ 3 CT > cf -5 Q_ fD 3 fD CU 3 H-' M 1—1

t—1 m

M I—»

t—'

h-> O cn CT

fD

O

OO

O coO CD 10 0 O l-J CD ro

O

O un -h

CT

n -P»

O U1 1—»

OH co I—1 -P» en <_n LP IO CO "vi h-1 -5

n 01 O CD CD ro CT)CU CO CO O CT co ro 1—" > LUO 0 fD CL fD CL Cu cf C fD fD r+ CL LO ~i

fD << 3 /—* c 11L 3

cu CT Cu 3 fD ct- O rct- C 0 3 ri 3

c+ I>

O

fD -O X 3 c O fD

m

-s

C

OX

Cu |—> 1—' • (—1

>_j t—> 3 C ctn I—1

t—'

ro 0 -•J

O CDO l_j co 00 on ci- cn -5 r+ Cu fD OJ ro CD t—1 00 in l—» O CT en rri r— n a -P» ro OH 1—1 (_n CO O CT co -P» Xt

fc: a

ctCU 1+ 1+ l+ l+ 1+ 1+ 1+ 1+ 1+ 1 + 1+ 1+ l+ 1+ 1 -5 n 0 3 1 CU CT 3 a l_l ro ro OJ 0 1—1

l_i

O 1—'

ro 0 0 h-1 1 Ct

aL ^1

CT COO on 00 ro

M cd Oi -P» OJ 1—1 CD -P* fD fD fD fD CL n

-5 0 n /~\ <

fD CT fD 3 LQ -? C+ s

< fD

-5 cn

(15 n0<

fD

•jo

Q 1—' M l_i

M 1 fD 0 O ro O 10 OTI co CT) co 00 CT Ui 1 n

CD h-1 ro

O ro LP 0 CT CT CTi CT 00

—1 1

overy

VI-4
experiments by GC/MS with selected ion monitoring. The 4-aminobiphenyl and dibenzothiophene were not resolved chromatographical ly

,

and therefore, the percent recovery represents an average recovery

for the two compounds together. GC/MS experiments, to be discussed

later, indicate that the dibenzothiophene is recovered much more efficiently (^100 percent) than the 4-ami nobiphenyl O10 percent).

GC/MS Analysis of Synthetic Aqueous Leachate Extracts

The synthetic aqueous leachate extracts were analyzed by GC/MS

with selected ion monitoring. Gas chromatographic separations were carried out on a 30 m x 0.25 mm i.d. SE-52 fused silica capillary

column. Helium was used as a carrier gas at an inlet pressure of

10 psig. The column was temperature programmed from 60° to 275° at

a rate of 4 °C/minute and was interfaced directly to the ion source

of the mass spectrometer. The mass spectrometer was operated in

the EI mode with an ionizing energy of 70 eV. Ion source tuning

parameters were set using PFTBA as a reference compound.

The synthetic leachate extracts were analyzed using commercial

software. A characteristic, intense ion for each analyte (in most

cases, the molecular ion, M+) was monitored with a dwell time of

100 ms. The ion monitored for each analyte, along with the chromatographic retention time are shown in table 4. The selectivity of

the SIM detection allowed each analyte to be determined free of

interferences, even in cases where analytes were not resolved

chromatographical ly. The dibenzothiophene (m/z 184) and 4-

aminobiphenyl (m/s 169) co-elute at 31 minutes, for example; yet

each is determined independently of the other. Each extract was analyzed in triplicate, and selected ion record peak areas were integrated after each run and ratios of the analytes to 2,3,4,5-

tetrachlorobiophenyl computed.

Concentrations of analytes in the extracts were determined by

the method of standard additions. 100 uL aliquots of each extract

were spiked with a known amount of each analyte detected in the SIM

analysis of the sample extract. The samples were then reanalyzed

by GC/MS with SIM under identical chromatographic and mass spectrometry conditions. Single ion record peak areas were integrated

for each analyte after each run and ratios of the analyte peak area

to the 2,3,4,5-tetrachlorobiphenyl internal standard computed.

Percent recoveries were calculated based on the amount of analyte

extracted (from the 2-point standard addition) and the amount of

analyte originally added to the 1 L water sample. These values are shown in table 5. The unusually high recoveries are believed to be

due to a volumetric error during the solvent concentration step.

It is critical that the volume of the organic extract be concentrated

to 1.0 mL, exactly. Concentration to volumes slightly less than

1.0 mL will lead to percent recoveries greater than the actual

values. There are additional volumetric errors possible during the

extraction and analysis scheme, some of which are noted below. Of

particular importance are the initial solvent concentration step

and the removal of exactly 100 uL of the sample for the standard

addition quantitation. We have experienced some difficulty in

VI-5
Table 4. GC/MS SIM Determination of Analytes in a Synthetic

Aqueous Leachate.

Ana ;yte Ion Monitored, m/z Re tention Time (min.) a

2- pi col ine 93. 0 3. 3 ± 0.0

phenol 94. 0 6. 5 ± 0.0

o-cresol 108. 0 8. 6 ± 0.0

naphthalene 128. 0 13. 0 ± 0.0

quinol ine 129. 0 14. 8 ± 0.0

n-tetradecane 57. 0 20. 5 ± 0.0

1,4- naphthoquinone 158. 0 20. 8 ± 0.0

acenaphthylene 152. 0 22. 1 ± 0.0

2-naphthol 144. 0 24. 3 ± 0.0

1-naphthyl amine 143. 0 24. 8 ± 0.0

4-aminobiphenyl 169. 0 31. 3 ± 0.0

dibenzothiophene 184. 0 31 3 ± 0.0

nhpnanthrpnp 178 0 32 1 ±0.0

carbazole 167 0 33 7 ± 0.0

2,3,4, 5-tetrachl orobi phenyl 292 0 39 5 ± 0.0

f 1 uoranthene 202 0 39 5 ± 0.0

benz[ a] anthracene 228 0 48 3 ± 0.0

a Column: 30 m x 0.25 mm i.d. SE-52 fused silica capillary col umn

T program: 60° initial, programmed @ 4°/minute to 275 °C

Carrier gas: He @ 10 psi

Retention times determined on HP 5985 GC/MS system which gives retention

data to the nearest 0.1 minute.

VI-6
Ol

—

h

n Q. •£» 1—I

ro a> h-' 3 Xj 3 T3

M zz. fD Hi 3 — 1 1 i n " 1 c Ol 1 ZT 1 o 3 fD OJ 3 3 fD — a n fD M O C7" 3 fD 3 QJ QJ 3 l fD 3 ZT -5 -

II I i ^ Qj Qj—j i i LJ vj QJ 3 e+

O r+ fD

O

n

QJ Ol

N 3 M 3 3" 3" T3 Ol -5 3" 1/1 o 3 L_l 3 O r+ O O rt- ZT a Ol Ol O o QJ <-+ 3" r* CP 3" 3" rt- ZT CL 3 <-+ 3 ZT fD -5 ZT —J. << O 3" fD fD fD f+ fD <T> —j. T3 << 3" o 3 ro Q_ ZT 3 3 O ZT OJ O Oi fD fD -s ro fD -a fD fD .o 3

r+ 01 ZT 3 —J. 3 c fD

fD

n ro << 3 fD

-5 fD 3 fD 3 3 3 fD o

rt> 3 3 fD fDa.

h-1

i—»

t-1 M i—1 h-1 t—1

i—'

h-' o 1—' o O o CO o X) X) O o t—' ro o O O CP en x> h-> cp LP lo X> h-1 o lX> ro cn CO CO o cn CO ro 1—

1—'

t-1 i—1 I—1 i—' o 00 ro ro CO o o cn o o oo IX) o cn J> -Pi CO i—1 IX) -e> o o ro X) -p» I—'

IX)

-fe cn cn co OJ ro -e» t—1 CO <x> OJ ID o

1+ l+ l+ l+ 1+ i+ i+ i+ 1+ 1+ -z. 1+ 1+ 1+ i+ 1+ a o i—>

h-»

i—>

1—> o o 00 t—» o QJ i—»

1—'

ro i—> o

CO CO o cp cn h-» i—1 ro o o cn -e* -p» -p» LP MOO

I—1 ro

i—"

i—1 roMi—»

ro

cn

Mro

-p» o -p» cn

CO

1—> MO

O

-P»

1+ i+ i+ l+ 1+ 1+ 1+ l+ 1+ 1+ ^1 I—1 ro

IX) (-> CP cn

I—1 I—1 OJ

OJ

(—'

h-1 o1

1 aQJ

h->

I—1 M 1—1 O 1—'

X)

1—» o co LP

1+ 1+ 1+ 1+ 1—»

h-1 1—1

I—

-P» CO

LP

CO

LP ' v 3

II OJ

QJ '<

fD cr

CPn

2:

-5 CO — —1 x: —h 3 — -5O

I—1 QJ 3 —1 r+

r~ a> fD ni c co 3 —' o n 3

Tj r+ 3 3 3- —

c-fT

~5 r+ Z \r— r+ n s—' — • O—n 3 x:3

"D

X 3 r+ 3 -53 — n

rf

—

u z n

m 3" X QJ

<-< r+ 3

-5 3 n

Qj c O <

r* 3

rc -5 Q. z

to0—

3=

cH? QJ

fD < nc fD <

ro

VI-7
adding 1.0 pL aliquots of the 2,3,4,5-tetrachlorobiphenyl internal

standard solution with good precision. In a separate series of

experiments, three 1.0 mL aliquots of the methanol synthetic

leachate solution were placed into clean vials. 1.0 uL of a 10

pg/pL solution of 2,3,4,5-tetrachlorobiphenyl was added to each

vial with a 1.0 pL Hamilton syringe. The samples were analyzed by

GC/MS with SIM and peak area ratios of the analytes to the 2,3,4,5-

tetrachlorobiphenyl computed. The observed relative precision in

the ratios fell in a range from 5-25 percent (see table 6). This

degree of imprecision may cause problems with the quantitative data

on real world samples.

Possible Volumetric Errors in Extraction/Analysis Scheme

1.0 mL MeOH solution

1.0 L H

2 0

extract, concentrate

1.0 mL extract exactly!

add 1.0 pL 2,3,4,5-tetrachlorobiphenyl

internal standard

GC/MS SIM Analysis

100 pL aliquot (l/10th of sample) exactly!

+• 10 pL standard addition solution

GC/MS SIM Analysis

GC/MS Analysis of SRC II Vacuum Still Bottom Bulk Aqueous Leachates

Aqueous leachates of the SRC II Vacuum Still Bottom (VSB)

material were prepared by the Laramie Energy Technology Center

using EPA extraction procedure (EP) and ASTM leaching procedures.

Two EP aqueous leachates and two ASTM aqueous leachates were extracted and analyzed by gas chromatography with flame ionization

detection, and by gas chromatography/mass spectrometry in the SIM

and f ul 1 -scanni ng modes.

The resultant chromatograms show a number of minor peaks which

elute at the known retention times of the target analytes. The

samples were therefore analyzed by gas chromatography/mass spectrometry, in the full-scanning mode to confirm the presence of the

analytes, and in the SIM mode for quantitation.

Total ion chromatograms were prepared of the SRC II VSB EP and

ASTM-A bulk leachate extracts. The major peaks in the chromatoVI-8
o3

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r+3"

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in o-5ro oQJ

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rt- fD fD TJ QJ 3"

n 3 3- 3 3 O 3" QJ o QJ fD -5 ro fD T3 fD fD .o 3

QJ 3" 3 3 c fD n (t) *< 3 fD

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(V

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CL cn CTt CTt o t—1 ro CD ro cn ro ro ro 3 n as QJ 3 i—•

as cn t—»(X) 00 ID cn en CO ro js» tn Cn I—1 -J ro ro M ro CP 00 co CO CT> < C CO a> cn cn cn o t—1 ro cn i—1 ro -P» cn ro ro i—

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VI-9
grams are phthalates and the f 1 uorophenol , azulene, and 2,3,4,5-

tetrachlorobiphenyl internal standards. A number of substituted

phenols were also detected in the sample extracts. Of particular

interest are the chlorinated phenol at approximately 21 minutes and

the brominated phenol at 23 minutes, tentatively identified from

their mass spectra and confirmed by a library search. Mass spectra

of these compounds were also taken. The presence of halogens is

clearly indicated by the characteristic isotope clusters in the

spectra. A blank leachate sample prepared under identical conditions

was not supplied, so it is impossible to state that these compounds

are definitely associated with the SRC II VSB leachate samples.

The EP and ASTM-A bulk leachates of the SRC II VSB were then

analyzed by GC/MS with SIM detection. Individual analytes were determined based on the analyte to 2,3,4,5-tetrachlorobiphenyl

ratios and comparison with a gravimetri cal ly prepared standard run under identical conditions. The concentrations of analytes detected

in the SRC II VSB EP bulk leachate are shown in table 7. The

concentrations fell in a range from approximately 1 part per

billion for phenol down to a barely detectable 23 parts per trillion

for f 1 uoranthene. In all cases, the observed concentrations are

well below the 10 parts per billion threshold value. The extremely

low concentrations are somewhat surprising, especially in view of

the known aqueous solubilities of a number of the analytes (see

table 8). Fl uoranthene , for example, has an aqueous solubility of

200 parts per billion at 25 °C, yet was detected at only 23 parts

per trillion; phenanthrene has an aqueous solubility of approximately

1 part per million, yet was detected at only 46 parts per trillion.

Both of these compounds were known to be present in the SRC II VSB

material. Concentrations of the analytes detected in the ASTM

leachates are somewhat higher than in the EP leachates (see table

9) but still well below the 10 parts per billion threshold. It seems likely, therefore, that there is some loss of organics during

the sample handling and extraction steps. The round robin exercises

on the synthetic leachates showed that we are able to efficiently

extract the analytes from water at the .10 parts per billion level.

These experiments were concerned with measuring the extraction

efficiency of the method only. We did not look into losses due to

adsorption on leaching vessel walls, filters, etc. Substantial

losses may be occurring during the filtration steps, especially on the 0.45 micron filters used in the preparation of the aqueous

leachates.

NBS has now used this method for the extraction and analysis

of two synthetic leachates and two SRC II Vacuum Still Bottom

aqueous leachates. Given this degree of experience with the

method, the following observations are noteworthy:

1) The method, when applied conscientiously, can be used to

efficiently extract and detect the target compounds from aqueous

leachates at the 10 ppb level. Nevertheless, losses as discussed

above are possible. The only analytes which present some difficulties are the 1 ,4-naphthoqui none and the 1-naphthylamine. The

phenols are all recovered 50 percent or better, and most of the

VI-10
polynuclear aromatic hydrocarbons are extracted quantitatively at

the ug/L 1 evel

.

2) Some tightening of the quantitation scheme seems necessary

in order to assure accurate quantitative results. Possible sources

of error in the GC/MS determination of extraction recoveries have

already been discussed. Most of the volumetric errors can be

avoided, although the ability to accurately add 1.0 |jL volumes of

the internal standard solution to the sample extracts may continue

to introduce imprecision and errors in the quantitative data. The

2- point standard addition quantitation should be modified to a 3- point standard addition. The linearity (or lack of linearity) of

the curve in a 3-point standard addition. The linearity (or lack

of linearity) of the curve in a 3-point standard addition provides

some indication of how accurately the standard additions are made.

The 2-point standard addition provides no built-in check of this

type.

3) Losses of organics during the leaching and subsequent

filtration steps must be investigated. The detection of polynuclear aromatic hydrocarbons in the aqueous leachates of the SRC

II Vacuum Still Bottom material at levels several orders of magnitude

lower than their known aqueous solubilities suggests that substantial

losses may be occurring.

Table 7. Concentrations of Compounds in EP Bulk Leachate of

SRC II Vacuum Still Bottom Material.

Analyte Concentration (ug/L)

phenol 1.09 ± 0.08 (n = 2)

o-cresol 0.175 ± 0.05

naphthalene 0.203 ± 0.03

1,4- naphthoquinone 0. 078 + 0. 013

phenanthrene 0 046 + 0. 002

carbazole 0 460 + 0 09

f 1 uoranthene 0 023 + 0 01

VI-11
Table 8. Aqueous Solubility of Selected Organics Associated With

Hazardous Waste Leachates.

Compound Aqueous Solubility at 25 °

2-picol i ne very soluble

phenol 76.4 mg/gb

o-cresol 2.72 mg/gb

naphthalene 32000 ng/gc

qui no 1 ine sparingly soluble

d

1,4-naphthoqui none sparingly soluble d

acenaphthylene

acenaphthene 3930 ng/gc

2-naphthol 1.00 mg/gd

1-naphthyl ami ne 1.69 mg/gd

4- ami nob i phenyl slightly soluble3

dibenzothiophene sol uble a

phenanthrene 1003 ng/gc

carbazole insoluble^

f 1 uoranthene 200 na/a c

benz[a]anthracene 9.4 ng/gc

benzo[e]pyrene 2 ng/g

c

benzo[a]pyrene 1.6 ng/gc

peryl ene < 1 ng/g c

a CRC Handbook of Chemistry and Physics, 48th edition.

Octanol/Water Partition Coefficients and Aqueous Solubilities of

Organic Compounds, NBSIR 81-2406.

W. E. May, Solubility Behavior of Polycyclic Aromatic Hydrocarbons

in Aqueous Systems, ACS Advances in Chem . Series , #185, 7, pp. 143-192.

dMerck Index, 9th edition, Merck and Company, Inc. , Rahway, NJ.

VI-12
Table 9. Concentrations of Compounds in ASTM Bulk Leachate of

SRC II Vacuum Still Bottom Material.

Analyte Concentration (pg/L)

2-picol ine 0.24 ± 0.02 (n = 2)

phenol 6.68 ± 1.41

o-cresol 1.63 ± 0.27

naphthalene 0.38 ± 0.06

qui nol ine 0.39 ± 0.01

1,4- naphthoquinone 0.15 ± 0

dibenzothiophene 0.021 ± 0.01

phenanthrene 0.057 ± 0.01

carbazole 0.76 ± 0.16

f 1 uoranthene 0.016 ± 0.006

VI-13
ORGANIC LEACHATES - STATISTICAL ANALYSIS OF INTERLABORATORY DATA

by

Robert C. Paule

Two different inter laboratory experiments with organic

leachates have been completed. The following is a report on the

statistical analysis of the measurements from these experiments.

Experiment I

In the first experiment each laboratory was asked to take 3 one- liter portions of water and add a 10 ppb spike of 19 specific

organic compounds. Each one-liter portion (standards #1, 2, and

3) was individually extracted, concentrated, and analyzed 3 times

each by GC-MS and by GC measurement techniques. Averages for the

triplicate measurements were reported for each standard, and for

each method of analysis (GC-MS and GC). These data are given in

tables 1 and 2.

A within- and between laboratory analysis of variance [1,2]* was made for each compound and analytical technique (see columns

2-9 of table 3). The average concentration and its standard error (standard deviation of the average) are reported for each compound,

along with the within- and the between laboratory components of

standard deviation. At the bottom of the table the average results

are reported for compounds with greater than 50 percent recovery.

The averages (8.15 and 7.67 ppb) for the concentrations given at

the bottom of the table show that essentially the same results are obtained by both the GC-MS and the GC measurement techniques. This

is further confirmed by the data in column 10 which gives the

individual compound concentration differences between the two

measurement techniques. These differences are not statistically

significant, and are quite evenly distributed about zero.

Inspection of the average components of standard deviation at

the bottom of columns 4 and 5, and of 8 and 9, show that the

within- and the between laboratory components of standard deviation

are of similar magnitude. The two components for the GC-MS measure

ments tend to be slightly larger than for the GC measurements. All

four components, however, can be adequately approximated by a value

of 2 ppb. Thus, the standard error of a single laboratory's

measurements on a single solution is about 3 ppb, or 30 percent.

The overall recovery and the associated standard error for the

individual compounds from both measurement techniques are reported

in columns 11 and 12. The values given in these columns are based

on the use of a weighted average [1]. The recovery is about 8

ppb. Since a 10 ppb spike was used in the experiment, this corre- sponds to an overall recovery of 80 percent.

figures in brackets indicate the literature references at the end

this paper.

VI-14
The above summary statements are made for the large majority

of compounds that had greater than 50 percent recovery. Note,

however, that four compounds listed in table 3 had less than 50

percent recovery. These compounds are: n-tetradecane, 1-naphthylamine, 1-4-naphthoquinone, and 4-ami nobiphenyl . The recoveries of

these four compounds are quite low, and need to be reviewed by the

chemists of this interlaboratory exercise.

Experiment II

In the second experiment each laboratory made leachings from

SRC-II vacuum still bottom waste using methods A and EP. The

measurement data are reported in table 4, and the statistical

analysis is presented in table 5. This latter table gives the

average compound concentrations, the standard errors, and the

standard deviations for single laboratory results and associated

coefficients of variation. The relative precisions for the two

leaching methods are essentially the same (coefficient of variation ~ 55 percent). The method A leaching procedure extracts considerably

higher concentrations for seven of the eight compounds which were jointly measured. The differences in concentration between methods

A and EP are listed in column 10. The standard deviations of these

differences and the associated Student t values are given in

columns 11 and 12. The seven positive t values reflect higher

method A leachate concentrations. They border on being statistically

signi f icant.

References

[1] Paule, R. C. and Mandel , J., Consensus Values and Weighting

Factors, J. of Research of the NBS, 87, No. 5, Sept. -Oct.

1982.

[2] Mandel, J. and Paule, R. C. , Interlaboratory Evaluation of a Material with Unequal Numbers of Replicates, Anal. Chem. , 42,

1194-7 (1970), and Correction, Anal. Chem., 43, 1287 (1971).

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VI-18
Table 4. GC-MS Results Obtained on SRC- 1

1

Bottom Leachates.

ASTM Method A Leachates

Laboratory

a NBS Ames

3

Argonne

Compound (ug/£)

phenol 6.68 7 39.7

o-cresol 1.63 1 2.1

naphthalene .38 .6 .33

qui no 1 ine .39 .1 .34

1-4-naphthoqui none .15

b

phenanthrene .057

carbazole .76 1.8 1.14

f luoranthrene .016

2-picol ine .24

dibenzothiophene .021

n-tetradecane .1

Average of duplicate GC-MS measurements.

Not detected, and not used in calculations.

Vacuum Still

EPA Method EP Leachates

NBS

a Ames Argonne

3

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rf

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f-' M <

o-> o <f cr + + + c w> ro ho i—* Cl fD + fD -5 o ho OJ 3 < o ho rf (DCL

rf

VI-2Q
Leach Test Analysis on California Soil Test Material

A sample of a sediment material which had been spiked with six

chlorinated pesticides was submitted for analysis by the California

State Department of Health Services, Berkeley, California. Three

5.00 g samples were Soxhlet extracted with 300 mL of a 1:1 mixture

of hexane (distilled in glass) and acetone (distilled in glass).

Prior to extraction, 3 mL of aqueous 0.2 mol/L NH 4 C1 were added to

the sediment to ensure complete sample wetting. Also, 9.74 ug of

pentachlorobenzene (Cl 5 Bz) and 10.38 ug of 2,2' 4,4' ,5,

1 -hexachlorobiphenyl (C1 6 PCB) in 1 mL of hexane were added to each sample to serve as internal standards. Two solutions containing known

amounts of each analyte and internal standards were also Soxhlet

extracted for determination of analysis response factors.

All samples were Soxhlet extracted for 18 hours, after which

the unconcentrated extracts were analyzed by gas chromatography

(GC). The GC conditions employed for the analysis are summarized

in table 1.

Duplicate analysis of the calibration solutions yielded the

gram response factors presented in table 2. These values were subsequently used in the internal standard calculations for the

sediment extracts. Independent calculations of the six analyte

concentrations were made using each of the IS compounds. The three

sample extracts were analyzed at least in triplicate, and the

results are exhibited in table 3.

Sediment samples were also Soxhlet extracted with hexane

alone. These extracts, when analyzed, yielded results approximately

50 percent lower than the spike amount while showing a 15-30 percent

intersample standard deviation. These results led us to believe

that hexane was not an efficient extraction solvent, and resulted

in the second set of analyses with hexane/acetone as the extraction

solvent.

VI-21
Table 1. Gas Chromatographic Parameters.

Instrument:

Col umn:

Carrier:

Program:

Injector:

Split Ratio:

Detector:

Detector Flush:

Injector Temperature:

Detector Temperature:

Sample Size:

Electrometer:

Integrator:

Varian 3700

30 m x .25 mm SE-52 WCOT

Hel ium, 24 psig

150 °C for 3 minutes; 8 °C/minute

to 270 °C; hold 3 minutes

J&W splitter, split mode

20:1

CO

Electron capture, Ni constant current

Nitrogen at 30 mL/minute

300 °C

300 °C

1.5 uL

xl

Hewlett Packard 3388

Compound

Lindane

Heptachlor

Aldrin

Heptachlor Epoxide

Dieldrin

p,p'-DDT

Pentachl orobenzene

2,2' ,3,3' ,4,4'-Hexachlorobiphenyl

Table 2

Relative Gram Response Factor

0.920

0.793

0.892

0.828

0.795

0.602

1.00

0.577

VI-22
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VI-23
Multielement Analysis of Oils and Hazardous Waste Leachates

Using the Inductively Coupled Plasma Technique

R. L. Watters, Jr.

The inductively coupled plasma (ICP) technique has been applied

to the simultaneous multielement analysis of oil samples and leachates

of hazardous waste materials. This effort involved three principal

developments:

1) The design and construction of a high resolution direct

reading spectrometer system.

2) The application of a sealed-tube dissolution procedure to

the analysis of oil matrices.

3) The development of on-line data analysis software to

identify sources of variability in homogeneity assessment

and high-accuracy analysis of oil matrices and hazardous

waste leachates.

The spectrometer system consists of two Czerny-Turner spectrometers which are simultaneously illuminated by the plasma torch and

associated transfer optics. Each spectrometer can accept a photographic plate or multiple slits in the focal plane. A highresolution grating can also be installed in each to minimize

spectral overlap. Using this facility, the best spectral lines can

be chosen and exit slits can be positioned for multielement analysis.

The spectrometer system was set up in this way to determine simultaneously nine elements in the hazardous waste leachates. Other

elements are determined on an individual basis using one spectrometer in the monochromator mode. Leachates are routinely analyzed

for a total of eleven elements using the ICP.

Application of the ICP technique to a wide variety of matrices

requires that procedures be developed for both aqueous and organic

samples. Aqueous samples can be introduced into the plasma by

various types of nebulizers, but organic samples can present unique

sample introduction problems. The direct nebulization of oil

samples diluted in an organic solvent has been used with the ICP

technique. However, if the samples are of widely varying viscosities, or if they contain particulate matter, a digestion

procedure is required. Furthermore, pure element standards are more readily prepared in aqueous solution than in organic solvents.

The approach involves sample preparation procedures which reduce

the amount of nonrandom nebulizer variability. It has been found

that when samples of an organic matrix are wet ashed using perchloric acid, the resulting solutions cause appreciable nebulizer

pressure drift ("^1 psi). During simultaneous multielement analysis,

some element net intensities exhibit corresponding drift. The

degree of intensity drift for a given element depends on its optimum

observation point in the plasma flame relative to the compromise

observation point chosen for all elements. An alternate sample

digestion procedure has been used for the ICP certification analysis

VI-24
of SRM 1084 and 1085, Wear Metals in Oil. Ten elements were determined in aqueous solutions of the two materials following a sealed tube dissolution using hydrochloric and nitric acids. The

procedure was first described by Carius in 1869 [1] and has since

been modified to cover a variety of applications [2-5]. In this

particular case, up to 0.5 g of oil can be digested with the

resulting solution containing two percent by volume nitric acid.

Long/-term nebul izati>". exhibits no detectable pressure drift.

Once an analysis is performed, an approach to isolating the

variability associated with original sample batches is employed

using on-line data analysis of variance (ANOVA) software. The ICP

instrument minicomputer logs all data in 512 byte records that

cannot be accessed by ASCII editors or data analysis packages. The

output subroutine of a report writing program was modified to write

sample identification numbers and associated analytical data into a separate ASCII file. This file can be transferred to the NBS main

computer for analysis by the OMNITAB software or to the NBS storeroom

microcomputer for analysis by BASIC 80 software. For SRM homogeneity

studies, the file is transferred to the microcomputer for an analysis

of variance of hierarchic data with three sources of variation.

Estimates for variance in SRM bottles, sample preparation and

instrument drift, and instrument integrations can be calculated in

a total of five minutes after reading the data from the minicomputer

disc. An average value for each SRM bottle and the standard ANOVA

table were printed on one page for each element determined. For

application to leachate analysis, the data is transferred to the

NBS central computer fora one-way analysis using OMNITAB. This

routine separates the variance due to the leaching process from the

variance of the instrumental analysis. When an estimate of variance

among leachates of a common waste source is desired, the two-way

analysis of variance is performed by OMNITAB.

References

[1] Carius, L. , Liebigs, Ann. Chem. 116 (1869).

[2] Gordon, Charles, L. , J. Research NBS, 30, 107 (1943).

[3] Wichers, Edward, William G. Schlecht, and Charles Gordon, J. Research NBS, 33, 363 (1944).

[4] Gordon, Charles L. , William G. Schlecht, and Edward Wichers,

J. Research NBS, 33, 457 (1944).

[5] Kelly, William R. , personal communication.

VI-25
Polymer Modified Electrodes: Chemically Modified Electrode

Detectors for Halogenated Hydrocarbons

Elmo A. Blubaugh, Chawan-Kang Chiang, Richard A. Durst,

and

William T. Yap

Chemically modified electrode sensors may allow the selective

and sensitive detection of organohalide compounds. Thus, such sensors might be extremely useful for rapid but accurate analysis

of waste sites or for monitoring of existing or abandoned sites.

The decision to utilize polymer film electrodes was made with the

following advantages in mind: large chemical and physical stability

of polymer films, a great number of sites to immobilize the catalyst

of choice, and facile electron transfer.

Scanning electron micrographs of the originally proposed

polyphenylene oxide polymer films showed a very irregular and

i nhomogeneous polymer surface. This prompted the search for other

polymer films to attach to electrode surfaces. We have followed

two routes of investigation: electrochemical initiated polymerization of vinyl catalyst monomer and spin-dip coating of polymer

films. In the first route, the immobilization scheme involves

anionic polymerization through a chelated vinyl group. In the

second technique, the polymer films formed are of two types:

either electrostatic binding of a charged catalyst molecule or pendant chelating groups (i.e., pyridine) are the immobilization

agents. This second technique offers a great deal of flexibility

and freedom to optimize experimental conditions.

The catalytic system utilizing vinyl_polymerization was based

on [RuII(Bipy) 2 (4-vinylpyridine)] • 2PF 6 . With the following

reactions, a very strong luminescence is observed:

(1) Ru

ii

l v^± Ru

in

L

(2) Ru

IH

L + RC02

" Ru

H L + R + C0 2

"

(3) Ru

H L + C0 2

" L Ru

11

!/ + C0 2

(4) Ru

HI

L + Ru

n L" ' 2Ru

H L + hv

Inner Outer

Layers Layers

of Film of Film

where, L = (Biphy) 2 (4-vinylpyridine) and RC0 2 was 50 mM Na2 C 2 0 4

. We have demonstrated the catalytic oxidation of organic carboxylates

;

further work is being pursued in the catalytic reduction of organohal ides.

VI-26
We have spin-dip coated electrodes with polyvinyl pyridine.

To this modified electrode we have immobilized Nil I Schiff-base

complexes. These electrodes have shown reversible Nill/Nil

electrochemical behavior. With subsequent exposure of these

electrodes to 1,2-dibromoethane, a catalytic reduction wave was

observed. Further work is being pursued in the practical implementation of this system as an electrochemical detector.

Recently, we have utilized a cation exchange polymer sensor

(Nafion TM) to incorporate organic cation catalyst molecules.

Examples of the cation catalyst molecules we have investigated are methyl viologen and methylene blue. These organic cations show

reversible electrochemical behavior and are under further characterization.

Future work will be focused on investigating the effects of

polymer film cross-linking on film stability and electron transfer.

Other work will attempt to utilize the available photochemistry of

the excited state of RuII(Bpy) 3 for transport studies. Finally,

theoretical modifying and experimental work will be aimed at

developing mechanisms of electron transport and migration of ions

within the film.

VI-27
Combined Liquid Chromatography/Mass Spectrometry

Richard G. Christensen

Liquid chromatography (LC) can be used for the separation of

many nonvolatile and polar molecules that are not amenable to gas

chromatography (GC) and can handle many samples in matrices not

amenable to gas chromatography, such as water or heavy oil. Therefore, the coupling of a mass spectrometer (MS), which is a very

specific detector, to a liquid chromatograph has generated a great

deal of interest. If this could be accomplished, many of the

advantages of GC/MS could be realized with LC separation. Numerous

publications on LC/MS have appeared, and two methods have been used

in commercial instruments. However, neither of these types of

instruments has been used for quantitative analysis.

We have constructed a unique LC/MS interface that operates by

removing most of the excess solvent from the LC effluent stream as

it flows down a heated wire. The residual concentrated solution is

drawn into the vacuum of a mass spectrometer and volatilized into

the ion source. This interface and some applications of normal

phase chromatography have been described in Christensen et al .

,

Anal . Chem . 53_, 171 (1981).

A large fraction of analytical LC is now performed using

reversed-phase chromatography. It is, therefore, desirable to have

an LC/MS interface which will accommodate the aqueous solutions

used in that mode. An interface with an ul trasonically vibrating

probe tip has been developed to disperse these solutions into a vacuum. An early model, fitted with a poly(vinyl idene fluoride)

film, which served as a seat for the miniature needle valve, proved

to have a short lifetime. Therefore, a new valve was designed with

a seat formed by swaging the nickel capillary tube down upon the

tapered tungsten wire. The resulting valve was durable enough to

survive several months of intermittent operation.

For moderately volatile molecules, the system was sufficiently

stable to permit quantitation, but less volatile compounds showed

large, rapid variations in sensitivity. We believe that this

difficulty is linked to the size of the droplets generated. The

droplets from this probe are estimated to be about 25 mm in diameter.

Other workers whose interfaces spray liquid at higher pressures

report that the droplet sizes achieved are smaller, e.g., 5 mm. Special probes were designed and built with the aim of obtaining

smaller drops through larger amplitude of vibration or with higher

frequency of vibration, but in neither case was the desired result

obtained

.

Among the applications accomplished was the measurement of the

levels of various aliphatic acids in a shale oil process water.

» The difficulty of this analysis can be appreciated from examples of

other methods used: extraction and GC/MS with internal standards;

steam distillation followed by extraction and GC; ion exchange

stripping followed by LC with conductivity detector; extraction and

VI-28
deri vati zati on followed by GC. These obviously require considerable

time and effort. The LC/MS aliphatic analyses were performed by

simply injecting the aliphatic acid sample directly into the LC

with no pretreatment. A C-18 reversed-phase column was used with

water/methanol as solvent at 1 mL/minute. The responses of the

samples were compared with external standards.

A table of the results with the GC/MS results included for

comparison is shown below.

Concentration of Aliphatic Acids (ug/g) in a Shale Oil

Process Water

(Mean ± Standard Deviation of a Single Measurement)

Acid LC/MS GC/MSa

Butanoic Acids 91 ± 10

b 49.6 ±7.6

Pentanoic Acids 84 ± 10 71.9 ±8.9

Hexanoic Acids 87 ± 13 87.8 ± 4.4

Heptanoic Acids 136 149.5 ± 9.2

a Specific for n-acids.

b Includes n-butanoic and 2-methylpropanoic acids.

VI-29
Development of a Temperature Stabilization System for a D.C.

Plasma/Echelle Spectrometer

C. G. Blundell and M. S. Epstein

A major source of error in the analytical application of

direct-current plasma/Echel le spectrometry is thermal ly- induced

wavelength drift. This drift is a direct consequence of instrument

design, since the high temperature (6000 °C) plasma source is

directly mounted on the same aluminum baseplate as the spectrometer

optics. During plasma operation, a large thermal gradient is

established across the spectrometer which results in a drift of

wavelength and consequently a drift in intensity throughput.

System equilibration can take as long as eight hours with intensity

drift of 20 percent per hour. Since the drift is not linear and

difficult to model, a system was developed to eliminate the drift,

rather than try to correct for it.

The temperature stabilization system consists of several

thermistor probes which are placed at critical points in the

spectrometer, such as at the grating/prism mount. These probes are used as sensors for a temperature controller which regulates a heating tape surrounding the spectrometer baseplate to maintain a constant temperature (± .05 °C) at the probe position.

The system has significantly improved the spectrometer

stability and thus the precision with which measurements can be

made using the dc plasma. It has proved most useful in critical

simultaneous multielement applications, such as the determination

of nine elements in solid-waste leachates and 12 elements in

simulated nuclear waste leachates. In the latter case, the amount

of information that could be derived from the analytical results

was directly proportional to the measurement precision. Further

improvements in measurement precision will only be obtained by the

modification of sample transport techniques or by the application

of ratio (internal standardization) methods. Investigations in

these areas are proceeding.

VI-30
Development of a Quality Assurance Sludge Material for

Hazardous Waste Analysis

L. Hi 1 pert

The NBS Organic Analytical Research Division has been working

with the EPA to develop methods and reference materials for the

analysis of toxic organic constituents in hazardous wastes. The

first of the organic quality assurance materials consists of an industrial sludge which was diluted and fortified with eleven

priority pollutant organic compounds. The levels of the eleven

toxic organic compounds in the sludge were in the range of 1-40

parts per million. Quantitative measurements of the eleven organic

compounds added to the sludge were made by combined gas

chromatography/mass spectrometry. The use of high resolution fused

silica capillary columns coupled directly to the ion source of the mass spectrometer allowed separation of the compounds of interest

from nonanalyte interferences in the sludge. Selected ion monitoring

detection provided additional selectivity. The results of these

measurements enabled us to determine the accuracy and precision

attainable in the quantitative determinations of individual organic

compounds in a complex matrix, such as an industrial sludge. The

use of this material will allow the EPA to monitor the performance

of laboratories involved in the analysis of hazardous wastes.

VI-31

APPENDIX VII. THE WASTE-ENVIRONMENT-TECHNOLOGY MODEL:

A BRIEF EVALUATION AND ASSESSMENT

Harvey Yakowitz

Office of Recycled Materials

National Bureau of Standards

Washington, DC 20234

FOREWORD

The evaluation and assessment which follows utilizes some of

the results of hazard scoring reported by the developers of a model

known as the Waste-Environment-Technology Model. These results

have been used to suggest certain statistical inferences for

assessing degree of hazard posed by certain chemicals. Thus, the

results of the hazard scoring and its underlying foundation were assumed satisfactory for use in deducing statistical examples.

Note that the text is not meant to provide an exhaustive review of

the problems associated with the modeling of waste streams, economic

trade-offs in dealing with wastes, or determining absolute risks

relating to chemicals.

On September 28, 1982, the Science Advisory Board of the U.S.

Environmental Protection Agency held a public meeting to discuss

the RCRA Risk/Cost Policy Model Project (Phase 2 Report of June 15,

1982) which embodies the commonly referred to Waste-EnvironmentTechnology (W.E.T.) Model. The meeting was convened in order for

the Board to make public some of the findings of its review of

specific details of the W.E.T. Model. In addition, findings of

other representatives, the public, e.g., the Environmental Defense

Fund, Congressional Office of Technology Assessment were presented

before the Board.

The Board identified and addressed the following major issues:

1) Appropriate applications of the model. The potential

utilization of the model in policy and regulatory

decisionmaking processes was of particular interest. The

Office of Technology Assessment (OTA) suggested that

perhaps no model would be appropriate to this task.

2) Data requirements. All reviewers (Board members, SAB

constituents, representatives of the public/private

sectors) were deeply concerned about the avai 1 abi 1 i ty--or

lack thereof--cf reliable data base from which modeling

decisions and conclusions might be drawn.

3) Need for sensitivity analysis. General agreement was reached that sensitivity analysis for the various aspects

of the model, i.e., risks, economics, is needed. But a

VII-1
majority of the reviewers indicated that obtaining a valid sensitivity analysis, given the quality of

presently available data, would be very difficult.

4) Differences in types of health as well as environmental

risks exist. A desire was expressed for an accurate

means to evaluate the severity of hazards, e.g., cancer,

as contrasted with a minor irritant.

5) Rationalization of the economic and health related

assumptions used in the model. Several reviewers were concerned about the exact algorithm used—and its

validity—in order to obtain specific results for a given

waste stream.

6) Desire for expansion of the scope of the model. Some

reviewers were concerned that the number of waste streams

considered— 83 representing about 25 percent of the

waste generated—was insufficient. Other reviewers

suggested that the data were poor in any case. Still,

most agreed that a broader base would be useful.

A majority on the Board concluded that the present version of

the W.E.T. Model is "a good first step" in approaching an exceedingly

difficult set of problems. For example, the concept of using an order-of-magni tude scoring system in light of the available data

was acceptable although questions about some of the risk assumptions were raised. Further study of the modeling problem would seem to

be in order. The key issue is the requirement for critically

evaluated data in all of the areas encompassed by a model of this

type, e.g., health effects, threshold effects, mobility of chemicals

in the environment, and many others.

The text that follows does not deal with these issues, but

rather with the use of some results of the model. The basis of

hazard scoring of the model is presented; the results of this

scoring system have been used to suggest statistical inferences

concerning any method purporting to be a vehicle for assessing

degree of hazard posed by certain chemicals. Finally, a few

general comments on the use of the W.E.T. hazard scoring system are presented as well as some very broad economic implications of

adoption of this scoring system to parties-of-interest such as generators or treaters of waste.

The W.E.T. Matrix

In order to deal with the practical aspects of managing

hazardous wastes, the Waste-Environment-Technology (W.E.T.) Model was developed for the United States Environmental Protection Agency

(EPA) in order to derive, test and apply a degree-of-hazard framework

for regulating hazardous waste facilities. The Model was prepared

by three firms working under contract to EPA:

VII-2
ICF Incorporated

SCS Engineers

Clement Associates.

According to these firms:

"The risk posed by a waste stream is related to a number of

factors, the most important of which are:

o the inherent hazard and physical properties of the waste

stream, which depend primarily on the nature of the waste

stream and its chemical constituents;

o the quantity of the chemicals released and the medium into

which they are released, which depend on the size and nature

of the waste stream, and on the technology;

o the persistence of the chemicals, the rate of their dispersion,

and other factors governing exposure, which depend primarily

on the nature of the waste stream and on the environment;

o the size of the human population potentially exposed to the

chemicals, which depends primarily on the environment; and

o the presence of nonhuman systems that can be adversely

affected, such as sensitive ecosystems or valuable resources,

which depend primarily on the environment.

Thus, risk involves all three components of the W.E.T. matrix and

the risk scoring system accounts for all three.

"In this phase of developing the model, we (the model builders)

make four major decisions that greatly simplify the problem and

allow us to test our approach, while also preserving the factors

that will usually dominate any comparison of risk:

1) The scoring system is an index of risks to human health.

2) The scoring system combines all types of health risk into

a single numerical score; a second score characterizes

the range of uncertainty.

3) The scoring system characterizes the risks of waste

streams by their individual chemical constituents.

4) The scoring system assigns scores to the nearest order of

magnitude.

"There are two general problems in scoring risks to health

posed by hazardous wastes. First, most waste streams are complex

mixtures, and many are poorly characterized. Second, even if

adequate information were available on the composition of the

VI 1-3
wastes, for most chemicals, there is insufficient information on inherent hazard and environmental behavior to permit precise

estimates of risks. For these reasons, scoring for risks to health

is subject to large uncertainties and in many cases depends on scientific judgment. The scoring scheme we developed does, however,

base application of scientific judgment on a formal scientific

underpinning. By providing rigorous definitions of the factors to

be scored and by specifying numerical equivalents for the scoring

categories, it is possible to assign fairly precise scores to a number of well-studied chemicals. These scores can then guide the

assignment of scores to less well-studied chemicals and to

mixtures. .

.

"Many factors contribute to the risk posed by a W.E.T.--the

number of people potentially affected, the average intake per

person per day, the probability of response per unit of intake, and

the severity of response--and all are considered independently.

These factors are defined so that they interact mul tipl icati vely in

contributing to the overall risk. We assign scores to these

factors on an approximate logarithmic scale and then sum them to

provide a measure of overall risk:

1) log (risk) = constant + (sum of scores)

The constant is unspecified; thus, the system initially provides a measure only of relative risks.

"We define the overall risk presented by disposing of a waste

as the expected or most likely number of people affected. Since

some chemicals persist essentially forever after release into the

environment, the scoring system also assesses the risk of disposing

of the waste indefinitely. The system allows for the option of

discounting risks that do not occur until 30 or more years in the

future, but does not now discount risks.

"We define the major factors as follows:

2) Overall risk (expected number of people affected) =

P • E • H, where:

P = Population at risk (number)

E = Exposure (average intake per person per day)

H = Inherent hazard (probability of response per unit intake)

"As presented above, the overall risk is equated with the

number of people affected, irrespective of the type of effect. In

practice, some types of effects are generally regarded as more "serious" than others. To take account of this, the scoring system

could be generalized by adding a (multiplicative) index of severity,

which would approach a value of 1 for the most "serious" effects,

but might come close to a value of 0 for effects judged to be least

serious. The assignment of indices of severity involves value

judgments. Table 1 provides a flow chart for scoring inherent

hazard.

VII-4
TABLE 1

FLOW CHART FOR SCORING INHERENT HAZARD

REVIEW

TOXICOLOGICAL

DATA

DICHOTOMOUS RESPONSE GRADED RESPONSE

I

HUMAN

STUDIES

MED/10

I

ANIMAL

CHRONIC

STUDIES

MED/100

1

ANIMAL

SUBCHRONIC

STUDIES

MED/300

ESTIMATE OF HUMAN MED/10

CALCULATE INHERENT HAZARD

PER 1 mg/kg/day (UNIT RISK)

CALCULATE INHERENT HAZARD

PER 1 mg/kg/day

= 0.01 DIVIDED BY HUMAN MED/10

INHERENT HAZARD

PER 1 mg/kg/day

0.0005

0.0005 to 0.005 to 0.05

0.5

5.0 50.0

to

to

0.005

0.05

0.5

5.0

to 50.0

INHERENT HAZARD

SCORE

0

12

34

56

[MED = Minimum Effective Dose, i.e., the lowest dose which produces a clearly observable effect]

V I I-4a

"The submodel for exposure is:

3) Exposure (average intake per person per day) = Q • F • D. . I n .A

where: Q = Quantity of material handled

F = Expected fraction released

D. = Dispersion factor (concentration in the

ambient environment per unit of release)

I = Intake factor (breathing rate, consumption of

drinking water, and so on)

A = Absorption coefficient

The last three subfactors vary considerably from one environmental

medium to another. Hence, it is necessary to assign and sum exposure scores separately for each medium. The highest of the scores for the various media is essentially the measure of risk

because of the logarithmic scale (that is, any score less than the

highest is at most one- tenth as large and is not considered when

rounding).

"In our model, the overall risk depends linearly on the

quantity of material that is released. Unlike the other factors,

quantity is not an inherent property of the W.E.T. It can be

reduced, at increased cost, by improving the level of technology or

by dispersing the waste stream to other facilities. As noted

earlier, one of the objectives of the analysis is to explore the

trade-offs between cost and risk resulting from such changes.

Hence, the quantity released is not a consideration in the risk

scoring system. The final risk score is an estimate of the

logarithm of the overall risk per unit of material released.

Because uncertainties are large in many cases, the system

provides for assigning a measure of uncertainty to scores for both

inherent hazard and exposure. Uncertainties arise from four major

sources:

o lack of information (for example, on inherent hazard or environmental behavior);

o site-to-site variability within a W.E.T. (such as quantities

of materials released or hydrologic conditions);

o variability related solely to the environment (for instance,

differences in susceptibility within the population); and

o chance occurrence (such as probability of leakage).

"Although these types of uncertainties are formally distinct,

we assume that they can be combined meaningfully into a single measure of probability. We assume further that the distribution of

VII-5
probabilities (in this broad sense) for each factor is about

lognormal. Then the logarithmic score on each factor can be

characterized by a single expected value (mean) and variance, and

the variances can be combined by standard methods to yield a single measure of uncertainty in the overall risk. These overall measures

of uncertainty are, in practice, similar for many waste streams;

thus, they contribute little to the process of ranking. We found

some cases, however, where we judged the uncertainty in the risk scores to be substantially larger than average. The system provides

for identifying these cases and for carrying estimates of uncertainty

through the analysis.

"A number of exposure factors (number exposed, intake factor,

absorption coefficient) are measured on numerical scales; thus,

assignment of logarithmic scores is relatively straightforward.

The most difficult factors to score are inherent hazard and

environmental transport."

The model builders proceeded to score 140 substances largely

based on the EPA list of 129 priority pollutants. Appendix I provides a copy of these results; Appendix II contains the

uncertainty scores suggested by the W.E.T. model builders. Figures 1-4 show the distribution of inherent hazard score, H, and the

total score, W = H + E, for air, surface water, and ground water

paths. Note that "E" is the exposure adjustment for each of these

three media.

The cumulative distribution of the population represented by

the sample of 140 substances can be predicted by means of a con- fidence interval deduced by the methods of non-parametric statistics.

This prediction is possible since figures 1-4 indicate the

cumulative distribution of the sample. With a sample size of Q =

140, we may be 99 percent certain that the maximum deviation

between the cumulative distributions of £he population and of the

sample is equal to or less than 1.63/(Q)'5. For Q = 140, then this

deviation is ± 13.8 percent. In other words, the entire population

represented by the 140 substances can be represented by histograms

within ± 14 percent of those shown in figures 1-4. For example,

figures 1-4 indicate that 58 percent of the sample of 140

substances lie in the range 0 < W < 7. The statistical inference

is that 50 to 66 percent of the entire population represented by

the 140 substances lies in the range 0 < W < 7.

Some relationship between actual risk and these W.E.T. matrix

scores must exist. Furthermore, measurement uncertainties involving

the concentrations reported for various constituents must play some role in setting boundaries on any risk evaluation system such as the W.E.T. scheme. Then, too, the response of the W.E.T. scoring

scheme to changes in concentration of constituents which might be

escaping needs to be taken into account. In what follows, each of

these issues will be dealt with; in addition, the statistical

inference of utilizing the product of the population exposed, N,

with the inherent hazard and exposure to express risk will be

assessed.

VII-6
Ri sk- Concent rat ion Rel at ions hips

The dose experienced by some population or ecosystem as a result of hazardous waste operations or storage—via any path of

escape from a faci 1 ity— needs to be related to observed instances

of harm or the possibility of harm at some undefined future date.

In all of the following discussion, assume that the exposure or dose is meant to occur as a result of a hazardous waste facility.

Further, assume that the dose can be measured accurately and that

the sampling procedure is statistically valid.

Toxicity testing for incidence of adverse effects in animals

and humans as related to exposure or dosage always results in a sigmoidal or S-shaped dose-risk curve (see fig. 5). Under the

terms of the assumptions, zero dose means zero risk. But, the

cumulative probability of risk as a function of very low doses or levels of exposure is nearly impossible to measure or to predict

theoretically as indicated in figure 5.

For example, the question of a dose threshold arises immediately. If a threshold exists, then there are exposure levels of

certain substances, e.g., carcinogens, such that no matter how many

animals are exposed, none will exhibit cancerous tumors. Leading

authorities have stated flatly that resolution of the threshold

question is not possible given the current state of scientific

knowledge—even in a large-scale experiment involving several

thousand animals per exposure level.

