ted States

ironmental Protection

jncy

AllrlOl

Research and Development

Office of Environmental Engineering

and Technology

Washington DC 20460

EPA-600/7-80-125

June 1 980

vvEPA

NBSIR 80-1986

AlllDS D3bT33

A Summary of Oil

Shale Activities at the

National Bureau of

Standards 1 975-1979

Interagency

Energy/Environment

R&D Program

Report

RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental

Protection Agency, have been grouped into nine series. These nine broad cate- gories were established to facilitate further development and application of en- vironmental technology. Elimination of traditional grouping was consciously

planned to foster technology transfer and a maximum interface in related fields. The nine series are:

1. Environmental Health Effects Research

2. Environmental Protection Technology

3. Ecological Research

4. Environmental Monitoring

5. Socioeconomic Environmental Studies

6. Scientific and Technical Assessment Reports (STAR)

7. Interagency Energy-Environment Research and Development

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This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT

RESEARCH AND DEVELOPMENT series. Reports in this series result from the

effort funded under the 17-agency Federal Energy/Environment Research and

Development Program. These studies relate to EPA’s mission to protect the public

health and welfare from adverse effects of pollutants associated with energy sys- tems. The goal of the Program is to assure the rapid development of domestic

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This document is available to the public through the National Technical Information Service, Springfield, Virginia 22161.

A SUMMARY OF OIL SHALE ACTIVITIES AT

THE NATIONAL BUREAU OF STANDARDS

1975 - 1979

Edited by

National Bureau of Standards

UbrarVi Wl Admin. BWg.

FEB 87 1981

nal ticc — Oc/oo

ne>. g6 -/ffe

/‘fgb

Lottie T, McClendon

Office of Environmental Measurements

National Bureau of Standards

U. S. Department of Commerce

Washington, DC 20234

EPA-IAG-D5-E684

NBSIR 80-1986

This study was conducted

as part of the Federal

Interagency Energy/Environment

Research and Development Program

Prepared for

OFFICE OF ENERGY, MINERALS, AND INDUSTRY

OFFICE OF RESEARCH AND DEVELOPMENT

U. S. ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, DC 20460
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DISCLAIMER

This report has been prepared by cne Office of Environmental

Measurements of the National Bureau of Standards, and reviewed by the

National Bureau of Standards and the U.S. Environmental Protection

Agency, and approved for publication. Approval does not signify that

the contents necessarily reflect the views and policies of the U.S.

Environmental Protection Agency. In order to adequately describe

materials and experimental procedures, it was occasionally necessary to

identify commerical products by manufacturer's name or label. In no instance does such identification imply endorsement by the National

Bureau of Standards or the U.S. Environmental Protection Agency nor does

it imply that the particular products or equipment is necessarily the

best available for that purpose.
CONTENTS

Foreword i Abstract ii

Acknowledgment lii

1. Introduction 1 2. Summary 2

3. Summary of Workshop on Standard Reference Materials for

Oil Shale Processing 4

a. Introduction 4

b. Purpose of Workshop 4

c. Workshop Summary 5

d. Workshop Program 7 e. List of Attendees 9

4. Status of Oil Shale Research and Development at NBS . . . .11

a. Introduction 11

b. Raw Oil Shale 11 c. Shale Oil 14

d. Methods for the Quantitative Determination of

Individual Organic Compounds in Shale Oil 15

e. Existing NBS-SRM's Useful in Characterizing Oil

Shale and Oil Shale Products 43

5. Recommendations for Future Oil Shale Projects 45

Appendix A - Manuscripts presented during Workshop 47

Preparation of Standard Oil Shale Samples

OS-1, SS-1 , and SS-2 - T. Wilderman 48

Minor Elements in Oil Shale and Oil Shale Products - R. E. Poulson, et.al 67

Low-Temperature Spectroscopic Analysis of Polycyclic

Aromatic Hydrocarbons - E.L. Wehry, et.al 96

Appendix B - Information of NBS Standard Reference

Materials Applicable to Oil Shale 114
FOREWORD

The role of the National Bureau of Standards (NBS) in the Interagency

Energy/Environment R&D program, coordinated by the Office of Research

and Development, U. S. Environmental Protection Agency, is to provide

those services necessary to assure data quality in measurements being

made by a wide variety of Federal, State, local, and private industry

participants in the entire program. The work at NBS is under the direction of the Office of Environmental Measurements and is conducted in

the Center for Analytical Chemistry, The Center for Radiation Research

and the Center for Thermodynamics and Molecular Science. NBS activities

are in the Characterization, Measurement, and Monitoring Program category

and address data quality assurance needs in the areas of air and water

measurement methods, standards, and instrumentation. NBS outputs in

support of this program consist of the development and description of

new or improved methods of measurement, studies of the feasibility of

production of Standard Reference Materials for the calibration of both

field and laboratory instruments, and the development of data on the

physical and chemical properties of materials of environmental importance

in energy production. This report is one of the Interagency Energy/Environment Research and Development Series reports prepared to provide

detailed information on the NBS measurement methods and standards development

pertaining to Oil Shale activities. To provide a complete report on NBS

Oil Shale activities this document contains summaries of research and

development performed by NBS (parts of which were supported by the

Interagency Energy/Environment Program and parts of which were supported

by NBS directly appropriated funds and also funds obtained from other

Federal agencies). The source of the funding used to support the

various activities is so indicated in the appropriate places in this

document. It is hoped that this document will provide those researchers

involved in evaluating the environmental impact of increased Oil Shale

production with information on measurement methods and Standard Reference

Materials pertaining to data quality assurance in all aspects of their

studies.

!

' C. C. Gravatt, Chief

' Office of Environmental Measurements

: National Bureau of Standards

I

i
ABSTRACT

This report provides a summary of NBS Oil Shale activities covering

the period 1975 to 1979. At the start of this period a Workshop on Standard Reference Materials (SRM's) needed for Oil Shale Processing was held at NBS and served to provide the priority guidance for the future

of this program. A summary of the recommendations of that Workshop, the

manuscripts presented during the Workshop, and the list of attendees is

included in this report. The status of the Oil Shale Research at NBS is

also presented consisting of developmental work on the feasibility of

producing an Oil Shale and a Shale Oil Standard Reference Materials

characterized for both trace inorganic and trace organic constituents.

Additionally, information is given dealing with the development of

measurement methods appropriate for Oil Shale and Shale Oil trace inorganic and trace organic analysis. Several papers are also included

giving additional details on these matters. Other NBS Standard Reference

Materials, which may be appropriate for the use by the Oil Shale community,

are described briefly within this document. Finally, recommendations

for future Oil Shale projects dealing with the development of measurement

methods and Standard Reference Materials at NBS are presented.

ii
ACKNOWLEDGMENT

The Office of Environmental Measurements, the National Bureau of

Standards gratefully acknowledges the partial support of this work from

the U.S. Environmental Protection Agency under the Interagency Energy/

Environmental Agreement EPA-IAG-D5-E684. The Center for Analytical

Chemistry of NBS gratefully acknowledges the support of the Department

of Energy (Office of Health and Environmental Research) for the work

described dealing with the development of methods for the quantitative

determination of individual organic compounds in Shale Oil. Additionally,

we acknowledge the considerable work of Mr. Donald Becker of NBS who was responsible for the initial planning and conduct of the Workshop on the

needs for Standard Reference Materials for Oil Shale Processing.
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SECTION 1

INTRODUCTION

The purpose of this report is to summarize the National Bureau of

Standards' (NBS) activities in oil shale and oil -shale products. The

role of NBS in oil shale research and development, is to provide those

services necessary to assure data quality in measurements being made by

a wide variety of Federal, state, local, and private industry participants

in oil shale technology. Development of a compatible data base to assess the total effect of oil shale development upon our environment is

a necessity if rational and logical decisions are to prevail in planning

and developing this energy resource in an environmentally and economically

acceptable manner.

A series of eight Workshops were conducted during 1975-1976 by the

NBS and the Environmental Protection Agency to assess the needs and

kinds of chemical standards and reference materials required for mon- itoring the environmental effects associated with energy development.

The second workshop of the series was held November 24-25, 1975 at NBS.

The objective of this workshop was to obtain input to NBS from pertinent

experts on Standard Reference Materials, homogeneous intercomparison

materials, and analytical methodology needed for the accurate analysis

of environmental samples associated with oil shale processing. A

summary of this workshop, recommendations made by the participants, as well as some of the papers presented on oil shale activities during the

workshop are included as part 3 of this report. Part 4 of this report

provides a summary of the oil shale research and development efforts

performed at NBS over the past five years. The scope of work for on- going and future oil shale projects are summarized in part 5.

1
SECTION 2

SUMMARY

The assessment of the environmental implication and impact of new

and expanding energy techniques requires that an effective multimedia

monitoring and measurement assurance system be maintained. Development

of a compatible data base to determine the source, transport, and fate

of environmental pollutants is a necessity if rational and logical

decisions are to prevail in planning the types, pattern, and magnitude

of energy developments which are environmentally acceptable. In rec- ognition of this need, the Office of Management and Budget and the U.S.

Congress established an Interagency Energy/Environment Research and

Development Program in 1975 under the direction of the U.S. Environmental

Protection Agency. This program established a mechanism for the planning,

coordination, and allocation of research and development funds for

environmental pollution control technologies associated with energy

development.

As part of the Interagency Energy/Environment Program, an EPA/NBS

interagency program was initiated in 1975. The overall objective of

this program is to provide quality assurance for environmental baseline

data in those geographical areas where the impact on the environment of

energy development is or is projected to be of major magnitude. NBS

activities within this program concern the development of measurement

methods. Standard Reference Materials (SRM's) and instrumentation in

support of programs for evaluating environmental effects of increased

energy development. The measurement methods and SRM's developed at NBS

will help to ensure comparability and compatibility among energy related

measurements made in the laboratory and in field monitoring.

The 1973 Oil embargo spurred the National government to focus on the development of new energy technologies to meet our Nation's increased

energy demands. One of the industries activated and spotlighted for

technology development was the oil shale industry. By 1975, planning,

design and environmental study efforts were underway on several oil

shale tracts and the EPA had established a high priority Oil Shale

program with two primary objectives: (1) support the regulatory goals

of the Agency and (2) support and conduct research directed towards

ensuring the oil shale industry develop in the most environmentally

acceptable manner that was reasonably possible. However, with a shortlived oil embargo and very high construction costs, interest in developing

the oil shale industry slackened in 1976 and 1977 and many Agencies

reduced and/or directed priorities and funds from oil shale research and

development to other areas and environmental issues. The NBS activity

in oil shale has been in support of the objectives of other Agencies'

oil shale programs (i.e. EPA, DoE) and as such, the NBS activity over

the past five years has been impacted by the priorities and funding

directives from such agencies.

2
The first major accomplishment of the NBS Oil Shale Program for the

period 1975 to 1979 was a Workshop on Standard Reference Materials

and Measurement Methods required for Oil Shale processing to develop

priorities for the NBS activities in this program. It was concluded by

that Workshop that raw Oil Shale, (the approximately 25 gallon per ton

minus 200 mesh type) characterized for trace inorganic and trace organic

constituents was the highest priority. Second priority was a processed

shale material characterized for trace inorganic and organic constituents.

The third priority was a research material shale oil, and forth priority

was a research material process water. The second major accomplishment

was the analysis of trace elements in oil shale from one pilot plant

sample material. The third accomplishment was a comparison of gas

chromatographic profiles before and after radiation sterilization of

oil shale materials to ascertain the long-term stability of oil shale

samples. The fourth was the development of measurement methods for

an analysis of consent decree organics in shale oil based on high

performance liquid chromatography techniques. Finally, feasibility

studies were conducted on both the oil shale and shale oil materials

in order to assess the production of these two materials as SRM's.

The shale oil SRM material has been characterized for five trace organic

const! tutents and is expected to be available as SRM 1580 by April

1980. More work, as well as a shift in funds and priorities will be

needed to characterize the shale oil for trace inorganic elements.

The oil shale SRM is still under investigation due to the difficulty

at the present time of certifying the complete extraction of organic

compounds from the oil shale starting materials.

Future work at NBS is Oil Shale related activities will consist of

the completion of the development of measurement methods required for

certifying trace organic compounds in oil shale, thereby permitting

the production of an oil shale SRM certified for trace organic con- stituents. Additionally, all commercial shale operations will be

required to preserve water resources and to control effluent discharges.

In order to meet those requirements, measurement methods and Standard

Reference Materials will be needed for water discharge from oil shale

operations. Similarly, process and fugitive emissions into the ambient

air will require a variety of reference methods and Standard Reference

Materials. The specific materials required will need to be determined

after a careful analysis of the type of emissions found in pilot oil

shale activities.

3
SECTION 3

SUMMARY OF WORKSHOP ON STANDARD REFERENCE MATERIALS FOR

OIL SHALE PROCESSING

a. Introduction

On November 24-25, 1975, a workshop (sponsored by EPA and NBS) was

held at the National Bureau of Standards, Gaithersburg to determine the

needs and types of Standard Reference Materials which could be used for

monitoring the environmental effects of oil shale processing. Since the

adequate evaluation of environmental pollution is based largely upon the

results from chemical analysis, adequate reference materials are es- sential for quality assurance and inter-laboratory comparison purposes.

Thus, the objective of this workshop was to obtain input to NBS from

pertinent experts on certified reference materials, homogenous intercomparison materials, and analytical methodology needed for the accurate

analysis of environmental samples associated with oil shale processing.

Several papers were presented during the workshop and many fruitful

discussions took place on a variety of subject areas related to the

environmental aspects of oil shale processing (e.g., trace inorganic,

trace organic and gaseous pollutants, overview of environmental studies

to that date and the significance thereof, etc.). As a result of a number of obstacles, the Proceedings of this Workshop were not published.

Thus, three of the papers prepared for and presented during the Workshop

are attached as Appendix A of the report (with author's permission).

b. Purpose of Workshop - D. A. Becker

One of the purposes for this workshop involves what we can do to

help you and how you can get information to us so we can miximize our

return to you.

Accurate measurements in environmental monitoring is important

since a 100% deviation in measurement can mean either over controlling

or under controlling the process being monitored, both of which are undesirable.

NBS has three divisions involved in this program, the Office of

Air and Water Measurement, The Office of Standard Reference Materials and

The Analytical Chemistry Division.

What this workshop needs to discuss and determine includes the

needs of the oil shale industry for reference materials, the elements

needed and concentration levels involved, the requirement for organic

analyses, the suitability of current methods and how best such needs

can be met.

Priorities are needed from this workshop to determine what is to

be done realizing that NBS had limitations on funds, people, and time.

4
c. Workshop Summary

The following summary on the Oil Shale Processing Workshop covers

the major recommendations made under four main material types considered

as possible SRM's for oil shale operations: Raw Oil Shale; Spent Shale;

Shale Oil; and Process Water.

Raw Oil Shale :

The priority requirement for an SRM, to be used in the oil shale

processing field, was a powdered raw oil shale. Complete analysis of a raw oil shale SRM is needed to provide the foundation for batch production

analyses and to assess the environmental impact, and the immediate focus

would be. trace elements. This material should come from the Mahogany

zone oil shale, preferably Anvil Point, and contain approximately 25

gallons oil /ton. The material should be sterilized by Cobalt-60 radiation for stablility.

As in all grinding operations, the contamination by the grinding

materials can be severe. After due consideration, it was recommended

that alumina grinding balls be used if possible. The next best material

would be hardened steel rather than tungsten carbide which would cause cobalt contamination. It was also pointed out that there was a need for

care in shale grinding due to the possible degradation of the hydrocarbon

components caused by the heating and oxidation that occurs during the

grinding process. To minimize this problem, the material should be

ground in an inert atmosphere.

A final SRM sample size of 80 to 100 grams would be sufficient for

trace element use. Trace elements certified should include arsenic,

selenium, boron, molybdenum, lead, zinc, mercury, flourine, antimony,

cadmium, vanadium, cobalt, nickel, iron, uranium, thorium, chromium,

lithium, and beryllium. Calcium, magnesium and other major elements

should also be certified. In addition, carbon, hydrogen, nitrogen,

sulfur, and total and organic carbon should be certified along with the

moisture content. It was suggested that information on storage under

refrigeration be included since organic decomposition would be minimized.

Storage under refrigeration would also prevent the sample being left on the shelf where heat and light would speed up the decomposition process.

Due to the usefulness of the Fischer Assay determination, it was suggested

that an amount of the original material be split off at 60 mesh and used

as a Research Material for Fischer Assay determinations.

Although not of the same matrix, the currently available SRM's for

Coal (1632) and Fly Ash (1633) should be very useful in instrumental

procedure development.

Spent Shale

The second priority requirement was for a spent shale SRM. To

cover the present processes, two types of spent shale SRM's would be

needed. One material from the oxidative process (Paraho) and the other

from the reductive process (TOSCO II). The certification required for

these materials would be the same as that described for the raw shale

material. However, no information on Fischer Assay would be needed.

5
Shale Oil

The third priority material was shale oil. Four source possibilities exist for a shale oil standard: TOSCO II, Paraho, Occidental

and "in-si tu." It is expected that considerable compositional differences would occur among these four types due to the differences in

manufacture. The main analyses needed for shale oil could be confined

to those elements that are catalyst poisons.

It is expected that the shale oil will go through a refining

process to become standard petroleum products. As a result, the shale

oil did not carry a high priority as a needed SRM, but it was recommended

the oil be available as a Research Material.

Process Water

The fourth priority material recommended in the workshop was

process water. Since techniques are presently not available for cer- tification analysis of organics in water, the production of a process

water SRM was felt to be impossible at the time of the workshop.

However, considerable need existed for the development of methods for

trace organic analysis in effluents from shale oil processing.

Although the process water is alkaline, the soon to be released

water SRM (At the time of this workshop, the Trace Element in Water SRM,

1643 was not available. Since that time, SRM 1643 was sold out and SRM

1643a is ready for re-issue) should suffice for trace element analysis.

Individual laboratories would be required to modify the water SRM and

test procedures for their elements of interest.

It was recognized that the determination of trace organics in

water would become a serious problem as production Increased and analytical

methods would need to be developed in order to characterize process

waters for organic constituents.

6
d. Workshop Program

ENERGY/ENVIRONMENT WORKSHOP

SRM's FOR OIL SHALE PROCESSING

NOVEMBER 24-25, 1975

NATIONAL BUREAU OF STANDARDS

GAITHERSBURG, MARYLAND

November 24, 1975

Welcome - D. A. Becker, NBS

Introductory Remarks - G. D'Alessio, EPA

Statement of Purpose - D. A. Becker, NBS

Session I -

A. "Oil Shale Overview"

B. "Preparation of Standard Oil-Shale Samples

OS-1, SS-1, and SS-2"

T. R. Wildeman

Colorado School of Mines

Session II -

C. "Environmental Studies"

T. R. Wildeman

Colorado School of Mines

"Determination of Trace Metals in Oil Shale, Materials

Balance Studies"

M. T. Atwood

TOSCO

Session III -

"Environmental Effects of Organic Trace Elements in

Oil Shale and Waste Products."

J. J. Schmidt-Col lerus

Denver Research Institute

"Trace Elements in Oil Shale Liquid Products"

R. E. Poulson

ERDA, Laramie, WY

7
Session IV -

Open Discussion

Address

"NBS and Pollution"

J. R. McNesby

Office of Air and Water Measurements, NBS

November 25, 1979

Session V

"High Resolution Techniques for Analysis of Polycyclic

Hydrocarbons"

E. L. Wehry

University of Tennessee

"Speciation"

J. Fruchter

Battel le Northwest Laboratories

Session VI - Brief Remarks

"ERDA's Role in Energy and Environment"

G. J. Rotariu

ERDA

"Use of Standard Reference Materials"

J. P. Cali

Office of Standard Reference Materials, NBS

Discussion

Session VII - Closing Discussion

8
e. LIST OF ATTENDEES

Energy/ Environment Workshop

SRM's for Oil Shale Processing

Mark Atwood

The Oil Shale Corporation (TOSCO)

18200 West Highway 72

Golden, Colorado 80401

I. Lynus Barnes

Analytical Spectrometry

National Bureau of Standards

Washington, DC 20234

Donald A. Becker

Analytical Chemistry Division

National Bureau of Standards

Washington, DC 20234

Francis Bonomo

Denver Research Institute

2390 So. University Boulevard

Denver, Colorado 80206

Irving Breger

Office of Energy Resources

U. S. Geological Survey

National Center, Stop 923

Res ton, Virginia 22092

J. Paul Cali

Office of Standard Reference

Materials

National Bureau of Standards

Washington, DC 20234

Stephen Chesler

Bioorganic Standards

National Bureau of Standards

Washington, DC 20234

Bruce R. Clark

Analytical Chemistry Division

Holifield-Oak Ridge National

Laboratory

P. 0. Box X

Oak Ridge, Tennessee 37831

Jack Clarkson, L-404

Lawrence Livermore Laboratories

P. 0. Box 808

Livermore, California 94550

Richard H. Coe

Shell Development Co.

Westhollow Research Center

P. 0. Box 1380

Houston, Texas 77001

Gregory D'Alessio

Office of Research & Development

Environmental Protection Agency

Waterside Mall - R/D 681

401 M Street, SW

Washington, DC 20460

Jon Fruchter

Battel le Northwest Laboratories

P. 0. Box 999

Richland, Washington 99352

Donald B. Gilmore

Environmental Monitoring and Support

Laboratory

Environmental Protection Agency

P. 0. Box 15027

Las Vegas, Nevada 89114

Barry H. Gump

Bioorganic Standards

National Bureau of Standards

Washington, DC 20234

Harry S. Hertz

Bioorganic Standards

National Bureau of Standards

Washington, DC 20234

David Jones

Radian Corporation

Box 9948

Austin, Texas 78766

James R. McNesby

Office of Air and Water Measurement

National Bureau of Standards

Washington, DC 20234

Thomas W. Mears

Office of Standard Reference Materials

National Bureau of Standards

Washington, DC 20234

9
John A. Norris

Analytical Chemistry Division

National Bureau of Standards

Washington, DC 20234

Richard E. Poulson

ERDA-Laramie

Box 3395

University Station

Laramie, Wyoming 82070

Harry L. Rook

Activation Analysis

National Bureau of Standards

Washington, DC 20234

George J. Rotariu

Energy Research & Development

Administration

Washington, DC 20540

Robert Schaffer

Bioorganic Standards

National Bureau of Standards

Washington, DC 20234

Josef J. Schmidt-Collerus

Denver Research Institute

University of Denver

University Park

Denver, Colorado 80206

Haven Skogen

Occidental Oil Shale

P. 0. Box 2999

Grand Junction, Colorado 81501

Charles Taylor

Southeast Environmental Research

Laboratory

Environmental Protection Agency

College Station Road

Athens, Georgia 30601

John K. Taylor

Air and Water Pollution Analysis

National Bureau of Standards

Washington, DC 20234

Howard Taylor

Accu-Labs Research, Inc.

11485 West 48th Avenue

Wheat Ridge, Colorado 80033

Earl L. Wehry

University of Tennessee

W. Cumberland Avenue, SW

Knoxville, Tennessee 37916

Thomas R. Wil deman

Department of Chemistry

Colorado School of Mines

Golden, Colorado 80401

10
SECTION 4

STATUS OF OIL SHALE RESEARCH AND DEVELOPMENT AT NBS

a. Introduction

It has been long recognized that accurate baseline data and

effective and meaningful monitoring programs are essential to understanding the environmental impact of an industry. Thus, NBS efforts

in oil shale technology have been focused on developing measurement

methods and standards to help ensure accuracy, comparability and

compatibility among related measurements in the oil shale industry.

