E PA- 600/2- 76-160a 

June 1976 

IERL-RTP PROCEDURES MANUAL: 

LEVEL 1 

ENVIRONMENTAL ASSESSMENT 

by 

•-.W. Hamersma, S.L, Reynolds, and R.F. Maddalone 

TRW Sys[ems Group 

One Space Park 

Redondo B•ach, California 90278 

Contract No. 68-02-1412, Task 18 

ROAP No. 21AAZ-015 

Program Element No. lAB013 

EPA Project Officer: Robert M. Statnick 

Industrial Environmental Research Laboratory 

Office of Energy, Minerats, and Industry 

Research Trlangle Park, NC 27'/II 

Prepared for 

U.S. ENVIRONMENTAL PROTECTION AGENCY 

Office of Research and Development 

Washington, DC 20460 

PREFACE 

The Process Measurements Branch, IERL/RTP, has developed and recommended the implementation of a phased sampling and analytical strategy for 

Environmental Assessment Programs. The first phase, Level l, has as its 

goal the quantification of mass emissions within a factor of 2 to 3 for 

inorganic elements and organic classes. The second phase, Level 2, has 

as its goal the quantification and identification of specific compounds. 

The third phase, Level 3, has as its goal the continuous monitoring of 

indicator compounds as surrogates for a large number of specific compounds. 

This document represents the first time that a set of integrated 

sampling and analytical procedures for environmental assessment programs 

has been compiled. As such, it is anticipated that many readers might 

take exception with specific sampling and/or analytical tools; however, 

we feel that the recommended environmental assessment system is both 

valid and information effective. 

IERL/RTP Contractors or Grantees will use the system described in 

this document for Environmental Assessment Programs. It is anticipated 

that non-IERL/RTP organizations who are active in the environmental 

assessment field will also utilize this manual. 

This manual has been made as specific as possible, although it is 

recognized that it is impossible to specify the exact sampling and 

analysis procedure for every possible circumstance. When situations 

arise where alternative Level l sampling and analysis procedures are 

necessary or desired, the contractor is directed to submit his alternate 

plan to his project officer and the Process Measurements Branch, IERL-RTP, 

Research Triangle Park, for approval before actual work is initiated. 

I• •h•S docu•nt becomes universally implemented, then sets of 

comparable data will be generated and prioritization of the environmental 

insults associated with differing processes can be made. 

James A. Dorsey 

Chief, Process Measurements Branch 

iii 
TRW Document No. 

24916-6040-RU-00 

ABSTRACT 

This manual gives Level l procedures (recommended by Industrial 

Environmental Research Laboratory--Research Triangle Park) for personnel 

experienced in collecting and analyzing samples from industrial and 

energy producing processes. The phased environmental assessment strategy 

provides a framework for determining industry, process, and stream 

priorities on the basis of a staged sampling and analysis technique. 

Level l is a screening phase that characterizes the pollutant potential 

of process influent and effluent streams. 

The manual is divided into two major sections: sampling .procedures 

and analytical procedures. The sampling section is divided into five 

chapters: fugitive emissions, gases, aerosols, liquids (including s•urries), 

and solids. The analytical section is divided into three chapters: 

inorganic, Organic, and bioassays. 
ACKNOWLEDGEMENT 

This work was conducted under the direction of Dr. R. !i. Statnick, 

EPA Task order •anage•and administrative direction of Dr. L. D. Johnson, 

Industrial Environmental Research Laboratory, Research Triangle Park, 

North Carolina. The Applied Chemistry Department of the Chemistry and 

Materials Laboratory, Applied Technology Division, TRW Systems and Energy, 

Redondo Beach, California was responsible for the work performed on this 

program. Dr. E. A. Burns, Manager, Applied Chemistry Department, was 

Program Manager and the Task Order Manager was Dr. J. W. Hamersma. 

Special acknowledgement is given to the many helpful discussions with 

Mr. J. A. Dorsey, and Drs. R. M. Statnick, L. D• Johnson, and C. H. Lochm•ller of the EPA during the course of this task order. The extensive 

editorial and technical assistance provided by S. C. Qui•livan is also 

appreciated. 

The many helpful comments, suggestions, and criticisms from the following PMB/IERL-RTP Term Level of Effort contractors is also appreciated: 

Arthur D. Little, Inc., Sampling and Analysis of Organic l•aterials, 

Dr. P. L. Levins, project manager; Research Triangle Institute, Development of Environmental Assessment Control Technology Quality Assurance 

Programs, Dr. F. Smith, project manager; Aerotherm/Acurex CorD., Measurement Techniques for High Temperature/High Pressure Processes, Inc., Mr. 

F. E. Moreno, project manager; Southern Research Institute, Particulate 

Sampling Support, Dr. W. B. Smith, Droject manager; and TRC, !•c., the 

Research Corporation of New England, Fugitive Emissions Methodology, 

Dr. H. J. Kolnsberg, project manager. Special recognition, must be given 

to Dr. P. L. Levins, Arthur D. Little, Inc. and Dr. H. J. Kolnsberg, TRC, 

Inc., who provided direct input for Chapters VIII and IV, respectively. 

The Process Measurements Branch of IERL-RTP is also acknowledged for the 

input to Chapter X. 

v 
CONTENTS 

INTRODUCTION 

CHAPTER I. STRATEGY AND GENERAL INFORMATION 

1.1 D•finition of Strategies 

1.1.1 The Phased Approach 

1.1.2 Strategy of the Phased Approach 

1.1.2.1 Definition of Level I Sampling 

and Analysis 

1.1.2.2 Definition of Level 2 Sampling 

and Analysis 

1.2 Multimedia Sampling Procedures 

1.2.1 Classification of Streams for Sampling Purposes 

1.2.2 Phased Approach Sampling Point Selection 

Criteria 

1.2.3 Stream Prioritization Using the Phased Approach 

1.3 Data Requirements and Pre-Test Planning 

1.3.1 Process Data Needs 

1.3.2 Pre-Test site survey 

1.3.3 Pre-Test Site Preparation 

1.4 Analysis of Samples 

1.5 Accuracy and Precision of Results 

CHAPTER II. GAS AND VAPOR SAMPLING METHODOLOGY 

2.1 Introduction 

2.2 Sampling Test Preparation 

2.3 Gas Sampling Techniques 

2,3.1 High Pressure Line Grab Samples 

2.3.2 Slight Positive Pressure Grab Purge Sampling 

2.3.3 Negative Pressure Evacuated Bulb Sampling 

2.3.4 General Considerations 

2.4 Sampling Procedures 

2.4.1 Process Streams, Flues and Ducts 

2.4.2 Vents 

2.5 Sample Handling 

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vi 
CONTENTS (Continued) 

CHAPTER III. GASEOUS STREAMS CONTAINING PARTICULATE MATTER 

3.1 Introduction 

3.2 Particulate Ma£ter SamPling Methodology 

3..3 Preparing for Sample Collection 

3.3.1 Pre.Site Survey 

3.3.2 Personnel Requirements 

3.3.3 Equipment Preparation for Sample Collection 

3.3.3.1 Precleaning Procedures for the SASS 

Train and Sample Containers 

3.3.3.2 Apparatus Checkout 

3.4 Series Cyclone Sampling Procedure 

3.5 Sample Handling and Shipment 

3.6 Opacity Measurements 

3.7 Data Reduction 

CHAPTER IV. FUGITIVEEMISSIONS SAMPLING 

4.1 Introduction 

4.2 Airborne Fugitive Emissions 

4.2.1 Preparation for Sample Collection 

4.2.1.1 Pre-test Site Survey 

4.2.1.2 Measurement Equipment 

4.2.1.3 Personnel Requirements 

4.2.2 Sa•ling Procedures 

4.2.2.1 High Volume sampler Applications 

4.2.2.2 SASS Train Sampler Applications 

4.2.2.3 Gas SamPles 

4.2.3 Decision Aid for Appropriate Category Selections 

4.2.4 Sample Handling and Shipment 

4.2.5 Data Reduction for Airborne Fugitive Emissions 

4.3 Waterborne Fugitive Emissions 

4.3.1 Preparation for Sample Collection 

4.3.1.1 Pre-test Site Survey 

4.3.1.2 Measurement Techniques 

4.3.1.3 Personnel Requirements 

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vii 
CONTENTS (Continued) 

4.3.2 

4.3.3 

4.3.4 

4.3.5 

Sampling Procedures 

Decision Aid 

Sample Handling and Shipment 

Data Reduction for Waterborne Fugitive Emissions 

CHAPTER V. LIQUID AND SLURRY SAMPLING 

5.1 Introduction 

5.2 Preparing for Sample Collection 

5.2.1 Pre-test Site Survey 

5.2.2 Personnel Requirements 

5.2.3 Equipment Preparation 

5.2.3.1 Sample Containers 

5.2.3.2 Apparatus 

5.3 Sampling Procedures 

5.3.1 Heat Exchange Sampling Systems for High 

Temperature Lines 

5.3.2 Tap Sampling 

5.3.3 Dipper Sampling 

5.4 Liquid Sample Handling and Shipment 

CHAPTER VI. SOLID SAMPLING 

6.1 Introduction 

6.2 Pre-test Site Survey 

6.3 Solids Sampling Procedures 

6.3.1 Shovel Grab Sampling 

6.3.2 Boring Techniques 

6.4 Sample Collection and Storage 

CHAPTER VII. LEVEL 1 INORGANIC ANALYSIS TECHNIQUES 

7.1 Introduction 

7.2. Level I Analysis Methodology 

7.2.1 Elemental Analysis by Spark Source Mass 

Spectrometry 

7.2.2 Wet Chemical Analysis for Hg, As, and Sb 

7.2.3 Gas Chromatographic Analysis of Gaseous 

Components 

7.2.4 Analysis of Nitrogen Oxides 

viii 

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CONTENTS (Continued) 

7.2.5 Analysis of Leachable Material 

7.2.6 Analyses Specific for Aqueous Samples 

CHAPTER VIII. LEVEL 1 ORGANIC ANALYSIS TECHNIQUES 

8.1 Introduction 

8.2 Level I Organic Analysis Methodology 

8.3 Sample Preparation 

8.3.1 Aqueous Solutions 

8.3.2 Solids, Particulate Matter and Ash 

8.3.3 Sorbent Trap 

8.4 Analysis of Samples for Organics 

8.4.1 Gas Chromatographic Analysis of C I C 6 Range 

8.4.2 Gas Chromatographic Analysis of C 7 C12 Range 

8.4.3 Liquid Chromatographic Separation 

8.4.4 Infrared Analysis 

8.4.5 Low Resolution Mass Spectrometry 

CHAPTER IX. PARTICLE MORPHOLOGY AND IDENTIFICATION 

9.1 Introduction 

9.2 Particle Characterization 

9.2.1 Handling Particles for Microscopic Examination 

9.2.2 Photomicrography and Particle Sizing for 

Fugitive Emissions 

9.2.3 Visual Identification 

CHAPTER X. BIOLOGICAL TESTING 

10.1 Introduction 

10.2 Health Effects Bioassays 

10.2.1 Acute Toxicity (In-vitro) Test 

10.2.2 Mutagenicity (CarcinogenicitY) Screening Test 

10.3 

10.2.3 LD50 Screening Test 

Ecological Effects Bioassays 

10.3.1 Aquatic Effects 

10.3.2 Terrestri•al Effects 

REFERENCES 

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ix 
CONTENTS (Continued) 

APPENDIXES 

A Design and Preparation of a Field Testing Unit 

A. 1 Advantages 

A.2 Components and Layout 

B Process Data Needs 

C Liquid Chromatography Separation Procedure 

C.1 Procedure for Column Preparation 

C.2 Preparation of the Sample 

C.3 Loading Sample on the Column 

C.4 Chromatographic Separation into 8 Fractions 

D Preparation of XAD-2 Resin 

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X 
ILLUSTRATIONS 

6. 

7. 

8. 

9. 

10. 

11. 

12. 

13. 

14. 

15. 

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17. 

18. 

19. 

20. 

21. 

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25. 

26. 

27. 

28. 

29. 

31. 

Multimedia Sampling Approach overview 

Basic Level Sampling and Analytical Scheme for 

Particulates and Gases 9 

Basic Level ISampling and Analytical Scheme for 

Solids, Slurries, Liquids i0 

Typical Process Flow Diagram for Limestone Venturi 

Spray Tower System 12 

High Pressure Line Grab Purge Sampling Apparatus 23 

Low Pressure Grab Purge Sampling Apparatus 24 

Evacuated Grab Sampling Apparatus 25 

Source Assessment Sampling Schematic 30 

Cyclones and Water Cooled Probe 31 

XAD-2 Sorbent Trap Module 32 

Flue Gas Sampling Flow Diagram 33 

Sample Handling and Transfer Nozzle, Probe, Cyclones 

and Filter 42 

•ample Handling and Transfer XAD-2 Module 44 

Sample Handling and Transfer Impingers 45 

Sampling Categories for Level 1 Airborne Fugitive 

Emissions 48 

Decision Example for "Worst Case" Site 51 

Expanded View of Connections of XAD-2 Cartridge to High 

Volume Sampler 53 

Sampler Flow Rate Settings for Dust 56 

Plug Collector for Fugitive Water Samples 62 

Level 1 Water Runoff Fugitive Emissions Characterization 64 

Sampling Methods as a Function of Stream Type 65 

SamRling Apparatus for HPHT Lines 71 

Field Handling Scheme for Liquid/Slurry Samples 74 

Multimedia Analysis Overview 82 

Level 1 Inorganic Analysis Flow Scheme 83 

Sample Preparation for SSMS Elemental Analysis 86 

Hg, Sb, As Sample Preparation and Analysis 88 

Multimedia Organic Analysis Overview 94 

Level 1 Organic Analysis Flow Diagram 95 

Particle Characterization Flow Scheme 106 

Level I Multimedia Mobile LabQratory 120 

xi 
TABLES 

Recommended Sample Sizes and Detection Limits 

SASS Train Impinger System Reagents 

List of Analyses to be Performed on Liquid/Slurry 

Samples 

Decision Matrix for Solid Sampling 

Recommended Gas Chromatographic Parameters for 

Analysis of Inorganic and Organic Species 

Solvents Used in Liquid Chromatographic Separations 

Level i Mobile Van Equipment 

Process •ata Needs for Phased Environmental Assessment 

Liquid Chromatography Elution Sequence 

Page 

19 

39 

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78 

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122 

124 

128 

xii 
INTRODUCTION 

This procedures manual has been prepared for the Industrial and 

Environmental Research Laboratory of the Environmental Protection Agency, 

Research Triangle Park, North Carolina, 

It is written so that the sampling and analysis professional can plan 

and execute the sampling and analytical portion of a source assessment program. This manual is not intended for use by an inexperienced professional 

staff or by technicians. Analysis procedures are included as schemes with 

descriptions for all the samples obtained b.v the methods delineated in 

Chapters II through VI. For those samples which are analyzed as part of 

the sampli.ng procedure and for those samples which must be analyzed on-site, 

reference is made to analysis both in the sampling and appropriate analysis 

chapters. 

The sampling procedures in this manual are designed to be an integral 

part of the phased environmental assessment and apply primarily to Level I. 

The purpose of this initial effort is to obtain preliminary environmental 

assessment information, identify problem areas, and provide the basis for 

the prioritiz•tion of streams, components and classes of materials for 

f•rther consideration in the overall assessment. As such, the results of 

the sampling and of the corresponding analysis procedures are quantitative 

within a factor of + 2 to 3. A detailed discussion of the approach along 

with the criteria used for method selection is given in Chapter I. 

In the preparation of this manual applicable sampling literature was 

reviewed and a set of appropriate sampling procedures for each of five 

sampling categories was then defined. Included in these procedures are 

criteria for sample site selection, sampling equipment and manpower require- 

'ments, amount of sample required, and special sample preservation techniques. 

Samples for which on-site analyses are necessary are identified along with 

the appropriate procedures. 

Chapters II through VI of this manual center around five different 

types of Level l sampling activities that can be found in most industrial 

complexes: gas and vapor samples, gaseous streams containing particulate 

matter, fugitive emissions sampling, liquid and slurry sampling, and solids 

X'111 
sampling. In this way, the complex and difficult task of organizing the 

manpower and equipment necessary for a successful field test is facilitated. 

Each chapter also includes sections on the general problem, preparations 

needed for the tests, sampling procedures, and on-site analysis or packaging 

of samples for shipment. 

Chapters VII specify a Leve• i analysis scheme along with a description 

of the analysis for each of the sample types described. These three chapters 

are entitled: Analysis of Inorganic Materials, Analysis of Organic Materials, 

Particulate Morphology and Identification, and Biological Testing. The 

schemes identify the methods of analysis, anticipated output and. predicted 

level of effort required to implement each analysis scheme. 

This manual also identifies the ancillary process data required to 

estimate mass emission rates, emission rates per unit of products or other 

calculations necessary for an environmental assessment. The accuracy 

requirements are consistent with the Level I environmental assessment 

philosophy. 

This manual has been made as specific as possible, although it is 

recognized that it is impossible to specify the exact sampling and analysis 

procedure for every possible circumstance. When situations arise where 

alternative Level l sampling and analysis procedures are necess.ary or 

desired, the contractor is directed to submit his alternate plan to his 

project officer and the Process Measurements Branch, IERL-.RTP, Research 

Triangle Park, for approval before actual work is initiated. 

xIv 
CHAPTER I 

STRATEGY AND GENERAL INFORI•ATION 

The Process Measurements Branch of IERL/RTP has developed a threetiered or phased approach to performing an environmental source assessment. 

In this phased approach, three distinctly different sampling and analytical 

activities are envisioned. While each of the three phases is briefly described in Section 1.1, this procedures manual focuses on the Level i sampling•and analysis effort. 

This manual describes for an experienced professional a set of sampling 

and analytical procedures which are compatible with the information requirements of a comprehensive Level I environmental assessment. This manual is 

not intended for use by inexperienced personnel. A comprehensive environmental assessment involves multimedia environmental source sampling. The 

techniques described in Chapters II through VI will provide an adequate 

sample of fugitive air and water emissions, ducted air and water emissions, 

liquids and slurries, and solids for the analyses described in Chapters Vll 

through X. The overall sampling and analysis effort is designed to be 

quantitiative in nature with an overall accuracy of a factor of ±2 to 3. 

I.I DEFINITION OF STRATEGIES 

The phased sampling and analytical strategy was developed to focus 

available resources (both manpower and dollars) on emissions which have a 

high potential for causing measurable health or ecological effects, and to 

provide comprehensive chemical and biological information on all sources 

of industrial emissions. Discussions of this philosophy, the informationcost benefits, and a summary of the application of the phased approach to 

sampling and analysis follow. 

1.1.1 The Phased Approach 

The phased approach requires three separate levels of sampling and 

anal•tical effort. The first level utilizes quantitative sampling and 

analysis procedures accurate within a factor of 2 to 3 and: I) provides 

preliminary environmental assessment data, 2) identifies problem areas, 

and 3) formulates the data needed for the prioritization of 
energy and industrial processes, streams within a process, components within a stream, and classes of materials for further consideration in the 

overall assessment. The second, Level 2, sampling and analysis effort, 

after having been focused by Level 1, is designed to provide additional 

information that will confirm and expand the information gathered in 

Level 1. This information will be used to define control technology needs 

and may, in some cases, give the probable or exact Cause of a given problem. The third phase, Level 3, utilizes Level 2 or better sampling and 

analysis methodology in order to monitor the specific problems identified 

in Level 2 so that the critical components in a stream can be determined 

exactly as a function of time and process variation for control device 

development. 

1.1.2 Strategy of the Phased Approach 

The phased approach recognizes that it is impossible to prepare for 

every conceivable condition on the first sampling or analysis effort. In 

some cases, unknown conditions and components of streams will result in 

unreliable information and data gaps that will require a significant percentage of the sampling or analysis effort to be repeated. 

There is a possibility that many streams or even the entire installation may not be emitting hazardous substances in quantities of environmental 

significance. Conversely, certain streams or sites may have such 

problems that a control technology development program can be initiated 

in parallel with a Level 2 effort. If either of these situations coulld be 

determined by a simplified set of sampling and analysis techniques, considerable savings could result in both time and funds. 

A second possibility is that budgetary limitations may require prioritizing a series of installations so that the available funds can be used 

in assessing those installations most in need of control technology. Here 

again, a simplified sampling and analysis methodology would be advantageous 

to the overall environmental assessment effort. 

2 
The phased approach offers potential benefits in terms of the quality 

of information that is obtained for a given level of effort and in terms 

of the costs per unit of information. This approach has been investigated 

and compared to the more traditional approaches (Ref. i)and has been found 

to offer the posibility of substantial savings in both time and funds 

required for assessment. 