Next, if no threshold is assumed, i.e., one molecule of the

substance has some finite—even if vani shingly smal 1—probabi 1 i ty

of causing harm, the relationship of the exposure to risk level

must be correctly known as the exposure approaches zero. Here two

other uncertainties intervene: 1) What is the minimum detectable

limit of concentration of the emanations from the site in the

various paths and media via which the emanations can travel? 2) Is

there any valid mathematical statistical model for extrapolating

from detectable levels to zero exposure?

Minimum detection limits for certain organic and inorganic

species have been reported in the so-called part-per-bi 1 1 ion range.

Such determinations —especially in heterogeneous mixtures and

media— have wide ranges of uncertainty (large confidence intervals)

and are exceedingly difficult to perform. (Note that one part-perbillion corresponds to about 600 trillion molecules of the substance

under test.) Accurate measurement at low exposure levels is likely

to be difficult to obtain and is likely to be very expensive.

Consider now models for extrapolating from measurable exposure

data to the risk at lower exposures. In one experiment, some 24,000 female mice were subjected to a known bladder and liver

carcinogen in order to study dose responses down to a one-percent

tumor incidence, i.e., the concentration of the carcinogen which

would cause one mouse in 100 to develop liver or bladder tumors.

VII-7
Results of these tests were not especially enlightening. For

example, a linear extrapolation and a "Weibull model" which is a statistical probability distribution having a finite starting point

for estimating life distributions as a function of exposure, were applied to the data.

For a one in a million risk (P = 10 -6

) of liver cancer in the

mice, an 0.045 part-per-bi 11 i on dose of the carcinogen was predicted by the linear model; the Weibull model predicted a 4.5

part-per-bi 11 ion dose for P = 10~6 or an exposure of 100 times

greater for the same risk.

The EPA Carcinogen Assessment Group has stated that:

"There is no really solid scientific basis for any mathematical

extrapolation model which relates carcinogen exposure to cancer risks at the extremely low level of concentration that

must be dealt with in evaluating the environmental hazard."

With respect to the prediction of "time-to-tumor" data, there

is no agreement between available models. Results are different,

and certainty of prediction appears impossible at present.

As stated by the Congressional Office of Technology Assessment:

"The accuracy of the relation between exposure and incidence

(of adverse effects) is always limited. Practical restraints

on the number of animals that can be tested means that the

data are always subject to significant experimental error; it

also means that only relatively high incidences, almost always

greater than 10 percent, can be measured in the experiments.

There is also no agreement about which mathematical models

best extrapolate from the exposure levels measured in studies

to those encountered in the environment. Linear models,

which assume that incidence is proportional to exposure at low

exposure levels, are used by Federal agencies."

Note that use of a linear model tends to be "conservative," i.e.,

it predicts a higher cumulative probability for harm at lower

exposure levels. As a practical matter, there is often no alternative to the linear model.

Apparently, there is no unambiguous valid means to directly

relate the probability for harm to a measured exposure level at low

exposure levels. This situation poses another challenge:

o Estimation of the potential population who might be exposed to

effects from the site and determination of the proportion of

this population who might suffer harm as a result of the

existence of the site.

The proportion of the population in the exposure area who

would be unaffected if the site did not exist can be found via

VII-8
application of the theory of competing risks. For example, a person in the exposure area may be ill for reasons entirely

separate from the existence of the site. The elements of the

problem may be stated as follows:

Given :

y = Number of population in exposure area now who are not ill

u = Number of population in exposure area showing adverse

effects which might be attributed to chemical exposure via some path

z = Number of population in exposure area who would be

unaffected if dump did not exist

Requi red :

"z" in terms of "y" and "u"

Steps :

Let dz be the decrement of "z" in a small time.

Let dy be the decrement of "y" in the same small time.

If "z" individuals were subject to adverse effects due to

chemicals, then

dz = - dy

y

3

But: We must subtract from this value of dz the decrement arising

from suffering of adverse effects caused from exposure to

chemicals via some path. We must make such a subtraction

since the "z" individuals are--by hypothesis of this problem--

not liable. This decrement is

(z/y)du.

Therefore

,

dz = - dy + - du

y y

(We utilize +(z/y)du and not -(z/y)du since "z" and "y" decrease while

increases.

)

VI 1-9
Rearrangi ng: —dz _ dy . du

= + — , so

z y y

»

log z = log y + J" ~ , and

r dU

z = ye J —

At some time "x" incremented via dt, Equation (6) can be rewritten

as

The right-hand side of this expression can — in principle—be

estimated. But, in practice, obtaining the necessary data in

unambiguous form and over a period of time represents a formidable,

if not impossible, problem in epidemiology. Hence, great uncertainty

in identifying members of the exposed population who suffer harm as

a result of the hazardous waste site is likely to be the case.

At this point, the chief difficulty for the regulatory process

should be clear: How to implement mandates to control possible

risks associated with waste disposal in a fair, objective and

accountable manner by using rational approaches such as scientific

and technical data and cost-benefit analyses. These approaches tend

to emphasize economic cost factors, but the concerned portion of

the public generally considers that the health and environmental

amenities at stake are unmeasurable in economic terms; in fact,

most of the public probably wishes "zero exposure" from waste

di sposal

.

If the regulatory process operates utilizing quantitative

targets for defining a waste as

" hazardous " and if exceedingly low

concentrations of substances in the waste must be achieved, costs

of control rise rapidly. Obviously, the lower the required con- centration, the higher the cost of control. Hence, some balance

between these costs and exposure is needed. Once a risk is

accepted as real, i.e., worthy of regulatory attention, the

stringency of the regulation depends on economic and technical

factors to be workable.

One proposed method for taking these factors into account is

to classify wastes destined for disposal into categories depending

upon the substances, their concentrations and their propensity to move and/or to persist in the environment by any path. Thus, high

concentrations of a known carcinogen, which moves rapidly and is

persistent, might require a more stringent level of control than

lower concentrations of the same substances; a different substance

which moved more slowly or was not a known carcinogen might require

less control and so on.

VII-10
In principle, this classification scheme is appealing since

only the most objectionable wastes would require the most expensive

monitoring and treatment. In practice, immediate difficulties

present themselves in how to set the classifications and to

administer control over them in a fashion acceptable to the public.

Some of the technical difficulties will be apparent from an examination of table 2 in which two objective and competent groups

of scientists attempted to define cancer risk 1 from drinking water

containing one part-per-bi 1 1 ion (one microgram per liter) of known

carcinogens. The table purports to indicate the number of persons

per million exposed who are likely to fall victim to cancer from

drinking this water. Note that in several cases, a tenfold to

hundredfold difference exists between the two estimates. Data

taken from table 2 are shown plotted in figures 6 and 7 assuming a linear relationship between concentration and excess cancer risk.

These results may be used to link the W.E.T. matrix scoring system

with approximate actual hazards.

Examination of the range of inherent hazards, H, per 1 mg/kg/day

(1 PPM per day) as shown in table 1 suggests that when H is 4 or more, the inherent hazard exceeds unity, i.e., the hazard, whatever

its nature, would seem to be assured to all who were exposed. In

addition, values for H of 4 or more appear to be well beyond the

range where dose and risk are linear. Linear response ceases when

the 2 hazard exceeds 0.1 to 0.15. (See fig. 5.)

Reference to table 2 indicates that if the hazard is in the

1 inear range, i.e.

,

4) Hazard = mC where

x

C is the concentration of the substance causing hazard,

and m is the slope of the linear relation,

then for vinyl chloride with C = 1 PPM, "H"* is approximately 0.1

(CAG data) or 0.002 (NAS data)

x The W.E.T. scheme gives H = 3 for

a hazard of 0.1 and H = 1 for a hazard 0.002. The score listed by

the model builders is H of 2 for vinyl chloride.**

1 H ss mC^ (with risk H and 1 ppb can calculate m)

2 expressed as fractional excess tumor incidence with linearity

assumed up to D = ID in figure 5.

* re: vinyl chloride from table 2 (original draft read "m" not

"H", it is corrected here).

** See bottom table 1, p. 4.

VII-11
TABLE 2

Concentration of Drinking Water Contaminants

and Calculated Excess Cancer Risk

NAS

a CAG

b

10" 6 10" 6

ug/lc ug/lc

Acrylonitri le 0.77 0.034

Arsenic ND 0.004

Benzene ND 3.0

Benzo(a)pyrene ND ND

Beryllium ND 0.02

Bis(2-chloroethyl )ether 0.83 ND

Carbon tetrachloride 9.09 0.086

Chlordane 0.056 0.012

Chloroform 0.59 0.48

DDT 0.083 ND

1,2-Dichloroethane 1.4 1.46

1,1-Dichloroethylene ND 0.28

Dieldrin 0.004 ND

Ethylenedibromide 0.11 0.0022

ETU 0.46 ND

Heptachlor 0.024 2.4

Hexachlorobutadiene ND 1.4

Hexachlorobenzene 0.034 ND

N-ni trosodimethylamine ND 0.0052

Kepone 0.023 ND

Lindane 0.108 ND

PCB 0.32 ND

PCNB 7.14 ND

TCDD ND 5.0 x 10

Tetrachloroethylene 0.71 0.82

Trichloroethylene 9.09 5.8

Vinyl chloride 2.13 106.0

3 _ U Standardized to 10 risks from National Academy of Sciences Drinking

Water and Health (266) for consumption of 1 1/water/day.

^Recal cul ated to exclude aquatic food intake from Cancer Assessment

Group, Ambient Water Quality Criteria (104). Standardized to 1

1/water/day intake.

Average adult water consumption is 2 1/day.

d

Not discussed.

SOURCE- Office of Technology Assessment.

VII-12
If one is interested in the range where inherent hazard and

concentration is linear, the scale of inherent hazard apparently

needs to be shifted. Figure 8 shows the inherent hazard scale

suggested by the model builders as well as a proposed shift based

on the data of table 2. In other words, the distribution of

inherent hazard scores determined by the model builders is

acceptable but the slope of a linear relationship utilizing these

scores can be expressed as:

5) m = 10

(W" 10) if C x

is in PPB.

Hence, hazard is suggested as

6) Hazard « 10 (W~ 10)

C x where

H as inherent hazard from the model

E as "exposure" from the model; presumably the value of

"E" accounts for persistence, bioconcentration, mobility,

etc.

The proposed shift*** agrees with the H values determined by the

model builders within one unit in about two-thirds of the cases where the substances in table 2 have been scored by the model

builders and within two units for about 85 percent of such cases. Since the uncertainty in "W" values suggested by the model builders

is ± 1.4 to 2.5 units of W (see Appendix II), this agreement is

considered satisfactory.

Some Considerations in Evaluating Exposure from a Hazardous Waste

Faci 1 i ty

Presumably, any index describing degree of hazard will increase

as the danger of environmental and/or health risk increases. Thus,

the value of the index must be made to depend, as q intitatively as possible, on the likely fate of various wastes in various environments

The following summarization indicates some relations of physicochemical properties to environmental behavior:

^ Region in figure 4, p. 11, as discussed on p. 17.

W

- 10 ***m = 10 w = 10 + log

lf) m w is the inherent hazard score

H = mC is the inherent Hazard per ppm.

NAS (vtnyl chl ori de)

m = 2.13 x 10 ^ gives w = 4.33 and inherent hazard, H = mC

x = 2.13 x 10" 3 for 1 ppm.

CAG (vinyl chloride)

-4

m = 1.06 x 10 gives w = 6.03 and inherent hazard, H = mC = 1.06 x 10 * for 1 ppm. (1 ppm is used since W.E.T. scheme

uses this)

x

VII-13
Physical Chemical Data Related To:

1. Sol ubi 1 i ty in Water Leaching, degree of adsorption,

mobility in environment

2. Latent Heat of Solution Adsorption, leaching, vaporization

from surfaces

3. Partition Coefficient Bioaccumulation potential,

adsorption by organic matter

4. Hydrolysis Persistence in environment and

biota

5. Ionization Route and mechanism or adsorption or uptake,

persistence, interaction with

other molecular species

6. Vapor Pressure Atmospheric mobility, rate of

vaporization

As an example, many compounds which accumulate in the tissues

of living organisms have been found to have a low water solubility

but a high solubility in non-polar solvents. The partition

coefficient of such compounds provides a fair measure of their

tendency to accumulate in living organisms. This, coupled with a resistance toward reaction, gives an indication of transmission

from one trophic level to another as well as of bio-accumulation.

The solvent usually selected is n-octanol since it is convenient to use and resembles the adipose tissue of certain living organisms.

With regard to leaching, the important factors are the water

solubility of the hazardous waste mixture, adsorption, soil type

and moisture, and percolation velocity. One would expect the

amount of chemical carried in the soil to be proportional to the

amount of water available to dissolve the specific species; temperature must also play an important role in leaching since it

affects solubility.

Assume that there is an existing or proposed land-based site

in which possibly hazardous discards have been (or will be) placed.

The site can be a pit, pond, lagoon, landfill or land spread,

deep-well injection, salt dome or encapsulated (fixed) deposit.

Note that abandoned sites can be taken into account as well. In

addition, airborne effluents and residuals from an incinerator can

be included. Almost certainly, the following general questions

will have to be dealt with in some detail:

a) What is present?

This question requires that qualitative analysis for all

constituents be carried out. Generators and disposers

VII-14
can, of course, check incoming shipments fairly

accurately. In the case of old sites, some means of

accurate qualitative analysis sensitive to very low

levels of various constituents must be developed. Thus,

sampling protocols and relatively rapid identification

procedures are needed--which are economically affordable.

Clearly, organizations such as ASTM will need to compare

sampling protocols, develop and evaluate various test

methods and agree on standards of comparison.

b) How much material is present or planned for the site?

Total amounts of potentially hazardous substances will be

of interest to any local jurisdiction.

c) How long has the site been in its present location? Are

records available?

This information is needed if an appropriate monitoring

scheme for emanations from the site is to be developed.

d) What is in the vicinity of the site? Are its boundaries--

in three dimensions —well defined?

Paths by which emanations from the site may migrate into

ecosystems, e.g., via ground water, surface water, air,

soil, etc., must be determined. Population density and

land use are also required.

e) Are constituents escaping from the site?

Soil characteristics need to be assessed, e.g., composition, permeability to the constituents at various

depths, conductivity, pH and others. In the case of

long-term or abandoned sites, baseline data are needed as well. Rainfall, rain pH and rain analyses are needed as well. Perhaps the appropriate leaching medium for any

given site is the liquid which filters through a system

of local soil subjected to having local rainwater poured

over it. In fact, a total geological and hydrological

study of the vicinity of the site is likely to be

necessary. Again, standard practices, tests and data

reporting protocols are required. The California Air

Resources Board has suggested a series of estimate air

emissions from 1 andspreadi ng , surface impoundments, and

landfills containing constituents often found in

hazardous wastes. In the absence of consistent methods,

conflicting results are likely to occur.

f) Determination of potential for harm:

o Quantitative determinations of constituents present must be

carried out in order to determine possibility of exposure of

VII-15
humans or ecosystems to the constituents of the site. This

requirement implies development of a measurement assurance program so that the results from complex and expensive tests

such as GC/mass spectrography can be translated, on a con- trolled basis, to less complex and less expensive tests having

similar precision and accuracy. Of course, a valid sampling

technique is implied as well.

In this context, the question of guarding against or detecting

concentrations above a certain datum becomes of interest. The

datum may be set by regulatory action or the probability of

adverse effects if the concentration exceeds some datum which

may have been determined empirically. In any event, classical

statistical considerations (nonparametri c tolerance limits)

can be used to determine how many samples must be investigated

in order to calculate some probability of finding a proportion

of the total population below the datum. For example, for a probability of 99 percent that 99 percent of all possible

tests will be below the largest concentration measured, some 459 separate analyses are required. Conversely, if four

separate analyses (replicates) are performed, one can only be

70 percent certain that 70 percent of all possible tests will

fall below the largest of the four concentration values

measured.

Research is needed to determine the relationship between

easily measured parameters, e.g., pH, and the potential for

adverse effects. In any case, statistical uncertainties are likely to make "legally accurate" concentration determinations

difficult to achieve.

Kinetics of what is present in terms of local surroundings

In this case, research is required to determine constituents

and their concentrations as they move in a specific ecosystem

by a variety of paths as a function of time. This problem is

the monitoring problem, i.e., concentration as a function of

distance and time to define increased exposure to the contents

of the site.

If all of the needs described to this point were met, i.e.,

rapid, accurate qualitative and quantitative measurements of

effluents from the site in a statistically valid fashion, the

net result would be a determination of exposure to the contents

of the site as well as a determination of who and what are exposed at a given level. No mistake should be made in

thinking that obtaining these data is simple, straightforward

or inexpensive in terms of professional talent, equipment and

dollars. Yet, without these data, no valid statement concerning exposure levels can be made.

VII-16
The W.E.T. scheme utilizes simple dispersion relations and some subjective judgments based on common sense to arrive at a scoring system for exposure via several paths for various potentially harmful substances.

For a real situation, the distribution of the cumulative

probability for adverse effect of a sum of various constituent

concentrations at a given time and place is required. Clearly, the

preference of any model builder will be to obtain a valid con- tinuous function to represent observed discrete measurement values.

The choice of logarithmic scaling by the W.E.T. Model allows simple

dispersion relations since the errors of these relations coupled

with measurement errors will not cause rapid W.E.T. scale changes.

Whether or not more accurate theoretically representations are considerably more useful in a practical sense is impossible to

state given the data available.

Determining the Exposed Population

The W.E.T. Model builders did not discuss in detail how to

isolate the exposed population. In fact, determining the exposed

population, i.e., the group subjected to higher than baseline

concentrations of the substances from a site, is no simple

challenge. In principle, the various paths by which substances

might reach the group can be identified. Monitoring, which relies

on qualitative and quantitative determinations, at various points

away from the site can be implemented. Thus, what— if anything—is

escaping and how much will be known as a function of distance from

the site. When the slope of the concentration against distance

curve changes upward, the boundary for a particular path can be

located. Wind, other climatic factors, and water flow patterns may

well alter the results over a period of time. Airborne or rainbased factors may enter. Concentrations of substances produced by

other means than the waste disposal site may intervene, e.g., from

the plants generating the waste or other sources. Thus, attempting

unambiguous identification of who is exposed to higher concentrations of potentially harmful substances from a waste disposal site

is likely to be exceedingly difficult, time-consuming, expensive,

and inaccurate.

But, even if the exposed population, N, could be accurately

determined and the risk of excess cancer or other disease were

known accurately, prediction of adverse events due to hazardous

waste requires a statistical estimation scheme. Since the risks

tend to be fairly small in a probabilistic sense, the Poisson

distribution function would seem to represent the appropriate

statistical estimator.

Consider the Poisson function:

(7a) P

k

(t) = e" qt

^

VII-17
P.(t) is probability that exactly "k" events occur in half-closed

time interval of length equal to "t." q is a parameter indicating

average number of illnesses per unit time.

Def i ne:

(7b) A = qt, the expected number of illnesses.

Then, the Poisson distribution function is

h

(8) F(x) = I P k

(t) =

k=0

F(x) is the probability that the number of illnesses actually

observed, S, is less than or equal to "X". h = [x] is the integer

satisfying h < x < (h+1).

Tables of probabilities according to the Poisson distribution

can be found in most statistics textbooks. Basically, determining

the excess risk for adverse effect renders the exposed population

dichotomous, i.e., a proportion "p" of the individuals have a certain characteristic (illness due to the hazardous waste) while

the remaining proportion (1-p) do not have it. For a Poisson

distribution N

p = A. Thus, if 1000 persons were exposed to 1.1 PPM

of chloroform in their water according to figure (2), the risk (or

p) is 10- 3 and A = N

p = (1000)(10-3

) = 1.0. Figure (9) shows F(x),

the probability of the number of illnesses observed versus a discrete number of individuals, X, from the population, N, for

several values of A. For example, with A = 1.0 we may be 37

percent certain that no one will be harmed and 100 percent certain

that no more than five persons will be harmed. (For ingestion of

water from a hypothetical well containing the highest detected

concentrations of commonly found contaminants, p has been estimated

at 7.5 x lO"4 or if N is 1300, then A = 1.0.) But if the value of

A increases, say because of contaminants escaping from a hazardous

waste facility, the distribution of probability for adverse effect

shifts and broadens as shown in figure (9). Therefore, for a population of citizens who have been exposed, a key question is

"What is the value of A for our group?" A second key question is

"What is the probability that no one will be harmed as a function

of concentration of some substance having a given W.E.T. score, W?"

In order to approach answers to these questions, some assumptions must be made:

o The population exposed is representative of the U.S. population in age and general health characteristics.

o The hazardous waste contaminants are the only external source

of adverse effect on this population.

VII-18
Since X is defined as N

p and since in turn, P may be defined as mC

in the linear hazard-concentration range, then by Equation (6):

(9) X = 10 (W" 10)

NC

x where

W is W. E. T. score , H + E

N is population exposed to a substance having a W.E.T. score of W for the path of interest, and

C is the concentration in parts per billion (PPB)

or the substance in the path of interest. C is in

PPB.

x

Figure 10 shows A as a function of concentration for various values

of W. The detection limit for many substances in air or water media

is about 5 to 10 PPB; for soils and sediments this limit is about

25 to 100 PPB. As a waste management strategy, if 0 < W < 5, the

material can be handled in any facility such that escape of con- stituents resulting in a concentration of up to 100 PPB can be

isolated from the general ecosystem near the facility. For 6 < W < 7, some judgment will be needed on the ability of the facility to

be isolated from the ecosystem. For W of 8 or more, destruction is

often likely to be necessary since, if even a small group is

exposed to concentrations below the detectabi 1 i ty limit, the

probability for harm may be fairly high. Of course, each situation

will need to be considered individually in order to make practical

decisions. For example, if proof exists that a proposed or existing landfill operation is essentially isolated from water

sources and if the site is also isolated with respect to people,

then landfill for substances up to W = 8 or more might be given

consideration.

The statistical probability that no one is likely to be harmed

by exposure to some concentration of a potentially hazardous

substance can be calculated. This probability is given by the

first term in the Poisson series:

(10) P q = exp(-A)

\

X -2 - 2 since F(x) = — e = e for x = o

Fiqure 11 shows P versus X for 0.01 < X < 10. a O - ~

From Equation (7b):

(11) P Q = exp - [mNC

x

]

From this expression, the absolute value of the error on P q can be

found as:

VII-19
(12) |AP | - |P £nP [M2 + m2 JjrA 2

] 1/2

I

Figure 12 shows |P J for various values of P as a function of the

composite error in determining the population* exposed, the concen- tration and the value of the slope relating hazard to concentration.

If Equation (9) is utilized, then

(13) P Q = exp - [10

(W" 10) NC

x

]

Figure 13 shows the probability that no one in an exposed population

assumed as 1000 persons will be harmed if detectable concentrations,

C DL , of 5, 50, and 80 PPB of some substance having a given W value

are confirmed. The curves shown also indicate the changes in P if errors in C^. are made; say by actually having 80 PPB present but

apparently measuring 50 PPB. In addition, if N were 10,000 rather

than 1000, and C-.. was 5 PPB, one would be able to read P from the

C,DL = 50 PPB curve. Curves similar to those shown in figure 13 can

be used to evaluate specific situations.

Consequences of the W.E.T. Model Scaling System

Since any value of the W.E.T. score W in the range 0 < W < 5 produces little change in the statistical risk distribution very

little, the most economically advantageous method for treatment and

disposal can be chosen by the parties of interest, e.g., generator,

service company, regulators — local, State, or Federal. Furthermore,

the range of 0 < W < 5 allows fairly wide latitude in groups of

contaminants, concentration and exposure allowed. For 5 < W < 7, more care is required in choosing appropriate strategies; specific

situations will need to be decided on a case basis.

When W exceeds 6, several strategies are possible. For liquid

wastes where W exceeds 6, incineration will probably be recommended,

since landfilling "free liquids" is likely to be strongly opposed

in the political arena. But treatment plants purporting to blend

and neutralize various liquid wastes might be allowed to take such

wastes. After treatment, the W value might be reduced to 6 or

less. Then solidification or encapsulation might be chosen as the

"ultimate" disposal method depending on the economic tradeoffs

vis-a-vis incineration. For viscous materials, i.e., most sludges,

the range 6 < W < 8 will create uncertainties as to proper treatment

As a guess, local authorities will be left to deal with this

problem. The same is likely to be true of solids.

For the range where W exceeds 8, destruction is likely to be

the choice of most of the parties-of-interest in view of the

potential liabilities. However, in some cases other choices may be

justi f ied.

VII-20
In the case of abandoned sites, the W.E.T. model scaling

allows a radial distance for cleanup to be chosen quickly, since an acceptable value of the "How clean is clean?" question is answered

as soon as P is chosen for all potential escape paths and the W

values and concentrations of the constituents are found.

The W.E.T. Model Scaling System allows for relatively straightforward monitoring and post-closure costs. First, relatively large

changes in concentration of escaping constituents make small

changes in the value of the probability for harm (figs. 10 and 13).

Thus, time should be available to observe and, if necessary, to

take remedial action without alarming the surrounding population.

With regard to insurance issues, the range 0 < W < 5 should

lead to one band of lower premiums, the range 6 < W < 8 should be

the next risk band, while for W > 8, the highest premium will be

required. If liability and regulatory decisions are based upon

these three bands, e.g., little liability for W < 5 or 6, then the

hazardous waste problem can be reduced to economically manageable

proportions for the generators.

The key issue will be to convince the public that the W.E.T.

Model represents reality with respect to the perceived risks. If

this can be done, the nature of the scaling system allows for

hazardous waste management at an acceptable economic cost to the

generators. Furthermore, one can argue that the scaling system

provides for "degree of hazard" at lowest implementation costs--

both technical and administrative. Indeed, the scaling system does

provide two or three breakpoints for degree of hazard, i.e., W < 5,

5 < W < 7 or 8, and W > 8.

Some Broad Economic Implications of Adoption of the W.E.T. Model

Generators : Cost could be reduced for managing hazardous wastes

since much solid material can go to landfill, i.e., W < 5. For

very low W values, delisting might be in order. Obviously,

liability and insurance costs are likely to be reduced as well if

it can be shown that the generator's wastes prior to treatment and

disposal had a low value for W.

Service Companies : Rules are clear--keep W as low as possible. If

the value of W can be proven, then the company is in "compliance

with regulations." Hence, liability, insurance, analytical and

monitoring costs can be reduced. Profitability should increase at

slightly lower gross charges per ton as some of these savings are bartered back to customers of the facility. Prices for disposal

will probably increase as W increases.

Transporters : A uniform manifest system showing the "W" value of

the waste as it leaves the generator should reduce transporter

liability and might lower transport costs and opposition to

transport through certain jurisdictions. In any case, a fixed

system will be in place in order to serve as a foundation for

whatever precedents the courts set.

VII-21
Regul ators : The W.E.T. Model allows for considerable bargaining in

setting regulations, since, within reason, regions of W can be

selected to give regulations a "tough" or "easy" appearance without

substantially altering real risk.

Sitting Commissions : A framework to ease public fear of morbid

consequences would exist. Then negotiations for a facility could

proceed on more conventional lines, i.e., economic bargaining. The

same apparent latitude available to regulators would exist.

Incinerator Operators (Land and Sea) : Most wastes and all liquids

with W > 6 are candidates for destruction.

The General Pub! ic : If costs of disposal do decrease, perhaps some

of these savings will wend their way indirectly to the general

public. The key for advocates of the W.E.T. scheme is to get the

public to think in W.E.T. Model scaling numbers rather than actual

risks.

General Conclusion

The W.E.T. Model can provide a framework for hazardous waste

management which is likely to be acceptable to most parties-ofinterest. The key is to understand all of the technical, legal,

and economic implications of the Model so as to be able to

negotiate the strongest position for one's own interests.

Certainly, the Model can be manipulated to reach almost any

desired outcome provided all of its ramifications are clearly

understood and can be put in perspective. The key will be to

utilize this knowledge for appropriate policy and economic

purposes. Since the framework will accommodate most outcomes,

manipulation of the Model will allow for flexible control of

hazardous waste issues without requiring major policy departures.

VII-22
i. T3

Z3

01 -ao

E

CO

orLU

CD

in 3

Q

cr<

N

<

T3

0)a

o

r—>

<u T3

i/> 01co

u

ro

LU

orLU

C\J

00\

LO

CD

H

LU

o m

fO

o

ro m

CVJ O

C\J in in

A0N3n03dd

T3C

(0 . N C>

fO »—

t

X

c -a

O) c

t- 01

o> a.

-c Q. c <

01 O) ai c to o

CO m

0)u

c e <o u CO O 3

4-> in I- l/> JC 3

O

a. j- iH fO

• N

t—( (T3 > O

i- rH 3

cn s-

•r- o

VII-23
VII-24
a:

=>CO

CM

or

a> lu

CD

CM

CD

lO

in

CD

H

LU

ro

CM

10

fO

o

ro

10CM O

CM

to A0N3n03dd

U1

<V

(Jc

n3

-Q3

on

31O

T3U

UJN

mo

5-O

0)

i-o

u

to

<DO

OJC

O

-C

inE

i- sz O) +J O TJ

!-> Q.

i/) •r- i- 1 OJ

4->IB

• 5 m. a> i—i u

i—i rc > *+-i- m d

s- t/1 cn fO

Ll_ >

VII-25
CVJ

4)U

C

to

*-> -Q

tn3

O

T3

S_

A3

o

01 3

l_U

yj

O

O

CD CNJ GO

Is- \ LU

CO QD

CD |_j

LjJ

ro O

ro m

CVJ o

OJ

if) O

A0N3flD3dd

t-o

u

o

O

e

cnc

•r-3o

.c

i/> E

(T3 Dl -C O +>

•4-> fO

i/l Q. X i-<u +J

i—i C

> 3

O

U O) D

•f— *f— u_ >

VII-26
90

D D D

Dose of test chemical

a Excess tumor incidence (percent) is defined as: tumors in exposed population _ tumors in control population

number of exposed population number of exposed population

a sigmoid dose-response curve, mfralinear between O and Pi linear extrapolation

supralinear extrapolation

line projected to a threshold

SOURCE: Office of Technology Assessment.

Figure VII. 5. A stylized dose-response curve and some extrapolated curves.

VII-27
CO

rr

rro

<

o

CO

CO

UJ

o

X

yj

Q

LU

_l

O

<

CHLOROFORM

, I DICHLOROETYLENE

CCL

ACRYLONITRILE

Br

200 600 1000 1400

CONCENTRATION (PPB)

1800

Figure VII. 6. Calculated excess cancer risk as a function

of concentration of chemicals shown in drinking water.

Assumes linear dose-response relationship in region shown.

(EPA Carcinogen Assessment Group Data.)

VII-28
CONCENTRATION (PPB)

Figure VII. 7. Calculated excess cancer risk as a function

of concentration of chemicals shown in drinking water.

Assumes linear dose-response relationship in region shown

(National Academy of Sciences data).

VII-29
10° = 1.0

2 3 4 5

INHERENT HAZARD SCORE

Figure VII. 8. Inherent hazard score as a function of inherent hazard as given by the W. E.T. model builders (Table

1) and as proposed in terms of the data in Table 2.

VII-30

I

1

I

1

i

i

SI

li

i

^8

i
0.50

0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

8 10 12 14 16 18

Figure VII. 9. Poisson distribution probability, F(x), versus number affected, x. Distributions are shown for several

values of A. in addition the corresponding values of W = ET

for a population of 1000 are also shown.

VII-31
IPPB IOPPB O.I PPM IPPM 10 PPM IOOPPM 0.1% 1.0

log C x

Figure VII. 10. Value of Poisson parameter, X, as a function of concentration of potentially hazardous substance

for various W.E.T. scores, W.

VII-32
oi >\> 10 o y

o

(ALO

•t—O

Q.

co

• I—

1-1u

c

n

IB

o

E

U

Co

cJ

w

JQ

tOo

t.

rH <

•—i 1- > 0)

4- E

OS S-

•i- (TJ

VII-33
mNC x ="lnP0

Figure VII. 12. Absolute values of the expected uncertainty

in the probability that no one will be harmed by exposure

to a potentially hazardous substance as a function of uncer- tainties in determining the concentration of the substance,

"C " the total population exposed, "N" , and the relationship

between hazard and concentration, "m".

VII-34
0.9999

0.999

0.99

0.98

0.95

0.90

0.80

0.70

0.60

0.50

0.40

0.30

0.20

0.10

0.05

0.02

0.01

0.005

0.001 I0.0001

C DL=50PPB

C DL=80PPB

C DL=5PPB

ASSUMES N= 1000

2 3 4

VALUE OF W

Figure VII. 13. Probability for no one in an exposed population of 1000 persons being harmed for detectabi 1 i ty limit

concentrations shown as a function of W.E.T. score, W.

VII-35
APPENDIX I

SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Hazard by Medium

Inherent Air Surface Ground- Air Surface Grounc

Compound Bazard Water water Water water

A 8 C . D E F G

(A+B) (A+C) (A+D)

Acenaphthene 3 3 2

______

6 5 9

Acenaphthy1 ene 3 3 2 5 6 5 8

•Acetaldehyde 2 2 § 3 4 2 9

• Acetonitrile 2 6 © 7 a 2 9

Acrolein 5 2 0 3 3 5 12

Acrylaraide 3 2 4 6 5 7 9

•Acrylonitr ile 5 3 3 a 5 12

4-Aminobiphenyl J 2 9 0 6 4 4

Anthracene 3 4 4 5 3 7 8

Antimony 5 4

'1 3 9 12 12

•Arsenic 5 3 3 7 3 12 12

Asbestos 3 4 4J 0 3 7 3

a-BHC 2 5 3 3 3 5 7

8-BHC 2 S 3 5 7 5 7

Y-BHC 2 5 3 5 7 5 7

* Bar iua 3 4 4 4 7 7 7

•Benzene 2 4 0 6 6 2 B

Benzidine 2 3 0 0 5 2 2

VII-36
SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Hazard by Medium

Compound

inner enc Hazard

A

Air

B

Surface

Water

C

Groundwater

D

Air

E

(A+B)

Sur f ace Water

F

(A+C)

Gr ound- water

G_

(A+D)

'Benzo (a) anthracene 2 4 6 5 6 8 7

Benzo(a) pyrene 6 4 6

c5 10 12 11

Benzo (g , h , i ) perylene 3 4 8 5 7 11 8

Benzo (k) fluoranthene 2 4 6 5 / 9 8

3 1 4-Benzofluoranthene 2 4 6 5 6 8 7

Beryllium 6 4 2 2

1 A 10 8 8

Bis (2-chloroethoxy )

methane

3 1 0 0 4 3 3

'Bis (chloromethyl) ether 5 1 0 0 6 5 5

Bis (2-ethylhexyl)-

phthalate

1 3 6 6 4 7 7

Butane 0 3 0 7 3 0 7

Butene/Butadiene 0 2 0 7 0 7

'Cadmium 5 4 6 5 9 11 11

Carbon disulfide 5 6 0 7 11 5 12

Carbon tetrachloride 3 8 0 6 11 3 9

Chlordane 3 4 0 5 7 3 8

Chloroacetaldehyde 4 3 0 6 7 4 10

4-Chloroaniline 2 3 1 5 5 3 7

Chlorobenzene 3 4 0 6 7 3 9

VII-37
SCORES FOR 140 SUBSTANCES

Adjusted Inherent

Exposure Adjustments Hazard by Medium

Inherent Air Surface Ground- Air Surface Grounc

Compound Hazard Water water Water water

A BCD E F G

(A+B) (A+C) * (A+D

Chloroform 3 5 0 6 S 3 9

4-Chloro-2-methylphenol 2 0 6 5 2 8

2-Chlorophenol 2 3 0 7 5 2 9

Chromium (VI) 5 4 7 7 9 12 12

•Chrysene 4 s 5 8 10 9

Copper 3 4 1 1 7 4 4

Creosote 2 1 7 4 3 9

•Cyanide 4 0 7 11 4 11

Cyclohexane 2 0 6 5 2 8

Dibenzo (a ,h) anthracene 4 5 5 7 9 9

Di-n-butyl phthalate 2 3 6 5 5 8

* 1 , 2-Dichlorobenzene 1 1 6 5 2 7

1 , 3-Dichlorobenzene 1 1 6 5 2 7

1, 4-Dichlorobenzene 2 1 6 6 3 8

3 , 3-Dichlorobenzidine 2 0 5 3 2 7

*1, 2-Dichloroethane 3 0 6 7 3 9

*1, 1-Dichloroethene 3 0

6' 7 3 9

*D ichloromethane 2 0 7 6 2 9

2 , 4-Dichlorophenol 2 3 1 6 5 3 8

VII-38
SCORES FOR 140 SUBSTANCES

Adjusted Inherent

Exposure Adjustments Hazard by Medium

Inherent Air Surface Ground- Air Surface GroundCompound Hazard Water water Hater water

A BCD E F G

(A+B) (A+C) (A+D)

2,4-Dichlorophenoxy- 2 acetic acid

1.2-Dichloropropane 2

1. 3-Dichloropropene 4

0,0-Diethyl S- 4 (2- (ethylthio) ethyl)

ester of phosphorc—

thioic acid

0,0-Diethyl phosphoric 4 acid O-p-nitrophenyl

ester

1,2-Dimethyl hydrazine 4

2.4-Dimethyl phenol 4

Dimethyl phthalate 0

Dimethyl sulfate 4

4 , 6-Dinitro-2- 3 raethylphenol

2,4-Dinitrophenol 3

*2, 4-Dinitrotoluene 3

2 , 6-Dinitrotoluene 3

1,4-Dioxane 2

Dodecane 2

Endrin 4

4 0 6

2 0 6

4 3 5

2 0 6

2 2 6

4 16 0 0 0

3 16

3 16 3 16 3 16 3 0 7

3 0 6

4 4 5

6 2 8

6 4 10

8 7 9

6 4 10

6 6 10

4 1 6

\ 4 4

6 4 9

6 4 9

6 4 9

6 4 9

5 2 9

5 2 8

8 8 9

VII-3'9
SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Bazard by Medium

Compound

Inherent

Hazard

A

Air

B

Surface

Water

C

Groundwater

D

Air

E

(A+B)

Surface

Water

F

(A+C)

Ground

water

G

(A+D)

•Epichlorohydr in 3 4 0 7 S 3 10"

Ethylbenzene 2 3 0 6 5 2 8

Fluor ene 3 4 2 6 7 5 9

Fluorine *(fluorides) 3 4 7 7 7 10 10

Formaldehyde 5 3 © 1 S 5 12

Bexachlorobenzene 3 5 <S 5 8 9 8

•Hexachlorobutadiene 2 3 0 5 5 2 7

Bexachlorocyclopentadiene5 3 0 5 8 5 10

'Hexachloroethane 1 0 s 8 1 6

Hexachlorophene 3 4 2 5 7 5 8

Bexane 3 0 7 4 i 8

Hydrazine 2 3 6 6 7 10

Hydrogen chloride 4 N/A N/A 7 N/A N/A

Hydrogen sulfide 4 N/A N/A 8 N/A N/A

Indeno(l,2,3-c,d)-

pyrene

6 5 7 9 8

Isophorone 2 4 0 6 6 2 8

Lead 5 4 3 2 9 8 7

Maleic anhydride 3 2 0 0 5 3 3

VII-40
SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Hazard by Medium

Compound

Inherent Air Surface GroundHazard Water water

A BCD Air Surface GroundWater water

E F G

(A+B) (A+C) (A+D)

•Mercury 5 4 3 0 9 8 5'

Methomyl 3 2 2 5 5 5 8

Methyl bromide 3 5 0 6 e 3 9

Methyl chloride 1 5 0 1 6 1 8

•Methyl ethyl ketone 0 3 0 7 3 0 7

Methyl hydrazine 6 2 0 6 8 6 12

Methyl par atnion c9

* JJ

£

-J j w 1 0

Naphthalene 1 4 0 s 5 1 7

2-Naphthylamine 2 3 3 s 5 5 8

•Nickel 4 4 2 2 8 6 6

•Nitrobenzene 2 4 S 5 6 2 7

Nitrogen oxides 3 3 N/A N/A 6 N/A N/A

2-Nitrophenol 2 3 0 6 5 2 8

4-Nitrophenol 3 3 1 6 6 4 9

N-Nitrosodimethylamine 4 3 0 5 7 4 9

N-Nitrosodiphenylamine 1 3 0 5 4 1 6

Octachlorostyrene 3 5 6 5 8 9 8

PCB-1016 5 4 6 5 9 11 10

PCB-1221 5 4 3 5 9 8 10

VII-41
SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Hazard by Medium

Compound

Inherent Air Surface GroundHazard Water water

A BCD Air Surface GroundWater waterE F G

(A+B) (A+C) . (A+D)

PCB-1232 6

PCB-1242 6

PCB-1248 5

*PCB-1254 6

PCB-1260 6

•Parathion 6

>entachlorophenol 4

Phenanthrene 3

•Phenol 4

Pyrene 3 Pyridine 2

Selenium 4

Silver 2

Sodium 2

Sulfur dioxide 3

2,3,7,8-Tetrachloro- 6 dibenzo-p-dioxin

*l,l,2,2~Tetrachloro- 4 ethane

0

2

3

4

3

3

3

2

I

3

1

7

5

7

N/A

5

5

5

5

5

5

5

S

5

6

5

5

7

5

5

N/A

5

10

10

3

10

10

10

7

7

S

7

6

8

6

6

7

8

10

6

8

S

10

11

9

7

5

5

6

3

11

7

9

N/A

11

11

11

10

11

11

11

10

8

10

8

7

"1

7

7

N/A

11

10

•Tetrachloroethene

VII-42
SCORES FOR 140 SUBSTANCES

Adjusted Inherent

Exposure Adjustments Hazard by Medium

Inherent Air Surface Ground- Air Surface GroundCompound Hazard Water water Water water

A B C D E F G

(A+B) (A+C) (A-+D)

Thallium 5 4 0 0 9 5 5

V

Toluene 1 3 0 7 4 1 8

'Toluene diamine 3 3 5 6 6 8 9

>Toluene-2, 4-diisocyanate 6 3 3 6 9 9 12

o-Toluidine 1 2 0 0 3 4. X hydrochlor ide

'Toxaphene 3 4 1 5 7 4 8

1,2, 4-Tr ichlorobenzene 2 4 0 6 6 2 8

'1,1, 1-Trichloroethane 1 6 0 7 7 1 8

1,1, 2-Trichloroethane 1 5 0 6 6 1 7

Trichloroethene 4 3 0 5 7 4 9

2, 4 ,6-Trichlorophenol 1 3 1 7 4 2 8

'Vanadium 5 4 7 7 9 12 1.

Vinyl chloride 2 3 0 7 5 2 9

Zinc 2 4 4 4 6 6 6

•Actually used in one of the data base's 83 waste streams

N/A—not applicable

VII-43
C V DO CI IDC ADJUSTMENT SCORES

1

1 ab

1 be

Half-Life Air Surface Water

i Ground Water

3 minutes 0

30 minutes 1 0

6 hours 2 1 0

3 days 3 2 1 30 days 4 3 2

1 year 5 4 3

10 years 6 5 4

100 years 6 5 1,000 years 6

If bioaccumulation factor in fish is 10 , add K-2 points for K£3; leave

score unchanged for K£2.

*Tf chemical is removed by conventional water treatment, subtract factor

based on degree of removal (90 percent removal = -1; 99 percent removal = -2).

If adsorbed to solid surfaces, subtract points according to degree of

adsorption (99 percent adsorption = -2; 99.9 percent adsorption = -3).

Note: Air scores include removal by atmospheric washout as well as degradation. Surface-water scores include sedimentation and volatilization as well as degradation. Ground-water scores include irreversible adsorption.

VII-44
APPENDIX II

UNCERTAINTY SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Bazard by Medium

Compound

Inherent Air Surface GroundHazard Water water

A BCD Air

E

Surface

Water

F

Groundwater

G

7 A

2 +B

2 /a2 *:2 •J A2 +D

2

Acenaphthene 1.5 1 1 1 1.8 1.8 1 .

8

Acenaphthylene 1.5 111 1.8 1.8 1.8

Acetaldehyde 1 111 1.4 1.4 1 .4

Acetonitrile 11 1 1 1.4 1.4 1 .4

crolein 1111 1.4 1.4 1.4

Acrylamide 1111 1.4 1.4 1.4

Acrylonitrile 1.4 1.4 1.4

4-Ami nobiphenyl 1111 1.4 1.4 1.4

Anthracene 1.5 111 1.8 1.8 1.8

Antimony 1.5 1 1 1 1.8 1.8 1.8

Arsenic 1.5 1 1 1 1.8 1.8 1.8

Asbestos 1111 1.4 1.4 1.4

a-BHC 1.4 1.4 1.4

B-BHC 1.4 1.4 1.4

Y-BHC 1.4 1.4 1.4

Barium 1.4 1.4 1.4

Benzene 1.4 1.4 1.4

lenzidine 1.4 1.4 1.4

VII-45
UNCERTAINTY SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Hazard by Medium

Compound

Inherent Air Surface GroundHazard Water water

Air Surface GroundWater water

K a C 0 E F G

yA

2 +B

2 yA

2 -c

2 yA

2 +D

2

Benzo (a) anthracene 1 l 1 1 1.4 1.4 1.4

Benzo(k) fluoranthene 1.5 1 1 1 1.6 1.8 1.8

3 1 4 -Ben zof1 uor an thene l 1 1 1.4 1.4 1.4

Benzo (g,h, ijperylene 1.5 1 1 i.e 1.8 1.8

Benzo(a)pyrene 1 1 1 1.4 1.4 1.4

Beryllium 2 l i 1 2.2 2.2 2.2

Bis (2-chloroethoxy )

methane

1 l i 1 1.4 1.4 1

Bis (chlor omethyl) ether 1 A A

1 A JL . 41 A X . 4 X1 A. 4

Bis (2-etnylhexyl)

phthalate

1 1 A

sii

1 A 1.4 1 A 1.4 1 A X • 4

Butane 1 I 1 1.4 1.4 1.4

Butene/Butadiene I 1 1 1.4 1.4 1.4

Cadmium 1 1.5 1.5 1.4 1.8 1.8

Carbon disulfide 1 1.5 1 1 1.8 1.4 1.4

Carbon tetrachloride 1 i 1 1.4 1.4 1.4

Chlordane 1 1.5 1 1 1.8 1.4 1.4

Chloroacetaldehyde 1 1 I 1.4 1.4 1.4

4-Chloroaniline 1 1 1 1.4 1.4 1.4

Chi or obenzene 1 1 1 1.4 1.4 1.4

VII-46
UNCERTAINTY SCORES FOR 140 SUBSTANCES

Adjusted Inherent

Exposure Adjustments Hazard by Medium

Inherent Air Surface Ground Air Surface Ground

Compound Hazard Water Water Water Water

A BCD E F G

TaW V

/A^CT

Chloroform 1

4-Chloro-2-methylphenol 1

2-Chlorophenol 1

Chromium (VI) 1

Chrysene 1

Copper 1.5

Creosote 1

Cyanide 1.

5

Cyclohexane 1

Dibenzo (a, h) anthracene 1

Di-n-butyl phthalate 1

1.2-Dichlorobenzene 1

1.3-Dichlorobenzene 1

1.4-Dichlorobenzene 1

3,3 '-Dichlorobenzidine 1

1,2-Dichloroethane 1

1,1-Dichloroethene 1

Dichloromcthane 1

2,4-Dichlorophenol 1

1.4 1.4 1.4

1.4 1.4 1.4

1.4 1.4 1.4

1.4 2.2 2.2

1.4 1.4 1.4

1.8 1.8 1.8

1.4 1.4 1.4

1.8 1.8 1.8

1.4 1.4 1.4

1.4 1.4 1.4

1.4 1.4 1.4

1.4 1.4 1.4

1.4 1.4 1.4

1.4 1.4 1-4

1.4 1.4 1.4

1.4 1.4 1.4

1.4 1.4 1.4

1.4 1.4 1.4

1.4 1.4 1.4

VII-47
UNCERTAINTY SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Hazard by Medium

Lunpounu

Inherent Air Surface

Hazard Water

A B w

Ground

Water

Air

E

Surface

Water

Dr

Ground

Water

Q

/a2 +b

2 /a24C 2 /a2 +d

2

2, 4-Dichlorophenoxyacetic acid

1 1 1 1 1.4 1.4 1.4*

1, 2-Dichloropropane 1 1 1 1 1.4 1.4 1.4

1, 3-Dichloropropene 1 1 1 1 1.4 1.4 1.4

0,0-Diethyl S-

(2- (ethylthio) ethyl)

ester of phosphor o- thioic acid

1 1.5 1 1 i.e 1.4 1.4

0,0-Diethyl phosphoric

acid O-p-nitrophenyl

ester

1 1.5 1 1 1.8 1.4 3

1,2-Dimethyl hydrazine 1 1 1 1 1.4 1.4 1.4

2,4-Dimethyl phenol 111 1 1.4 1.4 1.4

Dimethyl phthalate 1 1 1 1 1.4 1.4 1.4

Dimethyl sulfate I 1.4 1.4 1.4

4,6-Dinitro-2-

methylphenol

1.5 1 1 I 1.8 1.4 1.4

2,4-Dinitrophenol 1 1.4 1.4 1.4

2,4-Dinitrotoluene 1 1 1.5 1.5 1.4 1.8 1.8

2, 6-Dinitrotoluene 1 1 1.5 1.5 1.4 1.8 1.8

1, 4-Dioxane 2 1.4 1.4 1.4

Dodecane I 1.4 1.4 1.4

Endrin 1 1.4 1.4 1

VII-48
UNCERTAINTY SCORES FOR 140 SUBSTANCES

Adjusted Inherent

Exposure Adjustments Hazard by Medium

Compound

Inherent

Hazard

A

Air Surface Ground BCDHater Water

Air

E

Surface

Water

F

Ground

Water

G

v/a2 +B

2 yA

2 4c2 A2 *d2

Epichlorohydr in 1 1 1 1.4 1.4 1.4

Ethylbenzene 1 1 1 1.4 1.4 1.4

Fluor ene 1.5 1 1 1 1.8 1.6 1.8

Fluorine (fluorides) 1 1 1 1.4 1.4 1.4

Formaldehyde 1 1 1 1.4 1.4 1.4

Hexachlorobenzene 1 1 1 1 1.4 1.4 1.4

Jexachlorobutadiene 1 1 1 1 1.4 1.4 1.4

pentadiene

1.4 1 A X.I 1 A

Hexachloroethane \ 1 1 1 1.4 1.4 1.4

Hexachlorophene 1 111 1.4 1.4 1.4

n-Hexane 1.4 1.4 1.4

Hydrazine 1.4 1.4 1.4

Hydrogen chloride 1 N/A N/A 1.4 N/A N/A

Hydrogen sulfide 1 N/A N/A 1.4 N/A N/A

Indeno(l,2,3-c,d)-

pyrene

1.4 1.4 1.4

Isophorone 1.4 1.4 1.4

Lead 0.5 2.1 2.1 2.1

Maleic anhydride 1.4 1.4 1.4

VII-49
UNCERTAINTY SCORES FOR 140 SUBSTANCES

Adjusted Inherent

Exposure Adjustments Hazard by Medium

Compound

Inherent

Hazard

A

Air Surface Ground BCDWater Water

Air

E

Surface

Water

F

Ground

Water

G

A2 +B2 Jk2 +c

2 A2 +D

2

Mercury 1.5 112 1.8 1.8 2.5

Methomy

1

1 1 1 1 1.4 1.4 1.4

Methyl bromide 1 1 1 1 1.4 1.4 1.4

Methyl chloride 1 1 1 1 1.4 1.4 1.4

Methyl ethyl ketone 1 1 1 1 1.4 1.4 1.4

Methyl hydrazine 1 1 1 I 1.4 1.4 1.4

Methyl parathion 1 1 1 1 1.4 1.4

Naphthalene 1 1 1 1 1.4 1.4 1.4

2-Naphthylami ne 1 1 1 1 1.4 1.4 1.4

Nickel 2 1.5 1.5 1.5 2.5 2.5 2.5

Nitrobenzene 1 1 1 1 1.4 1.4 1.4

Nitrogen oxides 1 1 . 5 N/A N/A 1.8 N/A N/A

2-Nitrophenol 1 1.5 1 1 1.8 1.4 1.4

4-Nitrophenol 1 1.5 1 1 1.8 1.4 1.4

N-Nitrosodimethylarai ne 1 1.5 1 1.5 1.8 1.4 1.8

N-Nitrosodiphenylami ne 1 1.5 1 1 1.8 1.4 1.4

Octachlorostyrene 1.5 1.8 1.8 1.8

PCB-1016 1.5 1.8 1.8 1.8

PCB-1221 1.5 1.8 1.8 1.8

VII-50
UNCERTAINTY SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Hazard by Medium

Compound

Inherent

Hazard

A

Air Surface

Water

B C

Ground

Water

D

Air

E

Surface

Water

F

Ground

Water

G

v/a

2 +B

2 /a2

-k: 2 v/a

2 +D

2

PCB-1Z32 1 • 3 1 1 1 X . 0 1.8 1.8

PCB-1242 1.3 1 1 1 X . o 1.8 1.8

PCB-1248 1.5 1 1 1

1 D 1.8 1.8 1.8

PCB-12>4 1 c X . 3 1 1 1 X • 0 1.8 1.8

PCB-1260 X • 3 1 1 1 X1 • Ro 1.8 1.8

Parathion 1 1.5 1 1

1 Q 1.8 1.4 1.4

entachlorophenol 1 1 1 1 1.4 1.4 1.4

Phenanthrene 1.5 1 1 1.8 1.8 1.8

Phenol 1 X 1.4 X1 A• 4

Pyrene 1.5 1 1 1 1.8 1.8 1.8

Pyridine 1 1 x 1 1.4 1.4 1.4

Selenium 1. 5 1.5 1.5 1.5 2.