The following discussion describe NBS activities on powdered oil shale

and shale oil

.

b. Raw Oil Shale

As a result of the recommendation from the workshop on "SRM's

for Oil Shale Processing" (Section 3 of the report), NBS obtained

samples of oil shale from TOSCO (originated from Parachute Creek

Area) and oil shale from the Energy Research Center at Laramie,

Wyoming (originated at Anvil Points Area) in early 1976. In addition

to the workshop recommendation, the experience obtained in producing the

Coal and Fly Ash materials (i.e. SRM 1632 and 1633) for trace element

certification provided the basis for NBS's initial focus on trace

elements in the raw oil shale. The two oil shale materials were ground

according to recommendations set forth at the workshop and prepared for

the preliminary assessments required of a potential Standards Reference

Materials (e.g., homogeneity, elemental profile, suitability.

Instrumental Neutron Activiation Analysis (INAA) was used to

provide a preliminary assessment of the trace element concentration

of minus 200-mesh TOSCO oil shale. The elemental concentrations

observed are listed in Table 4-1 with the estimated analytical un- certainties which could be obtained. To conduct this study, the NBS

SRM 1632 (coal) was used as the reference material. The NBS SRM 1633

(Fly Ash) was treated as an unknown sample material along with the oil

shale material during the study for comparison purposes. Several oil

shale samples have been semi-quanti tatively analyzed using emission

spectroscopy by NBS scientists in conjunction with work being performed

for another NBS program. While the results are very preliminary using

this technique some of the elemental concentrations obtained agree

favorably with those obtained using INAA (e.g. Na,K, Fe, Cr).

A portion of the oil shale material was radiation-sterilized,

analyzed for its trace element content by INAA, and the results obtained

compared to the trace element concentration of the unsterilized oil

shale to determine if there were changes in the elemental concentration

of volatile elements. A preliminary interpretation of the results,

indicated there were no significant elemental concentration differences

in the two materials.

Additionally, high resolution gas chromatography was conducted on the unsterilized and the radiation sterilized oil shale. Extracts of the

oil shale analyzed with or without cobalt-60 irradiation sterilization of

the oil shale gave identical chromatograms. Evaluation of the organic

11
extraction efficiency is needed to quantify organics present in the oil

shale.

As a result of the trace element assessment, the TOSCO oil shale

was chosen as the material to be used for production of the first trace

element oil shale SRM. In June, 1978, NBS received a batch of processed

TOSCO oil shale (about 1200 lbs.) to begin the certification process.

However, by that time, the other agencies had directed its resources

be used by NBS to support their other priority programs. The certification

program for trace elements in oil shale is currently at a standstill.

Method development for trace organic analysis is currently in progress

and preliminary studies will be conducted on the TOSCO oil shale to assess

the feasibility for its use as a trace organic SRM.

12
TABLE 4-1

Elemental Concentrations (yg/g unless Indicated) and

Estimated Uncertainties Attainable

Oil Shale

SRM 1632*

Coal

SRM 1633

Fly Ash

Na {%) 1.6 5% 0.040 0.34

K {%) 1.0 5% 0.27 1.6

Rb 63 5% 20 120

Cs 3.4 5% 1.4 7.9

Ba 540 5-10% 330 3100

Sc 4.6 5% 3.7 27

Cr 32 5% 20.2 120

Fe {%) 1.8 5% 0.87 6.4

Co 9.0 5% 5.6 40

As 64 5% 5.9 62

Se 3.5 5-10% 2.9 11

Sb 2.8 5-10% 4.3 6.9

La 20 5% 11.3 89

Ce 34 5% 20.4 160

Sm 2.5 5% 1.83 14

Eu 0.52 5% 0.38 3.0

Yb 0.85 5% 0.70 4.9

Lu 0.18 5% 0.14 1.0

Hf 1.5 5-10% 0.95 7.8

Ta 0.30 10-15% 0.21 1.5

Th 4.7 5% 3.0 25

* Reference Material Used for Calculation of the Oil Shale Values.

13
c. Shale Oil

The potential carcinogenicity of processed oil shale and its products

has received widespread attention in the press and is presently a primary

concern of environmentalists. The determination of trace elements and

trace organic compounds in very complex mixtures (e.g. processed oil

shale, feedstock, process streams, plant effluents) is very difficult.

Many of the analytical techniques that have been used in the past to

characterize oils and effluents from petroleum technology are inadequate

or cannot be applied to the characterization of oil shale materials. As

a result, NBS's efforts have focused on developing measurement methods

to accurately identify and quantify individual organic compounds in

complex matrices. The certification of trace organic Standard Reference

Materials for shale oil, liquified coal, etc. are contingent upon the

development of accurate methods for quantifying individual toxic and/or

carcinogenic compounds in such complex matrices.

NBS obtained a quantity of shale oil from Oak Ridge National

Laboratory in 1978, to apply NBS developed methods and assess the feasibility of preparing a trace organic Shale Oil SRM. The results of

these efforts are described (Sec. 4.d of this report) in the draft,

"Methods for the Quantitative Determination of Individual Orgnaic

Compounds in Shale Oil." In addition to the financial support from

the ERA Interagency Energy/Environment Research and Development

Program, the work described in this draft was performed with partial

financial support from the Office of Health and Environmental Research

of the Department of Energy. The authors of this draft are in the

process of finalizing their work for publication. A Shale Oil SRM,

1580, certified for five polycyclic aromatic hydrocarbons (PAH) —

pyrene, fluoranthene, benzo(a)pyrene, benzo(e)pyrene, o-cresol —

will be available from the NBS Office of Standard Reference Materials

by April 1980.

14
d. Methods for the Quantitative Determination of

Individual Organic Compounds in Shale Oil*

H. S. Hertz, J. M. Brown, S. N. Chesler, F. R. Guenther,

L. R. Hilpert, W. E. May, R. M. Parris, and S. A. Wise

Organic Analytical Research Division

National Bureau of Standards

Washington, DC 20234

* This paper is being submitted to the Journal of Analytical Chemistry

for publication in

15
Brief

Acid-base extraction and high performance liquid chromatography are used to fractionate shale oil. Capillary gas

chromatography, high performance liquid chromatography and gas

chromatography-mass spectrometry are used to identify and

quantify individual compounds in the shale oil fractions.

16
Abstract

Several techniques have been investigated for quantitating

individual organic compounds in shale oil. Emphasis was focused

on acid-base extraction and high performance liquid chromatography

as independent methods of shale oil fractionation. Gas chromatography, gas chromatography-mass spectrometry and high performance liquid chromatography were used for individual compound

quantitation utilizing external and/or internal standards or

standard addition techniques. The following compounds were

measured in the shale oil: pyrene, fluoranthene, benzo (e) pyrene

,

benzo (a) pyrene , phenol, o-cresol, acridine, and 2,4,6-trimethylpyridine. Comparable results were obtained by the various

methods for extraction and quantitation.

17
Increasing energy demand in the United States and reliance

on foreign sources of petroleum have resulted in a national

program designed to develop new sources of energy. The conversion of coal to gaseous or liquid fuels and the utilization

of oil shale and tar sands are some of the energy sources that

appear promising. In terms of energy, it is estimated that

domestic coal and oil shale reserves are 8000x10^^ and 400x10^^

BTU, respectively, while petroleum reserves are only 200x10^^

BTU (1). However a serious and still largely unknown complication of developing these alternate fuels is their potentially

deleterious impact on man and the environment. To evaluate this

impact properly, it will be necessary to analyze the feedstock,

process streams, plant effluents and final product for their

trace element and organic compound content. The accurate quantitative analysis of individual organic compounds will become

increasingly important as mutagenicity testing on chromatographic fractions generated from various fuels and effluents

expands. These tests should eventually allow scientists to

relate health effects to known amounts of specific compounds.

One method for assuring the accuracy of the necessary

quantitative analyses is the use of suitable quality assurance

standards or Standard Reference Materials (SRM’s). The certification of such trace organic SRM's is contingent upon the development of the analytical expertise to achieve individual compound

quantitation in complex matrices such as shale oil, liquified

coal, or petroleum. In the past many of the analytical techni18
ques that have been used for the evaluation of synthetic oils

have been taken from petroleum technology (2-4). These analyses

generally involve an initial separation of the mixture into

compound classes by solvent extraction techniques followed by

various methods of further characterization. The procedures

that have been used for further characterization were usually

designed for the determination of physical and chemical properties of distillate fractions which are important to product

characteristics but are not designed for individual compound

identification and quantitation.

Recently several methods for the analysis of specific

classes of compounds in samples of petroleum, shale oil and

synthetic coal liquids have been reported. Jackson et a^ (5)

determined hydrocarbon types in shale oil distillates by use of

a hydroboration-acid adsorption technique; McKay and coworkers

(6) utilized a chromatographic-infrared technique to characterize nitrogen bases in high boiling petroleum distillates.

Uden e^ ^

(7) have characterized the acidic and basic fractions

of shale oil by gas chromatography-Fourier transform infrared

spectroscopy Popl ejt (8) have used frontal elution on silica

gel followed by adsorption chromatography on alumina and gel

permeation chromatography to characterize polynuclear aromatic

hydrocarbons (PAH) in white petroleum products. Suatoni and

Swab (9) developed a "back-flush” high performance liquid

chromatographic technique for the determination of total saturated

and aromatic hydrocarbons from crude oils and synthetic crudes

19
derived from coal. Several workers (e.g. 10) have recently

applied mass spectrometry to class specific analysis of coal

liquids. Dark and McFadden (11) employed HPLC and liquid

chromatographymass spectrometry for the characterization of

coal liquefaction products; and, Clark ejt al (12) have used

both solvent extraction and chromatographic techniques for the

isolation of alkanes and PAHs from shale oil. However, none of

these methods was developed for the accurate quantitative

analysis of individual compounds.

To enhance the accuracy of environmental measurements , we

have developed methods for quantitating individual toxic and/or

carcinogenic compounds in alternate fuels. In particular,

methods for determining the concentrations of several phenols,

N-heteroaromatic compounds (aza-arenes) and PAH in shale oil

are reported in this paper. Initial emphasis has focused on

the evaluation of an acid-base extraction scheme and a preparative

HPLC procedure as independent methods for shale oil fractionation.

Various gas chromatographic (GC) , gas chromatographic-mass

spectrometric (GC-MS) , and high performance liquid chromatographic

methods have been investigated as means of individual compound

identification and quantitation.

Experimental

Shale Oil Sample . The shale oil analyzed in this work is

from a 150-ton retort for in-situ simulated combustion operated

by the Laramie Energy Research Center, Laramie, Wyoming. The

shale is from the Mahogany zone of the Colorado Green River formation. An 8 L sample of this shale oil was obtained by NBS

20
from Bruce R. Clark at Oak Ridge National Laboratory, Oak Ridge,

Tennessee. The shale oil underwent centrifugation at Oak Ridge

to separate water ('v^40l) and sludge from the oil. This shale

oil has been utilized for analytical methods development at Oak

Ridge (13). A subsample of 1 liter was removed from the 8 liter

bulk sample. Aliquots of ''^5 mL each were sealed in amber glass

ampoules for subsequent analyses. The samples were analyzed to

measure the concentration (yg/g) of pyrene, fluoranthene, benzo(a)-

pyrene, benzo (e)pyrene , phenol, o-cresol, 2 , 4 , 6- trimethylpyridine

,

and acridine.

Extraction

Acid-base extraction . The shale oil sample was separated

into three fractions (acids, bases, and neutrals) using an

extraction procedure adapted from Schmeltz (14) . This procedure

is shown schenratically in Figure 1 for a 0.5g sample. For the

determination of the PAHs an additional liquid- liquid partition

step using dimethylformamide (DMF) /water was utilized to separate

the aliphatic hydrocarbons from the PAHs. This procedure for

the isolation of PAHs in complex mixtures has been previously

reported by Bjorseth (15).

HPLC extraction (fractionation) The shale oil sample was

diluted ('^O.lg/mL in methylene chloride) prior to fractionation

on a preparative scale aminosilane column (yBondapak NH

2

, 30 cm

x 8 mm i.d.). A sample containing approximately 14 mg of shale

oil was injected onto the column using a loop injector. A

mobile phase flow rate of approximately 5 mL/min was employed.

21
Standards of the compounds to be determined and the compounds

utilized as internal standards for quantitation were injected

to determine the appropriate e]^ution volumes for fraction

collection. The fractions were collected in centrifuge tubes

and reduced to 50-500 yL by passing nitrogen over the sample.

Chromatographic conditions for the HPLC fractionations are

presented in Tables I, II, and III.

Quantitation

HPLC Quantitation . Analytical liquid chromatographic

analyses were performed on an instrument equipped with a gradient

pumping system, loop injector and spectrophotometric and spectrofluorimetric detectors. A digital integrator and strip chart

recorder were used for data acquisition.

A determination of the volume of the sample loops for both

the fractionation and analytical HPLC system was accomplished

through use of a gravimetric procedure. The loops were initially

filled with mercury. The mercury was swept from the loops into

a tared weighing dish with approximately 1 mL of pentane. The

bulk of the pentane was decanted and the remainder was allowed

to evaporate. This process was repeated five times for each

loop. The mass of mercury displaced from the loop was determined gravimetrically . The volumes of the loops were calculated

using the density of mercury and were 137.7±1.2 and 12.98±.06

yL, respectively.

As shown in Table I, one of the methods for quantifying

phenol and o-cresol was a sequential HPLC procedure. Phenol and

o-cresol were separated from the shale oil matrix and collected

22
in separate fractions. The concentration of each of these

compounds in the collected fractions was determined by use of

an internal standard method. A known amount of phenol (as an

internal standard) was added to the fraction containing o-cresol

and o-cresol was added as an internal standard to the fraction

containing phenol. Both fractions were reduced in volume to

approximately 100 yL with a stream of nitrogen. These fractions

were then chromatographed on an octadecylsilane column

using 40% acetonitrile in water as the mobile phase, and ultraviolet detection at 270 nm. The concentration of phenol and o^- cresol in the shale oil was then calculated by comparing the

chromatographic peak heights of the analyte and internal standards and applying factors for the differences in detector

response and losses during evaporation.

Pyrene, fluoranthene and benzo(a)pyrene were also determined by a sequential HPLC method (See Table 1) . The PAHs were

initially separated from the shale oil matrix and then the

analytes were separated from other PAHs by chromatography on a

Cj^g column with a water-acetonitrile mobile phase. Further

selectivity was obtained by monitoring the chromatographic

effluent f luorometrically , with excitation and emission wavelengths optimized for detection of each analyte. Quantitation

was achieved using an external standard.

GC Quantitation . Gas chromatographic analyses were performed

on a gas chromatograph modified for use with wall-coated open

tubular glass capillary columns (WCOT) . The resolving power

23
of these columns is illustrated in Figure 2 which is a chromatogram of shale oil bases. It would have been impossible to

quantitate these complex mixtures using gas chromatographic

methods without these high efficiency columns.

Quantitation by GC was always performed using an internal

standard method with peak areas determined using a digital

integrator. Internal standard compounds were chosen which possessed similar chemical properties to that of the analyte and

were never obscured by measurable chromatographic interferences

(co-eluting compounds) . The internal standards were added to

the shale oil at the earliest possible point in the analysis

scheme. Standards containing accurately known amounts of

standard and analyte were taken through the entire quantitation

procedure to determine response factors. These response factors

thereby reflect not only differences in detector response but

also chemical and physical properties such as extraction efficiencies and volatility losses which might occur during extract

concentration. Details concerning the sample preparation and

GC conditions used in the determination of the selected shale

oil constituents are summarized in Table II.

GC/MS quantitation . Gas chromatographic -mass spectrometric

analyses were performed on a standard gas chromatograph, modified

for use with WCOT columns, interfaced to a quadropole mass

spectrometer with dual disk data system. Chromatographic columns

were interfaced to the mass spectrometer either through a gold

jet molecular separator, or an ’open split' (16) constructed

24
of Ni tubing (1/16" OD x 0.010" ID) which was deactivated (17)

and restricted to allow a flow rate of 1.5 mL/min into the ion

source. The operating pressure in the ion source manifold was

1.0 X lO"^ torr. The mass spectrometer was operated in the

electron impact mode under the following conditions: interface

temperature 250-275°C, ion source 200°C, analyzer 100°C, electron

energy 70 eV. Gas chromatographic separations were carried out

on the columns and under the conditions noted in Table III.

A standard addition technique was generally used for

individual species quantitation (see Table III). For each

compound to be determined, four shale oil samples, with different

known amounts of the analyte added, were fractionated. The

standard additions were made over a range of zero to three times

the approximate concentration of the analyte, based on a preliminary quantitative determination of the compound in the shale

oil using an external standard method. The ’spiked' shale oil

samples were subjected to either an acid/base solvent extraction

or an HPLC fractionation. The samples were reduced to 100 yL

under a stream of nitrogen, and suitable aliquots analyzed by

GC/MS with selected ion monitoring. To circumvent the

need for accurately measuring volumes during the extraction cr

fractionation, and to compensate for variable injection volumes

onto the GC column, a second compound natively present in the

shale oil, and in the same compound class as the compound being

determined, was monitored as a volume correction standard. The

specific compounds used as volume correction standards for each

25
analyte are listed in Table III. Selected ion monitoring was

chosen as the means of analysis for its sensitivity and selectivity. The ions (generally the molecular ions) for the analytes

and the internal standards (volume correction standards) were

monitored in real time in 0.1 amu increments to insure that the

signal was sampled at the top of the mass peak. Dwell times of

either 50 or 100 ms were used to insure at least 20 data points

across a chromatographic peak. Single ion records were integrated after each run, and a ratio of the peak area for the

analyte to the peak area of the internal standard (volume

correction standard) was computed. This ratio was plotted

against the concentration of the analyte (in ppm) added to the

shale oil. The concentration of the analyte natively present in

the shale oil was determined from the intercept with the abscissa,

using a linear- least squares program.

Fluoranthene and pyrene were also determined in the shale

oil without any prior acid/base extraction or HPLC fractionation. Approximately 0.5g of shale oil was diluted to 10 mL with

methylene chloride. A known amount of 9 , 10-dimethylanthracene

('V/SO yg) was added to the solution as an internal standard. One

to two yL aliquots of this solution were analyzed by GC/MS using

selected ion monitoring. The chromatographic conditions were as

noted in Table III. Single ion records for the ^/z 202 ion (for

fluoranthene and pyrene) and the ^/z 206 ion (for 9 , 10-dimethylanthracene) were clean enough to allow integration of peak areas

Response factors for fluoranthene and pyrene relative to the

26
9,10-dimethylanthracene were determined under identical GC/MS

conditions from gravimetrically prepared solutions of these

compounds. Concentrations of fluoranthene and pyrene were

determined from these response factors and ratios of the area

of the compound being determined to that of the internal standard.

Results and Discussion

The major aim of this study was to develop independent

analytical methods for the quantitative determination of individual toxic and/or carcinogenic compounds in an alternate fuel.

The development of a minimum of two such independent methods is

a necessary prerequisite to the certification of a Standard

Reference Material needed as a quality assurance standard in the

rapidly expanding fields of energy, environmental and trace

organic analytical research. We have shown that individual

organic compounds can be quantitated in a shale oil matrix and

that diverse methodology will, if properly applied, yield comparable results. In addition we have reported a new HPLC method

for preliminary shale oil fractionation, a novel GC/MS quantitation technique which has been shown to greatly enhance analytical

selectivity relative to conventional GC techniques, and finally

an HPLC fluorescence method which allows individual PAHs to be

measured in the presence of other PAHs. The success of the

HPLC fluorescence method can be attributed to: 1) the chromatographic selectivity obtained by reverse phase HPLC, and 2) the

detection selectivity obtained through use of fluorometric

monitoring of the chromatographic effluent. (PAHs have very

27
characteristic excitation and emission spectroscopic properties

which can be used both for identification and selective detection.)

The results obtained by the two independent methods of sample

extraction (classical acid/base solvent extraction and HPLC

fractionation) and three methods of quantitation (high perform.ance

liquid chromatography, gas chromatography with flame ionization

detection and gas chromatography-mass spectrometry using single

ion monitoring) are summarized in Table IV.

Many laboratories are now involved in qualitative examinations of pilot run alternate fuels, and an increasing number of

laboratories are becoming involved in the quantitative analysis

of constituents of alternate fuels. However, the accuracy base

needed to compare quantitative analyses performed by different

investigators is not now available. As part of a preliminary

assessment of the environmental impact of oil shale development,

researchers at the TRW Environmental Engineering Division and

the Denver Research Institute summarized the available quantitative data on the presence of benzo (a) pyrene in various fuels

and natural materials (18) . In addition several researchers

have determined the concentrations of various PAHs in a limited

number of coal-derived liquefaction products (19,20). However,

even in these limited studies the basis for intercomparison of

data is lacking.

In simultaneously developing independent analytical methods

as presented in this paper, one is afforded a unique opportunity

for comparative evaluation of efficiency and precision of the

28
methods. The greatest improvement in efficiency noted during

this study was the incorporation of HPLC fractionation as a

replacement for classical extraction techniques. The acid/base

extraction (Fig. 1) is a laborious procedure which requires

several days to generate the acidic, basic and neutral fractions. Furthermore, once the extraction has been completed, the

samples must be subjected to a high resolution chromatographic

separation to allow individual components to be sufficiently

separated for quantitation free from interferences. On the

other hand, the HPLC fractionation procedure provides a rapid

(less than 1 h) method of preparing shale oil fractions which

are considerably less complex than the three initial fractions

generated by the acid/base extraction scheme. Using a preparative scale aminosilane column and modifying the mobile phase

composition from 100 percent hexane to 100 percent methylene

chloride, it is possible to elute a wide range of compounds from

non-polar PAHs to the more polar phenols and aza-arenes. Figure

3 is an ultraviolet detection recording at 270 nm of the liquid

chromatography to generate the phenolic fractions. The upper

trace is a chromatogram of shale oil and the lower trace is a

chromatogram of various compounds used to determine retention

volumes for the phenols of interest. As one can see the PAHs are

eluted unretained when using 100 percent methylene chloride as

the mobile phase. (The PAHs are isolated according to the number of

Condensed rings using n-hexane as the mobile phase [21]). One

should also note in comparing results obtained on the small

29
, polar compounds, phenol, o-cresol, and 2 ,4 ,6-trimethylpyridine,

that there is an indication of greater precision in any single

method of quantitation when using HPLC fractionation rather than

the acid/base extraction.

As mentioned above, in addition to the two methods of

sample preparation, three methods of individual compound quantitation were utilized. The gas and liquid chromatographic methods

of quantitation, which utilized either internal or external

standards, required some assumptions and/or prior analyses. For

the internal standard methods one had to assume that the standard behaved similarly to the component of interest and one had

to show that its native level in the sample was insignificant

relative to the amount added (which should be added to approximate the concentration of the analyte) . IVhen all appropriate

internal standards were natively present at a significant concentration (the phenols in this study) , the internal standard

had to be added after HPLC fractionation had segregated the

analyte, thereby requiring the assumption that no losses ocurred

during fractionation. Where only an external standard was used

an assumption of instrument (detector) stability was required,

as well as an assumption that no losses occurred during sample

preparation. The gas chromatography-mass spectrometry with

single ion monitoring and standard addition techniques required

none of these assumptions and provided further selectivity by

lack of interference from co-eluting compounds in the gas

chromatography due to the mass selectivity. To the extent

30
that values generated by GC-MS with standard addition agreed

with the HPLC and GC only values, the assumptions discussed

above were valid.