The three sampling and analysis levels are closely linked in the 

overall environmental assessment effort. Level I •dentifies the questions 

that must be answered by Level 2, and Level 3 monitors the probl:ems identified in Level 2 to provide information for control device design and development. For example, if a Level I test indicated that polycyclic organic 

material (POM) might be.present in significant amounts and gave a positive 

mutagenicity test, Level 2 sampling and analysis wouldbe designed to 

determine the exact quantities of organic constituents, the percentage of 

POM, and the identity of as many specific POM compounds present as economically possible. In addition, using the Level I data and any available 

Level 2 results, the sample would be retested for cytotoxicity and mutagenicity in order to confirm and expand the total bioassay information. A 

test for carcinogenicity would also be run if the results of these tests 

are positive. The entire data package could then be used to design the 

control technology research and development needs for the stream in the 

Level 3 effort. 

A detailed explanation of Level i and Level 2 sampling and analyses 

along with their expected outputs is given in the following sections. 

Because Level 3 sampling and analysis is totally process-and even sitespecific, neither a general approach nor sampling and analysis methodolo• 

gies can be specified and for this reason, Level3 will not be discussed 

further. 

1.1.2.1 Definition of Level 1Samplin• and Analysis 

The Level 1 sampling and analysis goal is to identify the pollution 

potential of a source in a quantitative manner with a target accuracy factor 

of ±2 to 3 (0.3). At the initiation of an environmental assessment, 

little is known about the specific sampling requirements of a source both 

practically and technically, and hence the emphasis is on survey tests. 

3 
For this reason, no special procedure is employed in obtaining a statistically representative sample and the chemical, physical, and biological testing has survey and/or quant.itative accuracy •onsistent with the characteristics of the sample. 

At this level, the sampling and analysis is designed to show within 

broad general limits the presence or absence, the approximate concentrations, and the emission rate of inorganic elements, selected inorganic 

anions, and classes of organic compounds. The particulate matter is further 

analyzed through size distribution as well as microscopic examination in 

order to determine gross physical characteristics of the collected material. 

Biotesting is designed to obtain information on the human health effects 

and biological effects of the sample. 

The results of this phase are used to establish priorities for additional testing among a series of energy and industrial sources, streams 

within a given source, and components within streams. Level I has as its 

most important function the focusing of sampling and analysis programs on 

specific streams and components for the Level 2 effort. It delineates 

specific sampling, analysis and decision-making problem areas, and directs 

and establishes the methodology of the Level 2 effort so that additional 

information needs can be satisfied. If it can be proven that equivalent 

Level 1 data exist for all streams of interest, then a Level 1 effort 

need not be conducted. If partial data exists, Level 1 must be performed 

on all streams. 

Another possible exception to the strict adherence to the Level I 

technique involves the application of slightly more sophisticated procedures where specific pollutants of high current interest are concerned. 

In this case, the approach would involve a more complex Level 2 sampling 

and/or analytical strategy in the initial Level 1 plan. 

1.1.2.2 Definition of Level 2 Samplin• and Analysis 

The Level 2 sampling and analysis goal is to provide definitive data 

required in the environmental assessment of a source. The basic questions 

to be answered and major problem areas have been defined in Level I for 

maximum cost and schedule efficiency. Consequently, Level 2 sampling and 
analysis is characterized by obtaining statistically representative samples, 

accurate stream flow rates, and by identification and quantification of 

specific organic species and/or classes and inorganic elements and/or 

species. Biotesting in selected areas is expanded. 

Although Level 2 sampling and analysis require the use of methodology 

considerably more complex than that used in Level I, it will not always 

be true that a Level 2 effort at a given site will be more manpower intensive than the Level 1 effort. In many cases, the Level 1 effort will so 

thoroughly delineate the streams and components of these streams of interest 

that the Level 2 effort may be less costly than the Level 1 effort. Some 

possible cases are: 

• A flue gas source where volatile organic components were 

the only materials .found in a sample which were of environmental interest; thus additional samples would be needed 

for complete analysis. The additional samples could be 

taken using a simple organic sampling train operated by one 

man out of a Car instead of the SASS train operated by a 

crew from a van. 

A source where the only stream of interest is an ash or 

refuse stream with significant leachable inorganic elements of environmental interest.• On Level 2, a representative sample would be taken and accurately analyzed 

only for the elements of interest. 

A fugitive emissions problem which can be defined by conventional instruments and a meteorological station operated 

from a conventional van. 

A source emitting Particulate matter of which only one or 

two size fractions are significant or of interest for either 

organic components or specific trace inorganic elements. 

A source that only has a water problem, and either organic 

components or trace inorganic elements must be analyzed and 

the stream monitored for accurate flow rates. 

A source where trace inorganic elements are found at generally low enough levels where they are not of environmental 

significance. The fuel or other raw materials may be 

monitored to establish that the inorganic constituents are 

never input at levels high enough to cause an environmental 

problem. 

Level 2 would thus provide sufficient detailed information concerning 

the problems delineated by Level 1 such that control stream priorities, 

5 
total environment insult, and an initial estimate of process/control system 

regions of overlap can be established. 

1.2 MULTIMEDIA SAMPLING PROCEDURES 

The Level I procedure described in this manual can be utilized to 

acquire process samples, effluent sampleS, and feed stock samples. The 

Level 1 environmental assessment program must, at a minimum, acquire a 

sample fromeach process feed stock stream, from each process effluent 

stream, and of fugitive air/water emissions. The feed streams data are 

necessary to establish a baseline for comparison. The effluent stream 

sampling program is required to determine the mass emissions rate and 

the environmental..insult which will result. Sampling and analytical procedures which are required to support in comprehensive environmental 

source assessment must be multimedia in nature. 

1.2.1 Classification of Streams for Sampling Purposes 

The basic multimedia sampling strategy shown in overview form in 

Figure 1 has been organized around the five general types of sampling found 

in industrial and energy producing processes rather than around the analytical procedures that are required on the collected samples. This facilitates the complex and difficult task of organizing the manpower and equipment necessary for successful field sampling and establishing meaningful 

units of cost. 

The five sample types are: 

• •as/Va o•_•- These are samples for light hydrocarbon and 

inorganlc gas analysis, They include samples from input 

and output process streams, process vents, and ambient 

air. 

o Liquid/Slurry Streams Liquid streams are defined as those 

containing less than 5 percent solids. Slurries are defined 

as those containing greater than 5 percent solids. Nonflowing pastes are considered solids. 

• Solids -These include a broad range of material sizes 

from large lumps to powders and dusts, as well as nonflowing wet pastes. Because the distinction between Solids 

and slurries can become blurred, the reader should Consult 

both Chapters V and Vl when in doubt. 

• Particulate or Aerosol Samples -This involves sampling in 

contained streams such as ducts or stacks. 

• Eu•itive Emissions -These are gaseous and/or particulate 

emissions from the overall plant or various process units. 

Flow diagrams which show the overall relationship of the samples to 

the analysis scheme are shown in Figures 2 and 3. 

1.2.2 Phased Approach Sampling Point Selection Criteria 

The selection of sampling points in processes where phased level 

sampling techniques are employed relies on the concept previously stated: 

that Level 1 sampling is oriented towards obtaining quantitative data with 

relaxed accuracy requirements for determination of the pollution potential 

of a source, whereas Level 2 sampling is intended to acquire more accurately 

the data necessary for a definitive environmental assessment on prioritized 

streams. Stream parameters such as flow rates, temperature, pressure, and 

other physical-characteristics will be obtained on both levels within the 

accuracy requirements of a given level of sampling. For example, a Level 1 

particulate matter sample is obtained at a single point under pseudoisokinetic 

conditions. This means that the sample is acquired at the point of average 

velocity which has been determined by a velocity traverse taken at typical 

points in the stream. The sample is withdrawn by means of,a flow rate through 

the SASS Train Cyclones (see Chapter Ill) by using a probe nozzle which is 

specifically selected for isokinetic conditions; however, this flow rate 

must not be allowed to change since a change in flow rate will alter the 

particle cutoff efficiency of the cyclone system. In Level 2, however, 

where quantitative data are required, isokinetic samples must be withdrawn 

using a full traverse with a port in specific locations away from ducting 

bends and other obstructions in order to ensurea sample representative of 

the actual effluent. The recommendations in this manual are restricted 

to Level 1 sampling and analysis criteria only. 

8 
INORGANICS 

ELEMENTS AND 

LCA•/MS 

SASS TRAIN [NORGANICS ABSORPTION IMPINGERS 

.•,.RACTION I-'•E OIIGANICS ][IN•Ih•II•CMRAiCS•I•AI•AsTION 

SAME AS ABOVE 

ON-SITE GAS 

INORGANIC CHROMATOGRAPHY OR 

(GRAB) APPROVED ALTERNATIVE 

•-,[ EXTRACTION ]• 

PHYSICAL SEPARATION 

INTO 8•CLASSES 

SEE CHAPTER X 

.•LIQUOT FOR GAS 

PHYSICAL SEPARATION 

LC/IR/MS 

INTO FRACTIONS, 

Figure 2. Basic Level 1 Sampling and Analytical 

Scheme for Particulates and Gases 

9 
LEACHABLE 

MATERIALS 

ORGANICS 

BIOASSAY SEE CHAPTER X 

QA PHYSICAL SEPARATION 

INTO FRACTIONS LC/IR/MS 

ELEMENTS AND 

SELECTED ANIONS 

SOLIDS 

SOLID/ 

LIQUID 

LIQUIDS 

INORGANICS ELEMENTS AND 

SELECTED ANIONS 

PHYSICAL SEPARATION 

ORGANICS INTO FRACTIONS 

LC/IR/MS 

INORGANICS ELEMENTS AND 

SUSPENDED NIONS 

SOLIDS 

ORGANICS 

BIOASSAY SEE CHAPTER X 

INORGANICS ELEMENTS AND 

SELEaED ANIONS 

SELECTED 

WATER SEE• SECTION 7.2.6 TESTS CHAPTER 

(AQUEOUS) 

ORGANIC 

EXTRACTION 

OR DIRECT 

ANALYSIS 

ORGANICS EHYSICAL SEPARATION 

>CI2 INTO FRACTIONS 

LC/IR/MS 

ORGANICS ALIQUOT FOR GAS 

<C12 CHROMATOGRAPHIC 

ANALYSIS 

Figure 3. Basic Level 1 Sampling "and Analytical Scheme for Solids, Slurries and Liquids 

10 
Similar considerations apply to site Selection for sampling liquids 

and solids. On Level 1, liquid samples can be taken from tanks or other 

container• without depth •integration and from pipes using a simple tap 

sample rather than using a multiported probe to take a time integrated 

sample. In slurry streams, an effort should be made to sample a turbulent 

or well mixed area, but this and other requirements can berelaxed considerably for Level I site selection. 

In the case of solids sampling, the standard procedures used in sampling piles and stationary containers are relaxed on Level 1 both by taking 

fewer increments to make a composite and by relaxing or eliminating the 

requirements for depth integrated sampling. For moving solid streams, a 

simplified sample is obtained by reducing or eliminating the number of 

increments required for the time averaging aspect of the s•mplingprocedure. 

in most cases, Level 1 sampling method• generally encompass approved 

standard EPA, ASTM, and API techniques. Modifications are then made to 

these techniques to adapt them to the time and cost constraints consistent 

with the Level 1 sa•ling philosophy. These modifications include: 

i) reducing port selection criteria; 2) eliminating the requirements for 

traversing, continuous isokinetic sampling, and.replicate sampling in the 

collection of particulate matter; and 3) use of grab samPles for ambient, 

water, and solid samples. Using these sampling point selection criteria, 

a sampling point selection model illustrating Levels I and 2 sampling 

points as developed in another program (Ref. 1) is shown in Figure 4 for a 

wet limestone spray tower system installed at Paducah, Kentucky. 

1.2.3 Stream Prioritizat•on Using the Phased Approach 

Industrial and energy producing processes are highly complex systems 

consisting of a wide variety of interrelated components. Level 1 sampling 

will show that many influent and effluent streams have no environmentally 

significant impact. These data can be used to reduce the number of samples 

required for Level 2 substantially, and can permit reallocation of resources. 

Thus, comprehensive stream prioritization based on the Level 1 sampling 

and analysis effort will identify streams with widely varying environmental 

priorities. In many cases, the Level 1 information will be sufficient to 

11 

eliminate certain streams entirely from the Level 2 effort, In other cases, 

limited resources may require the omission of Certain low priority streams. 

1.3 DATA REQUIREMENTS AND PRE-TEST PLANNING (Ref. 1, 2, 3, 4, 5, 6) 

The final decision to test a particular plant will be the result of 

the prior•tization studies and of the preliminary selection process based 

on the site selection criteria of a given program, and on the data requirements of the overall program or general EPA objective. 

Before the actual sampling and analysis effort is initiated, the data 

requirements must be established and used to help identify test requirements as well as any anticipated problems. The following paragraphs present a general summary of these requirements and planning function which 

must be applied or expanded to meet the needs of the individual tests to 

be performed. Specific recommendations concerning data requirements associated with each of the process streams are discussed in the appropriate 

chapters of this manual. 

1.3.1 Process Data Needs 

Before traveling to a plant for a pre-test site survey, it is necessary 

to become familiar with the process used at the site. This involves 

understanding the chemistry and operational characteristics of the various 

unit operations as well as any pollution control processes. It is particularly important to know that detailed relevant process data are necessary 

for the sampling and analysis effort as well as for the overall environmental assessment. The reasons for this are: 

1) From a knowledge of the process and the composition of 

input materials and products, conclusions about pollutants 

likely to be found in waste streams can be drawn 

2) One must know where to look for waste streams, including 

fugitive emissions 

3) One must know how plant operating conditions are 

likely to affect waste stream flow rates and 

compositions 

4) Thorough familiarity with the process permits design 

of a proper sampling programs 

13 
5) Thorough knowledge of the interrela•ion•k-•mo• 

process variables permits extrapolation to conditions in other sizes of the system being assessed, and 

6) Detailed process data are the basis from which control technology development programs proceed, should 

environmental assessments indicate such need. 

Familiarization with the process is also necessary so that a checklist of 

the requisite data can be developed, including temperatures, pressures, 

flow rates, and variations of conditions with time for the pre-test site 

survey. 

For any given sampling and analysis task, the data collected must 

be consistent with the overall Level I objectives. Thus, the minimum 

amount of data for a given stream is flow rate per unit time at a given 

temperature and pressure. Additional data that may be necessary are 

average flow per unit time, the effect of process variations on stream 

flow and composition., and normal variations in flow and compositions with 

variations in process cycling. Appendix A contains a checklist of appropriate data that may be collected. It is expected that professional 

sampling and analysis personnel in conjunction with the EPA Project 

Officer and PMB-!ERL-RTP will select the appropriate data requirements for 

a given industry. 

1.3.2 Pre-test Site Surve• 

After establishing the necessary process data needs and selecting a 

tentative set of sampling points, a pre-test site survey should be performed. At the test site, the survey team should meet with the plant 

engineer to verify the accuracy of the existing information and arrange 

for the addition of any •issing data• Using this information, the survey 

team will then proceed to select the actual sampling sites with the following criteria in mind: 

The sampling points should provide an adequate base of data for characterizing the environmental impact of the 

source on the environment within a factor of 2 to 3. 

When possible, each sampling point should provide a 

representative sample of the effluent streams. (This is a desirable but not a strict requirement of Level I sampling). 
o The sampling site must have a reasonably favorable 

working environment. The Survey personnel must consider the temperature and noise level in the sampling 

areas, if protection from rain or strong winds exists, 

and whether safe scaffolding, ladders, pulleys, etc., 

are present. 

The identification of support facilities and services is an essential 

aspect of the site survey. In an effort to minimize the requests made 

upon the operators and scheduling problems for these support services, 

it is desirable that the test van operate completely independently of 

external support facilities. The large electrical power requirements of 

the test van and th• sometimes limited electrical power availability at 

many industrial/commercial sites make it important that the van carry 

sufficient electric generating capacity to operate all test and support 

equipment. The van should also carry a water tank for essential services. 

Where available, electrical power and water services may be connected for 

auxiliary service. These and other specific mobile laboratory fabrication 

requirements for Level 1 Sampling and analysis are presented in Appendix B. 

The results of the pre-test site survey must be sufficiently detailed 

so that the field test problem of sampling the correct process stream 

at the proper sampling location and using the appropriate methodology will 

be completely defined prior to arrival of the field test team at the source 

site. 

1.3.3 Pre-test Site Preparation 

Since in most cases the manpower requirements for site preparation are 

usually low to moderate, a relatively low effort was assumed for site 

preparation, under the assumption that major modifications required in 

extreme cases are out of the scope of this manual. 

Thus, it was assumed that the erection of scaffolding and the provision 

of power will be a major part of site preparation; a further assumption was 

that the required manpowerwill be associated to a large eXtent with stack 

sampling, the most complex sampling procedure. Preparation of other sites 

was assumed to be minimal and/or part of the actual sampling procedure. 

The installation of special samplers, valves, fittings, etc. is considered 

beyond the scope of a Level 1 sampling effort.. 

15 
1.4 ANALYSIS OF.SAMPLES 

Chapters Vll through X specify analysis schemes and procedures that 

will provide data relatable to all existing EPA standards and those additional data requirements specified above for Level 1 environmental assessment. These schemes identify accepted methods of analysis, anticipated 

output, and the estimated level of effort required to im•lemen• the analysis scheme. 

There are seven categories of analysis: 

• Organic Analysis Survey techniques are used to 

identify compound classes by functional group. 

• Inorganic Element Analysis Based on spark source 

mass spectroscopy (SSMS) which can perform a general 

survey of all effluent streams for possible inorganic 

elements. 

• Particulate Morphology Inaludes microscopic examination of shape, size distribution, surface features 

and possible source. 

• Water Analysis- Reagent test kits will be used as 

a supplement for those analYses that are•not covered 

by SSMS or organic analysis. 

• Gas Chromatographic Analysis Consists of On-site analysis of gaseous and/or low boiling organic and inorganic 

s•ecies. 

• Opacity- This test will be performed using a simple 

Ringelmann Chart. 

• Bioassay Testing Includes selected health and 

ecological testing on all solid and liquid samples, 

and is designed to measure the environmental and 

health effects potential of a given source stream in 

a broad and general manner. 
Fable 1 shows the recommended sample volumes that must be collected 

which will result in the listed sensitivities when the recommended analysis method is used. These sensitivitieshave been selected by PMB-IERL-RTP 

for both inorganic and organiccomponents so that all species Of current 

interest can be analyzed at levels which at present are the lower limits 

of environmental concern. 

1.5. ACCURACY AND PRECISION OF RESULTS 

The accuracy and precision requirements for a Level 1 environmental 

assessment have been discussed in general terms as being quantitative within 

a factor of ±2 to 3. In general, most of the sampling and analysis procedures which have been selected for this Level 1 manual are adaptations of 

standard EPA, ASTM, API, etc., methods which have a accuracy and/or precision factor of ±10-20 percent or better. These requirements, however, 

have been reduced to fit the .economic and philosophical constraints for a 

Level 1 environmentalassessment. In order to determine emissions from a 

given site to within a factor of 52 to 3, both the sampling and analytical 

methods must have a precision which is better than a factor of 2. Thus, if 

the sampling parameters for a given sample along with the corresponding analyses both had a precision within a factor of 2, then the overall precision cam 

be calculated on the basis of equation (i). 

2 

•tota] •/•sampling + •nalysis eq.(1) 

Then, if x were the true value, and the precision limits for both sampling 

and analysis are within a factor of 2.0, the individual values would 

range from O.SX to 2X. Substituting these values into equation (1) 

gives a range from O.3X to 3.8X for the precision of the final value which 

is to be used for the environmental assessment. (For the lower limit 

Otota I = X •0..•= O.3X and for the upper limit, •total X +•8X 2 3.8X). 

17 
Table I. Recommended Sample Sizes and Detection Limits 

Sample Source Sample Type Inorganic Organic 

Stack 30m3 3 (1,06Oft) 

Gas d) 3 liters 

Ambient Air 480m 3a) 

(17,00Oft 3) 

Liquid 10 liters 

(2.5 gal) 

Solid I kg 

(2.2 Ib) 

a)' Particulate Matter O.01ug/m 3 2•g/m 3 

lOug/m 3 

General Components, 1 mg/• 3e) lO0pg•m 3f) •I Sulfur Compounds g) l•g/m j 1•g/mJ 

Particulate Matter O.01pg/m• 30•g/• 3 a) 

b) Sorbent Trap, >C12 O.01,g/m• l•g/mJ• 

c) Sorbent Trap, •6-C12 O.01•g/m j lO•g/m j 

lpg/l h) 10•g/l 

1 mg/g 100 ng/g 

a) 

b) 

c) 

d) 

f) 

g) 

h) 

At STP 

The analysis is terminated for organic material if less than 15 mg 

(0.5 mg/m 3) of organic components are extracted from the total sample. 