1

2.1 2.1

Silver 1 1 1.4 1.4 1.4

Sodium 1 1 1.4 1.4 1.4

Sulfur dioxide 1 1 N/A N/A 1.4 N/A N/A

2,3,7, 8-Tetrachlor o- dibenzo-p-dioxin

1 1 1.4 1.4 1.4

1,1,2, 2-Tetrachloroethane

1 1 1.4 1.4 1.4

Tetrachloroethene 1 1 1.4 1.4 1.4

VII-51
UNCERTAINTY SCORES FOR 140 SUBSTANCES

Exposure Adjustments

Adjusted Inherent

Hazard by Medium

Compound

Inherent

Hazard

A

Air Surface Ground BCDWater Water

Air Surface

Water

F

Ground

Water

G

7a2 +b

2 /a2 +c2 yA

2 +D 2

Thallium 1.5 1 1 1 1.8 1.8 1.8

Toluene 1 1 1 1 1.4 1.4 1.4

Toluene diamine 1 1 1 1 1.4 1.4 1.4

Toluene diisocyanate 1 1 1 1 1.4 1.4 1.4

o-Toluidine hydrochloride

I 1 1 1 1.4 1.4 1.4

Toxaphene I 1.5 1 1 1.8 1.4 1-

1/ 2, 4-Trichlorobenzene 1 1.4 1.4 1.

1,1, 1-Trichloroethane 1 1.4 1.4 1.4

1, 1, 2-Trichloroethane 1 1.4 1.4 1.4

Trichloroethene 1 1.4 1.4 1.4

2,4 , 6-Trichlorophenol i 1.4 1.4 1.4

V? - ad i um 2 2.2 2.2 2.2

Vinyl chloride 1 1.4 1.4 1.4

Zinc 1 1.4 1.4 1.4

VII-52
APPENDIX VIII . SURROGATES AS SUBSTITUTES FOR PRINCIPAL

ORGANIC HAZARDOUS CONSTITUENT VALIDATION OF

INCINERATOR OPERATION

W. Tsang and W. M. Shaub

Chemical Kinetics Division

Center for Chemical Kinetics

Washington, DC 20234

Recent regulations on the incineration of hazardous wastes

have focussed attention on the selection of Principal Organic

Hazardous Consti tuent(s) (POHCs) and the use of the POHC concept as

a means to validate incinerator performance. We discuss some of

the problems inherent in such an approach and propose an alternative

methodology involving the use of fluorinated compounds as surrogate

markers for destruction efficiency. The factors that make these

compounds suitable candidates are summarized. These factors

include high thermal and chemical stability, non-toxicity and

availability of sensitive detection methods. Various operational

problems are considered. The compound SF 6 is commended as a suitable surrogate for indicating that required destruction removal

efficiency of the incinerator for POHCs has been achieved.

Introduction

Present day regulations regarding the incineration of hazardous

waste mixtures [l] 1 involve the selection of the Principal Organic

Hazardous Constituent (POHC) and the demonstration through test

burns of its destruction removal efficiency (DRE) at the 99.99

percent level or better. The latter is expensive, and there are claims that the proposed methodology may be subject to many

problems [2]. Furthermore, subsequent to the qualification test

there are no means for determining whether the incinerator continues

to operate properly. In this report, we call attention to the

possibility of using tracer compounds, deliberately added to the

waste mixture in small quantities, whose extent of decomposition

can serve as a measure of proper incineration. This procedure is

equivalent to the use of a surrogate for the principal organic

hazardous constituent. However instead of dependence on the

vagaries of the hazardous waste mixture yielding up a particular

POHC, it will be possible to select compounds that are particularly

compatible with a specific detection methodology. The general

consequences are drastic simplifications of the entire validation

procedure and considerably more accurate results. Real time or at

least periodic determinations of DRE are possible. Indeed, one can visualize direct coupling of emission measurements with feed rates.

1 Figures in brackets indicate the literature references at the end

of this paper.

VIII-1
We begin with some general considerations regarding properties

of such tracers. This exposition leads to the identification of a variety of perf 1 uori nated organics as candidate compounds. We will

then demonstrate that these compounds have the required thermal

stability features as well as favorable chromatographic and spectroscopic properties. Finally, we conclude by discussing a variety of

operational problems and possible deficiences in the methodology.

General Considerations

Some of the desirable properties for molecules that are to serve

as tracers include:

The compound in question should be considerably more stable

than the POHC of the hazardous waste mixture. This property is

mandated by the requirement for 99.99 percent destruction of the

POHC. For practical purposes, we will be interested only in the

addition of small quantities of the tracer to the reacting mixture.

If this tracer were to be destroyed to the same or greater extent

as the POHC, then even more severe demands would be placed on detection capabilities. On the other extreme, if a substance is

too stable, then one has the equally undesirable situation where

destruction of the POHC will result in trivially small reduction in

tracer concentration. These constraints make it difficult for one compound to cover the entire range of possibilities. However, the

possibility of obtaining several compounds with overlapping ranges

of i nci nerabi 1 i ties , spanning the entire scale, should be an achievable goal

.

Having restricted the number of molecules that need to be

considered, it is obvious that the ideal analytical methodology

will be one with the greatest selectivity. This simple result can

be placed in contrast to the situation with POHCs where one is

forced to use the most general detection technology with all the

attendant problems and cost. On this basis, infrared absorption

with a laser source represents a particularly attractive possibility.

Such a system permits real time monitoring of the behavior of the

characteristics of the incineration system. Alternatively, gas

chromatography with columns and detectors specific to the surrogate

can also fill such a need.

Finally, there are several obvious and necessary properties,

low cost, non-toxici ty , minimal corrosion problems and absence from

any possible hazardous waste mixture.

These constraints are severely limiting. They lead inescapably

to the conclusion that perf luorinated compounds represent optimum

candidates. Such compounds absorb very strongly in the infrared.

Special columns are required for gas chromatographic separations.

Perf 1 uori nated compounds are extraordinarily sensitive to electron

capture detection, are relatively simple to make and are may be

found in extensive amounts in hazardous waste mixtures. The

combustion product HF does represent a possible corrosion problem.

It is expected that the small amounts formed will not cause noticeable effects.

VI 1 1-2
Inci nerabi 1 i ty

In an earlier report [3] we have characterized the chemical

processes that control the destruction processes in an incinerator

in terms of a variety of elementary processes. These include

unimolecular decomposition and bimolecular processes involving

radical attack on the hazardous waste. The fundamental relation is

1*0*1 = kun

. (Hz) 2 k

bi CV (Hz)

dt

i where k . and k^. are the unimolecular and bimolecular rate

constants, and is an attacking radical specie. These rate

constants have fundamental significance in the sense that they are

an intrinsic property of the molecule(s) in question and thus can

be used in all contexts. They are different than rates used in

process applications which are of great utility in process optimization but are difficult to use in other contexts. The general

picture in terms of physical variables usually considered in

hazardous waste incineration - wide ranging temperatures (ambient

to flame conditions) and residence times in the 1 second range, is

that of decomposition of the more unstable compounds by unimolecular

mechanisms at the lower temperatures. The subject to attack by OH

radicals and decompose via a bimolecular mechanism. Implicit for

the latter process to occur is the assumption that OH and indeed

other small radicals 0, H are present in equilibrium concentration

[3]. Such an approach, taken in conjunction with the existing data

base, permits the establishment of a rank ordering of substances

with regard to i nci nerabi 1 ity. We note in passing that our ordering

is radically different from that proposed by EPA which is based on the heat of combustion. Nevertheless the chemical kinetic scale

does correspond to experience and is in striking contrast to

predictions based on heat of combustion. The latter predicts for

example, that explosives such as nitroglycerine are more difficult

to destroy than aromatic compounds such as benzene [4].

We now consider the following compounds, CF4 , C 2 F 6 , C3 F 8 , ^4^10. CF 3 C1 and SF6 as candidate tracers. We begin by analyzing

the bimolecular processes. For the case of OH attack, note that

HO-X bonds are relatively weak, ^or H0-C1 it is possible to

estimate a value in the 50-70 kcal (4.184 joules = 1 calorie)

range [5]. However, the bond strength of the C-F, C-Cl and S-F

bonds are in the 129, 86 and 95 kcal range respectively [5]. The

consequence is that OH abstraction is a highly endothermic process.

This result is in striking contrast to hydrogen atom abstraction

from hydrocarbons where the resulting H-OH bond is 117 kcal and the

overall reaction is highly exothermic. In terms of rates, the

consequence is that, compared to hydrogen abstraction processes,

the dehal ogenation reaction is many orders of magnitude smaller. A

similar argument can be made for oxygen atom attack.

Next consider hydrogen atom attack which is an almost thermally

neutral reaction with respect to abstraction from the C-F bond and

strongly exothermic for the S-F and C-Cl abstraction process.

Nevertheless, published results give [7].

VI 1 1-3
k(H + SF

6 - HF + SF

5

) = 10

15 exp(-44000/RT)cm3

/mol -s

and

k(H + CF

4

-> HF + CF

3

) = 10

15 ' 3 exp(-30000/RT)cm3 /mol-s

Although the A-factors (pre-exponenti al term) appear to be high,

the measurements are at high temperature and the consequence of the

high activation energy is to make the rates of these processes very

small compared to the abstraction of H or CI atoms from a hydrocarbon

backbone. Certainly the rate will not be faster. The rate expression

for CI abstraction from CF^Cl is [6].

k(H + CF

3

C1 + CF

3 + HC1) = 10 13,2 exp(-8100/RT)cm3

/mo1 -s

This rate is very close to the comparable abstraction from methyl

chloride but much slower than most H abstraction processes.

Furthermore, we recall that OH is present (except in fuel-rich

systems) in higher concentrations than hydrogen atoms; abstraction

processes for the latter are in general slower than those with OH

present. Note that large polyatomic organic radicals such as CH3 are vastly less effective in abstraction processes than inorganic

species such as OH, 0 or H. Thus, for these tracers under incineration conditions, bimolecular decomposition processes will be

extremely slow as compared with most hazardous wastes. As a result

of these considerations, we make the assumption that the most

important mode of decomposition is by unimolecular bond breaking

processes.

We have listed in table 1 a variety of information dealing

with the unimolecular decomposition characteristics of the six

candidate tracers. These data involve the bond dissociation

energy, defined as AH (reaction) at 298 K, an estimated rate

expression for bond cleavage and the temperatures required for

99.99 percent, 99 percent, and 63.4 percent destruction. The first

number is the familiar four nines destruction limit. However as noted earlier the determination of 0.01 percent (100 ppm) of a substance present in trace quantities may well make inordinate

demands on the analytical methodology. On the other hand, as will

be shown subsequently, the very favorable analytical characteristics

of these compounds allows them to be detected at very low levels.

However, the data in table 1 indicate that tracers having lower

destruction efficiencies will be more suitable for achieving the

goal of using surrogates to calibrate DRE. These numbers were derived from the integrated equation for unimolecular decomposition

rate constant x time = In [initial concentration/final

concentration]

with time equal to one second. Data are included in table 1 for

the temperature range of 1100 to 1400 K for all except perfluorinated methane which spans the range of 1800 to 2000 K. In

general, there should be no problem in finding other compounds that

will be useful at progressively lower temperatures. One suspects

VI 1 1-4
that various fluorinated aromatic and other unsaturated compounds

can be found to cover the 1400-1800 K gap.

Note that the rate expressions shown in table 1 are subject to some uncertainty. There has been a direct determination of SF 6 decomposition [7], and Lyman [8] has recently re- i nterpreted the

data. The numbers shown in table 1 are directly taken from the

latter work. The results for perf 1 uori nated ethane were derived

from the rate of combination of perf 1 uori nated methyl radicals and

the thermochemistry of the reactions. The result we obtained is more than a factor of 10 slower than a measured determination

reported about fifteen years ago [9]. We believe that the

interpretation of the earlier data is incorrect.

For the other compounds, the pre-exponential factors have been

estimated by analogy. For example, we use the same A- factor for

CF 3 C1 decomposition as that experimentally determined for CF 3 Br.

[10] The bond energies are fairly well established. We have also

taken into consideration pressure effects using well established

techniques (11).

An examination of the data in table 1 suggests that the

temperature range over which a particular molecule is effective as

a tracer is limited. Hence, the necessity for a number of such

compounds. Presumably, for any mixture of hazardous organic

wastes, convenience will dictate a temperature that is not substantially larger than that which will yield the required four-nines

destruction of the principal organic hazardous contaminant. For

most of the organics in the EPA listing of hazardous compounds,

these proposed surrogate substances will fulfill this role.

A question requiring consideration is whether any of these

tracers are more stable than possible products of incomplete

combustion such as hexachl orobenzene and dioxin. There is con- siderable justification [12] for the usual assumption that such

compounds along with the PCBs are among the most recalcitrant of

organics with respect to incineration. Some results are summarized

in table 2: Apparently SF 6 , C 2 F 6 and CF 3 C1 are candidate tracers

for assuring destruction of hexachl orobenzene and inferential ly the

PCBs, since the rate of CC1 bond cleavage in these systems should

be comparable. Similarly, C 3

F 8 and C 4 F 10 can also serve this role

for "dioxin-1 i ke" compounds.

Perf 1 uoromethane is obviously much too stable for the present

purposes. Substantial destruction of this compound requires

temperatures hundreds of degrees above those necessary for the

destruction of all organic hazardous wastes on the basis of chemical

considerations. Nevertheless, its very stability, suggesting that

it will survive the usual incinerator environment can be an extremely

useful property as will be discussed in a subsequent section.

Clearly there are compounds whose properties make them very

suitable as surrogates for four-nines removal of hazardous organic

waste. However, a cautionary word is necessary. Many of the

properties have been estimated and are subject to some uncertainty.

Experimental verification is thus very important.

VI 1 1-5
Detection

We next consider the methodology for the detection and quantitation of dilute amounts of these candidate tracers. Specifically,

we will examine analysis by gas chromatography and infrared spectroscopy. With respect to the former, there is a vast literature (13) on the resolution of fluorinated compounds. For stationary phases

such as charcoal or silicone oil, separation can be achieved

through boiling point differences. With ordinary hydrocarbon

substrates, perf 1 uori nated compounds are barely retained since they

have very high activity coefficients. Taken together with the fact

that these compounds all have very low boiling points, simple

unambiguous identification by retention time can be readily

accomplished. Furthermore, electron capture detectors are extremely sensitive to such compounds. Such detecters are com- pletely insensitive to the light inorganics and hydrocarbons that

are most likely to create interferences. The sensitivity limits

appear to be in the part-per-bi 1 1 ion or lower range. Thus, it is

clearly feasible to take a "grab sample" or samples and make a direct measurement of tracer concentrations at any time or times

during the course of an incineration burn. This procedure is

considerably simpler than the more complex and expensive analytical

methodology that is absolutely necessary for the determination of

the four nines destruction of a selected Principle Organic Hazardous

Constituent. Particular attention is called to the practical

possibility of making replicate measurements on a daily or even hourly basis. This activity would help to ensure that statistically significant results are being achieved. Constant monitoring

of incinerator performance is even a possibility. Finally, these

candidate surrogate compounds have been utilized as atmospheric

tracers in the context of air pollution problems [14]. The overall

methodology is thus of the order of 15 to 20 years old.

Next consider infrared spectroscopy for the detection of the

listed surrogates. All of these compounds have one or more strong

absorption bands in the infrared [15-18]. There is, however, the

possibility that one or more of the POHCs or other combustion

products might have overlapping absorptions at a given wavelength.

This problem is significantly reduced because of the high degree of

wavelength selectivity obtainable in infrared laser probing of the

gas mixture. Thus this analytical method is most advantageous.

Table III shows reported representative maximum absorption coefficients for some of the candidate tracers at wavelengths corre- sponding to C02 gas laser emission lines. In the cases of C 2 F 6 , C 3

F 8 and n-C 4F 10 , considerably more data regarding laser line

coincidences is needed at the present time. The absorption coefficients are such that limiting detection sensitivities are commonly as low as approximately 10 ppb and in the case of SF 6 , ppt

detection is a possibility. Careful standardization/calibration of

measurements may be necessary due to variations associated with

laser operating characteristics and the variation of the absorption

coefficient with pressure and temperature. The technological

requirements for these measurements are straightforward and well

within the state of the art. Reliable, low power C02 laser sources

VI 1 1-6
are commercially available, and when used in conjunction with

photo-acoustic detection, provide another example of a powerful

approach to the problem of monitoring tracer concentrations. The

literature is replete with other examples of laser optical mon- itoring techniques which have ready application here [19].

Appropriate signal averaging, modulation and dual wavelength

referencing methods in conjunction with particulate filtering,

where necessary, can provide for virtually real-time, continuous

monitoring of statistically representative samples of the combustion effluent stream.

Some work remains to be accomplished in terms of acquisition

of spectroscopic data for determination of high temperature

absorption coefficients of the tracer species if real time, high

temperature in situ monitoring of the incinerator effluent stream

is desired. However, for most applications, one may alternatively

wish to consider thermally quenching the effluent stream and making

measurements at room temperature where more is known about the

absorption properties of most of these gases. This procedure may

somewhat reduce the real time nature of the measurement to a short

time-averaged value. But results will probably not be impaired in

any serious manner. Most commercial incinerator equipment control

variables are likely to require even longer times for modification

if adjustments in the incineration operation are required. In this

respect, for many applications, flow stream diversion and grab

sampling may be acceptable.

Practical Aspects

In the earlier sections, we focussed on the specific properties

of molecules which make them suitable as surrogates for the Principal

Organic Hazardous Constituents and indeed as Products of Incomplete

Combustion. We will deal with now a variety of operational problems

which are of key importance in field operations. First, consider

the appropriate quantities of tracers that should be used. With

detection limits in the 1 to 10 ppb range, and assuming a dilution

factor of 50 during combustion, the concentration of the tracer

e.g., SF 6 , in the input waste stream must be of the order of 500 to

5000 ppm if four-nines destruction of the tracer is necessary. On

the other hand, if the tracer is sufficiently stable , then in the

most favorable situation one can start at levels in the input waste

stream as low as 30 to 300 ppb. We expect that input waste stream

tracer concentrations in the 1-20 ppm level will satisfy a.1

1

requirements. Thus, for a typical hazardous waste operation that

incinerates on the order of 75,000 liters/day, the use of « 0.5-5

kg/day of tracers will be required. Most of the candidate compounds

are available from standard supply houses. For the fluorinated

compounds, costs are of the order $2.00-$10.00 per kg.

The cost of analytical instrumentation can be compared to the

gc-ms that is usually required for the determination of four-nines

destruction of the principal organic hazardous component. For the case of gas chromatography with electron capture detection, the

cost is about ten times less. For infrared detection the factor

VI 1 1-7
will be of the order of 3 to 4 less. Additional cost benefits

derive from the one pass analysis as opposed to the necessity of

collecting and pre-concentrati ng samples for gc-ms analysis.

Finally, by concentrating on a few surrogates as opposed to the

entire EPA listing of hazardous chemicals, one anticipates additional saving and improved efficiency and accuracy resulting from

the accumulated experience of carrying out the same procedure by

all operators.

An important issue in using this technique is the proper

introduction of the tracer into the incinerator. Obviously, the

preferred method of introduction should be through the waste

stream. Since we are interested in a quantitative measure of the

extent of decomposition of the tracer, constant composition with

respect to air and waste streams must be maintained. Proper

blending of surrogate and waste streams may be a serious problem.

We suspect that instead of direct mixing in the waste stream prior

to injection, the best practical procedure will be to inject in

close proximity to the latter.

An alternative possibility is to use a pair of tracers, one of

the which is completely stable under incinerator conditions and the

other less stable and thus subject to decomposition. If relative

concentrations are known, then the ratio of compounds left after

passage through the incinerator will give a very high accuracy

value for the extent of decomposition of the surrogate. On the

basis of our earlier discussion, CF 4 would seem to be an ideal

candidate for the stable internal standard. There are many

advantages to this mode of operation: Blending requirements can be

significantly relaxed. Absolute concentration levels need not be

precisely maintained. One can in fact visualize periodic injection

and analysis which would have great advantages with respect to

material and operational costs.

A drawback to this technique may arise from the high volatility

of the surrogates. There is no question that any substance that is

vaporized upon introduction into the incinerator environment will

experience situations exactly akin to that faced by the tracers.

Thus, the surrogate deals specifically with gas phase substances.

On the other hand, a non-volatile hazardous material or one that is

strongly absorbed onto a particulate effluent may experience

situations that are different than that faced by the tracer. We

are uncertain about the importance of such effects but suspect that

in systems having a great deal of particulate emission, departures

from ideality will be most serious. These problems are discussed

in some detail in a recent report [20]. There may well be a specific particulate concentration level above which tracer results

begin to deviate. However, it is possible that the present particulate standards called for via regulations will be sufficient.

Obviously, experimental work on this and other issues raised in the course of this paper is needed if this methodology is to be appropriately applied.

VI 1 1-8
Conclusions

If, as suggested by current regulations, hazardous organic

wastes can be ranked according to their i nci nerabi 1 i ty , then it

should be possible to select a number of tracer compounds that can act as surrogates for the Principal Organic Hazardous Constituent.

Such an approach can lead to simplifications and uniformities in

analytical methodologies and bring about important cost savings as well as increased reliability. A number of fluorinated compounds

have been selected as possible surrogates and the rationale for

such a choice is indicated in terms of kinetic properties of these

compounds under incineration conditions. Gas chromatographic and

infrared detection appear to be the analytical methods of choice;

detection limits in the ppb range appear to be possible. Some

potential operational problems are discussed; the need for experimental verification is stressed.

VI 1 1-9
References

[1] Incineration Standards for Owners and Operators of Hazardous

Waste Management Facilities, Interim Final Rule and Proposed

Rules; 40 CFR, 122, 264, 265, January 23, 1981, pg. 7666-690.

[2] R. M. James, H. K. Dillon and M. C. Miller, "Survey Methods

for the Determination of Principal Organic Hazardous Constitutents (POHCs) I. Methods for Laboratory Analysis"

presented at "Eighth Annual Research Symposium, Land Disposal,

Incineration and Treatment of Hazardous Wastes" March 8-10,

1982, Fort Mitchell, Kentucky, Sponsored by USEPA.

[3] W. Tsang and W. Shaub, "Chemical Processes in the Incineration

of Hazardous Materials", in Hazardous Waste Detoxification

(J. Exner, ed. ) Ann Arbor, MI, 1982, pg. 61-92.

[4] T. Bonner, B. Desai , J. Ful 1 enkamp , T. Hughes, E. Kennedy, R. McCormick J. Peters and D. Zanders, "Engineering Handbook for

Hazardous Waste Incineration" Draft in fulfillment of EPA

Contract No. 68-03-2550, November, 1980.

[5] J. A. Kerr and A. F. Trotman Dickenson "Strength of Chemical

Bonds" in Handbook of Chemistry and Physics , CRC Press, Boca

Raton, Florida, 1980.

[6] J. A. Kerr and S. J. Moss, " Handbook of Bimolecular and

Trimolecular Gas Reactions ", CRC Press, Boca Raton, Florida,

1981.

[7] J. F. Bott and T. A. Jacobs, J. Chem. Phys. , 50, 3850-3855

(1969).

[8] J. L. Lyman, J. Chem. Phys., 67, 1868-1876 (1977).

[9] E. Tschuikow-Roux, J. Chem. Phys., 43, 2251-2256 (1963).

[10] W. Tsang, to be published.

[11] P. J. Robinson and K. A. Hollbrook, "Unimolecular Reactions",

Wiley, London, 1972.

[12] W. Shaub and W. Tsang, "Physical and Chemical Properties of

Dioxin in Relation to their Disposal" in Human and Environme ntal Rates of Chlorinated Dioxins of Related Compounds . (A.

Young, ed. ) Plenum Press, New York pp. 731-747, 1982.

[13] A. B. Littlewood Gas Chromatography Academic Press, New York,

1962, p. 450.

[14] B. E. Saltzman, A. I. Coleman and C. A. demons, Analytical

Chemistry, 38, 753-758 (1966).

VI 11-10
[15] J. I. Steinfeld, I. Burak, D. G. Sutton and A. V. Nowak, J. Chem. Phys., 52, 5421-5434 (1970).

[16] E. R. Murray, Optical Eng., 17, 30-38 (1978).

[17] L. J. Radziemski, Jr., R. F. Begley, H. Flicker, N. G. Nereson

and M. Reisfeld, Optics Letters, 3, 241-244 (1978).

[18] K. Walzer, M. Tacke, and G. Busse, J. Chem. Phys., 73,

3095-3097 (1980).

[19] C. K. N. Patel , Laser Detection of Pollution", Science 202 , 157-173 (1978).

[20] W. M. Shaub and W. Tsang, "Dioxin Formation in Incinerators",

submitted to Environmental Science and Technology.

VIII-11
> N -o cn co r- 1

0> c C\J CTl ao cn cn co

'1

o

Oi .Q /—

i

5-

0) ro En

kes (kc /—

s

a (0 U. Ll_ CJ o CJ CJ c a; 1 I 1 i o o CO CJ CJ CJ

S3 —

-

r- o

CJ CO CO i—

«3" CO CO U_ U_ Ll_ U_ Ll_ U_ CM OO rj" CJ CO CJ CJ CJ CJ

VII 1-12
Table 2. Temperature for Decomposition of Recalcitrant Hazardous Wastes

Hexachl orobenzene

11 -4 7

k

bl

- (OH + hexachlorobenzene) 10 cc/mol-s; with OH =10 exp(-35000/RT)mol/cm

k

u (hexachlorobenzene) = 10

16 exp(-92000/RT)

99.99% destruction at 1323 K in 1 second

Dioxin

k

bi (OH + dioxin) 3 x 10

11 cc/mol-s; with OH = lO" 4,7 exp(-35000/RT)mol/cm3

k(dioxin) = 3 x 10

15

exp (-80000/RT)

99.99% destruction at 7194 K in 1 second

V 1 1

1 -1

3
Table 3. Infrared Spectroscopic Properties of Some Candidate Tracers

Estimated minimum

detection limit

Compounds Absorption coeff. (atm ^cm ) Position (absorption)

SF C 304 944. 1948 10 ppb 16,17

b

CF

4

0.4 1073.2785 8 ppm 18

CF

3

C1 5 1084.6325 6 ppm 19

VII 1-14
APPENDIX IX. RESEARCH APPROACHES FOR DETERMINING COMPATIBILITY

OF POLYMERIC LINER MATERIALS WITH HAZARDOUS WASTES 1

A successful polymeric liner must retain its mechanical and

barrier properties in the presence of permanent contact with water

containing diluted hydrophilic or suspended hydrophobic substances

or solid particles. The first two kinds of material may diffuse

into the polymer and eventually transform into a soft rubbery

material or even disintegrate it by chemical attack. Solid particles may abrade the polymer surface and thus gradually degrade

the useful properties of the hydrophilic material.

A hydrophobic polymer would reject the majority of the hydrophilic material. But the active oxygen containing compounds could

oxidize and hence disintegrate the polymer. The hydrophobic

character of a part of the dissolved molecules, which are prevailingly hydrophilic since they are dissolved in water, may permit

partial diffusion into the polymer. The polymer may be adversely

affected in a way similar to although less rapid than that of the

hydrophobic suspended material. The hydrophobic molecule of the

suspended liquid particles may diffuse into the polymer and depress

its glass transition temperature so much that the mechanical

strength of the swollen polymer is no longer adequate. The oxidative and other types of chemical reactions are the same as formerly mentioned with hydrophilic substances although in this case the action may extend more rapidly to deeper regions of the

polymer because the molecular diffusion of hydrophobic material in

the polymer may be substantially higher.

Hence, careful consideration is needed for the selection of

the proper polymeric materials to be used as a liner for a given

industrial or any other kind of effluent waste. Three types of

action have to be considered: 1) diffusion with the ensuing

lowering of the glass transition of the swollen polymer; 2)

oxidative or any other type of chemical action which may lead to

the disintegration or at least softening of the polymer; and 3)

mechanical stress or abrasion. The effects are not independent.

They may be strongly synergistic. As a polymer softens it becomes

much less abrasion resistant. The softened or disintegrated

material as a rule permits a much faster diffusion of penetrants

than the unaffected material.

The first two effects may be studied in an apparatus which

permits the investigation of the mechanical properties of the

polymer after extended contact with either flowing or standing

liquid containing dissolved hydrophilic or suspended hydrophobic

liquid component. The design of suitable apparatuses should permit

simultaneous measurements of diffusion and the effects of diffusants

on mechanical properties. The optimal specimen geometry should

take account of the dependence of the penetration depth on the

square root of time and that softening and chemical reaction

Prepared by Polymer Science and Standards Division, National

Bureau of Standards.

IX-1
effects mainly depend on the local concentration of the penetrant.

Hence, the effects are much faster and easier to observe in thin

films particularly if the diffusion can proceed from both sides of

the film.

The abrasion of polymeric liner materials can be investigated

through a simulation of flow patterns. Abrasion is a purely

mechanical effect of a liquid containing solid particles. It can

be substantially enhanced by swelling or partial disintegration of

the polymer.

In principle, the effects of the gaseous environment on the

mechanical properties of thin films can be investigated using an instrument-designed and built at NBS-which permits simultaneous

measurements of sorption, diffusivity, strain, and stress. The

interdependence of the first two with the last two effects facilitates the study of sorbed vapor on the mechanical properties of

the film and on the rate of the effect.

A film that has sorbed a vapor, gas, or liquid will also have

a lower glass transition temperature and, hence, will become

rubbery. In such a softened state, the imposition of a strain will cause the stress to decrease and stress relaxation rate to be

enhanced with some concurrent effect on sorption and diffusivity.

The time dependence of the modulus or rigidity of the film during

diffusion may be determined from the stress and the imposed strain.

Damage to the film may be ascertained by comparing the modulus of

the sorbed or desorbed film to that of the dry film. Hence, stress

relaxation may be used to indicate some degree of compatibility of

penetrant and film. Changes in temperature also influence the

modulus and diffusivity and, therefore, may enhance damage or degradation of the film. The instrument mentioned above may be

used to monitor the lowering of the modulus of the film at different

temperatures and different concentrations of penetrant in the gas or vapor phase. In certain cases, the instrument may be used to

determine simultaneously the uptake of the penetrant.

IX-2
APPENDIX X. REGULATORY CONTROL OF HAZARDOUS WASTE LEVEL

R. T. Matthews

This presentation presents a snapshot survey of the States in

controlling hazardous waste management as of September 28, 1982.

OUTLINE

Introductory Remarks: Status of the authorization of State

programs under Subtitle C, RCRA

o Impact of the reduction in federal funding on State hazardous

waste management programs

o State planning and administration approaches

o Institutional and organizational structures

Regulatory Similarities and Differences at the State Level

Pertaining to

o Waste Definition and Criteria

o Waste Exclusions/Exceptions

o Financial Requirements, Penalties, Licenses

State Measurements Needs Addressing:

o State laboratory capabilities

o Analytical requirements and administrative procedures

Federal, State Priorities in Terms Of

o State Authorization

o Permits: TSDF Facilities

o Degree of Hazard

o Siting

Summary and Outlook

REDUCTION IN FEDERAL FUNDING AND ITS IMPACT ON STATE HAZARDOUS

WASTE MANAGEMENT PROGRAMS

Subtitle C, RCRA provided substantial levels of authorized

funding to those States undertaking the federal hazardous waste

management program. In the previous administration, the EPA

Assistant Administrator for Water and Waste Management assured the

States that Federal funding for State solid and hazardous waste

X-1
management programs would be available for five years, albeit on a scale decreasing to zero. To date the appropriated funds available

for State hazardous waste management grants have not been at

authorized levels. Moreover, Subtitle D funds for solid waste

management were terminated September 1981. Currently EPA has

encouraged the States to adopt a user fee system in order to become

self-supporting in both solid and hazardous waste management.

For example, with FY 79 budget authorization provided for

$134. 5M for Subtitle C activities, only $56. 9M was dispensed to the

States with $11. 2M earmarked for State solid waste management

activities, $15M for the President's resource recovery urban grants

program, and $15M for Subtitle C programs. In FY 1980, EPA allocated

$18. 6M Subtitle C, $10M for Subtitle D, and $10M for resource

recovery planning. The States have testified that federal

assistance must be continued and increased under Subtitle C to $60M

for FY 1983, $80M for FY 1984, and $100M for FY 1985 in order to assure State-to-State program consistency is achieved as well as to

provide for protection of public health and the environment. In contrast, the current federal budget for Subtitle C calls for 16

percent reduction from $41. 7M to $35. 1M.

EPA's policy strategy document Coping With The FY 1983 Budget

Reductions states that the "true cost of implementing Phase II of

the hazardous waste management program is unknown. The risk of

States refusing or returning the Hazardous Waste and Underground

Injection Control Program" exists. Indeed ten States have

indicated that withdrawal or consideration of withdrawal from the

national hazardous waste management program is likely should

adequate federal funding not be forthcoming. For these States

remaining in the federal system, funding assistance is recognized

as severely insufficient.

Since 1977, State grants have been allocated according to a formula heavily weighing population and geographic criteria. With

the promulgation of the full set of Subtitle C regulations, the

dispersal of funds will adhere to the criteria set forth in the

statute, Section 3011:

o Volume of wastes generated, transported, treated, stored and

disposed of in the State;

o Extent to which such wastes impact on public health and the

envi ronment

;

o Whether or not the State hazardous waste planning addresses

inactive hazardous waste storage, treatment and disposal

facil i ties

;

o Other factors deemed appropriate by EPA Assistant

Administrator.

Some States either have no facilities within their respective

borders, and/or are net exporters of hazardous waste. Therefore,

X-2
such States could anticipate a reduction in federal grant monies

while at the same time striving to upgrade programs and enforcement

in order to obtain interim or final authorization.

States are facing a financial di 1 emma--they have undertaken

commencement of, or continuation of, hazardous waste management

program in accord with federal requirements while at the same time

facing a total loss of solid waste federal funding and a substantia

reduction of federal hazardous waste funding. State regulatory

agencies are trying to justify maintaining adherence to federal

requirements for consistency and obtaining funding from other

sources. Without stable sources and levels of funding State

directors will have difficulty in maintaining adequate staff and resources to issue permits and to assure equitable enforcement.

Consequently, many States are following EPA's recommendation and

imposing user fees. Examples of the approaches taken are herein

highl ighted:

Louisiana : The Department of Natural Resources, Hazardous Waste

Division is supported by a fee system delineated in the State plan

consisting of:

o One-time application fee is charged to cover application,

evaluation and other related program costs. There is no fee

for applications for minor modifications.

The applicant is required to calculate his appropriate applica

tions fee according to the schedule included in the permit

application form:

Item Fee

Site analysis, per acre $ 250

Process and plan analysis 1,000

Facility analysis, per facility 500

Management/financial analysis 1,000

o Permit maintenance fees are charged to cover costs of administration and other program costs.

o Annual disposal fees per site

Commercial, off-site 25,000

Non-commercial, off-site 5,000

Non-commercial, off-site and

non-continuous 5,000

On-site 2,500

Excess funds over program cost generated by annual fee shall

be credited to the following year's budget.

o In addition, a $1,500 fee per facility is billed bi-annual ly

to support the manifest and emergency response sections.

X-3
o A waste disposal fee is based on volume of waste, and bills

are sent on a quarterly basis. Generators of hazardous waste

are not billed. The fee structure is:

Oklahoma : The Industrial Waste Division, Department of Health is

pursuing several avenues to secure the fiscal resources to support

its staff. The division had assumed in its budgets for FY 1982 and

FY 1983 a 20 percent increase in Federal funding each year.

Currently the State's portion of the division's budget is provided

for in the department's general appropriation. While this

appropriation should increase in FY 1983, additional funds will be

required. The shortfall of funds must come from State sources. Therefore, the division has adopted a fee system for hazardous

waste generators, transporters, and treatment, storage, and

disposal facilities. The goal is the achievement of selfsupporting program.

New York : The Department of Environmental Conservation considered

a fee system but does not expect those fees, if collected, to

replace all needed federal funds.

Programmatic Consequences : The consequences of federal funding

cutbacks are apparent in the solid waste management area. For

example, the national open dump inventory is not complete and,

hence, States will have difficulty in bringing those sites

determined under State law to be open dumps into compliance or to

closure. Furthermore, the States most likely will not complete the

inventory. The situation has developed that many of the sites

inventoried and determined to be dumps, as well as those not

inventoried, may become repositories for hazardous wastes. The

resultant regulatory burden on the State's hazardous waste management program is predictable.

State hazardous waste management activities such as site

investigation, litigation, and remediation regarding inactive

hazardous waste sites are not eligible for application of federal

grant funds.

Since the State agencies support concurrently both solid and

hazardous waste management programs, the total amounts to be

generated should be calculated accordingly. States are, and will

continue to be seeking legislative authority to impose funding

systems to support existing solid and hazardous waste management

programs. These funding sources may include, but are certainly not

limited to, permit fees, generation and/or disposal charges based

on volume and/or waste type, spill contingency funds, funds for the

closure and postclosure care of treatment and disposal facilities.

Some States have indicated a concern for placement of the funding

burden on small generators, or upon a limited number of generators.

less than 1,000 tons

1,000 tons to 10,000 tons

10,000 tons to 100,000 tons

100,000 tons to 1M tons

More than 1M tons

$ 1,000

2,000

3,000

4,000

5,000

X-4
Therefore, the identification of generators and disposal site

operations capable of supporting the fee system--such as federal

faci 1 i ties--requi res consideration and examination.

Planning and Administration : Under Subtitle C, Section 3006, EPA

in consultation with the States, set forth guidelines by which a State may receive authorization to administer the federal hazardous

waste management program. Early on, the States identified as an issue the distinction between authorization as outlined in RCRA as opposed to delegation as provided in the Clean Air Act, Clean Water

Act, and the Safe Drinking Water Act. Under RCRA, the States

programs are authorized in lieu of the federal hazardous waste

management program. Therefore, the State's goals are primary and

the State's unique characteristics of administration and planning

are retained.

The State's program is authorized if two conditions are met:

1) the program is equivalent to federal standards and regulations;

and 2) consistent with other authorized State programs. The

equivalency debate between EPA and the States during the authorization process has sometimes been heated. EPA's interpretation

became a question of the State program being identical to, rather

than equivalent to, the federal program. According to State

spokesmen, EPA headquarters, in the past has not been able to judge

substantial equivalence and so has not been able to direct the

federal regions regarding the definition of the term. To data EPA,

according to the States, has interpreted equivalent to mean identical,

while the States insists on the interpretation equal in effect.

There has resulted considerable disparity between regions as to

which State programs are judged equivalent.

There is general agreement, however, that the federal regulations are a minimum requirement and the States are free to set more stringent standards. An important constraint on the latter action

is that a State may not impose any requirement that might interfere

with the free movement of hazardous wastes across State boundaries

when the waste is destined for a storage, treatment, or disposal

facility holding a RCRA permit.

States receive authorization in two stages: interim and

final. A substantially equivalent State program must meet the

following criteria for interim authorization:

o control as nearly an identical universe of waste as is

controlled by the federal program;

o cover all types of hazardous waste facilities in the State;

o be based on standards that provide substantially the same degree of human health and environmental protection as do the

federal standards; and

o be administered through procedures that are substantially

equivalent to procedures in the federal program.

X-5
Because EPA has promulgated the Section 3004 TSDF standards in

several stages, the agency determined that States may apply for and

receive interim authorization in stages. Phase I, interim

authorization allows States to administer programs in lieu of, and

corresponding to, that portion of the federal program which covers identification and listing of hazardous waste (40 CFR Part 261) and

interim status standards for hazardous waste treatment, storage,

and disposal facilities (40 CRF Parts 262, 263). EPA, however,

handled the granting of interim status for these TSDF facilities

directly.

Phase II, interim authorization allows the State to administer

permit programs for hazardous waste treatment, storage, and disposal

facilities; the permits must apply standards substantially equivalent

to the federal, Part 264, standards. In short, as each component

of the Part 264 standards is promulgated, EPA announces in the

Federal Register notice that the States may apply for interim

authorization for that component as well as previously promulgated

components.

This interim authorization is effective for 24 months beginning six months after the promulgation data of the regulation. A

State may apply for interim authorization during Phase I and later

amend its application in accordance with Phase II requirements. If

a State does not apply for and receive interim authorization, EPA

must administer a federal hazardous waste program in that State.

In the latter case, the federal and State programs co-exist.

A State need not apply for and receive interim authorization

in order to be eligible for f i nal authorization. States may apply

for final authorization anytime after the beginning of Phase II interim authorization. Again, if a State does not obtain final

authorization, EPA must administer a federal hazardous waste

program in the State. As in interim authorization, both the State

program and the final federal program co-exist.

Although EPA required 3.5 years to develop and to promulgate

the rules and regulations for Subtitle C (May 1980), Phase I interim authorization could be granted to each State only if the

applications was approved by EPA prior to November 19, 1980. In

the States' view, this six month period was an extremely short time

frame to develop an application on which detailed managerial,

technical, and personnel decisions had to be made. Moreover, draft

EPA guidance on applying for interim authorization was not available

to the States until July 1980, with further guidance coming to the

States in August 1980. This restrictive time frame made it all but

impossible for States to receive interim authorization without

directly adopting all the federal regulations to that date by

reference.

A 31 State poll was conducted to determine the problems the

States experienced during the interim authorization application

X-6
process. Of the 31, 17 States had applied directly for interim

authorization, 12 States had applied for cooperative agreements

prior to interim authorization, and two States had applied for both

at the same time. The review time varied from one to six months.

The length of time for review by EPA was directly proportional to

the extent that the State had a hazardous waste program in place.

The States which adopted the federal regulations verbatim had the

least trouble; the States with a more complex hazardous waste

program found great difficulty in meeting the equivalency

provisions of the statute.

EPA encouraged States which did not seek interim authorization

to reach a cooperative agreement with the agency for all or a portion of the federal program. In the development of such arrangements, the assignment of the responsibilities for major elements of

the program were not clearly defined. In most cases, work was to

be performed in a joint effort by EPA regional personnel and State

personnel. However, EPA generally ended up in a supervisory

capacity with State personnel actually performing the inspection

work. EPA, however, retained the final authority in any determination for enforcement purposes.

In summary, according to the States' reports, the submittal of

draft and final interim authorization applications and cooperative

agreements was a frustrating, time-consuming experience. A short

turn around time, lack of EPA guidance, and the complexity of the

federal regulations, added to the burden of the assumption of the

program.

States ooted for framing the hazardous waste management

programs in three ways:

o In some States, the hazardous waste management program must be

consistent and equivalent with the federal program (e.g., West

Virginia).

o In other States, the law requires that the program be no more stringent than the federal program (e.g., Colorado).

o In the remaining States, statutory language requires that

State programs be at least as strict as the federal program.

Consequently, the legislative and regulatory approaches

employed by the States are different despite the fact that most

States have interim authorization and many (EPA estimates 40) will

receive final authorization. The issue of State-to-State consistency must be dealt with in the final authorization process.

The permit applicant would do well to be cognizant of the

specific State's difficulty in obtaining authorization and to be aware of the particular mind set at work in the State. In order to

appreciate the differences, a capsule presentation of a few selected

State hazardous waste management programs is in order:

X-7
Institutional and Organizational Structures : Three distinct

institutional and organizational structures are prevalent in solid

and hazardous waste management:

o Single State health and/or environmental protection agency

with one division being charged with solid and hazardous waste

management;

o Single State health and/or environmental protection agency

with separate divisions for solid and hazardous waste

management;

o Two separate regulatory agencies for solid and hazardous waste

management.

For the latter case, examples are the States of Texas and

Cal ifornia.

Pennsyl vania : The Department of Environmental Resources is the

agency responsible in the Commonwealth for administration of all

statutory responsibilities and programs related to the protection

of the Commonwealth's air, water and land resources. The Bureau of

Solid Waste Management is the entity within the Department with

primary responsibility for implementation of Pennsylvania's solid

waste program. The term "solid waste" includes hazardous waste,

residual waste (non-hazardous industrial waste), and municipal

waste.

The Bureau of Solid Waste Management administers and enforces

a comprehensive State hazardous waste program in conformance with

requirements of Subtitle C, RCRA. Administration and enforcement

of this program is conducted according to the provisions of the

Pennsylvania "Solid Waste Management Act" of 1980 (Act 97,

effective September 1980) and "Chapter 75, Solid Waste Management

Rules and Regulations."

Rules and regulations regarding the criteria and listing of

hazardous waste were promulgated on July 15, 1980 and became

effective August 2, 1980. The remainder of the hazardous waste

regulations were proposed to the Environmental Quality Board on September 17, 1980, and became effective on November 18, 1980.

Upon the effective date, all rules and regulations became effective

and enforceable; compliance with such rules and regulations is

required of all existing facilities.

As part of the Department of Environmental Resources' Deputate

for Environmental Protection, the Bureau has a structure which

places the primary emphasis on regional control and responsibility,

with a central staff that provides technical and policy guidance,

assistance, and support to the regions.

There are seven Regional Solid Waste Management Offices

throughout the Commonwealth. Each has a specific geographic area

for which it is responsible. Each office consists of two functional

X-8
sections —Operations and Faci 1 i ties--under the direction of a Regional Solid Waste Manager. The facilities sections have two

major tasks to perform: 1) to review and issue permits to new solid waste facilities; and 2) to provide technical services to the

regional staff in such areas as engineering, soils, and geology.

At the regional level, the operations section's primary concerns

are the enforcement of solid waste management standards, monitoring

and inspection of solid waste facilities, and investigation of

complaints involving violations of State solid waste laws and

regul ations.

Louisiana : The passage of Act 334 in 1978 authorized the establishment of a comprehensive waste control program under the primary

auspices of the Department of Natural Resources (DNR). The statute

also provided for the promulgation of regulations and a Hazardous

Waste Management Plan (HWMP). In 1979, the program was amended by

Act 449, the Louisiana Environmental Affairs Act (LEAA), in order

to bring the program within the reorganization of the State's

environmental agencies. Under the guidance of the Environmental

Control Commission, DRN retained the primary authority for the

administration of Louisiana's hazardous waste management program.

The Department of Natural Resources Office of Environmental Affairs

is the lead agency of Louisiana's hazardous waste management

program. The Division of Hazardous Waste within OEA bears the

responsibility for implementing the comprehensive hazardous waste

regulatory program, which incorporates the mandatory provisions of

RCRA, Subtitle C.

Among the powers and duties of the office are: 1) the holding

of hearings; 2) the issuance of orders and determinations including

emergency cease and desist; 3) the advising, consultation, and

cooperation with other State agencies and political subdivisions,

and federal government, other States, interstate agencies, interest

groups; 4) the encouragement and/or conduct of studies, investigations, and research; 5) the collection and dissemination of environmental protection information; 6) the receipt and budgeting through

DNR of appropriated monies and the administration of grants; 7) the

assumption of authority to administer delegated programs under

federal legislation; 8) the issuance of permits, licenses, registration, variances, or compliance schedules when such authority is

delegated to the Office of the Commission; and 9) the investigation

of suspected violations and the obtaining of samples.

The Environmental Control Commission, established under LEAA,

is composed of seven members--The Secretaries of the Department of

Natural Resources; Wildlife and Fisheries; Health and Human Resources;

Commerce, Transportation and Development; Culture, Recreation and

Tourism; The Commissioner of Agriculture, or their designees. The

Attorney General, or his designee, serves as counsel for the

Commission.

The Assistant Secretary of the Office of Environmental Affairs

serves as the Commission Secretary. The five Division Administrators

X-9
within the Office, for Air, Water, Hazardous Waste, Solid Waste,

and Nuclear serve as technical secretaries to the Commission. The

Commission's powers and duties include: 1) to adopt, amend, or repea" all rules and regulations, and standards for the protection

of the environment; 2) to grant or deny permits, licenses, registrations, variances, or compliance schedules; 3) to delegate such

power to grant or deny to the Assistant Secretary; 4) to issue

orders or determinations; 5) to review or appeal any order of the

Assistant Secretary; 6) to conduct studies or investigations; 7) to assume authority for the administration of programs under federal

environmental legislation; and 8) to assume authority for the

control and regulation of hazardous wastes.

In practice, the Office has been delegated responsibility for

the development of the hazardous waste program, for its implementation and review and for the issuance of permits for non-commercial

facilities, to adopt proposed regulatory amendments, to request

that the Office conduct studies and investigations, and to issue

orders and determinations.

Management of wastes in Louisiana is the responsibility of the

following agencies:

Hazardous waste: Office of Environmental Affairs, Department

of Natural Resources

Office of Conservation, Department of Natural

Resources

Department of Agriculture

Department of Health and Human Resources

Office of Environmental Affairs, Department

of Natural Resources

Mi ssi ssippi : The Mississippi Solid Waste Disposal Act of 1972

grants the State authority to promulgate regulations pertaining to

hazardous waste management including a regulatory program to

effectively control the generation, treatment, storage, transportation and disposal of hazardous wastes. The Mississippi State Board

of Health is the lead agency in implementing such a program, but

several other entities are involved in carrying out specific

program requirements, including Bureau of Pollution Control, Bureau

of Geology, Bureau of Marine Resources, and the Department of

Transportation.