The use of GC/MS single ion monitoring in conjunction with

standard addition techniques provides a novel, accurate and extremely selective means for individual compound quantitation.

The only possible interference in this mode of operation is a co-eluting compound with a peak at the same m/z ratio in its

mass spectrum. To minimize this possibility, several other ions

in the spectrum of the component of interest are periodically

monitored to assure that the relative peak areas for these ions

are in the same ratio as for an authentic sample of the pure

analyte

.

To assure maximum sensitivity the ion to be used for quantitation was monitored at several 0.1 amu intervals to confirm

that the signal of maximum intensity was used for peak area

calculations. This principle is demonstrated in Figure 4 which

contains single ion records for 2 ,4 , 6-trimethylpyridine (M^, m/z

121) and for a dimethylethylpyridine [(M-1)^, m/z 134] , the

volume correction standard. Three independent area determinations were made at each peak maximum (m/z 121.2 and m/z 134.2).

These numbers were averaged and the area ratio was then used for

one data point in the standard addition determination (see

Figure 5) . Despite the mass specificity, a small shoulder which

represented about 2 % of the total peak area was observed on

the m/z 134 peak. As can be seen in Figure 5, several GC-MS

31
determinations were made at each concentration of added 2,4,6-

trimethylpyridine and the x-intercept of the least squares fit

of the data indicated a native concentration of 1214±64 ppm

2 ,4 ,6-trimethylpyridine in the shale oil sample.

As can be seen from Table IV the overall agreement between

the various methods of quantitation and extraction was quite

good, even at the 951 confidence level. The poorest betweenmethod precision was obtained in the determination of 2,4,6-

trimethylpyridine . This imprecision was probably related to the

sample preparation aspects of the work, due to the volatility of

the compound. An indication of this is the fact that the GC-MS

standard addition value is the highest and should be independent

of volatility losses.

This shale oil sample has been analyzed by various national

and university laboratories , to evaluate interlaboratory precision

in the determination of trace organic compounds in alternate

fuels. The results of this intercomparison study are being

compiled for publication.

Acknowledgements

Partial financial support from the Office of Health and

Environmental Research of the Department of Energy and from the

Office of Energy, Minerals, and Industry within the Office of

Research and Development of the U.S. Environmental Protection

Agency under the Interagency Energy/Environment Research and

Development Program, is gratefully acknowledged.

32
In order to specify procedures adequately, it has been

necessary to identify some commercial materials in this report.

In no case does such identification imply recommendation or

endorsement by the National Bureau of Standards, nor does it

imply that the material identified is necessarily the best

available for the purpose.

33
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36
Compound

Sample

Preparation

Internal

or

External

Chromatographic

Conditions

for

Analysis

Determined

Standard 1 * c z o c o O o CO o 1 •H CN CN l-l as tH » >-i CO 4J X z 00

4J (U CO (U CO z CO c 6 0> l-l 4J z z l-l u JJ 01 C c o •H CJ CJ cO fO •H X •H 3 o CO CO y X a 4-1 CO rH rH X Z z c o X c pH 01 CJ CJ •H

0) CO 6^ • • I-H • N ^ )-l O r S'? £ ^s £ £ o o 1 O • 01 o C o C ^S IS CO (V 3 i-H c c vO so o c 1—1 c 1 •H 01 o o UO NT o (U CM o O £ o C'. o r-. 1 liO •H '3- •a- CN '0- CN o • CN

to * CO o a • 1 a CO CO 4J r 4-1 • *H 4J c s •H c CO £ c y C CO C g CO B IS £ B C C B E £ 3 •• 0) 3 •H o 3 IS 3 e 3 O C

fH c o iHN CO rH o i-H o iH CM o O o O O c o o •H O •H o •H U •H CO e o CN 01 -O' u 4-1 y 4-1 y 1 4-1 c X U y z y

00 o 1 00 1 00

y CDy 00

y

rH (1)

m f-H c rH 4J rH 4J Z O 4-1 1 4J C a^ 1 •H •• c 1 y 1 y 1 CM 0) CJ (U o CN| o c o CJ •o (J z CJ z z

•a •H z o •H

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1 Solvent extraction scheme for the preparation of shale oil

sample, adapted from Schmeltz (14).

2 Capillary gas chromatogram of shale oil bases. Conditions:

30m SP-1000 column, 100 °C for 4 min and then temperature

programmed to 220 ®C at 2°/min, flame ionization detection.

3 Preparative scale liquid chromatogram of shale oil. The

upper trace is a chromatogram of shale oil and the lower

trace is a chromatogram of a mixture of pure compounds used

to determine retention volumes of phenolic compounds.

(2 , 4 , 6- trime(|)OH e 2 ,4 , 6- trimethylphenol) . Conditions: semipreparative aminosilane column, methylene chloride mobile

phase and' ultraviolet detection at 254 nm.

4 Single ion records for 2 , 4 , 6- trimethylpyridine (TMP) and a dimethylethylpyridine (DMEP) . Three area determinations for

each peak are shown at the m/z value of maximum intensity.

The area of a small shoulder on the DMEP peak is also

indicated

.

5 Linear least squares fit for the data point obtained in the

determination of 2 , 4 , 6 - trimethylpyridine (2,4,6-TMP) by the

standard addition method. The absolute value of the xintercept represents the negative of the concentration of

the analyte in the sample.

42
e. Existing NBS-SRM's Useful in Characterizing Oil Shale and Oil

Shale Products

Over eighty SRM's are now being used to assure measurement com- patibility in air and water pollution analyses. Some of these materials

could be useful and provide a common reference base for those mea- surements being made in on-going oil shale projects. Those materials

currently available from NBS which could be useful in trace element

measurements in oil shale and oil shale products are given in Table 4-2.

It should be noted that several standards are available for the same element, but indicated in the table by different numbers (e.g. SRM 1621

and 1622). This occurs because the same element has been certified at

varying concentrations in the same matrix. Additional information on the materials listed in the above Table can be found in Appendix B.

43
TABLE 4-2

Existing NBS-SRM's Applicable to Characterization of

Oil Shale/Oil Shale Products

(Liquids) •

SRM Number liEi

1621

1622

1623

1624

1634

Sulfur in Residual Fuel Oil

Sulfur in Residual Fuel Oil

Sulfur in Residual Fuel Oil

Sulfur in Distillate Fuel Oil

Trace Elements in Residual Oil

1636

1637

1638

Lead in Reference Fuel

Lead in Reference Fuel

Lead in Reference Fuel

(Solids)

1630

1631a

1632a

1633a

1635

1648

Mercury in Coal

Sulfur in Coal

Trace Elements in Bituminous Coal

Trace Elements in Coal Fly Ash

Trace Elements in Sub-bituminous Coal

Trace Elements in Urban Particulate Matter

44
SECTION 5

RECOMMENDATIONS FOR FUTURE OIL SHALE PROJECTS

The environmental impact associated with commercial oil shale

operations can be expected to produce air and water pollutants, in

addition to other potential adverse impacts on the environment. Development of measurement methods and/or standards to ensure quality

baseline data and effective monitoring systems is a necessity if

logical and rational policy decisions are to prevail in developing

mitigation strategies for adverse environmental impacts caused by the

oil shale industry.

All commercial shale operations will be required to preserve

water resources and control effluent discharges. To meet these re- quirements, effluents will need to be characterized, controlled, and

monitored. Similarly, process and fugitive emission into the ambient

air may arise from a variety of sources related to oil shale processing

and a monitoring program for these emissions will also be required.

Thus, appropriate standards must be available to provide data quality

assurance for measurements made on oil shale effluents as well as emissions into the atmosphere. More importantly, accurate measurement

methods must be in place to identify, quantify and certify individual

pollutants in a variety of complex matrices which will serve as standards/SRM's for the oil shale industry.

Recommendations for further work at NBS in oil shale products is

summarized in Table 5-1. These recommendations reflect suggestions/input

obtained during conversations with scientists involved with the characterization of oil shale products.

45
Table 5-1

Recommendations for Further NBS Work

- Produce a Raw Oil Shale SRM, certified for all trace elements

of potential environmental or product development concern

- Develop methods needed to produce a Raw Oil Shale SRM, certified

for trace organic pollutants (with focus on criteria organic

pollutants)

- Develop/modify methodologies necessary to certify all trace

elements of potential environmental or product development

concern in: 1) Shale Oil; 2) Oil Shale retort water; 3) and/or

other associated aqueous phases

- Extend the trace organic certification program on shale oil to

include more criteria pollutants (specifics to be determined

through negotiations with interested parties)

- Assist responsible monitoring agencies in developing protocols

for "traceability" in oil shale (and associated products) mea- surements

46
APPENDIX A

Manuscripts Prepared for/Presented During Workshop

47
PREPARATION OF STANDARD OIL-SHALE SAMPLES

OS-1, SS-1, and SS-2

Thomas Wildeman

Chemistry Department

Colorado School of Mines

Golden, Colorado 80401

Work performed under a grant from the Colorado Energy Research Institute

48
This report provides background on the standard oil shale

Scunple, OS-1, and the two standard spent shale samples, SS-1 and

SS-2. It describes the geology of the site, the mining and retorting processes used, the manner of preparation of the samples,

possible sources of contamination, and suggestions on further

preparation of standard samples. References to more detailed

discussion are also included.

Site Description, Geology, and Chemistry

The shale samples came from the Dow mine of Colony Development

Co., so named because it was purchased from the Dow Chemical Co..

The Colony Development Oper. is a consortium of energy corporations

with fhe Oil Shale Corp. (TOSCO) and the Atlantic Richfield Co.

(ARCO) being the primary participants (1, 2) . The location of the

Dow Property (shown in Figiire 1) is at the head of Parachute Creek

in the Piceance Creek Basin, Colorado, 17 miles north of Grand

Valley, Colorado (1).

The actual mining operation is on two 30 foot vertical sections

called the Upper Bench and Lower Bench which start at 10 feet below

the Mahogany Marker and proceed down for 60 feet. This places the

samples in the Mahogany Zone of the Parachute Creek Member of the

Green River Formation as shown in figure 2 (3, 4) . Oil-shale

reserve experts call this the Mahogany Zone of the Upper Oil-Shale

zone and consider it to be one of the richest oil zones in the

Piceance Creek Basin with yields ranging from 28 to 79 gallons/

ton (4)

.

Assays conducted by TOSCO show the Upper Bench shale as

yielding 37-39 gal/ton and the Lower Bench shale 33 gal/ton.

Roehler (3) describes the depositional environment as saline

49
Figure 1. Taken from Reference (1) .

50
51
lacustrine (saltwater lake) in which organic muds were deposited

and saline waters enhanced the growth of planktonic algae. The

brines settled to deeper parts of the lake so that evaporitedeposit minerals are not as prevalent in these shales.

Although there is no published drill core information on the

Dow Property, Union Oil Co. has released information on its property

which lies to the south and west of the Dow Property (5)

.

The

drill core data published in Donnell's report (4) contain no information on this area. Perhaps the most significant study relating

to these samples is that by Desborough's group (6, 7) on a sample

from a drill core which lies on the Dow Property. The approximate

site of this hole labeled C-230 is shown in figure 1. Even though

the vertical variation in the Green River Formation can be considerable, the proximity of this sample to the standard oil-shales

described here will make for interesting comparisons.

1 Table I lists the composition information on this sample. The j four samples Desborough (6) analyzed from the Mahogany Zone in 1

t

1 Colorado are chemically and mineralogically quite similar; however,

the range in oil yield was 48 to 71 gal/ton which is higher than

the 33-39 gal/ton range of the Dow mine. It appears that shales

with lower oil yields have greater concentrations of dolomite and

i smaller concentrations of quartz and pyrite. Other data available i

i on this C-230 Scimple include the chemical composition of carbonate 1

I grains, electron microprobe images, and information on arsenic *

(6, 7).

I

i Mining and Retorting Procedures

i The mining and retorting processes to be used on the Dow Property , are considered to be the closest to immediate industrical scale-up and

52
Figure 3. Colony

mining operation

in the Middle Fork

Canyon.

Figures taken from

Reference 8.

Figure 4, Room—and—pillar two bench mining cycle.
Figure 5. A schematic of Colony's mining and oil-shale

processing procedure taken from reference 8

.

Figure 6. A flow diagram of the TOSCO II process taken from

reference 2.

54
hence have been well studied and described. Figure 3 shows the layout

of the mining operation in the canyon of the Middle Fork of

Parachute Creek and figure 4 shows the function of the Upper and

Lower Benches in the mine (1, 8) . If operating today, this would

be the largest room-and-pillar mine in the world.

The TOSCO II retorting process has also been described in

detail (1, 2, 9). Figure 5 schematically shows the whole process

and figure 6 is a flow sheet of the retorting operation. This

process has some unique characteristics that should be kept in

mind. First, it uses recycled hot solids (%" ceramic balls) as

a heating agent as opposed to internal combustion of gases with”

in the retort or external fuel-fired retorting. This allows

better control of the retort temperature and the TOSCO I I process

probably keeps the temperature lower (482°C, 900°F) than other

retorting methods. Second, the feed stock is crushed to a smaller

size (“*5" mesh/ including fines) than other processes which exclude

feed stock below 1/8” and crush to 3 in. pieces. Furthermore, the

pyrolysis drum crushes the shale still further so that the bulk of

the spent shale is less than 200 mesh; other processes, can end up

with clinkers. Finally, the oil recovery in. the TOSCO II process

appears to be better, typically 100% of Fischer Assay, than other

processes, about 80-90% of Fischer assay.

Preparation of Standard Samples

All the samples were mined from fresh faces in the Dow mine

in 1974, crushed to -Jj mesh and delivered in 100 ton lots to the

TOSCO research facility in Golden, Colorado. OS-1 was taken from

a residual pile of approximately 3 tons of -h mesh feed stock

which was mined from the Upper Bench and assayed at 37 gal/ton.

SS-2 is spent shale resulting from the retort operations at TOSCO 's

55
Denver pilot plant on Nov. 11, 1974 on the same feed stock from

which OS-1 was taken. SS-1 is spent shale resulting from retort

operations at the pilot plant on August 23, 1974 on feed stock

from the Lower Bench which assayed at 33 gal/ton. The amounts

collected were 31 lb. of SS-1, 24 lb. of SS-2, and 60 lb. of OS-1.

The spent shale sajaples were wet with tap water and

so were air dried at room temperature for two weeks.

Ninety percent of the spent shale was -200 mesh materia,!

the other 10% was partially retorted stock which was greater than

10 mesh. These pieces were hand ground in a porcelain mortar and

added to the sample. Approximately 5% of SS-1 and SS-2 will not

pass through a 100 mesh sieve. No other processing of the spent

shale samples was done prior to blending and splitting.

The raw shale required extensive crushing and grinding to

prepare it for blending and splitting. The objective here is to

grind to minus 65 mesh since the analysts at TOSCO have shown that

this will provide a more representative sample of the bulk feed

stock when 100 gm is used for Fischer assay (10) . First, the half

inch feed stock was crushed in a hardened steel jaw mill to minus

4 mesh particles and then in a hardened steel roller mill to minus

10 mesh particles. Grinding was then attempted using a ceramic

ball mill but the shale particles are siirprisingly hard and resinous

and the ceramic balls just bounced off the particles. Grinding

to minus 65 mesh would have taken at least one day for each charge,

so this method of grinding was abandoned. Instead a "shatterbox”

was used. This was quite effective, but the action of the grinding

rings generated some heat. Charges were ground for no more than

30 sec. so the loss of volatiles would be kept to a minimum. The

56
BLENDING &

SPLITTING

OF

OS oo

UJXO

CO

>-<

CO

CO<

CO

UJ

CL2<

CO

CO ^ W lij

X H- o 3 «a

w ^ CL CO «

I: CO

w ^ Cl o - O

I- -I o < CL IS. CQ CO

o> e

UJ

O

J. 2 O CO ^

CO < CL

CO CO

s: <

COo

CM

x“2< < “•

c.

ffl <» «

lO

X H- o —

»- -1 < CL

CD CO

57

Figure

7.

Splitting

and

blending

scheme

for

OS-
ground shale was sized by passing thrdugh a 70 mesh stainless steel

mechanical sieve. The full 60 lb. of shale feed stock was processed in this fashion. The crushing and grinding operations

also blended the bulk sample to some extent. All the crushers

and griners were cleaned and portions of shale were processed and

discarded before processing the sample.

For each of the three samples, blending and splitting were

performed simultaneously by taking each split and recombining and

mixing and then splitting again. This was done 5 times on the

first two splits and 4 times on the subsequent two splits. The

16 fractions resulting from the splitting were then blended by

hand on a polyethylene sheet and two 75 gm samples were taken from

each fraction. In the case of the raw shale, 7-100 gm Fischer

assay charges were also taken from each 1/16 fraction. What remained of each sixteenth fraction was placed in a polyethylene

bottle and labeled Batch 1, split 1-16. The 75g samples were packaged in glass bottles and labeled Batch 2, split 1-32. All bottles

were rinsed with 1-1 HNO3 and deionized water and dried before

use . The bottled samples have been stored in a sealed polyethylen<

container in a vault at a constant temperature of 10°C. Figure 7

is a diagram of the splitting scheme for OS-1.

Comments Concerning Contamination

The steel crushers , grinders and sieves used to process OS-1

can all be a source of contamination to various degrees. A U.S.

Geological Survey group# in a study of contamination by steel crushers

and grinders, found that Fe can be increased by as much as 1.5 %

Ni - 60 ppm. Mo - 20 ppm, V - 10 ppm, Cu - 30 ppm, and Mn - 1000 ppm

(11) . The main source of contamination appeared to be disc-type

58
metal grinders. Another study on the grinding and sieving of small

samples showed that contamination will most likely be inhomogeneous

and cause a widely abherrent result in a trace element analysis (12)

Stainless steel sieves can contribute about 3 ppm Ni, 3 ppm Mn, and

20 ppm Fe to a sample. Flannagan, in the preparation of the U.S.G.S

standard rocks (13) , could detect no contamination from the use of

jaw crushers and rollers in those samples. The following is an

assessment of the level of contamination introduced during the prepa

ration of OS-1.

First, all implements used were previously used for crushing

and grinding oil-shale and were cleaned with some of the sample

which was discarded so there is little possibility of cross contamination from previous samples. Processing by the jaw crusher and

roller crusher may have added bits of steel in an inhomogeneous

fashion but this could be eliminated by passage of a magnet over the

powder. The shatterbox actually grinds the sample against itself

and when the _steel rings are touching, the sound changed and the

grinder was stopped and a new charge added. Thus, contamination

will be much less severe than that by using steel plates. Contamination could come from the stainless steel sieve. Comparing

the levels of contamination mentioned above with those abundances

listed in Table I, it is likely that grinding added up to 10% of

Ni and fin to OS-1, up to 5% of Fe, Cu, and Mo, and up to 1% V to the

sample.

Homogeneity Tests

A simple test of the homogeneity of the standard samples has

been made using an x-ray fluorescence analysis method for Rb and Sr

devised by Doering (14) . This method uses rock powder ground to

59
minus 200 mesh packed in a small nylon planchet. The analysis has

been calibrated using standards in which the Rb and Sr contents have

been analyzed by isotope dilution and yields the Rb/Sr to +3% at the

95% confidence level and the abundances of Rb and Sr to +6% at the

67% confidence level.

Eight samples of about 10 g were randomly chosen from eight

different 75 g splits of each standard and were ground in Spex

Mixer/Mill using a tungsten carbide chamber to -200 mesh. The 24

samples were all analyzed on the same day to eliminate instrument

drift and bias in packing the charges in the planchets. The results

are summarized on Table II. The mean, range, standard deviation,

and relative standard deviation are used according to the definitions

prescribed in Analytical ChCTiistry , 46, p. 2258, 1974. The mass

absorption coefficients were determined by making a count of the

compton scattered photons at a 20 angle of 21°.

The range and trend in the values for the mass absorption

coefficient directly correlate with the Rb and Sr abundances.

Coarser material won't pack as densely into the planchet thus

yielding a lower mass absorption coefficient and also a lower value

for the abundance of Rb or Sr, Thus, the deviations in the results

appear to be caused by grinding and packing and not by true differences

in the abundances of the two trace elements in the different splits.

The conclusion is corroborated by the fact that the results for the

spent shales, which are much finer in grain size, exhibit better

precision. The conclusion is that the different splits of all three

standard samples are homogeneous to within +5%.

60
Suggestions for Next Time

Grinding the raw shale using the shatterbox is definitely

the best procedure unless a large supply of ceramic ball mills

are available. Grinding chambers for the shatterbox are also

available in tungsten carbide and alumina ceramic. The tungsten

carbide would add apprecic±)le Co and a trace of Ti, but it is

quite expensive (12), The alumina adds appreciable Al, Co, Ga,

auid Li and may take longer for grinding (12) . Unless money is

no problem, contamination by grinding will have to be tolerated.

The contamination by sieving can be eliminated by testing

how long it takes to grind a uniform charge to less than 65 mesh

in the shatterbox and then grinding for that period of time.

Pulverizing the samples to a smaller grain size such as -200

mesh may release volatile organic fractions and inorganic species

such as Hg, AsH^r and H2 Se. This possibility increases because of

the dusty character of oil-shale, because of the larger surface

area of the smaller grains, and because heating of the sample may

occur during the longer grinding periods. In any event, tests

should be performed on some scrap oil-shale to determine the

amount of dust producing and the amount of heating that occurs

upon grinding.

61
REFERENCES

1. Kilburn, P.D., Atwood, M.T., and Broman, W.M., (1974), Oil

shale development in Colorado: Processing technology and

environmental impact. In: Guidebook to the Energy Resources

of Piceance Creek Basin Colorado, D.K. Murray ed. , Rocky

Mountain Assoc, of Geol., Denver, Colo., pp. 151-164.

2. Hendrickson, I. A., (1974), Oil shale processing methods.

In: Proceedings of the Seventh Oil Shale Symposium, Quart,

of Colo. Sch. Mines, v. 69, no. 2, pp. 45-69.

3. Roehler, H.W., (1974), Depositional environments of rocks in

the Piceance Creek Basin, Colorado. In: Guidebook to the

Energy Resources of Piceance Creek Basin, Colorado, pp. 57-64.

4. Donnell, J.R., (1961), Tertiary geology and oil-shale resources

of the Piceance Creek Basin between the Colorado and White

Rivers Northwestern Colorado, U.S. Geol. Survey Bull. 108 2-L,

pp. 835-891.

5. Stanfield, K.E., Rose, C.K., McAuley, W.S., and Tesch, W.J.,

(1957), Oil yields of sections of Green River Oil Shale in

Colorado 1952-54, U.S. Bur. Mines Rept. Inv. 5321, 132 pp.

6. Desborough, G.A., Pitman, J.K., and Hoffman, C., (1974),

Concentration and mineralogical residence of elements in rich

oil shales of the Green River Formation, Piceance Creek Basin,

Colorado and the Uinta Basin Utah - a preliminary report,

U.S. Geol. Survey open file rept. 74-77, 14 pp.

7. Desborough, G.A. and Pitman, J.K., (1974), Significance of

applied mineralogy to oil shale in the upper part of the

Parachute Member of the Green River Formation, Piceance Creek

Basin, Colorado. In: Guidebook to the Energy Resources of

Piceance Creek Basin, Colorado, pp. 81-89.

8. Marshall, P.W., (1974), Colony development operation roomand-pillar oil shale mining. In: Proceedings of the Seventh

Oil Shale Symposium, Quart. Colo. Schoool of Mines, v. 69,

no. 2, pp. 171-184.

9. Prien, C.H., (1974) Current oil shale technology: A summary.

In; Guidebook to the Energy Resources of Piceance Creek Basin,

Colorado, pp. 141-150.