Assumes that the XAD extract is 2 liters and a 1 •l sample is injected 

into a G.C. with a flame ionization detector with a 0.1 ng detection 

limit. 

A maximum sample •ize of 10 ml is assigned for all cases. 

Detection limit is approximately 1 ppm. 

Detection limit is approximately 0.1 ppm. 

petection limit is approximately 1 ppb. 

Assuming a 0.1 ml sample for SSMS electrode formation and a lO-9g 

instrument sensitivity. 

18 
From this explanation, it can be seen that when it is stated that 

results are accurate with a factor of three, it means that actual va•ue 

may lie in a range from 1/3 that value to more than 3 times the value. 

It should be noted that this is a target accuracy and that some procedures 

may easily meet these criteria while for others, it may be a slightly 

optimistic. 
CHAPTER II 

GAS AND VAPOR SAMPLING METHODOLOGY 

2.1 INTRODUCTION References I, 3, 4, 7, 8, 9, 10) 

This chapter discusses the general methodology for obtaining gaseous 

samples for analysis. Obtaining a representative sample from a simple 

gaseous stream can be complicated by stratification from incomplete mixing 

or by variations in stream components over a period of time. For the purpose of Level 1 assessment, a single grab sample is sufficient, although 

planning is necessary to ensure that sample acquisition is made at a 

reasonably representative point (position and time) in the stream or process cycle (see Chapter I). 

This chapter discusses the sampling methodologies applicable to the 

following stream types: 

• Process streams, vents, and effluents. 

• Fugitive gaseous emissions. 

Gaseous process streams refer to contained gases being transported 

from one area to another. These streams exist under conditions which range 

from a slightly negative pressure to highly pressurized pipeline systems. 

Also, the contents of gaseous process streams range from corrosive and 

toxic process effluents to complex organic mixtures. For the purposes of 

source assessment, only those internal streams which process influents and 

effluents to the environment are considered for sample acquisition. Consequently, internal process streams are seldom of concern since they do 

not constitute influents or effluents in contact with the environment. 

Exceptions to this rule involve such streams existing prior to control 

devices or which are held for interim periods prior to discharge, such as 

holding or surge systems situated in-line prior to flare discharge. 

Gaseous process vents are generally found in tank farm areas or in 

various system operations requiring pressure surge variability. 

Gaseous process effluents refer to ducts or flues which are exhausted 

to the atmosphere and for the purposes of this chapter only the CI-C 6 

20 
and inorganic gaseous effluents from these units are considered. The 

particulate content along with higher molecular weight hydrocarbons are 

obtained via the Source Assessment Sampling System, which is discussed in 

detail in Chapter III. 

FuBitiv e Baseous emissions result from various process leaks such as 

those found in pumps, valve seals, ducting or process connections and the 

open transfer or storage of liquid process raw materials, intermediates, 

and products. 

2.2 SAMPLING TEST PREPARATION (References I, 3, 4) 

Complex process operations represent diverse conditions which require 

careful planning of the sampling activity. This planning should be based 

on data compiled from actual plant records or from plant personnel familiar with the characteristics of each sampling location. A pre-test 

Level I site survey of process streams and vents for sampling g•seous components involves the following six steps: 

I) Obtaining detailed, accurate process flow diagrams. They 

should be as current as possible and can be updated and 

supplemented by conversations with plant personnel. 

2) Tracing the process flows to establish gaseous outputs. 

Using the process flow diagrams as a guide, a physical 

inspection of the systemmust be conducted to uncover any 

undocumented output sources or unrecorded equipment 

modifications. 

3) Locating and itemizing process vents. 

4) 

s) 

Locating and itemizing stacks and flares. 

Selecting representative sites. The goal of Level 1 

sampling is to uncover any pollution sources and to 

quantify the emission levels within a factor of 

±2 to 3. If, in this sense, toxic materials are discovered, then a fu11-scale Level 2 analysis will be 

initiated to quantify the problem. Thus, the selection of representative Level l sampling sites should 

reflect this philosophyof obtaining the type of a 

sample for analysis rather than typical compliance 

testing criteria. 
6) Recording the physical parameters of the stream in as much 

detail as possible to facilitate the sampling effort and 

to aid in post-sampling data reduction. Specific guidelines regarding parameters of interest may be found in 

Appendix B. 

Aside from these genera] considerations, there are two specific requirements for gas and vapor sampling: 

i) All process streams and vent systems recirculated into 

process streams will require in-line valves for 

sampling. 

.2) All vents to the atmosphere require a means of access 

as well as suitable working space for personnel 

involved in the sampling process. 

2.3 GAS SAMPLING TECHNIQUES (References 11, 12, 13, 14, 15, 161, 17, 18) 

As stated in Section 2.1, a single grab sample of each stream in 

question is sufficient for Level I needs. The grab sample may be taken 

in one of three ways, depending on the pressure of the stream in question. 

These three grab sample types are high pressure line, grab purge and 

evacuated grab samplers, and are illustrated in Figures 5, 6 and 7 

respectively. 

2.3.1 High Pressure Line Grab Samples 

The apparatus illustrated in Figure 5 is used when the pressure is 

high enough in the stream to require a side-split-bleed to provide a sufficient pressure reduction for effective bulb purge. The •ampling bulb 

is the dual valve positive displacement type aBd is 3 liters in volume. 

The bulb must be purged with approximately tem volumes of the stream 

gas before the sample is isolated. 

A smali glass wool plug is inserted in-line prior to sampling to 

prevent the influx of particulate matter into the bulb during the purge 

and sample collection periods. 

22 



2.3.2 Slight Positive Pressure Grab Purge Sampling 

The positive displacement dual valve glass sampling bulb described 

above may also be used in ducts, pipes or vent systems where line pressure is slight. Since the pressure is slight, however, a side-bleed is 

not required for pressure reduction. Figure 6 shows the apparatus configuration for this sampling method." A small glass wool plug is inserted 

in-line before sampling is begun, and approximately ten volumes of sample 

gas must be purged through the bulb prior to isolation of the sample. 

2.3.3 Negative Pressure Evacuated Bulb Sampling 

Figure 7 illustrates the sampling bulb used for sampling negative 

pressure systems or open effluent lines such as vent systems or point 

fugitive emissions (the latter are discussed in Chapter IV). 

The bulb is also 3 liters in volume; however, it is the single 

valve evacuated type rather than the dual valve positive displacement 

type. The number of bulbs required for a given sampling effort will be 

known as a result of the pre-test site survey (Section 2.2). The bulbs 

are then evacuated in the field using a small vacuum pump from the mobile 

van or trailer. The evacuated bulbs are then taken to their respective 

sites for sample acquisition. 

The entrance nozzle of the bulb must be fashioned so that a piece of 

tubing can be attached. The tubing acts as a probe to be inserted into 

either the duct or vent and should be made from I/4 inch OD Teflon tubing 

12 inches in length. 

The tube attached to the evacuated bulb is inserted into the vent or 

negative pressure duct and the sample is withdrawn. 

2.3.4 General Considerations 

For safety reasons, all of the above described sampling bulbs must 

be encased in a protective jacket of styrofoam. 

Cleaning of the containers is especially important in order to prevent contamination of samples. New glass containers should be conditioned 

prior to use by allowing them to stand full of distilled water for several 

days. This conditioning process may be accelerated by rinsing the container with dilute hydrochloric acid followed by distilled water. 
After use, containers should be thoroughly cleaned. A 2:11 mix of 

Alconox or abrasive cleaner and water may be used followed by a tap water 

rinse. The container is then rinsed with a i:1 mixture of H2SO 4 and 

HN03, followed by a tap water rinse of the acid, followed by a final flush- 

•ng with three volumes of high purity water. 

Sampling bulbs cleaned in this way may then be dried, filled with 

nitrogen and stored until ready for Use. 

2.4 SAMPLING PROCEDURES 

This section briefly describes the problems and considerations 

involved in sampling process streams, fl•ues and ducts, and vents. 

2.4.1 Process Streams, Flues and Ducts 

A prpcess stream may require any of the three previously described 

grab sample types depending on the nature of the stream. A stream under 

elevated positive pressure will require the apparatus described in Section 2.3.1. Streams under only slight positive pressures and streams 

under negative pressures will require the apparatus described in Sections 2.3.2 and 2.3.3 r•spectively. 

Whatever sample type the process conditions require, the primary 

issue involves the careful planning needed for the selection of the.most 

representative sampling point. Frequently, pipeline, duct and vent systems consist of composite streams wherein the main or primary stream is 

joined in one or more places by secondary streams. When this is the case, 

a sampling point must be Chosen far enough downstream of the joint to 

ensure component homogeneity. An optimum choice for sample withdrawal in 

gaseous systems is at a point downstream from a bend in the pipe or duct, 

since a bend induces turbulence and therefore homogeneity. 

In-!ine valves or sampling ports must also be assessed for their 

compatability with available apparatus. For example, the process port 

or valve entrance will in many cases be larger than the bulb entrance. 

To solve this problem, a series of.one-hole stoppers Of various size 

increments may be used to fit over the bulb nozzl'e entrance. 

27 
For the high pressure (Figure 5) and low pressure (Figure 6) sample 

collection, all sample containers must be purged with approximately ten 

volumes of the sample gas prior to collection of the sample (•his should 

take approximately 2 minutes). For the subatmospheric pressure (Figure 7) 

sample collection, the sample should be collected by slowly cracking the 

valve and letting the sample bleed in (approximately 30 seconds). 

2.4.2 Vents 

Vent systems generally consist of relief tubes or exit.ducts regulated by in-line pressure release valves. Vents are found in holding 

tanks and storage tanks and are usually discharged into the air when the 

tank pressure exceeds the pressure setting of the in-line valve. The 

velocity of the gases being emitted from vent systems, as well as the time 

duration of the vent cycle, is directly proportional to: 

1) The diameter of the vent tube, 

2) The headspace volume of the system being vented., and 

3) The pressure setting of the in-line relief valve. 

Units or tanks with pressure vent releases to ambient air are sampled 

with a 3-1iter evacuated bomb (Figure 7). The important considerations in 

obtaining vent gas samples are: 

• The sample must be taken whi|e the vent cyc|e is in pro• 

gress. (Cycle periods for individual processes should 

be known as a result of the pre-test survey). 

• The entrance nozzle of the bomb should be situated so 

that a representative sample of the vent effluent is 

obtained without contamination by ambient air. 

2.5 SAMPLE HANDLING (References 3, 14• 15) 

All gas samples described in this chapter will be analyzed by gas 

chromatography using procedures described in Chapters VII and VIII. 

Because many streams contain components which will interact with one 

another, it is .important that the sample be delivered to the mobile unit 

as soon as possible to avoid significant alteration. 

Glass sampling bulbs must be encased in styrofoam protectors to avoid 

breakage and possible injury to members of the sampling team. 
CHAPTER III 

GASEOUS STREAMS CONTAINING PARTICULATE MATTER 

3.1 INTRODUCTION 

Stationary source particulate matter sampling and analysis have been 

restricted to streams of high mass loading because the sampling flowrates 

of the sampling equipment have not been high enough to collect an adequate 

amount of material in a reasonable length of time (Ref. 3, 6, ]9). In 

addition, healtheffects data indicate that an adequat e assessment of the 

collected particulate matter requires size fractionation into at ]east 

four size fractions (Ref. 6• 20). Also, provision must be made for the 

collection of volatile trace elements and organic species. For all of 

these reasons, the EPA (IERL-RTP) has developed and specified the use of 

the Source Assessment Sampling System* (SASS) train (Figures 8, 9 and lO) 

for the collection of particulate and volatile matter in addition to the 

gaseous samples discussed in Chapter II. 

The sampling train consists of a stainless steel probe which enters 

an oven module containing 3 cyclones and a filter. Size fractionation is 

accomplished in the series cyclone portion of the SASS train, which 

incorporates the cyclones in series to provide large quantities of particulate matter size-classified into three ranges: a) >lO •m, b) 3 •m to lO •m, 

and c) •m to 3 •m. Together with a standard 142 mm filter, a fourth cut, 

<l •m is obtained. Volatile organic material is collected in a XAD-2 

sorbent trap. The XAD-2 trap is an integral part of the gas treatment system which follows the oven containing the cyclone system (see Figure 8). 

The gas treatment system is composed of four primary components: the gas 

conditioner, the XAD-2 adsorbent trap, the aqueous condensate collector, and 

a temperature controller. The XAD-2 sorbent is a porous polymer resin with 

the capability of adsorbing a broad range of organic sPecies. Some trapping 

of volatile inorganic species is also anticipated as a result of simple 

impaction. Volatile inorganic elements are collected in a series of 

impingers. The pumping capacity is supplied by a lO-cfm high volume vacuum 

Manufactured by Aerother• Corporation, 485 Clyde Avenue, Mountain View, Ca., 94042, Tele. (415) 964-3200. 

29 
>Z 

O> 

'uO 

Z 

30 
31 
,32 
pump, while required pressure, temperature, power and flow conditions are 

obtained from a main controller. 

A schematic for flue gas sampling and analysis, which forms the basis 

for this chapter, is shown in Figure II. Details of the sample handling 

and transfer procedures are presented in Section 3.5. 

Knowledge ofthe size distribution of particles emitted from given 

industrial or energy sources is important to considerations of engineering, 

environmental and health effects. In the first instance, design and/or 

evaluation of particulate matter control devices rely upon these data. 

Secondly, it may be predicted that the large particulate ma•ter fraction 

will deposit inclose proximity to the source, whereas the fine particulate 

matter which is more difficult to control, will be carried airborne for long 

distances. These minute particles can often affect weather and visibility 

and may possibly modify the heat balance of the earth. 

'3.2 PARTICULATE MATTER SAMPLING METHODOLOGY (References 4, 15, 21, 22, 23) 

In normal research and compliance testing, great care is taken to 

ensure that isokinetic conditions are maintained and that a proper traverse 

is performed. A Level l sample is acquired at the point of average velocity 

which is determined by a velocity traverse. The sample:is withdrawn at a 

constant flow rate using a nozzle which is specifically selected for isokinetic conditions when the testis initiated. For the accuracy requirements of Level l, this flowrate is allowed a slippage of from •30 percent 

to +50 percent Of the specified isokinetic rate. Conditions existing outside of. the above specified marginmust result in SASS train shutdown for 

an inspection of the problem. The cause of the deviation from isokinetic 

conditions frequently may be traced to cyclic variations in grain loadings 

or simply to • continuous high grain loading density, as.well as an increase/ 

decrease in gas velocity, or the inability of the pump to pull the volume 

required to meet .particulate matter collection requirements. 

Two possible situations occuring within the SASS train will manifest 

pressure variations outside of the acceptable margin. They are: 

I) Clogging of the probe nozzle, and 

2) Clogging of the backup filter. 

The only possible solution in both cases requires SASS train shutdown and 

concomitant probe nozzle cleaning oN filter replacement. 

3.3 PREPARING FOR SAMPLE COLLECTION 

3.3•I Pre-Site Survey 

After performing the general site survey and obtaining the necessary 

process data as described in chapter I, the survey personnel should select 

the appropriate sampling site with the following criteria in mind: 

• When possible, each Sampling point should provide a sample 

which represents as closely as possible the chemical composition 

and mass emission rate of the effluent stream. (This is a 

desirable but not a strict requirement of Level l sampling as 

described in Section 1.3 and 3.2). 

• The sampling site must have a reasonably favorable working 

environment. The survey personnel will consider the temperature and noise level in the sampling areas, whether protection 

from rain or strong winds exists, and whether safe scaffolding, 

ladders, pulleys, etc., are present. 

• Having located the appropriate sampling location, the physical 

characteristics of the stream (temperature, flow, grain density, 

etc.) should be determined from run engineers. 

It is intended that the results of the pre-test site survey be sufficiently detailed, so that the field test problems of sampling the correct 

flue gas stream at the proper sampling location and of using the appropriate 

methodology will be completely defined prior to arrival of the field test 

team at the source site. These data should be recorded in the form of a 

pre-test survey report. 

3.3.2 Personnel Requirements 

The personnel requirements are related to the magnitude of the sampling 

task; however, .certain general correlations can be made. These correlations can be scaled in a reasonably linear fashion and then applied to the 

sampling task at hand in order to tailor manpower and time requirements to 

.fit the task (Ref. l, 6, 24). 

The acquisition of a Level l sample using a SASS train generally requires 

two and i.n some cases, three persons for equipment assembly and disassembly. 

After assembly the •rain requires from one to one and one-half persons for 

operation. The remaining manpower is then available for other on-site 

efforts. 35 
Each SASS train run will consist of approximately a five•hour period 

(specific sample acquisition criteria are described in Section 3.4). The 

number of required personnel for this function will not increase regardless 

of the.number of sample sites, provided that a sufficient time allotment 

exists within the sampling task to allow for consecutive sampling. 

Manpower projections can then be determined by considering the number 

of SASS particulate m•tter •amp1• •qui•d t• C-•rac•e••e the •site in question"• 

the time required for the acquisition of each sample (determined as a function of analytical objectives), and the number of personnel and/or samplers 

available for the task. 

3.3.3 Equipment Preparation for Sample Collection 

The following sections discu•s •.• •p• prepa•at•onrequi• for 

the SASS train, including cleaning procedures of the train components and 

sample containers, and apparatus checkout. The SASS train schematic and 

3.3.3.1 Precleanin• Procedures for the SASS Train and Sample Containers 

(References 3, 4, 6, 25, 45) 

The SASS train is the•most complex sampling unit discussed in 

this manual, and an overall generaiiz•d •ie•ni•g p•Ocedur• cannot be established. Two primary cleaning methodologies are required. The first 

methodology, described in this section, concerns the technique involved 

in producing biologically inert surfaces throughout the SASS train. The 

second methodology, described in Section 3.5 (Sample Handling and Shipment), 

presents the techniques required for cleaning or removing sample from 

various parts of the train after the run. 

The first stage in preparing the sampling train and sample containers 

for sample coliection is prepassivation with a nitric acid solution. All 

surfaces in the sampling train which come in contact with sample, as well 

as all sample containers andcontainers for the impingers, should be 

prepassivated by a one-hour standing contact with l:l (V/v) aqueous nitric 

acid. 

Two separate approaches are used for subsequent cleanings: one for 

SASS train components and organic sample receptacles; and the other for 

bottles holding impinger solutions. The first group is cleaned in three 
successive stages using a different solvent in each stage. The solvents 

used are distilled water, isopropyl alcohol and methylene chloride, in the 

order listed. This procedure removes all extraneous particulate matter and pro-. 

duces a clean, dry surface. As each part is treated with the final solvent 

(methylene chloride), it is purged dry in a filtered stream of air •r dry 

nitrogen and inspected throughly for any sign of contaminating residue, 

scale, rust, etc. A contaminated train component may •o__•t be used in a 

sampling run. All equipment treated in the above fashion must be placed 

in a clean area to await the next test. Disassembled components of the 

sampling train which trap particulate matter are to be draped with cleanroom grade nylon until ready for use. 

The bottles holding the impinger solutions are cleaned in two successive 

stages, involving distilled water, followed by isopropyl alcohol. 

The field area in which these cleaning operations are performed must 

be as clean as possible under existing field conditions. An enclosed space 

is required in which reasonable precaution has been taken to remove spurious 

dust, dirt or particulate contaminants. Reasonable precaution is intended 

to mean that the area has been swept clean, doors or significant draft 

inducing sources have been closed and c•earroom grade nylon has•een 

spread Over the work bench area. 

3.3.3.2 Apparatus Checkout 

The following tasks should be performed in the home base laboratory 

prior to field arrival: 

I) Gather together all components required for complete system 

assembly. 

2) Clean components in accordance to the above described 

procedure. 

3) Leak check the entire system. 

Besides the cleaning procedures, leak checking the train prior to 

field use is one of the most important pre-test tasks to be performed. 

This simple procedure can save hours of sampling time in the field. The 

leak checking procedure involves sealing.the probe tip, turning on the 

pumping system, and observing flow meter gauges for the existence of any 

appreciable flow. The a11owable leak rate for the SASS train is 0.05 cfm 
at a pressure of 20 inches •f Hg. The instructions accompanying the train 

will present in detail the steps involved in,leak checking the system. 