Mining waste:

Agriculture

waste, on-site:

Infectious waste:

Other solid

waste:

The Solid Waste Disposal Act of 1974, Section 17-17-27(1 )(j)

,

provides that the rules and regulations written by the Mississippi

State Board of Health which cover the management of hazardous waste

must "be equivalent to the United States Environmental Protection

Agency's rules and regulations." The hazardous waste regulations

X-10
which have been adopted by the State track the federal regulations

almost explicitly with several sections (including 261 and 265) are taken verbatim from the federal regulations. The few minor differences that do occur in the regulations are due either to circumstances unique to the State and are additions to the federal

regulations that provide for a slightly more stringent degree of

control by the State. State Board of Health will issue all

hazardous waste incinerator permits, take all legal actions to

enforce the hazardous waste regulations, and manage the manifest

system wherever appropriate. The Bureau of Pollution Control will

implement both the interim and final hazardous waste incinerator

regulations. DSWM will acquire concurrence from Bureau of Geology

on the suitability of a site from a geological standpoint and the

adequacy of the monitoring system before issuing a permit.

Texas : In Texas, two agencies have designated authority for the

management of solid and hazardous wastes under the Texas "Solid

Waste Disposal Act." The Texas Department of Water Resources is

responsible for industrial solid waste management, and the Texas

Department of Health is responsible for municipal solid waste

management. In accord with the State statute and the Governor's

designation under Section 4006, RCRA, the departments share

responsibility for hazardous waste management in the State.

Neither department may subordinate its authority or responsibility

to the other department. However, by mutual agreement, the Texas

Department of Water Resources is the lead agency for the purpose of

facilitating communication between the State and EPA.

Virginia : Although the Commonwealth of Virginia has had a solid

waste program since 1971, the hazardous waste element of the

program is in the developmental stages.

The 1979 session of the Virginia General Assembly enacted the

"Solid and Hazardous Waste Management Act." This legislation gives

the Commonwealth of Virginia the legislative base to create a comprehensive solid and hazardous waste management program totally

consistent with the requirements of RCRA.

The Code of Virginia, Chapter 6, Title 32.1, Article 3 assigns

the Board of Health the responsibility for carrying out the purposes

of Virginia's solid and hazardous waste program and adopting

compatible federal standards. The Board may also collect fees from

persons operating or using facility to finance such custody and

maintenance. The Division of Solid and Hazardous Waste Management

is the organizational portion of the Department of Health which is

responsible for the planning, development and implementation.

Oklahoma : The Oklahoma Controlled Industrial Waste Disposal Act

was enacted at about the same time the Federal Resource Conservation and Recovery Act was enacted, and regulates the same elements

as RCRA. These include: regulatory authority over generators,

transporters, treatment, storage, and disposal facilities, manifest

systems, financial security requirements, facility employee

x-n
qualifications, waste lists and waste criteria with specified

exceptions. The program encompasses "Controlled Industrial Waste"

except for field related wastes produced by the oil and gas industry.

The wastes are identical to those excluded from coverage by RCRA

under 40 CFR 261.4(b)(5). In order to insure equivalency between

the Federal hazardous waste universe and the Oklahoma Controlled

Industrial Waste universe, the State has incorporated all of 40 CFR

Part 261 by reference with certain amendments which serve to

encompass a somewhat larger universe. In addition, Oklahoma has

retained its existing Appendices A-l and A- 2 which are functionally

similar to 40 CFR Part 251.31 and 261.32 and Appendix VIII to 40

CFR Part 261, respectively. Program is administered by the Oklahoma

State Department of Health's Industrial Waste Division.

Waste Definition and Criteria : States seeking authorization must

at a minimum encompass the hazardous waste universe set forth by

EPA. States, with or without benefit of authorization, have and

will continue to expand upon this universe. State methods for

exemption or exclusion, or exception, will also vary in procedural

and analytical requirements. Some States categorize waste streams,

some classify sites by waste types received; some States are attempting both. The Oklahoma legislature in passing the enabling

legislation, used the term controlled industrial waste rather than

the term hazardous waste. For all intents and purposes, the terms

have the same meaning. However, Oklahoma amended and reduced by a factor of 10 the EPA toxicity limits, so that the limits for

determining if a waste is hazardous is lOx national primary drinking water standards, in comparison to lOOx as set forth in the

federal standards. Therefore, the universe of wastes deemed

hazardous is larger in Oklahoma than that set forth nationally by

EPA.

Texas facility owner or operators must develop a written waste

analysis plan. This section requires an owner or operator before

he treats, stores, or disposes of any hazardous waste, to obtain a detailed chemical and physical analysis of a representative sample

of the waste. The plan must specify:

o the parameters for which each hazardous waste will be analyzed

and the rationale for the selection of these parameters;

o the test methods which will be used to test for these parameters;

o the sampling method which will be used to obtain a representative

sample;

o the frequency with which the initial analysis of the waste

will be reviewed or repeated to ensure that the analysis that

hazardous waste generators have agreed to supply is accurate;

and,

o for off-site facilities, the waste analysis plan must also

specify the procedures which will be used to inspect and, if

X-12
necessary, analyze each movement of hazardous waste received

at the facility to ensure that it matches the identity of the

waste designated on the manifest.

In addition, Texas Department of Health administratively

determines a hazardous waste as that identified in 40 CFR Part 261,

Subpart C:

o one or more kilograms in a calendar month or at any time of

any commercial product or manufacturing chemical intermediate

identified as acute hazardous waste and having the generic

name listed in Section 261.33(e);

o one or more kilograms in a calendar month or at any time of

any off-specification commercial chemical product or manufacturing chemical intermediate which, if it met specifications,

would have the generic name listed in Section 261.33(e);

o 10 or more kilograms of discarded (or, intended to be discarded)

containers (or any containers exceeding 20 liters capacity),

in a calendar month or at any time, that have been used to

hold any chemical identified as acute hazardous waste and

having the generic name listed in Section 261.33(e). However,

these materials are not hazardous wastes, if: a) the container

or inner liner has been triple rinsed using a solvent capable

of removing the commercial chemical product or manufacturing

chemical intermediate; b) the container or inner liner has

been cleaned by another method that has been shown in the

scientific literature, or by tests conducted by the generator,

to achieve equivalent removal; or c) in the case of a container,

the inner liner that prevented contact of the commercial

chemical product or manufacturing chemical intermediate with

the container has been removed;

o One hundred or more kilograms, in a calendar month or at any

time, of any residue or contaminated soil, water or other

debris resulting from the cleanup of a spill, into or on any

land or water, or any commercial chemical product or man- ufacturing chemical intermediate identified as acute hazardous

waste and having the generic name listed in Section 261.33(e).

New York : has modified the definition of "discarded" to include

material being burned as a fuel for energy recovery, to ensure that

such wastes are included in the definition of solid waste. Moreover,

New York has listed PCBs as a hazardous waste.

In Louisiana hazardous wastes are identified by criteria for

definition and by classification:

o Category I: Those known chemicals and process streams whose

hazardous nature have been prescribed by prior determination

X-13
and which are presented in either of the two lists of Appendix

A of the State regulations.

o Category II: Those special waste categories defined in

Section 4. 2. IE, generally consisting of large volumes with

consistent characteristics such as typical mining wastes.

o Category III: Other wastes possessing any of the characteristics of the hazard classes listed in Appendix A of the State

Regulations and carrying a hazard rating of 2 or higher as specified. Hazard classes of concern are igni tabil ity

,

corrosivity reactivity and toxicity.

In addition, a special waste category is established which includes

two specific waste streams—red mud and gypsum residue, and one generic cl ass--wastewaters in the NPDES treatment trains.

Waste Exclusions/Exceptions

In some cases, the difficulty lies in determining whether or not a waste is excluded, exempted, excepted, from the hazardous

waste program. In Texas, a hazardous waste which exhibits characteristics established in 40 CFR Part 261, Subpart C but not

specifically identified and listed in Subpart D is not subject to

the regulations, if:

o the waste is beneficially used or reused or legitimately

recycled or reclaimed

o the waste is accumulated, stored, or physically, chemically or biologically treated prior to the beneficial use or reuse or legitimate recycling or reclamation.

Such wastes meeting the characteristics detailed in Subpart C and listed in Subpart D are excepted but not exempted if the waste

is transported or stored prior to being used, recycled, or reclaimed.

Flyash, bottom ash, slag, and flue gas emission control waste

generated primarily from the combustion of coal or other fossil

fuels are non-hazardous. Municipal hazardous waste generators are

not subject to the requirements for identification, and notification, but generators must ensure the wastes is properly handled on site or disposed of in an authorized off-site facility.

The issue at hand is development of a regulatory stance which

encompasses the universe of hazardous wastes while at the same time

encourages rather than stifles recovery of materials in regulated

waste streams. Consequently, the regulated community will face

the dilemma of deciding whether or not a waste is encompassed or

not, and if so what portions of the record keeping, manifesting,

and permitting requirements are applicable.

X-14
Financial Requirement, Penalties, Licenses

While RCRA does not impose permit or licensing requirements on hazardous waste transporters, many States either license or certify

hazardous waste transporters. In Pennsylvania no person or municipality may transport hazardous wastes within the State without a departmental license. Moreover, transporters must file adequate

bonds with the Department of Natural Resources.

While many States enacted legislative amendments to increase

penalty schedules up to the federal level in order to evidence

equivalency with RCRA files, Pennsylvania's are more stringent:

o summary of fense--$100 minimum fine, $1,000 maximum, or a maximum of 30 days imprisonment

o misdemeanor, third degree--$l,000 minimum fine, $25,000

maximum, and/or maximum of year imprisonment.

o misdemeanor, second degree--$2,500 minimum fine, $50,000

maximum, and/or a maximum of two years imprisonment.

o felony, second degree--$2 ,500 minimum fine, $100,000 maximum,

and/or between two and ten years imprisonment.

o felony, first degree--$10,000 minimum fine, $500,000 maximum,

and/or between two and twenty years imprisonment.

While RCRA does not prohibit transport licenses and more stringent penalties, neither does the federal statute preempt the

States from enacting "perpetual care" funds in addition to the

financial requirements set forth in federal regulations. The

issues of "perpetual care" funds application and compensatory

legislation at the State and federal levels face the entire

regulated community.

State Measurement Needs : State administrative entities have

identified a plethora of technical assistance needs in hazardous

waste management which range from personnel training to satellite

mapping. One major need that deserves attention in relation to its

potential short and long term economic and legal ramifications,

is the States' ability to sample, test, measure and analyze hazardous

wastes.

In 1980 the Office of Recycled Materials, National Bureau of

Standards sponsored a study by the Association of State Territorial

Solid Waste Management Officials (ASTSWM0) to determine State

measurement needs for both Subtitle D; solid waste management, as well as Subtitle C; hazardous waste management. The results of

this study are accurately and sufficiently expressed in ASTSWM0

congressional testimony: "Laboratory measurement needs for waste

characterization and monitoring of facilities is a critical unmet

need, without which formulation of a standard RCRA quality assurance program cannot be achieved."

X-15
EPA requires that within 60 days of the effective date of the

memorandum of agreement between the EPA Regional Office and the

State for authorization of the State program, a review be conducted

to define the existing capability of the designated laboratory to

conduct the hazardous waste analytical program.

Of the States surveyed by the Association in its study (Texas,

Virginia, Mississippi, New York, Pennsylvania, Oklahoma, and

Louisiana) each employs a different organizational and procedural

method to conduct the analytical programs.

Loui si ana : currently uses a commercial laboratory, although a joint laboratory with other divisions of the Office of Environmental Affairs, Department of Natural Resources, is planned. A

contract laboratory will be used for the immediate future. Since

the DNR is dependent upon contract laboratories for sampling and

analysis, the department has developed an Analytical Operations

Procedures Manual. Standard test methods and equivalents are referenced and special test protocols outlined. Any laboratory

which desires to be considered for use must employ established EPA

test procedures or other recognized methodology where EPA has not

set procedures. Certification will be required where such a system

exists and must comply with applicable federal, State, and local

regulations. Annual audits will be conducted. This evaluation

will include processing of spikes and blanks as developed by EPA.

Oklahoma : utilizes the services of the Water Quality Laboratory

within the Department of Health for its sampling needs. The

laboratory while well equipped with state-of-the-art instrumentation,

has personnel who are not familiar with scope of the RCRA hazardous

waste program, its measurement needs, or the laboratory needs of

the Industrial Waste Division. Communication with field personnel

is minimal, however, the laboratory has initiated a quality control

program which includes duplicate and spike analysis, control charts

and monthly reports to verify that the quality control program is

being maintained. To date only a few samples have been required

for analysis.

Pennsylvania : utilizes the services of the Bureau of Environmental

Laboratories. The laboratory has been handling solid waste samples.

Problems have occurred in communication with field personnel,

particularly conveyance of the handling of the sample and subsequent determination and evaluation of analytical results. The

laboratory does not have a manual but has prepared a short description providing necessary chemical analysis, standard methods of

analysis, and evaluation techniques for state-specified parameters.

The Virginia Division of Consolidated Laboratories performs all

laboratory work for the State. The laboratory is divided into

sections: 1) Forensics; 2) Bureau of Microbiological Sciences; 3)

Bureau of Product Regulation; and 4) Bureau of Environmental

Sciences which conducts sampling in water, air, drinking water,

radiation health,

X-16
blood lead levels, and solid and hazardous wastes. Quality

assurance is emphasized. The Board of Health and the Chesapeake

Bay Commission want to donate funds for new equipment for the

laboratory, but cannot do so until more space is available. The

laboratory is currently handling approximately 100 samples per year

of hazardous waste.

Mi ssi ssippi laboratory support will be available as needed with

laboratory arrangement made prior to sampling, except in cases of

spills or emergencies. Sampling and sample transport is the duty

of the Division of Solid Waste Management personnel; laboratory

personnel will have responsibility for non-field analytical testing

only. The Bureau of Pollution Control Laboratory will provide

analytical services for ground water and surface water samples.

Additional services (e.g., organic scans, tests for ignitabi 1 i ty

,

reactivity) are provided on a contractual basis by another lab or

by a private laboratory.

In New York waste analysis requirements are set forth according to

the facility type: tanks, surface impoundments, waste piles, secure land burial facilities, land treatment/food chain crops,

unsaturated zone monitoring, closure and postclosure, incinerator,

energy recovery facility, thermal facility and chemical, physical,

biological treatment processes. The Department of Health must

approve of ancillary laboratories.

The Texas Department of Health Laboratory requires additional

facilities, test equipment, staff, and safety devices. The

laboratory has, however, an interim EPA certification to perform

analyses of samples under the Safe Drinking Water Act. The laboratory also conducts approved analyses of wastewater treatment

effluent for the Texas Department of Water Resources in its program

under the Clean Water Act. In FY 1981 the department requested

$72,000 for laboratory support in order to meet the EPA protocol

for quality assurance. The request included $33,000 for equipment

for improved capability for organic and inorganic monitoring.

In recent public meetings on the final land disposal regulations, EPA representatives have reminded the regulated community

that the testing methods cited in Appendix VIII are guidelines, and

recommend test methods in certain areas are absent. States can require or accept differing testing and analytical techniques to be

conducted in varying institutional frameworks. Given the measurement needs cited by the quality assurance at the State level,

comparability among the States cannot be assumed.

The impact on the regulated community is obvious-- in the short

term, the inclusion/exclusion of a waste stream in a regulatory

program may require substantial, expensive testing; and, in the

long term, identifying and analyzing waste samples from closed or abandoned facilities may result in financial burdens either misplaced or overplaced on specific generators.

X-17
Federal, State Priorities . EPA stated the federal priorities in a memorandum from headquarters to the regions and States: "We expect

to be able to begin calling Part B permit applications for existing

incinerators in the fourth quarter of FY 1982. However, there is a six month lag in the effective data for both the standards for land

disposal facilities and the supplemental standards for surface

impoundments. Therefore, we will not be able to call in Part B for

these facilities until the second quarter of FY 1983." In FY 1983,

the regions and States are likely to concentrate their activities

in the following areas:

o State authorization

o Interim status compliance and enforcement

o Permitting

While permit activities will be receiving a much higher level

of attention in FY 1983 than before, there will still be many years

before all hazardous waste facilities receive RCRA permits. In the

interim the regions and States should conduct an adequate number of

inspections to ensure that facilities are complying with the

interim status standards or the authorized State analogue. Compliance inspections for groundwater monitoring and land disposal

facilities are likely to be the most important. Every land

disposal facility is to be inspected during FY 1983 to determine

compliance with the groundwater monitoring requirements.

In summary, specific high priority activities are expected to

be:

o program development for interim and final authorization

o compliance inspections and enforcement of groundwater

monitoring at all land disposal facilities

o issuing permits to incinerators

o completing action on storage and treatment permits called in

during FY 1983

o calling in Part B and beginning the permit issuance process

for land disposal facilities.

In addition, States can develop implementation schedules which

will ensure siting of the necessary hazardous waste management

facilities within State borders. State plans can also encourage

waste exchanges and other waste utilization practices.

Many States have already begun development or support of such

activities (Texas, Virginia). However, the permit applicant for a new facility would be wise to ascertain the particular State's

priority before embarking on an expensive site survey an preparation

program.

X-18
Degree of Hazard : Many States have approached the problem of

differentiating waste streams according to volume, impact on public

health an the environment, acceptability of land versus treatment

management. In congressional statements, the States have supported

a national approach to this concept and described a proposed work

scope submitted to EPA:

o evaluation of current State laws and regulations to determine

consistency among States and substantive deficiencies in terms

of promulgated or proposed regulations under Subtitle C.

o analysis of State insurance requirements

o collection and evaluation of existing data on hazard criteria

o recommendations of a technically feasible and cost effective

implementation procedure for achieving a nationally uniform

State managed RCRA Subtitle C program for protecting human

health and the environment.

o assessment of State institutional barriers to the implementation of the proposed procedure.

o identification and prioritization of needs required of the

selected implementation procedure.

While EPA has declined to fund this coordinating activity,

many of these activities are already underway in the States and in

the private sector. The consistency of data collection and evaluation, and the availability to all interested parties remain open

for review and discussion. 1

Si ti ng . Many States, such as Pennsylvania, currently do not have

any waste treatment, storage, disposal facilities permitted within

their borders. Other States such as New York have limited land

disposal and treatment capacity but no incineration capacity within

their borders. To address and alleviate this limitation, State

legislatures have enacted siting statutes. Two examples illustrating different approaches to the problem are the New Jersey Hazardous

Waste Facility Siting Act (S1300) and the Massachusetts Hazardous

Waste Facility Siting Act (Chapter 21D).

The New Jersey Hazardous Waste Facility Siting Act established

a Commission comprised of three industry members, three local

officials, and three environmentalists. The Commission is charged

to propose sites for new facilities based upon facility siting

criteria established by the New Jersey Department of Environmental

Nevertheless , States could use proposed degree-of-hazard schemes

to set disposal fees on a per ton basis. For example, if the W-E-T

scheme (see Appendix VII) were chosen, fees could be set on some basis such as that illustrated in Fig. AX(1). In this instance, per

ton fees have been made to depend on W-E-T score and potential

population, N, who might be exposed. (Note added by H. Yakowitz)

X-19
10,000

0 2 4 6 8 10 12

W.E.T. NUMBER, W

Figure X.l. Possible per ton disposal fees, F, vs. W-E-T number

(N is number of persons who might be exposed).

X-20
Protection. The Commission may designate alternate or additional

sites for new major hazardous wastes facilities at the request of

the hazardous waste industry; the requestor will have the burden of

proof concerning the suitability of the site in proceedings. If

the DEP license is granted, the owner/operator may construct and

operate the facility without regard to any local requirements or ordinances

.

The Massachusetts Hazardous Waste Facility Siting Act is

different than the New Jersey concept in that this law is predicated on the belief that the facility siting matters are best

addressed through negotiations between developers and the host

communities. Those negotiations are to be conducted on a case by case basis. Host communities are represented by local assessment

committees in the negotiations process.

The State Site Safety Council is composed of eight State

commissioners, six representatives of State professional organizations, and seven members of the public. The Council addresses

the social and economic impact of proposed facility projects and

awards technical assistance grants to local assessment committees

in order that they may evaluate proposed facility projects and

determine the compensation to be paid by a facility developer. The

compensation must address the adverse impacts to communities

abutting that in which the facility is to be sited. A siting

agreement is reached through compromise and any impasse is resolved

through binding arbitration. The statute also provides that no

local license or permits for the facility are to be required of a .developer which were not required on or before the effective date

of the act.

The expectation that States will be reviewing the possibility

of locating such facilities on or near federal lands is reasonable

and discussions are underway in some western States. Community

acceptance and the site specific aspects of postclosure engineering

and financial responsibility remain at issue.

Summary and Outlook

Despite funding shortages and dilemmas, States will continue

to assume, administer, and expand their respective hazardous wastes

programs. Funding will be supported through a combination of fees

and appropriations. By 1984, the majority of States are likely to

have authorized hazardous waste programs in place. Concurrently,

as a result of federal funding and staff reductions and completion

of State assumption process, the direct involvement of federal

regulatory agency can be anticipated to lessen. Implementation

issues (e.g., State-to-State consistency) will come to the fore.

Resolution at the regional level will be attempted. Technical

difficulties will arise should States measurements needs not be

addressed. Debate on perpetual care and victim compensation will

be aired in Congressional and State legislative debates as part of

the regulated community need to be apprised of the legislative,

technical and economic issues.

X-21
References

[1] "State Solid Waste Management Plans, Guidelines for

Development and Implementation," Federal Register , August 28,

1980, pp. 38534-38546.

[2] Hazardous Waste Management Committee Report , Association of

State and Solid Waste Management Officials, January 1981.

[3] State Measurement Needs : State Prof i les (Volumes II through

VII, Oklahoma, Louisiana, Pennsylvania, Mississippi, Virginia,

Texas, by the Association of State and Territorial Solid Waste

Management Officials, September 1981; and, (Volume IX; New

York) October 1982.

[4] Testimony of Norman H. Nosenchuck, Director, Division of Solid

Waste, New York Department of Environmental Conservation as President of ASTSWMO and on behalf of the National Governors

Association Subcommittee on the Environment before the Senate

Subcommittee on Intergovernmental Relations, Governmental

Affairs Committee, November 24, 1981.

[5] Testimony of N. Nosenchuck, as President of ASTSWMO, before

the House Subcommittee on Commerce, Transportation, and

Tourism, Committee on Energy and Commerce, March 31, 1982.

[6] Testimony of N. Nosenchuck, as President of ASTSWMO, before

the House Subcommittee on Commerce, Transportation and

Tourism, Committee on Energy and Commerce, April 21, 1982.

[7] Testimony of N. Nosenchuck, as President of ASTSWMO, before

the Senate Subcommittee on Environmental Pollution, Committee

on Environment and Public Works, April 26, 1982.

[8] Guidance for FY1983 RCRA Waste Program , Memorandum from Rita

Lovelle, EPA Assistant Administrator for Waste and Emergency

Response, to EPA Regional Offices, June 1982.

[9] "Hazardous Waste Management System, Permitting Requirements

for Land and disposal Facilities", Federal Register , July 26,

1982, pp. 32274-32388.

[10] Logistical Systems to Support Ocean Incineration of Liquid

Hazardous Wastes , prepared for the Office of Maritime

Technology, MARAD/DOT, by Henry S. Marcus and Charles T. Daniel, Massachusetts Institute of Technology, August 1982.

X-22
APPENDIX XI . DEVELOPMENT AND USE OF A SIMULATION MODEL FOR THE

ECONOMIC ANALYSIS OF RESOURCE RECOVERY OPTIONS

David R. Barton, Economist

Quantitative Analysis

Patrick MacAuley

Industry Economist

Bureau of Industrial Economics

U.S. Department of Commerce

Xl-i
FOREWORD

Dr. Harvey Yakowitz

Chief, Office of Recycled Materials

National Bureau of Standards

Washington, DC 20234

The Secretary of Commerce under Subtitle E, Resource Conservation and Recovery Act of 1976 (P.L. 94-580) is charged to provide a forum for the exchange of technical and economic data relating to resource recovery facilities. The Office of Recycled Materials in

support of this mandate identified a major economic issue faced by

communities in selecting resource recovery systems: the provision

of the maximum energy output for the least cost versus the reuse of

materials in the municipal waste stream. This issue, often described

as the "burn v. recycle" dilemma, has entailed the enactment of

local waste flow control ordinances, protests from public and

private sector recycling organizations, notably companies engaged

in post-consumer newsprint recovery, as well as potential facility

operators and the financial community. The Office of Recycled

Materials commissioned this report, prepared by the Bureau of

Industrial Economics, U.S. Department of Commerce, to provide

interested parties with an economic assessment tool necessary to

evaluate the financial aspects of each option on a case-by-case

basis. Consequently, this report does not attempt to provide a definitive answer to the "burn v. recycle" issue but to provide a method to consider economic tradeoffs in selecting a particular

waste management option. A community's decision in reviewing resource recovery options is predicated on the specific financial,

legal, institutional, and political aspects which can only be

quantified or addressed by affected parties at a particular point

in time.

Recognition is wel 1 -deserved for the efforts of the following

individuals who prepared and assisted in the preparation of this

report:

James M. Owens

Director, Office of Basic Industries

Bureau of Industrial Economics

Diana Friedman

Office of Basic Industries

Bureau of Industrial Economics

David Barton

Economist, Quantitative Analysis

Bureau of Industrial Economics

Patrick MacAuley

Industry Economist

Bureau of Industrial Economics

Xl-ii
A SIMULATION MODEL FOR THE DEVELOPMENT AND USE OF AN ECONOMIC

ANALYSIS OF RESOURCE RECOVERY OPTIONS

Abstract

A simulation model was developed and used in differing sce- narios in order to conduct an economic analysis and comparison of resource recovery options. Five solid waste disposal strategies

with specific parameters were compared economically. Under con- ditions specified in case studies, resource recovery facilities were found less economically desirable than landfill ing. Concurrent factors which would tend to make resource recovery an economically preferable alternative are 1) steam prices over $4.00

per 1,000 lbs in 1980 prices; 2) landfill costs over $18 per ton;

3) resource recovery facility construction costs less than $28,000

per ton/day of capacity; and 4) operating and maintenance costs

below $9 per ton of garbage. Operating rates above 90 percent of

intended throughput are necessary for efficient operation; thus

experimental or overambi tious designs should be approached with

caution.

Source-separated waste newspapers are usually more valuable as fiber to make recycled newspaper than as fuel. However, when steam

is valued at more than $4 per thousand pounds, source-separated

waste newspapers may be more valuable as fuel.

The reader is cautioned, that 1) any simulation model may not

exactly reflect conditions in one's own community; and 2) should be

employed as one of many methods available to the decisionmaker.

Lastly, a model is a tool in the decisionmaking process and not a rigid determinant of any one particular solution.

Xl-iii
Table of Contents

Page

Purpose of Study XI-1

Background XI-1

Description of the Model xi-6

Description of Input Variables XI-11

Source Listing of Program X

I -19

Results of the Economic Simulations X 1-22

Figure 1 - Economies of Scale in RRF Size X

I -3

Figure 2 - Trade-Off Prices for Waste Newspaper X I -7

Figure 3 - Trade-Off Prices for Garbage Disposal .... X I -44

Table 1 - Construction Costs for RRF's Producing XI-4

Steam Only

Table 2 - Operation and Maintenance Cost per Ton of XI-5

Garbage Processed RRF's Producing Steam Only .

Table 3 - Energy Prices per Unit, for Newspapers and

Selected Fossil Fuels X

I -8

Table 4 - Base Case Assumptions X

I -23

Table 5 - Results of the Economic Simulations for the

Base Case X 1-25

Table 6 - Sensitivity of Decision Model to Sales Price

of Steam X 1-27

Table 7 - Sensitivity of Decision Model to RRF

Construction Costs X

I -28

Table 8 - Sensitivity of Decision Model to Landfill

Costs X 1-29

Table 9 - Sensitivity of Decision Model to Operating and

Maintenance Costs XI-30

Table 10 - Sensitivity of Decision Model to Operating Rate

of Resource Recovery Facility X

I -32

X I - i v
Page

Table 11 - Sensitivity of Decision Model to Conversion

Efficiency of RRF X 1-34

Table 12 - Sensitivity of Decision Model to Wastepaper

Prices X 1-35

Table 13 - Sensitivity of Decision Model to Transportation

Costs for Paper X 1-36

Table 14 - Sensitivity of Decision Model to Extra Collection

Costs for Source Separated Newspaper X

I -38

Table 15 - Sensitivity of Decision Model to Energy Price

Increases X

I -39

Table 16 - Sensitivity of Decision Model to Interest Rates,

Present Value Discount Rates, and Inflation

Rates XI -40

Table 17 - Sensitivity of Decision Model to Wastepaper

Price Increases X

I -42

Table 18 - Sensitivity of Decision Model to Landfill Cost

Inflation Rate XI-43

Table 19 - Sensitivity of Decision Model to Overbuilding

for Growth in Demand XI -45

Appendix C - References XI -46

XI-v

Purpose of the Study

This economic simulation model was developed with dual

objectives

:

1) To help the National Bureau of Standards Office of

Recycled Materials simulate the economics of proposed

Resource Recovery Facilities (RRF's) in order to analyze

the economic merits of each scenario.

2) To determine the economic trade-offs involved in selling

waste newspapers to paper recyclers instead of burning

the paper in resource recovery facilities to generate

energy. The analysis of trade-offs is done chiefly from

the point of view of the municipal planner.

Background

Until recently garbage has generally been considered a nuisance rather than a resource. In passing the Resource Conservation and Recovery Act (RCRA) of 1976 (P.L. 94-580), Congress

recognized the potential value of materials and energy in the

garbage, as well as the environmental benefits of reducing the need

for disposal

.

Approximately 60 recovery facilities have been completed or are under construction 1

. Some of them are designed to recover

scrap metals and glass, and all of them are designed to recover energy from the combustible components of garbage. The economics

of resource recovery are such that the potential energy revenue is

much greater than the potential revenue from recovered scrap

metals and glass. Thus, the make-or-break operation in a recovery

facility is the energy recovery operation.

There are several basic methods for recovering energy from

garbage, the most common of which are:

1) Mechanically producing a refuse-derived fuel (RDF) for

sale as a boiler fuel

.

2) Burning garbage to produce steam, which is then sold to

an industrial facility or used for district heating and

cool ing.

3) Burning garbage to produce steam which is used to

generate electricity, for sale to an electric utility.

4) Burning garbage along with sewage sludge in order to

jointly dispose of both wastes.

National Center for Resource Recovery, Washington, D.C.;

NCRR Bulletin, September 1980.

XI-1
5) Capturing landfill gases from mature disposal sites.

While difficulties in producing a marketable fuel have been

encountered, facilities employing the first method have provided

RDF. The third and fourth methods are more complex and are not at

present widely used. The fifth method, methane from landfills, is

not an alternative to landfilling. The second method, burning

garbage to raise steam, is the most common type of RRF and is the

focus of this study.

Until recently, economies of scale in recovery facilities was

a commonly held belief. A survey of existing RRF's which produce

steam challenges this belief. The costs for fourteen facilities

with production capacity ranging between 50 and 1200 tons per day

indicate that the capital cost per ton of capacity does not

decrease with size, and may even increase. (See table 1 and figure

1. ) Study further reveals no obvious economies of scale in

operating and maintenance costs per ton of throughput. (See table

2. )

These conclusions regarding economies of scale require further

assessment. Even though the plants listed in tables 1 and 2 were

planned to be or are operating, steam-producing RRF's, there is

still wide variation among them. For example, some attempt to

recover scrap metals from the garbage while others did not. Some

have back-up boilers. Some were built with longer facility life.

Furthermore, to a great extent, the high operating costs per ton of

garbage input experienced by large RRF's result from low capacity

utilization rates. With increasing experience, large RRF's may be

able to operate at rates closer to full capacity, thus spreading

costs over more input tons.

Although the apparent lack of economies of scale may not be

good news to planners in Standard Metropolitan Statistical Areas

(SMSA's), medium-sized towns may be attracted to resource recovery.

Assuming the citizens of a municipality generate 4.2 pounds of

garbage per capita per day (national average), a town with a population of 25,000 produces enough garbage for a fifty ton per

day recovery facility. There are approximately a thousand towns in

the United States with 5,000 or more inhabitants, which could

individually or jointly sponsor a recovery facility of this size.

Paper and other post-consumer wastes have been recycled for

decades. Recycled newsprint has historically been obtained from

"source separated" waste newspapers. Newspapers account for about

7 percent of municipal solid waste. In 1980 only about one fourth

of this 7 percent was source separated and recycled 2

. Twenty-five

percent of the newsprint produced in the U.S. in 1980 was

2 Bureau of Industrial Economics, U.S. Department of Commerce;

Marketing Information Report: 1980, Waste Newspapers in Four

South Atlantic States, 1982.

XI-2
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XI-3
Table 1. Construction Costs for RRF's Producing Steam Only

Capacity Cost

Capacity tpd / ton

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Nashville, TN 530 78,000

Harrisburg, PA 720 49,700

Braintree, MA 250 29 ,600

Baltimore City, MD 600 65,300

Average 375 tpd $49,800 /ton

Total 4875

Range 50-1200 $13,300-$78,000

Note: Construction costs were inflated to approximate 1980 dollars,

using the Department of Commerce Composite Construction Cost Index.

XI-4
Table 2. Operation and Maintenance Cost per ton of Garbage Processed

RRF's Producing Steam Only

Salem, VA

N. Little Rock, AR

Norfolk, VA

Nashville, TN

Harrisburg, PA

Baltimore City

Average

Capacity

(tpd)

100

100

180

530

720

600

372 tpd

Gross 0 & M

Cost

per ton burned

($/ton)

$17.12

12.00

29.63

17.70

14.25

14.00

e

$17.5/ton

e = estimated for 1980. 1979 cost was $12.87/ton

Note: Operation and Maintenance costs for following facilities were

not available: Osceola

Crossvil le

Waukesha

Portsmouth

Oceanside

Braintree

Saugus

XI-5
manufactured using source separated newspapers 3

. The key feature

of source separation is that the consumer separates the newspapers

from other trash, which are collected separately, either by private

groups or municipal collection services. Source-separated newspapers are unlikely to constitute more than two to four percent of

the total garbage flow for most municipalities.

Newspapers are one of the most valuable constituents of

garbage, in terms of both fiber value and energy content.

Unfortunately, paper recycling and energy recovery are mutually

exclusive uses for wastepaper. As uses for wastepaper expand,

competition for waste newspapers will increase.

Allocation of the finite supply of waste newspapers among

competing uses may not always be resolved by market forces. In order to ensure adequate input to energy producing recovery

facilities, some local government sponsors have passed "flow

control" ordinances. These ordinances usually limit the extent to

which private sources can collect source-separated newspapers, and

often require that all postconsumer waste be directed to the

recovery facility for processing.

The value of paper as a fuel varies not only according to time

and location, but also according to the fuel it is being substituted

for. For example, if market price of waste newspaper is $66 per

ton, 4 newspapers are much more expensive per million Btu than is

coal at $25/ton, but newspaper is considerably cheaper than No. 2 fuel oil at $42/barrel . (See table 3.) Thus, if paper displaces

fuel oil, or if the steam from a RRF is being sold to a customer

willing to pay a high price for a guaranteed supply of energy,

paper can be an economical fuel.

Description of the Model

The model simulates a recovery faciTity which produces steam

for sale to an individual customer for heating, cooling, or industrial

purposes. The simulation model estimates the financial viability

of specific configurations of resource recovery facilities. The

model also examines the trade-offs involved in selling waste

newspaper for recycling vs. burning in a recovery facility.

3 This estimate was deduced by Howard Post, paper industry analyst

for the Bureau of Industrial Economics, from the American Paper

Institute Publication Paper, Paperboard, and Woodpulp Capacity

and Fiber Consumption, 1980 .

^Bureau of Industrial Economics, U.S. Department of Commerce;

Marketing Information Report: 1980, Waste Newspapers in Four

South Atlantic States , 1982. This was the average waste newspaper

price in four Southeastern States in 1980.

XI-6
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XI-7
Table 3. Energy Prices per Unit, for Newspapers and Selected Fossil Fuels

Commodity Price* Energy Content Energy Price

Dry Newspapers $66/ton 14mmBtu/ton $4.71/mmBtu

Bituminous Coal $25/ton 26.2mmBtu/ton $0.96/mmBtu

No. 2 Fuel Oil $42/bbl 5.8mmBtu/bbl $7.24/mmBtu

Residual Fuel Oil $31/bbl 6.3mmBtu/bbl $4.92/mmBtu

Interstate Natural Gas $2.10/mcf 1 .03mmBtu/mcf $2.04/mmBtu

Note: Prices may vary widely by location and over time. Prices reflect

market charges and do not address the material handling, burning

characteristics or environmental impacts of different fuels.

5U-8
While non-financial considerations often are pivotal in the

decision whether or not to build a RRF, this analysis deals almost

exclusively with financial considerations. The environmental

benefits of a RRF may be worth the extra cost to a community in

order to mitigate landfill requirements.

A significant consideration for municipal planners is that resource recovery facilities are not a total replacement for land

disposal. After garbage has been burned in a RRF, ash and other

unburnt waste remains. A rule of thumb is that the unburnt residue

is equal in volume to about 20 percent of the input garbage. This

residue must be disposed or utilized in some fashion (e.g., road

patch)

.

An option examined in the model is landfilling. This non- recovery option for garbage is the most prevalent form of disposal

in the United States. It is the only alternative for the non- recyclable portion of the garbage.

The model produces estimates of the net benefits from five

alternative waste management options. These five strategies

consist of combinations of 1) landfilling, 2) energy recovery, and

3) resource recovery. The five alternative options are:

1) Landfilling all garbage, no source separation of

newspapers.

2) Source separating newspapers, landfilling the remaining

garbage.

3) Source separating newspapers, and burning the remaining

garbage in a RRF with no back-up fuel.

4) Burning all garbage in a RRF with no back-up fuel, no source separation of newspapers.

5) Burning all garbage in a RRF using source-separated

newspapers as back-up fuel.

The first option, landfilling, is self-explanatory. Landfilling will always yield negative financial benefits (i.e.,

costs), but landfill may nevertheless be the least-cost method of

disposal if the other options are money-losing propositions.

The second option requires source-separating newspapers so that the newspapers meet market specifications. This paper is then

sold and the remaining garbage landfilled.

The third option requires source separating newspapers and

burning the residue in an RRF; thereby producing steam for sale.

There is no attempt to recover waste materials such as glass,

aluminum, or ferrous metals. Burning garbage reduces landfill

costs, and this saving is added to the net revenue from sale of

steam and sale of newspapers.

XI-9
The fourth option assumes that all garbage, including news- papers, is burned in the RRF without source separation. Again,

burning garbage reduces landfill costs and this saving is added to

steam sale revenues.

The fifth option is an important variation of the fourth. In this case source-separated newspapers are used as a back-up fuel to

improve the combustion of garbage. Slugs of wet garbage or other

low combustibles can hamper burning thereby creating a serious

operating problem for steam-producing RRF's. Some facilities use backup fuels such as natural gas or #2 fuel oil to improve combustion and to help in start-up 5

. This practice nullifies much of the

energy-conserving rationale for resource recovery, and this practice

will become increasingly more expensive if energy prices rise.

Source-separated newspaper has a high energy value if kept dry

until needed. Dry paper burns cleanly, has an energy content of

about 14 million Btu/ton. The model allows for a higher operating

rate for this option as compared to a facility that does not use back-up fuel , such as options three and four.

The model utilizes twenty-nine (29) input variables. If the

first three variables—capaci ty , constructed cost, and ton/day--are

not known, the program will estimate them. This is done by assuming

that the construction cost for a given facility will be the same on

a per capita basis as that specified as the national average.

These 29 input variables are defined in table 4.

The model is dynamic, calculating costs over the 20-year life

of the options with changing-prices. There is an economy-wide rate

of inflation forecast for the period, with differential rates of

increase optional for energy prices, paper prices, and landfill

costs. The model utilizes the concept of present value, in which

benefits from future years are discounted by a rate of return to

make future dollars comparable to present dollars.

The "bottom line" in the model is the average annual present

value of each of the five options. The option that has the 1 argest

average annual discounted value over the twenty-year period is the

most economic. In most of the economic simulations all five

options have a negative present value. This is not surprising,

since disposal of garbage has always been a cost to society.

5 U.S. Conference of Mayors, Akron: A Case Study of Economic Development

and Resource Recovery , March 1980.

U.S. Conference of Mayors, Nashville: A Case Study of Economic

Development and Resource Recovery, March 1980 .

U.S. Conference of Mayors, Saugus: A Case Study of Economic Development

and Resource Recovery , March 1980.

XI-10
The model arbitrarily assumes that the RRF will experience a 20-year life, and is financed with 20-year bonds. In reality the

useful life of these facilities is impossible to predict with

certainty. Although the structures will probably last more than 20

years, the facility may become obsolete long before the end of its

physical life.

Although this simulation model contains no explicit consideration of subsidies for energy producing facilities, the effects of

many types of subsidies may be evaluated with this model via

comparative analysis. That is, a simulation is run for a specific

case without subsidy(ies) and then compared to a simulation where a subsidy's effect on a variable is incorporated. Examples would

include: 1) a full faith and credit guarantee by the federal

government of the bonds used to finance the RRF might reduce the

interest rate from 12 percent to 9 percent; and/or 2) federal

government price guarantees that could increase the sales price of

steam by $1.00 (or more) per thousand pounds.

Description of Input Variables

PPrice = Sales Price of Newsprint per ton Most paper dealers

will consider long-term contracts to purchase waste newsprint from

a municipality. Unless a long-term contract can be obtained, the

sales price could fluctuate wildly and no market might exist during

recessions. A long-term contract should include a provision

indexing the sales price to some measure of inflation.

SPrice = Sales Price of Steam (per thousand pounds) Since

every steam-supply situation is unique, the sales contract will be

custom-designed to the situation. The sales price of steam is

often based on the cost of alternate fuel. For example, the price

per 1,000 pounds of steam may be stated as 0.15 times the price of

a ton of coal. This type of formula contains a built-in cost

escalator, which is essential in any long-term contract.

The decision model does not deal directly with subsidies for

recovery facilities, because it is not certain what kinds of

subsidies, if any, will be available. However, through judicious

use of the model, most types of subsidies can be simulated.

It is usually assumed that energy prices will increase somewhat

faster than the general rate of inflation. The model allows for a special energy inflation rate if the planner thinks this would be

appropriate.

LFLCOS = Landfill costs per ton of garbage dumped These costs

would include the annualized expenses of purchasing and improving

the site, as well as the operation and maintenance of the facility.

For those instances where municipal landfills generate revenues greater than all expenses, this model would understate the attractiveness of the landfill option. Conversely, where landfills

operate at a loss or where land costs are amortized at less than

replacement costs, this model would overvalue the landfill option.

XI-11
As far as this economic simulation is concerned, landfilling

and ocean dumping are the same option.

Although it is usually assumed that landfill costs will

increase at the same rate as overall inflation, the model allows

planners to assume a different rate for landfills. For example, if

a landfill site suitable for 20 years can be purchased for a fixed

principal and interest cost, then landfill costs should increase

more slowly than average. On the other hand, where landfill

capacity is limited and land costs are increasing faster than

overall inflation, it would be appropriate to use a higher

escalator factor.

TRMill = Transportation to Paper Mill (per ton of paper) A BIE

survey found that transportation costs averaged 14 percent of the

mi 11 -delivered price of waste newspapers. Costs ranged from $5 to

$17.50 per ton, and averaged $8.45 per ton. Paper sales contracts

may or may not include transportation costs. If the paper customer

pays the freight, this item would be zero. Otherwise the paper

mill purchases waste newsprint at it unloading platform, with the

seller bearing the cost of transportation and handling. The model assumes that transportation costs will rise at the same rate as overall increases. (Although transportation consumes greater

quantities of energy, energy costs are usually about 15-20 percent

of trucking costs.) Although transportation costs vary widely, a preliminary estimate can be obtained as follows:

Cost per ton = 20<£ x (Distance to paper mill + return trip).

This formula gives 1980 costs. Distances are expressed in miles.

If rail transport is available, the cost could be much less.

TRLFL, TRENR, TRXX = Transportation to Landfill, Transportation to RRF , and Transportation from RRF to LandfiTT These are the

per-ton costs of transporting garbage from the end of the collection run to the disposal facility, plus the return trip. If there

is a central collection point where garbage is sent by truck or

rail to the disposal facility, transportation costs would begin at

this point.

A rough estimate of the total transportation costs per tonmile is $0.20 in dollars including the mileage for the return trip.

The model assumes that transportation costs will rise at the same

rate as overall costs.

CSEP = Extra Cost of Source-Separating Waste Newsprint (per

ton ) Unless waste newsprint is source-separated, it will become

too contaminated to be recycled. In most municipalities where

waste newsprint is source-separated there is no measurable cost,

since the public does this as part of the waste disposal process.

It might be argued that there should be come cost allowance for

public inconvenience or for the cost of policing a source- separation ordinance. Otherwise this cost factor should be zero.

XI-12
CCOL = Extra Cost of Collecting Source-Separated Garbage (per

ton

)

Because of special handling and storage requirements, it is

normally more expensive to collect source-separated newsprint.

Waste newsprint would have to be collected in a separate truck or stored in a separate section of the collection truck. It would

normally have to be transported to an assembly area where it might

have to be stored before it could be shipped to the paper mill.

CONCOSTA = Total Constructed Cost of RRF This cost factor

includes the entire capital outlay - land, plant, equipment, access

roads, auxiliary facilities - needed to construct and operational

facility. Because this cost varies with size, location, and vendor

this value should be obtained from an engineer's evaluation.

An analysis of thirteen operating steam RRF's found that the

constructed cost of garbage-burning capacity ranged from $13,300

per ton-day to $128,000 per ton-day, with an average cost of

$54,800 per ton-day (all costs converted to 1980 dollars). The

facilities ranged in size from 50 tons per day to 720 tons, with no significant trend in economies of scale.

INTRATE = Interest Rate on Municipal Bonds The rate used

should be the rate that would be incurred on a new issue of longterm general obligation bonds. Although it once was standard

practice to use the average rate on outstanding bonds, this is no longer appropriate because current marginal rates are much higher

than current average rates. This value should be entered as a decimal

.

DISRATE = Discount Rate for Present Value of Future Dollars

Present value is a financial concept which deals with the fact that

a dollar receivable at some future date is less valuable than a dollar owned at present. (In layman's terms, a bird in the hand is

worth more than one in the bush). The value of future dollars is

discounted at a rate which makes them comparable to dollars in

hand. In theory, determining the discount rate is a complicated

exercise in evaluating future inflation rates, risk analysis, and

alternate uses of funds. In practice it may be acceptable to use

the municipal bond interest rate as the discount rate for a preliminary analysis. A more advanced analysis should consider using

a discount rate somewhat higher than the interest rate, in recognition of the risks that would be incurred. The value should be

entered as a decimal

.

OPMAINA = Annual Operation and Maintenance Costs for the RRF

per ton 0&M costs can best be determined by an engineering analysis,

since these costs can vary widely with plant size, location, and

facility design. It is noteworthy that most existing RRF's have

experienced cost over-runs. An analysis of nine operating steam

RRF's shows that 0&M costs per ton of garbage burned averaged

$17.45 per ton in 1980, with no significant trend in economies of

scale.

XI- 1 3
Annual Sales of Steam (in thousands of pounds) This value is

determined internally by the decision model. It is the product of

the Btu value of the fuel per ton, the number of thousands of

pounds of steam per million Btu's, the designed burning efficiency,

tons per year of newspaper burning capacity, and the capacity

utilization rate.

RINF, INCEN ,_ INCPAP , INCLFL = Forecasted Inflation Rates The

effects of inflation will distort a long-range investment decision,

especially since various cost factors will be increasing at different

rates. For example, this model allows the planner to assume that

the value of energy will grow at a faster or slower rate (INCEN)

than the average inflation rate (RINF) . This capability also

exists for paper prices ( INCAP) and for landfill costs ( INCLFL )

.

Forecasting the basic inflation rate is a perilous process, but for

present purposes the interest rate for municipal bonds is used as the forecasted inflation rate. Many forecasts of energy prices assume that over the next 20 years these prices will increase about

3 percent faster than the Consumer Price Index. Wood prices have

increased more sharply than the Producer Price Index since 1970

(but at a slower pace than energy prices), and the U.S. Forest

Service expects this trend to continue for the rest of the century.

Trends in landfill costs are very dependent upon location.

RRFSIZEA = Total Capacity of RRF These estimates should be

stated in tons per year. This would include all garbage, including

newsprint.

WNEWS = Source Separated-Newsprint as Percent for Total

Garbage Flow On a nationwide basis, newsprint accounts for 7 percent of the solid waste stream. This represents the upper limit

of what could be collected and sold. In practice some waste

newsprint is already collected in paper drives. Furthermore,

uncooperative consumers may refuse to source-separate their waste

newsprint. The city can substantially increase source separation

through public relations, police enforcement, and/or refusal to

collect unseparated garbage. The amount of source-separated waste

newsprint collected should be expected to range between 0_ percent

and 5_ percent of total garbage collection. If the municipality

passes and enforces a "flow control" ordinance and makes a serious

effort to encourage source-separation of newsprint, then it should

be at the higher end of this range. Conversely, if a municipality

has no flow control and does not intend to strongly encourage

source-separation, then it will be near the low end of the range.

Capacity Utilization Rates for RRF's In practice, very few

RRF's operate at 100 percent of their expected output. Four

categories of unscheduled problems which have caused low capacity

utilization rates are:

1) insufficient solid waste delivered to RRF;

2) operating difficulties;

XI-14
3) inability to generate as much salable steam per ton of

garbage as had been expected; and

4) inability to sell as much steam as the facility could

produce

.

For the sake of simplicity, the model uses one measure of

efficiency to encompass all four types of operating inefficiencies.

The efficiency measure is the ratio of actual output sold (in

pounds of steam) to ful 1 -capacity output (in pounds of steam). A

review of operating RRF's showed that many of them were operating

at well below expected capacity. A RRF using source-separated

newsprint as a supplementary fuel would probably achieve an efficiency rate 5_ to _10 percent higher than a RRF which does not

use a supplementary fuel.

LDGrowth = Annual Rate of Growth in Solid Waste Flow Resource

recovery facilities are often oversized to accommodate expected

growth. If this is the case, then the projected annual growth rate

should be entered as a decimal. If no growth is projected in the

waste flow to be handled by the RRF, then zero should be entered

here.

In some cases "loadgrowth" would be in increments, as modules

are added to the RRF. Through skillful manipulation of the model,

this situation could be simulated in large part, although some hand

calculations would be required.

FLOW = Flow of Solid Waste in First Year, in tons per year

This refers to all post-consumer solid waste, including source separatable newspapers. If this value is not known, enter zero and

the computer will calculate this on the basis of population and

estimated pounds of garbage per day per capita.

POP = Population to be Served by Proposed RRF These input

data are only needed if the flow is not known. IT flow is already

known, enter zero.

LBCAP = Pounds of Garbage Generated per Capita per Day These

input data are only needed if the total garbage flow is not known.

If flow is already known, enter zero.

On a national average basis, it is estimated that 4.2 pounds

of postconsumer waste is generated per person per day. Although

this can usually be used as a preliminary estimate, the quantity

and composition of garbage vary widely among communities.

Description of the Computer Program

The economic simulation model is programmed in the Statistical

Analysis System language (SAS), which requires an IBM-compatible

computer. [Commerce Department users can quickly access the

program through the National Institutes of Health ADP system. Use

of the NIH system requires a rudimentary understanding of WYLBUR.]

XI-15
The program is listed in Exhibit 1. It is set up to process

data entered in batches added after line 118.

Although there are 29 input data cells, only 26 or 27 items

actually need to be entered. This is because the program is

designed to estimate the size and cost of the facility if this

information is not already known. Thus, if FLOW, CONCOSTA, and

RRFSIZEA are not known, enter zero for these values and enter data

for POP and LBCAP. The computer will then estimate the size and

cost of the RRF based on construction cost of $55,000 per ton/day,

which was the national average in 1980. Conversely, if FLOW,

CONCOSTA and RRFSIZEA are known, then enter the data for these

values and enter zero for POP and LBCAP. The computer will then

estimate the size and cost of the RRF based on a construction cost

of $55,000 per ton/day, which was the national average in 1980.