10. Goodfellow, L., and Atwood, M.T. (1974), Fischer assay of oil

shale procedures of The oil Shale Corporation. In: Proceedings

of the Seventh Annual Oil Shale Symposium, Quart. Colo. Sch.

Mines, V. 69, no. 2, pp. 205-219.

11. Myers, A.T. , and Burnett, P.R., (1953), Contamination of rock

samples during grinding as determined spectrographically

.

Amer. Jour. Science, 251, pp. 814-830.

62
12. Thompson, G., and Bankston, D.C., (1970), Sample contamination

from grinding and sieving determined by emission spectrometry.

Appl. Spectroscopy, pp. 210-219.

13. Flanagan, F.J., (1967), U.S. Geological Survey silicate rock

standards. Geochim. Cosmochim. Acta., PP« 289-308.

14. Doering, W.P., (1968), A rapid method for measuring the Rb/Sr

ratio in silicate rocks. U.S. Geol. Survey Prof. Paper 600C,

pp. C164-C168.

63
TABLE I

Mineral and Chemical

C-230

Composition of OilMahogany Zone ( 6 ) Shale from Core

Major

Elements

in Percent Trace Elements in ppm

Si02 28 Li 70 Zn 80

AI

2

O

3

6.6 B 100 Ga 10

^®

2

^ 3.2 F 1200 As 30

MgO 4.0 Sc 5 Se 1.5

CaO 7.2 Ti 1200 Sr 295

K2O 1.1 V 200 Y 10

Na20 1.8 Cr 30 Zr 60

^2°5 0.2 Mn 224 Mo 30

Total Sulfur 1.65 Co 12 Cd <.6

Ash 62.1 Ni 30 Sb 3

Cu 70 Ba 300

La 45

Hg 2.9

Pb 43

Oil Yield: 68.8 gal/ton

Minerals

:

Raw Shale: Quartz, dolomite>> albite, analcime, calcite >>dawsonite

Shale Ashed: Quartz >>dolomite, albite, (anhydrite)

@ 525°C

64
SS-2

Table II. Results of homogeneity tests for Rb and Sr on the

standard oil-shale and spent-shales.

OS-1 SS-1

Number of Samples 8 8 8

Range for Sr (ppm) 553-615 966-1051 747-793

Average for Sr (ppm) 584 1006 771

Standard dev. for Sr (ppm) 24 28 17

Relative std. dev. for Sr (%) 4.1 2.8 2.2

Range for Rb (ppm) 55.8-63.9 66.6-73.8 78.6-82.2

Average for Rb (ppm) 60.1 70.2 80.7

Standard dev. for Rb (ppm) 2.7 2.1 1.5

Relative std. dev. for Rb (%) 4.5 3.1 1.9

Range for Rb/Sr 0.101-0.105 0.068-0.071 0.101-0.10

Average for Rb/Sr 0.103 0.070 0.105

Standard dev. for Rb/Sr 0.001 0.001 0.002

Relative std. dev. for Rb/Sr 1.1 1.5 2.1

Range for MA* 7.71-8.43 9.91-11.12 9.61-10.45

Average for MA 8.06 10.7 10.3

Standard dev. for MA 0.27 0.37 0.3

Relative std. dev. for MA 3.3 3.5 2.8

* MA is mass absorption coefficient in cm^/gm

65
Discussion

Question :

Answer:

Question :

Answer :

Question :

Answer:

following Wil deman Presentation -

What do you know about the composition of the flue gas?

Water, carbon dioxide, carbon monoxide, the ammonia and

H

2

S are stripped out. Very small amount of oxides of

nitrogen. Very little SO

2

due to absorption in the spent

shale. Some parti culates^from the grinding action of

the ball mill

.

Is there organic nitrogen in the shale oil?

The shale oil contains 1 to 8% Nitrogen.

What happens to the ]% sulfur in the shale and shale oil?

The sulfur in the oil comes out as H^S and would be re- covered and sold as sulfur. The inorganic sulfur is found

mainly in the spent shale.

66
MINOR ELEMENTS IN OIL SHALE AND OIL-SHALE PRODUCTS

by R. E. Poluson, J. W. Smith, N. B. Young, W. A. Robb, and T. J. Spedding

Laramie Energy Research Center, Energy Research and Development

Administration, Laramie, WY 82071

67
MINOR ELEMENTS IN OIL SHALE AND OIL-SHALE PRODUCTS

by

R. E. Poulson, J. W. Smith, N. B. Young, W. A. Robb,

and T. J. Spedding

ABSTRACT

This paper presents order of magnitude analyses for minor elements in

several Green River Formation oil shales, shale oils and retort waters. The

oil shale analyses are found to be remarkably uniform throughout a wide region

Crude shale oils and retort waters were found to have some large variations in

trace elements. The cause of the variations could not be determined from the

available data. The need for standard reference materials and methods, along

with cooperative testing for oil shale and its products was discussed.

68
MINOR ELEMENTS IN OIL SHALE AND OIL-SHALE PRODUCTS

R. E. Poulson, J. W. Smith, N. B. Young

W. A. Robb, and T. J. Spedding^

INTRODUCTION

Accurate analyses of oil shale and its products are important in perfecting

control technology for a developing industry and in anticipation of a need for

effluent regulation. Both organic and inorganic compounds are of concern, but

this paper is limited to only a part of that concern, ie. elemental analyses

without regard to particular chemical compounds.

Methods for accurate analysis are not available for all elements of possible concern in oil shale and oil-shale products. In the case of the total

oil-shale resource this does not seem a serious deficiency because an accurate

analysis of some particular oil shale would probably represent only that material which was analyzed. It is possible that a few feet up or down in the

formation, different results would be obtained. Furthermore, it is the biological availability of the oil shale and the oil-shale product constituents

which seems more important environmentally than the exact elemental content.

Although accurate minor element analyses on any given oil shale or product

may be of small intrinsic importance, the ability to make accurate analyses has

an important role in revealing possible routes of biological availability of

oil-shale constituents. In a similar way, useful oil-shale processing information may be obtained when routes for unwelcome intrusion of trace elements into

sensitive points in processing schemes (catalytic reactors, eg.) may be recognized. One means toward this end is of course the material balance study which

1 All authors are with the Laramie Energy Research Center, ERDA, Laramie, WY.

69
must begin with accurate oil-shale sampling and analysis and be completed with

comparably accurate product sampling and analysis.

The objective of this paper is to present a large body of data, primarily

for information, with emphasis on minor elemental contents of oil shale and oilshale products and to point out deficiencies in the data. We believe these

deficiences indicate the need for standard reference materials with certified

analyses for oil shale and oil-shale products, and the need for a cooperativelaboratory analytical program based on those standard materials. The development of techniques giving accurate results should then lead to means for evaluating transport of these minor elements in a processing plant or into an

ecosystem.

The data presented are termed survey analyses. By this is meant total

elemental analyses except for C, H, N, 0, In, and in some cases Re. The data by

and large are of order of magnitude precision only. Somewhat better precision

was expected with the techniques used, but the data nevertheless serve to show

comprehensively the range of elemental contents of oil shale in the Green River

Formation Mahogany zone, in a saline zone far below it, and of shale oils and

coproduced retort waters derived from Anvil Points, Colorado mine run shale.

Most previous work with Green River oil shale has been limited to selected

elements (J_, except for that of Cook (^) who presented a survey

analysis on a pyrolyzed oil shale. In the present work, survey analyses were

made using spark source mass spectrometry (7.) ^^or minor elements complemented by

various techniques which are more common for major elements and some minor

e 1 ements

.

2 Underlined numbers in parentheses refer to references at the end of this

report

.

70
EXPERIMENTAL

Oi 1 Shales

Two Green River Formation oil-shale zones were sampled for analysis, the

Mahogany zone in Colorado and Utah and a saline zone below the Mahogany zone in

Colorado. All shale samples were jaw-crushed to between 6" and 1/4" then

reduced by core grinding to minus 8 mesh. Samples were reduced to minus 100

mesh in a hammermill and blended in a plastic V-mixer. The source of the 10

Mahogany zone cores is shown in table 1. A more detailed discussion is presented by Smith (^) . The saline zone samples were from an 821 foot section from

USBM-AEC Colorado Corehole No. 3 in the Northern Piceance Creek Basin. Samples

were composited 10 foot intervals and were (in increasing order of depth) nos.

2, 16, 25, 32, 53, 83, 73, and 83 of reference (^) . Sample no. 2 began at 1909

feet below Kelly bushing (elevation 6,397 feet).

Spark source mass spectrometry, neutron activation and X-ray fluorescence

analyses were done directly on raw oil-shale powder. The detectability limit

for elements in oil shales was taken as 0.1 ppm in the mass spectrometr i c measurements. The X-ray fluorescence work used gonlometric analysis (9^). In addition, silicate concentrates were prepared from the Mahogany zone composites by

hydrochloric acid treatment, principally to remove carbonates, followed by 500°

C ashing prior to X-ray fluorescence analysis. Elemental detectabilities in Xray fluorescence as used are shown in table 2.

Shale Oils

Crude shale oils were obtained from retorts listed in table 3 using the

indicated oil shales. Oils with "F" suffix were filtered through Whatman 42

paper before analysis. Oils with "U" suffix were unfiltered crude shale oils

* Jointly funded by U.S. Bureau of Mines and U.S. Atomic Energy Commission.

71
were pyrolyzed at 450° C before analysis. Mass spectrometr i c detectability for

elements was 0.1 ppm in some runs and 0.01 ppm in others. Footnotes in the data

tables indicate which applies in various samples. For oils and waters auxilliary

analytical methods were used for major elements and certain minor elements.

These methods are listed in table 4.

Retort Waters

Retort water was water formed with the oil and decanted from it. The

waters were all from the Laramie 10-ton simulated in situ retort. Shales and

particle sizes are listed in table 5* Each water was "deoiled" by filtering

through diatomaceous earth at 25° C. Subsequent separation of phases on standing

and cooling in storage presented an analytical problem. In such cases the

"deoiled" water was homogenized before sampling.

Water samples were evaporated to dryness and for mass spectrometry were

ashed at 450° C. The radioactivity measurements were made directly on the

residue from drying. A pure uranium standard was used. Uncertainties were

±50 percent because of the occurrence of uranium progeny to an undetermined

extent

.

RESULTS AND DISCUSSION

As mentioned earlier, an accuracy of a factor of three was expected for

mass spectrometr ic analyses based on results with other materials. It will be

seen that order of magnitude is closer to the case for the work at hand. In the

discussion of the results for oil shale and oil-shale products, there are not

enough data to pinpoint sources of errors. It cannot be determined whether the

principal analytical problems are instrumental, sample handling or sample

preparation. The data will be discussed showing inconsistencies, consistencies and such conclusions as seen warranted by order of magnitude analyses.

72
Oi 1 Shales

Results for Mahogany zone oil-shale samples are shown in table 6. Samples

4A and 5A were prepared as samples identical to k and 5 submitted for analysis.

If the results for duplicates A and 4A and 5 and 5A are considered, and a factor

of ten allowed for analytical precision on such a survey type analysis, many results are still outside that boundary. This illustrates the need to determine

whether the problem is in sampling or analysis and to develop appropriate methods

and materials for standardization.

Results from neutron activation analysis agree qualitatively with the mass

spectrometr i c data. However, the mercury analyses of oil shale by neutron activation analysis, appear not very precise as seen for duplicate analyses on

samples 6 and 10.

Except for lead, x-ray fluorescence analysis for raw shale powder in table

7 and silicate concentrates in table 8 agree qualitatively with the spark source

mass spectrometry (table 6). Limits of detection by this technique were in many

cases well above those of mass spectrometry. Advances in x-ray fluorescence

techniques have resulted in improved sensitivities for most elements but no

results are currently available.

Alkali metal analyses by flame photometry for both HCl-soluble and insoluble

fractions of the Mahogany-zone samples are shown in table 9. These results

agree qualitatively with the survey results of table 6 for the major element

sodium and for potassium except for sample 5. Results for the minor element

lithium agree qualitatively with those of mass spectrometry and seem to be

closer to the values for the 4A and 5A samples than to values for k and 5-

These data confirm nevertheless the concept that the Mahogany-zone oil

shales of table 6 are remarkably uniform in their minor element content over a

wide region of the Green River Formation. Variations are no more between different cores than between duplicate samples.

73
The oil shales In table 10 represent a vertical array in the saline-zone

below the Mahogany-zone, covering an interval of over 800 feet. Here also we

see little variation in trace elemental concentrations compared to probable

analytical uncertainties. Indeed, within those limits the results agree with

those for the Mahogany-zone samples.

The analyses of Desborough, Pitman, and Huffman (^) for 33 elements in

Mahogany zone and R-^ zone oil shales agree in order of magnitude with results

here from the Mahogany and saline zones. The early work of Stanfield, et al (J_) stated little variation was observed in 18 minor elements with oil-shale grade

(organic content) for six samples from various ledges near the Mahogany marker

in the vicinity of Rifle, Colorado. The results of Smith and Stanfield (^) for

12 minor elements in Uinta Basin Utah oil shales are also consistent with the

data on Colorado oil shale. The net observation from all this work is the

remarkable uniformity in minor elemental composition in Green River Formation

oil shales. This is consistent with the theory of Smith concerning the geochemical genesis of Colorado's Green River Formation (10).

Crude Shale Oils

Table 11 shows survey analyses for crude shale oils from four different

retort systems shown in table These oils were subjected to low temperature

pyrolysis before analysis in contrast to the oil shales which were run directly.

Ancillary standard methods were used for certain elements as shown in table 4.

The three oils reported in six columns to the right of table 11 were analyzed

with and without filtration. There appears to be no systematic variation of

results with filtrations so that it was assumed the differences observed were a

result of the sampling and analysis scheme. Here as with the oil shales a

factor of ten is required to reconcile most of the analyses for the low level

constituents in the filtered and unfiltered samples.

74
In contrast to the monotonous similarity of oil shales mentioned by Smith

(10), shale oils and retort waters have shown some real differences in trace

elemental composition. To the far left of table 11 results for two oils, lOT29U and IOT- 3 IU, from the same retort are shown. Operating parameters were

different, but it has not been possible to correlate elemental analysis with

the parameters of various runs (11). There appear to be unequivocal differences in trace element contents of these oils, however. The analysis in table

11 shows a 12:0.01 ratio in uranium contents for IOT- 3 IU oil relative to lOT29 U oil. This difference has been confirmed qualitatively by alpha spectrometry. The corresponding retort waters also show elevated uranium contents

as will be discussed in the next section.

Another real difference in the oils is the arsenic content. The analysis

of the Rock Springs, Wyoming in situ oil shows 0.5 Ppm and is the lowest of the

five oils analyzed. If we add to this comparison the results of Burger et al

( 12 ) showing ^0 ppm for a shale oil produced by a proprietary process we see the

possibility of nearly one-hundredfold range of arsenic levels in a variety of

oils. We will discuss some of the possible causes for trace elemental differences in oil-shale products after we have discussed the retort water data.

Retort Waters

Table 12 shows survey analyses for retort waters produced in the Laramie

10-ton retort from retorting of shale particle size ranges shown in table 5- No

correlation of water properties with retorting parameters was detected (11).

Several standard water quality parameters were run by separate laboratories.

Parenthetical results in table 12 illustrate anything from fair agreement to

gross disagreement in values reported. Here again it is not known whether the

problem is sampling or analysis.

75
The water IOT- 3 I shows a 4.6:0.023 ratio of uranium content relative to

lOT -29 which tends to confirm the similar results with these two oils. The

uranium content of the waters was also confirmed with alpha spectrometry. Other

waters (produced from this system) have since been found showing radioactivity

up to 200 ppm uranium. A major elevation in tin level appears for the IOT- 3 O

water. Most other differences in trace elements appear reconcilable by the

uncertainties of the survey analyses.

In summary for retort waters as with the crude shale oils differences are

definitely detectable among products even of nominally very similar sources.

Source of Variations of Trace Elements in

Crude Shale Oils and Retort Waters

The existing data for Green River Formation oil shales indicates a widespread uniformity in minor elemental composition. It is surprising that there

would be thousandfold differences in trace elemental compositions of oils and

waters produced under apparently similar conditions. There are at least three

factors in oil-shale retorting which might lead products to differ. The data to

date cannot confirm or deny any of these however. First, the minor element

composition of the oil shale used may be different in spite of the evidence at

hand. Secondly, the retorting processes involved may be different in ways not

yet understood. Finally the products themselves may be subject to special

external influences after retorting, as for example the incursion of groundwater

into an in situ process after the pressure developed in retorting has subsided.

The applicability of these factors to the observed uranium and arsenic variations

In the products will be considered now.

The occurrence of enhanced uranium content in the IOT- 3 I products over

the lOT-29 products might have been ascribed to particle size either as an

effect on retorting or as a separative effect of crushing with uranium being

76
enhanced in the 0-1" fraction. This does not appear to be so because a subsequent run with 3""6" shale from the same source also showed enhanced uranium

content in the products yielding over 200 ppm uranium in the water as determined by alpha spectrometry. More detailed measurements on a well defined

system are required to pin down the causes of the variations.

There is an interesting possibility as to the cause of variations in

arsenic levels in the various oils. The oil with the lowest value is the Rock

Springs, Wyoming Site k in situ produced oil which was liberally washed with

alkaline groundwater. The proprietary oil mentioned above had the highest

arsenic level and was produced in the driest way of any. Using the average of

the "U" and "F" values, the other oils in table 11 were intermediate in arsenic levels and in water contact with the 10-ton and 150-ton simulated in

situ processes being much wetter than the gas combustion process. Alkaline

washing is the basis for some processes for arsenic removal from shale oil

( 12 ) and this may be the explanation for this observation. At present an

equally valid explanation would be shale source because the in situ oil was

from the Green River Basin (Wyoming) of the Green River Formation. Again

a more detailed study is necessary to pinpoint variables.

Suggestions for Further Work

The variability of the oil-shale product trace elemental composition is

intriguing with respect to environmental control technology, and raises significant questions. To answer such questions, retorting experiments with material balance assays of the elements of concern will be needed. To help such

studies, the analytical methodology for minor elements in oil shale and oilshale products needs to be improved based on the results we have presented here.

A program such as the National Bureau of Standards Standard Reference

Materials (SRM) work seems well suited in helping to develop methodology for

77
attainment of accurate results for oil shale and oil-shale product minor elements.

If one looks to the SRM program, reference materials for trace elements in oils

and water do exist. These could be useful, with some alteration, in analyses

of shale oil and retort water and spent shale if the certification list were

extended to include more elements of environmental concern » None of the

existing water standards are alkaline, or have organic contents of up to 2^

that are characteristic of oil-shale retort waters, or up to 10^ occuring in

some oil-shale formation waters (_l_l_) . There is, however, no standard comparable to raw oil shale with respect to its intimate mix of organic and

refractory inorganic material. For these reasons it is suggested that work on

an SRM for oil-shale liquid products could be an extension of existing standards but for oil shale a new standard would need to be prepared and certified.

The certification of existing standards for oil, water, and ash along with

a new standard for raw oil shale should aim at certification of all elements of

potential environmental or product developmental concern. It would be useful,

for example, to have an oil certified for antimony, arsenic, beryllium, boron,

cadmium, chromium, cobalt, copper, fluorine, gallium, iron, lead, lithium,

manganese, mercury, molybdenum, nickel, selenium, tin, uranium, (with progeny),

vanadium, and zinc. Not all of these elements have been reported in shale oils,

but traces may occur in oil shales so methods should be available for screening

products until the fate of these elements is well understood.

As an adjunct to the preparation of standard reference materials, a cooperative laboratory test program would probably do much to show up problems in

application of methodology. In addition to the analysis itself, guidelines in

sampling of oil shale and its products will need to be developed before any

analytical technology can be applied to a real process. This will require a

determination of the degree of heterogenity which might exist with respect to

78
minor elements In oil shale, spent shale, shale oil and associated aqueous

phases.

Work in progress at the Laramie Energy Research Center will soon be published

on analyses of leach waters from raw and spent shales from the Laramie 10-ton

retort runs reported in this paper along with results from other runs. A program on analysis of selected trace elements in runs from the Laramie Control ledState Retort ( 13 ) is being undertaken. The charge to this retort has been

riffled at 1/8 to 1/2 in particle size and might be more homogenous than the 10-

ton retorting charges.

SUMMARY

Order of magnitude minor elemental analyses for several Green River Formation

oil shales, shale oils, and retort waters were presented. The oil-shale analyses

showed a remarkable uniformity between Colorado Piceance Creek Basin Mahogany

zone and saline zone oil shales. Comparison with earlier data of other workers

extends this uniformity to rich and lean Mahogany zone oil shales, to the Mahogany

and R-A zones of the Piceance Creek (Colorado) and Uinta (Utah) Basins.

Crude shale oils and retort waters were shown to have variations in trace

elements of up to 10 even in products from very similar retorting runs. The

cause of such variations could not be determined from the data. Possible

important variables, postulated but not yet evaluated, are heterogeneity In the

oil shale, subtle differences in retorting processes, or special external influences, on the products after retorting.

Survey type analysis were shown to be larger than expected, but the survey

analysis with only order of magnitude precision was shown useful in delineating potential problems. The expected gain from more precise analyses was

shown to be with respect to differentiating the causes of product variability

in oil-shale retorting.

79
Suggestions for further work were for the generation of an oil-shale

standard reference material through the National Bureau of Standards or other

program with certification for a list of many elements of potential environmental

and processing concern. It was also recommended that existing SRM's for oil,

water and ash should be extended in certification for a larger list of elements.

A cooperative i nterl aboratory analysis program was suggested. The need for

development guidelines on sampling of oil shale and products was pointed out.

80
REFERENCES

1. Stanfield, K. E., I. C. Frost, W. S. McAuley, and H. N. Smith. Properties

of Colorado Oil Shale. BuMines Rl ^825, 1951, 12 pp.

2. Smith, J. W. , and L. W. Higby. Preparation of Organic Concentrate from

Green River Oil Shale. Anal. Chem. , v. 32, I960, pp. 1718.

3. Smith, J. W. Ultimate Composition of Organic Material in Green River Oil

Shale. BuMines Rl 5725, 16 pp.

k. Smith, J. W. and K. E. Stanfield. Oil Yields and Properties of Green

River Oil Shales in Uinta Basin, Utah. Intermountain Assoc. Petrol.

Geol . Ann. Field Conference (Guidebook), v. 13, 1964, pp. 212-221.

5. Desborough, G. A., J. K. Pitman, and Claude Huffman, Jr. Concentration

and Mineralogical Residence of Elements in Rich Oil Shales of the Green

River Formation, Piceance Creek Basin, Colorado, and the Uinta Basin,

Utah.--A Preliminary Report. U.S. Dept. Interior, Geol. Survey, open-file

report 74-77, 1974, 14 pp.

6. Cook, E. W. Elemental Abundance in Green River Oil Shale. Chem. Geol.

V. 11, 1973, pp. 321-324.

7. Brown, R. , M. L. Jacobs, and H. E. Taylor. A Survey of the Most Recent

Applications of Spark Source Mass Spectrometry. American Lab., November

1972.

81
8. Smith, J. W. , and N. B. Young. Determination of Dawsonite and Nahcolite

in Green River Formation Oil Shales. BuMines Rl 7286, 1969, 20 pp,.

9. Campbell, J. C., and J. W. Thatcher. Fluorescent X-ray Spectrography

:

Determination of Trace Elements. BuMines Rl 5966, 1962.