3.4 SERIES CYCLONE SAMPLING PROCEDURE 

Assuming that the series cyclone system has been cleaned in accordance 

with the specification presented in Section 3.3 prior to arrival at the site 

and that all process characteristics have been determined and recorded as 

outlined above, a Level I sample may be taken as follows (Ref. 6): 

I) Assemble sampllng apparatus in accordance with the 

manufacturer's specifications. 

2) Warm up those components that require preheating. These are 

the probe, the oven, and the temperature control fluid in 

the XAD-2 Module. Under most conditions 15 to 30 minutes 

ar t required for preheating. Theoven and probe should be 

maintained at 205oc (400OF). The temperature of the cartridge should be kept at 20°C (68OF). 

3) 

 ̧4) 

Measure the stack temperature, moisture content, and velocity profile. Determine the position in the stack which corresponds 

to the average stack velocity. 

Leak test the system. As mentioned earlier in Section 3.3.3.2, 

the equipment should be thoroughly leak-checked prior to site 

arrival. If this has been done properly, the on-site leak test 

should simply be a precautionary formality to ensure that all 

fittings are properly tightened. 

Using the procedures and calibration curves supplied by the 

manufacturer, compute the appropriate sampler flowrate and the 

proper nozzle size. 

6) Fill the impinger bottles with the reagents specified in 

Table 2. 

7) Install the nozzle on the probe, and then insert the probe 

into the stack or duct. The nozzle should be in the proper 

posit!on in the duct, as determined in (3). 

8) To initiate the sampling run, turn on the vacuum pump and 

throttle the intake valve to achieve the flowrate determined 

in (5). (A 3- to 5-cfm sampling rate should be achieved at 

the dry test meter.) 

9) During the course of the run, periodic checks and adjustment 

of flowrates and temperatures should be made. 

3B 

The quantities of sample needed in order to perform the required 

analyses are presented in Chapter I (Table 1). Naturally, the knowledge 

of whether or not these quantities have been acquired during the run cannot be obtained until subsequent gravimetric analyses have been performed. 

For this reason the PMB has developed a series of sampling guidelines 

criteria for acquiring the required quantity of sample during each run. 

These criteria are: 

At least one process cycle and 30 standard m 

3 (1060 scf) of the process effluent are-•-•-be sampled during each run. 

In the event that the process is not cyclic in nature, the 30 standard m3 figure must still be satisfied over a 

period of time conducive to obtaining a sample representative of process conditions. A sampling duration of five hours has satisfied this requirement in the 

past. 

To fulfill the above conditions it may be necessary on several 

occasions (due to high grain loading conditions) to interrupt the progress of the run to change the filter or nozzle due to clogging problems. 

This is an acceptable procedure; however, care must be taken to avoid contamination in the process of transfer. A detailed log should be kept to 

record'any relevant conditions pertaining to the change. 

3.5 SAMPLE HANDLING AND SHIPMENT (References 3, 4, 22, 25, 26) 

The procedures used in transferring acquired sample from various 

portions of the SASS train are extremely involved. To expedite the 

explanation of the procedures involved in sample transfer and handling, 

the subject is discussed in te•ms of a modular approach. For this reason, 

the SASS train is considered in terms of the following sections: 

1) Nozzle and probe, 

2) Cyclone system interconnect tubing, 

3) Cyclones, 

4) XAD-2 module, 

5) Impingers. 
At the 

transported 

I) 

conclusion of the sampling run, the train is disassembled and 

to the mobile lab unit Or prepared work area as follows: 

Open the cyclone oven to expedite cooling, disconnect the probe and cap off both ends. 

2) Disconnect the line joining the cyclone oven to •he XAD-2 module at the exit side of the filter and cap off a) the entrance to the I0• •yclone, b) the filter holder exit, and c) the entrance to the join line which was disconnected from the filter holder exit point. 

3) Disconnect the line joining the XAD-2 module to the impinger system at the point where it exits the XAD-2 module. Cap off the exit of the XAD-2 module and the entrance line to the impinger system. 

4) Disconnect the line exiting the drierite impinger at the point where it leaves the impinger and cap off the impinger exit. Discard ice and water from the impinger box to facilitate carrying. 

The solvent system which has been found to be the most effective for 

line rinse and final cleanout of adhered sample consists of a l:l mixture 

of methylene chloride (CH2CI2) and methanol (CH3OH). 

Since step-by-step procedural instruction in narrative .form would be 

voluminous, time-consuming to follow, and might be confusing to the reader, 

each Step is presented in the following series of flow diagrams (Figure 12 

to Figure 14). It is suggested that these diagrams be placed in an easily visible lo'cation near the cleaning area as an aid to the sample transfer 

activity. 

3.6 OPACITY MEASUREMENTS 

Opacity of stack effluent gas is a required Level 1 data point for 

each sampled stack. The method to be used for this evaluation is the 

iRingelmann technique which involves •he simple process of comparing stack 

effluent opacity to a hand-held grid composed of varying shades of grey 

from white to black. The technique usually requires a person who has been 

certified to take the reading; however, for Level I purposes, this require-. ment has been waived. 

41 
1 

I 

42 
43 
STEP NO. 

COMPLETE XAD.-2 MODULE 

AFTER SAMPLING RUN 

RELEASE CLAMP JOINING XAD-2 

CARTRIDGE SECTION TO THE UPPER 

GAS CONDITIONING SECTION 

REMOVE XAD-2 CARTRIDGE FROM 

CARTRIDGE HOLDER. REMOVE FINE 

MESH SCREEN FROM TOP OF CARTRIDGE. EMPTY RESIN INTO WIDE 

MOUTH GLASS AMBER JAR 

REPLACE SCREEN ON CARTRIDGE, REINSERT CARTRIDGE INTO MODULE. 

JOIN MODULE RACK TOGETHER. 

REPLACE CLAMP. 

OPEN CONDENSATE RESERVOIR 

VALVE AND DRAIN AQUEOUS 

CONDENSATE INTO A LITER 

SEPARATORY FUNNEL. EXTRACT 

WITH CH2CI 2 

STEP NO. 2 

CLOSE CONDENSATE RESERVOIR VALVE 

ELEASE UPPER CLAMP AND 

LIFT OUT INNER WELL 

WITH GOTH UNITIZED WASH BOTTLE 

(CH2CI2:CH3OH) RINSE INNER WELL 

SURFACE INTO AND ALONG CONDENSER WALL SO THAT RINSE RUNS 

DOWN THROUGH THE MOOULE AND 

INTO CONDENSATE COLLECTOR 

PLACE TO ONE SIDE 

RINSE ENTRANCE TUBE INTO MODULE 

INTERIOR. RINSE DOWN THE CONDENFLOW DOWN THROUGH THE SYSTEM 

SER WALL AND ALLOW SOLVENT TO 

AND COLLECT IN CONDENSATE CUP 

RELEASE CENTRAL CLAMP AND 

SEPARATE THE LOWER SECTION 

(XAD-2 AND CONDENSATE CUP) 

FROM THE UPPER SECTION (CONDENSER) 

THE ENTIRE UPPER SECTION IS NOW 

CLEAN. 

TION INTO THE CONDENSATE CUP 

RELEASE LOWER CLAMP AND 

REMOVE CARTRIDGE SECTION 

FROM CONDENSATE CUP 

THE CONDENSATE RESERVOIR NOW 

CONTAINS ALL RINSES FROM THE 

ENTIRE SYSTEM. DRAIN INTO AN 

AMBER BOTTLE VIA DRAIN VALVE. 

Figure 13, Sample Handling and T•ansfer XAD-2 Module 

44 
ADD RINSE FROM 

CONNECTING LINE 

LEADING FROM XAD-2 

MOD TO FIRST IMPINGER 

DIST. H20 AND ADD 

!MPINGER NO. 2 NALGENE 

CONTAINER 

DISTo H20 AND ADD 

•| MEASURE TOTAL 

J VOLUME FOR 

SINGLE ANALYSIS 

DRIERITE DISCARD 

Figure 14. Sample Handling and Transfer Impihgers 

45 
3.7 DATA REDUCTION 

Due to the complexity of the SASS train, a broad range of data is 

acquired as the result of each run. The subject of data reduction is discussed in detail in ChBpter I; however, certain aspects specific to SASS 

train samples are briefly presented here. 

After the laboratory analyses have been performed for a specific sample, the data can be applied to the process as a whole. For example, if 

the laboratory analysis detects 5 ppm Hg in a specific sample, this quantity 

can be applied to the weight of the total sample that was collected, and can 

then be further used to calculate the mass emission rate of the entire 

stream being characterized. In general, the process parameters and conditions determined during the pre-site survey (Section 3.3.1) will serve as 

the data base to which the analysis results can be applied. For example, 

data on duct or stack stream velocity and grain-loading density is used 

to calculate the particulate concentration and size distribution within a 

stream once the particulate weights from the cyclones and filter are measured. As a result of the data reduction process, general process effluent 

profiles can be developed for each parameter of interest. The molecular 

weight or class of organic or inorganic species may be plotted as a function of its location throughout the train. Volatility factors of particulate 

matter versus gas may be developed. Data points resulting from bioassay 

analyses may be accumulated. 

Data reduction relationships may also be drawn through a comparison of 

established matrices. For example, it may be noted upon comparison that a 

relationship exists between the organic matter distribution matrix and the 

bioassay matrix. Eventually, after several sampling efforts have been conducted for a specific process type (e.g., power plants, coal gasification 

operations, etc.), a complete characteristic effluent profile for that 

specific process may be established. 

46 
CHAPTER IV 

FUGITIVE EMISSIONS SAMPLING 

4.1 INTRODUCTION (References 2, 4, 27) 

Fugitive emissions are those air and water pollutants generated by 

any activity at an industrial site which are transmitted from their source 

directly into the ambient ai• or receiving surface and ground waters mithout first passing through a stack, duct, pipe or channel designed to direct 

or control their flow. The assessment of the effect of a specific fugitive 

emission on the environment requires determination of the amount of pollutants entering the atmosphere or receiving waters on a weight-or-volume 

per-unit-time basis. 

This chapter presents the basic strategies for the sampling of air-and 

waterborne fugitive emissions in Level I assessment effort. The sampling 

programs are' designed to provide estimates of the major process components 

emitted as fugitive emissions, within the accuracy limits discussed, in 

Chapter I. 

Fugitive emissions may be generated by almost any industrial operation, 

including those with specific emission control equipment. Airborne fugitive 

emissions consisting of particulate matter and gaseous pollutants may be generated 

by sources enclosed in buildings and transmitted to the atmosphere through 

structural openings or vents, or generated by sources in open areas and 

transmitted directly into the atmosphere. In this chapter, any source 

within a given site generating fugitive emissions which contribute to overall concentrations will be called a specific source. The overall fugitive 

emissions concentration resulting from the sum total of specific sources 

will be referred to as the site source. Waterborne fugitive emissions, 

which consist primarily of suspended and dissolved solids, may be generated 

by process leaks and spills, runoff from a wide variety of material storage 

piles, and fallout from emissions initially airborne. They are transmitted 

to surface waters by runoff and to ground waters by infiltration. Figure 15 summarizes the sampling categories for Level l airborne fugitive 

emissions. 
48 
Because of the unique nature of fugitive emissions, special techniques 

applicable to their diffuse nature are used. These techniques include 

upwind-downwind sampling techniques for site sources, downwind and free 

plume techniques for specific sources, sampling for waterborne fugitive 

emissions transported to surface waters, and percolation studies for waterborne fugitives transported to ground waters. The basic aim of this survey 

effort is not the precise quantitifcation of a given plant's fugitive 

emissions, but the determination of the fugitive pollution potential so that 

a detailed Level 2 effort can be planned and executed with a minimum amount 

of wasted effort. 

Unlike other chapters in this manual, the fugitive emissions chapter 

must be divided into two distinct parts in order to avoid confusion. The 

first part considers airborne fugitive emissions while the second considers 

fugitive emissions as they relate to waterborne contaminants. The discussions include technique descriptions, equipment r•quirements, system 

design and data reduction and manpower requirement estimates. 

4.2 AIRBORNE FUGITIVE EMISSIONS 

4.2.1 Preparation for Sample Collection (References 27, 28, 29) 

The following sections discuss the preliminary procedures required 

for sample collection, including the pre-test site survey, the preparation 

of measurement equipment, and personnel requirements. 

4.2.1.I Pre-test Site Survey 

The pre-test site survey for airborne fugitive emissions is extremely 

site specific and consequently requires many subjective judgments and is 

treated here in a very general manner. The predominant portion of the 

survey activity will involve a tour of the overall site in an attempt to 

identify existing specific sources. If specific sources are found to exist, 

they must be placed in one or the other of the following two categories: 

l) A specific source which generates a highly diffuse cloud .over an extensive area, such as coal or ash 

storage piles. 

2) A specific source which generates an emission which might be broadly or generally classified as a plume, such as a coke oven bank. 
Naturally, a wide variety of specific sources fall into a nebulous 

area which could apply to either one of the above two definitions. When 

this problem exists, the source is to be assigned to the first category. 

In addition, a specific source under consideration for fugitive 

emissions sampling must be significant enough to warrant the effort 

involved in making the characterization. This is also subjective and a 

pro or con'declsl•n must hinge on the likelihood of the emission's migration beyond the site boundaries. If uncertainty exists concerning specific 

source significance criteria, disregard the source under the assumption 

•hat the site source samples will supply the needed data. 

Having identified sampling positions for all significant specific 

sources within a site, the next step involves locating suitable upwinddownwind locations for the site source samplers. One or more upwind and 

downwind samplers are required, which depends on the location, size of the 

site or the homogeneity of the emissions as they exist at the boundary 

areas. 

Clearly, in view of the above criteria, a specific example cannot be 

developed to consider the diverse contingencies likely to be encountered 

throughout a variety of sites. However, an understanding of the magnitudes 

involved is facilitated by considering optimal sampler locations for a 

"worst case" site. Such a site is considered in the decision example 

shown in Figure 16 wherein optimum sampler locations are indicated for 

various specific sources as well as For the overall site, This decision 

aid is discussed in detail in. Section 4.2.3. 

4.2.1.2 Measurement Equipment (References 21, 27, 30) 

High Volume Sampler. The high volume sampler package identified for 

Level l sampling consists of three primary components: 

2) 

3) 

A commercially available, high volume filter device 

for particulate matter identification, 

An XAD-2 absorbent trap for >C 6 organics, and; 

A 5-cfm pump for the XAD-2cartridge. 

50 
x 

51 
In most common types of high volume filters, a high speed 

vacuum-cleaner type motor is utilized to draw large volumes of air through 

a filter to trap the entrained particulate matter on the filter surface. 

A number of such devices are commercially available and may be utilized 

interchangeably if the following general specification can be met: 

• Flowrate This should be variable between O.57m3/min 

and 1.7m3/min (20 to 60 cfm).This variability is needed 

in order to compensate for differences in particulate 

density. 

Filter size 20.3cm x 25.4cm (8"xi0") Spectrograde 

glass fiber filters (Gelman Instrument Co. or equivalent). 

Automatic Flow Control Most commercial instruments 

have optional automatic devices to keep a constant 

flowrate as particulate matter builds up. This type of control is recommended to promote accurate, unattended 

flow control. 

• Construction Lightweight and durable, capable of allweather operation in plant environments. 

Cyclic Timer The sampler should have the capability 

to sample continuously for a set period of time or 

intermittently during a sampling period to match the 

cyclic nature of plant processes. 

• Electric Generator In many cases, a portable electric 

generator(s) will be required to operate the samplers. 

In addition to these requirements, it is recommended that a particulate 

size fractioning head be added to the high volume sampler. Particle size 

fractioning heads are available (Anderson 2000 Inc.) which fit directly on 

high volume samplers. For Level 1 sampling, a single stage head (40 cfm) 

providing a cutoff at 3.5u and a back-up filter is recommended. 

Grab sampling of gases may be accomplished using 3-1iter containers 

as described in Section 2.3.3, 

The XAD-2 adsorbent trap is described as part of the source assessment 

sampling system (SASS) train in Chapter Ill. A similar trap (eqpal in 

volume but with different end fittings) is connected as an integral part 

of this system as indicated in Figure 17. 

52 
I/4 INCH 

SWAGELOK 

BULKHEAD 

COPPER 

TUBING 

WALL 

/ 

CONNECTOR "• " 

TO 5 cfm PUMP 

Figure 17. Expanded View of Connections of XAD-2 

Cartridge to High Volume Sampler 

53 
SASS Train. A detailed description of the SASS train which is to be 

used to sample Category 2 specific sources which generate plumes is presented 

in Chapter Ill. A detailed discussion of the application of the SASS train 

to fugitive emissions sampling will be presented below in Section 4.3. 

4.2.1.3 Personnel Requirements (References l, 2, 27, 29, 31) 

As an outgrowth of the pre-test site survey, the exact number of 

sampling locations required for the fugitive emissions study may be used as 

the basis for establishing manpower projections. Two team members are 

required to set up each high volume sampling station. Assembly and activation will require approximately two hours depending on sampling site 

accessability. Standard sampler housings as specified in Federal Register, 

Part 50, Section 5 (Ref. 30) are sufficient for Level l purposes; long 

elevating poles or platforms are not required. After activation, sampler 

operation is automatic and does not require supervision. Manpower requirements for the hi-vol sampling matrix may then be estimated as a function 

of the anticipated number of sampler locations. 

As indicated in Chapter Ill, Section 3.3.2, the SASS train requires two 

and in some cases three persons for assembly and disassembly. One to one 

and one-half persons are required for operation. These projections apply 

only to stack or duct sampling conditions where railings, platforms and 

supportive port openings are available, however. For fugitive emissions 

sampling, few or none of these conveniences will exist. The probe will in 

many cases have to be held or at least supported,•manually; continuous 

supervision will be required to ensure that the probe is held within the 

emissions plume. Obtaining the required amount of Sample (see Tab1•e •1) 

will often require extended sampling periods. Often, site geometry will 

require remote equipment setup with lengthy webbed cable probe extensions. 

which in turn will require heat tracing. These and a variety of other 

factors must be considered (depending on specific site requirements) before 

manpower estimates for this activity can be established. 

A best possible case assembly and disassembly will require from 3 to 4 

persons; operation will require no less than two persons. Still, a 

best possible case setup will require from 5 to 6 hours and the operating 

54 
pe•tod w111 depend on the density of the plume and the frequency of the 

cyc]e.(assumlng the process is cyclic). The decision to place a specific 

source in Category 2 for cost effectiveness reasons must not be made 

lightly. Figure 16 can again be used to clarify the genera] process 

magnitudes applicable to specific sampling types. 

4.2.2 Sampling Procedures (References 27, 28, 29, 30, 31) 

4.2.2.1 Htgh Volume Sampler Applications 

The modified high volume sampler, as described in Section 4,2.1.2, will 

be used in all ftrst category specific sources (see Section 4o2.1.1) and 

all site source sampling operations. 

The number and location of upwind-downwind devices used to collect 

samples are extremely important to the sucdessful completion of a Leve] 1 

sampllng matrix. The design of the system is influenced by such factors 

as source compiexity and slz•, site geometry and prevai]ing meteorological 

conditions. Generally, only one upwind device is required in order to 

supply background data and one or more downwind samplers are needed depending on the above stated factors. Downwind site-source samplers are to be 

removed as fa• as possible from any process operatioq since the objective 

tn this case tnvolves the collection of a measured portion of a homogeneous 

cloud as it passes beyond the plant boundary. 

First category specific source samp]es need only be taken on the downwind side of the source. These samp]es a•e all taken external to the source 

and should be placed within the actual cloud if possible.i In contrast to 

the site source samplers which are removed as far as possible from any 

process operaton, specific source samplers are placed as close as possible 

tO the actual speclftc source. 

Subjective estimates of existing cloud densities may be •plted to the 

curves provided in Figure 18 as a general guideline for time versus flowrate settings. 
130 

120 

0100 

RO 

2O 

(60 CFM) 

ow 

• 

0 

.566 M3/MIN FLOW 

(20 CFM) 

FLOW RATE CURVE TO BE USED 

WHEN DUST CONCENTRATIONS ARE 

ARE NOT VISIBLE 

CLEAR l• VERY LIGHT HAZE 

0 iO0 200 300 

,•G PARTICULATE/M 3 IN AMBIENT AIR 

FLOW RATE CURVE TO BE USED 

UNDER HAZE CONDITIONS 

LIGHT HAZE II, HEAVY HAZE 

R00 300 400 500 700 900 II00 

FLOW RATE CURVE TO BE USED 

WHEN DUST CONCENTRATIONS 

ARE VISIBLE 

HEAVY HAZE •' THICK DUST 

Figure 18. Sampler Flow Rate Settings for Dust 
4.2.2.2 SASS Train Sampler Appllcations 

Fugitive emissions falling into the second specific source category 

(see Section 4.2•I.1) are sampled with the SASS train. The minimum sample 

quantities per run, as shown in Table l, apply here as well. 