Lines 1 through 3 of the program are system cards relating to

the NIH computer system.

Lines 4 through 8 describe the input set and the names of the

29 variables. Each input data card must have data in exactly the same order as shown in lines 6 through 8. (The actual data are not

entered until after line 118.)

Lines 9 through 15 are data clean-up operations. These lines

are necessary because the program is designed to calculate FLOW,

RRFSIZEA, and CONCOSTA, if these values have not been developed in

advance. Line 10 calculates SSNP, the volume of source separatable

waste newspapers, based on FLOW and WNEWS. Line 13 calculates the

size of the smaller RRF that would be required if waste newspapers

were separated out of the garbage.

Lines 16 and 19 calculate the annual principal and interest

payments on the RRF for each year of its 20-year life. The formula

is a standard equation used in calculating fixed-payment mortgages.

Lines 20 through 28 are housekeeping steps which clear nine

data registers that will be used to keep running totals.

Lines 29 through 30 instruct the computer to perform the large

subroutine (on lines 31 through 116) twenty times. This subroutine

calculates the economics of each option for year N ( 1 , . . . 20 )

.

Lines 31 through 35 calculate changes that occur in the

dynamic variables 0PMANAN, SPRICEN, FLOWN, and SSNPN over the

20-year life of the RRF.

Lines 36 through 38 calculate the net energy revenue per ton

of source-separated newsprint burned in a RRF as back-up fuel

if the RRF operates at 100 percent of capacity . Line 36 calculates

the in-plant generating costs per ton of steam from burning SSNP.

Line 38 calculates the net energy revenue per ton of SSNP burned,

if the RRF operates at 100 percent of capacity.

XI- 1 6
Lines 39 through 41 calculate the net energy revenue per ton

of unseparated newsprint burned, if the RRF is operating at 100

percent of capacity. The methodology is very similar to that

described in lines 36 through 38.

Lines 42 though 46 calculate the net energy revenue per ton of

garbage from which SSNP has been separated, if the RRF is operating

at 100 percent of capacity. The output from these calculations,

ENREVZ, will be used to calculate benefits from a RRF which uses SSNP as a back-up fuel (a type B RRF).

Lines 47 through 52 calculate the net energy revenue per ton

of garbage other than SSNP, if the RRF is operating at 100 percent

of capacity. This differs from the calculation in lines 42 through

46 in that this situation refers to a RRF which burns garbage from

which SSNP has been removed and which uses no back-up fuel (a type

A RRF).

Lines 53 through 57 calculate the net energy revenue per ton

of garbage other than SSNP, if the RRF is operating at 100 percent

of capacity. This differs from the calculation in lines 47 through

52 in that this situation refers to a type A RRF which burns all

garbage, including all newspapers with no source separation,

without back-up fuel . Thus , in this case the energy value of the

garbage is slightly higher and the size of the RRF is slightly

larger, because source-separatable newspapers are included in the

garbage.

Lines 58 through 68 calculate changes that occur in eleven

dynamic variables over the 20-year life of the RRF. In all eleven

cases, the cause of the changes is price inflation expected over

the twenty years.

Lines 69 through 71 calculate BURNZ, which is the benefit per

ton of source-separatable newspaper burned as back-up fuel in a RRF. This value differs from ENREVZ in that it incorporates the

costs of operating at less than 100 percent of capacity as well as transportation costs, collection costs, and source separation

costs

.

Lines 72 and 73 calculate BURNY, which is the benefit per ton

of unseparated newspaper which is burned in a RRF along with the

rest of the garbage. Although there are no source separation costs

and the collection costs are lower, the energy value per ton is

less and the operating rate is lower.

Lines 74 through 76 calculate BURNX , which is the benefit per

ton of garbage (other than SSNP) burned with SSNP as back-up fuel.

(Type B RRF.)

Lines 77 through 79 calculate BURNW, which is the benefit per

ton of garbage burned in a RRF with SSNP removed at the source and

recycled to paper mills. (Type A RRF.)

XI-17
Lines 80 through 82 calculate BURNV, which is the benefit per

ton of garbage (other than SSNP) burned, with no back-up fuel and

with unseparated newspapers included in the garbage. (Type A RRF.)

Lines 83 through 87 calculate the total dollar benefits per

year in current dollars for each of the five options considered by

the. model. In the ALLDFL option all garbage and newspapers are landfilled. In the PRGLF option, source separatable newspapers are recycled and the remaining garbage is burned without back-up fuel

(Type A RRF). In the ALBRNB option source separated newspapers are burned as back-up fuel along with the remaining garbage (Type B RRF). In the ALBRNA option newspapers are not source-separated,

but rather all garbage is burned unseparated in RRF without back-up

fuel (Type A RRF).

Lines 88 through 97 convert nine of the most important products

from current dollar value to discount present value.

The elaborate procedure steps in lines 98 through 115 are necessary to calculate an average present value for each of the

five options over the 20-year life of the RRF. Lines 98 through

106 keep a running total of nine variables which a discounted

present value is calculated in lines 88 through 97. Lines 107

through 115 calculate the present value divided by 20, which are meaningless numbers for the first 19 years but in the 20th year

these values become the average present value of each variable over

the 20-year life of the RRF.

Input data are entered after line 118. Each data "card"

contains 29 variables and must be entered in three lines in exactly

the same order as in lines 6 through 8. The gap between lines 118

and 149 is large enough to handle batches of 10,000 "cards" at a time.

Lines 149 through 153 contain two SAS procedure steps. The

first procedure step sorts the data by case. As used here a "case"

is a set of assumptions, which is represented by one data "card" (3

physical cards).

Lines 150 through 153 instruct the computer to print ten data

items for each of the 20 years for each case. The ten data, items

are the net benefits for each of the five disposal alternatives,

expressed first in current dollars and second in discounted dollars.

Lines 154 through 156 are data development steps which

instruct the computer to output "bottom line" estimates for only

the 20th year of RRF life. As was discussed earlier, for the first

19 years this data is meaningless and could be confusing if it were

printed.

Lines 157 through 159 instruct the computer to print the

"bottom line" for each of the five options for each case.

XI-18
EXHIBIT I

Source Listing of Program

1. //PACBURN JOB ( WPP 1 , M924 , A

)

r MACAULE

Y

2. //PROCLIB DD DSN=Z ABCRUN. PROCLIB, DISP=SHR

2.1 //STP1 EXEC SA3, S0RT=30

3. //3YSIN DD *

4. DATA MSW;

5. INPUT

6. RRF3IZEA CONCOSTA FLOW LDGROWTH POP LBCAP WNEWS ENUSMSW ENSSNP ENUSNP

7. SPRICE PPRICE LFLCOS CONVEFF OPRATEA OPRATEB OPMAINA TRLDFL TRMILL TRENR

8. TRXX CSEP CCOL INTRATE DI3RATE RINF INCEN INCPAP INCLAND ; 9. IF FLOW = 0 THEN FLOW = POP * LBCAP * .183;

10. SSNP = WNEWS * FLOW

;

U. IF RRFSIZEA = 0 THEN RRFSIZEA =

12. (POP * LBCAP / 2000) * (1+ LDGROWTH ) «*20;

13. RRFSIZEB = RRFSIZEA * ((FLOW - SSNP) / FLOW);

14. IF CONCOSTA = 0 THEN CONCOSTA = RRFSIZEA * 55000;

15. CONCOSTB = CONCOSTA * ((FLOW - SSNP) / FLOW);

16. MORTA = CONCOSTA * (((1 + I NTRATE ) **20 )

/

17. <((1 + INTRATE ) **20 ) -1)) * INTRATE ; 18. MORTB = CONCOSTB * <<(1 + I NTRATE ) **20 )

/

19. ( ( ( 1- + INTRATE>**20> -1)) * INTRATE;

20. TBURNZ = 0 ; 21. TBURNY = 0;

22. TLCOST = 0 ; 23. TPVAL = 0 ; 24. TALLDFL = 0;

25. TPRGLF = 0;

26. TPRGBA = 0;

27. TALBRNA = 0;

28. TALBRNB = 0;

29. CASE = _N_;

30. DO N = 1 TO 20;

31. OPMANAN = OPMAINA * (1+ RINF) ~* ( N- 1 ) ; 32. SPRICEN = SPRICE * (l-MRINF + INCEN)) ** (N-l);

33. FLOWN = FLOW * (1 + LDGROWTH) (N-l);

34. SSNPN = SSNP « (1+ LDGROWTH )-*( N- 1 )

;

35.

36. STEAMZ = FLOWN * ENSSNP * CONVEFF * OPRATEE;

37. GENCOSZ = (MORTA + (OPMANAN FLOWN )) / STEAMZ;

38. ENREVZ = ENSSNP * CONVEFF - ':- c, RICEN - GENCOSZ);

39. STEAMY = FLOWN * ENUSNP * CONVEFF - OPRATEA;

40. GENCOSY = (MORTA + (OPMANAN <• FLOWN) ) / STEAMY;

41. ENREVY = ENUSNP * CONVEFF - (SPRICEN - GENCOSY);

42. STEAMX = FLOWN * ( ENUSMSW - (( SSNPN / FLOWN) * ENUSNP )) 43. * CONVEFF * OPRATEt : 44. GENCOSX = (MORTA + (OPMANAN FLOWN )) / STEAMX;

45. ENREVX = (ENUSMSW - ((SSNPN / FlOWN) * ENUSNP))

46. * CONVEFF * (SPRICEN - GENCOSX);

47. STEAMW = (FLOWN - SSNPN) * (ENUSMSW - ((SSNPN / FLOWN) •> ENUSNP))

48. * CONVEFF *• OPRATEA ; 49. GENCOSW = (MORTB + (OPMANAN - (FLOWN - SSNPN)))

50. / STEAMW ;

XI-19
51. ENREVW = (ENUSMSW - ( ( SSNF'N / FLOWN 1 » ENUSNF' ) ) 52. * CONVEFF * (SPR1CEN - GENCOSW) ; 53. STEAMV = FLOWN <- ( ENUSMSW - (( SSNPN / FLOWN) - ENUSNP ) ) 54. * CONVEFF * OPRATEA;

55. OENCOSV = ( MGRTA + ( OPMANAN * FLOWN)) / STEAMV;

56. ENREVV = (ENUSMSW - (( SSNFN / FLOWN ) * ENUSNP )

)

57. * CONVEFF * (SPRIG EN - OENCOSV);

58. LFLCOSN = LFLCOS * (1 + RINF + INCLAND ) ** (N-l);

59. TRLDFLN = TRLDFL * (1 + RINF)** (N-l);

60. TRXXN = TRXX * ( 1 + RINF ) *- (N-l) ; 61. PPRICEN = PPRICE * (1 + RINF + ZNCPAP) ** (N-l);

62. CSEPN = CSEP * ( 1 + RINF) ** (N-l);

63. CCOLN = CCOL * ( 1 RINF) ** (N-l);

64. TRMILLN = TRMILL * (1 + RINF )** (N-l )

;

65. LCOST = - ( LFLCOSN + TRLDFLN);

66. PVAL = PPRICEN - (CSEPN + CCOLN)

67. + (LFLCOSN + TRLDFLN) - (TRMILLN);

68. TRENRN = TRENR * ( 1 + RINF + INCEN) ** (N-l) ; 69. BURNZ = (OPRATEB * ( ENREV2

70. - (CSEPN + CCOLN + TRENRN))) -

71. (( 1 - OPRATEB) * (LFLCOSN + TRLDFLN));

72. BURNY = (OPRATEA * ( ENREVY - TRENRN ))

73. -(( 1 - OPRATEA) * (LFLCOSN + TRLDFLN));

74. BURNX = (OPRATEB * (ENREVX - TRENRN ))

75. - ( .2 * OPRATEB * ( LFLCOSN + TRXXN) + ( ( 1 - OPRATEB ) 76. * (LFLCOSN + TRLDFLN )))?

77. BURNW = (OPRATEA * (ENREVW - TRENRN ))

78. - ( .2 * OPRATEA * ( LFLCOSN + TRXXN ) + (<1 - OPRATEA)

79. * (LFLCOSN + TRLDFLN))) ; 80. BURNV (OPRATEA * (ENREVV - TRENRN ))

81. - (.2 * OPRATEA * ( LFLCOSN + TRXXN ) + ((1 - OPRATEA

82. * ( LFLCOSN + TRLDFLN )));

83. ALLDFL = FLOWN * LCOST ; 84. PRGLF = (SSNPN * PVAL) + ((FLOWN - SSNPN) *LCOST>J

85. F'F.'OBA = (SSNPN * PVAL ) + ((FLOWN - SSNPN) * BURNW)}

86. ALBRNA = (SSNPN * BURNY) + ((FLOWN - SSNPN) * BURNV) ; 87. ALBRNB = (SSNPN * BURNZ) + ((FLOWN - SSNPN ) * BURNX ) ; 88. DRN = ( 1 + DISRATE)** ( N- 1 )

j

89. DBURNZ = BURNZ / DRN;

90. DBURNY = BURNY / DRN;

91. DLCOST = LCOST / DRN;

92. DPVAL = PVAL / DRN;

93. DALLDFL = ALLDFL / DRN ; 94. DPROLF = PROLF / DRN ; 95. DPRGBA = PRGBA / DRN ; 96. DALBRNA = ALBRNA / DRN ; 97. DALERNB = ALBRNB / DRN ; 93. TBURNZ = DBURNZ + TBURNZ ; 99. TBURNY = DBURNY + TBURNY ; 100. TLCOST = DLCOST + TLCOST ; 101. TPVAL = DPVAL + TPVAL ; 102. TALLDFL = DALLDFL + TALLDFL ; 103. TPRGLF = DPRGLF * TPRGLF ; 104. TPRGBA = DPRGBA + TPRGBA ; 105. TALBRNA = DALBRNA + T ALBRNA ; 106. T ALBRNB = DALERNB + T ALBRNB ; 107. ALCOST = TLCOST / 20 ;

XI-20
APVAL = TPVAL /

• AE^JRNZ = TE'URNZ / 20 ; 1 1 0

.

AB'URNY = TBURNY / 20 ; 111. AALLDFL = TALLDFL / 20 ; 112. APRGLF = TPRGLF / 20 ; 113. APRGBA = TFRGE'A / 20 ; 114. AALBRNA = TALBRNA / 20 ; 115. AALBRNB = TALBRNB / 20 ; 116. OUTPUT MSW;

117. END;

118. CARDS;

1 19. 1 0 0 0 .02 100000 4.2 .02 9 14 10

119. 3 66 10 .65 .8 .9 17.45 6 12 6 3

119. 3 0 5 .12 .12 .10 .03 0 0

149. PROC SORT DATA=MSW ; BY CASE;

150. PROC PRINT DATA=MSW ; VAR ALLDFL PRGLF PRGBA ALE'RNA ALBRNB

151

.

DALLDFL DPRGLF DPRGBA DALERNA DALBRNB ; 152. TITLE LANDFILL COSTS VS PAPER RECYCLING VS BURNING FOR ENERGY;

153. BY CASE;

154. DATA T50 (KEEP = AALLDFL APRGLF APRGBA AALBRNA AALBRNB CASE);

155. SET MSW ; BY CASE;

156. IF LAST. CASE = 1 THEN OUTPUT T50;

157. PROC PRINT; VAR CASE AALLDFL APRGLF APRGBA AALBRNA AALBRNB ; 15S. BY CASE;

159. TITLE LANDFILL COSTS VS PAPER RECYCLING VS BURNING FOR ENERGY;

160. /*

161. //

XI-21
Results of the Economic Simulations

As a starting point for analyzing the subject, a "typical" resource recovery facility was simulated as the "base case."

Although there are substantial variations among RRF's, the base case situation can provide valuable insights and serves as a frame

of reference for analyzing other situations. Table 4 indicates the

specific values of the variables assumed in the base case.

The results of the simulation for the base case are shown in

table 5. All five options show net losses under base case assumptions. The costs per year for each of the five disposal alternatives

are shown over the 20-year life of the facility. Given base-case

assumptions, the most economical alternative for the first 13 years

is to recycle source separated newspapers and dispose of the rest

of the garbage in landfills. During the last 7 years the most

economical alternative is burning all trash in the resource recovery

facility and using newspapers as back-up fuel. The most economical

strategy over the 20 years is determined by comparing the average

present value over the 20-year span. In the base case the most

economical alternative is recycle newspapers and landfill the

remaining garbage.

It is noteworthy that all five options yield negative financial

benefits under the base case conditions. The most economical

alternative is the one which costs the least. (These costs would

have to be defrayed by tipping fees, general revenues, or default

on the bonds.) Under the optimistic assumptions, there are situations in which RRF's can yield positive financial benefits. In any

event which ever method manages garbage at the least cost is the

most economical option.

In addition to the base case scenario there are numerous other

possible scenarios. The principal significant variations are likely to be site-specific. Seventy variations, covering the most

likely differences from the base case, were examined during the

sensitivity analysis. As might be expected, differing assumptions

produce different outcomes.

Sales Price of Steam

The single most significant variable in selecting an option

alternative is the sales price of steam. The base case assumed

$3/1000 pounds of steam, with variations to the base case from $1

to $10. The base case price of $1 per thousand lbs. of steam would

not make a recovery facility competitive with source separation of

paper and landfilling. However, a sales price of $4.00 per 1000

pounds could make recovery facility the preferred option. The

price for which a municipality can sell its steam is determined by

circumstances unique to each situation. Seven communities have

considered proposals that included estimates of steam prices

ranging from $2 to $13.70 per thousand pounds 6.

Unpublished Staff Report, Technical Advisory Center, Office of

Recycled Materials of a survey of proposals submitted to the U.S.

Environmental Protection Agency under the President's Urban Grant

Program, 1981.

XI- 22
Variable

Name

Table 4.

Base Case

Value

Base Case Assumptions

Brief Description

1. RRFSIZEA 0 Capacity of RRF, in tons of garbage per day

2. C0NC0STA 0 Constructed cost of RRF, in dollars

3. FLOW 0 Daily flow of garbage in first year, tons

4. LDGROWTH .02 Annual loadgrowth factor, if oversized RRF

5. POP 100,000 Population served by RRF in first year

6. LBCAP 4.2 Garbage generated per capita, in pounds per

day

7. WNEWSA .02 Source-separatable newspaper as fraction of

garbage

8. ENUSMSW 9 Energy content of separated garbage,

mil 1 ion-Btu 1 s/ton

9. ENSSNP 14 Energy content of separated garbage,

mill ion-Btu 's/ton

10. ENUSNP 10 Energy content of unseparated newspapers,

mil 1 ion-Btu 1 s/ton

11. SPRICE 2 Sales price of steam, $per 1000 lbs., first

year

12. PPRICE 66 Sales price of newspapers, $per ton, first

y Cd r

13. LFLCOS 10 Landfill cost, $per ton, first year

14. CONVEFF .65 Conversion efficiency of boiler, fraction

15. OPRATEA .8 Operating rate for RRF without back-up fuel

fraction

XI-23
Base Case Assumptions

Variable

Name

16. OPRATEB

17. OPMAINA

Base Case

Value Brief Description

18.

19.

20.

21.

22.

23.

24.

25.

TRLDFL

TRMILL

TRENR

TRXX

CSEP

CCOL

INTRATE

DISRATE

26. RINF

27

28

29,

INCEN

INCPAP

INCLFL

17.45

6

12

6

3

0

5

.12

.12

.10

.03

0

0

Operating rate for RRF, newspapers as back-up

fuel , fraction

Operating and maintenance costs per ton

of garbage (Based on an underuti 1 ization of

capacity

Transportation costs to landfill, $per ton

Transportation costs to paper mill, $per ton

Transportation costs to RRF, $per ton

Transportation costs from RRF to landfill,

$per ton

Cost per ton of source separating newspapers

Extra costs per ton of collecting newspapers

Interest rate on bonds to finance RRF

Rate used to discount the value of future

dol 1 ars

Average annual rate of inflation over

20 years

Incremental inflation rate for energy prices

Incremental inflation rate for paper prices

Incremental inflation rate for landfill costs

XI-24
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XI -25
On average, a large industrial customer with an existing

coal -fired steam system has a fuel cost of about 964 per thousand

pounds of steam (at $25/ton coal, 90 percent efficiency in 1981);

and, therefore, would be very reluctant to buy steam at a higher

price. (See table 6.) A customer with a serious pollution

problem, space problem, or capital problem may be willing to pay

more, but this type of customer may not be a good candidate for a 20-year sales contract. The base case value of $3 per 1000 pounds

of steam would thus seem to be on the high side, but a number of

municipalities have indicated they can sell their output at even higher prices.

Construction Costs

The construction cost per ton/day of garbage-burning capacity

varies widely among steam-producing RRF's, from $13,000 to $78,000

in 1980 dollars. Table 7 indicates that plants at the low end of

this cost range would tend to be competitive with landfill, while

the average cost facility ($50,000 per ton/day capacity) would not.

Facilities at the high end of the construction cost range would

incur a loss more than twice the cost of landfill ing.

Landfill Costs

Landfill costs are a major determinant of the viability of

recovery planning. Where landfill costs are greater than $18 per

ton, recovery tends to be more economical. (See table 8.) The

cost of landfill as used in the simulation model is a gross cost

which does not net out the revenues from tipping fees. (Since

tipping fees are often determined by political factors as well as cost factors, and since tipping fees would be charged by both

landfills and RRF's, the inclusion of tipping fees in the equations

would complicate the model without significantly increasing its

usefulness.

)

Operating and Maintenance Costs

Operating and maintenance (0&M) costs are a significant factor

in resource recovery economics. A survey of six RRF's indicated an average 0&M cost of $17.45 per ton of garbage burned 7

. Under

base-case conditions a RRF which kept 0&M costs below $10 per ton

would be more economical than a landfill. (See table 9.) Although

none of he six facilities surveyed had 0&M costs below $12 per ton,

operating experience and innovation could possibly reduce these

costs

.

7 U.S. Conference of Mayors, City Currents: Special Issue , March

29, 1982.

XI-26
co

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Operating Rates

Operating rates are expected capacity utilization rates with

allowance for normal downtime 8

. Although high operating rates do

not guarantee success, low operating rates can lead to economic

disaster. Low operating rates, often associated with unreliability, not only lead to reduced sales of steam, but also result

in high landfill costs in order to dispose of unburnt garbage.

Many existing facilities operate at low rates, which has been one

of the major reasons for their poor financial performance 9

. The

base case assumes that a proposed facility would operate at 90

percent of capacity using newspapers as back-up fuel or 80 percent

of capacity without back-up fuel.

As shown in table 10, a facility operating at 90 percent of

capacity spends about 30 percent more per ton to dispose of garbage

than does a landfill, while at a 60 percent operating rate the

per-ton disposal cost for facility would be double the landfill

cost. In addition to the financial costs of low operating rates

are greater physical landfill requirements which increase from 28

percent to 52 percent of the garbage flow as the operating rate of

the RRF declines from 90 percent to 60 percent.

The simulation model assumes that in the future fossil fuels

such as natural gas and fuel oil would not be extensively used as a back-up fuel. It is currently a common practice to use these

valuable resources to enhance burning during periods when wet or non-combustible garbage reduces burning efficiency. This not only

increases operating costs, but negates much of the energy-saving

benefits as well. A promising alternative is the use of dry

source-separated newspaper as back-up fuel instead of fossil fuels.

The model does not consider burning fossil fuels as auxiliary fuel.

The base case assumes that operating rate with source separated newspapers as a back-up fuel would be about 10 percent

higher than operating without such back up fuel, although this

level has not been demonstrated in an operating facility. If

operating rates in either case are equal, then the costs are also

about the same since the extra costs of separating and handling

newspapers are offset by the extra energy value.

8 For example, if a RRF is expected to operate at 1000 tons per day

for 360 days of the year, yet in fact experiences 36 days of

unscheduled downtime plus 36 days of operating at only 500 tpd,

then the operating rate would be 85 percent.

9 Ronald J. Alvarex, Hofstra University. Status of Incineration and

Generation of Energy From Thermal Processing of MSW . Proceedings

of the 1980 National Waste Processing Conference.

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XI-32
Energy Conversion Efficiency

The conversion efficiency of the boiler is not likely to have

a decisive effect on the economics of the RRF. (See table 11.) In light of the severe economic penalty for low operating rates, the

municipality should be just as concerned, if not more so, with

boiler reliability as with boiler efficiency.

A comparison of tables 10 and 11 shows that a change of one percentage point in efficiency costs about as much as a one percentage point change in operating rates. However, the downside

range for operating rates is much broader, given existing technology. Thus, for a facility using backup fuel , a reduction in

efficiency from 70 percent to 56 percent would cost $345,000

annually, while a reduction in operating rates (reliability) from

95 percent to 60 percent would cost $772,000 annually.

A RRF with the ironic combination of a 60 percent operating

rate and 56 percent efficiency would annually cost $1,050,000 more

than a RRF with a near-perfect combination of 95 percent operating

rates and 70 percent efficiency.

Wastepaper Prices

Under base-case conditions, wastepaper prices are not a decisive factor in the decision to burn or landfill garbage. (See

table 12.) The 1981 BIE survey of the wastepaper recycling industry

in the Southeastern U.S. found that waste newspaper prices averaged

$66 per ton, with the buyer usually paying freight 10

. Under these

conditions recycling would be very attractive. However, the

wastepaper market is subject to extreme price variability during a business cycle. In some cases waste newspapers cannot even be

given away.

Wastepaper prices do become significant in situations where

steam prices are substantially higher than the base case value of

$3.00 per 1000 pounds of steam. For example, if the steam price

was $4.00 per 1000 pounds, then wastepaper prices would have to be

at least $110 per ton to make paper recycling preferable to burning.

Figure 2 illustrates the more economical use of waste newspaper at

various combinations of prices for wastepaper and steam and assuming

base case conditions for all other variables. Under these conditions

with steam prices less than $3.25 per 1000 pounds, paper recycling

is preferable regardless of the wastepaper price, because the

facility is losing money with steam prices at or below $3.25. With

steam prices higher than $4.75 per 1000 pounds, wastepaper prices

would have to exceed $200 per ton. (See table 13.)

10 Bureau of Industrial Economics, U.S. Department of Commerce;

Waste Newspapers in Four South Atlantic States , 1980.

XI-33
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XI-36
Steam costs of $4.00 per 1000 pounds are the exception rather

than the rule in energy-intensive industrial operations. Therefore,

an industrial customer paying these high steam prices may have

difficulty remaining competitive in its field during the 20-year

life of a recovery facility.

Transportation Costs

Within the most common cost ranges, transportation costs for

waste newspapers are not by themselves a crucial determinant.

However, in conjunction with low paper prices, high transportation

costs could make recycling uneconomical. (See table 14.)

Special Source-Separation Costs

The extra costs of source-separating newspapers would not be

great enough to determine the most economical use of wastepaper.

The costs of source- separation are small relative to paper prices

and transportation costs. The public inconvenience of source- separation is external to this analysis, although this could be an important consideration in some cases. (See table 15.)

Interest rates, present value discount rates, and inflation rates

tend to move together, and thus are presented together in table 16

.

The higher the interest and discount rate the less attractive are recovery options. High inflation rates tend to make recovery

options attractive rf financing can be acquired at substantially

lower rates than the rate of inflation.

In table 16 the present value discount rate is equal to the

interest rate paid on municipal bonds. Although this probably

conforms to common practice, a higher discount rate should normally

be used to account for risk and reduction of the municipality's

remaining borrowing power. Higher discount rates would tend to

make recovery options even less economica'l than landfills and/or

source separation.

Energy and Inflation Rates

Many recent economic forecasts assume that energy prices will

increase faster than the overall inflation rate. The base case assumes that prices for energy will rise at an average annual rate

of 3 percentage points above the overall inflation rate, and that

steam sales contracts will have escalator clauses tying the price

of steam to the price of alternate energy supplies. A variety of

incremental energy inflation rates are simulated in table 15.

Under base case conditions energy prices would have to increase

annually 7 percent age points faster than the overall inflation

rate during the twenty -year period to make the facility more

economical than landfills. However, model users can input varying

inflation rates. (See table 16.)

XI-37
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XI-40
Landfill Inflation Rates

In some instances landfill costs have been increasing faster

than the overall rate of inflation. This is more likely to be true

for those landfills which have incurred exceptional costs resulting

from environmental regulations or where land prices have soared. A

large percentage of the cost of landfill can be fixed at the time

the landfill site is acquired. Landfill O&M costs are not likely

to increase much faster than the overall inflation rate except to

the extent that new regulatory requirements increase costs. Tables

8 and 15 indicate that cost increases for landfilling would have to

exceed the average annual inflation rate by 8 percent per year for

20 years to make recovery options more attractive than landfill

under base case conditions.

Wastepaper Inflation Rates

The wastepaper price inflation rate has virtually no impact on the most desired alternative, under base case conditions and for

steam prices of less than $3 per 1000 pounds. (See table 17).

However, for medium-high paper prices and medium-high steam prices,

this wastepaper inflation rate could become important.

Steam Prices vs. Landfill Costs

Steam prices and landfill costs are important variables in

determining the most economical means of garbage disposal. (See

table 18.) Therefore examination of these two variables together

is in order. Assuming base case conditions for all other variables,

figure 3 illustrates the results of the model at various combinations of steam prices and landfill costs. Recovery options become more attractive as landfill costs become higher. With landfill

costs above $30 per ton, recovery facility would be economical even with steam prices as low as $1.00 per 1000 pounds. Similarly, with

steam prices above $4.50 per 1000 pounds, recovery facility would

be economical even if landfill costs were near zero. However, the

great majority of the most likely combinations of steam prices and

landfill costs are in the "LANDFILL" area of figure 3.

XI-41
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References

[1] Determination of the Calorific Value of Refuse-Derived-Fuels

by Large-Bomb Cal orimetry , Summary of the 1978 Fiscal Year

Results, D. R. Kirklin, E. S. Domalski, D. V. Mitchell,

January 1980. (NBS-IR-80-1968)

[2] "Recent Federal Actions Which Will Affect Present Demands for

Discarded Fibers", Presentation by Dr. Harvey Yakowitz to

American Paper Institute. October 23, 1980.

[3] Test Procedures for the Determination of the Gross Calorific

Value of Refuse and Refuse-Derived Fuel by Conventional Bomb

and Large Bomb Cal orimetry, D. R. Kirklin, J. Colbert, P. Decker, S. Abramowitz, E. S. Domalski, June 1981.

(NBS-IR-81-2278)

[4] Thermodynamic Data for Waste Incineration, E. S. Domalski, W.

H. Evan, T. L. Jobe, August 1978. (NBS-IR-78-1479)

XI-46
APPENDIX XII. OVERVIEW OF RRPLAN

RRPlan is a computerized mathematical model developed for the

study of solid waste systems. The computer program, or model, has

been designed using a mathematical theory known as "linear programming." With this mathematical technique, it is possible to

find the precise values of a set of variables that will optimize a specified function, usually a cost function. Thus, if the variable

parameters are, e.g., site location, amount of paper recycled,

modes and routes of transportation, etc., the linear programming

technique will allow an analyst to determine the best choices for

these parameters in order to cause a cost (or profit) function to assume a minimum (or maximum) value. This linear programming

technique is designed to analyze linear functions, i.e., functions

that can be approximated by using several linear functions in the same manner that a curve can be approximated by several straight

lines. The RRPlan model uses up to three linear segments to

approximate non-linear cost functions.

The user of the model may select one of four modes of operation

1) Minimize cost, discounted and undiscounted.

2) Maximize net energy.

3) Minimize a linear combination of energy and cost.

4) Evaluate a specific plan.

Whatever mode of operation is selected, the output summary of

the model provided in the computer printout will include discounted

and undiscounted costs by type of cost and total, and net energy by

category. For each cost, annual and lifetime measures are given

and the discounted, undiscounted and energy requirement per ton of

MSW is given.

The preferred plan chosen by RRPlan balances the cost of haul

against the cost of larger facilities to derive the least cost

optimal solution. In order to do this, the program considers many

possible solutions in order to select the best choice. This

optimal solution also indicates the best fit into the available

markets for resource recovery or recycling. The cost of haul to

market and the prices received at the market add to or reduce the

cost of a possible solution.

The RRPlan may also be used to evaluate a single specific

plan. In this case, the solution is known and the model merely

describes the plan's cost and allocations and evaluates the future

cost and overall efficiency through the input of financial data

such as the interest rate and the discount rate.

The RRPlan solution will address the following questions:

XII-1
1) What type of facilities should be used and where?

2) What are the most efficient capacities to handle the

waste generated?

3) How much and by which mode of transportation should each

community ship its waste to each facility?

4) Which recoverables should be marketed?

5) How much of each type of recoverable should be marketed

and where?

6) What will the cost breakdown be?

The model analyzes the types of facilities such as landfill,

transfer station, incinerator with heat recovery, modular incinerator, etc., and matches these with the different locations where

they could be built or already exist. When locating a facility,

the model uses such factors as proximity to the source of waste,

the cost of that facility and the availability of markets. The

model will then choose the optimum size of each facility and match

that facility with the sources of waste generated.

The transportation linkages between the facilities (called

sites) and the communities, or sources of waste (called sources),

are determined by the model. These linkages will not only show how

much but by which mode of transport wastes should be shipped. The

different modes of transport are, for example, packers or large 18

wheel trucks. It is assumed that collection vehicles are homogenous

types of vehicles, i.e., some sort of packer. When long hauls are necessary, the model will locate a transfer station at a source so as to decrease haul costs, making the haul from that source to a site by van instead of a packer.

Recoverables, glass, metal, and paper may be either source separated or taken out as part of a process at a facility. The

distance to the market for these commodities and the cost to haul

them is one of the determining factors as to whether the com- modities are recovered or not. The cost of recovering the material

is also considered. Furthermore, the model determines which is more efficient: a) to recycle paper for its fiber value, or b) to

leave it in the waste stream for its Btu value if a heat recovery

system is offered. The model will determine what percent of paper

will be burned and what percent will be recycled as a function of

market price for recycled paper fiber and its fluctuation versus

the Btu value.

The most important question of cost is broken down into its

different component parts alone, along with a total cost figure and

a total cost per ton figure for the the whole plan. Costs may be

divided into operating and maintenance costs, capital costs,

finance costs, municipal costs, etc., or a summation of some of the

XII-2
different costs. The cost breakdown is given in constant dollars

or inflated dollars. These costs (discounted or undi scounted) are also minimized by the model.

General Information

The discount rate is needed to give future costs in constant

and 'meaningful dollar values. If a user is unsure of the discount

rate, 0MB figures should be used. 0MB currently suggests a rate of

10 percent for consistency. The inflation rate is needed to

determine future cost of inputs and the revenue from outputs; a differential rate of inflation for different commodities is also

input. (See Cost Categories Discussion.)

Percentages by weight for the different elements in the waste

stream should be given according to how much can be source separated and how much there is in total. If the particular

element such as ferrous metal is to be separated in a process, that

should be noted, and it should also be noted as to what percent of

the waste stream will be ferrous metal that is recoverable.

Residue is defined as anything that is not recoverable paper,

glass, or metal

.

Figures are generally available for Btu content of paper, but

the Btu value of residue (as defined above) and MSW as a whole may

vary from one area to the next.

The average price at the market for glass, paper, and metal is

the price received if the commodity is delivered directly to the

market, with the cost of haul figured separately. Average price means the expected price for that commodity in a known market,

allowing for slight fluctuations of market. If there are large

fluctuations of price due to recycling, it can be expected that source separation will cause a change in price given that price

which factors in any expected change.

The cost of collection includes only the cost up to the point

the truck is filled (or until the waste collected is hauled to be

processed). The source point is the central point of a community

which is considered the source of waste generated for that community

for the purposes of measuring distances. The cost of collection

can be considered the cost of getting the waste to that point from

where it will be hauled to the waste processing facility.

The incremental cost of source separation is the cost in

dollars per ton of pre-separated MSW. The cost of source separation includes the cost of source separation collection for paper,

glass, and metal if all of these, then the incremental cost of source separation should only include the cost of the items being source separated. The type of source separation program to be used

may affect cost significantly so it is important that the user choose a system of source separation before computing the cost.

For any source separation program to be successful, the public must

XII-3
be educated. This added cost should be included in the incremental

cost of source separation.

Sources are designated as belonging to one of three source separation categories:

1) No source separation

2) Routine source separation of paper, glass, and metal; or

3) Routine source separation with the separation of paper

dependent upon the price of paper.

At sources in the third source category above - separation - paper is burned only if the price for paper on the paper market

goes below a

" trigger" price which is specified by the user. This

trigger price system is described in detail in the Paper Market

Discussion below.

The price-dependent variation of the amount of paper that is source separated produces a hidden cost of recycling paper which

should be considered. While some paper may be recycled under the

trigger price system, the capacity of the facility must be potentially capable of accommodating all of the paper waste.

A ratio may be specified which indicates the extent to which

the costs of processing waste paper are generated by either actual or potential tonnage of paper processed. At the upper limit of

1.0, the ratio indicates that all of the cost of processing paper

comes from the actual amount of paper processed. At the lower

limit of 0.0, then the costs to the system arise from the maintenance of an unused potential for processing paper.

The cost of processing a ton of source separated paper is

calculated as the cost of processing a ton of source separated

paper in the same manner that a ton of MSW would be processed.

This cost of processing separated paper will probably be lower than

the cost of processing MSW for a number of reasons. Some of the

factors causing this lower cost are: greater compactabil ity , less

water content, ease of handling, etc. A ratio, or percentage, can then be calculated. For example, if it costs $9.00 to process a ton of separated paper as waste and $10.00 to process a ton of MSW,

then the ratio would be calculated as 9/10 - it costs 90 percent as much to process source separated paper as it does to process MSW.

This comparison between processing residue and mixed MSW is

essentially the same as the comparison between source separated

paper and MSW as described above. Of course, the ratio will

probably be different. It might even be the case that the cost of

processing residue will be larger than the cost of processing MSW.

Each user will probably calculate a different cost for processing

residue, depending on such factors as the composition of the

residue, the components that have been source separated, and the

effect of the source separation on the residue.

XII-4
Source

Source refers to where MSW is generated. MSW is, in fact,

generated by households, businesses, and industries. However, a source in the model is a conglomeration of these particular

sources - usually a town, a city, or a country. The area that is

being studied may be broken down into as many as sixty source

regions.

To identify each region, give it a name such as "Region #1."

An exact location of a source region should be given as a point in

the geographic or population center of the area, that can be used

for distance measurement purposes. This point is where all measurements are made from when considering the haul of MSW or source separated material to a processing facility or a market. Therefore,

it may be convenient to consider as the source point a point such

as a transfer station or the end of a collection route for a packer. The point chosen is considered, for the sake of the model,

as the point where all collection (and thus collection costs) end,

and where hauling (and thus all haul costs from the source) begin.

The area being considered by the model may be broken into as many

as 60 different sources, since that is the limit built into RRPlan.

It is suggested, however, that the user not use more than 30 sources.

The tonnage of MSW generated within a region is derived either

by multiplying population by per capita generation figures or from more accurate measures done by local sanitation authority.

The tonnage of MSW generated by a source region should be

stated in daily or annual terms, rather than per collection. The

amount collected per collection is of little use unless the frequency

of collections is known, so that an annual, monthly, weekly, or daily tonnage figure can be calculated.

The source may be offered options regarding source separation : 1) source separation will not be done; 2) source separation will

always be done for paper, glass, and cans; 3) source separation of

paper will depend on the price of paper in the market place. If

this option is chosen then paper will be burned for its Btu value

instead of being recycled when the paper price goes below a "trigger" price which is specified by the user. This trigger price

establishes a cut-off point above which paper is recycled and below

which it is burned.

More than one trigger price may be used. The number of

trigger prices must, be entered on a source information page. A

special section on the "Paper Market" is included below and dis- cusses this system of trigger prices in more detail.

The cost of hauling source separated glass, paper, and metal

is the cost per ton to haul these commodities to market. The most

efficient means of transportation should be considered, e.g.,

truck, rail or barge. The cost should be calculated as the total

XII-5
cost per ton to deliver to market considering the location of the

nearest market which can readily accept all of the glass, metal or paper which will be sent there. It is important to identify

markets for each of the source separated materials, and have a market for each source since there may be a different market for

different sources.

Cost Categories

Cost categories are RRPlan's method of accounting for

different costs. Every input that has a cost or a revenue (a

negative cost to a cost category) is associated with a cost

category under which that cost is classified. The output summary

of RRPlan reports all costs according to the different cost

categories.

The user must have at least two categories; one should be

operating cost and the other, capital costs. The user may define

any additional cost categories he wishes but each must be

designated as either a type of operating cost or a type of capital

cost. The user may want to use separate categories to divide

public vs. private costs or municipal costs vs. county or State

costs. The way they are divided does not affect the solution or

the summary of costs for the overall solution. The model does

however print the solution in terms of the cost categories for the

convenience of the user.

The user should assign a name and number to each category.

The user should then determine whether the category is an operating

or capital cost . Capital costs should be the costs of construction

or of large equipment. Operating costs include all revenues from

processes and everything not considered a capital cost. Maintenance

costs, cost of administration, salaries, etc. would all be con- sidered under operating cost.

For each type of category a differential inflation rate should

be given. The differential inflation rate is the difference

between the general inflation rate and the inflation rate for that

particular category given as either positive (greater increase in

prices), negative (a lower increase in prices, or a decrease) or zero (no difference from general inflation rate). This information

is needed to determine future costs in constant dollars, and to

give future current costs.

For capital cost categories, three additional questions must

be answered: useful life of the category, years to capitalization,

and the interest rate. The useful life of the category is the

length of time that the asset, whose cost is represented by this

category, will be useful to the owner for the purpose intended upon

purchase. An example is an incinerator which is expected to last

15 years; if it is assumed that in 15 years it will have to be

replaced, then the useful life is 15 years.

XII-6
The number of years to capitalize is the number of years

expected to pay off the loan, bond or whatever method was used to

borrow the money. The years to capitalize may be the same as or different from the useful life. The fewer years of capitalization

there are, the greater the per year cost, but interest cost will be

less. If useful life is longer than capitalization, the last years

of a facility will have very low costs compared to the years before

that.

The interest rate is the expected interest rate on the loan to

pay off this capital category. The interest rate may be a weighted

average of two or more interest rates, since there may be two or more loans used in a capital cost category. Two different loans

for one facility may be included in two different capital cost

categories.

Commodities

A commodity is defined by the model as the inputs and outputs

of processes. Commodities are the materials which are transported

between all geographical locations; anything which is hauled must

be defined as a commodity. Examples of input commodities are:

mixed MSW hauled in a packer or source separated residue hauled in

a trailer truck. Output commodities would be items such as: incinerated ferrous or steam. The commodities, just as the

sources, are numbered consecutively. The first five commodities

(numbered one through five) are determined by the model as:

1) mixed MSW hauled in a van (trailer truck);

2) mixed MSW hauled in a packer;

3) source separated paper hauled in a van;

4) source separated residue hauled in a packer; or

5) source separated residue hauled in a van.

These are all input commodities which are hauled from a source

to a process. All other commodities will be defined by the users,

most of these will be output commodities from a process to another

process or to a market. For example, the commodity "MSW hauled in

a Packer" may be the input at a particular process such as an incinerator. Three output commodities may be the result of the

incineration process 1) "Steam", 2) "Incinerated Ferrous", 3)

"Incineration Residue". These three commodities would be sent to

three different places, two to markets and one would go to another

process. "Steam" would be sold to a factor nearby, "Incinerated

Ferrous" would be hauled to a market and sold as ferrous scrap,

"Incineration Residue" would be hauled to a landfill process to be

buried.

XII-7
For each commodity the user must give the cost to haul that

commodity. The cost of haul can be given in two ways, cost per ton

mile, and cost per ton to haul between two locations.

The cost per ton mile will be the cost to haul a commodity

anywhere within the region for some constant rate divided by tons

and miles. If it cost $100 to haul ten tons of a commodity ten

miles then the cost would be $1.00 per ton per mile. When the

costs are given as per-ton-mile, the costs should be fairly

consistent throughout the area for hauls from one location to

another. Also when using the per-ton-mile haul cost method the user must specify the mode of transportation since the cost

per-ton-mile will vary with the size and type of vehicle used.

Some examples of specifying a mode of transport are the first five

commodities defined by the model. They specify transport by a packer or a trailer van since the haul cost for MSW or residue will

be different for each vehicle. Some examples of user defined

commodities would be "ferrous metal in a rail car" or "glass cullet

in a trailer truck." It is not necessary to specify the mode of

transport if there is only one.

The cost of haul per ton between two locations is the cost in

dollars per ton to haul from a source or site to a market or site.

The mode of transport is considered to be the most efficient way of

transporting the commodity between the two locations, the user need

not specify the mode of transport. The user merely has to specify

the source or site where the commodity is to be hauled and then

give the cost per ton to haul between these two points. An example

of this method is the following: the commodity "Incinerated

Ferrous" will be hauled from "Incinerator A," a process site to a market, "Rusty's Recycled Metal." The most efficient method of

transport is by rail to that market and the cost is $50 a ton. The user would therefore list the process site, the market it goes to

and the cost $50 per ton to haul between those two points. If the

commodity "Incinerated Ferrous" is being produced as an output at

another incinerator called "Incinerator B" and that the commodity

is being sold at "Daedlus" Scrap Metal and Wing Maker." Also, it

is determined that the most efficient mode of transport is by truck

and that the cost for the haul between these two locations, which

are closer together than the two in the first example, is only $25.

The user would list on the commodity sheet for "Incinerated Ferrous"

the two new locations and the cost for haul between them.

The user must give haul costs for the first five commodities

defined by the model unless they are not to be used, in which case

the haul costs are set at zero. The user may define up to fifteen

additional commodity categories. The other limitations on com- modities are the following: all processes at a particular location

must receive only one commodity as input; each process may output

as many as seven commodities; each market may receive only one commodity.

Paper Market

Source separated paper does not go to a process. Therefore,

market information for source separated paper should be entered

XII-8
separately from the other markets since it is treated differently

than other markets. Paper can be either sold for its fiber or

burned for its Btu value. The market for recycled paper determines

whether paper is recycled or not.

A price frequency distribution is how often the price of paper

fell within a certain interval of say $10 - $15. To draw up the

.distribution, define, for example, 3 intervals: $5 - $10, $10 - $15, $15 - $20, with $5 being the lowest price of paper. If the

price of paper for the last 2 years fell between $5 and $10 thirty

percent of the time and in the other 2 intervals thirty-five

percent of the time each, then that would be the price frequency

distribution.

Sites and Processes

Process refers to a generic type of facility, such as a landfill, incinerator, transfer station, etc. used to process solid

waste. Different operating and capital costs are associated with

different size facilities. The user should define four different

size facilities which are in general use, a minimum, two medium and

a maximum sized facility. Capital and operating costs should then

be given for each size. For example, the process waterwall incinerator may have sizes of 250, 500, 750, and 1000 tons per day,

representing the smallest, intermediate, and largest WW incinerators.

The operating and capital costs would be different for each size

facility. These different costs are used to make a cost curve for

operating cost and one for capital cost for each facility being

considered. The curve will give us the costs of each facility for

all the sizes within the intervals between four sizes defined by

the user.

The user must always define the first process as a new transfer

station which will be considered for all sources.

A site is the physical location where the processing of waste

occurs. More than one process may occur at each site.

Location of Site

Location is the exact address, or physical location of the

site. This is needed for the measurement of distances to and from

the site.

Site Preparation Costs

These costs are those incurred when preparing the site for a facility. They include roads, fences, land developed where the

facility would be, etc. They do not include the construction of

the facil i ty

.

Process Revenues

Revenues which are realized within the facility as well as from the sales of certain process related outputs are process

XII-9
revenues. For example, if an incinerator produces steam to

generate electricity to sell and also uses the steam to heat the

facility, the savings in heating costs is considered a process

revenue. For example, if steam could be used to generate

electricity which was fed into the grid, it would not be necessary

to define a separate commodity and market representing the sale of

the electricity produced.

Years to Capitalization

This is the number of years to capitalize the loan used to

have a facility at a site.

Remaining Useful Life

The number of years that the facility will remain functional

at a particular site is the remaining useful life.

Interest Rate

Interest rate is the rate of interest being paid on the loan

for a facil i ty

.

Landfill

If a landfill exists at the site (or is proposed) the information

required about it is:

1) The acre-feet of space remaining which can be used.

2) The amount of land used per ton of input. (In acre-feet)

Input

There is an input associated with each process. This input is

what is delivered to the facility to be processed. For a transfer

station, the input would be MSW in a packer; for an incinerator the

input could be MSW in a van, source separated residue, etc. Only

one commodity may be input into each process.

Outputs

Outputs from each process are the commodities which result

from processing. For each output, there is an output coefficient.

This coefficient is the ratio of the output from the process to the

input to the process. For example, incinerated ferrous is an output of incineration; then the output coefficient is equal ratio

to the incinerated ferrous in tons resulting from the incineration;

of a given number of tons of MSW input. For each output, there

must be an output coefficient. There may be as many as two outputs

from a process.

XII-10
Market

A market is a place where an output of a process, a commodi ty , is sold. An example of a commodity would be steam, which would be

output from an incinerator; the incinerator is a process. The

market would be, perhaps a factory located near the incinerator.

The firm that owns the factory is the name of the market . The

address is the exact location of the market.

A market is unl imited if the market will accept any amount of

the commodity which is produced; a limited market will only buy a certain amount of a commodity. A 1 imited market is often a declining price market . A declining price market is one where the

price per unit falls as the number of units increases toward the

limit of the market. For any market with a declining price, such

as steam, a price schedule should be provided which describes the

decreasing price.

A fixed price market is one where the price is the same regardless of the level of output. The price may be fixed even though the market is limited. In this case, the price would be the same even as the output of the commodity reached the market limit.

A commodity may be produced for more than one market. A

market that receives more than one commodity must have a questionnaire filled out for each commodity that the market receives.

An example would be a company that accepts both steam and residue

from a process.

A user needs to explain all sites from which the commodity is

coming to that market. For example, if the market is for incinerated

ferrous, then specify all sites that are offered incinerators as a process and might therefore sell ferrous to that market.

Capacity Limit

The capacity limit is the absolute maximum amount of input

which can be processed in a year by a facility at a specific site.

This does not have to be at the end of an interval, but can be

within it. The number should be in kilotons per year.

Energy Options

If the user wants to use one of the two energy modes in

RRPlan, either maximize net energy or optimize a linear combination

of cost and energy, he must input energy requirement information.

The easiest way of collecting the required data is to collect the

information along with the cost information. Every activity that

requires a dollar cost will probably require an energy expenditure.

For example, all haul cost information, collection, and source separation require an energy cost. All energy costs should be in

millions of Btu's. Aside from explicit activities in the model

XII-11
there are energy savings from recycling paper, glass and metal,

since the recycling process uses less energy. The savings in

energy should be noted for each of these.

As for steam or heat energy released during processing, an energy value in millions of Btu's should be provided for each

process showing the energy which is recovered from the waste

stream.

Complete details can be found in Publication List 96 and 98.

XII-12
APPENDIX XIII . TENTATIVE AGREEMENT FOR JOINT RESEARCH JAPAN —

UNITED STATES

(Period December 1981 to October 1982)

Both sides agree to pursue Item (1) proposed by Japan and Item

(2) proposed by U.S. to fullest extent possible:

(1) Gasification of Refuse Derived Fuel (Ebara Corporation)

AIST has been carrying out R&D involving dual fluidized bed

gasification of the organic (plastic rich) portion of municipal

refuse by operating a pilot plant at Yokohama, Kanagawa Prefecture,

since 1973. The entire task has been carried out by Ebara Corporation under contract. This research is scheduled to be completed by

the end of FY 1982 (March 31, 1982).