10. Smith, J. W. Geochemistry of Oil-Shale Genesis in Colorado's Piceance

Creek Basin. Rocky Mountain Assoc, of Geologists, D. K. Murray ed.,

1974, pp. 71-79.

11. Jackson, L. P. , R. E. Poulson, T. J. Spedding, T. G. Phillips, and H. B.

Jensen. Characteristics and Possible Roles of Various Waters Significant

to In Situ Oil-Shale Processing. Environmental 011-Shale Symposium Proceedings, Quart. Colo. School Mines, v. 70, No. 4, 1975, pp. 105-134.

12. Burger, E. D. , D. J. Curtin, G. A. Myers, and D. K. Wunderlich. Prerefining

of Shale Oil. Preprints, Div. Petrol. Chem. , ACS, v. 20, No. 4, 1975,

pp. 765-775.

13 . Duvall, J. J., and H. B. Jensen. Simulated In Situ Retorting of Oil Shale

in a Control 1 ed-State Retort. Proceedings of the Eighth Oil-Shale Symposium, Quart. Colo. School Mines, v. 70, No. 3, 1975, pp. 187-205.

82
TABLE

1.-

Description

of

cores

and

their

selected

sections o

0)

(/)

T30) 4-i o

<u(1) COo

<_)

vO o Osl oo LA oo

•u « LA LA

— • 4-J 1 LA CM o CM o lD CM c

(U VI- oo r— vO <r> LA CA CA o o o o 1 •— c •c 4-» 4-> 4-J <u L. o 0 O 0 o o o o o u <u LA 4-) 4-J 4-» -cr 4-4 4-> 4-1 4-f 4-J 03

0) • • 1/) U-. L. LA vO LA CM CA LA-:r

(U CM oo LA PO Csl LA fA CM V|- cn E oE

sz LA oo

O • • • 4-» CD LA o F— LA CA OO vO 4U c V|- oo o LA F— CO lO LA o

0) .

CM 1— F—

X

03

4-1

t/) 03 o O o -d- vO <rv-3- LA ^ lD oo F— vO • —

CL oo LA vO <r» o oo pp\ vI3 LA -o • F F— c 0 <0 •— z (/)

l/> 033

r—

3: 3 3 3 3 3 3 :s LU 03 • >

0£ o oo LA LA oo un vo OO CT\ -3" o CTi o^ o^ O^ CM 03 — >

4-1 • to to to to to to to to to to 03 1- • 03 —

LA LA vO viD F— c 03 0 c

4->

C • o O LA

O CM CM CM LA CM -cr

0) CM CA CM F— tO

—

03 03 •M </) CA Q. ^

nj

u o F— 03 o o o • — E o o o

>• c C ~o “D “O •o

O T3 o >-

4-» 03 03 V|- c c •— 0) 03 03 0) 03 03 03 JZ o 03 D CD CD CD C7> o VI- V|- M- VI- VI- V|- VI- 4-4 U) o O o o l_ u u L. L. L. C C -C

•— •— 03 03 03 03 fD 03 03 •— o 03 oc oc CD C3 C3 CD c: CO CD '

Z

03 0) (U 03 X 4-J o* o o O O o O o o _c 4-» OJ 03 LA

4-* o o o o O o o o o 4-» CM 03

V/) o o CJ o O

O o O

O >

o>

O

C JD CM •— CM CM •— 03 f— • LU t

• • • o • • o o o 03 c

0) z 03 o o z z Z i_ o 5 Z z 03 •—

(/) o c 03 03 > 4-1 D X L- 4-> o *— F— 03 C3 o -O 03 U t/) o o 03

03 > 03

XX 03 t/i 0) — O 4J 03 03 “D 03 03 u E •— l_ > Q1 LT\ 03 L. L. o 4-

03 -C 0) 03 03 JT. L. 03 o O o o Z O- z CD Z O Q z O O

VI- Q. o 0

(0 tn 4-» 03 03 * _C c c o 4-J 03 •— O U) 4-> z Z C 03 • • • F— 03 O

VIO VI- o o • —

— • — • • o o o O O o • “O

0) o o o </) c o O O D 1— D *— O 3 •—

03 CD •— 03 o D F— «— 03 o 03 o o 4-» 3 cn o 4^ •— •— U c •— C 03

C/> L. o o D o o o u 03 o •— 3

LlJ CD CO •— •— c 4-J F— U c M- M- V|- •— F— c 03 .

03 o • •— • • — 4-» F— o >

f— _Q •— to o to o o C 03

u

03 03 c • CD • 03 03 o s: 03 h- 3 r> ZD O- !3 CL D. C-) to F > 3 • — E 4-»

03

X to

03 o

Q. CN4 CA -cr 5 6 oo o Z D. E F—

03 to h* Csl

83
TABLE 2. - Limits of detectability for various elements in raw oil-shale powder and in silicate concentrates using

x-ray fluorescence

El ement Method ^ Detection1 imi t , ppm Element Method ^ Detect i on

1 imi t , ppm

Uran i urn A 13 Stront i urn A k

Lead A 21 Rub i d i urn A k

Thai 1 i urn A 21 Arsen i

c

A 5

Gold A 22 Gallium A 6

Lanthanum B 31 Zinc A 3 Barium B 17 Nickel A 3 Cesium B 97 Cobal

t

A 8

Iodine B 165 Manganese B 4

S i 1 ver A 10 Chromium B 3

Mo 1 ybdenum A 4 Vanad i urn B 4

Silicate Concentrate

Zi rcon i urn A 4

Ti tan i urn B 8

Calcium B 23

A - LiF crystal analyzer, air path, scintillation counter with

pulse height analyzer.

B - LiF crystal analyzer, helium path, gas-flow proportional counter

with pulse height analyzer. All elements determined with Ka line

except I, Cs, Ba, La, Tl , Pb, U with La line and Au with L3 line.

84
TABLE 3. Sources of crude shale oils

Symbol Oi 1 shale retort Oi 1 shale

lOT-29 LERC simulated in s i tu 1 0-ton Colo. 0-1"

lOT-31 LERC simulated in s i tu 1 0-ton Colo. 1-3"

ISOT-yl LERC simulated in s 1 tu 1 50-ton Colo. mine run 150T-F2 LERC simulated in s i tu 1 50-ton Colo. mine run IS-U^’3 Rock Springs Site 4 i n s i tu Wyo. , fractured

IS-F^’3 Rock Springs Site 4 i n s i tu Wyo. , fractured

Gc-yi Gas combust i on^ Colo. 0.25"-3"

GC-F2 Gas combust i on“^ Colo. 0.25"-3"

Unf i 1 tered oil.

^ Oil filtered through Whatman k2 paper.

^ Oil contained 28% bound water not removable by decantation.

^ USBM gas combustion retort operated by Colorado School of Mines

Research Foundation.

85
TABLE k. - Analytical methods used in conjunction with spark source

mass spectrometry for oils and water

Element Method

Calcium, Magnesium

Sodium, Potassium

Boron

Chloride

Fluor i de

Sulfur

Mercury

Atomic absorption (AA)

Flame photometry

Colorimetric (Curcumin or Carmine)

Titration (Silver or Mercury)

Specific ion electrode or SPADNS reagent

Gravimetric

Flameless AA (Hatch-Ott) for waters.

Flameless atomic fluorescence from gold

amalgam for oils

Uran i urn Alpha spectrometry of natural activity,

using a silicon surface barrier detector

and 1024 channel pulse height analyzer.

Results were ±50% with a detectability of

1 ppm.

Distillation to remove organics before this test.

86
TABLE 5. Sources of oil-shale retort waters^

Symbol 01 1 -shale retort Oil shale

lOT-28 LERC s imul ated i n s i tu 1 0- ton Colo. 0-20"

lOT-29 LERC simulated i n s i tu 1 0-ton Colo. 0-1"

lOT-30 LERC s imul ated in s i tu 1 0-ton Colo. 0-20"

lOT-31 LERC simulated i n s i tu 1 0-ton Colo. 1-3"

Each water was "deoiled" by filtering through diatomaceous

earth.

87
TABLE i. - ELEHCNTAl ANALTSCS OF MAHOGANY- ZONE OIL-SHALE COMPOSITE SAMPLES* USING SPARK SOURCE MASS SPECTROMETRY OF RAW SHALE POWDER

PPM IN COMPOSITE^ SAMPLE ! 2 I

R RA J 5A 6 I 8 g 1£.

ELEMENT

Uranium 1.7 2.R 1.6 3.} 5.2 Thorium 1.2 1.3 1.2 1.9 12 Bismuth <0.10 <0.10 <0.10 <0.10 3.5

Load’ 1.2 1.0 1.6 2.3 IR Tha 1 1 1 in . <0.67 0.72 <0.67 <0.59 0.80

Horcury** Cold Blatinum

Iridium Osmium Rhcnim^

0.61 I.R 0.63 O.RI ..6

Tun9$ten <0.01 0.03 0.09 0.03 2.1 Tantalum 0.6} 0.38 0.8R 1.5 0.87 Hafnlm <1.0 I.R 1.3 1.3 1.8 Lutecium <0.07 <0.08 <0.07 <0.06 0.38 Ytterbium «J.2R 0.32 0.80 0.30 1.6 Thul 1 ium <O.OS o.n <0.08 <0.07 0.10

Erbium 0.37 0.5R O.RR 1.0 0.28 Holmlm 0.18 0.20 0.37 0.16 0.33 Dysprosium 2.R 2.6 1.7 2.1 3.9 Terbium 0.2} 0.2R 0.23 0.2 0.87

Cadol inium 2.1 18 2.1 1.9 0.R3 Europium 0.6R 0.69 0.6R 0.56 2.0

Samarium 6.5 3.3 R.6 0.93 5.6 Neodymium 25 R2 19 23 2R Praseodynium 18 19 16 16 20 Cerium no 81 75 66 80

Lanthanum 50 RO 25 22 25 Barium 680 730 650 700 720

Cesium 0.07 0.07 0.07 0.06 5.7

Iodine 0.22 I.O R.5 2.0 29

Tel lurium 0.35 <0.38 <0.35 <0.31 Antimony 0.39 0.20 0.39 0.3R 3.0 Tin

Indium^ 2.9 1.5 2.9 1.2 3.5

Cadmium 0.05 0.05 0.05 0.02 I.R Silver

Pal ladlum Rhodium Ruthenium

<0.03 O.OR 0.08 <0.02 1.7

Molybdenum IR 15 IR 12 37 Niobim 5.2 5.6 5.2 R.6 IR Zirconium 27 29 27 12 60 Yttrium 50 27 50 22 18 Strontium 900 730 910 ROO •2700 Rubidium 76 82 no 67 • no

Bromine 0.33 0.35 0.33 0.29 IR Selenium ( }

** 3.3 (2.2) 3.5 3.3 1.3 (2. 5) 2.0 Arsenic^ ( )

** 18 (36) '9 33 86 (22) 51 Germanium 1.0 2.6 2.1 0.91 1.9 Gallium R.R II 10 9.0 II Zinc R.3 9.8 9.1 8.0 60 Copper R8 29 R8 R2 120 Nickel 380 220 290 330 280

Cobalt 8.0 7.0 8.6 II

1 ron >1* >12 >12 >12 >12 Manganese 190 160 3R0 190 320 Chromim 780 350 970 680 370 Vanadium 8R 90 180 73 100 Titanium >2600 • 1300 •2600 • 2000 • 1500 Scand im 3.R 16 6.9 6.0 2.7 Calcltn >U >12 >12 >12 >12 Potassium >1* >0.52 >0.52 >12 >12 Chlorine 91 98 250 IRO 76 Sulphur •2600 •R900 >2600 • 1800 >12 Phosphorus (

)** 1300(800) 650 610 530(800) R200

Silicon >12 >12 >12 >12 >12 Almlnurn >12 >12 >12 >12 >12 Magnesium >12 >12 >12 >12 >12 Sodlin >0.52 •R300 • 'lOOO 3500 >12 Fluorine Oeygen*

Nitrogen^

Carbon*

• 1200 • 1300 • 1200 • 1000 •RROO

Boron R2 RS R2 73 230

Beryl 1 Ium 2.R 0.90 2.R 2.1 0.60

LI thim 9.2 13 10 3.8 160

5-9 7.0 5.9 5.1 3.7 3.7 3.7 2.0 12 3.R 3.R 1.2 1.2 2.9 <0.10 1.7 <0.10 <0.10 <0.10 <0.10 <0.10

R.R 70 2.0 1.5 1.2/ 6.2 2.7

<1.1 O.RO <1.1 <1.1 <0.67 <0.67 <0.67

I.R ..6 0.38, 0.52 2.1 . ..e 0.93 0.31, 0.70

<0.0R l.l 0.06 O.IR <0.03 <0.03 0.09

1.3 1.9 1.3 1.3 I.R 0.8R 3.R <1.6 1.8 R.O <1.6 I.R I.R l.l <0.11 0.21 <0.11 <0.11 0.07 0.10 <0.07

1.3 1.6 1.3 2.5 0.80 0.80 0.80 0.13 0.10 0.16 0.19 0.10 0.12 0.12

I.R 0.28 0.80 0.80 0.51 0.89 0.51 0.29 0.33 0.29 0.29 0.27 0.18 0.37 2.7 3.R 3.7 1.8 1.9 2.R 2.R 0.36 0.87 0.36 0.36 0.23 0.23 O.R9 3.8 0.R3 3.R 3.R 2.1 2.1 R.6

1.0 1.2 1.0 1.0 0.6R 0.£R 0.96 9.0 3.3 R.8 7.2 5.1 3.0 R.6

77 2R 31 21 26 26. 56

13

• 9.3 13 6.6 8.3 8.R 18 210 80 60 60 75 75 75

17 25 RO RO 25 25 R2 610 750 610 610 680 680 680 0.10 8.5 0.2R 0.10 0.15 0.15 0.15 0.13 1.3 0.36 0.36 0.22 0.22 R50

<0.56 <0.56 <0.56 <0.35 <0.35 <0.35 0.5R 5.2 0.29 0.29 0.39 0.27 0.18 R.6 2.0 11 2.2 2.9 I.R 2.9

0.16 I.R 0.08 0.08 0.10 0.10 0.10

<0.0R 0.80 <0.0R 0.06 O.OR O.OR 0.18

10 37 22 22 IR IR IR 3.9 IR 8.3 3.9 5.2 5.2 5.2

22 60 22 22 27 IR 27 RO 18 RO 17 25 11 38 720 =2700 •IROO 720 910 R60 910

120 no 120 120 150 150 R50

1.2 28 0.52 1.2 0.76 0.57 3.3 5.2 3.5 5.2 (1.7) 2.R 3.3 3.3 2.9 (2.

C

28 23 28 (31,) 28 18 52 18 (2R) 2.9 I.R 1.7 1.6 1.0 l.l 2.1

16 II 16 16 10 10 R.R

IR 120 IR IR 21 21 32

77 RR 77 R3 27 R8 Rl 600 150 600 600 760 130 210

11 12 12 9.9 7.R

>1S >12 >12 >12 >12 >12 >12 390 180 300 380 220 200 2R0

770 190 •1000 770 280 280 280

130 100 130 280 86 8R 8R

<RI00 •3100 >1900 >RI00 • 1200 :2600 • 1200

16 2.7 II 5.R 69 3.R 6.9 >U >12 >12 >12 >12 >12 >12 2.7 >12 >12 >12 >12 >12 >12 220 60 260 260 160 250 3R0

.1900 >12 •RlOO =N100 >1200 •2300 • 1800 960 2P00 5R0 960(530) 170 170 3RO (L60) >U >12 >12 >12 >12 >12 >12 >n >12 >12 >12 >12 >12 >12

>12 >12 >12 >12 >12 >12 >12

RliOO >0.52 >0.52 =6R00 >0.52 >0.52 >0.52 3700 •2100 •3100 >1900 120 •2R00 >1200

110 120 66 66 R2 8R 8R 3.8 0.26 1.8 5.3 2.R l.l 5.6

1.9 160 II 6.8 6.6 18 2R

T""“'j^^7Tc>'”oT"jbout~"Ts''qTrTofr"pcT ton oil (hale were composited -U mcsht ground to -100 mesh and thoroughly blended. LA and 5A duplicate R and 5.

2 Elenenti not reported were below detectability of 0. I ppm. All elements standardized using National Bureau of Standards, Standard Reference Material

1632 . • codta Mhcr« 4ppllc«blc.

^ St4n<J«rl2ed u^in9 NBS’SRM 1633 * • CO»\ fly «sh.

** Nci^tron 4C(lvsilioo

^ lnt«rn«l »t«nd.»rd.

d Not d«tcrniined.

88
TABLE 7. - Elemental analysis of Mahogany-zone oil -shale composite

samples using x-ray fluorescence of raw shale powder

ppm of composite

Sample 1 2 3 5 6 7 9 10 Average

Element

Lead 120 130 130 130 120 1 10 1 10 97 130 100 118

Bari urn Zi rconium^

320 300 300 310 330 300 300 310 300 300 307

Stront i urn 780 850 740 740 790 730 790 790 790 760 776

Rubidium 63 59 65 67 64 66 65 62 64 60 64

Z i nc 39 38 40 41 39 38 38 35 34 35 38

Nickel 130 86 90 120 98 130 97 93 68 70 98

Manganese 420 430 430 440 420 420 410 400 390 420 418

Chromium 300 200 200 310 230 330 230 230 140 170 234

Vanad i urn Ti tan i um^

Ca 1 c i um^

78 73 78 84 84 78 78 78 78 78 79

Boron 53 58 66 76 68 67 66 66 1 10 136 77

^ Not detectable in raw oil shale under conditions used.

^ Major element, not determined.

89
TABLE 8. - Elemental analysis of Mahogany-zone oil-shale composite samples

using x-ray fluorescence of oil-shale silicate concentrates

ppm of composite

Sample 1 2 3 -t; 5 ~z— 7 9 10 Average

E 1 ement

Lead 68 83 88 91 83 82 87 72 81 86 82

Barium 140 120 120 130 120 90 100 1 10 1 10 100 114

Z i rcon i urn 39 37 41 37 38 41 37 39 33 33 38

St ront i urn 32 30 33 30 27 20 30 19 22 18 26

Rubidium 55 59 64 64 62 58 64 48 41 41 56

Z i nc 6 6 6 6 7 6 6 6 5 5 6

Nickel 1

1

10 10 1

1

1

1

10 1

1

10 9 9 10

Manganese 9 7 6 6 8 8 6 8 12 14 8

Chromium 20 15 13 14 12 16 13 17 18 18 15

Vanad i urn 66 62 59 59 58 60 54 68 69 76 63

T i tan i urn 1300 1300 1400 1400 1400 1300 1300 1300 1200 1200 1300

Calcium 480 420 440 380 410 280 380 290 340 380 380

Boron 38 30 37 52 54 52 47 49 77 97 53

90
TABLE

9.

“

HCl

soluble

and

insoluble

sodium,

potassium,

and

lithium

by

flame

photometry

in

Mahogany-zone

composite

cores

of

Green

River

oil

shale

CT\OroOvOO<v><r>000

co-T-^-a- (v^oo-a- r>.oooo

e

Q.

Q.

i) JDD

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91
TAtie 10. • CLEHENTAL ANALYSES or COLOAADO COKEHOLE NO. 3. SALINE-ZONE OIL-SHALE COHPOSITE

samples' USING SPARK SOURCE HASS SPECTROHETRY OF RAW SHALE POWDER

PPM IN COMPOSITE^

sample I 2 3 » i t 7 '8

ELEMENT

UranluM 5.7 2.3 0.30

Thorluii IJ 6.9 1.6

tIsflHJth 6.1 1.7 <0.52 Lead) 57 16 1.6 Thallltfi 1.6 0.60 <0.12 Hercury^

Gold Platinum

IrtdtiM 0Miu«

Khenlufl)) Tungsten J.9 l.l <0.32 Tantalun 1.5 0.87 0.63

Hafntufli 2.5 1.8 <0.55 Lutecium 0.61 0.21 <0.15 Ytterbium 1.3 1.2 <0.69

Thul 1 lum 0.07 0.09 <0.03 CrbluN 0.23 0.21 <0.08 Helmtum 0.66 0.16 <0.05 Dysprosium 3.t 1.8 <0.27

Terbiias l.l 0.63 <0.13 Gadolinium 0.65 0.63 <0.06 Curoptum 1.8 1.0 <0.18 Samarium 5,1 3.3 <0.50 Neodymium 29 18 2.6 Praseodymium 16 6.7 0.60 Cerium 65 60 6.0 LantiMnum 20 25 l.l Garium 680 750 61 Cesium 9.2 5.7 0.63

Iodine 1.6 0.06 41.20

Tel lurluB Antimony II 1.6 <0.21 Tin 1.6 2.0 0.35

Indium) Cadmium 0,56 0.67 0.10 Silver 0.28 0.60 0-.13 Palladium

Ahodium

lUitbenlum Holybdenum 30 17 8.7 Niobium 20 12 1.6 Zirconium 69 60 3.0 Yttrium 16 18 1.8 Strontium 610 750 59 Rubidium 92 57 II Bromine 23 6.0 60

Selenltfn 1.6 0.78 0.90

Arsenic) 25 13 2.6 Germanium 1.5 0.80 1.9 Gallium 18 11 l.l Zinc 69 60 12 Copper 63 33 22 NicUl 80 55 83 Cobalt 17 6.6 l.l Iron >l» >12 830 Aanganese 310 |80 9.0 Chromium 130 87 63 Vanadlun 82 100 10 Titanium el ZOO •1200 150

Scandliaa 6.6 2.7 Calcium >12 >12 >0.52 Potassiue >12 >0.52 800 Chlorine 230 600 >12 Sulphur >12 •6800 680 Phosphorus >0.52 •6200 510

SI 1 Icon >12 >12 >12 Aluminum >12 >12 >0.52 Magnesium >12 >12 >0.52 Sod lum >12 >12 >12 fluorine 860 •1000 360 Oaygen^ Hitroganh

Carbof^ Boron 52* 58 12 Beryllliaa 0.9* 1.0 <0.18 Lithium 6? 29 5.7

2.6 7.8 7.0 2.1 3.0

3.2 7.6 16 3.2 6.9

1.5 1.6 3.5 0.65 1.7 7.0 16 70 12 . 16 0.30 0.19 0.60 <0.12 0.60

0.66 2.6 l.l 0.66 l.l 0.87 6.8 0.87 0.65 0.87 0.55 0.77 0.79 1.6 1.8 <0.15 0.17 0.19 0.17 0.50 <0.69 0.68 0.70 0.61 1.6 0.03 0.03 0.08 0.06 0.08

0.10 0.13 0.28 0.12 0.28

0.07 0.36 0.33 0.16 0.16

0.90 2.0 1.8 0.90 1.8 0.19 0.96 0.63 0.32 0.87

0.21 0.67 0.63 0.21 0.71 0.26 1.3 • 1.2 0.60 1.2

1.7 3.7 3.3 1.7 3.3

12 20 20 5.1 12 6.7 10 9.3 2.0 9.3

20 53 80 60 60

' 9.2 26 37 II 25

130 330 300 300 520

l.l 2.7 5.7 5.7 II 13 2.5 0.67

O.ll 0.67 2.9

1.6 3.3 3.5 1.6 3.0

0.93 2.2 2.0 0.78 1.6

0.12 0.37 0.25 0.16 0.67

0.17 0.65 0.60 0.12 0.60

8.7 61 87 26 87 3.2 7.1 16 6.6 6.6

15 56 60 30 30 6.6 8.6 29 7.6 18 270 830 680 270 •1600

31 63 85 57 no

6.0 6.7 6.0 6.0 6.0

1.6 2.2 2.0 1.2 6.7

13 20 23 13 31 0.37 0.89 l.l 0.56 1.9 5.0 13 II 6.9 II 26 20 60 26 26

22 69 78 17 66 28 no 98 28 98 6.6 0.78 21 6.6 11 •3500 >12 >12 >0.52 >12

36 200 320 90 320

65 210 190 63 87 50 no 100 50 50 730 •1600 • 1500 550 •1500 0.12 1.3 6.0 1.2 2.7

>lt >12 >12 >12 >12

• 1600 •3800 >0.52 •3600 >0.52 280 160 28 35 76

•6800 >12 >12 •6800 >12 •2600 >0.52 •2600 •1200 •6200

>1* >12 >12 >12 >12 >12 >12 >12 >12 >12

>12 >12 >12 >12 >12 >12 >12 >0.52 >12 >0.52 360 •1200 •1000 560 •1000

23 65 120 39 66 0.26 ' 0.67 1.2 0.60 2.2

29 32 100 29 57

1 iM^lts M«r« c<xnposited from teivcted 10 Foot lnterv«li throughout «n 621 foot tcclion from a s«l Inc ione low the M»hOD«ny-*on«^

2 nwnt»*r»t*rei>oricd”llrro*b€lo- deteetdbl 1 1 ty of 0;1 ppm. All dlemcntt ttandbrdlibd utloQ Ndtlonal Buraiu of Stbndardl, StbndAPd Rafercncr Material (SRH) 1632, a coal, where applicable.