No two second category specific sources will ever have the same (or 

even similar) site geometry. Plume characteristics (temperature, area, 

ve10clty, density, composition, cyclic frequency• etc.) will also vary 

markedly depending on process type, size, meteorological conditions and 

the existence or nonexistence of control devices. Because of these 

extremely diverse conditons, only generalized procedures may be presented 

concerning fugitive emissions characterization with the SASS train. 

The first consideration involves taking every precaution to ensure the 

health and safety of personnel directly involved in the sampling task. 

Personnel assembling the train and especially the person responsible for 

holding the probe in the plume will be either partially or totally immersed 

.in the escaping gases, and depending on the nature of the effluent varying 

degrees of protective clothing will be required. Depending on the length, 

of exposure this may require clothing ranging from a simple dust mask to a 

complete fireproof outfit equipped with self-contained breathing apparatus. 

The second consideration involves .a choice of the optimum position for 

sample.withdrawal. This position cannot be chosen during the survey effort 

because specific sources of the second category (and in many cases, in the 

first category also) are dependent on a number of process and meteorological 

variables which either may or may not exist on the return trip. The optimum 

posi'tion for sample withdrawal should also be an acceptable location for all 

train components following the .probe. If the above integrated arrangement 

is not possible, the next best choice involves keeping probe and cyclone 

Oven together while removing the rest of the components towhatever distance 

the process geometry demands. If the arrangement is such that room for the 

probe only exists, the entire rema•nder of the system must be placed in a 
remote location. In any case, where one component of the train must be 

isolated from another component, the lines joining the two must be heat-traced 

to avoid condensation. Assembly and operation of the SASS .train is detailed 

in Chapter III. A fugitive emissions sample is taken with the SASS train by 

inserting the nozzle into the plume or cloud and pulling at the maximum 

allowable flowrate using the largest available nozzl'e. Naturally, the closer 

the nozzle to the emissions exit point, the denser the plume and the shorter 

the sample duration. 

4.2.2.3 Gas Samples 

The acquisition of gas samples for fugitive emissions requires very 

little elaboration here. All gas samples for Categories 1 and 2, as well 

as for site source upwind-downwind, will be taken by the evacuated grab 

sampling technique which is presented in detail in Chapter II. 

4.2.3 Decision Aid for Appropriate Category Selections 

As previously stated, the sampling matrix for airborne fugitive emission 

characterizatlon results from the Choice of three available options: site 

source samples, Category l specific source samples, and Category 2 specific 

source samples. The location of sampling positions for the site source 

case simply involves selecting the proper sites for the upwind and downwind 

samples. Sampling position for specific sources, which must be classified 

into Categories l or 2, are not as easily identified as the site source. 

For this reason, a worst-case model is presented (Figure 16) in which a 

wide variety of specific sources are known to exist. The model, which 

represents an integrated steel plant is not intended to be viewed as a 

specific case representation, but provides an example of many of the 

specific sources found individually in smaller and less complex operations 

grouped together as an integrated unit. 

As indicated in Figure 16, Category 1 is assigned to positions in 

relatively open areas but which are near specific sources of emissions: 

downwind from coal and coke piles, and limestone bins; and downwind from 

blast furnace and sintering operations, ore-treating operations, coke 

quenching and grinding operations. Category 2 is assigned to positions 

where plumes are generated, such as •oke •ve•.ba•k,and an open hearth 

furnace. 
4.2.4 Sample Handling and Shipment (References 3, 4, 6, 25) 

Quantitative transfer of the samples from the 3,5• size fractionating 

head and the filter is necessary in order to determine existing partlculate 

densities. The > 3.5• catch can be removed from the head by tapping the 

head and carefully brushing any adhering material i•to a tared high 

density N•Ige•e shipping container. The glass fiber filter must be 

transferred into a petri,dlsh and sealed without particulate matter loss. 

During the sampllng process, the filter materlals have been subjected to 

conditions which tend to weaken their cohesive properties, so care must 

be taken to prevent filter fragmentation during the transfer. 

After the sample containers have been sealed, the samples may be 

taken to the mobile van for shipment to the laboratory. 

The XAD-2 cartridges are emptied into amber glass jars with Teflon seals 

and shipped to the laboratory for extraction and analysis. The exact 

procedures for SASS train sample handling and train clean-up are given in 

Chapter III. 

SASS Train Samples Lines and containers are rinsed with methanol/ 

methylene chloride and stored in an amber bottle. 

Gaseous Samples All gass bulb samples are taken to the mobile facility 

for on-site instrumental analysis. 

4.2.5 Data Reduction for Airborne Fugitive Emissions (iReference 2, 

When the sampling program has been completed and the samples have been 

analyzed to yield qualitative pollutant concentrations in such terms as 

micrograms per cubic meter in the ambient air at the individual or combined 

downwind sampling sites, the measured upwind concentrations are subtracted 

to yield the concentration provided by the source at each sampler. A 

library of computer programs to assist in the performance of this assessment 

is maintained in the User's Network for Applied Models of Air Pollution 

(UNAMAP) atthe Environmental Protection Agency's Research Triangle Computer 

Center. Additional programs may be obtained through many environmental 

consultants. 

59 
4.3 WATERBORNE FUGITIVE EMISSIONS 

4.3.1 Preparation for Sample Collection 

The following sections discuss the preliminary procedures required for 

sample collection, including the pre-test site survey, the measurement 

techniques required, and personnel requirements. 

4.3.1.1 Pre-Test Site Survey (References 32, 33, 34, 35, 36) 

Like airborne fugitive emissions, waterborne fugitive emissions are 

very site specific. In designing a water fugitive emissions survey, the 

following general strategy should be used: 

I) Assess operating procedures to see where waterborne fugitive 

emissions originate, e.g., material storage piles, overflow 

from impoundments, runoff from construction, dust from 

conveyors. 

2) Obtain the necessary background information, including topographic data, soil data, geological information, hydrology, 

climatology and meteorology, surface cover, land use. 

3) Locate runoff sampling stations based on the drainage basins 

identified from a topographic survey. 

4.3.1.2 Measurement Techniques (References 32, 33, 34, 35, 37) 

A variety of techniques for the measurement of waterborne fugitive 

emissions is in use today. These techniques include water runoff, receiving 

body sampling and core sampling. The method of choice for the Level I 

characterization of waterborne fugitive emissions is surface runoff 

sampling. 

This method is utilized for sources that can be identified as contributors to the pollution of water at an industrial site and whose runoff during a rainfall may be isolated from that of other sources. An example of 

such a source is a storage pile containing materials which will be carried 

either as suspended or dissolved pollutants by surface runoff to the 

environment outside plant boundaries. 

Topographic data and a site survey are used to locate an array of 

samplers arranged to collect representative portions of the runoff during 

a rainfall. The samples are usually located in the ground as close to the 

source as possible and in natural gullies and channels. Samples are taken 

60 
at the onset of a rainfall and at intervals during the rainfall and analyzed 

to determine the. change in pollutant concentration as a function of the 

amount of runoff determined by rain gage measurements. This change in concentration may be used to estimate the amount of polluting material that 

may be expected to reach the receiving body as a result of any single or an 

entire season's rainfall. 

4.3.1.3 Personnel Requirements 

Personnel requirements for placing the sampling plugs are in most cases 

minimal. One team member will be able to complete the activity in a relatively short period of time. The actual time required is dependent on the 

proposed area of the monitored zone and the ease of accessibility to that 

area. 

4.3.2 Sampling Procedures (References 38, 39, 40, 41) 

For the sampling of contaminated runoff, such as a material storage 

pile, plug collectors similar to that shown in Figure 19 are used.* The 

plugs are driven into the ground at selected locations where runoff will 

occur, such as at the base of the material pile, and in material.gullies 

and channels. 

During a rainstorm or snow-melt, the collectors are changed at appropriate intervals depending upon runoff intensity. The collector contents 

are measured and analyzed for pollutants as discussed in Chapters VII and 

VIII. An estimate of the runoff flow is made from total rainfall data and 

soil permeability in the test area. 

4.3.3 Decision Aid 

The area designated for characterization must be carefu11y studied by 

those individuals responsible for this activity. Key areas to identify are: 

e Coal piles 

• Waste piles 

• Drainage trenches for plant system runoff, and 

• Possible overflow areas from holding ponds. 

Plugs are designed and built by Kahl Scientific Instrument Corp., 

P.O. Box 1166, El Cajon, California 92022 

61 
SURFACE WATER 

•,• 

••• 

•] 

ENTRANCE 

GROUND WATER 

SEEPAGE 

Figure 19. Plug Collector for Fugitive Water Samples 

Good areas for collector placement are: 

• Areas of lowest elevation where sample throughflow is 

evident, 

• Drainage ditches or channels, and 

Any areas between the complex under consideration, and a 

receiving body of water. 

Maximum precaution must be taken to ensure proper collector placement so 

that data obtained may be related to the proper source. Water runoff samples are similar to airborne fugitive emissions in that both specific 

source and site source samples are obtainable. Collectors placed for 

general plant runoff are analagous to site source upwind/downwind samples, 

and collectors placed for specific problem areas are analagous to specific 

source downwind Samples. 
4.3.4 Sample Handling and Shipment 

Runoff samples from specific sources are to be combined in order to 

perform a single analysis to characterize a potential problem area. This 

minimizes the error which might otherwise result from sample analysis on a 

unit basis. 

After combining the samples obtained from a specific source together 

into one unit, the resulting single sample is subjected to the same separation scheme indicated in Figure 23 (Chapter V). The only digressions 

from the Figure 23 flow plan are: 

I) BOD and COD analysis are not performed, and 

2) A lO-liter volume is not required. 

The stabilization procedure applicable to the resulting phases must 

concur with the directives indicated in Table 3. 

4.3.5 Data Reduction for Waterborne Fugitive Emissions (References 33, 37, 39, 41) 

The samples obtained from the runoff plug samplers are analyzed to 

provide pollutant concentrations as a function of time from the start of 

the sampling period rainfall. Plotted against the measured rainfall rate, 

they will provide an estimate of the amount of pollutant that can be 

expected to be received for that period, and, by extrapolation, the amount 

of pollutant that can reach the receiving body for any given number of rainfalls. Historical meteorological data on the average or maximum rainfall 

frequency and rate can then provide an assessment of the site or source 

contribution for a seasonal period. 

Figure 20 is a block diagram summary of the waterborne fugitive 

emissions Level I assessment programs described in this section. 
WATERBORNE FUGITIVE 

EMISSIONS 

SOURCES 

SURFACE RAINWATER 

RUNOFF 

PLUG 

SAMPLERS 

SAMPLE J ANALYSES 

RAINFALL 

MEASUREMENT 

HISTORICAL 

DATA 

DATA 

REDUCTION 

Figure 20. Level 1 Water Runoff Fugitive 

Emissions Characterization 

64 
CHAPTER V 

LIQUID AND SLURRY SAMPLING 

5.1 INTRODUCTION 

In any given industrial process operation, the probability is high that 

a number of the influent and/or effluent streams will exist in liquid or 

slurry form. Considering the multiplicity of liquid or slurry streams in 

typical plants, the number of possible sampling points becomes extensive. 

Figure 21 summarizes the types of streams generally found in industrial 

operations and the sampling •thods to be used. It should be noted that 

these streams are transported in a variety of ways which may range from 

closed pipes to open ditches and sluices. The three methods chosen for 

the Level I sampling of liquids and slurries are heat exchange, tap sampling and dipper sampling. Each method is discussed in detail in Section 5.3. 

Once the samples are collected, they may be analyzed on site or 

packaged for shipment and analysis at the laboratory (see Chapters Vll and 

PROCESS STREAMS 

LIQUIDS CONTAINING MISCIBLE 

AND IMMISCIBLE PORTIONS, 

WITHOUT SOLIDS 

B,C 

;UPERHEATED LINES 

A 

MOLTEN SOLID LINES SLURRIES 

B,C 

SAMPLING METHODS 

A HEAT EXCHANGE 

B TAP SAMPLE 

C DIPPER SAMPLE 

*TAP SAMPLE MAY BE TAKEN IN LINES OF THIS NATURE ONLY IF THE/vVkTERIAL IS 

LIQUID AT RELATIVELY LOW TEMPERATURES (i .e., CERTAIN PETROLEUM TYPES) 

Figure 21. Sampling Methods as a Function 

of Stream Type 

.65 
VIII). Streams may be organic or aqueous or may contain water/organics/ 

solids in miscible or immiscible fractions. The handling of these solutions 

will affect the reliability of the chemical or biological tests performed. 

Section 5.4 proposes a tentative field separation scheme to prevent sample 

loss or adulteration. This scheme is comprehensive enough to prevent 

sample los•, but is simple enough to implement in the field. 

5.2 PREPARING FOR SAMPLE COLLECTION 

5.2.1 Pre-Test Site Survey 

The same criteria for locating a gas sampling point can be applied to 

locating sampling sites for liquid samples. A review of those criteria 

and procedures is contained in Section 2.2, Chapter II. 

While the site selection criteria for gas and liquid sampling are 

generally the same, the test personnel must be aware of the problems 

associated with the sampling of liquids and how these factors affect the 

choice of a sampling site. Two factors will affect the selection of a 

sampling site for liquid/slurry streams: 

• Stream Homogeneity This is the most important problem 

that must be addressed by the site survey crew. Unlike 

gas streams which mix fairly evenly, liquid streams tend 

to be more stratified because of lower thermal agitation 

and higher fluid viscosities. 

• Stream Flowrate Large, slow-moving streams will offer 

more of a chance for stratification to occur. This 

factor is especially important in large pipes or open. 

sluices and ditches. 

These factors indicate that free-flowing streams should be sampled 

after points of turbulence (elbows) to collect samples of maximum homogeneity. Because of the possible stratification in slow moving open 

streams, a sampling point should be chosen so that a full stream cut can 

be made with a dipper sampler. Sluice gates or pipe outfalls offer a good 

opportunity to obtain a sample in this fashion. 

In all cases the main pipe or stream flow should be sampled. Because 

solids can accumulate in seldom-used vent or slip streams, these lines are 

not recommended for sample acquisition. Long slip stream lines are to be 

avoided, but can be used if the main line is inaccessible and if the slip 
stream line is f•us••wi•h several times 'the volume of liquid held in the 

line between the main line and the tap. 

5.2.2 Personnel Requirements 

The liquid and slurry sampling techniques presented in this chapter 

are uncomplicated, and under favorable conditions only one person is needed 

to perform the sampling effort. The•e are conditions, however, where additional manpower will be required. Many streams will require that a crew 

member work under conditions or in areas where the potential for physical 

mishaps is high. For example, using a dipper to sample an open stream 

might require a crew member to extend himself physically to reach the 

sampling point either by leaning from catwalks, reaching from ditch banks, 

or physically wading in the stream. In other cases, the closed stream will 

be under high pressure and temperature which will multiply the dangers 

involved in taking a sample. An additional crew member should be present 

here to ensure the safe completion of the task even though his active 

presence is not necessary for the sampling effort. 

5.2.3 Equipment Preparation 

5.2.3.1 Sample Containers 

Containers intended for sampling industrial water streams must be made 

of a high density polyethylene or polypropylene. Plastic bottles for aqueous 

stream samples should be cleaned by: 

a) Detergent wash, followed by 

b) Distilled water rinse, followed by 

c) 1:1 sulfuric and nitric acid mix. 

Organic samples., including CH2CI 2 extractions, must be placed in 

amber glass bottles to inhibit sample degradation. These amber glass 

bottles are 

a) 

b) 

c) 

d) 

e) 

f) 

cleaned by: 

Strong soap solution, 

Liberal tap water rinse, 

Distilled water rinse, 

Methanol rinse, 

Methylene chloride rinse, and 

Drying a clean, hot air stream or by placing in an oven 

at 40oc (140°F). 
After the apparatus has been cleaned and d•ied, it should be stored 

in boxes to prevent spurious contamination. 

5.2.3.2 Apparatus 

Sampling lines should be as short as possible to facilitate flushing 

and to reduce time lag. The lines must have sufficient strength to prevent 

structural failures. Lines intended for sampling streams under pressure 

must be designed in accordance with the specifications outlined in the 

American Standard Code for Pressure Piping. Where small diameter capillary 

tubing is used, it should be protected by a sheath of larger diameter pipe 

of adequate structural strength. Materials of construction should conform 

to the applicable specifications of the American Society for Testing and 

Materials as follows: 

Pipe (seamless ferritic alloy-steel for high temperature 

service) ASTM Designation A335. 

Tubing (seamless carbon-steel for high temperature service) ASTM Designation A179. 

• Tubing (seamless alloy-steel for high temperature service) 

ASTM Designation A608. 

Valves and fittings must be fabricated from materials similar to those 

used in the sampling lines and must also conform to the requirements of 

the specifications of the American Society for Testing and Materials as 

follows: 

• Steel (suitable for fusion welding up to 850°F) ASTM 

Designation A216 

• Steel (carbon forged) ASTM Designation Al05 

• Steel (alloy steel castings for use up to llO0°F) ASTM 

Designation A217. 

Materials for fabrication of sampling apparatus not intended for use 

in pressure applications are not required to meet such stringent specifications 

due to the significantly reduced safety requirements. The primary element 

of importance here is the fabrication of equipment from materials which will 

not contaminate the sample. It is preferable, therefore, that the sampling 

lines and collection reservoirs used for sampling liquid streams be made of 

Teflon because of its superior chemical inertness toward strong acids, 

alkalis, and other chemical reagents. 

68 
All portions of the sampling apparatus which come into contact with 

the sampled stream should be cleaned using the same procedure that was 

used in cleaning the container for that sample (see Section 5.2.3.1). 

5.3 SAMPLING PROCEDURES (References 42, 43) 

As indicated in Figure 21, all liquid and slurry streams can be divided 

into distinct sub-groups, each defined as a function of the physical makeup 

of the stream. Each stream, having been so identified, may be assigned a 

sampling procedure applicable to that stream type. As indicated in Figure 21, three specific methods are applicable; they are: 

a) Heat exchange, 

b) Tap sa•ling, and 

c) Dipper sampling. 

Where the stream to be sampled exists at a pressure high enough above 

atmospheric to provide an adequate sample flow rate, the removal of the 

•ample presents no problem. At near atmospheric pressures, special 

means must be provided to establish sample flow. This problem can be overcome by u•ing either a small pump to deliver the sample to the sample container organ evacuated sampling vessel. Prior to sample acquisition, all 

new sampling lines should be purged with line fluidto remove any deposits 

in the system lines and to condition the sampling lines. The period of time 

required will depend on the system line size and distance from the main 

stream. Once the lines have been flushed, sampling can begin. A lO-liter 

sa•le is required to perform the analyses identified in Chapters Vll.. 

and VIII. 

5.3.1 Heat Exchange Sampling Systems for High Temperature Lines 

The majority of .industrial systems utilize steam for a variety •f 

process applications ranging from relatively clean power plant operations 

to polluted lines resulting from stripping operations involving acid units, 

catalyst regeneration and scrubbing of polluted gas streams. In addition 

to pressurized process lines, various other process operations exist which 

contain superheated vapors Composed of effluents generally characterizable 
as reaction products. The sampling techniques described in this section 

pertain to all of •he above systems; however,for the sake of brevity, the 

term HT line (high temperature) will be used to represent all applications, 

unless otherwise indicated. 

The principle used in the sampling of HT lines involves the use of a 

water-cooled condenser system. Typical examples of apparatus used for this 

purpose are illustrated in Figure 22. As can be seen in Figure 22, two 

approaches are possible depending on whether the pressure in the line is 

above or below atmospheric pressure. The condensate from the stream is 

collected in a reservoir for later analysis. 

In sampling HT lines, it should be kept in mind that stream constituents will to some degree dissolve any substance contacted. For this reason, 

the area of the surfaces exposed to the sample and the time that the sample 

is in contact with these surfaces should be kept to a minimum. 

As indicated earlier in paragraph 5.2.3.2, all.tubing, valves, nozzles, 

and containers must be constructed from materials of sufficient strength to 

withstand the full pressure of the stream being sampled. Tubing diameter 

must be small enough so that storage within.coils and tubing and the 

resultant time lag of the sample through the system are minimal. The sampling operations presented in this section may be used with complete safety 

provided that proper caution is exercised. 