The U.S. is currently producing RDF from municipal refuse for

possible use as substitute or supplemental fuel. If RDF could be

converted into high quality gas in an efficient and economical

manner, some beneficial application might be found, e.g., better

market opportunities for waste-to-energy applications. Additionally, unwanted substances which are emitted by RDF in the course of its incineration may possibly be eliminated by gasification of RDF. It may be worthwhile to analyze the compositions of

gas and other substances produced by the pyrolysis.

The experiment can be carried out at the said pilot gasifier

in Yokohama. A specified amount (20 to 100 U.S. tons) of RDF will

be transmitted to Japan for this purpose upon request of Japanese

side. Data will be analyzed both in Japan and the U.S.

(2) Econometric models describing the market potential for various

forms of recycled materials and energy from waste have been

developed in the U.S. These models provide a basis for

selecting the optimum resource recovery strategy for a region

in terms of:

o Markets available for the products

o Technology selection

o Size of plant

o Transportation network

o Refuse supply

o Costs and revenues over the lifetime of the project

The data required for carrying out this analysis include:

XIII-1
o Specifications for the products to be sold, e.g.,

heat value, residues produced, pollution properties,

quantity produced per input ton of refuse

o Size of plant

o Efficiency of plant

o Requirement of plant for energy and other operating

costs

o Requirement of plant for labor

o Capital cost of plant

o Lifetime of plant

o Required treatment, if any, of input refuse

o Type and amount of emissions and residues from plant

The U.S. undertakes to carry out market potential studies in

several areas of the United States for any and all sets of data

provided by Japan. Mutual benefits will be:

o Japan learns if the processes and products being

produced can be marketed in the U.S. profitably.

o Japan learns direction for further research to

improve processes and products in terms of

marketability in the U.S.

o U.S. learns whether Japanese technology can aid in

dealing with solid waste management problems in

various regions of the United States.

Both sides agree to further consider the attached lists of

possible research items for possible action at a later time.

XIII-2
PROPOSED BY JAPAN

Possible Joint Research Items

(Jap. Gov. Institutes)

1. Combustion Studies of RDF or Other Solid Fuels

(Gov. Ind. Dev. Lab., Hokkaido, AIST)

There is a 25 cm square fluidized bed combustion reactor

now under test operation. Utilization of combustion heat by

heat exchange is studied here.

In response to the U.S. proposal (3), physicochemical

phenomena of combustion can be studied and some thermokinetic

data may be obtained. RDF, coal, and other organic waste, or their mixtures can be burnt in the reactor and emissions such

as HC1, NH 3 , CO, C0 2

, and hydrocarbons can be monitored.

2. Utilization of Ash Residues from an Incineration Plant

(National Chem. Lab. for Ind., AIST)

Treatment of ash residues from an incineration plant of

municipal refuse is an important issue from the view point of

reducing the environmental burdens and economically sound

methods to reuse such ashes need to be found. Research

involves effective classification of constituents in the ashes

and utilization process development on reclaimed substances as well as effective design of the incineration system.

3. Acid Hydrolysis of Cellulose Materials

(The same lab. as the above.)

It is necessary to find the most economical process which

would convert waste or low cost biomass into ethanol . Enzymatic

or acid hydrolysis process is first required to convert the

cellulose fraction of raw material into glucose.

A two-stage batch reactor of acid hydrolysis originally

designed is going to be examined.

XIII-3
PROPOSED BY UNITED STATES

Possible Joint Research Projects

1. Dusts created by the electric furnace process for the production of steel contain valuable metal units . Economically

sound methods to recycle such dusts on furnace-by-furnace

basis need to be found. Research involves particle identification, classification and design of a system to separate out

desired constituents.

2. Mill scales and sludges created by rolling processes in the

steel industry need to be doiled for reclamation of metal

units . Research involves characterization of such wastes and means to reclaim oils and/or energy plus metal units. Thermal

and chemical processes need to be compared.

3 . Combustion products created by burning refuse or mixtures of

fossil fuels and refuse derived fuels need to be studied in

order to prevent unwanted emissions, e.g., dioxin, and to

provide for most efficient firing characteristics. Research

involves setting up on-line monitoring for unwanted emissions

and determination of basic thermokinetic data on the firing

process. For example, co-firing of coal with refuse derived

fuel reduces SO emissions drastically. The mechanism for this

process should be deduced in order to optimize use of coal RDF

mixtures for power boilers.

4. More economical means of recycling plastics from mixed wastes

are needed. The Japanese are ahead of U.S. on the technology

to do so. Joint research on new uses for waste plastics could

be beneficial to the U.S.

5. The corrosion propensities of refuse and various forms of

refuse derived fuels need to be studied. Joint research could

aid in assuring that the potential for downtime or even failure of very expensive capital equipment is minimized.

Contact for Japan: S. Suzuki

AIST

Contact for U.S. : H. Yakowitz

NBS

XIII-4
APPENDIX XIII. GASIFICATION OF REFUSE DERIVED FUEL IN A

PAIRED FLUIDIZED BED PYROLYSIS UNIT

Results developed as part of the scientific exchange

program of the respective governments of Japan and the United States

Prepared cooperatively by the Agency of Industrial Science and Technology,

Ministry of International Trade and Industry, Government of Japan,

Ebara Corporation, Japan (acting for the Government of Japan),

and the National Bureau of Standards

Text prepared under the direction of Mr. S. Suzuki (AIST)

Text edited by Dr. Harvey Yakowitz (NBS)

XIII-5
Foreword

As part of the scientific interchange program initiated by the

United States Government and the Government of Japan, the Department

of Commerce was selected by the White House to be the pilot agency

for a project concerned with resource recovery from discards

originally destined for waste. Such discards include municipal

waste and industrial waste. Under terms of the agreement signed by

the President and the Prime Minister on May 2, 1980, the United

States and Japan will exchange small teams of government scientists

in order to examine resource recovery in the respective countries

and to formulate possible joint research ventures.

The Office of Recycled Materials of the National Bureau of

Standards (NBS/ORM), which was charged with fulfilling the duties

assigned to the Secretary of Commerce by Subtitle E of the Resource

Conservation and Recovery Act as ammended (P.L. 94-580; PL 96-482)

was designated as the U.S. contact point for this project. The

Japanese team visited the U.S. in December, 1981; NBS/ORM arranged

the itinerary and provided technical briefings and an overview of resource recovery activities. At that time, NBS/ORM and Japanese

representatives concluded an agreement for joint research to be

performed as part of the project. The text is as follows:

AGREEMENT FOR JOINT RESEARCH JAPAN-UNITED STATES

Both sides agree to pursue item (1) proposed by Japan and item

(2) proposed by U.S. to fullest extent possible:

(1) Gasification of Refuse Derived Fuel, RDF (Ebara Corporation)

AIST has been carrying out R&D involving dual fluidized bed

gasification of the organic (plastic rich) portion of municipal

refuse by operating a pilot plant at Yokohama, Kanagawa Prefecture,

since 1973. The entire task has been carried out by Ebara Corporation under contract. This research is scheduled to be completed by

the end of FY 1982 (March 31, 1982).

The U.S. is currently producing RDF from municipal refuse for

possible use as substitute or supplemental fuel. If RDF could be

converted into high quality gas in an efficient and economical

manner, some beneficial application might be found, e.g., better

market opportunities for waste-to-energy applications. Additionally,

unwanted substances which are emitted by RDF in the course of its

incineration may possibly be eliminated by gasification of RDF. It

may be worthwhile to analyze the compositions of gas and other

substances produced by the pyrolysis.

The experiment can be carried out at the said pilot gasifier

in Yokohama. A specified amount (20 to 100 U.S. tons) of RDF will

be transmitted to Japan for this purpose upon request of Japanese

side. Data will be analyzed both in Japan and the U.S.

XIII-6
(2) Econometric models describing the market potential for various

forms of recycled materials and energy from waste have been developed

in the U.S. These models provide a basis for selecting the optimum

resource recovery strategy for a region in terms of:

o Markets available for the products

o Technology selection

o Size of plant

o Transportation network

o Refuse supply

o Costs and revenues over the lifetime of the project

The data required for carrying out this analysis include:

o Specifications for the products to be sold, e.g., heat

value, residues produced, pollution properties, quantity

produced per input ton of refuse

o Size of plant

o Efficiency of plant

o Requirement of plant for energy and other operating costs

o Requirement of plant for labor

o Capital cost of plant

o Lifetime of plant

o Required treatment, if any, of input refuse

o Type and amount of emissions and residues from plant

The U.S. undertakes to carry out market potential studies in

several areas of the United States for any and all sets of data

provided by Japan. Mutual benefits will be:

o Japan learns if the processes and products being produced

can be marketed in the U.S. profitably.

o Japan learns direction for further research to improve

processes and products in terms of marketability in the

U. S.

o U.S. learns whether Japanese technology can aid in dealing

with solid waste management problems in various regions

of the United States.

Both sides agree to further consider the attached lists of

possible research items for possible action at a later time.

XII 1-7
PROPOSED BY JAPAN

Possible Joint Research Items

(Japanese Government Institutes)

1. Combustion Studies of RDF or Other Solid Fuels (Government

Industrial Development Laboratory, Hokkaido, AIST).

There is a 25 cm square fluidized bed combustion reactor now under test operation. Utilization of combustion heat by heat

exchange is studied here.

In response to the U.S. proposal (3) (see overleaf) physicochemical phenomena of combustion can be studied and some thermokinetic data may be obtained. RDF, coal, and other organic waste,

or their mixtures can be burned in the reactor and emissions such

as HC1, NH 3 , CO, C0 2 , and hydrocarbons can be monitored.

2. Utilization of Ash Residues from an Incineration Plant

(National Chemistry Laboratory for Industry, AIST).

Treatment of ash residues from an incineration plant of

municipal refuse is an important issue from the viewpoint of

reducing the environmental burdens, and economically sound methods

to reuse such ashes need to be found. Research involves effective

classification of constituents in the ashes and utilization process

development on reclaimed substances as well as effective design of

the incineration system.

3. Acid Hydrolysis of Cellulose Materials

(The same Laboratory as 2. above.)

It is necessary to find the most economical process which

would convert waste or low cost biomass into ethanol. Enzymatic or acid hydrolysis process is first required to convert the cellulose

fraction of raw material into glucose.

A two-stage batch reactor of acid hydrolysis originally

designed is going to be examined.

XIII-8
PROPOSED BY UNITED STATES

Possible Joint Research Projects

1. Dusts created by the electric furnace process for the productionof steel contain valuable metal units . Economically sound

methods to recycle such dusts on furnace-by- furnace basis need

to be found. Research involves particle identification,

classification and design of a system to separate out desired

constituents.

2. Mill scales and sludges created by rolling processes in the

steel industry need to be doiled for reclamation of metal units . Research involves characterization of such wastes and means to

reclaim oils and/or energy plus metal units. Thermal and

chemical processes need to be compared.

3. Combustion products created by burning refuse or mixtures of

fossil fuels and refuse derived fuels need to be studied in

order to prevent unwanted emissions, e.g., dioxin, and to

provide for most efficient firing characteristics. Research

involves setting up on-line monitoring for unwanted emissions

and determination of basic thermokinetic data on the firing

process. For example, co-firing of coal with refuse derived

fuel reduces S0

x emissions drastically. The mechanism for

this process should be deduced in order to optimize use of

coal RDF mixtures for power boilers.

4. More economical means of recycling plastics from mixed wastes

are needed. The Japanese are ahead of U.S. on the technology

to do so. Joint research on new uses for waste plastics could

be beneficial to the U.S.

5. The corrosion propensities of refuse and various forms of

refuse derived fuels need to be studied. Joint research could

aid in assuring that the potential for downtime or even failure

of very expensive capital equipment is minimized.

Contact for Japan: S. Suzuki

AIST

Contact for U.S.: H. Yakowitz

NBS

NBS/ORM arranged to ship to Japan about 35 tons of fluff RDF

produced at the Baltimore County, MD resource recovery facility.

This material arrived in Japan in early November, 1982.

In accord with the foregoing agreement, this RDF was gasified

in a pilot scale resource recovery plant in Yokohama. The results

of this gasification experiment are described in this NBS Special

Publication. The text, as received from the Agency of Industrial

Science and Technology of the Japanese Ministry of International

Trade and Industry, was edited by Dr. Harvey Yakowitz, Chief,

NBS/ORM.

XIII-9
Special thanks are given to the Text-Editing Facility of the

National Measurement Laboratory of NBS for preparation of the final

version of the report.

i

XIII-10
Abstract

The refuse derived fuel (RDF) produced at the Baltimore County

Resource Recovery Plant and provided by NBS to the Government of

Japan was gasified in a paired-bed pyrolysis unit, i.e., a fluidizing

medium (sand) was circulated between a pyrolysis reactor and a combustion reactor. Thus, pyrolysis and combustion occur separate

from one another; hence, the name "paired-bed."

The gas refining equipment consists of two chains, one for

pyrolysis gas and the other combustion exhaust gas:

1. A cyclone separates char from the gas coming from the

pyrolysis pyrolysis reactor. This char is fed to the

combustion reactor for burning. After the gas passes

through a heat exchanger and is quenched in a carbon

deposit protector, a tar-separator removes oil mist and

the gas is cleaned in a scrubber. A small portion of

this clean gas is pressurized by a blower, preheated in a heat exchanger and used to fluidize the pyrolysis reactor

bed; the remaining gas is sent to a tank for storage.

2. The exhaust gas generated by the combustion reactor is

discharged into the atmosphere after being treated by means of a two-stage cyclone and electric dust precipitator. The non-combustible substances contained in the

feed stock are discharged from the bottom of the combustion tower periodically.

The RDF was fed into the system at a rate of 0.6 to 1.0 tonnes

per hour. The pyrolysis reaction temperature was about 650 °C. The

following ultimate analyses were performed: (N.B. "T" is "Trace")

1. Feedstock

a. Main components

C, H, N , CI, Na, K, Ca, Ash.

b. Harmful components

Cu, Pb, Cd, T-Hg, As, T-Cr, Al.

c. Heat value

2. Pyrolysis gas components

a. Main components

H

2 , 0

2 , N2

, CH

4

, CO, C0

2

, CmHn.

b. Harmful gas components

HCl,'2H 0 S, NH., HCN, SO , NO . 4' ' x' x

c. Heat value

XIII-11
3. Flue gas

a. Main gas components

0 2 , N2 , CO, C0 2

.

b. Harmful components

S0

x , N0

x

, HC1, dust.

4. Ash

a. Main components

C, H, N, S, CI, Na, K, Ca.

b. Heavy metals

Cu, Pb, Cd, T-Hg, As, T-Cr, Al , etc.

5. Waste water

a. Main components

pH, EOD, COD, SS, n-Hex, Phenol, NH* Cl~ , CN~ , etc.

Results of the experiment include descriptions of:

o Gas and energy recovery rate.

o Evaluation of the data from public nuisance standpoint,

o Cost estimation.

From these results, the total process flowsheet for a commerical

plant, including pretreatment system was deduced. Thus, the final

output allows assessment of the commercial feasibility of the

paired fluidized bed pyrolysis unit under pilot plant conditions.

Key Words: Baltimore County (MD) Resource Recovery Facility,

Cooperative Research ( Japan-U. S. ) , pilot plant scale-up for resource recovery from waste destined for disposal, pyrolysis of refuse

derived fuel, refuse derived fuel gasification, solid waste management, waste-to-energy systems.

o Heat and material balance.

o Final economics.

XIII-12
Gasification of Refuse Derived Fuel in a

Paired Fluidized Bed Pyrulysis Unit

Report Completed

March 31, 1983

Received at NBS

April 11, 1983

Agency of Industrial Science and Technology,

Ministry of International Trade and Industry,

Government of Japan

In cooperation with Ebara Corporation, Japan

This work described in this report and the gasification

experiment were carried out in response to the--Tentati ve Agreement

for Joint Research Japan-United States, December, 1981.

XIII-13
CONTENTS

1. Background

2. Introduction

(1) Outline of Stardust '80

(2) Process flow of pyrolysis system

(3) Experiment

(4) Schedule

(5) Operating conditions

3. Experimental results

(1) Properties of products and residues

(2) Mass and heat balances

(3) Utilities

4. Implications of Scale-up to commercial plant size

(1) Process and scale

(2) Predicted gas and energy recovery rates

Figures

XIII-14
1. Background

The Agency of Industrial Science and Technology (AIST) in the

Japanese Ministry of International Trade and Industry (MITI) has

been a strong advocate of the National Resource Recovery System R&D

program since its inception in 1972. In 1978, as the final phase

of this program the pilot scale plant "Stardust '80" was constructed

in- Yokohama. Since 1979, many demonstration operations including

several periods of long-term operation, mostly using municipal

solid wastes from Yokohama as input material, have been performed

successful ly.

The goal of the program was to develop and demonstrate resource recovery methods and equipment which would represent best possible

technology for pollution control, safety and maintenance, which

would also allow for economically efficient recovery of resources. This goal has been largely achieved; the technology which has been

developed is now ready for commercialization.

Nevertheless, the location and profitable exploitation of

suitable markets for the recovered resources is the next challenge

which must be dealt with satisfactorily. The viability of a resource recovery system is largely dependent upon market capacity and

selling price of the recovered resources. Thus, part two of the

tentative agreement for joint research, Japan--Uni ted States

(December, 1981) calls for the application of National Bureau of

Standards resource recovery marketing and planning models.

.2. Introduction

(1) Outline of Stardust '80 Yokohama Plant

"Stardust '80 (Yokohama Plant) was operated in the

fiscal year 1979-1980 1 as a materials recovery prototype

system meant to recycle such useful resources as compost,

pulp, fuel gas and light-weight aggregates from municipal

refuse. (Material Recovery System -MRS- operation).

Since April, 1981, energy recovery systems have been in

operation— in both Yokohama and Tokyo-- to recover methane

gas and fuel oil. (Energy Recovery System--ERS—operation).

Fact Summary for Two-Bed Pyrolysis Gasifier

of Stardust '80 Yokohama Plant:

Openi ng: May 1979

Principal

s

Agency of Industrial Science and

Technology MITI (Owner)

Designer and Operator: Ebara Corp.

Vol ume: Design and actual; 24,000 kg per day in three shifts

The fiscal year in Japan begins on April 1.

XIII-15
Technol ogy Pyrolizer, dust collector, heat exchanger, gas

refiner and waste water treatment plant.

Products: Fuel, gas, electricity and steam.

Cost: $3 Million (1978 basis).

(2) Process flow of pyrolysis system

The pyrolysis gasification system consists of a pyrolysis

reactor and combustion reactor. A fluidizing medium (sand) is

circulated between two towers; the system is designed to perform

pyrolysis and combustion separately, for which reason it is called

"Two-Bed Type Pyrolysis."

Figure 1 shows the process flow. The input stock material is

fed into the pyrolysis reactor, and the fuel gas generated by

pyrolysis reaction is sent into the gas holding chamber after

undergoing char-separating, heat-exchanging and gas cleaning

processes. A portion of the resulting gas is recycled to the

reactor for utilization as fluidizer gas.

Meanwhile, the char (carbonized substances) generated in the

reactor is sent together with the sand to the combustion reactor,

where air is blown in to aid combustion. The remaining char, which

accompanies the pyrolysis gas, is intercepted and separated by means of a two-stage cyclone. The material is also burned in the

combustion reactor, where its energy contribution is utilized as a source of heat. The resultant energy generated by combustion is

transferred to the sand, which is then recycled to the pyrolysis

reactor.

The pyrolysis gas passing through the heat exchanger is

cleansed of oil, precipitated carbon bearing particles and noxious

gases by means of a spray tower and a scrubber. The scrubbing

water is sent to the waste water treatment unit where, after removal

of harmful substances, it is discharged into the local sewer system.

All of these operations are controlled by means of a centralized

system.

The exhaust gas generated by the combustion reactor is discharged into the atmosphere after being treated by means of a two-stage cyclone and an electrostatic precipitator. The non- combustible substances contained in the input stock material are discharged from the bottom of the combustion reactor periodically.

Features of Main Equipment Components

(i) Stock Material Feeder

The RDF is sent to the input stock material feeder (screw

type) from the storage silo by means of a constant rate feed

mechanism: the stock material feeder is of the solid-overflow type

so that the stock material usually can be kept at a constant level.

No bridging problems have been encountered to date with this

system.

XI I 1-16
The feeder unit has two- stages with a taper- type feeder

followed by a straight- type feeder which prevents gas leakage and

also prevents the stock material from being cracked at a low temperature. Therefore, even plastics, which previously were difficult to introduce properly, can be inserted very smoothly and at

a constant rate.

(ii) Reactor Body

The pyrolysis reactor and the combustion reactor are connected

by two pipes, which allows the fluidizer sand to circulate between

the two reactors. The temperature of the fluidizer sand, which has

undergone some reduction due to the endothermic thermal cracking

reaction occuring in the pyrolysis reactor, is sent to the sand

ejector together with whatever char is simultaneously formed. This

char reacts with the air stream introduced to blow the sand up to

the combustion reactor for burning; thus, the temperature of the

sand is raised. This hot sand is circulated back into the

pyrolysis reactor.

The sand circulation rate can be controlled satisfactorily by

merely injecting a small amount of air into the ejector section.

During operation, sand circulation rates ranging from 20 to 30

tonnes per hour have been maintained. In addition, the difference

in temperature between the upper and lower parts of the fluidized

bed can be stabilized to within ±2 °C, thus providing for a very

stable thermal field. The resultant pyrolysis gas has exhibited

high uniformity with few fluctuations in composition.

Incombustibles in the input stock material can be easily

separated and discharged by means of the air classifier stream.

The small amount of sand which is discharged along with these

incombustibles can be reintroduced into the combustion reactor

after the separation is accomplished.

(3) Experiment

An RDF gasification experiment was performed under the following conditions;

Place: Two-Bed Pyrolysis Gasification Subsystem

in Stardust '80, Yokohama Plant.

(Yokohama City, Kanagawa Prefecture)

Time: November 9-11, 1982

Stock

material

:

RDF (fluff) - 33.5 metric tons. Produced in Baltimore

County's Resource Recovery Facility, in Maryland, USA.

This material was provided through the National Bureau

of Standards. The entire amount was disposed via

gasification during the above mentioned three-day period.

XIII-17
(4) Schedule

On October 28, 1982, 33.5 tonnes of RDF were received and

placed in the storage pit of the Stardust 80 resource recovery

pilot plant. This RDF was confirmed to be in good condition (no

fermentation), despite the long transit time between the U.S. and

Japan.

A pyrolysis gasification experiment was carried out for three

days as follows:

November 8 Heat-up operation of reactor bodies

9-11 Pyrolysis gasification experiment

11 Blow- down operation

(5) Operating conditions

1 lists important operating parameters for this experiment.

Table 1

RDF feed rate 700 - 1200 kg/hr

Pyrolysis reaction temperature 640 - 680 °C

a

Combustion reactor temperature 700 - 740 °C

Both reactors maximum pressure 600 - 1000 mmAq-gauge

Fluidizer sand circulation rate 25 - 30 tonnes 1 hr

This range has been found to include the most suitable temperature

for recovering energy from refuse.

3. Experimental Results

(1) Properties of products and residues

(a) Pyrolysis product gas

Table 3 lists the concentration of the pyrolysis gas recovered

in this experiment, and figure 2 shows the relation between pyrolysis

reaction temperature and gas composition produced from RDF.

The maximum calorific value of the pyrolysis gas from the U.S.

RDF was equal to the that of the gas produced by the MSW of

Yokohama City. Pyrolysis gas yield is about 0.5 Nm3 /kg-dry RDF in

the temperature range 650 °C to 670 °C; higher temeratures yield

more H2 , CO and CH 4 rich gas and less C02 rich gas.

The pyrolysis gas contains several potentially harmful gases.

Table 4 shows the concentrations of such gases before and after

scrubbing of the pyrolysis gas. These potentially harmful gases

XIII-18
can be minimized by alkali cleaning and water cleaning. The

product gas can then be used in power plants and other industrial

applications where medium BTU clean fuel gas would be economically

advantageous.

(b) Exhaust gas

Table 5 lists the components and concentrations of the com- bustion reactor exhaust gas along with the values specified as standards for incinerator exhaust gas in Japan. The concentrations

of the potentially harmful gases without gas cleaning and without

additives for the elimination of HC1 are lower than the incinerator

exhaust standard values. Moreover, the results confirm that the

present system contains intrinsic 1 ow-NOx-produci ng capabilities.

This capability occurs, in our view, because the temperature of the

combustion reactor is lower than that of conventional incinceration

systems.

Therefore, water was added to the RDF in order to increase its

bulk density, and the RDF moisture content was thus raised to 35%.

With regard to HC1 gas concentration, satisfactorily low

levels were maintained without adding the HC1 gas absorbent Ca(0H) 2. Amounts of heavy metals are also satisfactorily low. Most of the

heavy metals in the RDF reported to the ash.

(c) Ash

Tables 6 and 7 respectively list the ash components and extraction procedure test results for the ash collected by the cyclone

and the electrostatic precipitator. Since the content of heavy

metals in the Baltimore County RDF is low, most of the heavy metals

reported to the ash. Each of the heavy metal values as determined

in this experiment satisfies Japanese Government mandatory requirements.

The ash ignition loss in weight is 1.9%; no unburned residue

could be found in the incombustibles discharged from both reactors.

(b) Waste Water

Table 8 lists the properties of raw and treated waste water

resulting from this experiment. The waste water treatment system

employs various physical-chemical treatments such as oil/water

separation, solid/liquid separation, stripping, filtration,

activated carbon adsorption, etc. The raw waste water has some organic contaminants (see BOD and COD) that exceed 1 percent, but

the concentrations of the heavy metals fully satisfy the standards

for Japan even in the raw waste water.

As a result, the treated water easily satisfies the requirements

set forth in the Kanagawa Prefecture Sewage Ordinance. This water

was therefore discharged to the local sewer system.

XIII-19
Table 2 lists the composition of the RDF provided for use in this experiment

Table 2. Composition of RDF

RDF

Moisture content

3 % 14 ~ 20

Bulk density t/m3 0.07 ~ 0.09

Calorific value Kcal/Kg 4650 (gross); 8370 BTU/lb

3690 (net); 6640 BTU/lb

r 38. 6%

un 5 7%

Ul timate 0 44. 1%

analysi s N 0 8%

S 0. 17%

CI 0 23%

Ash 9 8%

Paper 66. 7%

Texti le 21. 3%

PI astics 9. 3%

Composition Yard waste 2. 2%

Metals 0. 5%

Glass 0%

Garbage 0%

An inclined vibration conveyor, which is incorporated in the refuse

transfer line which was intended to carry the RDF from the storage

pit to the gasification site refuse silo, could not be used to

transfer the RDF (bulk density: 80hg/m3

) because this conveyor is

designed to deal with much heavier refuse (bulk density: around

250hg/m3

).

XIII-20
Table 3. Properties of pyrolysis product gas

Component

H 2

N 2

CH4

CO

C02

C 2 H4

C 2 H 6

C3

- Hydrocarbons

C 4

- Hydrocarbons

Calorific

val ue

kcal

Nm3

concentration (%)

15.3 - 16.2

1.9 % 3.9

12.9 16.2

32.0 ~ 34.6

17.5 22.9

4.5 ^ 6.0

2.8 ~ 3.0

3.3 * 3.7

1.3 <v 2.0

5450 ~ 5850 (gross)

5020^5400 (net)

* 610--655 Btu/ft3 ** 560--605 Btu/ft3

Table 4. Potentially harmful gas phase constituents in product gas

Components

H 2 S

SO

x HCN

NH3

HC1

NO

Before

scrubbi ng

520

230

711

142

790

Not detected

After

scrubbing

150

<10

14

<10

16

Not detected

unit: ppm

XIII-21
Table 5. Properties of exhaust gas

Inci nerator

Concent- exhaust

ration standard value

o

2 7.5%

Main gas N

2 81.4%

CO2 11. 1%

HC1 152 ppm <430

Harmful NOx 76 ppm <250

gas SOx <10 ppm <300a

Soot dust 0.06 g/Nm3 <0.1

Cd <0. 01 mg/Nm3 <0. 5

Heavy Metals etc. Pb 0.37 mg/Nm3 <10b

Cu 0.15 mg/Nm3

T-Cr 0.02 mg/Nm3

T-Hg <0.01 mg/Nm3

As <0.01 mg/Nm3 a Stipulated K value (K = 1.17).

General smoke emission standard values.

Table 6. Ash components

Concent- Concent- ConcentComponents ration (%) Components ration (%) Components ration (ppm)

C 1.1 Na 2.3 Cu 840

H <0.3 K 1.1 Pb 84

N <0.3 Ca 0.32 Cd 6

S <0.03 Al 5.9 T-Hg 0.01

CI 0.28 Ignition T-Cr 120

loss in 1.9

weight As 2.9

XIII-22
T,k

7

Q 7 i 3D i e /

.

Extraction procedure test value of asn

Concentration

Standard

val ue

Cd <0.01 <0. 3

Pb <0.1 <3

As <0.05 <1.5

Cr6 <0.05 <1.5

T-Hg <0.0005 <0.005

R-Hg Not detected Not detected

Org-P <0.01 <1

PCB <0.0005 <0.0C3

CN- <0.1 <1

unit: mg/1

Standard values for landfilling in Japan.

Table 8. Properties of raw and treated waste water

PH

BOD [mg/£]

COD "

Suspended Solids

Phenols "

Cd

CNPb

T-Hg

Cu

T-Cr

n-Hexane " NHj

CI

Raw

waste water

8.0

18,000

14,000

690

1,100

0.03

20

0.1

0.0006

<0.1

<0.05

230

340

1,200

Treated

waste water

7.3

50

90

19

<0.05

<0.01

<0.1

<0.1

0.0005

<0.1

<0.05

<5

136

900

Standard

val ue 5.7 ^ 8.7

<300

<300

<0.5

<0.1

<1

<1

<0.005

<1

<2

<5

Requirements set forth in Kanagawa Prefecture Sewage Ordinance.

XIII-23
(2) Mass and heat balances

Figures 3 and 4 illustrate the mass and heat balance relationships

obtained in this experiment. As shown in figure 3, 317 Nm of medium

BTU fuel gas was produced from 1139 kg (moisture content 35 percent)

of RDF in one hour. The gross calorific value ranges from 5450 ~

5850 Kcal/Nm3 in the pyrolysis reaction temperature range of 640 *

680 °C. The experimental results indicated that 191 Nm3 fuel gas

and 280 kg (6 kgf/m2

) steam could be recovered as products which

could in turn be supplied to some external location.

Details concerning mass and heat balance can be outlines as follows:

Gasification rate 1 51.3 % (Kcal -gas/Kcal -RDF)

Gas energy recovery rate 30.5 % (Kcal -gas/Kcal -RDF)

Total energy recovery rate2 36.2 % (Kcal-gas. steam/Kcal-RDF)

1 Gasification rate = calories of dry product gas

calories of dry RDF

total recovered calories

2z T * i 4. of gas and steam Total energy recovery rate = r , J a , , : _ nnr total colones of RDF

Experimental factors affecting the observed energy recovery

include the following as there were virtually no incombustibles in

the RDF:

(i) operations meant to separate and discharge the incombustibles

from the pyrolysis reactor were not necessary and

(ii) discharging the high temperature fluidizer sand (including

some incombustibles) from the combustion reactor was also

unnecessary. Therefore, typical input energy requirements

for the reactor were reduced and a significant amount of

auxiliary fuel gas (product gas) was thereby saved.

To correct the results of the energy recovery rate computed

for typical input RDF with a 15 percent moisture content (as

mentioned before, moisture was increased to around 35 percent by

the need to add water to the RDF) we used the following values:

Gas energy recovery rate 38.1 percent (Kcal -gas/Kcal -RDF) ; Total

energy recovery rate 43.8 percent (Kcal-gas. steam/Kcal-RDF).

(3) Utilities

Table 9 lists the operating costs of this gasification experiment.

Since the pilot plant was designed for the purpose of research

and development with respect to gasification technology:

1. Some equipment in the system, such as compressors and blowers,

has built-in excess capacity meant to cope with unusual

experimental conditions, e.g., aimed at the determination of

the upper limits of the system's operational capabilities.

XIII-24
2. In the waste water treatment system, physical -chemical treatment

facilities had to be employed instead of less costly biological

methods because of the long shutdown intervals occasioned by the

irregular testing schedule for Stardust 80. (With biological

treatment systems, it is difficult to maintain the function

properly while the system is not in operation).

The right hand column of table 9 therefore shows our estimate of operating

costs corrected to conform to optimal conditions.

Table 9. Utilities and operating costs

Consumption Cost in yen Corrected cost

per hour per refuse ton in yen per refuse ton

Electricity 340 kWH 5,236 2,510

a

Water 4 m

3 1,080 1,080

Town gas

b

2 Nm3 316 316

Nitrogen gas 0.7Nm3 210 210

Sand 15 kg 150 150

Chemical

s

for boiler 1 kg 800 800

25 % NaOH 9.4 kg 348 348

35 % H

z S04 6.5 kg 410 410

1 % coagulant 6.1 kg 134 134

Activated carbon 30 kg 9,750 270

c

Ca(0H)

z 0 kg

Nouri shi ng

salinity 0 kg 20

Total 18,434 6,348

a Since 52% of the electricity can be generated by a gas engine (see

description below) using recovered fuel gas, the purchase of only

163 kwh of electricity is needed.

b

Town gas is used for the pilot flame of the auxiliary burner.

With the physical —chemical treatment large amounts of activated

carbon are consumed, but in the case of the biological treatemnt,

almost all of them are saved.

XIII-25
Gas engine generator

Since 1980, the gas engine generator has been operated for more than 1,000 hours using over 70,000 Nm3 of recovered fuel gas.

We have confirmed that the gas recovered was sufficiently clean and

high in calorific value to use for the gas engine, and that the

efficiency of energy conversion was as high as 35%. The gas

engine employed in the Stardust '80 Plant is a slightly modified

standard diesel engine, the main specifications for this engine are

as follows:

Type 4 cycle, water cooled, vertical type

Cylinders 6—150 X 165

Generating power 300/1800 PS/RPM

200 kw

4. Implications of scale-up to commercial plant size

(1) Process and scale

In this section, computations describing the expected characteristics of a commercial-scale plant based on the Stardust '80 resource recovery system are discussed.

Calculations for the following two cases were performed by means of a modified computer program which was developed on the

basis of the previously described gasification experiment.

Case 1: Pyrolysis gasification plant (including gas engine

generator) stock material: RDF 1000 tonnes/day (produced

in the U.S.). In this case, RDF is gasified with the same process as that of the Stardust '80 Plant.

Case 2: Pyrolysis gasification plant (including pre-treatment

system and gas engine generator) stock material:

Municipal Solid Wastes from the U.S.: fOO tonnes/day.

Fig. 5 shows the schematic process flow of 'case 2.

In both cases, required electric power is assumed to be

supplied by a gas engine generator fed by product gas from the

gasification process.

In both cases, all the raw waste water coming from the product

gas refiners is assumed to be burned in the combustion tower.

MSW is separated into two parts (group A and B) by a selective

pulverizing classifier, see Appendix 2). After the ferrous metal

is removed, group B is shredded to a size less than 150 mm and fed

to the reactor, where it is gasified. A fraction of the product

gas is consumed by the gas engine generator to meet all demands for

electricity in the plant.

XIII-26
The material in group A is assumed to be discharged as residues to be

landfilled together with the incombustibles (glass, metals, etc.) discharged

from both reactors.

Table 10 lists the results of separation of U.S. municipal refuse

predicted by the SPC simulation model. This model was developed on the basis

of the results of the processing of over 20,000 tonnes of Japanese MSW taken

from various sources. The calorific value of the group B refuse is calculated as 4,600 Kcal/kg-dry (gross) or about 8300 BTU per pound.

Table 10. Results of separation of U.S. municipal refuse predicted

by Selective Pulverizing Classifier simulation model

Input retuse Group A brOUp D

Paper 42. 7 28.

1

CI 1 51. 7

Glass 11.

1

47. 0 3.

1

Metal 11.

1

1. 1 i. U

Plastics 9.9 0.7 13.5

Rubber 3.3 0 4.5

Texti le 5.9 0.1 8.1

Wood 11.9 8.6 14.2

Garbage 3.5 13.6 1.3

Others 0.6 0.8 0.6

Total 100 100' 100

Fraction 100 18.8 72. 9

b

Moisture 19.0 24.2 19.4

unit: %

Municipal solid waste of Baltimore County Md.

The remaining 8.3% is recovered as ferrous metal by magnetic

separators.

XIII-27
(2) Predicted gas and energy recovery rates

Figures 6-9 show the mass and heat balances applicable to case

1 and case 2, respectively. The efficiency of the plant for each

case was computed to be:

Case 1 Case 2

Gasification rate 52.8 % 47.1 %

Gas energy recovery 43.6 % 35.1 %

rate

Total energy recovery 57.1 % 40.5 %

rate

Tables 11-13 list the results of the calculations applicable

to required utilities, recovered materials, site area, personnel

and capital costs.

Table 11. Utility Requirements

Case 1 Case 2

City water (t/d) 969 560

Industrial water (t/d) 1790 1620

Chemicals (Ca(OH) 2

) (t/d) 5.3 8.3

Sand

3

(t/d) 4.8 7.4

a Average particle size is 0. 56 mm.

Table 12. Recovered materials

Case 1 Case 2

Fuel gas

a (Nm3 /d) 305 x 103 172 x 10 3

Steam

b

(t/d) 811 407

Ferrous metal (t/d) 0 70.5

a Calorific value of product gas

Case 1: 5650 kcal/Nm3 (630 Btu/ft 3

) Case 2: 5500 kcal/Nm3 (620 Btu/ft 3

)

k

Steam pressure: 16 kgf/cm2

These volumes of fuel gas and steam are those predicted to be

recovered after all other plant energy demands (including electricity)

have been taken into account.

XIII-28
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XIII-29
Appendix 1

Pretreatment Subsystem

The pretreatment subsystem handles such operations as the

weighing, receiving, storing and classifing of the collected refuse

mixture so as to supply each backend subsystem with stock material.

The main equipment in the pretreatment subsystem is the selective

pulverizing classifier (SPC).

The classifier has a circular shape and is approximately 3

meters in diameter and about 8 meters in length. The input refuse

mixture, delivered by conveyor is fed into the classifier, where

the refuse is classified via passing through a trommel. The

classified refuse is dropped out onto other conveyor belts provided

below the classifier and carried to each subsequent subsystem.

This equipment comprises a cylindrical rotary screen drum and a pulverizing scraper plate. The latter is incorporated into the

former but rotates at a speed different from that of the rotary screen drum. Thus, the refuse is pulverized and classified

simultaneously.

The first items of input refuse to be pulverized and

classified with the rotary screen drum are garbage, soil and sand

and glass and chinaware, all of which are relatively brittle; the

refuse so classified is referred to as Group I material. The

remainder of the refuse passes through the screen drum; water is

sprayed onto the refuse at the center of the pulverizing scraper

plate in the second screen drum. This water is absorbed by paper

and other materials in the refuse. The resulting mixture has lower

impact resistance and shearing force than the dry material. Thus,

the mixture can easily be pulverized on the pulverizing scraper

plate and selectively discharged from the second rotary screen

drum. The material so discharged is referred to as Group II. The

remaining refuse consists of plastics, metal cans, etc., which are highly resistant to impacts and shearing forces.

This material is referred to as Group III and is discharged at

the furthermost end of the drum. Table "a" lists the refuse com- ponents as classified by means of the selective pulverizing

cl assi f ier.

XIII-30
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XIII-31
The pretreatment subsystem includes the following features:

(a) Capable of simultaneously pulverizing and classifying

refuse in a single process and with a low rate of power

consumption.

(b) Group I is composed mainly of garbage, which may be used

for compost.

(c) Group II is composed mainly of paper, which may be used

for pulp.

(d) Group III is composed mainly of plastics, and is thus a favorable feedstock for gasification.

(e) In response to changes in input refuse composition or in

requirements for classification, the pretreatment subsystem

permits easy alteration of the degree of classification.

This control is achieved by changing the feedrate of

refuse in the drum and/or the relative velocity of both

the pulverizing scraper plate and the drum.

XIII-32
Appendix 2

Selective Pulverizing Classifier (SPC2)

1. Functions

(1) Separation capability: SPC2 can classify municipal

refuse into two groups, i.e., compostable materials and

non-compostabl e materials.

(2) Crusher: SPC2 can crush compostable materials in municipal

refuse into sizes suitable for aerobic fermentation.

Excessive crushing is avoided, because it not only wastes

power, but may also rupture dry batteries in the waste

could cause heavy metal contamination in the compost.

(3) Bag-breaker: SPC2 can cope with refuse collected in

plastic bags or boxes.

2. Features.

(1) SPC2 can be used directly to apply suitable moisture for

aerobic fermentation.

(2) SPC2 tends to operate properly even if bulky items such

as metal appliances are charged.

(3) Entanglement of long strings around the rotary shaft, a major problem with conventional shredders, is said to be

eliminated by the wrap prevention device specifically

developed for this machine. This feature renders the

manual removal of strings unnecessary and greatly reduces

maintenance time.

(4) Unlike conventional trommel type screens, this sieve is

unlikely to become clogged because of cleansing function

of scrapers.

(5) Because of its very low speed, this classifier creates

far less wear, noise and vibration than conventional

high-speed shredders. The SPC2 which incorporates both

pulverizing and classification by screening in one machine,

developed with full support of the Agency of Industrial

Science and Technology (AIST of MITI of Japanese government)

and was awarded the Directors Prize of the Ministry of

Science and Technology in 1977, and the Mechanical Institute

Prize in Japan 1978.

3. Brief description of equipment

(1) General. Pretreatment for composting refuse requires

three basic functions: 1) elimination of non-compostabl

e

materials, 2) size reduction without operating leakage

from dry batteries, and 3) moisture adjustment.

XIII-33
1) The elimination of non-compostabl e materials such as plastics, metals, textiles, etc., from raw refuse

before fermentation yields the following important

advantages:

a) The capacity of the fermenter can be increased

substantially by the elimination of non-compostabl

particularly plastic films and the like, which

have a large specific volume.

b) Heavy metals contained in the non-compostabl es may dissolve into the compost during the course

of the preliminary fermentation, thus lowering

the pH value of the final product.

c) Bulky textiles and long strings contained in

the refuse often become entangled in the stirring

mechanism of the usual type of fermenter.

2) Size reduction to obtain a large specific surface of

the material is preferable for fast fermentation.

Excessive pulverization, however, must be avoided,

since it not only requires a large amount of power

but also ruptures dry batteries leakage from which

may cause heavy metal contamination in the compost.

3) The moisture of the pretreated compostable material

must generally be kept within a limited range (about

40 to 60% depending on the type of fermenter) which

is suitable for aerobic fermentation.

(2) The Selective Pulverizing Classifier (SPC2): Based on the preceding three requirements, the SPC2 (Selective

Pulverizing Classifier) was developed. The SPC2 takes

advantage of differences in the resistance to destruction

of different material; both pulverization and classification by screening can be accomplished with the aid of

this one machine. As shown in appendix figure 1, the SPC2

consists of a rotating drum screen and a scraper rotating

at a different speed inside the screen.

As the refuse is fed continuously into the rotation drum,

almost all of the garbage (food waste) and brittle materials such

as dirt, glass and ceramics, and a fraction of the (flimsy) paper

are pulverized into particles or flakes and pass through the screen

(A Group). The remaining residues consisting of plastics, metals

and textiles etc., are discharged through the open end of the drum

(B Group).

In the case of dry refuse input, moisture can be increased by

spraying water from a tap built into the central shaft so that the

optimum water content for fermentation of A Group material can be

easily obtained. Additional moisture can also increase the paper

concentration in A Group owing to the resultant strength reduction

of the paper.

XIII-34
In the case of wet input (considerable amounts of wet garbage),

an increase in the relative speed between the drum and scraper

produces a considerable increase in the pulverizing effect and in

the concentration of dry paper in A Group which in turn decreases

its total moisture content.

Unlike the conventional shredder, which completely shreds all

the refuse, this classifier discharges B Group materials from the

drum end following the process of selective pulverization. This

refuse remains close to its orginal size. Almost all of the dry

batteries contained in the refuse maintain their original shape and

remain sealed.

Small batteries are discharged into the A Group without being

shredded. These batteries are separated by the magnetic separator.

The size of pieces of glass and ceramics discharged into A Group is

extremely large compared with that produced by conventional shredding.

These remnants can be easily removed after fermentation.

4. Engineering Aspects.

SPC2 consists of a rotating drum screen equipped with ridge

projections, rotating scrapers inside the drum screen, and a drive

unit which drives both the drum screen and the rotating scraper by means of one motor protected by a safety device.

The motion of the rotating drum screen is controlled by means

of a chain driven by the motor followed by a reduction gear. The

RPM value is kept constant within the range of 20 to 40 rpm.

The rotating scraper located inside the rotating drum screen,

is controlled by means of a belt driven by the SPC2's single motor

and a infinitely variable transmission. The RPM of the rotating

scraper is variable within the range of 40 to 80 rpm.

The rotational direction of the scraper is the same as that of

the drum screen, but the rotational speed is different. Therefore,

shear stress arises and pulverization occurs in the region between

the scraper and the ridge projection mounted in the inside of the

drum screen.

5. Separation Performance

Table "b" lists test results for separating a sample of

municipal refuse with the SPC2. As seen in this table, garbage

(kitchen refuse) was concentrated by a factor of about two, and

plastics and textiles, the main components of RDF, were almost

completely discharged through the open end of the drum as B Group.

Accordingly, the SPC2 was judged to be suitable separating

equipment for the plant producing both RDF and compost from municipal

refuse. Since the particle diameter of the compostable materials

(A Group) from SPC2 is pulverized and homogenized to a size of

about 20 to 40 mm, extremely good fermentation can be achieved.

XIII-35
6. Utility Requirement.

Electricity consumption of the SPC2 is 10 to 15kwh/tonne

(input refuse).

Table b. Test Result of SPC2

Municipal

Refuse A Group B Group

Composition

(%)

Composition

(%)

Classification (%)

Composition

(%)

Classification (%)

Paper 56. 3 58.

1

49.1 55.0 50.9

Garbage 14. 5 29.4 96.6 1.0 3.4

Texti le 10.0 0.6 3.6 18.5 97.0

Wood 2.6 1. 7 31. 0 3.4 69 0

Dirt 0.8 1.7 100.0 0.0

Glass 3.3 6.9 100.0 0.0

Metal 8.2 0.8 5.0 14.9 95.0

Plastics 4.3 0.8 10.0 7.2 90.0

Total (Dry) 100.0 100.0 100.0 100.0

Moisture

(Content) (%) 49.3 54.5 40.2

Each rate of classification described in this table assumes that

sewage sludge is not mixed with refuse. Mixing refuse and sludge causes an increase of classification rate of paper in the A Group.

XIII-36
XI 11-37
Figure XIII. 2. Gas concentration vs. pyrolysis temperature.

XIII-38
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XIII-40
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Steam

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Residues

SPC

MG

CR

TPS

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Selective Pulverizing Classifier

Magnetic Separater

Crusher

Two-bed Pyrolysis system

Gas Engine Generator

Figure XIII. 5. Schematic process flow.

XIII- 41
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XIII- 42
XIII- 43
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XIII- 44
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XIII- 45

APPENDIX XIV. A SIMPLE DEGREE OF HAZARD SYSTEM

FOR HAZARDOUS WASTES

H. Yakowitz

National Measurement Laboratory

National Bureau of Standards

Washington, DC 20234

The purpose of this brief exposition is to suggest a method

for classifying waste treatment, storage and disposal facilities

with respect to potential hazard posed by the existence of the

facility. Existing, proposed and inactive or abandoned facilities

can be classified by the method to be described; final disposal may

be by thermal destruction or burial.

HAZARD-CONCENTRATION RELATIONSHIPS

The dose experienced by some population or ecosystem as a result of hazardous waste operations or storage—via any path of

escape from a faci 1 ity--needs to be related to observed instances

of harm or the possibility of harm at some undefined future date.

In all of the following discussions, assume that the exposure or dose occurs as a result of a hazardous waste facility. Further, assume that the exposure can be measured accurately and that the

sampling procedure is statistically valid; these are admittedly

large assumptions.

Toxicity testing for incidence of adverse effects in animals

and humans as related to exposure or dosage usually results in a sigmoidal or S-shaped dose-hazard curve (see fig. 1). Here zero dose means zero hazard. But, the probability of harm to the

exposed population as a function of very low dose or levels of

exposure is extremely difficult to measure or to predict theoretically as indicated in figure 1. Note that "hazard" suggests a threat posed by chance or something largely beyond one's control

while "risk" may imply voluntary exposure to harm or loss.

Consider models for extrapolating from measurable exposure

data to the hazard at lower exposures. In one experiment, some 24

000 female mice were subjected to a known bladder and liver

carcinogen in order to study dose responses down to a one-percent

tumor incidence, i.e., the concentration of the carcinogen which

would cause one mouse in 100 to develop liver or bladder tumors 1

. Results of these tests were not especially enlightening. For

example, a linear extrapolation and a Weibull model were applied to

the data.

For a one-in-a-mi 1 1 ion risk (P = 10"6

) of liver cancer in the

mice, an 0.045 part-per-bi 1 1 ion dose of the carcinogen was predicted

by the linear model; the Weibull model predicted a 4.5 part-perbi 11 ion dose for P = 10~6 or an exposure of 100 times greater for

the same risk 1

.

XIV-1
The EPA Carcinogen Assessment Group has stated that:

"There is no really solid scientific basis for any

mathematical extrapolation model which relates carcinogen

exposure to cancer risks at the extremely low level of con- centration that must be dealt with in evaluating the

environmental hazard."

With respect to the prediction of "time-to-tumor" data, there

is no agreement between available models. Results are different,

and reliable prediction appears impossible at present 1.

As stated by the Congressional Office of Technology Assessment:

"The accuracy of the relation between exposure and incidence

(of adverse effects) is always limited. Practical restraints

on the number of animals that can be tested means that the

data are always subject to significant experimental error; it

also means that only relatively high incidences, almost always

greater than 10%, can be measured in the experiments. There

is also no agreement about which mathematical models best

extrapolate from the exposure levels measured in studies to

those encountered in the environment. Linear models, which

assume that incidence is proportional to exposure at low

exposure levels, are used by Federal agencies." 1

Note that use of a linear model as compared to other possible

extrapolation models, e.g., log-normal, log-logistic, Weibull,

predict a higher probability for harm at lower exposure levels. As

a practical matter, there is often no alternative to the linear

model, since there are essentially no empirical data to support

other extrapolation schemes.

Some of the technical difficulties will be apparent from an examination of Table I in which two objective and competent groups

of scientists attempted to define cancer hazard from drinking-over

an entire lifetime-water containing one part-per-bi 1 1 ion (one

microgram per liter) of known carcinogens. The table purports to

indicate the number of persons per million exposed who are likely

to fall victim to cancer from drinking this water. Note that in

several cases, a tenfold to hundredfold difference exists between

the two estimates. Data taken from Table I are shown plotted in

figures 2 and 3 assuming a linear relationship between concentration and cancer risk, in excess of that which would obtain if Cx were zero, i.e.,

P R = m

x

Cx where (1)

P R is the proportion of the exposed population who are likely to

suffer the adverse effect, m is the slope of the linear relationship obtained by dividing thi value tabulated (Table I) by C of 1

PPB, and C is the concentration of the constitutent , x, which is

presumed to pose the hazard.