> Slattdardlaed uilng NBS-SRM 1633. a coal fly aah.

^ Mi»t dclerialncd.

I Internal ttandard.

92
TMLC II. • ELEMENTAL ANALYSES OF CRUDE SHALE OILS> USING SPARK SOURCE HASS SPECTROMETRY

PPM IN OIL*

Sample 10T-29-U IOI- 3 I-U I50T-U 150T-F IS-U —rrr cc-u CC-F ELEMENT Uranium

Thorium

12

lltmuth 0.0A6 0.026 0.30 0.32

Lead

Thai 1 ium 0.098 0.32 l.l 0.11 1.0 0.13

Mercury* O.ll 0.16 0.51 0.16 0.67 0.72 0.22 0.25 Cold Platinum

Iridium Osmium

fthenlum^ Tungsten Tantalum Hafnium

lutecium Ytterbium

•Thul 1 ium Crblum Holmlum

0.021 0.26 <0.12 1.3 <0.16

Dysprosium Terbium

Oadol Inlum Europium Samarium

Neodymium

Praseodyntum Cerium

Lanthanum •arlum

Cesium

O.OII 0.028 0.23 0.10 0.32

Iodine 0.019 0.021 0.73 Tellurium

Antimony 0.018 0.016 0.18

Tin 0.16 0.27 1.6 0.62 3.7 0.97 IndliN^ Cadmium 0.11 Sllvar PAlltdlia

Rhodlua

RiiChcnli0 Molybdenum 0.67 0.68 16 7.2 1.8 6-3 1.6 1.0 Niobium Zirconium 0.023 0.15 Yttrium 0.26

Strontliai 0.093 0.20 Rubidium 0.013 Iromlne 0.037 0.095

Selenltfi 0.092 0.35 . 0.17 0.10 0.20 0.32 0.56 Arsenic 6.1 6.9 9.8 2.2 0.55 0.56 8.7 53 Carman liai 0.037

Galliiaa Zinc 0.56 1.2 3.5 3.8 1.7 2.2 3.6 9.6

Copper 0.087 0.15 0.62 0.11 0.55 0.56 1.5 1.5 Nickel 2.5 2.1 9.0 10 55 12 9.6 Cobalt 0.75 0.86 1.2 0.66 7.2 2.7 2.5 5.0 Irqn 19 33 25 8.3 71 66 390 380 Manganese 0.013 0.066 0.11 0.15 0.16 l.l 0.36

Chromlijm 0.021 0.090 0.22 0.26 0.28 0.23 0.33 Vanadium l.l 9.0 0.81 0.39 0.81 0.65 0.73 2.5 Titanium 0.052 0.89 0.33 0.36 2.1 2.0 1.6 0.50 Scandium

Calcium^ 3.6 39 2.3 0.66 5.1 2.9 17 32 Potass lue* 0.85 5.5 3.0 3.3 2.0 1.8 6.6 2.2 Chlorine^ 0.057 2.0 1.5 1.7 0.21 0.A2 0.68 l.l Sulphur^ 66 3.1 760 • 1700 •2600 •2000 •1600 •2300 Phosphorus 0.15 2i 1.3 0.29 0.76 0.72 1.2 6.0

SI 1 Icon 21 9.0 16 S.9 A.O 16 66 no

Alumtmaa 1.3 19 0.10 0.16 0.63 2.1 0.52 Hapneslum^ 0.38 2.0 <1.6 <1.6 <0.67 <1.8 99 < 2.2 Sodium^ <0.73 5.6 <36 <37 <16 <66 <71 <32 Fluorine* 0.071 0.10 2.7 3.0 0.35 2.8 0.89 Onyocn^

Ml tro9en^ Carbonk loron^ 3.8 2.1 2.9 8.6 0.79 1.3 larylllia

Lithium .0.26 0.062 O.IS 0.11

* For description of source see table }•

* Elements not reported krere below detectability of 0.01 ppm In IOT-29 and IOT-3 I othari 0.11 ppm. Otis uerc ashed at 650° C before M.S.

^ Determined by eltcrnete methods listed In table It. ^ Not determined,

s Internal standard.

93
TMU 12. - ELEHENTAL ANALYSES Of OIL-SHALE AETOAT WATEAS > USING SPAAK SOURCE NASS SPECTRONETAY

IM UATE|2

SwIe IOT-2U IOT-29 IOT-30 IOT-31

ELEKENT

Urtnlua

ThorliM IlMUth

O.OIS (<D* 0.02] (<0* 0.010 (<t)’

LmO

ThalltMi

O.IA 0.12. 0.062

N«rcurv*

Goto PUtlniw

IrldliM Osnlua

Rtimlua*

4.1

Tungsten Twttalua

Hafnlun

Lutaelu. Ytt.rblm

Thul 1 IlM Erblua Holalua

0.00] 0.00] O.OOS

0.00b

k.i (IB)* 0.011

0.001 0.17

0.10

0.02A

0.002

Oysproslua

T.rblua 0.002

GaUoI Inlua Europlua 0.010 SaMrIua 0.00] N.odyalui O.OOS 0.002 0.00] O.OOl Pr.saodyalua 0.00] 0.006 Carlua 0.001 0.00] 0.006 Lbnthanua 0.00] 0.010 0.005 •arlua 0.002 0.012 0.081 0.077 Catlua 0.005 0.002 O.OOS 0.002

lodin. 0.2] 0.005 0.]] 0.00] T.llurlus 0.001 Antlaony 0.005 0.009 0.006 0.0]6 Tin 16 8.9 >IOO 29 Indlua* Cadmiua

Sliver 0.2] 0.17 0.002 Palladium

Khodltfs Ruthenium

Holybdenum 0.1] 0.056 0.057 0.]6 Niobium 0.001 0.005 Zirconium 0.062 0.079 0.008 0.19 Yttrium 0.050 Strontium 0.00] 0.007 0.025 0.68 Rubidium 0.085 0.016 0.062 0.59 Iromlne 0.18 0.019 0.66 O.IJ Selenium 0.071 0.010 0.10 0.00) Arsenic 6.6 S.9 10 6.6 Cannanlum CalllMs

O.OOl 0.001 0.001 0.007

Zinc 0.67 0.26 0.6] 0.]] Copper 0.007 0.008 0.007 0.016

Nickel 0.]7 l.l 2.6 0.60 Cobalt 0.002 0.076 0.]2 0.0]

Iron 9.6 77 26 66 Hanganese 0.098 0.062 0.16 0.16 Chromium 0.01] 0.01

1

0.0)7 0.017 Vanadium 0.006 0.017 0.]2 II Titanium 0.75 0.66 2.1 21 Scandlm

Calcium^ ]6 (5.6) 0.61 (0.6) 0.70 (0.7) 0.5 (9.8) Potassltfs^ 16 (21) 1.6 (8) 12 (6) }] (70) Chlorine^ ' - (5500) - - (6500) - Sulphur^ ]6 (660) 16 (510) • 100 (6)0) 310 (5)0) Phosphorus 1.6 0.58 1.0 9.2

Sll Icon 6.0 1.7 ].5 II Aluminum 0.1] O.ll 0.l8 0.66

Nagneslbps^ 67 (55) 5.6 (1.2) 16 (5.9) 87 (280)

Sodliae’ 66 (120) 8.) (210) 16 (210) 130 (1300) fluorine* 56 (SO) 26 (]l) 16 62 (26) Oxys«n^

Hltr*09«n^ C«rbon^ ioron* 4.% S*2 8.1

8«ryl I Ign. LUMwt 0.004 0.03S 0.32 0.73

' For deter 1^1 ion of source «*e

^ Kl«*cnt» not reported were below detect«blMty limit of O.OOl ppm. Voters were eveporeted to dryoess

•nd rufi directly.

^ Determined by elcernete methods listed In table 47* Numbers In parentheses from another laboratory.

^ Hot determined.

^ Internal standard.

94
Comments following Mr. Poul son's talk.

Comment :

Comment :

Comment:

The mercury analysis is on raw oil by atomic absorption,

most other elements are done on ashed oil.

For water and oil separation you just decant. Oil in water

removed by filtering through wad of cellite to take out the

oil globules.

A standard oil shale would be useful in determining where

various materials go in the process. More standardized

methods are needed, for example how to define oil and water

phases.

95
LOW-TEMPERATURE SPECTROSCOPIC ANALYSIS OF

POLYCYCLIC AROMATIC HYDROCARBONS

E. L. Wehry, G. Mamantov, R. R. Keramerer, R. C. Stroupe, H. 0. Brotherton,

E. R. Hinton, Jr., P. T. Tokousbalides , and R. B. Dickinson, Jr.

Department of Chemistry

University of Tennessee

Knoxville, Tennessee 37916

96
LOW-TEMPERATURE SPECTROSCOPIC ANALYSIS OF

POLYCYCLIC AROMATIC HYDROCARBONS

E. L. Wehry, G. Mamantov, R. R. Kemmerer, R. C. Stroupe, H. 0. Brotherton,

E. R. Hinton, Jr., P. T. Tokousbalides , and R. B. Dickinson, Jr.

Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37916

A. INTRODUCTION

The possibility that oil shale processing may cause release of significant

quantities of polycyclic organic matter (POM) into the atmospheric and/or

aquatic environment has received consideration in the past and will receive

greatly increased attention as a shale oil Industry begins to develop. In

"ex situ" retorting of oil shale, significant amounts of POM are found to be

present in both the gaseous and liquid products of the retorting operation.^

In addition, the spent shale (which, it is envisioned, may be deposited as

fill into natural canyons in such areas as the Piceance Creek basin in Colorado)

contains significant quantities of POM, which may slowly volatilize into the air

2 or be leached by water. Some POM release may also be anticipated from "in

2

situ" retorting operations. Consequently, assessment of the environmental

impact of oil shale refining will require the availability of analytical

methodology for identifying, and quantitatively determining, individual polycyclic

hydrocarbons

.

The analytical chemistry of POM resulting from fossil fuel refining and

use is an extraordinarily complex problem, and it seems obvious that no single

technique, or group of techniques, will be a panacea. Our efforts have been

directed to exploration of the feasibility of using low- temperature Fourier

transform infrared spectroscopy, low- temperature steady-state fluorescence

spectroscopy, and time-resolved fluorometry in the analysis of POM. In all

of this work, we are strongly emphasizing the mode of sample preparation

commonly known as matrix isolation .

97
B. MATRIX ISOLATION

In matrix isolation (MI) spectroscopy, the sample (in the vapor phase)

is mixed with a large excess of an "inert" gaseous diluent, such as or Ar.

The gaseous mixture is then deposited upon a cold (ca. 20 °K) optical surface;

3 the quasicrystalline deposit is then examined spectroscopically. The objectives

of MI include:

(a) To minimize solute-solute interactions, in order that predictable

quantitative relationships ( e.g. , Beer's law in absorption spectrophotometry)

be satisfied.

(b) To minimize matrix-solute interactions, in order that the observed

spectral band widths be minimized and resolution enhanced - obviously a critical

requirement in the analysis of complex mixtures.

(c) To eliminate, whenever possible, contact of samples with liquid solvents, which may Introduce contaminants (a problem of particular concern with

very sensitive techniques, such as fluorometry)

.

Inasmuch as most polynuclear aromatic hydrocarbons are rather volatile,

4 converting then to the vapor phase is feasible by vacuum sublimation. A

sample cell for vacuum sublimation-Knudsen effusion is shown in Figure 1. The

sample is placed in the small glass tube shown at the left of the Figure; this

tube, which contains a small (^ mm) orifice at the left-hand end, is heated

resistively. This cell is attached to an evacuable cryostat head ( cf . Figure

2) via the 29/42 male glass joint at the right in Figure 1.

The cryostat head is in turn attached to a commercial closed-cycle

helium refrigerator, capable of operation in the 15-20 °K range; the mount

for the optical surface upon which the sample is deposited is attached to the

body of the refrigerator. The entire assembly (Figure 3) can be inserted into

virtually any spectrometer having a cell compartment which opens at the top.

98
C. FOURIER TRANSFORM INFRARED SPECTROSCOPY

Infrared (IR) spectroscopy has received virtually no use in POM analysis ,

owing to ( inter alia) the following difficulties:

(a) Insufficient sensitivity, requiring use of large or concentrated

samples (in which case Beer's law is unlikely to obtain) and lengthy spectral

scan times;

(b) Optical problems (due to lack of IR transparency of most solvents or

solid matrices) ; and

(c) The complexity of the IR spectra of many polycyclic hydrocarbons,

signifying that analyzing the spectrum of a complex mixture may be difficult or

impossible.

The first two of the problems cited above can be greatly alleviated by

use of the Fourier transform (FT) procedure for obtaining IR spectra, and the

third can be at least partially overcome by MI. FT-IR is a "multiplex"

spectroscopic technique; i. e. , all "resolution elements" of a spectrum are

6-9

viewed simultaneously by the detector , in contrast to the conventional

sequential scanning technique, wherein the resolution elements are viewed one at

a time. In IR spectroscopy, wherein detector dark noise is normally appreciable,

multiplexing results in a significant increase in signal-to-noise ratio, which

can be utilized either to examine samples too small to study by conventional

scanning spectrometry, or to obtain spectra in much shorter times than are

conventionally feasible. For example, we have obtained IR spectra of 50

nanomole quantities of polycyclic hydrocarbons with little difficulty by FTS-IR,

and a single FTS-IR spectral scan at a resolution of 8 cm ^ requires only 20 sec.

Consequently, S/N enhancement by repetitive signal averaging is widely employed

in FT-IR measurements.

The process of converting the "raw data" (optical interferograms) of

an FT spectrometer to absorption spectra involves a Fourier transformation

99
performed by computer. A digital computer is normally an integral component of

a FT spectrometer. This fact signifies that a number of data-handling operations,

such as storage of spectra of standard reference materials, background subtraction,

and scale expansion are readily executed. In addition, spectra of standards

can be compared with those of real sample mixtures; the techniques of pattern

recognition^^ can in principle be employed to identify specific sample components.

Once individual components have been identified, they may be subtracted ("stripped")

from the spectrum of a mixture^^, an operation which, in essence, can be

regarded as a form of "chemical separation by computer". All of this assumes,

however, that standard reference samples of the various sample constituents

exist, a situation which does not obtain at present.

The combination of MI sampling and FT-IR measurement is currently being

explored intensively in our laboratory. An example FT-IR spectrum of a threecomponent mixture is shown in Figure 4. It should be noted that the three

constituents (chrysene, benz (a) anthracene, and triphenylene) are isomeric;

they are difficult to separate by gas or liquid chromatography and virtually

12

impossible to resolve in a mixture by mass spectrometry. The three individual

compounds are readily detectable in the FT-IR spectrum, suggesting that FT-IR

will prove to be very useful for examining groups of closely related compounds

present in fractions obtained in the liquid chromatography of synthetic fuels.

D. LOW-TEMPERATURE FLUORESCENCE SPECTROMETRY

13

Fluorescence spectrometry has been widely employed in the analysis of POM ,

because of its high sensitivity, yet the technique, as conventionally performed,

is not well suited for the analysis of complex mixtures, for two principal

reasons

:

(a) Electronic spectra tend to be relatively broad and featureless,

especially in liquid solution, causing severe spectral overlap; and

(b) Energy transfer and quenching phenomena, which

100
can occur over distances comparison with molecular

diameters, can cause the "analytical response factor" for one solute to be

dependent upon the identities and concentrations of other solute species present

in the sample.

Each of these problems can be reduced in severity by use of low-temperature

\ matrices. Fluorescence spectroscopy in frozen solutions of organic fluorophores

has received considerable attention in the past; matrix isolation fluorescence

spectroscopy has received much less study. We are currently engaged in a

comparative study of frozen-solution and matrix-isolation fluorometry and phosphorometry of POM. Spectral resolution is significantly greater in either

frozen solutions or frozen rare-gas matrices than in fluid media; Figures 5

and 6 for a comparison of the liquid-solution and MI fluorescence spectra of

anthracene.

Though it is premature to state definitive conclusions, it appears that

frozen solutions may tend to provide superior spectral resolution to MI, particularly

14 15

if "Shpol’skii matrices" or "monocrystalline frozen solutions" are employed.

However, frozen-solution spectroscopy is very susceptible to quantitative imprecision, owing to microcrystallite formation and aggregation of solute species

16

upon freezing. There is reason to believe that MI, which is not susceptible

to such effects, will be the preferred technique for low-temperature quantitative

fluorometry.

In order to "isolate" solute molecules from each other for fluorescence

spectroscopy in a low-temperature solid matrix, the sample-to-matrix ratio must

be very small (perhaps 1:5000). It is particularly important to employ very

dilute samples in order to minimize the effects of long-range energy transfer,

which is often very efficient in mixtures of arenes.^^ Thus, very sensitive

detection systems (high-gain photomultipliers; photon counting) may be required,

and freedom of the matrix from luminescent impurities is absolutely crucial.

lOl
In this respect, MI is clearly superior to frozen-solution spectroscopy; it is

much easier to remove fluorescent organic impurities from argon or nitrogen

than from n-octane or tetrahydrofuran.

E. TIME-RESOLVED FLUOROMETRY

It is often asserted (correctly) that emission measurements are inherently

more selective than absorptiometry, because there are two wavelength parameters

in an emission measurement but only one in absorption. Less widely recognized

is an additional parameter - time - which can be employed in emission, but not

in absorption, to seek additional resolution of mixtures. The luminescence decay

times for organic molecules are finite (ca . 10 nsec for fluorescence and ca .

1 msec for phosphorescence). Consequently, if the luminescence spectra of two

solute species cannot be resolved spectrally, it is conceivable that they can

be resolved in the time domain, if their luminescence decay times differ appreciably.

18

Time-resolved phosphorometry is a well-established procedure ; timeresolved fluorescence experiments are more difficult to perform because of the

nanosecond decay times. The recent development of laser systems (modelocked

19 20 cavity-dumped ion lasers and synchronously pumped dye lasers ) which can

produce subnanosecond pulses at repetition rates variable from 100 MHz to single

shot, together with development of detection and transmission-line systems which

21 can operate in the gigahertz frequency region , signify that time-resolved

fluorescence spectroscopy is now a feasible technique in analytical chemistry.

We are currently engaged in construction and evaluation of a timeresolved fluorometer, shown in block-diagram form in Figure 7. The principal

component of the instrument is a modelocked, cavity-dumped argon ion laser, which,

when frequency-doubled, will produce 1 nsec pulses at 2573 X (where virtually all

polynuclear hydrocarbons absorb) at repetition rates as great as 100 MHz. The

basic electronic readout device is a sampling oscilloscope which, with relatively

102
minor modifications, can be made to function in a manner analogous to a boxcar

21 integrator signal averager. Both fluorescence decay times (intensity vs. time

at a fixed wavelength) and time-resolved fluorescence spectra (intensity vs.

wavelength at a fixed "time window", 75 ps wide, following firing of the laser)

can be acquired with an instrxoment of this type.

The performance of time-resolved MI or frozen-solution fluorometry should,

by concomitant use of spectral and temporal resolution, extend the applicability

of fluorescence assay to complex samples of structurally similar molecules.

F. REQUIRED STANDARD MATERIALS

In recognition of the theme of this Workshop, it is appropriate to

conclude this paper with a brief statement of our views pertaining to SRM’s.

In all of our studies, a "reference library" of spectral data (FT-IR spectra,

Ixjminescence spectra, fluorescence decay times) must be acquired before any useful

studies of "real samples" can be carried out. At present, in the specific

field of POM analysis, many of the most important (carcinogenic) compounds

cannot be acquired from commercial sources; in fact, significantly fewer of these

materials are commercially available now than in 1970! Those materials which

are available are often of questionable purity. There do not appear to exist

well-defined channels for obtaining these materials from non-commercial sources.

We would contend that there is a very significant need for SRM samples

of the important polycyclic aromatic hydrocarbons, having definite, known

purity, available to a wide variety of workers by well-defined, well-publicized

channels. Until such a situation is achieved, research in the analytical

chemistry of POM will be significantly hindered. Eventually, SRM’s of shale

oil (and other synthetic fuels) must be made available, but we find it difficult

to believe that such SRM's will be of widespread utility until SRM's of the

individual components of synthetic fuels exist.

103
REFERENCES

1. Report on the Conference-Workshop of the Analytical Chemistry of Oil Shale

and Shale Oil, Washington, D. C., 24-25 June 1974, National Science Foundation,

p. 57.

2. F. Bonomo, in Ref. 1, p. 133-186.

3. B. Meyer, "Low Temperature Spectroscopy", American Elsevier, New York, 1971.

4. J. L. Monkman, L. Dubois, and C. J. Baker, Pure Appl.' Chem. , 2A, 731 (1971).

5. National Research Council, "Particulate Polycyclic Organic Matter", National

Academy of Sciences, 1972, pp. 297-298.

6. P. R. Griffiths, "Chemical Infrared Fourier Transform Spectroscopy", Wiley,

New York, 1975.

7. A. G. Marshall and M. B. Comisarow, Anal. Chem . , 47 , 491A (1975).

8. P. R. Griffiths, C. T. Foskett, and R. Curbelo, Appl. Spectrosc. Rev ., 31 (1972).

9. G. Horlick, Appl. Spectrosc ., 22 , 617 (1968).

10. P. C. Jurs and T. L. Isenhour, "Chemical Applications of Pattern Recognition",

Wiley, New York, 1975.

11. T. Hirschfeld, "Computer Unmlxing of Unknown Sample Mixtures", Anal. Chem. , submitted for publication.

12. R. A. Hites, paper presented at Symposium on Polynuclear Aromatic Hydrocarbons,

Battelle Memorial Institute, Columbus, Ohio, October 17, 1975.

13. E. Sawicki, Talanta , 16 , 1231 (1969).

14. G. F. Kirkbright and C. G. de Lima, Analyst , 99 , 338 (1974).

15. M. Lamotte and J. Joussot-Dubien, J. Chem. Phys ., 61 , 1892 (1974).

16. E. L. Wehry, Fluorescence News , 21 (1974).

17. A. A. Lamola and N. J. Turro, "Energy Transfer and Organic Photochemistry",

Interscience, New York, 1969, pp. 37-43.