5.3.2 Tap Sampling (Reference 44) 

Contained liquids may be divided into two broad categories: those 

which are in motion (lines) and those which are not (tanks or drums). 

Usually, a specific sampling technique is applied to each of the above 

two categories in order to accommodate the differences in sample characteristics, such as stratification. A flowing stream containing particulate 

mattem will be stratified. A tank sample may also be stratified but in 

the static sense rather than in the fluid sense. Moving streams•are traditionally sampled using a techni, que called continuous sampling. This involves 

sample removal from a tap which is connected to a probe inserted into the 

line, Static liquid samples (tanks or large drums) are sampled using a 

techDique called tap sampling. 

For the purposes of Level 1, the effort of inserting a probe into the 

line is too time-consuming to be efficient. Consequently, all contained 

liquids will be sampled using the tap method, as per ASTM D-270 (Ref. 44). 

Tap sampling, as described in this chapter, describes a wide variety 

of grab techniques. In general, this type of sampling implies that a 

sample is taken at a tap from a line or tank wall. This approach is used 

for moving liquid or slurry streams. The procedure is also applicable to 

streams under pressure or elevated temperature provided that the proper 

safety precautions are exercised. For systems under pressure, lines should 

be cracked very slowly to avoid injury caused by sudden surge due to 

.entrained air pockets or accumulated solids around the valve opening. 

Streams under elevated temperatures should be sampled using a heat 

exchanger system such as is described in ASTM D-270 (Ref. 44). 

Tap samples are collected by inserting the sample line (a thOmoughly 

washed Teflon line) into the sampling bottle so that it touches the bottom. 

(After first flushing the sample line at a rate high enough to remove all 

sediment and gas pockets.) The sample bottle should be thoroughly rinsed 

with sample prior to filling and the sample line flow must be regulated so 

as not to exceed 500 ml/min. If sampling valves or stopcocks are not 

available, samples may be taken from water-level or gage-glass drain lines 

or petcocks. 

5.3.3 Dipper Samplin 9 

The dipper sampling procedure is applicable to sampling sluices or 

open discharge streams of thick slurry or stratified composition. The 

dipper is made with a flared bowl and attached handle, long enough to 

reach the sluice or discharge areas. The bowl portion must be coated with. 

Teflon. 

A dipper sample is obtained by inserting the dipper into the freeflowing stream so that a portion is collected from the full cross-section 

of the stream. Sample portions are to be taken at time intervals chosen 

so that a complete sample is collected which is proportional to the pumped 

quantity. The gross amount of sample collected should be approximately 

0.1 percent, but not more than 40 gallons, of the total quantity being 

sampled. As noted previously, this should be at least 10 liters or reduced 

to that quantity for analysis. 

72 
Although it is generally agreed that time-integrated sampling techniques are too sophisticated for Level 1 application, the lack in uniformity 

often found in thick or stratified slurries may require special consideration in some cases. The site survey will produce information on process 

cycles so that the sampling times and points cover the most representative 

period and location of discharge. 

5.4 LIQUID SAMPLE HANDLING AND SHIPMENT 

As mentioned previously in Section 5.1, sample handling is an important 

consideration where liquids are involved. The entire spectrum of liquid 

samples exists within the bound• of the following six categories: 

1) Aqueous 

2) Aqueous/organic 

3) Organic 

4) Aqueous/solid 

5) Organic/solid 

6) Aqueous/organic/solid. 

These samples must be stabilized prior to shipment for laboratory analysis. 

Figure 23 shows a field handli:ng scheme for liquid/slurry samples. This 

scheme has been modified (Ref. 45) to handle suspended particulate matter. 

Figure 23 shows the worst ca•e (Aqueous/Organic/Solid), but is also applicable to the simpler cases. 

It is recommended that in-field separations and specific preservation 

techniques, rather than a general all-purpose approach that is not specific 

forinorganic, organic and biological prese[vation, be followed. Table 3 

outlines the application of Figure 23 to less complicated systems. It 

should be noted that both BOD and COD samples are typically taken before 

filtration. Sulfite should be determined in the field and as soon as the 

samples are returned to the lab. 
DRY AND WEIGH 

FOR TOTAL 

SUSPENDED SOLIDS 

AQUEOUS/ORGANIC/SOLID 

10 LITER SAMPLE 

• [CAREFULLY LITER TRANSFER 

TO AVOID 

ENTRAINMENT-BOD, COD 

FOR 

SEE TABLE 3 FOR SAJ•APLE 

PRESERVATION AND 

CHAPTER VII FOR INORGANIC MATERIAL ANALYSIS 

SEE CHAPTER 

Y[lJ FOR 

ORGANIC 

ANALYS1S 

F•gure 23. Field Handling Scheme for Liquid/Slurry Samples 

74 
75 
CHAPTER VI 

SOLID SAMPLING 

6.1 INTRODUCTION (References 46, 47) 

Solid sampling covers a broad spectrum of material sizes from large 

lumps to fine powders and dusts. There is an equally diverse assortment 

of potential sample sites including railroad cars, barges, trucks, large 

heaps, plant hoppers and conveyor belts. Obviously, no one sampling method 

or piece of equipment can accommodate all possible situations. Furthermore, all of the above sampling locations may contain products of widely 

varying consistency. For the purposes of this chapter, the consistency of 

solid samples ranges by definition from anhydrous or dry solids to thick, 

nonflowing pastes, 

The recommended Level 1 sampling technique is the grab sample. In 

general, the Level I and Level 2 solid sampling techniques are identical 

except that in the case of Level 2 sampling, a series of grab samples is 

taken over a period of time from a conveyor belt or over a larger area for 

stationary storage sites such as railroad cars or large heaps. In cases 

of extreme sample variability, a larger grab sample consisting of several 

increments or shovelfuls is required on Level I, In most cases, the difference between the Level l .sample and a time-averaged Level 2 sample is only a 

matter of degree rather than of technique. 

The following sections present the sampling approaches applicable to 

input and output solid streams and storage piles. 

6.2 PRE-TEST SITE SURVEY (References 8, 48) 

Solid input and output streams in most process operations consist of 

fuels, primary reaction components, treatment or maintenance chemicals, 

salable output products or output refuse products. These solids range 

from very fine powders to very coarse lumps. This variation in sample 

consistency influences the sampling technique to be used which must be 

establ%hed in thepre-site survey. For the purpose of the pre-test site 

survey, therefore, the following questions must be answered: 

1) Can the material be sampled as it enters or leaves the 

process, or must it be sampled in its storage or pile form? 

76 
2) If the material can be sampled as it enters or leaves 

the process, what is the nature of the conveyor system (belt, worm screw, duct) and what is closest 

available sampling location to process entry, and 

farthest available sampling location from process 

exit? 

3) What is the consistency of the material (powder, coarse 

grain, lump) and what is the apparent variance within 

this consistency, and 

4) What is the approximate size of the storage reserve and 

what is the method of access to said reserve? 

Each of these parameters must be identified before the procedures in 

the following section can be adequately implemented. 

6.3 SOLIDS SAMPLING PROCEDURES 

Level I solid sampling procedures use three manual grab sampling 

techniques: shovel or grab sampling; boring techniques, which include 

pipe or thief sampling; and auger sampling. Data obtained from the pretest site survey concerning the physical characteristics of the sample, 

together with the optimum choice of sampling location will determine the 

appropriate sampling technique. Table 4 presents a sampling matrix showing the appropriate sampling technique as a function of physical characteristics and actual location of the sampling points. 

Each of the grab sampling techniques is discussed in detail in the 

sections to follow. 

6.3.1 Shovel Grab Samplin• IReferences 20, •2, 47, 49) 

Raw material piles of relatively coarse lump size (ore piles, aggregate 

piles, coal feed, etc.) are sampled using a fractional shoveling technique. 

The shovel Used in this procedure is of the square-edged variety measuring 

12.inches wide. 

In sampling from belt conveyors, one full cross-section the width of 

the shovel blade is taken as the sample. 

Where ladder or tray conveyors are sampled, one shovelful from one 

compartment is removed. 
Table 4. Decision Matrix for Solid Sampling 

PHYSICAL NATURE 

OF SAMPLE 

FINE POWDER 

COARSE POWDER 

BE LT 

CONVEYORS 

N/A 

N/A 

LADDER TRAY 

CONVEYOR 

SHOVEL 

GRAB FROM 

ONE TRAY 

SHOVEL 

GRAB FROM 

ONE TRAY 

SCREW DUCT OPEN STORAGE BINS 

CONVEYOR SAMPLE PILES OR SILOS 

ONE SHOVEL ONE SHOVEL PIPE OR PIPE OR 

FROM POINT FROM EXIT THIEF THIEF 

OF EXIT IF ENCLOSED 

FROM TOP IF 

OPEN 

ONE SHOVEL PIPE PIPE• THIEF.OR 

FROM POINT THIEF OR AUGER 

OF EXIT AUGER 

ONE SHOVEL 

FROM EXIT 

IF ENCLOSED, 

FROM TOp IF 

OPE•N 

COARSE GRAIN 

LUMP 

CROSS 

STEAM CUT, 

ONE 

SHOVEL 

CROSS 

STE •J•4 CUT, 

ONE 

SHOVEL 

SHOVEL 

GRAB FROM 

ONE TRAY 

N/A ONE SHOVEL 

FROM EXIT 

IF ENCLOSED, 

FROM TOP 

IF OPEN 

N/A N/A N/A 

AUGER AUGER 

FOUR SHOVEL OR 

SHOVELS, AUGER 

ONE FROM 

EACH 

SIDE 

Screw conveyors transfer sludge-type materials (such as ash effluents) 

and are usually enclosed systems. Theoptimum sampling point for these 

systems is the content exit. If this point is located in an unreachable 

position, the sample must then be Withdrawn from the entrance or exit area, 

depending on whether the stream is influent or effluent using a pipe, thief 

or auger technique (Section 6.3.2). 

Duct conveyors consist of either gravity feed systems or chaindrive 

scrapers and may be open top or enclosed depending on the fineness of the 

solid being transported. Open duct conveyors are sampled by removing one 

shovelful of material from the top from the adjoining catwalk. Closed ducts 

are sampled by taking one shovelful from the exit point. If these points 

are unreachable, the sample must be taken from the storage pile using a 

pipe, thie• or auger (Section 6.3.2). 

6.3.2 Boring Techniques (References 22, 46, SO) 

Pipe borers represent another class of solid sampling methods applicable 

to materials stored in piles, silos or bins. The pipe is inserted into the 

material t• be sampled at regular intervals. The method is fairly reliable, 

providing that the pipe is long enough to reach the bottom of the material. 

However, it is only applicable to fine or powdered dry materials, because 

78 
lumps or any stickiness will jam or plug the pipe. Small pipe borers can 

be used to sample material in sacks or cans. There are primarily two pipe 

designs that give best results, One is a simple pipe that is tapered so 

the end first inserted is smaller in diameter than the handle end. A more 

:sophisticated design, known as a thief, makes the sample more representative 

vertically. It consists of two close-fitting concentric pipes sealed at 

the base in a conical point. Longitudinal slots are cut along the side of 

each pipe. The thief is inserted with the slots turned away•from each other 

and then, when the sampler is in position, the outer pipe is rotated, lining 

up the slots and allowing the inner pipe to fill with sample. For proper 

results with any design of pipe borer, the.opening through which the sample 

material passes (slots or circular pipe •nds) must be larger than the 

largest particle size. 

Auger samplers, a form of drill, pack the sample in the helical groove 

of the auger and can be enclosed in a casing if the nature of the sample is 

such that it will spill when the auger is removed from the.hole. Like pipe 

borers, they are simple to use and have the further advantage of being 

applicable to a greater variety of materials. For example• augers work 

well for materials that are packed too hard for the insertion of a pipe 

sampler. For very packed materials, machine-driven augers are available. 

However, if spillage is a serious problem, a thief type pipe sampler is 

the better choice. 

6.4 SAMPLE COLLECTION AND STORAGE (References 3, 20, 22, 50) 

It is always preferable to sample a moving stream either in pipes or 

off conveyor belts rather than stationary storage sites. This is particularly true if the sample has a wide particle size distribution. Stored 

containers or heaped beds of m•terial tend to settle, segregating the particles according to size and density, and it is difficult to compensate for 

this bias during sampling. Furthermore, large masses of stored material 

are extremely difficult to handle. The interio• portions are relatively 

inaccessible, and the amount of time and space needed to move the material 

enough to take a representative sample can become prohibitive. However, 

such situations can generally be avoided by a good sampling test plan. 

7 ̧9 
Typically in a process test for trace elements the solid materials 

of interest are the feed materials and the residues from particulate matter 

scrubbers such as baghouses, high energy venturis, and electrostatic precipitators. Raw feed stock as it passes through the process stream may 

pick up other materials as contaminants and therefore differs greatly in 

composition from the final feed to the process. Consequently, samples 

should be taken at the last possible site before the stream is fed into the 

process. This means that sampling will generally be conducted from a feed 

hopper, if accessible, or from the pipes or conveyors which feed the materials 

to the process. Similarly, scrubber residues can be sampled from the collection hopper o6 from pipes going to the hopper. Extra handling steps 

only increase the chances of the sample becoming contaminated. 

When samples are taken from conveyor belts, the standard procedure is 

to stop the conveyor at regular intervals (e.g., every 10 or 15 minutes) 

and shovel off a section of the material. Flat-nosed shovels with straight 

perpendicular sides are best for this type of sampling. 

Samples collected in accordance with the above prescribed procedures 

should be stored in air-tight, high density polyethylene containers until 

ready for analysis. Large samples should be placed in metal containers 

lined with polyethylene bags. 

80 
CHAPTER Vll 

LEVEL 1 INORGANIC ANALYSIS TECHNIQUES 

7.1 INTRODUCTION (References 1, 2, 51) 

Sampling and analytical programs can at a minimum be divided into 

three distinct categories. The first category is compliance testing 

where the procedures along with their precision are delineated in the 

Federal Register. A second type of sampling and analytical program is 

designed to support specific R&D programs and the precision and accuracy 

of the data are defined by its end uses. The third type of program is 

designed to provide information which can be utilized in each of the 

specific levels of a phased environmental assessment. 

In respect to the Level I environmental assessment as described in 

this manual, a goal for precision and accuracy within a factor of two 

to three of the rate of input and emission composition is desired. 

achieve this goal, the analytical results must have an accuracy•f -50 to 

+100 percent assuming a sampling accuracy of -50 to 100 percent (Section 1.5). 

Samples obtained in accordance with the procedures outlined in the 

preceding chapters will be either gases, liquids, or solids. The multimedia analysis flow scheme presented in Figure 24 represents the way in 

which each of the sample types is split for organic and inorganic analysis. 

The inorganic analysis scheme is detailed in a companion flow diagram 

(Figure 25). 

The analytical methods chosen for this manual are the recommended 

techniques for Level 1 determinations. They represent the optimum approach 

to an integrated multimedia assessment effort and should be considered 

comprehensively rather than independently. For example, on-site GC is 

identified for general Level I inorganic gas analysis. Viewed independently, 

a variety of alternative techniques will provide satisfactory Level 1 data 

for inorganic gases; yet within the integrated Level I analysis format, 

the GC can also be used for organic gases and consequently becomes the 

optimum choice. 

81 ̧ 
82 
-7- 

83 
Level i samples are analyzed without making assumptions regarding 

the content of any given sample. Consequently, the analysis plan is 

designed to create a network capable of screening all incoming samples in 

such a way that no environmentally significant element or species escape 

undetected. This "screening network" applied to Level I inorganic analysis 

is designed to detect: 

• Inorganic elements in all influent and effluent streams, 

• SO2, NOx, CO, 02, C02, N 2, H2S, COS, NH3, HCN and (CN)2 in 

gaseous streams, 

• pH, acidity, alkalinity, conductivity, BOD, COD, dissolved 

oxygen, dissolved solids, and suspended solids in water 

streams in addition to inorganic elements, and 

• Leachable cations and anions from samples which are solids 

(particulate matter from SASS, slurry solids, etc.) 

In this way, environmentally important components or streams are identified 

and prioritized so that the Level 2 effort can be directed to the most 

environmentally significant streams. 

The following sections in this chapter describe special considerations 

in the analysis of Level 1 samples. 

7.2 LEVEL 1 ANALYSIS METHODOLOGY 

The analysis of samples from the Level i sampling effort will require 

the use of methods applicable to gases, liquids and solids. Solids and 

liquids will be analyzed for elements including the halogens by spark 

source mass spectrometry (SSMS) after the proper sample preparation. 

Liquids will be analyzed directly for complex anions using reagent test 

kits (Hach or Bausch and Lomb) either in the field or in the laboratory 

(see Table 3, pg. 75). These same reagent kits will be used to analyze 

the leach solutions from the solid samples. Gas samples will be analyzed 

on site for inorganic components by gas chromatography (GC I. The following 

paragraphs discuss the application of these analysis approaches to the 

samples collected. 

84 
7.2.1 Elemental Analysis by Spark Source Mass Spectrometry 

(References 52 through 62) 

There are two general types of SSMS detection systems: photographic 

plate, and electrical detection. For Level 1 survey purposes, the photographic system using the "just disappearing line"technique will be applied. 

To achieve the highest sensitivity, a series of exposures of the photoplate 

is made using the sample, fol.lowed by a series of exposures with a reference sample. Precision and accuracy are highly dependent on spectral line 

widths and shapes. These parameters define optical densities which are 

converted to ion densities by means of calibration curves. A number of 

computer-oriented systems for the derivation and integration of ion intensity 

profiles have been developed for use in accurate and precise determinations. 

Four specific groups of samples for inorganic element analysis result 

from a Level 1 sampling survey: 

1) XAD-2 trap, 

2) Aqueous samples, 

3) Organic samples (liquid or solid), and 

4) Particulate matter, including probe and cyclone 

washes and ash samples. 

In order to analyze these samples for trace elements by SSMS, two 

general sample conditions must be met: 

1) The sample, if it is not a conductor, must be placed 

into a conducting medium (graphite), and 

2) The sample must be as free as possible from organic 

matter which can complicate spectra interpretation. 

Figure 26 shows in schematic form how each sample type is prepared to 

meet these conditions; further explanation is given In the following 

paragraphs. 

Aqueous liquid samples can meet the two conditions simply by adding a 

small amount of the sample to powdered graphite and allowing the water 

to evaporate. (One ml of solution is needed to obtain a i ug/l sensitivity 

assuming a basic SSMS sensitivity of 10"9g.) The graphite is then pressed 

into an electrode. Particulate matter, ash, and fuels will require more 
86 
extensive preparations consisting of reducingthe organicmaterial content of 

the matrix. This matrix reduction step consists of ashing the sample by Parr 

bomb combustion of the sample over HNO 3. An aliquot of this sample is 

then formed into an electrode in the. same manner as the aqueous samples. 

Analysis of the XAD-2 sorbent trap for trace elements is a unique 

problem because little is known about volatile element retention of the 

sorbent trap. In addition, adsorption is not uniform throughout the length 

of the trap. For this reason, the XAD-2 sorbent is first thoroughly mixed 

to ensure a homogeneous sample, and then a 2-g aliquot of the sorbent is 

used in a Parr bomb combustion over HNO 3. The inorganic elements are then 

determined by SSMS, and the remainder of the sample is then used for organic 

analys'is (Chapter VIII.) 

7.2.2 Wet Chemical Analysis for H• As and Sb (References 63• 64) 

While SSMS can theoretically analyze any element, it has been found 

in practice that Hg, As, and Sb are analyzed poorly by SSMS. Thus, these 

elements are determined by atomic absorDtion spectroscopy (AAS) or wet 

chemicals methods. Figure 27 summarizes the analysis scheme for Hg, As, 

and Sb for each of the four general types of samples. This scheme presents the dissolution techniques for the various samples so that once the 

sample is in solution, the appropriate AAS or colorimetric procedures can 

be performed. 

Since several additional sample preparation steps are included in the 

analysis scheme, care must be taken to avoid contamination. Clean working 

areas set aside for trace material analysis are required. Reagent blanks 

on all solutions, acids and reagents must be run to ensure accurate results. 

Analysis of water, particulate matter, ash and fuels for Hg, As,;and 

Sb is accomplishedwith well known analysis schemes. In the •D-2 analysis, the samples are treated as fuels and bomb combusted. These analyses 

have few in.terferences. 