XIV-2
DETERMINING THE EXPOSED POPULATION

Determining the exposed population, i.e., the group subjected

to higher than baseline concentrations of the substances from a site, is no simple challenge. In principle, the various paths by

which substances might reach the group can be identified. Monitoring, which relies on qualitative and quantitative determinations at

various points away from the site, can be implemented. Thus,

what—if anything— is escaping and how much will be known as a function of distance from the site. When the slope of the concen- tration against distance curve changes upward, the boundary for a particular path can be located. Wind, other climatic factors, and

water flow patterns may well alter the results over a period of

time. Airborne or rain-based factors may enter. Concentrations of

substances produced by other means than the waste disposal site may

intervene, e.g., from the plants generating the waste or other

sources. Thus, attempting unambiguous identification of who is

exposed to higher concentrations of potentially harmful substances

from a waste disposal site is likely to be exceedingly difficult,

time-consuming, expensive, and inaccurate.

ESTIMATION OF HAZARD

But, even if the exposed population, N, could be accurately

determined and the hazard of cancer or other disease were known

accurately, prediction of adverse events due to hazardous waste

requires a probabilistic estimation scheme. Since the hazards tend

to be fairly small in a probabilistic sense, the Poisson distribution function may represent an appropriate model.

Consider a fixed unit of time, T, in which certain events may

occur. Assume that the events occur independently and that for

periods of time, At, which are very short in comparison to T, the

probability of one event is proportional to the length of time At,

i.e., is equivalent to CAt/T, where "C" is constant during the time

period T. Assuming the probability of two or more events in time

At is negligible and defining Ct/T as A:

x k -A

F(k) = ^—

(2)

k!

In other words, the probability that "k" events will occur before

time "t" is given by the Poisson distribution.

If the time interval is taken to be a human being's lifetime

and if the "event" is taken to be the occurrence of an adverse

effect due to exposure to the hazardous waste consti tutents , then

the value of A for an exposed population of human beings, N, can be

estimated. Assume some proportion, "p" of individuals in the

population, N, suffer an adverse effect due to exposure to the

hazardous waste; the remaining proportion, (1-p), do not suffer the

adverse effect. If the product Np is equal to or less than five,

then the parameter "A" in equation (2) can be taken as Np. Since

XIV-3
the time interval is taken to be a lifetime, the value of \ is the mean number of occurrences of the event, i.e., adverse effect due

to exposure to hazardous waste, within the exposed population. The

probability of occurrence of the event within the specified time

interval will be very small compared with the total number of

occurrences of such events, and the Poisson distribution thus may

represent an appropriate model for our purposes.

If 1000 persons were exposed to 1.1 PPM of chloroform in their

water according to figure 2, the hazard (or p) is 10""3 and A = Np = (lOOOXlCT3

) = 1.0. Note equation 2 indicates that the probability

that no one in the exposed population will be adversely affected,

is simply:

(3)

Furthermore, if the linear risk relationship of equation 1 is

utilized to determine the proportion of individuals likely to be

adversely affected due to the presence of constituent x at con- centration C , then

\ = m NC

x x (4)

since \ = NP^, i.e., \ is related to population size. Hence, if

the slope, m , the exposed population, N and the concentration C can be determined:

P = exp[-(m NC )] o KL

x x

J (5)

The parameter P , the probability that no one in the exposed

population is adversely affected, provides an appropriate figure of

merit for ranking the potential hazard from a site. But un- certainties in determining the value of N and C for specific

situations and the more general problem of ascertaining values of

"m" for potentially harmful substances suggest that large un- certainties in determining P are likely to occur,

the uncertainty AP can be estimated as:

In any event,

AP P £nP

o o

/AC

2n

(6)

Equation (6) assumes errors are independent. Furthermore, the

approximation to | AP | becomes worse as the values of (Am/m),

(AN/N), (AC /C ) bec8me large. Nevertheless, equation (6) can be

used as an ¥nd¥cator to show that unacceptably large values of | AP

( are likely to occur.

Members of the exposed population can point to the difficulties

in ascertaining m, N, and C as a means to exclude proposed facilities

or to demand immediate remedial action—which may or may not be

warranted—in the case of existing facilities. Finally, uncertainties

in P could increase the chances for persons associated with the

facility to be held liable under state and/or Federal statutes.

XIV-4
While the concept of utilizing P as an appropriate means to

classify possible risk from the facility is appealing, practical

application of equation 5 could be exceedingly difficult. Therefore, some means to deal in a practical sense with site specific

characteristics in an appropriate fashion is needed. In particular,

the issues of "How clean is clean?" for inactive sites as well as reasonable performance measures for existing and proposed facilities

need to be addressed. Furthermore, whatever method is selected

must provide a means to account for cost effectiveness of proposed

actions based on the results of applying the method. The remainder

of this paper will propose a method which:

o Utilizes P as the basic measure of hazard,

o

o Takes into account site specific characteristics.

o Is amenable to fairly rigorous uncertainty analysis.

o Provides guidance as to the monitoring and analytical

regime required for a specific facility.

o Avoids the problems associated with determining the

"exact" population exposed, N and with determining the

slope of the hazard relation, m

x

.

o Utilizes—in most instances—critical ly evaluated data as inputs.

THE EXTENDED PRELIMINARY POLLUTANT LIMIT VALUE METHOD

The Preliminary Pollutant Limit Value (PPLV) method for human

health effects was developed by Rosenblatt and co-workers at the

U.S. Army Medical Bioengineering Research and Development

Laboratory. These authors have published a series of articles and

reports detailing the basis of the method as well as various

practical applications 2 "7

. In addition, basic chemical data

required for input to the model have been critically evaluated and

published8

. Therefore, only a brief summary of the basic PPLV

method will be presented here:

"Initially, each pathway for transfer of a pollutant from the

environment to man is treated as if it involved either (a) one environmental compartment, or (b) a series of successive

compartments containing the pollutant at equilibrium. Transfer

from the final compartment to humans is considered a non- equilibrium process occurring at an assumed rate. A PPLV is

that concentration of the pollutant in the first compartment

that is calculated to result in reception by the target human

being of exactly the acceptable daily dose, Dj, via one or more pathways. The basic concept may be modified as the

situation requires." 7

XIV-5
Figures 4 and 5 indicate the basic processes and assumptions in

schematic form. Table II presents some results from reference 2

giving some PPLV values for seven compounds in soil. Rosenblatt

has indicated that PPLV's are not standards or criteria but they

are values which can be used to choose alternative courses of

action for:

o Developing renovation options for contaminated areas,

o Suggesting limits on land utilization near facilities,

o Specifying monitoring conduct.

o Establishing analytical sensitivity requirements.

The basic premise is that once a PPLV is found for a specific

area in which the treatment-storage-disposal facility is presumably

contained, if the concentration of the constituents can be reduced

to PPLV or are never allowed to exceed PPLV, then the interaction

of humans with the area or its products is "safe" for any exposed

population, i.e., the acceptable daily dose of the pollutants will

not be exceeded. However, the questions of what occurs if PPLV is

exceeded or if the cost of achieving PPLV is prohibitively large

remain to be dealt with.

If PPLV is achieved, the exposed population is presumed to

have some extremely small probability to suffer adverse effects.

Note well that PPLV is site specific and only the population for

which the particular PPLV has been computed is included in this

assumption. If linearity between the proportion of affected

individuals and PPLV is assumed, then

P R = (PPLV)m

x (7)

But since PPLV supposedly includes N, then, in this case,

P

R = A = (PPLV)m

x (8)

If PPLV is achieved, then the probability that an adverse effect

will occur is supposedly very small. If an assumption is made that

this probability is to be 10*4

, then m

x may be estimated as:

m = 10-VPPLV (9)

x If P

R were taken as something other than 10*4

, clearly m would

then be different. Hence, under these assumptions, A at PPLV is

10-4 and P which is exp(-A) is 0.9999. Thus, if PPLV is achieved

there is a°99.99% chance that no one in the exposed population will

be harmed. If PPLV is exceeded we assume that A increases linearly

with concentration of constituent x, i.e.:

A = 1CT4C /PPLV (10a)

XIV-6
and

P Q = expC-CLO-4 C /PPLV)]. (10b)

The assumption that A increases linearly with C seems likely to

provide a reasonable rate of increase for A in vS'ew of the previous

discussion pertaining to extrapolation models. The concept of

acceptable daily dose, Dj, is related to lifetime hazard in the

PPLV formulation so that equation (10) is consistent with our previous assumptions regarding the applicability of the Poisson

the PPLV basis. Nevertheless, the assumpN remains to be investigated in more

P vs. the ratio (C /PPLV). Clearly,

C can exceed PPLV Sy a considerable amount

But the uncertainty in P due to uncerof PPLV and the measurement of C still

process as well as with

tion of independence of

detail. Figure 6 shows

figure 6 indicates that

before P falls to 0. 95.

tainties in the computation

needs to be considered:

AP o_/ 1Q

" 4c

x

N

P \ PPLV ,

AC 2^

x

\ + / A(PPLV) \

PPLV /

(11)

If a term, E, is defined as:

2

E = AC

/ A(PPLV) \

2

I PPLV

J

AA _ r A

, then (12)

(13)

As with equation (6), the errors are assumed independent and the

approximations for AP /P and AA/A become worse as APPLV/PPLV

and/or AC /C increase*. °If some estimates for "E" can be made,

then cumu^at^ve probability as a function of E can be estimated as well. With regard to the term (AC /C ), the National Bureau of

Standards (NBS) evaluated analytical clata obtained in the vicinity

of the Love Canal in Niagara Falls, New York9

. In addition, NBS

has investigated several aspects of the challenges to the analytical

chemist posed by low levels of constituents in variable matrices 10. Based upon these results, a reasonable range for the uncertainties

in determining the concentration of constituent X is 0<AC /C <5,

with a most probable value being about 0.5 to 1.

So far as uncertainties in PPLV are concerned, Rosenblatt and

co-workers have discussed sources of error in some detail but have

not carried out a formal quantitative analysis. Three major

sources of uncertainty are:

XIV-7
0 The assumption of equilibrium between environmental

compartments.

The statistical extrapolations yielding "safe" doses of

various constituents.

Uncertainties in data with respect to likely fate of

various constituents in various environments. For

example, the following summarization indicates some relations of physicochemical properties to environmental

behavior:

Physical Chemical Data

1. Solubility in Water

2. Latent Heat of Solution

Related To:

Leaching, degree of adsorption,

mobility in environment.

Adsorption, leaching, vaporization

from surfaces.

3. Partition Coefficient

4. Hydrolysis

5. Ionization

6. Vapor Pressure

Bioaccumulation potential, adsorption

by organic matter.

Persistence in environment and biota.

Route and mechanism or adsorption or uptake, persistence, interaction with

other molecular species.

Atmospheric mobility, rate of

vaporization.

Reference 8 has considered both the availability and validity of

current data in these areas. In addition, NBS has sponsored

critical data reviews and original research aimed at improving

these data 10 " 13 as have many other institutions. Given these

uncertainties, a range for A(PPLV)/PPLV of 0<A(PPLV)/PPLV<15 with

the most probable value being about 5 or 6 seems to be reasonable.

Nevertheless, more formal analysis is warranted to provide a better

estimate.

From these considerations an approximate cumulative probability

curve for the term E h AAA could be constructed. This curve is

shown as figure 7; the curve indicates that there is a 95% cumulative

probability that the term "E" does not exceed eleven. Given this

result, the 95% upper bound for P can be calculated. Figure 8

shows this result as well as a repeat of equation (lib). These

results indicate fairly clearly that if the ratio C x/PPLV exceeds

100, then significant uncertainty in determining P may occur. Nevertheless, the 95% probability curve for the upper bound of P is available as a guide for personnel responsible for action at the

site in question.

XIV-8
SUMMARY AND CONCLUSIONS

The Poisson statistical distribution is suggested as an appropriate approximation to the potential distribution of adverse

effects in a population exposed to substances, such as toxic

wastes. The probability that no one in the exposed population will

be harmed is a reasonable ranking parameter to describe the hazard

from a facility treating, storing and/or disposing of such wastes.

However, this parameter may be subject to a number of uncertainties

A method to estimate both the probability that no one in an exposed population will be adversely affected and the uncertainty

associated with this estimate has been developed. The basis for

this method is the preliminary pollutant limiting value (PPLV)

technique developed by Rosenblatt and co-workers at the U.S. Army

Medical Bioengineering Research and Development Laboratory. The

PPLV method has been extended to consider the possible consequences

of exceeding the safe limiting concentration calculated as PPLV.

Results indicate effects for exceeding PPLV by factors up to 100.

If PPLV is exceeded by more than 100, the probability for adverse

effects in the exposed, population increases rapidly.

Nevertheless, the extended PPLV method can be applied to

proposed, existing or inactive treatment, storage, and disposal

facilities including those that dispose by thermal treatment or burial. Application of the extended PPLV method can provide a basis for selecting economically and environmentally sound options

regarding activities associated with the site. Inactive or abandoned sites can also be ranked if necessary. Thus, the extended

PPLV method might provide a simple degree of hazard system.

XIV-9
REFERENCES

1. Congress of the United States, Office of Technology

Assessment, Assessment of Technologies for Determining Cancer

Risks from the Environment , 240 pp., June, 1981.

2. Rosenblatt, D. H. , Dacre, J. C. ; and Cogley, D. R. , "An

Environmental Fate Model Leading to Preliminary Pollutant

Limit Values for Human Health Effects," U.S. Army Medical

Research and Development Command Technical Report 8005, 47

pp., April, 1980 (AD B0499172).

3. Dacre, J. C. , Rosenblatt, D. H. , and Cogley, D. R. , Environmental Science and Technology 14, 778-784 (1980).

4. Rosenblatt, D. H. and Small, M. J., "Preliminary Pollutant

Limit Values for Alabama Army Ammunition Plant," U.S. Army

Medical Research and Development Command Technical Report

8105, 48 pp., August, 1981 (AD A104203).

5. Rosenblatt, D. H. , "Environmental Risk Assessment for Four

Munitions-Related Contaminants at Savanna Army Depot

Activity," U.S. Army Medical Research and Development Command

Technical Report 8110, 14 pp., November, 1981 (AD A116650).

6. Rosenblatt, D. H. and Kainz, R. J. , "Options and Recommendations for a Polybromobiphenyl Control Strategy at the Gratiot

County, Michigan Landfill," U.S. Army Medical Research and

Development Command Technical Report 8204, 36 pp. , August,

1982.

7. Rosenblatt, D. H. , Dacre, J. C. , and Cogley, D. R. , "An

Environmental Fate Model Leading to Preliminary Pollutant

Limit Values for Human Health Effects," Chapter 15 in

Environmental Risk Analysis for Chemicals , R. A. Conway, ed.

,

van Nostrand Reinhold, Co., New York, (1982), pp. 474-505.

8. Lyman, W. J., Reehl , W. F. and Rosenblatt, D. H. , Handbook of

Chemical Property Estimation Methods , McGraw-Hill, New York

(1982).

9. NBS Review Panel (W. H. Kirchhoff, Chairman), "Review of

Material Provided by EPA on the Analysis for Organic Chemicals

in the EPA Love Canal Monitoring Study," NBSIR 82-2511, 46

pp. , May, 1982.

10. Yakowitz, H. (ed.), Final Report--NBS Office of Recycled

Materials (1983)--in press.

11. Wasik, S. P., Tewari, Y. B. , Miller, M. M. , and Martire, D.

E. , "Octanol /Water Partition Coefficients and Aqueous

Solubilities of Organic Compounds," NBSIR 81-2406, December,

1981, 56 pp.

XIV-10
12. Wasik, S. P., Tewari , Y. B. , Miller, M. M. , and Purnell, J.

H. , J. Res. NBS 87 (4) 311-315 (1982).

13. Mackay, D. and Shiu, W. Y. , "A Critical Review of Henry's Law

Constants for Chemicals of Environmental Interest," J. Phys.

Chem. Ref. Data 10 (4) 1175-1199 (1981).

XIV-11
Table I. Concentration of Drinking Water Contaminants

and Calculated Excess Cancer Hazard of One- i n-a-Mi 11 i on

NAS

a CAG

b

Acryl oni tri 1 e. Arsenic

Benzene

Benzo(a)pyrene

Beryl 1 i um

Bi s(2-chloroethyl ) ether.

Carbon tetrachloride....

Chi ordane

Chi oroform

DDT

1 ,2-Dichloroethane

1,1-Dichloroethylene. . . . Dieldrin

Ethyl enedi bromi de

ETU

Heptachlor

Hexachlorobutadiene

Hexachlorobenzene

N-ni trosodimethyl ami ne.

.

Kepone

Li ndane

PCB

PCNB

TCDD

Tetrachloroethylene

Trichloroethylene

Vinyl chloride

ug/1 ug/1

0. 77 A A A 0. 034

ND 0. 004

ND 3. 0

ND ND

ND 0. 02

0. 83 ND

9. 09 0. 086

0. 056 0. 012

0. 59 0. 48

0. 083 ND

1 .

4

1 . 46

ND 0. 28

A AA A 0 . 004 kl A ND

A "1 "1 0. 11 0. 0022

A AC 0. 46 kl A ND

0. 024 2. 4

ND 1.4

0.034 ND

ND 0.0052

0.023 ND

0.108 ND

0.32 ND

7.14 ND

ND 5.0 x lO" 6

0.71 0.82

9.09 5.8

2.13 106.0

Standardized to hazards from National Academy of Sciences Drinking

Water and Health for consumption of 1 1/water/day.

Recalculated to exclude aquatic food intake from Cancer Assessment

Group, Ambient Water Quality Criteria. Standardized to 1 1/water/day

i ntake.

c Average adult water consumption is 2 1/day.

d

Not discussed.

SOURCE: Office of Technology Assessment.

XIV-12
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XIV-T3
90

D D D

Dose of test chemical

a Excess tumor incidence (percent) is defined as: tumors in exposed population _ tumors in control population x 100

number of exposed population number of exposed population

a sigmoid dose-response curve; infralinear between O and Pi linear extrapolation

supralinear extrapolation

line projected to a threshold

SOURCE: Office of Technology Assessment.

Figure XIV. 1. A stylized dose-response curve and some extrapolated

curves

.

XIV-14
200 600 1000 1400 1800

CONCENTRATION (PPB)

Figure XIV. 2. Calculated excess cancer risk as a function of

concentration of chemicals shown in drinking water. Assumes

linear dose-response relationship in region shown. (EPA Carcinogen Assessement Group Data.)

XIV-15
CONCENTRATION (PPB)

Figure XIV. 3. Calculated excess cancer risk as a function of concentration of chemicals shown in drinking water. Assumes linear doseresponse relationship in region shown. (National Academy of Sciences

data.)

*IV-16
XIV-17
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XIV-21
f
APPENDIX XV . CHARACTERIZATION OF MILLSCALE STEEL WASTES

E. S. Domalski and Y. B. Tewari

Chemical Thermodynamics Division

W. A. MacCrehan

Organic Analytical Research Division

J. R. Moody

Inorganic Analytical Research Division

and

J. A. Walker

Chemical Kinetics Division

National Bureau of Standards

Washington, DC 20234

XVi
Table of Contents

Page

I Introduction XV-2

II Particle Size Distribution Study XV-3

III Extraction of Hydrocarbon Oil from Mi 11 scale XV-5

IV Oil Recovery XV-8

V Gel Permeation Liquid Chromatography XV-9

VI DSC Experiments XV-13

VII Summary and Conclusions of Experimental Results. . . . XV-14

Appendix - Description of Deoiling Plant XV- 17

XV- ii
List of Tables

Table No. Page

I Particle Size Distribution of Mi 11 scale (as received). XV-4

II Particle Size Distribution of Deoiled Millscale. . . . XV-4

III Apparent Extraction Efficiencies (percent) XV-7

IV Apparent Mass of Millscale Extracts XV-8

V Retention of Molecular Weight Standards XV- 10

VI Chromatographic Conditions XV-11

VII Comparison of Extraction Efficiency of Different

Solvents XV- 12

XV-iii
List of Figures

Figure No. Page

1. GPL Chromatogram, Mi 11 scale Extract

Methyl isobutyl ketone solvent XV-23

2. GPC Chromatogram, Mi 11 scale Extract

Freon 114 solvent XV-24

3. GPC Chromatogram, Mi 11 scale Extract

Methyl ethyl ketone solvent XV-25

4. GPC Chromatogram, Mi 11 scale Extract

Hexane solvent XV-26

5. GPC Chromatogram, Mi 11 scale Extract

XAD-2 solvent XV-27

6. GPC Chromatogram, Veedol #57 Lubricant

(Prior to use) XV-28

7. GPC Chromatogram, Brooks Lubricant

(Prior to use) XV-29

8. GPC Chromatogram, Veedol #56 Lubricant

(Prior to use) XV-30

9. DSC Thermogram, Brooks Mill Lubricant XV-31

10. DSC Thermogram, Veedol #56 Mill Lubricant .... XV-32

11. DSC Thermogram, Veedol #57 Mill Lubricant .... XV-33

12. DSC Thermogram, Mi 11 scale Extract

Bethlehem #2 XV- 34

13. DSC Thermogram, Mi 11 scale Extract

Republic #1 XV-35

14. DSC Thermogram, Millscale Extract

Inland #2 XV-36

I

XV- iv
Preface

The American Iron and Steel Institute (AISI) requested the

assistance of expertise at the National Bureau of Standards in

cooperating on the problem of reprocessing of mi 11 scale and

mi 11 scale sludge. Hence, the purpose of this study is to

investigate the appropriate chemistry to remove the oils and

greases (hydrocarbons) from the mi 11 scale waste so that an ironrich material can be recycled into the steelmaking process. The

emphasis will be on the determination of the physical properties of

the mi 11 scale and hydrocarbon oil, which will affect the extraction

chemistry, and not on the identification and precise determination

of a few compounds. Comparison of unused grease and the oil

extracted from the mi 11 scale will be sought with a view toward

interpreting the changes in chemistry as they relate to steel

processing.

Disclaimer

Certain commercial equipment, instruments, or materials are identified in this report to specify adequately the experimental

procedure. Such identification does not imply recommendation or endorsement by the National Bureau of Standards, nor does it imply

that the materials or equipment identified are necessarily the best

available for the purpose.

XV-1
I. Introduction

The manufacture of steel products into slabs, sheets, blooms,

billets, or bars requires that they be worked or formed in a hot

strip-rolling process. During the working or forming, these

products undergo oxidation, cooling, and washing with a high

pressure water spray. The hot steel surface is exposed to both

oxygen from the air and wash water. As a result of the exposure,

layers of iron oxides formed on the surface are flaked off. As the

steel product is rolled into the desired form, one layer of scale

is broken off and is replaced by a new layer. A new scale is

generated everytime the steel product is shaped or rolled. During

the rolling process, the scale falls through the roll tables into a trough or sewer through which rapidly-flowing water is passing. A

large amount of oils and greases enter and are used to lubricate

the roll tables and shaping equipment. The scale, water, oil, and

grease combine to form a steel waste of heterogeneous particle

size. The easily filtered, large particle material (about 1 mm to

.1 cm) is referred to as mi 11 -scale. A mi 11 -scale sludge is also

generated by sand filtration of the waste water and has a smaller

particle size (about 1 urn to 1 mm). Past practice has been to

dispose of the mill-scale and sludge in land fill operations at the

plant site. The sludge required special treatment such as dumping

into lagoons or ponds. Filtering of some of the solids was often

necessary as well as special treatment of the leachate. In certain

cases, blending of the sludge with inert slag materials was required

prior to the landfill operation.

Since the mi 11 -scale is approximately 70 percent iron, and the

sludge is approximately 30 percent iron, economic considerations

suggest recovery of these metal units. However, difficulties arise

when these wastes are used directly as feed stock in the sintering

process because of the hydrocarbon impurities acquired from the

lubricants in the hot rolling process. The hydrocarbon on the

mi 11 scale is between 0.3 and 10 percent oil by weight and as much

as 50 percent oil by weight of the sludge. The hydrocarbon on the

scale interferes with the sintering process of preparing ore for

the blast furnace. Sintering involves a careful mixing of iron ore with limestone and coal, followed by firing at red heat in a reducing gas atmosphere. The resulting coarse mix is bound

together by calcium ferrite and can be fed directly into the blast

furnace. Difficulties arise when the oily millscale is used as a feed because the hydrocarbon residue of the heavy grease is not

burned in the sintering process, but is volatilized. When the

waste air and gas is filtered with an electrostatic precipitator,

the filter bags get clogged with hydrocarbon residues and can catch

fire. In some instances, explosions have occurred when volatilized

hydrocarbons and air reach certain mixed proportions in the electrostatic precipitator.

XV2
Disposal costs for both mi 11 -scale and sludge are likely to

increase as the regulations for waste disposal established through

the Resource Conservation and Recovery Act (RCRA) are implemented.

Some estimates suggest that these costs could possibly approach $50

per ton of waste. Recent figures place the annual levels of

mill-scale and sludge generation by the U. S. steel industry at

about three million tons per year (or 8000 tons per day).

A field trip to the Bethlehem Steel Corporation facility at

Bethlehem, Pennsylvania was made by E. S. Domalski, J. A. Norris,

W. A. MacCrehan, and Y. B. Tewari on Friday, February 5, 1982 to

obtain a clearer understanding of the steel waste problem from

actual observation of mi 11 -scale generation by a hot rolling steel

process. The rolling or working of an I-beam (about 150 ft. in

length) was observed in which layers of iron oxides were flaked off

during the rolling process by the mechanical action of the mill and

cooling water. About 2.5 percent of the metal units are lost in

this hot- rolling process.

Mi 11 scale samples were received from the Bethlehem Steel

Corp., Inland Steel Corp., and Republic Steel Corp. for study in

this project. The Bethlehem Steel Corp. also provided three

samples of hydrocarbon lubricants so that specimens would be

available for testing as they are (i.e., unused) prior to their

application to roll tables or shaping equipment.

After having examined the available information on the

recovery of metal units from mi 11 scale, the following project goals were selected: (1) to establish the particle size distribution of

the mill scale samples, (2) to determine their hydrocarbon content

by at least two methods, (3) to identify the general nature of the

hydrocarbon oil (i.e., aliphatic vs. aromatic) and to indicate,

when possible, any changes in the hydrocarbon lubricants by

comparison to lubricants prior to their use, (4) to study the

efficiency of different solvents with respect to the solubilization

and extraction of hydrocarbon oil from the millscale, and (5) to

determine the temperature range over which volatilization of the

hydrocarbon lubricants occurs.

II. Particle Size Distrubution Study

The particle size distribution of millscale obtained from

three steel industry sources was determined by gravimatrical ly

analyzing the fractions initially obtained by sieving. Table I contains a listing of the particle size distribution of oily

millscale (as received), whereas in Table II the particle size

distribution of deoiled millscale (using a solvent extraction

method) is listed. The distribution listed in Table II shows that

nearly 30 percent of millscale consists of very fine particle sizes

(-50 mesh size).

XV3
Table I. Particle Size Distribution of Millscale (as received).

Bethlehem Inland"3 Republ ic

Screen Size weight fraction weight fraction weight fraction

+10 mesh

b

0.30

7 0.207 0.17

g -10 + 20 mesh 0.18c 0.34. 0.20.,

o 3 3

-20 + 30 mesh 0.08

5

0.33

5 0.09

3

-30 + 40 mesh 0.07

g

0.05

g

0.10

g

-40 + 50 mesh 0.13

? 0.04

2 0.12

g

-50 mesh 0.20

g

0.00

g

°- 28

6

a

Mi 11 scale was very oily (wet) and difficult to sieve.

Table II. Particle Size Distribution of Deoiled Millscale.

Bethlehem Inland Republic

Screen Size weight fraction weight fraction weight fraction

+10 meshb

0.26., 0.13

? 0.15] -10 + 20 mesh 0. 1

9

& 0.29

Q

0. 19

2

-20 + 30 mesh 0.09

] 0. 1

1

5

0.12

Q

-30 + 40 mesh 0.06

g

0.084 0.10

Q

-40 + 50 mesh 0.08

y

0.10

] 0.132

-50 mesh 0.29

?

0.274 0.304

'10 mesh = 1.7 x 10~ 3

meter

-3

50 mesh = 0.29 x 10 meter

XV-4
The Bethlehem Steel and Republic Steel samples were qualitatively

similar in particle size distribution when examined as- received.

The Inland Steel sample was oily (wet), and this condition apparently

caused sufficient small particle agglomeration to skew the particle

size distribution as compared to the other samples. However, after

deoiling of this sample by solvent extraction, results for all

three samples yield a similar particle size distribution, especially

at smaller particle sizes. The figures listed in Table II are indicative of the true solids distribution once the binding effects

of the oils have been removed.

III. Extraction of Hydrocarbon Oil from Mi 11 scale

Sampling

A single five gallon 1 can of millscale from Inland Steel was used for all of the following tests. Preliminary observations

indicated extreme problems with sample heterogeneity. Because of

this heterogeneity, the entire contents of the can were subjected

to a repetitive quartering process (cone and quarter) until two

dozen replicate samples of approximately three hundred grams each were produced. The quartered samples appeared to be homogeneous,

but, within 24 hours, signs of segregation were visible within the

24 sample jars. Therefore, either the entire bottle was used for

testing or the bottle was thoroughly mixed before taking subsamples.

Ignition

The initial tests on these blended samples were designed to

determine the total amount of volatile residue actually present.

For these tests, a tube furnace was used to heat the samples in a flowing nitrogen stream which kept oxygen and water away from the

sample. At low temperatures, the condensate at the outlet of the

tube furnace appeared to be water but upon attaining 200 °C the

odor of some volatile material was quite apparent; at 250 °C the

sample generated a white smoke. Arbitrarily, 500 °C was chosen for

the sample ignition temperature, because no volatiles were detected

in the N 2 gas stream and because the ignitions produced reproducible

results.

A number of samples from different bottles were ignited to

500 °C for one hour under N 2 gas. The average sample size was about 15 g and the average loss on ignition was 2.07 wt. percent.

The precision of these measurements was 0.15 percent, relative

standard deviation (RSD). However, in this ignition experiment,

all volatiles are measured, and therefore a separate determination

of water by the Karl -Fischer titration was performed by S. Margolis

of the Organic Analytical Research Division. One disadvantage of

this method is that water which is occluded or bound as water of

x l U.S. gallon = 3.78533 liters

XV-5
crystallization is not likely to be titrated. We believe that, in

this case, all of the water present was adsorbed and hence

titratable. In addition, because of the sensitivity of the

measuring instrument, only small (^100 mg) samples could be used

for analysis. This size restriction created an additional problem

since the bulk sample was originally very heterogeneous. The

average value found for the water content was 0.72 wt. percent

whicti in turn indicates, by difference, that the average amount of

volatile oil present was ~1.35 wt. percent.

Extraction

To test the relative efficiency of the extraction power of

various solvents, a Soxhlet extraction apparatus was used; a 300 g

sample size was chosen in an effort to minimize the effects of

sample heterogeneity. The purpose of these extractions was to

measure the weight loss of the samples after 2, 6, and 18 extractions for each of the four solvents tested. To do this, the

experiment was stopped after the requisite number of extractions,

and the sample was drained of excess solvent before removing the

sample from the apparatus. The remaining solvent was removed by vacuum drying at room temperature. The sample was then re- equilibrated at room temperature and humidity before weighing. We

assumed that the most volatile components, which could be lost upon vacuum drying, were actually extracted before the first vacuum

drying.

The concentration of volatiles was calculated directly from

the weight loss on extraction. As a second means of deducing the

concentration of. volatiles extracted, a small (10 g) sample was removed after each extraction experiment and subjected to the one hour tube furnace ignition. The sum of the loss on extraction and

the residual volatiles should equal 2.07 percent. The solvent

complicated matters since it was not possible to know when the

procedure for removing solvent (drying) from the sample did not

also remove water or other volatiles. The removal of excess solvent was necessary in order to determine the amount of oil

extracted from the sample.

The results obtained from the extractions and ignitions are tabulated in Table III. Freon 114 (1 ,2-dichlorotetraf luoroethane)

was definitely less effective than the other solvents. To some degree this effect may be attributed to its lower boiling point.

Extraction temperatures in the Soxhlet were lower than the boiling

points of the solvents, but the extreme difference in temperatures

may well account for the inefficient extractions with Freon 114.

Interestingly enough, all solvents yield approximately the same ultimate degree of extraction efficiency. The efficiency

differences between hexane, methyl isobutyl ketone, and methyl

ethyl ketone are less than the estimated experimental errors.

XV-6
Table III. Apparent Extraction Efficiencies (wt. percent).

Solvent Hexane

Methyl Isobutyl

Ketone

Methyl Ethyl

Ketone Freon 114

2 Extractions 1.5, 1.5

Q

] - 4

8

0.9

Q

Ignition °' 4

6

0.4

g

0.5

g

1.1

7

TOTAL 2.02 1.99 2.07 2.07

6 Extractions 17

6

1.6

8

Ignition 0.4

3 0.5, 0.5

? 0.8

6

TOTAL 2.19 2. 18 2.23 2.12

18 Extractions 1.7, 1.6

?

1.6

6 1.4,

Ignition 0.3

8 0.5

2

0.5

6

0.6.

TOTAL 2. 11 2. 19 2.22 2.08

Total estimated volatiles 2.07%, including 0.72% H 90.

Also, of potential interest is the behavior of the dry

(ignited) steel samples. All of these samples exhibited an affinity for water and had an average gain of 0.04 percent on exposure to air. Vacuum drying removed this water as well as solvent (and presumably volatile oils) so that exposure to the

atmosphere after drying was used to preserve a consistent basis for

a sequence of weight measurements. One sample was ignited to

1000 °C under N 2

, and it exhibited a further loss of 0.48 percent

compared to the ignition at 500 °C. This step caused visible

alteration in the sample (such as partial fusion); and thus, it is

difficult to know in detail what processes took place. Some

inorganics are volatile at this temperature while few, if any are volatile at 500 °C. In addition, since no odorous emissions were detected or visible emissions observed during the temperature

programming from 500 to 1000 °C, most of the volatile organics are probably lost in the 20 to 500 °C temperature range.

The total weight loss of these samples, whether by ignition to

500 °C or by separated extraction and then ignition is about 2.1

percent. It is likely that at least part of the 0.7 percent water

in the samples is extracted by the solvents and equally likely that

part of the oil fraction is not estimated. It is significant that

by whatever path used, figures of ~2. 1 percent total volatiles and

extractables are obtained. For this extraction procedure, Freon

114 was the least efficient solvent while the others chosen for

testing were quite similar in performance.

XV7
IV. Oil Recovery

The objective of the solvent study was to compare the efficiency of different solvents for the extraction of oil from

millscale. Solvents of different polarity were chosen ranging from

methyl ethyl ketone (the most polar), methyl isobutyl ketone, Freon

114, to hexane (least polar). Also a solid extractant, Rohm and

Haas Amberlite XAD-2 (a polystyrene/divinylbenzene copolymer), was used as a model for solid phase oil recovery.

The millscale solvent extracts from a Soxhlet apparatus were

taken for rotary evaporation and analysis. For the solid extraction sample, XAD-2 was mixed with the millscale in a ratio of 1:10,

and the mixture was heated at 100 °C for 1 hour while being shaken.

The XAD-2 was then separated by floatation on water, collected,

dried, and then extracted with methyl ethyl ketone. The resulting

extract was then handled in the same manner as the Soxhlet extracts.

In each case, the solvents were removed by rotary evaporation under vacuum at 50 °C. The resulting "millscale extracts" from each

solvent and XAD-2 were then weighed. The results were as listed in

Table IV.

Table IV. Apparent Mass of Millscale Extracts.

Grams Oil Extracted

Solvent per 300 g Sample Percent Oil Extracted

Methyl isobutyl ketone 2.34 0.78

Freon 114 2.11 0.70

Methyl ethyl ketone 1.88 0.63

Hexane 1.65 0.55

XAD-2 0.19 0.063

Few inferences may be drawn concerning the recovery of oil (by

mass) as considered from the viewpoint of the effect of solvent

polarity. The moderately polar solvent methyl isobutyl ketone

provided the best recovery of oil by weight. However, Freon 114 (a

relatively nonpolar solvent) ranked second in extraction efficiency,

followed by the most polar solvent (methyl ethyl ketone), and

finally the poorest efficiency was found using hexane. Differences

between these results and the previously reported gravimetric

results for the extractions may have been caused by loss of very

volatile hydrocarbons and water during rotary evaporation.

These results would lead us to conclude that a moderately

polar solvent is best for de-oiling mill scale. Thus, solvents

with polarities between that of methyl isobutyl ketone and

Freon 114 should provide satisfactory oil recovery. However, this

XV-8
conclusion must be tempered with the realization that many other

parameters, besides the polarity of the solvent, must be considered

in the extraction efficiency. The boiling point of the solvent

comes into play since it determines the temperature of the Soxhlet

extraction. Other properties such as solvent viscosity may determine

the rate at which the solvent can diffuse into the mill scale

particles.

The oil recovery achieved by using XAD-2 (the solid polystyrene

adsorbent) was fairly low. However, this experiment demonstrated

that at least some oil could be recovered by a solid adsorbent and

perhaps more oil could be recovered if higher temperatures than

100 °C were used. XAD-2 is too expensive ($6/1 b- ) to use for

de-oiling mi 11 scale, but other solids such as dry wood chips or charcoal might be more cost-effective.

V. Gel Permeation Chromatography

Gel permeation chromatography (GPC) was used to provide

information about the molecular weight fractions of the mill scale

extracts. This approach employs a high pressure pump which forces

the solvent through a packed bed consisting of a polymer gel with a control led, 0 uni form pore size. In this work, a polystyrene column

with a 200 A

2 pore size was used with toluene as the flowing

solvent. The solvent and polymer gel must possess similar

polarities because the separation is based on a purely physical

separation - diffusion. The sample molecules are forced along with

the flowing solvent, but are also diffusing in and out of the gel.

Molecules that are smaller than the pore size can diffuse into the

stagnant solvent of the gel. Larger molecules will not so diffuse

and thus will be carried more rapidly by the flowing solvent.

Large molecules will elute from the column first followed by

progressively smaller molecules. Although the separation mechanism

is based on molecular size, this quantity is linearly related to

the molecular weight for compounds of a homologous series.

The GPC system can be calibrated with a series of standards of

known molecular weight, and the log of the retention volume or time can then be plotted against the molecular weight. A straight line curve was obtained for a series of n-alkanes. Several standards

for aromatic compounds were also tested in order to determine their

respective retention characteristics; results are reported in

Table V. Aromatic compounds (benzene, perylene, and the polystyrene

standards) have much smaller size (and hence, longer retention

times) relative to the alkanes for an equivalent molecular weight.

° -10 2 Angstrom (A) = 1 x 10 meter

XV-9
Table V. Retention of Molecular Weight Standards.

Retention Time

Compound Class Molecular Weight (minutes)

Pentane (C

&

) n-al kane 72 3. 325

Heptane (C

?

) n-al kane 100 3. 175

Decane (C-jq) n-al kane 142 3. 000

Tetradecane (C^) n-al kane 198 2. 900

Hexadecane (C^) n-al kane 226 2. 775

Benzene aromatic 102 4. 45

Perylene aromatic 252 4. 20

Polystyrene

Standards

PS-1 aromatic 800 2. 75

PS-3 aromatic 4,000 2. 35

PS-6 aromatic 50,000 2. 25

The retention times for PS-3 and PS-6 are almost identical (2.35 versus 2.25 minutes) even though the molecular weights are 4,000

and 50,000, respectively. The structure of these two compounds is

much larger than the average pore size of the column. This property

causes them to be totally excluded from the pores of the gel, and

thus elute at very short retention times with very little resolution

between the two standards.

The detection approaches used were differential refractive

index (RI) and ultraviolet absorbance (UV). The refractive index

detector produces an output signal that is the difference in

refractive index between the sample and the reference solvent. For

this work, components with lower refractive indices than toluene

(the reference) are displayed above the baseline. Compounds that

have lower refractive indices include straight and branched chain

alkanes. Multi-ring aromatic compounds have a higher refractive

index than toluene and are displayed below the baseline. An

absorbance detector was also used being set at a wavelength of

315 nm (the cut-off of the toluene solvent). This detector

measures the absorbance of sample molecules so provides a selective

response for aromatic compounds of moderate and high molecular

weight.

XV-10
The conditions for the gel permeation analysis are detailed in

Table VI.

Table VI. Chromatographic Conditions.

Parameter Value

Sample size 20 uL loop injection of 50 mg oil/1000 mg toluene

Solvent Toluene flowing at 1.5 mL/minute

Column

Detectors

Polymer Laboratories PL gel 100A (200 A effective

pore diameter), 10 urn particles, 60 x 0.77 cm

Waters R401 differential ref ractometer sensitivity 4X

Kratos Spectroflow 773 UV absorbance detector,

wavelength 315 nm, sensitivity 0.75 AUFS

The actual chromatograms obtained from the mill scale extracts

(Figures 1-5) and roller lubrication greases (Figures 6-8) are

included. The molecular weight and class identifications are detailed in Figure 1, based on the response obtained for the

calibration standards.

There are several characteristic features of the lubrication

greases that should be noted: All have a fairly large amount of an aromatic fraction of molecular weight greater than 3500 amu. They

also have a large aliphatic fraction of molecular weight around

500. There is a large quantity of material having an aromatic

fraction with a molecular weight between 3500 and 300, with a maximum concentration of compounds of molecular weight 600 to 800.

Finally, there is a small aliphatic fraction with molecular weights

below 100.

The mi 11 scale extracts show several distinct differences from

the original lubrication greases. The high molecular weight

aromatic fraction (greater than 3500) is substantially diminished.

The moderate molecular weight aromatics (3500 to 300) are also

diminished, especially the fraction with molecular weight below

1000. The high molecular weight aliphatic fraction (at about

500 amu) is virtually the same in the extracts as in the lubrication greases. There is actually a higher proportion of low

molecular weight aliphatics in the extracts than in the parent

1 ubricants.

The respective individual solvents can be compared for their

efficiency of extracting the different fractions of the mi 11 scale

oil by a qualitative examination of the peak heights. Table VII

summarizes the results of this comparison:

XV-11
Table VII. Comparison of Extraction Efficiency of Different Solvents.

- - Molecular Weight Fraction Recovery3

- -

Arpmatics - Aliphatics -

High MW Moderate MW High MW Low MW

Solvent (>3500) (3500-300) (<500) (<100)

Hexane + +++ ++ +++

Freon 114 ++ +++ +++ ++

Methyl isobutyl ketone + ++ ++ +++

Methyl ethyl ketone ++ +++ +++ ++

XAD-2 + + + +

^here best recovery is symbolized by +++.

The GPC data are a direct indication of the concentration of

detectable components in different molecular weight categories.

However, for the mi 11 scale extracts an additional parameter must be

considered when evaluating the results given in Table VII. The mass of oil extracted will also determine the relative response for

each molecular weight fraction. This effect is particularly

apparent for the results obtained for methyl isobutyl ketone. The

experimentally determined peak heights indicate that this solvent

is not very good for extracting the first three molecular weight

fractions. However, because this solvent was so efficient at

removing low molecular weight aliphatic compounds (and perhaps

undetected low molecular weight aromatic compounds), the other

fractions are effectively diluted by these components. The most

oil was recovered by methyl isobutyl ketone; and thus, some of the

fractions are diluted and give correspondingly low peak responses.

Several general statements can be made about the oil removed

from millscale by the various liquid solvents. The oil is depleted

in the high molecular weight aromatic compounds (>3500) compared to

the mill lubricants. This result could be caused by one of two

distinct factors: Some of the large aromatic compounds may have

been "cracked" by the high temperature milling process into smaller

fragments and then lost by volatilization. The second, and perhaps more likely possibility, is that this high molecular weight fraction

is not being completely removed from the mill scale by the solvents

tested under the conditions chosen.

XV- 12
Another characteristic of the extracts is the lower proportion

of low molecular weight aromatics, especially of molecular weight

below about 1000. These components are significantly depleted

compared to the lubricants. Since these components should be

easily extracted by all the solvents, they may have been lost by

volatilization in the milling process or lost during sampling,

shipping, and storage.

The high molecular weight aliphatics recovered by the Soxhlet

extraction are very nearly equal to what is present in the lubricants

for all solvents. However, a larger amount of low molecular weight

aliphatic components occurs in the extracts, especially for hexane

and methyl isobutyl ketone. This observation is of particular note

since some of this fraction will be volatilized in the rotary

evaporation step. This significant increase, relative to the other

components, is probably due to cracking of larger aliphatic com- ponents in the heat of the milling process. This fraction may be

of the greatest significance to the explosion problem found when

untreated mi 11 scale is used as sinter feed. These low molecular

weight aliphatics, such as butane, perhaps branched pentanes, and

hexanes, are quite volatile and form explosive mixtures with air

even at low concentrations of vapor and may contribute significantly

to the explosions observed when untreated mi 11 scale is used as sinter feed.

VI. DSC Experiments

Three lubricating greases which are commonly used in rolling

mills were examined using differential scanning calorimetry (DSC)

to determine their initial and peak decomposition temperatures and

when possible to obtain an estimate of their calorific values.

Experiments were conducted with air as the purge gas at 700 kPa

(100 psig) and at a controlled heating rate of 20 °C per minute.

The resulting data are shown in Figures 9, 10, and 11. These

figures indicate the presence of two prominent classes of organic

compounds with peak temperatures in a low (257, 275, 276 °C) range

and high (472, 480, 484 °C) range. A third less prominent peak (or

shoulder) appears at about 300 °C.

Lubricating greases obtained by means of de-oiling mi 11 scale

samples from Bethlehem, Republic, and Inland Steel Corps, using

solvent extraction procedures were examined. DSC thermograms

showed peak temperatures for the initial class of organic compounds

undergoing decomposition at 310, 324, 325 °C; see Figures 12, 13

and 14. Calculation of calorific values for the extracted lubricating greases from Republic and Bethlehem mi 11 scale samples yielded

5162 J/g and 4817 J/g.

The thermal stability of each of the three extracted greases

measured by DSC was limited to 400 °C. Above this temperature, a rapid transition was observed which was manifested by several sharp

temperature spikes in the thermogram. This phenomenon is usually

associated with sample ignition or explosive decomposition. This

XV-13
result was not observed in the unused grease. The cause of this

difference may be related to the thermal history of the greases

during the rolling process which resulted in a higher molecular

weight material that may be oxidized very rapidly above 400 °C.

VII. Summary and Conclusions of Experimental Results

Particle Size Studies

Considering the source and nature of mi 11 scale samples, it is

not too surprising that the millscale shows evidence of considerable

heterogeneity (Tables I, II). As with the Inland sample, the

presence of a slight excess of oil can cause a large decrease in

the apparent number of fine particles. Yet, when this sample was de-oiled by solvent extraction, the number of -50 mesh particles

found was very similar to the other millscale samples.

These considerations suggest difficulty in any attempt to

prepare a "representative" sample or in preparing a single large

homogeneous lot of material for use as a reference standard.

Indeed, later experience in handling these samples demonstrated

that after the process of laboriously coning and quartering a very

large sample to obtain 300 g samples, the sub samples themselves

later experienced some re-segregation.

Extraction Studies

Two different procedures were developed in order to determine

the amount of oil in a specially prepared set of replicate samples.

In the first procedure, a simple ignition to 500 °C under nitrogen

was used to determine the weight loss from the samples. Although

the temperature chosen was somewhat arbitrary, we believe it to

be high enough to remove most volatiles and oils. Above 500 °C, no condensate could be observed on the cold parts of the combustion

apparatus. In addition, most of the DSC thermogram results

(Figures 9-14) suggest that the oils are volatilized below 500 °C.

The water content of the samples was unexpectedly high (0.72

percent) and this in turn caused increased difficulty in determining

the amount of oil present. The ignition yielded an average of 2.1

percent volatile with a RSD of 0.003 percent (absolute). By

difference, this result suggests an oil content of ~1.35 percent

with a substantial uncertainty.

The second method used four different solvents in a Soxhlet

apparatus in an attempt to characterize the relative extraction

efficiency of the solvents. As shown in Table III, this effort was largely unsuccessful because all of the solvents, except for Freon

114, proved to be very good solvents for these extraction studies.

If the average value of 2.15 percent oil found after 18 separate

extractions by the four solvents is used, and the same correction

for a water content of 0.72 percent is used, an apparent oil

content of 1.43 percent is found. Considering the substantial

XV- 14
uncertainties involved, this finding is in very good agreement with

the 1.35 percent figure obtained by the combustion tube method.

Oil Recovery

After the removal of solvent by rotary evaporation, the four

sample extracts were weighed to yield a figure for the percentage

of oil recovered from the samples (Table 10). Qualitatively, the

amount of oil recovered from each solvent is similar — yet all

samples yield an assay for oil which is about one half that

obtained by solvent extraction and gravimetry (~0.66 percent

average vs 1.43 percent). Although there may be a procedural bias

built into one or both methods, the rotary evaporation probably

caused a loss of a substantial amount of oil through volatilization.

Gel Permeation Chromatography

All of the extracted oil residues (as described above) were analyzed by gel permeation liquid chromatography together with

samples of typical lubricants (e.g., Veedol). A comparison of the

results, as illustrated in Figures 1-8, demonstrates that all of

the solvents used gave good recovery of moderate molecular weight

aromatics as well as all aliphatics. High molecular weight

aromatics were not well extracted, presumably due to the relatively

low temperature of the Soxhlet extraction.

The relative proportions of low molecular weight aromatics are depleted in the extracts relative to the lubricants whereas the

relative proportions of the low molecular weight aliphatics are increased. No clear explanation for this difference was found.

DSC Experiments

The results of these experiments are illustrated as DSC

thermograms in Figures 9-14 and may be summarized as follows: Two

prominent peaks were found for the unused lubricating greases, and

these peaks correlate well with the gel permeation-1 iquid chromatography studies of the same materials. Peak decomposition temperatures between 470-485 °C for unused lubricating oil may correspond

to the high molecular weight formation observed by gel permeationliquid chromatography. The 500 °C temperature used for the combustion tube-nitrogen sweep of the samples is well above the highest

peak observed. The peak decomposition temperatures between 310-

325 °C for the millscale extracts could correspond to the high

molecular weight aliphatic fraction observed in the gel permeation

liquid chromatography study.

Concl usions

Fairly large samples (300 g) were required to give reasonably

significant data for the comparison of the relative extraction

efficiencies of four solvents. Since all of the solvents except

XV- 15
Freon 114 exhibited high efficiency, the chances are good that a less costly and more environmentally acceptable solvent than Freon

114 can be found. Experiments such as these may prove useful in

studying and optimizing operational mi 11 scale deoiling operations.

The very simple measurement of loss on heating to 500 °C (under N2 ) may prove to be a useful method for measuring the efficiency of

deoiling plants. The method is quick (1 hour), precise (»1

percent relative), consumes little sample (15 g), but does require

a correction for the water content of the sample.

XV- 16
APPENDIX

Description of a Deoiling Plant

I. Selection of a Process and Solvent

Several methods of deoiling of steel waste have been investigated and are described in the literature [1]. These may be

classified into three groups:

1) Thermal incineration

2) Saponification and solution in large quantities of

water

3) Washing with organic solvent

The incineration method is high in energy consumption. Also,

it creates a secondary exhaust control problem with additional

energy requirements, and a tertiary waste water problem. (Such an installation can scarcely be constructed without a gas scrubber.)

The heating of one ton of scale to 600 °C (red heat) consumes

about 110 kWh as thermal energy. The fuel consumption of a rotary

kiln installation with flue gas afterburner and wet scrubber,

working in the USA, is reported to be 261 kWh/t scale.