18. R. P. Fisher and J. D. Winefordner, Anal. Chem . , 44 , 948 (1972).

19. R. Arrathoon and D. A. Sealer, Phys . Rev . , A4 , 815 (1971).

20. J. M. Harris, R. W. Chrisman, and F. E. Lytle, Appl. Phys. Lett. , 26 , 16 (1975).

21. F. E. Lytle, Anal . Chem. , 46 , 817A (1974).

104
FIGURE CAPTIONS

Figure 1. Cell for vacutim sublimation-Knudsen effusion of polycyclic hydrocarbons.

Figure 2. Knudsen cell assembly attached to cryostat head.

Figure 3. "Complete" refrigerator assembly, for operation at 15-20 °K, with

head and Knudsen cell assembly attached. This is a closed-cycle refrigeration

system; no liquid refrigerants are used.

Figure 4. MI FT-IR spectrum of equimolar mixture of three isomeric polycyclic

hydrocarbons (chrysene, benz (a) anthracene, triphenylene)

.

Figure 5. Liquid solution fluorescence spectrum of anthracene.

Figure 6. MI fluorescence spectrum of anthracene.

Figure 7

.

Block diagram of time-resolved fluorometer. The laser can also

be operated in the CW mode. Thus, a high-resolution emission monochromator

is employed, so that the same optical arrangement can be employed for both

time-resolved and steady-state (conventional) fluorometry.

105
FIGURE 1

106
FIGURE 2
FIGURE 3

i' m

108
CibHi 2

Mixture

TRIPHENYLENE,

CHRYSENE,

BENZ[A]ANTHRACENE/

Ng

MATRIX

MATRIX

:

SAMPLE

=

250

EQUIMOLAR

MIXTURE

- 1

mg

of

each

109

iL

1550

1450

1350

1250

1150

1050

950

850

750

650

550

450
ANTHRACENE

IN

CgHia
ANTHRACENE

IN

300:1

,il

ni

440

430

420

410

400

390

380

370
>- o

I UJ X (T

3

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EO 5^ Q.- ^ O o 2 ^

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6 2 o -

x: o O ®

Q. ® (/) Q. = £

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E

ow

JZu

o

co

S

<MO

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0)Ol

(/)

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.5 "O

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112

Romp

Trigger

Signal

Generator
Comment following Wehry's talk.

Comment: Your technique sounds very informative. The main problem I

' see is the need for pure compounds to define the individual

spectra. For shale oil just determining the compounds present

in several hundred peaks, determining each and preparing in

a pure form would appear to be a near impossible job.

113
APPENDIX B

Information on Existing NBS-SRM's

Useful for Characterizing Oil Shale/Products

114
u. s. Alexander

National Qu: A. V.

of Commerce

rowbridge.

Standards

rector

Certificate of !3nalj>£iis!

Standard Reference Material 1621

Sulfur In Residual Fuel Oil

Sulfur Content 1.05±0.02 weight percent

This Standard Reference Material is intended as an analytical standard in the determination of sulfur in residual fuel oil. It is a commercially available oil having the

following inspection properties which are supplied for identification only: gravity, 22.6°

API; flash point, 136 °F; furol viscosity at 122 °F, 21 seconds; pour point, 40 °F; Ramsbottom carbon residue, 3.3 percent ; ash, 0.02 percent ; water, not detected ; and sediment

0.01 percent.

Sulfur was determined gravimetrically as barium sulfate after combustion in a Parr

Oxygen Bomb using 1-g samples. The method used is similar to ASTM Method D-129. It differs only in that any iron present is removed with ammonium hydroxide before the precipitation of the sulfur as barium sulfate. The uncertainty shown represents the 95-percent confidence limit of the mean based on 30 determinations and allowances for known

sources of possible error.

The oil sample was supplied by the Esso Research and Engineering Company of

Linden, New Jersey. Sulfur analyses were performed by B. S. Carpenter, R. A. Paulson,

and W. P. Schmidt of the Microanalysis Section.

Washington, D. C. 20234

December 11, 1967

W. Wayne Meinke, Chief

Office of Standard Reference Materials

115
U. S. Departi^i^- of Commerce

Alexander E^i^rowbridge,

Secr^ry

National A. V. Standards

rector

Certificate of ^nalpsiisJ

Standard Reference Material 1622

Sulfur In Residual Fuel Oil

Sulfur Content 2.14±0.01 weight percent

This Standard Reference Material is intended as an analytical standard in the determination of sulfur in residual fuel oil. It is a commercially available fuel oil having

the following inspection properties which are supplied for identification only : gravity,

16.9° API; flash point, 152 °F; furol viscosity at 122 °F, 186 seconds; pour point, 30 °F;

Ramsbottom carbon residue, 11.9 percent; ash 0.05 percent; water, not detected; and

sediment 0.01 percent.

Sulfur was determined gravimetrically as barium sulfate after combustion in a Parr

Oxygen Bomb using 1-g samples. The method used is similar to ASTM Method D-129. It differs only in that any iron present is removed with ammonium hydroxide before the precipitation of the sulfur as barium sulfate. The uncertainty shown represents the 95-percent confidence limit of the mean based on 17 determinations and allowances for known

sources of possible error.

The oil sample was supplied by the Esso Research and Engineering Company of

Linden, New Jersey. Sulfur analyses were performed by B. S. Carpenter, R. A. Paulson,

and W. P. Schmidt of the Microanalysis Section.

Washington, D. C. 20234

December 11, 1967

W. Wayne Meinke, Chief

Office of Standard Reference Materials

116
U. S. DepartiSif^ of Commerce

Mauric^i^. Stans

National BurS^^ij Standards

L. M. Brana^nto; Director

Olcrtiftcate of ^nal^sto

Standard Reference Material 1623

Sulfur in Residual Fuel Oil

W. P. Schmidt and R. A. Paulson

Sulfur Content 0.268 ± 0.004 weight percent

This Standard Reference Material is an analytical standard for determining sulfur in residual fuel

oil. It is a commercially available fuel oil having the following inspection properties that are supplied for identification only: gravity, 27.0 °API; flash point (Pensky-Martens), 170 °F ; viscosity

(kinematic), 5.8 centistokes; pour point, 47 °F; carbon residue (on 10 percent bottoms),

0.31 percent. Tbe following analytical data are not certified, but are reported for information only:

carbon, 87.4 percent; hydrogen, 12.0 percent; water, not detected (<0.1 percent); sediment, not

detected (<0.01 percent); ash, not detected (<0.005 percent); and vanadium 3 ± 1 ng/g.

Sulfur was determined gravimetrically as barium sulfate after combustion in a Parr Oxygen

Bomb using 1-g samples. The method is similar to ASTM Method D-129. It differs only in that any

iron present is removed with ammonium hydroxide before tbe precipitation of the sulfur as barium

sulfate. Tbe uncertainty shown represents the 95-percent confidence limit of the mean based on

12 determinations and allowances for known sources of possible error.

The material was supplied by the Esso Research and Engineering Company of Linden,

New Jersey. Vanadium was determined by T. E. Gills, using non-destructive neutron activation

analysis.

The overall direction and coordination of the technical measurements leading to certification were performed under the chairmanship of J. K. Taylor.

The technical and support aspects involved in the preparation, certification, and issuance of this

Standard Reference Material were coordinated through the Office of Standard Reference Materials

by T. W. Mears.

Washington, D. C. 20234 J. Paul Cali, Chief

April 7, 1971 Office of Standard Reference Materials

117
U. S. Departrifceqjj’ of Commerce Maurice- H. Stans ssecMtary

National BArea? «£ Standards

L. M. BraitBe9iiV', Director

Ctterttficale of

Standard Reference Material 1624

Sulfur in Distillate Fuel Oil

W. P. Schmidt and R. A. Paulson

Sulfur Content 0.211 ± 0.004 weight pereent

This Standard Referenee Material is an analytieal standard for determining sulfur in distillate fuel

oil. It is a eommereially available oil having the following inspection properties that are supplied for

identifieation only: gravity, 33.8 °AP1; flash point (Pensky-Martens), 138 °F; viseosity (kinematie),

2.7 centistokes; pour point, — 16°F; earbon residue (on 10 percent bottoms), 0.15 percent. The

following analytical data are not certified, but are reported for information only: carbon,

86.6 percent; hydrogen, 12.5 percent; water, not detected (<0.1 percent); sediment, not detected

(<0.01 percent); ash. not detected (<0.005 percent); vanadium, 14 ± 1 ng/g.

Sulfur was determined gravimetrically as barium sulfate after combustion in a Parr Oxygen

Bomb using 1-g samples. The method is similar to ASTM Method D-129. It differs only in that any

iron present is removed ^vith ammonium hydroxide before the precipitation of the sulfur as barium

sulfate. The uncertainty shown represents the 95-percent confidence limit of the mean based on

12 determinations and allowances for known sources of possible error.

The material was supplied by the Esso Research and Engineering Company of Linden,

New Jersey. Vanadium was determined by T. E. Gills, using non-destructive neutron activation

analysis.

The overall direction and coordination of the technical measurements leading to certification were performed under the chairmanship of J. K. Taylor.

The technical and support aspects involved in the preparation, certification, and issuance of this

Standard Reference Material were coordinated through the Office of Standard Reference Materials

by T. W. Mears.

Washington, D. C. 20234 J. Paul Cali, Chief

April 7, 1971 Office of Standard Reference Materials

118
U.S. Department of Commerce

Juanita Kreps

Secretary

*

National Bureau of Standards

Ernest Ambler. Director

JJational Jiumu

fflsrttftcats of

of Standards

(Anal^ote

Standard Reference Material 1630

Trace Mercury in Coal

This Standard Reference Material is intended as an analytical standard for the determination of trace mercury

in coal. The material is a commercially available coal that was crushed to a size of 2 1 0 to 500 micrometers with a

roll crusher. From a total of 500 packaged bottles, 30 were randomly selected for analysis. Duplicate

determinations were made on 0.5 g portions of 25 of these bottles, and single determinations were made on the

other five. The mercury content of this material was obtained by destructive neutron activation analysis.

The recommended value is the average of these 55 determinations on 30 bottles, which was found to be; Mercury content = 0.13 /ug/g

The recommended value is not expected to change by more than ± 1 in the last significant figure.

A study of homogeneity showed no variability among bottles that could not be accounted for by analytical error. Duplicate samples from the same bottle indicated a homogeneity for mercury of ± 5% (relative).

The mercury content was also determined by flameless atomic absorption spectrometry, yielding an average

value of 0.14 /ug/gSelenium was also determined using destructive neutron activation analysis. The value obtained, which is not

certified but included for information only, was found to be 2. 1 /itg/g. The homogeneity testing and analyses for certification were performed in the NBS Analytical Chemistry

Division by T. E. Gills and H. Rook under the direction of P. D. LaFleur.

The technical and support aspects involved in the preparation, certification, and issuance of this Standard

Reference Material were coordinated through the Office of Standard Reference Materials by C. L. Stanley.

Washington, D.C. 20234 George A. Uriano, Chief

August 1, 1979 Office of Standard Reference Materials

(Revision of Certificate dated 1 1-2-71 Editorial Revision only.)

(over)

119
ANALYTICAL PROCEDURE

The bottles containing the samples were allowed to remain open at room temperature (about 25 °C) for twenty-four hours.

The coal samples, along with solution standards of mercury and NBS Standard Reference Material 1571

(Orchard Leaves) used as a control, were encapsulated in cleaned quartz vials. The geometry of both the samples

and the standards were optimized so that flux monitors were not needed. The samples were irradiated for four

hours at a thermal flux of 6 X 10*^ n cm ^ sec The samples were allowed to decay for three days to minimize

the personnel dose rate. The samples were postweighed into porcelain boats and burned in a combustion tube. The volatile mercury compounds and other volatile products liberated during burning were trapped in a liquid

nitrogen cold trap. The cold trap was allowed to warm to room temperature. The mercury compounds were then

transferred to polyethylene bottles by washing the cold trap with concentrated nitric acid and water. For this analysis, '^^Hg produced by *’^Hg(n,7) '^^Hg was used as the measuring activity.

Bromine-82, an interfering isotope, was separated from the sample by using the classical silver bromide

precipitation.

The samples were counted on a 22 cm^ Ge(Li) detector connected to a 2048-multichannel analyzer. The

accumulated data was processed by computer for peak identification and integration. The concentrations were

determined by using a Standard Comparator Method.

NOTE TO USER

It is suggested that persmis using SRM 1630 to check their analytical technique should adopt the following

criteria. If the average, X, of N replicate measurements on this SRM is found to lie in the interval—

0.127

0.013

< X< 0.127 +

0.013

\/l^

then the analytical technique used gives a result compatible with that found at NBS. However, if the value Xlies outside this interval, then the technique should be examined for possible bias or miscalibration.

NOTE: The above expression is not rigorously correct. It does not include a possible component for between laboratory variability nor sources of systematic error.

SRM 1630

Page 2

120
U. S. Departrt^nt.^ of Commerce

Frederick B. Dent

Secr«tary

’ ?

National Burw^'of Standards

Richard W. Rf^trarts, Director

Rational ^umu of ^tanrfartts

Olcrttftcaie of (Anal^ote

Standard Reference Material 1631

Sulfur in Coal

Rolf A. Paulson

This Standard Reference Material is intended primarily for use as an analytical standard for the

determination of sulfur in coal. It is also certified for ash content. This standard consists of three

different low-volatile bitu minus coals, ground to pass a 60-mesh sieve, packaged separately. Each

coal is certified for its sulfur and ash contents on an as-received basis.

Percent by Weight

Coal Sulfur Ash

A 0.546 ± 0.003 5.00 ±0.02

B 2.016 ± .014 14.59 ± .09

C 3.020 ± .008 6.17 ± .02

The certified values are the means of 20 determinations of sulfur and 10 determinations ot ash on 10 samples selected randomly from the lot of 2500 samples. The uncertainty represents the half

widths of the 95% confidence intervals of the certified values. There was no evidence of heterogeneity of composition within the uncertainty limits reported.

The coals have been analyzed by four cooperating laboratories with results consistent with the

certified values. All of the analytical work is summarized under the supplementary information.

The overall coordination of the technical measurements leading to certification, was under the

chairmanship of J. K. Taylor.

The technical and support aspects involved in the preparation, certification, and issuance of this

Standard Reference Material were coordinated through the Office of Standard Reference Materials

by C. L. Stanley.

Washington, D. C. 20234 J. Paul Cali, Chief

August 15, 1973 Office of Standard Reference Materials

(over)

121
Supplementary Information

Analysis of Material

The methods of analysis used for certifying this material were essentially those identified as ASTM method D271. The following laboratories cooperated with NBS in the analysis of these

coals: Association Technique de Tlmportation Charbonniere, Hampton Roads Laboratory, Newport

News, Virginia; Combustion Engineering Inc., Windsor, Connecticut; Eastern Associated Coal

Corporation, Pittsburgh, Pennsylvania; and U. S. Bureau of Mines, Coal Analysis Laboratory, Pitts- burgh, Pennsylvania.

Summary of Supporting Analytical Values

Coal Laboratory Sulfur, % Ash, %

1 0.540 ± 0.006 4.847 ± 0.044

2 .579 ± .006 4.792 ± .074

3 .551 ± .016 5.134 ± .085

4 .569 ± .017 4.865 ± .051

1 1.972 ± .016 14.50 ± .16

2 2.019 ± .014 14.58 ± .06

3 1.969 ± .031 14.61 ± .19

4 1.988 ± .028 14.58 ± .16

1 3.018 ± .018 6.126 ± .031

2 3.035 ± .031 6.013 ± .092

3 2.915 ± .017 6.092 ± .056

4 2.998 ± .020 6.045 ± .072

For the work performed in the cooperating laboratories the values for sulfur are the averages of

twelve determinations. The values for ash are the averages of twelve determinations except laboratoiy No. 1, whose values are based upon 18 determinations for coals A and C and 17 determinations

for coal B. The uncertainties are the 95 percent confidence limits.

Originally, the moisture content of these coals was to be certified; however, the lack of homogeneity in this respect prevented certification. Therefore, these values are reported for information

only. The ranges of NBS values for moisture were: Coal A, 0.72 to 1.06 percent; Coal B, 0.48 to 1.00 percent; and Coal C, 0.15 to 0.70 percent.

Source of Material

Coal A - Keystone Mine No. 2, West Virginia

Coal B - Colver Mine, Pennsylvania

Coal C - Stigler Bed, Arkansas

These coals were procured and ground through the assistance and courtesy of David E. Wolfson

and Forrest E. Walker, L. S. Bureau of Mines, Pittsburgh, Pennsylvania.

Use of Material

All analytical values are reported on an as-received basis so that no drying procedures should be

used. The coals are packaged in hermetically sealed envelopes each containing approximately 3.g of

the material. It is recommended that the envelopes be opened only at the time of analysis and that

any unusfjd contents be discarded.

122
U.S. Department of (’ommeri-e Juanita M. Kreps

Secretjirj'

iMaliimal Bureau of Standanis Kmest Ambler, Avtiiif: Direrlur

^atioital of ^tandarrfo

Ctrlifttafc of (^nalgsta

Standard Reference Material 1632 a

Trace Elements in Coal

(Bituminous)

This Standard Reference Material is intended for use in the calibration of apparatus and techniques employed in the trace element analysis of coal and similar materials. The material should be dried without heat to constant weight before use. The recommended procedures for drying are either vacuum drying at ambient temperature for 24 hours,or freeze drying in which the drying chamber is kept at room temperature. When not in use, the material should be kept in a tightly sealed bottle and stored in a cool, dark place. Long-term P>1 year) stability of this SRM has not been

rigorously established. NBS will continue to monitor this material and any substantive change will be reported

to purchasers.

The certified values given below are based on at least a 250-mg sample of the dried material, the minimum

amount that should be used for analysis.

Element' Content, ngjg Element

Content, yigjg

. . a,b

Arsenic 9.3 1 Mercury®’* 0.13 ± 0.03

Cadmium‘S’ 0.17 0.02 Nickel*

’** 19.4 ± 1 Chromium‘S’* 34.4 ± 1.5 Selenium®’* 2.6 ± 0.7

Copper®’* 16.5 ± 1 Thorium*’* 4.5 ± 0.1

I c,d,f Iron 11,100 ± 200 Uranium* 1.28 ± 0.02

Lead*’*' 12.4 + 0.6 Vanadium*’® 44 ± 3 Manganese®’* 28 + 2

c,d Zinc 28 ± 2

1. Methods of Analysis:

a. Atomic Absorption Spectrometry e. Neutron Activation

b. Photon Activation f. Spectrophotometry

c. Isotope Dilution Mass Spectrometry g. Flame Emission Spectrometry

d. Polarography

2. The estimated uncertainty is based on judgment and represents an evaluation of the combined effecus of method imprecision. possible systematic errors among methods, and material variability for samples of 250-mg or more. (No attempt was made to derive exact statistical measures of imprecision because several methods were involved in the determination of most constituents.) The overall direction and coordination of the analytical measurements leading to this certificate were performed

in the Analytical Chemistry Division under the chairmanship of L. J. Moore.

The technical and support aspects involved in the preparation, certification, and issuance of this Standard

Reference Material were coordinated through the Office of Standard Reference Materials by W. P. Reed.

Washington, D.C. 20234

January 23, 1978 123

(over)

J. Paul Cali, Chief

Office of Standard Reference Materials
PREPARATION, TESTING, and ANALYSIS

This material was prepared from one lot of coal designated as Pennsylvania Seam Coal. It was prepared under

the auspices of F. Walker and J. Douebruck of the U.S. Bureau of Mines, Pittsburgh, Pennsylvania. The

prepared and ground coal was then sieved through a 250 /um (No. 60) sieve and thoroughly blended in a V-type

blender.

Samples for homogeneity testing were taken from the top, middle, and bottom of three bulk containers of coal,

and analyzed by neutron activation analysis for scandium, chromium, iron, cobalt, cerium, and thorium.

Replicate analyses of 250-mg samples indicated a homogeneity for these elements of ±2% (relative). The

homogeneity measurements were performed in the NBS Analytical Chemistry Division by R. R. Greenberg.

Certification analyses for the various elements were made in the NBS Analytical Chemistry Division by T. J. Brady, B. I. Diamondstone, L. P. Dunstan, M. S. Epstein, M. Gallorini, E. L. Gamer, T. E. Gills, J. W.

Gramlich, R. R. Greenberg, S. H. Harrison, G. M. Hyde, G. J. Lutz, L. A. Machlan, E. J. Maienthal, J. D. Messman, T. J. Murphy, and T. C. Rains.

The following values are not certified because they were based on a non-reference method, or were not deter- mined by two or more independent methods. They are included for information only.

Antimony

Cerium

Element

Content

(Mg/g)

(0.58)

(30)

Cesium

Cobalt

(2.4)

(6.8)

(0.54)

(8.49)

(

1 . 6) (31)

Europium

Gallium

Hafnium

Rubidium

Scandium (6.3)

(wt. %)

(3.07)

(1.64)

(0.175)

Aluminum

Sulfur

Titanium

124
U.S. Department of Commerce

Juanita Ms. Kreps

Secretary

National Bureau of Standards

Ernest Ambler, Director Rational ^ureau af ^tanttarrfg

(lerttficate of ^Analysts

Standard Reference Material 1633a

Trace Elements in Coal Fly Ash

This Standard Reference Material is intended for use in the calibration of apparatus and methods used in analyses of coal fly ash and other materials with similar matrices for trace elements. This material should be

dried to a constant weight before using. Recommended procedures for drying are: (1) drying for 24 hours at ambient temperature using a cold trap at or below -50 °C and a pressure not greater than 30 Pa (0.2 mm Hg);

(2) drying in a desiccator over P2 O5 or Mg(C 104)2 . When not in use, the material should be kept in a tightly sealed bottle. Long term (>3 years) stability of this SRM has not been rigorously established. NBS will continue to monitor this material and any substantive change will be reported to purchasers.

The certified values given below are based on at least a 250-mg sample of the dried material, the minimum

amount that should be used for analysis.

Element' Content^ Element Content

%_ Mg/g

Calcium®’'’’* 1.11 ± 0.01 Mercury®’* 0.16 ± 0.01

I a,b,c Iron 9.40 ± 0.10 Nickel®

’*’’**’* 127 ± 4

Potassium®’*’’* 1.88 ± 0.06

. . b,d , e Lead 72.4 ± 0.4

Magnesium®’*’ 0.455 ± 0.010 Rubidium®’*’’*’* 131 ± 2

Sodium®’* 0.17 ± 0.01 Selenium®’*’* 10.3 ± 0.6

Silicon*’*’ 22.8 ± 0.8 Strontium®’*’* 830 ± 30

till. Thorium*’’* 24.7 ± 0.3

A

• a,c Arsenic 145 ± 15 Thallium*’’* 5.7 ± 0.2 Cadmium*’’*’**’* 1.0 ± 0.15 Uranium*’ 10.2 ± 0.1

. a,b,c Chromium 196 ± 6 Zinc®’*”**’*’* 220 ± 10

Copper®’*’’* 118 ± 3

i

1. Methods of Analysis:

“Atomic Absorption Spectrophotometry or Flame Emission 'X-ray Fluorescence Spectrometry

Spectrometry Inductively Coupled Plasma Emission Spectrometry

Isotope Dilution Mass Spectrometry *Isotope Dilution Spark Source Mass Spectrometry

“^ Neutron Activation Gravimetry

Polarography

2. The estimated uncertainty is based on judgment and represents an evaluation of the combined effects of method imprecision, possible systematic errors among methods, and material variability for samples

of 250-mg or more. (No attempt was made to derive exaa statistical measures of imprecision because

several methods were involved in the determination of most constituents.)