87 
o 

oo 

88 
7.2.3 Gas Chromatographic Analysis of Gaseous Components 

Gaseous samples to be analyzed will come from various sources 

including: 

• 

• 

• 

• 

• 

Stacks•, 

Vents, 

Process input streams, 

Process product streams, and 

Ambient air. 

These samples must be analyzed for both inorganic and organic species 

over a span of concentrations ranging from sub-ppm levels for sulfur compounds to several percent for CO 2 and water in stack gas effluents. 

Because many of the samples which are taken, especially those which contain H2S and other sulfur species, are unstable due to wall absorption or 

possible chemical reaction, it is recommended that the GC analysis be 

performed on site. This also eliminates the shipping of a potentially 

large number of bulky sample containers and permits additional sample 

taking if a problem area is identified. 

Recent advances in gas chromatography have led to the development of 

sensitive and compact instruments that are practical for field applications. 

In addition, multidetector units such as those manufactured by Meloy, 

Beckmann, Tracor and others expand the scope of analYsis to include 

virtually all gaseous species without having a van full of gas chromatographic units. It •s recommended that a multidetector unit capable of 

detecting sulfur compound at the ppb level be purchased for an environmental assessment van. 

Because no single unit is suitable for all proposed analyses, a set 

of columns, temperatures, and detectors is shown in Table 5. Organic 

species are shown because they will be present in most samples along with 

the inorganic species. It is not expected that the proposed set of conditions will be suitable for all mixtures and all possible concentration 

ranges. If a unique situation should arise, an alternative set of analysis 

conditions should be selected and submitted tO the project officer and 

PMB-IERL-EPA for approval. 

89 
9O 
The actual on-site analysis will be accomplished by using an evacuated 

vessel to sample the port, vent, or ambient air• This vessel will then be 

returned to the mobile van and attached to the gas chromatograph via an 

automatic gas sampling valve. The sampling vessel will automatically be 

sampled and the gas analyzed on the GC. The vessel can then be stored for 

further analysis back at the laboratory or purged, cleaned and evacuated 

for further use in the field. 

7.2.4 Analysis of Nitrogen Oxides 

Two gases of environmental interest (NO and NO 2) are not measured 

routinely On a gaschromatograph. The Level 1 analysis of NO/NO 2 concentrations will be performed using the chemiluminescence method. Although 

this is a state-of-the-art analysis technique, it is substantially less 

labor-intensive than EPA Method 7. This method as adapted to Level 1 

analysis involves admitting gas samples into a 3-1iter evacuated flask, as 

described in Chapter II. The sample is then transported to the instrument 

and analyzed. Because a major portion of the analysis time on the 

instrument involves calibration, it is recommended that only sufficient 

calibration to maintain a minimum accuracy of ± a factor of 2 (+100 percent, -50 percent) be performed. 

7.2.5 Analysis of Leachable Material (Reference 25• 

The analysis of water and HCI leachable material from solids can be 

performed by the standard procedures. Spark source mass spectrometry will 

be used for elements, halogens, and total sulfur, while reagent test kits 

will supplement SSMS by performing a variety of tests for complex anion 

species. 

7.2.6 Analyses Specific for Aqueous Samples 

•References 37, 65, 66, 67, 68, 69) • 

In addition to the general inorganic elemental analysis specified in 

this chapter and the organic analysis specified in Chapter VIII, the following analyses must be performed on all aqueous samples: 

• Acidity 

• Alkalinity 

• .pH 

• BOD 

• COD 

91 
• Conductivity 

• Total dissolved solids 

• Anion analysis for SO 4 

• Total suspended solids 

• Dissolved oxygen 

• Ammonia 

• HCN 

NO2-/N03-, and CO 3 

All these analyses can be performed either in the field or the laboratory using reagent test kits, although practicable considerations will 

usually indicate that all analyses except BOD, COD, and suspended solids 

will be done in the field. These kits, which are manufactured by Hach or 

Bausch and Lomb, use a series of procedures that usually follows a modified and simplified version of standard methods. The reagents are encapsulated and stored in smaYl plastic pillows in pre-measured quantities 

until opened fo• analysis. Upon addition of the reagent or reagents to 

the sample, component concentrations are determined colorimetrically or 

turbidimetrically using reference color discs or portable photometers. In 

some cases endpoint titrations are used. Although they are not as accurate 

as the standard laboratory procedures, they have sufficient accuracy for 

Level I objectives and provide the following advantages which qualify them 

for Level 1 survey use: 

Sample preservation The need for involved sample preservation schemes is eliminated by on-site 

analysis. 

• Storage space The need for large areas for sample storage is eliminated. 

Simplicity The reagent test kits are designed to 

be used by non-technical personnel. 

On-site analysis This points out specific problem areas allowing more detailed sampling by the survey team, if necessary. 

When used in the•aboratOry for analysis of leachables, they provide quick, inexpensive analyses for the required data. 

92 
CHAPTER Vlll 

LEVEL 1 ORGANIC ANALYSIS TECHNIQUES 

8.1 INTRODUCTION 

In order to ensure that important emission problems do not go 

undetected, and at the same time to allow the evaluation of a large number 

of sources in a cost effective manner, a simple set of analytical survey 

methods is presented in this chapter. Rather than to represent a comprehensive analysis, the objective of these Level I procedures is to provide 

an estimate of the predominant classes of organic compounds present in a 

given sample. As a result, the methodology is designed to determine the 

presence or absence of all major classes of organic compounds within the 

factor of two quantitative objectives of the Level I analysis. In addition, these methods can be performed in most laboratories and by a technical 

staff with limited previous experience. 

Samples obtained in accordance with the procedures outlined in Chapters II through VI will be either gases, liquids, or solids. The multimedia analysis flow scheme presented in Figure 28 shows how each of the 

sample types is split for organic analysisr 

8.2 LEVEL 1 ORGANIC ANALYSIS METHODOLOGY 

An overview of the methodology to be used for the Level I organic 

analysis is shown in Figure 29. This methodology deals with the preparation of the samples to provide a form suitable for analysis, and with their 

subsequent analysis. 

As indicated in Figure 29, the extent of sample preparation required 

varies with sample type. The low molecular weight CI-C 6 hydrocarbons are 

determined by gas chromatography on site and require no preparation. 

Organic liquids, such as fuel oils, Will not need pretreatment and are 

placed directly into the analysis scheme. However, the majority of the 

samples, including the SASS train components, aqueous solutions such as 

scrubber waters, and bulk solids such as coal or slag, require extraction 

with solvent prior to analysis. This extraction separates the organic 

portion of the samples from the inorganic species and allows analysis to 

)roceed without complication. The analysis of organic extract or organic 
SAMPLE PREPARATION ANALYSIS 

= z 

•o 

94 
FOR C1-C 6 

HYDROCARBONS 

ALIQUOT 

FOR CI-CI2 

HYDROLIQUIDS 

ORGANIC 

ANALYSIS 

SOLUTIONS MATERIALS 

ALIQUOT 

(R 600 rag) 

LIQUID 

CHROMATOGRAPHI 

SEPARATION 

Figure 29. Level 10rqanic Analysis Flow Diagram 

95 
liquid then proceeds by first taking an aliquot of the sample or extract 

for direct GC analysis of compounds boiling in the range of C7-C12 hydrocarbons (I00-200°C). Then an infrared (IR! spectrum is obtained on the 

second aliquot. This IR spectrum provides an indication of the types of 

functional groups present in the sample and also provides a control check 

point for subsequent analyses. All functional groups identified in this 

total sample must be accounted for in the succeeding steps. 

The sample extract or organic liquid is separated by silica gel liquid 

chromatography (LC), using a solvent gradient series, into eight fractions 

of varying polarity. The weight of each of these fractions is obtained so 

that one can determine the distribution of the sample by the various class 

types. An IR spectrum is then obtained on each LC fraction for determination of the types of functional groups present. A low resolution mass 

spectrum (LRMS) is also obtained on all fractions which exceed the concentration threshold criteria in order to determine the principal compound 

types present in each fraction. For the sample streams identified in the 

Level i scheme, these concentrations, computed back to the source, are: 

• Gas (particulate, sorbent trap, etc.) 0.5 mg/m 3 

• Solids I mg/kg 

• Solutions 0.1 mg/l 

Care must be taken in this computation to correct for those C7-C12 

compounds that wereanalyzed by GC and not lost in the LC concentration 

step. 

It should be emphasized that sample contamination and solvent impurities 

are common problems in organic analysi s The best possible laboratory procedures must be used along with verified pure solvents. Blanks and controls 

should be run for each stage in the analysis scheme. 

8.3 SAMPLE PREPARATION 

This section presents sample preparation procedures that are appropriate 

for most samples. The specific solvents indicated should be used where 

possible. In the case of unusual sample requirements, an alternate procedure should be selected and presented to the project officer and the Process 

Measurements Branch, IERL-RTP, for approval. An aliquot of sample extracts 

will be set aside fo.r direct gas chromatographic analysis of. materials in 

96 
the C7-C12 boiling range• It is necessary to obtain the total weight of 

organics inthe solvent extract, to obtain an IR on a portion from this 

extract, and to concentrate the extract for the LC separation. The appropriate stage at which to conduct each of these steps (gravimetric analysis, 

IR, concentrate) will depend on the quantity and solubility of the sample. 

When possible• it is recomended to have at least 10 mg of sample for 

the gravimetric analysis. Prior to the LC analysis step, it is recommended that the solvent solutions be concentrated to i to 10 ml. The 

Kuderna-Danish apparatu s for volumes less than one liter is recommended 

for sample concentration, and a rotary evaporator is recommended for 

volumes which exceed this amount. 

8.3.1 Aqueous Solutions 

Extraction of aqueous solutions should be carried out with methylene 

chloride using a standard separation funnel fitted with a Teflon stopcock. If necessary, ammonium hydroxide or hydrochloric acid should be 

used to adjust the pH of the water to neutral before extraction. Normally, 

three 500-ml methylene chloride extractions of 10-1iter samples should be 

sufficient. 

8.3.2 Solids• Particulate Matter and Ash 

All solid material including products, raw materials, cyclone, probe 

and filter particulate, and ash should be extracted for 24 hours with 

methylene chloride in a Soxhlet apparatus. The Soxhlet cup must be previously extracted in order to avoid contamination. COver the sample 

with a plug of glass wool during the extraction to avoid carry-over of 

the sample. 

8.3.3 Sorbent Trap 

The XAD-2 resin from the sorbent trap is extracted with pentane. 

After the resin is removed from the SASS train cartridge, homogenized, and 

a 2-g portion is removed for the inorganic analysis, the balance is 

extracted to remove the organic material. A large Soxhlet extraction 

apparatus, available from several manufacturers, must be used tO extract 

the 400 ml of resin. The resin is then transferred to a previously cleaned 

extraction thimble and secured with a glass wool plug. Approximately 

97 
2 liters of pentane is added to the 3-1iter reflux flask. (The dumping 

volume of an appropriate commercial extractor is 1500 ml.) The resin is 

extracted for 24 hours. The boiling pentane in the flask should be examined 

periodically to determine whether additional solvent is needed to replace 

that lost by volatilization. 

If large quantities of polar materials are extracted, they may precipitate in the boiling flask near the completion of the extraction. Addition 

of cool methylene chloride to the flask, after extraction is complete, will 

simplify the subsequent transfer and analysis steps. 

The XAD-2 resin should not be extracted with methylene chloride in 

the Soxhlet apparatus because the compatibility of this resin with methylene 

chloride has not been fully evaluated. 

8.4 ANALYSIS OF SAMPLES FOR ORGANICS 

The analysis of each of the prepared or isolated samples for organic 

compounds follows the scheme introduced in Figure 29. The overall scheme 

is based upon an initially recommended scheme (Ref. 51) which has been 

revised based upon subsequent laboratory evaluations (Ref. 70). 

The LC/IR/LRMS procedure will provide reliable data on the compound 

types present in the samples for the relatively high boiling compounds. 

Unfortunately, the SASS train will not capture (and retain for analysis) 

the organic compounds with boiling points in the CI-C 6 range (up to 70°C); 

and the volatile materials in the C7-C12 range (lO0-200°C) are lost in 

various degrees in the sample concentration steps required for the full 

analysis. Consequently, separate gas chromatography procedures have been 

devised for the analysis of these two ranges of materials. 

8.4.1 Gas Chromatographic Analysis of C l C 6 Range (Ref. 71 through 75) 

The on-site gas chromatographic requirements for analysis of the 

C I C 6 gases was presented in detail in Table 5 in Chapter VII. For 

organic analysis the GC system should be calibrated for retention time and 

quantity with a C 1 C 6 n-paraffin mixture. 

The conditions recommended for this analysis are: 

Column: Porapak Q, 100/120 mesh, 6' 

Detector: Flame Ionization 

Temperature: Isothermal at 100°C 

981 
The temperature calibration curve is prepared in the•standard manner 

(Ref. 75). The GC system will simply be separating and analyzing mixtures 

of materials with a given boiling point range (and polarity in some cases), 

rather than individual pure •ompounds. 

hydrocarbons are: 

Gas • 

Methane, C 1 -161 

Ethane C -88 2 

Propane, C 3 -42. 

Butane, C 4 0 

Pentane, C 5 36 

Hexane, C 6 69 

The boiling points of the C 1 C 6 

However, since the chromatogram peaks will represent mixtures of materials 

present in a certain boiling range, rather than pure, individual compounds, 

it is recommended that material observed in the chromatogra• be reported 

as present in the ranges given below: 

1 -160 to -100 

2 -100 to -50 

3 -50 to 0 

4 0 to 30 

5 30 to 60 

6 60 to 90 

If, from other information, it is thought that the species being 

analyzed are solely the C I C 6 hydrocarbons, the basis of the data may 

be reported as such and the chromatogram peaks ass;'gned accordingly. 

99 
8.4.2 •as•Chromatographic Analysis of C 7 CI? Range 

The samples used for this analysis are the methylene chloride and 

pentane extracts before concentration, and the neat organic liquids. 

Organic species boiling in the range of the C 7 C12 hydrocarbons which 

would otherwise be lost by evaporation can be analyzed in a manner similar 

to that described above for the C 1 C 6 gases. The major difference is 

the solvent interference and GC requirements. Even for the dilute sorbent 

trap extracts a flame ionization detector is sufficiently sensitive for 

analysis to require only a one-microliter sample. 

The conditions recommended for this analysis are: 

Column: 1.5% 0V-I01 (or SE-30) on GasChrom Q, i00/120 mesh, 

I/8" OD x 6' SS 

Detector: Flame ionization 

Temperature Program: Isothermal at 50°C for 5 min., then 

program at lO°C/min to upper limit 

of 150°C. 

The initial isothermal portion of the temperature program is required to 

allow the solvent to elute prior to the C 7 hydrocarbon. It will probably 

be desirable to prepare solutions of the neat organic liquids in order to 

prevent overloading and degradation of the column. 

The basic calibration and reporting requirements are the same as for 

the C 1 C 6 gases. The boiling points of the hydrocarbons and recommended 

reporting ranges are: 

vapor Bp (oc) 

Heptane, C 7 98 

Octane, C 8 126 

Nonane, C 9 151 

Decane, C10 174 

Undecane, C11 196 

Dode•ane, C12 216 

7 

8 

9 

lO 

II 

12 

90 to llO 

.110 to 140 

140 to 160 

160 to 180 

180 to 200 

200 to 220 

SinCe the numbers of possible compounds in these ranges are very large, 

it is recommended that material and its quantity simply be reported as 

IO0 
being present in these rangeS. Any specific compound assignments should 

be supported by confirmatory data and may be beyond the scope of the 

Level 1 analysis. 

8.4.3 Liquid Chromatographic Separation 

The detailed procedure for the liquid chromatographic (LC) separation 

is given in Appendix C. All sample extracts and neat organic liquids are 

subjected to this procedure, if sample quantity is adequate. A 100 mg 

portion of the sample is preferred for the LC, but smaller quantities down 

to a lower limit of about 8 mg may be used. The sample is separated into 

approximate classes on silica gel using a gradient elution technique. The 

solvent sequence used for the procedure is given in Table 6. 

Fraction No. 

I 

2 

3 

4 

5 

6 

7 

8 

Table 6. Solvents Used in Liquid 

Chromatographic Separations 

Solvent Composition 

Pentane 

20%' Methylene Chloride in Pentane 

50% Methylene Chloride in Pentane 

Methylene Chloride 

5% Methanol 

20% Methanol 

50% Methanol 

5/70/30, Conc. 

in Methylene Chloride 

in Methylene Chloride 

in Methylene Chloride 

HCl/Methanol/Methylene Chloride 

The LC Separation procedure is not a high resolution technique and 

consequently there is overlap in class type between many of the fractions. 

Fraction 1 contains only the paraffins and possibly some olefins. Fractions 2 through 4 contain predominantly aromatic species. The smaller 

aromatics (benzene, naphthalene) will tend to elute in the early fraction 

(2) while the larger aromatics (benzpyrene, etc.) will tend to elute in 

Fractions 2 through 4. Some low polarity oxygen and sulfur containing 

species may also elute in Fraction 4 but most of these will not elute 

until addition of methanol. 

i01 
Fractions 5 through 7 will contain the polar species including phenols, 

alcohols, phthalates, amines, ketones, aldehydes, amides, etc. The distribution of class type between Fractions 5 through 7 will be a function of their 

polarity and affinity for the silica gel. Some weakacids may elute in 

Fraction 7. 

The very polar species, primarily acids such as carboxylic acids and 

sulfonic acids, will elute in Fraction 8. 

After each fraction is collected, it should be transferred to a tared 

aluminum micro weighing dish for evaporation and gravimetric analysis. 

Fraction 8 should be dried in a glass container because of its hydrochloric 

acid content. Each fraction is subsequently analyzed by IR and, when the 

quantity is sufficient, LRMS (see Section 8.4.5). 

8.4.4Infrared AnaIxsis 

The total sample extract, or neat liquid, and the eight LC fractions 

are analyzed by infrared (IR) spectrophotometry. IR spectra are obtained 

on KBr salt plates using methylene chloride to transfer the sample to the 

plates. A grating spectrophotometer should be used. Sample quantity is 

adjusted so that the maximum signal of the strongest peaks •s about 10% 

transmission. The transmission Signal of the most intense peak should 

not be less than 10%. 

Spectra are interpreted in terms of functional group types present in 

the sample or LC fraction. The many reference texts (Ref. 76 through 79) 

in this area are of considerable help in interpreting theiR spectra. 

8.4.5 Low Resolution Mass Spectrometry 

Low resolution mass spectra (LRMS) are obtained on each LC fraction 

which has sufficient quantity, when referenced back to the source. For 

the various samples.those quantities are: 

Gas SASS train samples 

Ambient air Particulate 

Ambient air Sorbent trap 

Solids 

Aqueous solutions 

O.5mg/m 3 

I ug/m 3 

0.5 mg/m 3 

I mg/kg 

0.1 mg/1 

102 
,The mass spectrometer should preferably have a resolution (m/Am) of 

1000, batch and direct probe inlet, variable ionizing voltage source and 

electron multiplier detection. Volatile samples are analyzed by insertion 

in the batch inle:t. It is anticipated, however, that most samples will 

require analysis via the direct insertion probe. A small quantity of 

sample is placed in the probe capillary and inserted into a cool source. 

The temperature is then programmed up to vaporize the sample. Spectra 

are recorded periodically throughout this period. Spectra are normally 

obta•ned at 70 ev ionizing voltage, but low voltage (10 ev) spectra may be 

much simpler in some cases. Spectra may be obtained at both high and low 

voltage dictated primarily by the spectra obtained. 

Interpretation of the spectra is guided by knowledge of the LC separation scheme, the IR spectra, and other information about the source. Data 

are grouped by homologous series based on a most probable structure assignment. Molecular ion series and fragment ions help to identify compound 

classes. Polynuclear aromatic hydrocarbons are characterized by intense 

double ionization. Many other factors go into the interpretation of the 

spectra guided by the sample itself, experience, and literature references. 

The compilations of reference spectra (Ref. 80 through 83) are particularly 

helpful in the task of reducing the LRMS data. 

103 
CHAPTER IX 

PARTICLE MORPHOLOGY AND IDENTIFICATION 

9.1 INTRODUCTION 

Level i particle morphology and identification use techniques 

designed to study the physical (including structure) and chemical properties of individual particles so that qualitative information concerning 

the potential health effects of the collected particulate matter can be 

determined. An environmental assessment effort generates particulate 

matter samples from the SASS trains and from high volume samples collecting fugitive emissions. An important part of the morphological examination of particulate matter is the identification of contributing sources, 

e.g., fly ash, bottom ash, coal dust, catalyst, etc., so that a detailed 

Level 2 particulate matter sampling effort can be planned. 