Washing with detergents to remove oil is also judged to be

unfavorable and expensive as the costs for detergents are intolerably high especially when combined with the cost of treating the

resultant waste water. The latter task stretches prevailing legal

tolerances. It seems absurd to convert a disposal problem, with

much effort, into a waste water problem.

Only the process of deoiling of millscale with solvents seems practical without significant effort and expense to avoid secondary

pollution of the environment. The necessary process technology has

been developed and utilized successfully [2] to deoil steelwaste in

Europe. Freon 11 (trichlorofluoromethane was the solvent used for

the extraction process. However, this solvent may not be acceptable

to the U.S. Environmental Protection Agency due to its adverse

environmental effects. Therefore, one wishes to select a low

boiling hydrocarbon as an extracting solvent. The selection of an appropriate solvent should be based on the following criteria:

1) Favorable threshold limit value for work place atmosphere

and not injurious to health.

2) Trace amount remaining in deoiled grease should be

nonflammable or burn cleanly, thus to avoid explosions

during sintering.

3) Chemically stable and easy to recycle.

4) Effective removal of greases and oils from the millscale.

5) Economic practicability, favorable price.

XV-17
Several hydrocarbons have been examined as solvents for

extraction of oil from millscale. Based on deoiling efficiency,

hexane may be used as an extracting solvent. Hexane is relatively

cheap and non-toxic, and trace amounts of hexane remaining in

deoiled grease will burn cleanly and will not pollute the atmosphere.

Unlike Freon 11 used in European Plant, hexanes are highly flammable

liquids and increase the risk of fire in work place. However, U.S.

food industries have been using hexane as a solvent to extract oil

from grains. So the flammability problem apparently can be handled

by means of the existing technology in food industries.

II. Major Features of the Plant

The plant consists of three processing units:

(A) the deoiling unit

(B) the solvent reclamation unit

(C) the exhaust air cleaning unit

III. Deoiling of Millscale

In the millscale doiling unit, adherent grease and oil are removed from the scale by the solvent Freon 11*; the scale is then

washed with hot water to vaporize adherent solvent. This unit is

covered by a gas and vapor-tight hood, into which a large,

refrigerant-cooled condensor is incorporated.

The screened greasy scale is taken from the hopper and fed by

weight into the material entrance sluice. The drawing off of scale

from this entryway is regulated by means of a load cell in such a manner that a full material column will always be maintained

sufficient to form a seal against the escape of solvent vapors.

Inside the subsequent double screw mixer, the greasy material

is mixed with solvent in order to break up scale and sludge lumps

held together by grease. The mixture then falls into the solvent

bath. While the scale is sinking in free fall to to the bottom of

the bath, the oils and greases are dissolved. The scale is drawn

off the bottom of the solvent bath by an ascending screw conveyor,

and above the bath level it is rewashed with clean solvent. As the

scale is conveyed further upwards the solvent is drained from it.

Stil 1 -adherent solvent remains are vaporized by means of hot water

in a scavenging rinse trough which brings the scale into a hot

water bath. With a dewatering screw conveyor, the scale is then

moved out of the water system to the draining area, outside of the

building. At the same time, the rinse trough and screw conveyor

serve as a seal against the escape of solvent vapors on the discharge

s i de

.

* Solvent Freon 11 can be replaced by hexane.

XV-18
The hot process water moves in a closed circuit, losses to the

scale being made up with fresh water additions. The overflow from

the rinse trough is cleaned in a laminated settler and a non- clogging screen before it is returned to the sump.

The heat losses from the water due to the evaporating of

residual solvent, and from the associated heating of the scale, are restored in the condensor of the refrigerating engine. Water is

reheated to about 53 °C* and is then returned to the solvent

scavenging rinse trough.

IV. Solvent Reclamation

The solvent utilized for the dissolving of oils and greases is

completely reclaimed in a three-stage distillation plant:

The grease and oil-bearing solvent, the "mi seel la", flows over

the brim of the solvent bath into a collecting channel leading to

the miscella collecting tank. On its way, the mi seel la passes a magnetic filter and a non-clogging screen for filtration.

A partial flow is pumped back into the double screw mixer of

the deoiling unit; the main part is charged to the solvent recovery

system.

In the first distillation stage, which is constructed as a forced circulation evaporator, about 90 percent of the solvent is

recovered. The miscella is preheated with hot water to 23 °C*,

then heated up to 24.5 °C* under atmospheric pressure (1 atm). The

required process heat is collected from the connected solvent

condenser by means of a heat pump. The heat is transferred via a secondary refrigerant circuit. The pressure gradient necessary for

heat recovery is induced by a turbo compressor.

The liquefied clean solvent returns to the ascending screw conveyor of the deoiling unit, above the solvent bath level, for

rewashing of the scale.

From the first-stage evaporator, the concentrated liquid

oil /sol vent mixture is pumped into a second distillation stage,

which is also constructed as a forced circulation boiler.

This stage works at 50 °C* and 1.1 atmosphere pressure. The

process heat is delivered by hot water. The vaporized solvent is

recondensed by refrigerant and flows also into the screw conveyor

of the deoiling unit.

* Conditions will change due to the use of hexane as solvent.

XV- 19
This (further) concentrated miscella flows continuously into

the batch evaporators of the third distillation stage. In this

stage, final solvent vaporization is effected at about 100 °C* and

under vacuum. During filling of the evaporator and heating of the

miscella to 100 °C* the solvent vapors are vented under normal

pressure to the condenser inside the gas-tight hood covering the

deoiling unit and thereby liquefied.

When filling is finished, the apparatus is set for vacuum

evaporation. At first the pressure is lowered to 133 mbar* (100 mm

Hg pressure), thereafter to about 27 mbar (20 mm Hg pressure)*. As soon as this pressure is reached, (at about 100 °C*) the discharge

valve opens.

The oil/grease mixture obtained in this manner contains only

traces of solvent, lying near the limit of analytical determination.

The oil/grease mixture is delivered to the waste oil treatment

plant of the steel works. The oil has a calorific value which is

in the range of that of heavy fuel oil.

VI . Cleaning of Exhaust Air

As already mentioned, the deoiling unit is sealed by the feed

hopper on one end and by the water bath on the other side. Gases

in this range are captured in a gas hood. The solvents are mostly

liquefied by means of a condenser in the hood, and are returned to

the screw conveyor. The air which is brought in with the scale,

saturated with solvent vapor, is drawn out and cleaned in an air

cleaning installation.

The solvent-saturated air is treated in an ejector and a bubble tray column with cold absorption oil. The solvent vapors

are absorbed by the oil, and the cleaned air is discharged.

Regeneration of the absorption oil is effected by heating it up to

90 °C* and by expanding, first into a flash cyclone at 100 mm Hg*

and then into a falling-film evaporator at 20 mm Hg pressure*.

The solvent vapors are compressed and recondensed by the vacuum pumps, and the liquified Freon 11* is recycled into the

deoiling process.

Summary

Fires occurring in precipitators of modern sinter plants can

be attributed to the introduction of hydrocarbons into the sinter

mixture. Oi 1 -containing scale must, therefore, be de-oiled before

it is sintered if conventional technology is used. For this

purpose, a process has been developed, by which oils and greases

are removed from the scale by use of the solvent Freon 11; hexane

can be substituted, however. The use of this solvent allows for a nearly total solvent recovery from the separated oil/grease mixture,

and also permits the application of large heat pumps to the circuit.

Conditions will change due to the use of hexane as solvent.

XV-20
A plant constructed for 50 t/h scale would have a solvent

consumption of about 1 kg/t scale at an average inbound oil content

of 0.4 percent. The overall energy consumption, thermal and

electrical, amounts to 14 kWh/t. The residual oil content in the

deoiled mi 11 scale is about 0.01 - 0.03 percent.

This deoiled mi 11 scale is usable in the sinter mix without any

difficulties.

This study was funded by the NBS Office of Recycled Materials

in response to the needs of the U.S. steel industry as represented

by the American Iron and Steel Institute (AISI), Committee on General Research, Unit 2 - Removal of Hydrocarbons from IronBearing Wastes.

XV-21
References

[1] Balajee, S. R. , Deoiling and Utilization of Mi 1 1 sca^e. First

EPA Symposium on the Iron and Steel Pollution Abatement

Technology. November 1, 1979.

[2] Barnes, T. , AISI Committee Correspondence. December 29, 1981.

XV-22
Aromatics

MW >3500

Aliphatics

MW ^ 500

Aliphatics

MW< 100

t

Inject

8 12 16 20

Minutes

Aromatics

MW>3500 Aromatics

MW 3500 to 300

XV-23
Freon Extract

Inject Minutes

Figure XV. 2. GPC chromatog ram, mill scale extract Freon 114

solvent.

XV-24
Methylethylketone Extract

Inject Minutes

Inject Minutes

Figure XV. 3. GPC chromatogram, mill scale extract methyl ethyl

ketone solvent.

XV-25
Hexane Extract

XV-26
XAD-2 Extract

|

4 8 12 16 20

Inject Minutes

Figure XV. 5. GPC chromatogram, millscale extract XAD-2 solvent.

XV-27
XV-28
Brooks

f

Inject

8 12 16 20

Minutes

T

0.075 AUFS

1

J.

1

j

4 8 12 16 20

Inject Minutes

Figure XV. 7. GPC chromatogram, Brooks lubricant (prior to u

XV-29
Veedol # 56

l— j « i 4 8 12 16 20

Inject Minutes

I i i i i i |

4 8 12 16 20

inject Minutes

Figure XV. 8. GPC chromatogram, Veedol #56 lubricant (prior to

use)

.

XV-30
<M"0 MO Id ^osH

xv-31
XV-32
u

CM

o

CAT) MO Id ^osH

XV-33
(Mw) MO Id

XV-34
<MW) MO Id ^DaH

XV-35
XV-36
APPENDIX XVI.

Evaluating the Risks of Solid Waste Management Programs:

A Suggested Approach

Robert E. Chapman

and

Harvey Yakowitz

National Bureau of Standards

Washington, D. C. 20234

Background

Solid waste management is among the most complex municipal or regional

governmental tasks facing policy makers today. The physical problem of where

to locate needed facilities is further complicated by the increasing costs of

disposal, new technologies, environmental regulations and the unavailability

of the land for landfill. The problem becomes even more challenging when one notes that solid waste management facilities may exhibit economies of scale in

construction and processing. This possibility implies that the benefits

associated with lower per unit processing costs can only be achieved through

regionalization. However, the process of regionalization creates two

fundamental problems: (1) the complexity of the regional system design; and

(2) the need for political consensus. Both of these problems may be addressed

by developing and clearly presenting technical and economic data about the

consequences of various regional approaches. Finally, by opting for

regionalization, decision makers must weigh the benefits of reduced processing

costs against the risks of cost overruns which are inherent in large

construction projects.

The approach outlined in this paper attempts to integrate the regional

planning problem with a technique for evaluating the risks of resource recovery options. This is accomplished in two stages. First, the Resource

Recovery Planning Model (RRPLAN) is described. This section of the paper

summarizes the model's assumptions, major components and modes of operation.

An algebraic statement of the problem is then given along with a description

of the solution algorithm. The second section consists of an in-depth case study for central Mississippi. A coordinated set of questions are hypothesized and solved to illustrate how the model would be applied in an actual planning context. The model's results are then used to develop

statistical relationships which permit an explicit assessment of project

risk.

The Resource Recovery Planning Model (RRPLAN)

Over the past decade, there has been a proliferation of mathematical models

dealing with such issues as facility location, vehicle routing and manpower

planning (Liebman [1975]). Due to unrealistic data requirements or the

complexity of using and interpreting the model's results, the application of

these models to the solid waste management problem has sometimes been

XVI -1
disappointing. More recent modeling approaches have attempted to couple the

analytical power of the computer with the ability to organize systematically

the thoughts of the decision maker so that important pieces of information are not overlooked (Jenkins [1982], Chapman and Berman [1983]). From these

experiences, it is possible to define a set of criteria that any model which

purports to deal with solid waste management problems should satisfy. At a minimum, any such model should be able to derive explicitly the effects of

alternative financial and cost-sharing arrangements, allow for economies of

scale, and be amenable to sensitivity analysis associated with a well-chosen

set of "what-if" questions.

Although the general solid waste management problem poses some formidable

difficulties to decision makers, the economic analysis of resource recovery

options is significantly more complicated, since an in-depth analysis of

facility design and cost as well as market size, structure and location is

required. In order to address these complicating factors, RRPLAN deals with

two interdependent issues. On the one hand, RRPLAN explicitly incorporates

potential economies of scale in the construction and operation of a solid

waste processing facility. The model is thus able to support the basic

tradeoff of savings from centralized processing versus the costs of additional

haul required to bring such savings about. On the other hand, RRPLAN uses a detailed cost accounting system to attack the economic issues by carefully

estimating the effects on overall program costs due to decisions affecting

siting, routing, marketing and financing. By integrating the technical issues

of processing with these four major decision points, RRPLAN permits a wide

variety of questions to be examined carefully.

RRPLAN may be thought of as a descendant of two earlier models. These models

are known as WRAP, Waste Resource Allocation Program (Berman [1977], Hensey

[1977]), and RAMP, Recovery And Market Planning (Berman [1976]). Both models were developed by the Mitre Corporation, the former through funding from the

Environmental Protection Agency. There are substantial differences between

the two models, especially regarding their software support systems and their

treatment of market structure. Both models use the same optimizer as RRPLAN.

In WRAP, as in RRPLAN, a front end is available to build the equations for

input into the optimizer, and a back end is available to interpret the

solution. In RAMP a more sophisticated equation structure is available,

including the full market structure in RRPLAN, but the user must prepare

equations for direct input into the optimizer, and must interpret its

solution. The major focus of WRAP is on the identification of a preferred

plan which includes the best candidate sites, the appropriate processing and

disposal technology at each site, the sizing of each site and all

transportation linkages among centers of waste generation, processing sites,

and disposal sites. A major weakness of WRAP is its implicit assumption that

any market for recoverables (e.g., ferrous products and newsprint) is

unlimited. If market saturation is an important consideration, then WRAP'S

solution would represent an overly optimistic plan which could lead to serious

cash flow problems if the plan were implemented. RAMP adds the saturation

effect by incorporating both declining price and limited size markets.

XVI -2
RRPLAN, on the other hand, incorporates all of the capabilities of WRAP and

RAMP, as well as numerous enhancements which render its cost accounting system

far superior to those used in its predecessors. Furthermore, RRPLAN' 8 more reasonable data requirements than WRAP, coupled with the type and nature of

its output, should permit RRPLAN to greatly facilitate the regional planning

and decision making processes. RRPLAN contains a more realistic cost model,

built-in source-separation options, an automatic dedicated transfer station

function, user-defined cost, energy, and commodity categories, and an extensive analysis of costs by source and site, including a projected

full-cost tipping fee for each site.

RRPLAN is a computer model designed with three purposes in mind. First and

foremost, is the ability to generate a preferred plan for resource recovery.

Second, is the capability to evaluate a scenario specified by the decision

maker for technical and economic feasibility. Third, is its use as a tool to

facilitate the decision making process by providing answers to many what-if

questions through an in-depth sensitivity analysis.

The model has five basic modes of optimization. Each mode serves to define

the type of objective which is to be minimized or maximized. The first two

modes of optimization minimize the total cost of the regional plan over a specified planning period. The first mode minimizes the discounted costs of

the regional plan. Such an objective function would be required if both the

timing and magnitude of cash flows are important. If only the magnitude of

cash flows is important, then the second mode, minimization of undiscounted

costs, should be chosen. The choice of discounted rather than undiscounted

costs, or vice-versa, may cause both the costs of the plan and the physical

flows within the system to differ. The first mode, minimize lifetime

discounted cost, is the preferred criterion for plan selection and evaluation.

The third mode of operation seeks to maximize the net energy of the regional

plan (i.e., energy produced (saved) from (due to) resource recovery activities

minus all other energy inputs). Such an objective function might be useful in

comparing various waste-to-energy programs. The fourth mode of operation

seeks to minimize a linear form (weighted sum) of program cost and net energy

categories. This approach might prove useful in comparing mixtures of

traditional and waste-to-energy programs if some form of matching formula for

funds was in effect. This mode of optimization will permit the user to weight

cost or energy categories other than equally. The fifth mode focuses on the

topic of scenario evaluation . For example, a region may propose a plan which

needs to be evaluated from the viewpoint of technical and economic

feasibility. Typical questions addressed under this mode of operation would

include the following: Are all facilities able to process the indicated waste

stream without exceeding their rated capacity, or that of plants down the line

into which they feed? Can resources be reallocated so that overall costs are reduced?

In order to handle the five types of objectives just discussed, RRPLAN

includes a set of cost categories, energy categories, and commodities. Cost

categories are the heart of RRPLAN' s accounting system. They are included so that the differential impacts of the regional plan on the various segments of

the population, as well as financial transfers into the region from marketing

XVI -3
activities, can be measured. Individual cost categories are classified as either operating (i.e., recurring annual costs) or capital. Each cost

category has a cost growth scenario (differential inflation rate) associated

with it, so that it may increase more (or less) rapidly than the general rate

of inflation. Financial arrangements are explicit in all capital cost

accounting. All capital items, except those currently in use, are assumed to

be purchased at the beginning of the planning period. Replacements which occur within the planning period are inflated by the differential inflation

rate from the first year of the planning period to the year of replacement. A

standard amortization calculation is used to generate an annual cost for each

year of the capitalization of the loan. A series of cost summation categories

permit the user to aggregate cost categories having differential inflation

rates, useful lives, etc., into a single cost summation category for further

analysis. Energy categories may be handled in a similar manner. The model

greatly facilitates the process of performing a detailed cost analysis, once a solution has been found, by leaving the user ample opportunity to define the

types of commodities processed and sold (e.g., municipal solid waste (MSW) and

steam). The use of separate commodity categories also permits one to measure

the effects of differential transportation costs (e.g., handling MSW versus newsprint) as well as cost-sharing arrangements for processing and/or

revenue-sharing arrangements among municipalities for marketing activities.

The basic structure of RRPLAN consists of a set of equations and activities

relating sources of solid wastes, sites where the wastes can be processed and

markets for energy or recovered materials. Figure 1, a capsule summary of the

major physical system details, outlines the relationship between the model's

equations and activities.

Both the model and the physical system begin with a source of waste, or "waste

generation zone." At this point RRPLAN permits the user to offer two types of source separation for consideration or to ship the mixed MSW directly to a processing facility. Under the first source separation scenario, the model assumes that all paper, glass and cans are removed from the waste stream, sent

to a central collection point, and then shipped to the respective market.

This option is referred to as unconditional source separation. Under the

second source separation scenario, paper, glass and cans are always removed

but paper is treated separately. As in the previous scenario, cans and glass are sent to the central collection point and marketed. Paper, on the other

hand, is put to two possible uses which reflect both its fiber value in

recycling and its energy value in combustion. This option is referred to as conditional source separation. The rationale behind this scenario is as follows. If the price of paper exceeds some prespecified price (up to five

such "trigger" prices are available) then it will be marketed for its fiber

value; otherwise the paper will be burned. If multiple options are offered at

a source, the model selects the preferred option. For example, all

transportation linkages emanating from the source in figure 1 are coded to

differentiate whether the link is carrying wastes or recoverables . The same coding system is used throughout the diagram. If source separated paper, cans and glass (or any other marketable commodity) are to be shipped to the market,

then they flow along the clear linkage. If, on the other hand, mixed MSW or the residue from source separation is to be shipped, then flow occurs along

the shaded linkage. Note that all wastes generated enter into transportation.

XVI -4
Each transportation, processing, and marketing activity has associated with it a set of costs. For transportation, these costs include the periodic

replacement of the rolling stock as well as the cost of physically hauling the

wastes or recoverables . The facilities where processing takes place require

greater care in cost accounting. For example, there may be site preparation

costs (e.g., access roads) over and above the plant construction costs and the

normal costs of day-to-day operations. No economies of scale are assumed in

transportation. However, economies of scale are admissible for both facility

construction and all future processing activities. Thus, the model can capture the basic trade off of savings from centralized processing versus the

costs of additional haul required to bring such savings about. In addition to

costs, the appropriate capacity associated with a processing facility at a particular site (site-process combination) can be selected. The setting of a capacity can be based on either political or technical constraints. Setting

a capacity would thus prevent the model from shipping to a single site more waste than would be technically or politically feasible.

Two types of markets are also shown in the diagram. RRPLAN treats the markets

for energy (e.g., steam or electricity) and materials in a much more comprehensive manner than WRAP. RRPLAN can handle four types of market

structure: (1) unlimited fixed price markets; (2) capacitated fixed price

markets; (3) declining price markets with no upper limit; and (4) capacitated

declining price markets. An example of an unlimited fixed price market might

be an electric utility which will purchase any amount of electricity from the

plant at a flat rate of kt per kWh. An example of a capacitated declining

price market might be a nearby industrial facility which will purchase process

steam for $3 per K (thousand) lbs for the first 900 M (million) lbs; but will

pay only $2 per K lbs for the next 900 M lbs; and can not productively use the

steam above 1800 M lbs. The market is considered saturated at 1800 M lbs.

RRPLAN also permits revenue sharing arrangements among municipalities to be

incorporated into the market analysis.

The model approaches the difficult problem of siting and sizing solid waste

processing facilities by first approximating non linearities in the capital

and operating cost functions with up to three linear segments. Each segment

has an intercept (a fixed charge) and a slope (an incremental cost associated

with increased processing activities) . The introduction of fixed charges

imposes certain complications, due to the existence of local optima. Such

circumstances require a specially designed optimization technique to generate

meaningful solutions. The technique used in RRPLAN involves a fixed-charge

linear programming algorithm with a forcing procedure meant to insure that the

model can pass over an area of temporarily increasing cost in the solution

domain (i.e., a local optimum) to find the true optimum (Walker [1976]).

RRPLAN adds new forcing methods representing a significant improvement over methods used in other models (Berman, Chapman and Hung [1983]) in which each

site (or site-process combination) which was in the solution is forced out of

the solution and vice-versa. This approach permits the solution domain to be

searched in a more coordinated way by operating on all activities (e.g.,

transportation, processing, marketing) associated with a particular site (or

site-process combination). WRAP's method of single or double column (i.e.,

the activities described in table 2) forcing is of questionable efficiency,

particularly where a site is linked to three or more sources or other sites.

XVI -5
Furthermore, column forcing operates from within the optimizer, so it is blind

in the sense that there is no information within the optimizer on what the

various columns (activities) represent.

Assuming that cost minimization is the sole objective of the decision maker,

the problem to be solved by the optimizer may be stated as

n minimize Z = J f i^ x l) equation 1 j»l

subject to the linear constraints

AX = b (i)

X > 0

where

(ii)

fjCXj) « cjXj + kjfij (iii)

with

6j = 0 if xj = 0

6

j = 1 if xj > 0.

The vector X contains n elements known as activities (e.g., shipments of MSW

from a source to a site). The tilde is used to distinguish the vector, X ,

from the elements xj . The matrix A contains m rows and n columns. (It is

assumed that n is greater than m. ) The rows refer to the equations defined in

table 1 and the columns to the activities defined in table 2. The cj in

condition (iii) are variable costs and the kj are the fixed charges. (The kj

values are required to be greater than or equal to zero. If the activity has no fixed charges, then kj is equal to zero.)

RRPLAN as a Planning Tool: A Case

Application for Central Mississippi

After preliminary testing of the REPLAN model with data from New York City's

Department of Sanitation and the California Solid Waste Management Board, the

model was applied to data from a three county area surrounding the city of

Jackson in central Mississippi. The primary objective was to determine how

RRPLAN could be used as the basis for developing the economic requirements for

a variety of municipal solid waste options which might be exercised in the

Jackson area.

XVI -6
XVI -7
TABLE 1 Equations Used by RRPLAN

Equation Type Purpose

Source balance equations Requires all waste generated at each source to be entered into transportation.

Source paper balance equations

Site input residue balance equations

Requires all source-separated paper to

be entered into transportation.

Generates a residue activity at a site

equal to the residue arriving at the

site.

Site input paper balance equations Generates a paper activity at a site

equal to the paper arriving at the

site.

Site input balance equations for

MSW and other commodities

Requires the total amount of MSW and

other commodities arriving at a site

to equal the amount of processing

activity at the site.

Site output balance equations Generates transportation activities

of a commodity from a site equal to

the process output of the commodity

at that site.

Market input balance equations Generates a total market activity

equal to the amount of the commodity

arriving at the market.

Site capacity constraints Insures that processing at a site does

not exceed capacity.

Land capacity constraints Insures that land use does not exceed

land available at any landfill.

Market bounds Requires the sum of activity at a market in segments less than or equal

to the jth (Kj<5) segment to be less

than or equal to the jth cumulative

bound for the market.

Constraint on artificial

processing activities

Provides an upper bound for artificial

activities used to preserve the

structure of the A matrix.

XVI -8
TABLE 2 Activities Considered by RRPLAN

Activity Purpose

Transportation category 2 Site-to-site shipments.

Transportation category 3 Site-to-market shipments.

Transportation category 4 Source-to-site shipments of unseparated MSW.

Transportation category 5 Source-to-site shipments of unconditional

source separated MSW (national paper

market3

)

.

Transportation category 6 Source-to-site shipments of unconditional

source separated MSW (local paper market).

Transportation category 8 Source-to-site shipments of pre-separated

paper (local paper market).

Transportation category 9 Source-to-market shipments of pre-separated

paper (local paper market).

Transportation categories 11-15 Source-to-site shipments of conditional

source separated MSW (national paper market)

with 1 to 5 trigger prices.

Residue activities Measures thousands of tons per year of

source-separated residue arriving at a site.

Paper activities Measures thousands of tons per year of

source-separated paper arriving at a site.

Process activities Measures number of commodity units processed

per year per linear segment at a site.

Market activities Measures number of commodity units purchased

per year per linear segment at a market.

Artificial processing

activities

Take on arbitrarily small values to preserve

structure of the A matrix.

NZ Relieves infeasibilities associated with an advanced starting point.

NZX Relieves infeasibilities when evaluating a prespecified plan.

aThe nature of the paper market depends on whether the quantities of paper

processed by the model will or will not affect the price. If the price is

unaffected, then the market is designated as national. If the price is

affected, then the market is designated as local.

XVI -9
Data on costs, markets, amount of MSW, inflation rates, and sites in the

Jackson area were provided by the Bureau of Pollution Control of the

Mississippi Department of Natural Resources. In summary, approximately 360

thousand tons per year (KTPY) of MSW were calculated to be generated in the area. Steam and/or electricity from a potential waste-to-energy facility

could be marketed — steam to the packing industry and electricity to the

local untility. Source separation was not to be implemented regionally; there was litle or no market for recovered materials except aluminum. Landfill

could be used if necessary (i.e., siting could be accomplished). Financing

for a waste-to-energy facility could probably be obtained at a 10 percent rate

for a 15 year term; the useful life of the facility was anticipated to be 20

years

.

The first task for RRPLAN was to estimate the cost of an all landfill-no

recovery option given collection costs, disposal costs, land costs and labor

and transportation costs in the Jackson area. This computation was meant to

provide a datum against which all other options could be compared. RRPLAN

computed the discounted cost of this option as $21.20 per ton for the 20-year

period beginning January 1, 1985 and ending December 31, 200A. This cost can

be interpreted to mean that it would take $21.20 of money at January 1, 1985

value to collect, transport, and dispose of one ton of Jackson area MSW (i.e.,

all MSW for 20 years could be disposed at this discounted cost). All

subsequent RRPLAN claculations were discounted on the same basis. Hence, in

what follows, all costs are on the same basis (i.e., discounted to a present

value as of January 1, 1985). A cost difference between two options of $1 per

ton on this basis results in a $7.2 million cost difference for the total of

20 years since 20 years times 360 KTPY is 7.2 million tons of MSW.

A waste-to-energy facility was then considered at a site in the city of

Jackson. In the absence of such a plant, eight landfills in the tri-county

region surrounding Jackson would continue to receive 360 KTPY of MSW at a discounted cost of $21.20 per ton. Once the new facility was in place, RRPLAN

predicted that about 300 KTPY of waste could be processed there. Several

landfills would cease operations; the remainder of the MSW would go to the

rest. RRPLAN never predicted that siting, construction and use of transfer

stations would be economically advantageous for the Jackson area. Note that

RRPLAN selects the optimum activity level for each site (i.e., waste tonnage)

and the most economical transportation linkages to utilize these sites. For an input of 300 KTPY, facility capacity needs to be about 1150 tons per day.

A sensitivity analysis was then performed to determine how variations in the

capital cost of the facility and anticipated revenues would affect the

discounted cost per ton. Two basic scenarios were analyzed. The first was based on steam sales to the packing industry. The second was based on electricity sales to the local utility. For both scenarios, we assumed

that one ton of MSW would yield either 6 MBTU (million BTUs) of steam or 625

kwh of electricity for delivered use. These figures assume an incinerator

efficiency of 67 percent for steam conversion and a turbine efficiency of 35.6

percent. The results of the sensitivity analysis are summarized in tables 3

and 4. The steam and electricity revenues shown in these tables should be

viewed as representing likely ranges for the facility rather than negotiated

contract values.

XVI- 10
The data from tables 3 and 4 were fitted using the ordinary least squares

routine of the DATAPLOT statistical analysis package (Filliben [1982]). In

both cases, the response variable was the discounted cost per ton. The

explanatory variables were: (1) an intercept term constrained to a value of

$21.20, representing the cost of the all landfill option; (2) the capital cost

of the facility in millions of dollars; and either (3) the revenue per MBTU of

steam output; or (4) the revenue per kwh of electricity output. The estimated

values of these relationships are shown in equations 2 (steam) and 3 (electricity)

:

DCS = 21.20 + 0.118'CAPS - 2.775'REVS equation 2 (65.55) (-68.34)

and

DCE

= 21.20 + 0.129*CAPE - 2.749*REVE equation 3 (29.35) (-31.42)

where

DC* = discounted cost per ton;

CAP* capital cost of the facility in millions of dollars;

REV* = revenue per unit of output delivered; and

* = S (steam) or E (electricity).

The values in parenthesis beneath each coefficient are the t-statistics

associated with the fit. The importance of the explanatory variables is

reflected in the high values of the t-statistics. A cursory review of

equations 2 and 3 indicates that the coefficients have the proper signs and assume values which are of the same order. However, an important difference

is that, other things being equal, the discounted cost of the electricity

supplying facility is somewhat more sensitive to changes in capital cost and

less sensitive to changes in revenues.

If ST* (* = S or E) is designated as the savings per ton of MSW handled as compared to the all landfill option, then

ST* = 21.20 - DC* equation 4.

The value for DCg (equation 2) or DCE (equation 3) may then be inserted into

equation 4. If ST* is positive, then the recovery option is more economical

than the all-landfill option. Conversely, if ST* is negative, then the

recovery option is less economical than the all landfill option. A value of

ST* equal to zero defines the break-even point between the landfill and

recovery options. The break-even points, in terms of revenue per unit of

output, for each type of recovery facility are given by equations 5 (steam)

and 6 (electricity):

XVI-11
Table 3 Discounted Cost Per Ton of MSW

Processed for a Waste-to-Energy

PI ant Supplying Steam

STEAM FACILITY COST IN MILLIONS OF DOLLARS

REVENUES3 75 85 100

2.50 23.16 24.27 25.93

3.33 20.93 22.04 23.71

4.17 18.70 19.81 21.48

5.00 16.08 17.20 18.87

aDollars per MBTU.

Table 4 Discounted Cost Per Ton of MSW

Processed for a Waste-to-Energy

Plant Supplying Electricity

Electricity FACILITY COST IN MILLIONS OF DOLLARS

Revenues3 80 90 100 110 120

4 21.21 22.33 23.44 24.55 25.66

5 18.03 19.14 20.25 21.37 22.48

6 15.19 16.30 17.42 18.53 19.64

3Cents per kwh,

XVI-12
REVS =

and

(0.0425) -CAP S equation 5

REVE

= (0.0469) -CAPE equation 6.

Break-even points for five capital cost figures are summarized in table

5. As may be seen in equations 5 and 6, the revenues required to break even

are more sensitive to changes in the capital cost of the electricity producing

facility.

Table 5 Break-Even Points for Selected

Capital Outlays

TYPE OF FACILITY COST IN MILLIONS OF DOLLARS

FACILITY 80 90 100 110 120

STEAMa 3.40 3.83 4.25

ELECTRICITY^ 3.75 4.22 4.69 5.16 5.63

aDollars per MBTU in revenue required to break-even.

"Cents per kwh in revenue required to break-even.

Since the turbine represents a considerable additional first cost, the cost of

a facility to generate electricity is likely to be higher than that of a facility to generate steam. Thus the value of DCE

- DCS is of interest in

evaluating the additional initial risk:

DCE - DCS = (0.129'CAPE - 0.118CAP S

) - (2.749'REVE - 2.775'REV S

) equation 7.

Equation 7 may now be used to calculate the affordable extra turbine costs for

any given value of DCE - DCg which is deemed to make the risk acceptable. In

general, if a firm value of REV E is available, then the revenue per MBTU of

steam to be equivalent is:

REV S = - (0.046'CAPE

- 0.043'CAP S

) + 0.360'(DCE - DCg) + 0.99l*REVE

equation 8.

XVI- 13
If, on the other hand, a firm value of REV3 is available, then the revenue per

kwh of electricity to be equivalent is:

R£VE

- (0.0A7-CAPE - 0.043 -CAP S

) - 0.364-(DCE - DCS

) + 1. 009- REV s equation 9.

Thus, a complete risk analysis for any reasonable baseline scenario can be

performed in terms of the market prices for steam and electricity as well as for the capital cost of the facility. It is important to point out, however,

that all of these calculations assume that approximately 300 KTPY will

actually be processed at the facility, and that all of the energy recovered

from the MSW processed can be sold. The effect of changes in the baseline

tonnage processed (KTPY^) on the discounted cost per ton remains to be

analyzed.

In order to compute the relationship, and hence sensitivity of DC* to the

baseline tonnage processed, the following equation may be used:

DC* - a + b'(CAP*/KTPY) + c'RPT* + e equation 10

where RPT* the revenue per ton of MSW input ; and

e a (stochastic) disturbance term.

If a tipping fee is charged per ton of MSW input, then its value would be

incorporated into RPT* along with any revenues from steam or electricity

sales. The values of a, b and c in equation 10 are functions of the RRPLAN

input data (e.g., discount rate, terms of loan, useful life of the facility).

The analysis of the central Mississippi case study indicates that

DC* - 21.20 + B*«(CAP*/KTPY) - 0.449* RPT* equation 11

where 3* - 39.50 if * - E (electricity); or 34.37 if * - S (steam).

As in the previous cases, a, has been constrained to a value of $21.20, the

discounted cost per ton for the all-landfill option.

Equations 10 and 11 closely resemble the one suggested by Yakowitz [1981] for

the approximate break-even cost for any resource recovery facility. The

crucial difference is that equation 10, if based on results from RRPLAN,

represents fully discounted dollars over the lifetime of the facility whereas

the relation given by Yakowitz represents current dollars for the first year

of a publicly owned facility.

The relationship given in equation 10 is a general economic expression

governing resource recovery or most other businesses where a product is

produced via the use of capital equipment and sold on a per unit basis. For

the case of resource recovery, one wishes to minimize the values of a, b and

c. In effect, the fixed-charge linear programming algorithm of RRPLAN

XVI- 14
implicitly selects values for a, b and c, given the problem structure imposed

by the input data, so as to minimize DC*. However, uncertainties in a, b and

c depend upon:

(1) the mathematical formulation of the problem;

(2) the algorithm used to implicitly solve for the optimal mix of a, b

and c; (3) the input data (e.g., discount rate, inflation rate, useful life

of the capital stock, transportation network); and

(4) the stochastic nature of a, b and c (e.g., as reflected by the

width of the confidence intervals about the predicted values).

If all variables in equation 10 are subject to uncertainty, then the total

differential may be used to approximate the risk associated with the baseline

values

:

ADC* = a'(Aa/a) + b' ( CAP*/KTPY) ' [Ab/b)+( ACAP*/CAP*)-(AKTPY/KTPY)

]

+ c*RPT'[(Ac/c)+(ARPT/RPT)] equation 12

The first, second and fifth A ratio terms of equation 12 are associated with

uncertainties in the estimates of a, b and c. The other A ratio terms are associated with uncertainties in the input data. Note that uncertainties in

the input data will affect the estimates of the parameters a, b and c. These

effects will be of a second order nature, however, and are modeled through the

inclusion of the stochastic term in equation 10.

Equation 12 is a capsule summary of the economic and technical challenges

facing planners and decision makers in selecting the best resource recovery

scenario. Through reference to this equation, local planners can assess the

effect of specific uncertainties on the economics of any resource recovery

scenario. For example, if only KTPY can vary, then equation 12 becomes

ADC* = - b* ( CAPA /KTPY) * (AKTPY/KTPY) equation 13

where the minus sign in equation 13 indicates that a decrease in tonnage will

result in an increase in the discounted cost per ton, DC*. For example, if

the capital cost of the facility was $100 million and 300 KTPY were to be

processed, then a decrease of 15 KTPY would result in an increase of

approximately 50 cents per ton for a steam-producing facility or 60 cents per

ton for an electricity-producing facility.

A closer examination of equation 12 is now in order. If a nominal revenue of

$30 per ton is assumed along with a five percent range on each variable and a two percent range on each of the three parameters (based on the width of their

90 percent confidence intervals) , then the increase in discounted cost could

be as high as $3.00 per ton, or 15 percent of the estimated value of the

XVI-15
discounted cost per ton. Hence, for purposes of planning, the uncertainty can perhaps be approximated by a figure of 20 percent. Thus, if a combination of

costs, tonnages and income can be obtained such that RRPLAN predicts a reduction in DC* of $3 to $4 with respect to the all landfill option (which is

also subject to similar uncertainty calculations), then the risk associated

with investing in the resource recovery facility is probably worth serious

consideration. Although equation 12 provides valuable information on how

costs may vary due to uncertainty, it does not yield an explicit measure of

risk. In order to remedy this deficiency, a series of Monte Carlo experiments

were performed. The three explanatory variables (CAP*, RPT* and KTPY) in

equation 11 were the focus of the experiment. Based on previous work on probabilistic cost estimation (Vergara [1977]), the capital cost of the

facility, CAP*, was assumed to be lognormally distributed with a mean of $85

million and a standard deviation of $7 million for the facility serving the

steam market and a mean of $105 million and a standard deviation of $10

million for the facility serving the local utility. The lognormal

distribution is particularly attractive for large construction projects

because it is asymmetric. Consequently, the lognormal distribution explicitly

allows for low-probability high-cost events. Since the revenue per ton, RPT*,

is dependent on the outcome of contract negotiations, we assumed that the revenue per unit (i.e., per MBTU or kwh) was uniformly distributed. For a uniform distribution, each value within the range is equally likely. The

range considered was $2.50 to $6.00 per MBTU for steam and kt to bi per kwh

for electricity.

The treatment of random variations about the volume of waste processed is more complicated since the rate of waste generation may increase. Two scenarios were thus hypothesized. In the first, the amount of MSW processed was assumed

to be normally distributed with a mean of 300 KTPY and a standard deviation of

30 KTPY; this case corresponds to a "No Growth Scenario". In the second, the

amount of MSW processed was assumed to be lognormally distributed with a mean

of 300 KTPY and a standard deviation of 40 KTPY, this corresponding to a "Growth Scenario". A lognormal distribution was selected for the growth

scenario because it shifts the bulk of the probability distribution towards

higher rates of processing (e.g., more waste is generated, so more is

available for processing) . The standard deviation was increased from 30 to 40

KTPY to highlight the uncertainty associated with such growth projections.

The Monte Carlo experiments were carried out through application of the NBS

DATAPLOT statistical analysis package. As a first step, a vector of random

numbers from the standard forms for each of the three probability

distributions were generated. Vectors of length 100, 200 and 500 were tried

to assess the impact of sample size on the results. A qualitative analysis of

the experiments indicated that the results were relatively insensitive to

sample size. The random numbers were then used to generate a vector of random

values for CAP*, KTPY and RPT* based on the ranges and parameter values given

earlier. These values were then inserted into equation 11. The resultant

estimates of discounted cost per ton were then sorted from smallest to

largest. The ranked estimates (i.e., order statistics) were then used to

construct a frequency based probability distribution.

XVI- 16
For a given value of discounted cost per ton, dc, such a distribution shows

the probability that the "true" cost will fall below dc. If dc is taken to be

the cost of the all-landfill option, then the experiment shows the probability

that the cost of the waste-to-energy facility will fall below the all-landfill

option. A similar statement can be made for a selected risk margin (say $3, or a value of dc equal to $18.20). The results of the Monte Carlo experiment

based on a sample size of 500, are summarized in figures 2 and 3. Figure 2 presents the results of the no-growth scenario experiment; figure 3 summarizes

the growth scenario experiment. The horizontal axis of each figure records

the discounted cost per ton, whereas the vertical axis records the probability

that discounted cost falls below the estimate.

An examination of figure 2 reveals several important points. First, the

discounted cost per ton for the facility producing steam is always less than

the discounted cost for the facility producing electricity. The major reasons

for this difference are the magnitude of the capital outlay ($105 million vs $85 million on the average) and the size of the 8 coefficient in equation 11 (i.e., 0 E

> 6g)« Second, if the discounted costs for each facility are compared to those of the all-landfill option, the facility generating steam

has a probability slightly in excess of 0.7 that the incurred costs will fall

below the $21.20 figure. The facility generating electricity, on the other

hand, has a corresponding probability of approximately 0.6 (i.e, investment in

the electricity generating facility is about 15 percent more risky than

investing in the steam generating facility). Third, the $3 margin (i.e., a discounted cost of $18.20) can be achieved with a probability of slightly over

0.4 if the facility which generates steam is selected. If the facility which

generates electricity is chosen, however, the probability is reduced to a value of approximately 0.15. These figures imply that Investment in a steam

generating facility could be expected to better the $3 margin 40 percent of

the time, whereas investment in the electricity generating facility could be

expected to better the $3 margin only 15 percent of the time. Finally, highly

unprofitable events can occur with both types of facilities. For example, the

probability of exceeding a discounted cost of $22.00 per ton is 0.2 for the

steam generating facility and 0.3 for the electricity-generating facility.

When the rate of generation of the waste stream is allowed to grow, a slightly

different picture emerges. Figure 3 shows that the probabilities that the

facilities will incur costs below the $21.20 figure are virtually unchanged at

0.7 for steam and 0.6 for electricity. This result may be explained in part

by noting that a switch from the normal to the lognormal distribution was made

for the volume of MSW produced. The ratio of two lognormal (CAP/KTPY)

distributions can be converted to a normal distribution through a non-linear

transformation of variables. The variance resulting from the transformation

is the sum of the variances of the two distributions. The symmetry of the

normal distribution and a slightly tighter variance (hence standard deviation)

therefore tends to reduce the maximum and increase the minimum values of DC.

The changes are not in the same proportion, however. Since KTPY enters

equation 11 in the denominator, equal increases above 300 KTPY will result in

smaller changes in DC than will equal decreases below 300 KTPY. Both

XVI- 17
18.20 21.20

DISCOUNTED COST IN DOLLARS PER TON PROCESSED

SOLID = STEAM; DOTTED = ELECTRICITY

OUTPUT OF 6 MBTU OR 625 KWH PER TON OF MSW INPUT

FIG.

2

RISK ASSESSMENT FOR STEAM VS ELECTRICITY

(NO GROWTH)

XVI- 18
10

>-

_)

<

CDO

tr

Q.

LU

>

O

100

80

60

40

20

15

T I |

I I 20 25

' '

'

10

30

t |

i i r 35

I I I

15 20

18.20 21.20

25 30

100

80

60

40

20

0

35

DISCOUNTED COST IN DOLLARS PER TON PROCESSED

SOLID = STEAM; DOTTED = ELECTRICITY

OUTPUT OF 6 MBTU OR 625 KWH PER TON OF MSW INPUT

FIG.

3

RISK ASSESSMENT FOR STEAM VS ELECTRICITY

(GROWTH SCENARIO)

XVI-18a
1
probability distributions are therefore steeper than their no-growth

counterparts. With regard to the $3 margin, the steam-generating facility

still has a probability of 0.4 of incurring costs less than $18.20, whereas

the electricity generating facility has fallen to a probability under 0.05.

The data shown in the two figures thus provide a strong argument in favor of

the facility supplying steam to the local packing industry. The decision of

whether or not to proceed with a resource recovery facility should also

include a similar analysis of the costs of landfilling. Such an analysis,

based on a coordinated set of RRPLAN runs, would establish the likely lower

and upper limits on the discounted cost for the all-landfill option. These

costs could then be compared with those presented in figures 2 and 3 to

determine if the steam-producing facility was still competitive.

Concluding Remarks

The role of RRPLAN in assessing resource recovery options can be summarized as follows:

(1) RRPLAN identifies a minimum cost plan by comparing the various DC*

values for each option.

(2) In every case, the optimizer minimizes individual DC* values as a function of the specific input data offered by the user.

(3) RRPLAN does not compute unique values for the variables a, b, and c in equation 10.

(4) By varying the input data to RRPLAN, specific estimates for a, b,

and c, as well as preliminary estimates for the uncertainties in

these variables can be obtained. RRPLAN probably provides the best

available means to predict a, b, and c accurately.

(5) Equation 12 represents the "risk evaluator" for a specific set of

data and the uncertainties in these data.

(6) A planning basis for a waste management strategy is incomplete until

all terms in equations 10 and 12 are evaluated numerically for

various options.

Thus, RRPLAN, if used properly, provides the foundation for planning. But

considerable additional assessment may well be necessary in order to choose

the proper strategy for a given region. This assessment involves

probabilistic estimation for the input variables (discount rate, costs, etc.),

followed by multiple RRPLAN evaluations. The results will provide values for

all terms in equations 10 and 12. Unless all of these steps are taken, RRPLAN

results need to be treated with extreme caution. The lack of a coordinated

approach or reliance on outmodel or inaccurate data significantly increases

the risks of adopting a resource recovery plan. The U.S. has had several cases where resource recovery options have not lived up to proponents'

XVI -19
expectations. RRPLAN and the approach outlined in this paper provides an opportunity to avoid some of these pitfalls.

RRPLAN, as developed for and by the National Bureau of Standards' Office of

Recycled Materials, represents an appropriate means to begin evaluation of

specific resource recovery options for a city, state, or region. The input

data requirements will tend to require the prospective RRPLAN client to

determine each item of data as accurately as possible. Careful data

assessment, intelligent use of RRPLAN and solutions to equations 10 and 12

should help to reduce the risk associated with resource recovery. In turn,

the data gathering process and the subsequent RRPLAN and probablistic analysis

should clearly highlight potential or actual institutional problems.

Acknowl edgements

The authors wish to express their appreciation to Jack McMillan, Director,

Division of Solid Waste Management, Bureau of Pollution Control of the State

of Mississippi for providing the data upon which the case study was based and

for critiquing our results. Dr. Grace Yang and Stefan Leigh, National Bureau

of Standards, also provided many useful comments on how to apply DATAPLOT to

the problem of risk assessment. Special thanks goes to Ed Berman, Edward B.

Berman, Associates, Inc., for his pioneering role in the development of the

RRPLAN model.

References

Berman, E.B., Use of RAMP (Recovery And Market Planning) for the Evaluation of

Policy Issues in Resource Recovery , mimeo, 1976.

Berman, E.B., WRAP - A Model for Regional Solid Waste Planning: User's Guide,

U.S. Environmental Protection Agency, SW-574, 1977.

Berman, E.B., R.E. Chapman and H.K. Hung, Program Documentation for the

Resource Recovery Planning Model , National Bureau of Standards, NBS1R 83-2745,

1983.

Chapman, R.E. and E.B. Berman, The Resource Recovery Planning Model: A New

Tool for Solid Waste Management , National Bureau of Standards, Special

Publication 657, 1983.

Filliben, J. J., "DATAPLOT — An Interactive High-Level Language for Graphics,

Non-Linear Fitting, Data Analysis, and Mathematics," Proceedings of the Third

Annual Conference of the National Computer Graphics Association , 1982.

XVI-20
Hensey, V., WRAP - A Model for Regional Solid Waste Planning: Programmer's

Manual , U.S. Environmental Protection Agency, SW-573, 1977.

Jenkins, L. , "Parametric Mixed Integer Programming: An Application to Solid

Waste Management," Management Science , Vol. 28 (1982), pp. 1270-1284.

Liebman, J.C., "Models in Solid Waste Management," in S. Gass and R. Sisson,

A Guide to Models in Governmental Planning and Operations , (Potomac, Maryland

Sauger Books, 1975), pp. 139-164.

Vergara, A.J., Probabilistic Estimation and Applications of Portfolio Theory

in Construction , unpublished Ph.D. thesis, University of Illinois, 1977.

Walker, W.E. , "A Heuristic Adjacent Extreme Point Algorithm for the Fixed

Charge Problem," Management Science , Vol. 22 (1976), pp. 587-596.

Yakowitz, H. , "Recent Federal Actions Which Will Affect Prices and Demands fo

Discarded Fibers", in Technical Activities 1981 Office of Recycled Materials , National Bureau of Standards, NBSIR 81-2417, 1981, pp. 119-142.

XVI -21
II0
NBS-114A (REV. 2-8C) U.S. DEPT. OF COMM. BIBLIOGRAPHIC DATA

SHEET (See instructions)

PUBLICATION OR

REPORT NO. NBS SP 662

2. Performing Organ. Report No 3. Publication Date September 1983

4. TITLE AND SUBTITLE

The National- Bureau of Standards Office of Recycled Materials 1976-1932

Final Report of Activities and Accomplishments Pursuant to the Mandates of Section 383C

of the Energy Policy & Conservation Act and the Mandates of Subtitle E of the Resource

Conservat i on and Recovery Act 5. AUTHOR(S)

Harvey Yakowitz, Editor

6. PERFORMING ORGANIZATION (If joint or other than NBS, see instructions)

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

7. Contract/Grant No.

8. Type of Report & Period Covered

Final

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State. ZIP)

Same as item 6.

10. SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number: 83-600573

Document describes a computer program; SF-185, FlPS Software Summary, is attached.

11. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here) This report is meant to serve two purposes: (1) Summarize the activities and accomplishments of the Office of Recycled Materials of the National Bureau of Standards

(NBS/0RM) undertaken in response to legislative directives from 1976 through 1982;

(2) Provide a compilation of FY 1982 activities of NBS/0RM.

During its six and one-half year lifetime, NBS/0RM fulfilled virtually all of the

legislative directives with which NBS was charged. Waste oil and other materials

destined for waste were the subject of requirements for test method development,

evaluation and subsequent production of standards and guidelines for specifications.

More than 125 publications and reports remain as a tangible legacy of NBS/0RM. In

addition, the methods and standards developed under the guidance of NBS/0RM have been

adopted throughout the recycling community. This report places major MBS/0RM activitie

in perspective and provides a point of embarkation for anyone wishing to utilize or adapt NBS/0RM results. In addition, the Report indicates that NBS fulfilled the

legislative requirements in a timely, accurate, and efficient manner.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolons)

Characterization of materials; econometric modelling; hazard assessment; hazardous

waste management; incineration; ocean incineration; recycled materials; refuse derived

fuels: solid waste management: state measurement needs: used oil characterization

13. AVAILABILITY waste-to-energy conversion.

OH Unlimited

| | For Official Distribution. Do Not Release to NTIS

k^l Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.

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[~J Order From National Technical Information Service (NTIS), Springfield, VA. 22161

14. NO. OF

PRINTED PAGES

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