Washington, D.C. 20234

April 18, 1979

(over)

125

George A. Uriano, Chief

Office of Standard Reference Materials
The overall direction and coordination of the analytical measurements leading to certification were performed

in the Center for Analytical Chemistry under the chairmanship of L. A. Machlan.

The technical and support aspects involved in the preparation, certification, and issuance of this Standard

Reference Material were coordinated through the Office of Standard Reference Materials by W. P. Reed.

PREPARATION, TESTING, AND ANALYSIS

This fly ash material was supplied by a coal fired power plant and is a product of Pennsylvania and West Virginia

coals. It was selected as a typical fly ash and is not intended as a fly ash from a specific coal or combustion process, The material was sieved through a # 170 sieve and blended for 2 hours in a Vee blender. The material was then

removed and placed in a series of bulk containers from which specific samples were taken.

Twelve bottles were selected for homogeneity tests. These samples were analyzed for cobalt, chromium,

europium, iron, scandium, and thorium by nondestructive neutron activation analysis. The observed standard

deviations for both 50 and 250 mg samples were consistent with counting statistics indicating that the fly ash is homogeneous within ± 5% (relative) based on these elements. The homogeneity analyses were performed in the

NBS Center for Analytical Chemistry by R. R. Greenburg and J. S. Maples. Analyses for the various elements were made in the NBS Center for Analytical Chemistry by the following analysts: J. R. Baldwin, T. J. Brady,

E. R. Deardorff, M. G. Dias, L. P. Dunstan, M. S. Epstein, E. L. Gamer, T. E. Gills, C. A. Grabnegger, J. W.

Gramlich, R. R. Greenberg, S. Hanamura, S. H. Harrison, E. F. Heald, H. M. Kingston, E. C. Kuehner, L. A. Machlan, E. J. Maienthal, J. S. Maples, J. D. Messman, L. J. Moore, P. J. Paulsen, P. A. Pella, T. C. Rains, K. J. R. Rosman, T. A. Rush, P. A. Sleeth, and R. L. Waters, Jr. The following values are not certified because they are based on a non-reference method, or were not determined

by two or more independent methods. They are included for information only.

Element Content Element Content

%

Aluminum 14 Europium 4

Barium 0.15 Gallium 58

Titanium 0.8 Hafnium 7.6 Mg/g Manganese 190

Beryllium 12 Molybdenum 29

Cerium 180 Antimony 7 Cobalt 46 Scandium 40

Cesium 11 Vanadium 300

126
U.S. Departniisnt of Commerce

Juanita "M. Kreps

Swretary

.National :Bufeau uf Standards

Ernest Ambler, Acting Director Rational ^ureau

Certificate of

of ^tanttarrfs

(Attal^oio

Standard Reference Material 1634

Trace Elements in Fuel Oil

This Standard Reference Material is intended for use in the calibration of apparatus and evaluation of methods

used in analyses of fuel oil and other materials with similar matrices for trace elements. When not in use, the

material should be kept in a tightly sealed bottle. Long term stability of this SRM has not been rigorously

established. NBS will continue to monitor this material and any substantive change will be reported to purchasers.

The certified values given below are based on at least a 250-mg sample of the material, the minimum amount

that should be used for analysis.

Constituent Certified Value*

2 Estimated Uncertainty

Percent by Weight

Sulfur 2.14*

, 0.02

Mg/g

Vanadium 320“ ' 15 Nickel 36'“' 4

Iron 13.5“ ' ' 1.0 Zinc 0.23“ ' 0.05 Lead .04l‘*

' .005

1. The certified values are based on the results of 4 to 15 determinations by each of at least two

analytical techniques.

a. Neutron Activation

b. Combustion with Titrimetry

c. Atomic Absorption Spectrometry

d. Isotope Dilution Mass Spectrometry

e. Polarography

2. The estimated uncertainties are not less than the 95% confidence limits computed for the analyses and include sample variations, possible method differences, and errors of measurement. The overall direction and coordination of the analytical measurements leading to certification were performed

in the Analytical Chemistry Division under the chairmanship of P. D. LaFleur and D. A. Becker.

The technical and support aspects involved in the preparation, certification, and issuance of this Standard

Reference Material were coordinated through the Office of Standard Reference Materials by C. L. Stanley.

Washington, D.C. 20234

January, 1978

(Rev. of Cert, dated 5/14/75.

Editorial changes only.)

J. Paul Cali, Chief

Office of Standard Reference Materials

(over)

127
PREPARATION, TESTING, and ANALYSIS

The material was obtained through a commercial supplier from a refinery on the island of Aruba in the West

Indies, and is essentially a “No. 6 Fuel Oil” as defined by the American Society for Testing and Materials.

A random scheme for sample selection was designed and a statistical analysis of the homogeneity data was per- formed by J. Mandel of the NBS Institute for Materials Research. Fifteen of 500 bottles were selected for homogeneity tests. These samples were analyzed for vanadium by nondestructive neutron activation analysis.

Replicate analyses on 250-mg samples indicated homogeneity within ±2% (relative) based on this element.

X-ray fluorescence analyses for sulfur on bulk samples before bottling support the conclusion of acceptable

material homogeneity. The homogeneity analyses were performed in the NBS Analytical Chemistry Division

by T. E. Gills, M. Darr, and R. Myklebust. Analyses for the various elements were made in the NBS Analytical

Chemistry Division by the following analysts: R. W. Burke, B. S. Carpenter, M. S. Epstein, E. L. Garner, T. E.

Gills, J. W. Gramlich, L. A. Machlan, E. J. Maienthal, T. J. Murphy, E. Orvini, T. C. Rains, H. L. Rook,T. A. Rush, and S. A. Wicks.

The following values are not certified because they are based on a non-reference method, or were not determined

by two or more independent methods. They are included for information only.

Constituent Content'

Mg/g

Arsenic (0.095)'

Beryllium KOI)”

Cadmium (<.01)'

' Chromium (.09)' Mercury (.0023)'

Manganese (.12)'

I. These values are not certified.

a. Neutron Activation

b. Spectrophotometry

c. Polarography

128
L'.S. Department of Commerce

Juanita Kreps

Secretar>-

National Bureau of Standards

Ernest Ambler, Acting Director ^urcau of ^^tanrfarrfo

Certificate of (Anal^oio

Standard Reference Material 1635

Trace Elements in Coal

(Subbituminous)

This Standard Reference Material is intended for use in the calibration of apparatus and techniques employed in the trace element analysis of coal and similar materials. The material should be dried without heat to constant weight before use. The recommended procedures for drying are either vacuum drying at ambient temperature for 24 hours, or

freeze drying in which the drying chamber is kept at room temperature. The moisture content of this material is approximately 20%. Because of this moisture level, it is recommended that small individual samples be dried

immediately before use.Drying of large samples may result in a violent discharge of water vapor and resultant

loss of sample. When not in use, the material should be kept in a tightly sealed bottle and stored in a cool, dark

place. Long-term p>l year) stability of this SRM has not been rigorously established. NBS will continue to monitor this material and any substantive change will be reported to purchasers.

The certified values given below are based on at least a 250-mg sample of the dried material, the minimum

amount that should be used for analysis.

Element* Content, ^ig/g^ Element* Content, /ug/g^

Arsenic*’** 0.42 + 0.15 Nickel'’** 1.74 ± 0.1

Cadmium'’**’* 0.03 + 0.01 Selenium*’* 0.9 ± 0.3 Chromium'’* 2.5 + 0.3 Thorium'’* 0.62 ± 0.04

Copper*'*' 3.6 + 0.3 Uranium' 0.24 ± 0.02

I c,d,f Iron 2390 + 50 Vanadium*’' 5.2 ± 0.5

Lead'’** 1.9 + 0.2

_• c,d Zinc 4.7 ± 0.5 Manganese*’* 21.4 ± 1.5

1. Methods of Analysis:

a. Atomic Absorption Spectrometry e. Neutron Activation

b. Photon Activation f. Spectrophotometry

c. Isotope Dilution Mass Spectrometry g. Flame Emission Spectrometry

d. Polarography

2. The estimated uncertainty is based on judgment and represents an evaluation of the combined effects of method imprecision, possible systematic errors among methods, and material variability for samples

of 250-mg or more. (No attempt was made to derive exact statistical measures of imprecision because

several methods were involved in the determination of most constituents.) The overall direction and coordination of the analytical measurements leading to this certificate were performed

in the Analytical Chemistry Division under the chairmanship of L. J. Moore.

The technical and support aspects involved in the preparation, certification, and issuance of this Standard

Reference Material were coordinated through the Office of Standard Reference Materials by W. P. Reed.

Washington, D.C. 20234

January 23, 1978 (over)

129

J. Paul Cali, Chief

Office of Standard Reference Materials
PREPARATION, TESTING, and ANALYSIS

This material was prepared from one lot of subbituminous coal from the Eagle Mine of The Imperial Coal

Company, Erie, Colorado. The material was ground and sieved thru a No. 65 (230 nm) sieve by the Colorado

School of Mines Research Institute. The material was then blended in a V-type blender.

Samples for homogeneity testing were taken from the top, middle, and bottom of three bulk containers of coal,

and analyzed by neutron activation analysis for sodium, scandium, chromium, iron, cobalt, lanthanum,

cerium, and thorium. Replicate analyses of 2S0-mg samples indicated a homogeneity for these elements of

± 2.5% (relative) except for chromium, which was homogeneous within counting statistics of ± 6%. The homogeneity measurements were performed in the NBS Analytical Chemistry Division by R. R. Greenberg. Certifi- cation analyses for the various elements were made in the NBS Analytical Chemistry Division by T. J. Brady,

B. 1. Diamondstone, L. P. Dunstan, M. S. Epstein, M. Gallorini, E. L. Gamer, T. E. Gills, J. W. Gramlich,

R. R. Greenberg, S. H. Harrison, G. M. Hyde, G. J. Lutz, L. A. Machlan, E. J. Maienthal, J. D. Messman,

T. J. Murphy, and T. C. Rains.

The following values are not certified because they were based on a non-reference method, or were not deter- mined by two or more independent methods. They are included for information only.

Content

Element (Mg/g)

Antimony (0.14)

Cerium (3.6) Cobalt (.65) Europium (.064)

Gallium (1.05)

Hafnium (.29) Scandium (.63)

(wt. %)

Aluminum (0.32)

Sulfur (.33) Titanium (.02)

130
S. Departi^|y^<

Rogers3 cQb.

'of Commerce

Morton

National Richard W.

Standards

fta, Director Rational ^ureau of ^tanitardo

Olertiftcate

Standard Reference Materials

1636, 1637, 1638

Lead in Reference Fuel

This Standard Reference Material is intended for use in the calibration of instruments and

techniques used for the analysis of lead in gasoline. Samples of the leaded 91-octane-number

reference fuel (See page 2 for composition) are supplied at four concentrations, nominally 0.03,

0.05, 0.07, and 2.0 g/gal. The assigned Standard Reference Material numbers (1636, 1637, 1638)

refer to the composition of sets containing the above nominal concentrations in varying

combinations. The composition of each set is given in Table 1 on the reverse page.

The certified values for lead content are given in units of Mg/g- From these certified values the

lead concentrations in g/gal and g/1 at 20 °C and 25 °C were calculated. These values are given in

Table 2. N ominal

Lead Concentration

g/gal

0.03

0.05

0.07

2.0

Certified

Lead Concentration

/^g/g

12.31 ± 0.06

19.68 ± 0.05

27.70 ± 0.06

772.7 ± 1.5

The uncertainties cited represent the pooled 95 percent confidence intervals for a single

determination with allowances for known sources of possible error. The certified values were

determined by isotope dilution mass spectrometry and supported by atomic absorption spectrometry.

The samples of leaded reference fuel should be protected from light. The ampoules should be

opened only at time of use. No attempt should be made to keep the material in opened ampoules

for future use.

Matrix effects may be observed with various gasolines. Certain adjustments in analytical data

may be necessary based on individual knowledge of the magnitude of these effects.

The lead in reference fuel samples were prepared by the Phillips Petroleum Co. of Bartlesville,

Oklahoma. Isotope dilution mass spectrometry measurements were performed by T. J. Murphy, N.

M. Cabman and E. F. Heald of the Isotopic Analysis Section, I. L. Barnes, Chief. Atomic

Absorption Spectroscopy Measurements were performed by R. Mavrodineanu, J. R. Baldwin, and J. L. Weber of the Spectrochemical Analysis Section, 0. Menis, Chief.

The technical and support aspects involved in the preparation, certification and issuance of

these Standard Reference Materials were coordinated through the Office of Standard Reference

Materials by T. W. Mears.

Washington, D. C. 20234

March 25, 1975

131

(over)

J. Paul Cali, Chief

Office of Standard Reference Materials
Table 1 Number of ampoules of each concentration contained in

Standard Reference Material 1636, 1637, and 1638

Nominal Lead Concentration (g/gal)

SRM 0.03 0.05 0.07 2.0

1636 3 3 3 3

1637 4 4 4 - 1638 - - - 12

Table 2

Composition of leaded referenee fuels in g/gal and g/1

Lead Concentration®

Nominal g/gal g/1

g/gal 20 °Cb 25 °C 20 °C 25 °C

0.03 0.0322 0.0320 0.00851 0.00845

.05 .0515 .0512 .01360 .01352

.07 .0725 .0721 .01915 .01903

2.0 2.024 2.012 .535 .531

The lead concentrations given in this table are considered accurate within a coefficient of variation of 0.005. The concentration in g/gal at 20 C is given in the sample labels. The concentrations (C) in g/gal were calculated using the equation:

^

3785.4

10^ The concentrations (C) in g/1 were calculated using the equation:

pc

Cg/i -

Mg/g

10» The density (p) of each concentration was measured at 20 °C and 25 “C using a modification of

ASTM Method D1217. The stated interlaboratory reproducibility of this method is 0.00003 g/cm^.

Densities of the leaded fuels are given in the following table.

Nominal Concentration

g/gal

Density at 20 °C

g/cm^

Density at 25 °C

g/cm^

0.003 0.69126 0.68710

.05 .69127 .68711

.07 .69127 .68711

2.0 .69196 .68774

The 91 -octane-number reference fuel is a mixture of 91 percent by volume (0.899 mol-fraction)

2,2,4-trimethylpentane and 9 percent by volume (0.101 mol-fraction) n-heptane. Lead was added in the form of tetramethyllead-tetraethyllead motor mix.
i

NBS

Standard

Reference

Materials

U.S. Department of Commerce

National Bureau of Standards

Standard Reference Material 1648

Urban Particulate Matter

Fall, 1978

The NBS Office of Standard Reference Materials announces the availability of SRM 1648, Urban Particulates. This SRM is a fine particle dust consisting of 2 grams of material certified for a variety of trace and minor

constituents.

The material used for SRM 1 648 is a portion of a large lot of material collected over a period of 1 1/2 years in the

vicinity of St. Louis, Missouri, and should be representative of dust found in many urban areas. SRM 1648 is intended for use as a reference material by scientists making environmental measurements and developing

analytical techniques. Because this SRM represents a large homogeneous quantity of urban dust, it should

prove useful to scientists who wish to study the environmental impact of urban dust.

This SRM is certified for arsenic, cadmium, chromium, copper, nickel, zinc, uranium, iron and lead content. Method dependent information is also provided for nitrate, ammonium, sulfate, silicate, and the freon-soluble

components.

SRM 1648 may be purchased from the Office of Standard Reference Materials, Room B31 1, Chemistry Building, National Bureau of Standards, Washington, D.C. 20234, for $88 per 2-gram unit.

1278

133
U.S. Department of Commerce

Juanita Kreps

Secretary

National Bureau of Standards

Ernest Ambler. Director JSureau of ^tandardo

(ttcrfiftcatj of (Analgoto

Standard Reference Material 1648

Urban Particulate Matter

This Standard Reference Material is intended for use in the calibration of methods used in the chemical analysis

of atmospheric particulate matter and materials with similar matrices. The material is atmospheric particulate matter collected in an urban location.

The certified values are based on measurements of 6 to 30 samples by each of the analytical techniques indicated.

The estimated uncertainties include those due to sample variation, possible methodology differences, and errors of measurement (see Preparation and Analysis). The certified values are based on a sample size of at least 100 mg of the dried material. The material should be dried at 105 °C for 8 hours before use.

Element Mg/g Element Weight %

Arsenic*

* 115 ± 10

, a b c e Iron 3.91 ±0.10

t

• 3 b C d Cadmium 75 ± 7

. .a b d Lead 0.655 ± .008 Chromium**

* 403 ± 12

a b e Copper 609 ± 27

Nickel" 82 ± 3 abed

Zinc 4760 ± 140

Uranium** 5.5 ± 0.1

* Atomic Absorption Spectrophotometry

Isotope Dilution Mass Spectrometry

' Neutron Activation Analysis

** Polarography

' Spectrophotometry

The overall direction and coordination of the technical measurements leading to certification were performed

under the chairmanship of J. K. Taylor.

Tlie technical and support aspects involved in preparation, certification, and issuance of this Standard Refer- ence Material were coordinated through the Office of Standard Reference Materials by W. P. Reed.

Washington, D.C. 20234 J. Paul Cali, Chief

November 16, 1978 Office of Standard Reference Materials

(over)

134
Preparation and Analysis

This SRM was prepared from urban particulate matter collected in the St. Louis, Missouri, area in a baghouse

especially designed for this purpose. The material was collected over a period in excess of 1 2 months and, therefore, is a time-integrated sample. While not represented to be typical of the area in which it was collected, it is believed to typify the analytical problems of atmospheric samples obtained from industrialized urban areas. The material was removed from the filter bags by a specially designed vacuum cleaner and combined into a

single lot. This product was screened through a fine-mesh sieve to remove most of the fibers and other

extraneous material from the bags. The sieved material was then thoroughly mixed in a V-blender, bottled, and

sequentially numbered.

Randomly selected bottles were used for the analytical measurements. Each analyst examined at least 6 bottles, some of them measuring replicate samples from each bottle. No correlation was found between measured

values and the bottling sequence. Also, the results of measurements of samples from different bottles were not

significantly different than the measurements of replicate samples from single bottles. Accordingly, it is believed that all bottles of this SRM have the same composition.

The analytical methods employed were those in regular use at NBS for certiHcation of Standard Reference

Materials, except as noted in the following paragraphs. Measurements and calibrations were made to reduce

random and systematic errors to no more than one percent, relative. The uncertainties of the certified values

listed in the table include those associated both with measurement and material variability. They represent the

95 percent tolerance limits for an individual sub-sample, i.e., 95 percent of the sub-samples from a single unit of

this SRM would be expected to have a composition within the indicated range of values 95 percent of the time.

The following values have not been certified because either they were not based on results of a reference

method, or were not determined by two or more independent methods. They are included for information only.

All values are in units of /big/g of sample, unless otherwise indicated.

Aluminum (3.3 wt. %) Lanthanum (42)

Antimony (45) Magnesium (0.8 wt.%)

Barium (737) Manganese (860)

Bromine (500) Potassium (1.0 wt.%)

Cerium (55) Samarium (4.4)

Cesium (3) Scandium (7)

Chlorine (0.45 wt %) Selenium (24)

Cobalt (18) Silver (6)

Europium (0.8) Sodium (0.40 wt%)

Hafnium (4.4) Thorium (7.4)

Indium (i.o: Titanium (0.40 wt.%)

Iodine (a# Tungsten (4.8)

Vanadium (130)

135
The values listed below are based on measurements made in a single laboratory, and are given for information

only. While no reason exists to suspect systematic bias in these numbers, no attempt was made to evaluate such

bias attributable to either the method or the laboratory. The method used for each set of measurements is also

listed. The uncertainties indicated are two times the standard deviation of the mean.

Nitrogen (NO3 ) Nitrogen (NH4) Sulfate

Si02

Freon Soluble

(1.07% ± 0.06)

(2.01% ± .08)

(15.42% ± .14)

(26.8% ± .38)

(1.19% ± .47)

The above values were determined by the methods indicated below:

Nitrate - Extraction with water and measurement by ASTM Method D992.

Ammonia - NaOH addition followed by steam distillation and titration.

Sulfate — Extraction with water and measurement by ASTM D516.

Si02 — Solution and measurement by ASTM Method E350.

Freon Soluble — Extraction with Freon 113, using the method described in “Standard

Methods in Examination of Water and Waste Water,” 14th Edition, p. 518,

American Public Health Association, Washington, D.C.

J. W. Matwey supervised the collection of the material as well as sieving and bottling. The following members

of the staff of the NBS Center for Analytical Chemistry performed the certification measurements: R. W. Burke;

E. R. Deardorff; B. I. Diamondstone; L. P. Dunstan; M. S. Epstein; M. Gallorini; E. L. Gamer; J. W. Gramlich;

R. R. Greenberg; L. A. Machlan; E. J. Maienthal; and T. J. Murphy.

136
TECHNICAL REPORT DATA

(Please read Instructions on the reverse before completing)

1. REPORT NO. 2. EPA-600/7-80-125

3. RECIPIENT'S ACCESSION NO.

4. TITLE AND SUBTITLE

A Summary of Oil Shale Activities at the National

Bureau of Standards 1975-1979

5. REPORT DATE

6. PERFORMING ORGANIZATION CODE

7. AUTHOR(S)

Lottie T. McClendon

8. PERFORMING ORGANIZATION REPORT NO. NBSIR80-1986

9. PERFORMING ORGANIZATION NAME AND ADDRESS

Office of Environmental Measurements

National Bureau of Standards

Washington, DC 20234

10. PROGRAM ELEMENT NO. 684BE

11. CONTRACT/GRANT NO. EPA lAG D5 E684

12. SPONSORING AGENCY NAME AND ADDRESS

Office of Environmental Engineering & Technology

Office of Research & Development

Environmental Protection Agency

Washington, DC 20460

13. TYPE OF REPORT AND PERIOD COVERED

Final

14. SPONSORING AGENCY CODE

EPA/ORD/17

15. SUPPLEMENTARY NOTES

16. ABSTRACT

This report provides a summary of NBS Oil Shale activities covering

the period 1975 to 1979. At the start of this period a Workshop on Standard Reference Materials (SRM's) needed for Oil Shale Processing was

held at NBS and served to provide the priority guidance for the future

of this program. A summary of the recommendations of that Workshop, the

manuscripts presented during the Workshop, and the list of attendees is

included in this report. The status of the Oil Shale Research at NBS is

also presented consisting of developmental work on the feasibility of

producing an Oil Shale and a Shale Oil Standard Reference Materials

characterized for both trace inorganic and trace organic constituents.

Additionally, information is given dealing with the development of

measurement methods appropriate for Oil Shale and Shale Oil trace inorganic and trace organic analysis. Several papers are also included

giving additional details on these matters. Other NBS Standard Reference

Materials, which may be appropriate for the use by the Oil Shale community,

are described briefly within this document. Finally, recommendations

for future Oil Shale projects dealing with the development of measurement

methods and Standard Reference Materials at NBS are presented.

17. KEY WORDS AND DOCUMENT ANALYSIS

a. DESCRIPTORS b. IDENTIFIERS/OPEN ENDED TERMS c. COSATl Field/Group

Measurement Methods

Oil Shale

Standard Reference Materials

Water Pollution Control 7B

7C

18. DISTRIBUTION STATEMENT

Release to Public

19. SECURITY CLASS (This Report)

Unclassified

21. NO. OF PAGES

142

20. SECURITY CLASS (This page)

Unclassified

22. PRICE

EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDI Tl ON I S O BSO LE TE ^U.S. GOVERNMENT PRINTING OFFICE: 1980-311-046/171



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