The Level 1 effort described in this chapter is based on field weights 

and microscopic techniques which include photomicrography, particle size 

distribution, and polarized light micrography (PLM). 

• Field weight Preliminary weights will act as a control for contamination and/or loss of sample. 

• Photomicrography Field or laboratory photographs will provide sample control and stability checks during shipping and handling and will provide preliminary visual identification of particles and 

particle characteristics. (It is recommended that 

a color photomicrograph be taken in the field for documentation of the sample and its stability). 

• Size distribution Size distribution of fugitive emissions particulate should be determined using the photomicrograph. 

• Polarized light micrography (visual identificati'on) Using polarized light._(R•f" 84, 85, 86• the particu- late matter is viewed under a microscope; particles down to 0.5• can be identified by •hysical appearances. 

Although the procedures described in this chapter are straightforward, 

they do require a degree of skill, experience and the ability to make consistent subjective evaluations on the part of the personnel performing the 

work. Component identification should be carried out by a trained technician and/or microscopist either internally or in a commercial laboratory 

,i104 
specializing in the procedures described in this chapter. The same personnel 

or commercial laboratory should be used for each individual or series of 

environmental assessments. In either case, cost guidelines such as those 

in Reference i or as specified by the projectofficer should be followed 

so the cost of the microscopic analysis does not exceed its utility. 

9.2 PARTICLE CHARACTERIZATION 

Figure 30 presents a flow chart for the Level 1 identification and 

Characterization of unknown particles. The tests indicated in the figure should be performed in conjunction with the macro inorganic and organic 

tests performed on the complete sample fractions (see Chapters VII and VIII). 

To obtain a maximum amount of information from a given sample, a detailed 

discussion of particle analysis by microscopy can be found in Ref. 84. 

9.2.1 Handling Particles for Microscopic Examination 

Whenever the particulate sample is handled, care must be taken to 

avoid contamination or mutilation. The mounting of the sample should be 

performed in a dust free environment. Furthermore, for sizing purposes, 

any manipulations that would grind or crush the sample should be avoided. 

Although the mounting of particulate, matter from the cyclones is 

straightforward, the material collected on filters, especially if matted 

filters are used, can cause several problems. Care must be taken to ensure 

that any removal process does not dislodge any of the filter material. In 

many cases, the quantity of particulate matter collected on the filter 

material may be small and difficult to remove. If a sufficient layer of 

particulate matter is collected so that a small (1-10mg) quantity can be 

scraped off, then a complete microscopic analysis can be performed. If the 

particles cannot be removed from the filter, only a photomicrograph for 

quality control and preliminary visual identification can be taken. 

9.2.2 Photomicro•raphy and Particle Sizing for Fugitive Emissions 

After the particulate matter has been mounted, a color photomicrograph 

is taken to identify the sample and to check chemical stability. This 

photograph will be part of the documentation that accompanies the sample 

as it is logged and stored. If long periods of time occur between sampling 

and analysis, the original photomicrograph is compared to a recent one to 

determine if any physical change has occurred in the sample. 

105 
106 
The microphotographic procedure is thoroughly discussed in Ref. 84. 

In all cases, the exact conditions used (lighting, magnification, mounting 

liquid, etc.) should be noted so future comparisons involve the same photographic conditions. 

Since particles are irregularly shaped, the term "diameter" is really 

not applicable in descriptions of particle size. Two general approaches 

have been developed to approximate the measurement of this parameter. The 

projected diameter is the diameter of a circle equal in area to the profile 

of the particle when viewed normal to the positions of greatest stability 

(Ref. 87). The statistical diameter takes some average linear measure of 

the projection of the particle in a fixed direction, assuming the particles 

are randomly oriented (Ref. 88). Statistical diameters can be measured as 

the mean distance between two tangents on Opposite sides of the particle 

image (Feret's) or the mean length of a line that intercepts the particle 

image and divides it into equal areas (Martin's). 

The selection of the precise method of diameter measurement is not 

well defined. The projected diameter corresponds closely to sedimentation 

measurements (Ref. 88), while Feret's and Martin's diameters are slightly 

greater and less than the p•ojected diameter, respectively. For a more 

detailed discussion of the procedures, the reader is directed to Ref. 88. 

9.2.3 Visual Identification 

In many cases, the trained technician can identify particulate matter 

by visual observations and comparison to known samples using polarized 

light micrography (Ref. 84). Particles are first viewed dry mounted with 

top lighting and the crystal shape or structure is observed. The shape, 

the col or, and cleavage of the crystals and other visual characteristics 

are together used to identify or narrow the list Of possible compounds. 

107 
CHAPTER X 

BIOLOGICAL TESTING 

I0.1 INTRODUCTION 

Biological testing must be considered an integral part of the phased 

approach to environmental assessment. Although the primary emphasis in 

this and related documents (Ref. 1, 2, 3, 22, 25, 27, 45, and 51) is on 

traditional chemical and physical tests, biological (bioassay) tests are 

required in order to provide direct evidence of complex biological effects 

such as synergism, antagonism and bioavailability. Since in most cases, 

this information cannot be derived from physical and chemical tests on 

samples consisting of complex mixtures, biological testing will be incorporated into all three levels of the phased environmental assessment. As 

applied to Level 1, biological testing is limited to whole sample testing 

which is consistent with the survey nature of this level. Biological testing on fractionated samples or on specific components of a given sample 

involves a certain degree of quantification that is more appropriate to 

Level 2 or 3 testing. 

At present, specific biological test procedures have not been completely identified and, therefore, cannot be incorporated into the manual. 

Thus, although bioassy testing has been identified in Figures 1 and 2 

(Chapter I), exact testing requirements have not been consistently delineated 

in the detailed flow diagrams presented in Chapters II-VI. It should also be 

noted that the samples size specified in Table 1 (Chapter I) may be modified 

when the exact biotesting procedures are identified. 

The EPA's Office of Health and Ecological Effects (OHEE) is presently 

developing detailed bioassay requirements and test procedures, and it is 

expected that the initial recommendations will be available in August, 1976. 

Moreover, a Level l bioassay procedures manual similar to this manual will be 

issued in January, 1977. The following sections discuss the types of tests 

and the scope of the manpower required for the Level 1 environmental 

assessment. It should be noted that, although these tests indicate current 

thinking by OHEE, the final recommendations may be significantly expanded 

or reduced. 

108 
10.2 HEALTH EFFECTS BIOASSAYS 

Several test procedures are currently under consideration for stream 

prioritization based on potential health effects; these tests include an 

acute toxicity (in-vitro) test, a mutagenic screening test, and a LD50 

screening test. Although these tests do not provide a directly correlatable measure of effects on human health, they are incorporated to provide 

an indication of potential adverse effects, to permit semi-quantitative 

prioritization of samples, and to direct further health effects studies. 

All health effects procedures must be conducted at EPA-approved laboratories. 

10.2.1 Acute Toxicity (In-vitro) Test 

An estimate of the acute cellular toxicity of solids can be obtained 

from an in-vitro cell mortality test utilizing aveolar macrophages .from 

rabbit lungs. The test consists of incubating the solid sample in a culture 

medium for 24 hours, adding the macrophages to the sample and determining 

the number of dead and living cells after a second incubation period. Cell 

mortality is determined by means of a dye exclusion technique, i.e., living 

cells will not incorporate the dye and are distinguishable from the dead 

cells which will..This test procedure requires approximately 0.5 grams of 

sample and 2 to 4 days for completion of a limited dose response series. 

Present manpower estimates are in the range of I to 2 man-days per series. 

10.2.2 Mutagenicity (Carcino•enicity) Screening Test 

The mutagenic screening test is performed according to a modification 

of the procedure developed by Ames and co-workers (Ref. 89, 90, 91), and is 

also used as a measure of the potential carcinogenicity of a sample. Three 

histidine deficient Salmonella typhimurim strains (TA-1535, TA-1537, and 

TA-1538) are Used; the reversion of the strains to prototrophy indicates 

mutation. The three strains have defective DNA repair systems as well as 

defective lipopolysaccharide coats, and exhibit extreme sensitivity to 

observable mutational events. 

The test consists of dissolving particulate matter samples in dimethylsulfoxide (DMSO), followed by exposure of the bacterial populations to the 

dissolved particulate material on plates using an agar overlay method. 

Appropriate controls, blanks, and bacterial toxicity tests are included. 

The test procedure requires 0.5 grams of sample and 2 to 5 days for 

109 
completion of a limited dose response series. Estimated manpower requirements are approximately 2 man-days per series. 

10.2.3 LD50 Screening Test 

The LDso test is used as a measure of acute toxicity in a whole 

animal. The test is performed by administering known levels of the sample 

to a small population of mice and extrapolating the mortality rate tO 

obtain an LDso value. The test procedure requires 14 days and 15 grams of 

sample. Manpower requirements are approximately lman-d•y. The information 

obtained can be supplemented by performing the mutagenic screening test 

described in Section 10.2.2 on urine samples and detection of toxic metabolites produced by the animal. This would add approximately 1.2 man-days 

to the test cost. 

10.3 ECOLOGICAL EFFECTS BIOASSAYS 

A number of test procedures are currently under consideration for 

evaluating the effect of samples on aquatic and terrestrial forms of life. 

These p•ocedures will utilize selected species of animals and plants to 

provide an indicationof the short term toxicity of samples to non-human 

forms of life. In addition, the tests can potentially be extended to 

measure bioaccumulation and entrance into the food chain. 

10.3.1 Aquatic Effects 

Acute toxicity tests are conducted by exposing selected aquatic species 

to several levels of pollutant concentration and determining the mortality 

rate. Fathead minnows and daphnia are widely used in assessing fresh water 

effects. Comparable marine organisms are the sheephead minnow and mysid 

shrimp. All tests require 2 to 4 days for completion. The fresh water 

tests require about 1.2 man-days and 40 liters of sample. The daphnia and 

Shrimp require approximately 3-4 man hours and 10 liters of sample. These 

tests can also be.expanded to include bioaccumulation studies by chemical 

tissue assay at an added cost of 6 man-days per sample. 

10.3.2 Terrestrial Effects 

Although simple general tests for effects on terrestrial forms of life 

have not been as widely developed or applied as aquatic tests, a few specifiC 

techniques are available. The measurement of ethylene produced by plants 
exposed to air pollutants has been used successfully to assess the health 

hazards of some pollutants. This test requires 4 hours and takes approximately:2 man-hours. Measurement of the 02 consumption and CO 2 p.roduction 

of soil samples containing microorganisms can also be used to assess the 

impact of gaseous, liquid or solid samples. Such tests require 600 hours 

for completion and are inexpensive. Finally, exposure of a microcosm contai.ning a number of terrestrial species (plants and animals) to samples has 

been used in a few instances. This test requires 20 days and manpower 

requirements range from 2 to 4 man-days per system. 

111 
REFERENCES 

.7. 

10. 

Hamersma, J. Wo, and Reynolds, S. L., "Field Test Sampling/Analytical Strategies and Implementation Cost Estimates; Coal Gasification and 

Flue Gas Desulfurization," EPA-600/2-76-O93b, U. S. Environmental 

Protection Agency, Research Triangle Park, N. C.,April 1976. 

Dorsey, J., C. Lockmuller, L. Johnson, and R. Statnick. "Guidelines 

for Environmental Assessment Sampling and Analysis Programs Level i•" 

U. S. Environmental Protection Agency, Research Triangle Park, N. C. 

Mar 1976, 35 pp. 

12. 

Hamersma, J. W., and Reynolds, S. L., "Tentative Procedures for 

Sampling and Analysis of Coal Gasification Processes," EPA Contract No. 

68-02-1412, Task Order No. 3, U. S. Environmental Protection Agency, 

Research Triangle Park, N. C., Mar 1975, 150 pp. 

Brenchley, D. L., Turley, D. C., and Yaime, R. G., "Industrial Source 

Sampling," 1st ed, Ann Arbor Science Publishers, Ann Arbor, Mi., 

1973, 439 pp. 

ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 

Annual Book of ASTM Standards, Part 23, D1357-57, American Society 

for Testing and Materials, Philadelphia, Pa., 1971, pp 291-297. 

C]ausen J., Grant,. A., Moore, D., and Reynolds, S. L., "Field Sampling 

for Cytotoxicity Test Samples," EPA Contract No. 68-02-1412, Task 

Order Nos. 8, 14, 15, U. S. Environmental Protection Agency, Research 

Triangle Park, N. C., Sept 1975, 87 pp. 

Bombaugh, K., Cavanaugh, E., Dickerman, J., Keil, S., Nelson, T., 

Cowen, M., and Rosebrook, D., "Sampling and Analytical Strategies for 

Compounds in Petroleum Refinery Streams," Vol. I and II, EPA Contract 

No. 68-02-1882, U. S. Environmental Protection Agency, Research 

Triangle Park, N. C., 1975. 

Application of El Paso Natural Gas Co. before U. S. Federal Power 

Commission, Docket No. CP73-.131, El Paso, Tx., Aug 1972. 

Danielson, J. A., "Air Pollution Engineering Manual," 2nd ed, Air 

Pollution Control District, County of Los Angel.es, Los Angeles, 

Ca., 1973, p 987. 

Shaw, H., and Magee, E. M., "Evaluation of Pollution Control in 

Fossil Fuel Conversion Processes in Gasification", EPA-650/2-74-O09-C, 

U. S. Environmental Protection Agency, Research Triangle Park, 

N. C., July 1974. 

ASTM Committe• D,3 a•d D'5• ITG••-•••; Coal and Coke," 1971 

Annual Book of ASTM Standards, Part 19, Dl145-53, American Society 

for Testing and Materials, Philadelphia, Pa., 1971, pp 1208-1213. 

ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 

Annual Book of ASTM Standards, Part 23, D1605-60, American Society 

for Testing and Materials, Philadelphia, Pa., 1971, pp 349-380. 

112 
13. 

14. 

15. 

!6. 

17. 

18. 

19. 

ASTM Committee D-3 and D-5, "Gaseous Fuels; Coil and Coke•" 1971 

Annual Book of ASTMStandards, Part 19, D1247-54, American Society 

for Testing and Materials, Philadelphia, Pa., 1971, pp 222-231. 

Leithe, W., "The Analysis of Air Pollutants," Ist ed, Ann ArborHumphrey Science Publishers, Ann Arbor, Mi,, 1970, p 150. 

U.S. Environmental Protection Agency, Federal Register 36, 24876 

(1971). 

Intersociety Committee, "Methods of Air Sampling and Analysis,"Ist ed, 

American Public Health Association, Washington, D.C., 1972, p 480. 

Mueller, P.K., Chairman, "Methods in Air Pollution and Industrial 

Hygiene Studies," 12th Conference, University of California, Los 

Angeles, Ca., !971, p 170. 

American Conference of Governmental Industrial Hygienists, "Air 

Sampling Instruments," 4th ed, ACGIH, Cincinnati, Oh., 1972, pp S-I 

to S-50. 

Lapson, W.F., Dehne, H., and Harris, D.B., presented to 67th Annual 

Air Pollution Control Association meeting, Denver, June 1974. 

20. Silverman, L•, Billings, C., and First, M., '!Particle Size Analysis 

in Industrial Hygiene," Ist ed, Academic Press, New York, N.Y., 

1971, 371 pp. 

21. Ahuja, S., Cohen, E., Kneip, T., Lambert, J., and Zweig, G., "Chemical 

Analysis of the Environment and Other Modern Techniques," Ist ed, 

Plenum Press, New York, •.Y., 1973, 384 pp. 

22. Flegal, C. A., Starkovich, J. A., Maddalone, R. F., Zee, C., and Kraft, 

M. L., "Procedures for Process Measurements, Trace Inorganic Materials," 

EPA Contract No. 68-02-1393, U. S. Environmental Protection Agency, 

Research Triangle Park, N. C., July, 1975, 130 pp. 

23. Geiver, P. M., in "Air Pollution," Volume II, A. C. Stern, Ed., Academic 

Press, New York, N. Y., 1968, p 249. 

24. 

.25. 

Deming, W. E., "Some Theory of Sampling," 1st ed, John Wiley and Sons, 

Inc., New York, N. Y., 1955, 500 pp. 

Maddalone, R. F., and Quinlivan, S. C., "Technical Manual for Inorganic 

Sampling and Analysis," EPA Contract No. 68-02-1412, Task Order No. 16, 

U. S. Environmental Protection Agency, Research Triangle Park, N. C., 

Apr 1976, Section 01-04. 

26. ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 

Annual Book of ASTM Standards, Part 23, D2928-71, American Society 

for Testing and Materials, Philadelphia, Pa., 1971, pp 832-858. 

27. Kolnsberg, H., "Technical Manual for the Measurement of Fugitive 

Emissions,,' EPA-600/2-76-O89-A, U. S. Environmental Protection Agency, 

Research Triangle Park, N. C., 1976. 

113 
28. 

29. 

30. 

31. 

32. 

33. 

34., 

35: 

36. 

37, 

38. 

39. 

40. 

41. 

Vandergrift, A., Shannon,L., Lawless, E., Borman, P., Sailee, E., 

and Reichel, M., "Particulate Pollutant System Study, Volume Ill 

H•ndbook of Emission Properties," EPA Contract NO. 22-69-104, 

U. S. Environmental Protection Agency, Durham, N. C., 1971, p 629. 

ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 

Annual Book of ASTM Standards, Part 23, D2682-71, American Society 

for Testing and Materials, Philadelphia, Pa., 1971, pp 699-710. 

U. S. Environmental Protection Agency, Federal Register 36, 22384 

(1971). 

Seeley, J. L., and Skogerboe, R. K., Anal. Chem. 46, 415 (1974). 

Midwest Researc h Inc., and Hittman Associates & Co.,•"Methods for 

Identifying and Evaluating the Nature and Extent of Non-Point 

Sources of Pollutants," EPA-430/9-73-014, U. S. Environmental Protection 

Agency, Washington, D. C., 1973. 

"Handbook for Monitoring Industrial Wastewater," U. S. EPA Technology 

Transfer Series, U. S. Environmental Protection A•ency, Washington, D. C., ]973. 

McCoy, J. W., "Chemical Analysis of Industrial Water," 1st ed, 

Chemical Publishing Co., New York, N. Y., 1969, pp 175-176. 

Lager, J. A., and Smith, W. A., "Urban Stormwater Management and 

Technology An Assessment," EPA-600/2-75-065, U. S. Environmental 

Protection Agency, Cincinnati, Ohio, December 1974. 

Taras, M. J., Greenburg, A. E., Hoak, R. D., and Rand, M. C., 

"Standard Methods for the Examination of Water and Wastewater," 

13th ed, American Public Health Association, New York, N. Y., 1971, 

874 pp. 

Shelley, P. E., and Kirkpatrick, G. A., "An Assessment of Automatic 

Sewer Flow Samples," EPA-600/2-75-065, U. S. Environmental Protection 

Agency, Cincinnati, Ohio, December 1975. 

Sridharan, N., and Lee, G. F., J. of Water Pollution Control Assoc. 46, 

684 (1974). 

Wanielista, M. P., Yousef, Y. A., and MCLellan, W. M., presented at 

the 48th Annual Water Pollution Control Federation Conference, Miami 

Beach, Fl., Oct 1975. 

Chamberlain, T., Jones, D., Trost, J., and Grant, A., "Interim Report 

for Fabrication and Calibration of Series Cyclone Sampling Train," 

EPA Contract No. 68-02-1412, Task Order No. 7, U. S. Environmental 

Protection Agency, Research Triangle Park, N. C., Apr 1975, 54 pp. 

Brookman; G. T., Martin, D. K., Bender, J. J., and Persio, J. V., 

"Evaluation of Waterborne Fugitive Emissions," TRC Project 32593 

Task 02 Report, Wethersfield, Ct., June 1976, 151 pp. 

114 
42. ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 

Annual Book of ASTM Standards, Part 23, D1066•67T, American Society 

for Testing and Materials, Philadelphia, Pa., 1971, pp 125-135. 

43. ASTM Committee D-19 and D-22, "Water; Atmospheric Analysis," 1971 

Annual Book of ASTM Standards, Part 23, Dl192-64, American Society 

for Testing and Materials, Philadelphia, Pa., 1971, pp 190-195. 

44. ASTM Committee D-2 and F-7, "Petroleum Products-LPG, Aerospace 

Materials, Sulfonates, Petrolatum, Wax," Part 18, D270-65, American 

Society for Testing and Materials, Philadelphia, Pa., 1971, pp 47-71. 

45. Faeirhelier, R., Marn, PI'J., Harris, D. H., and Harris, D. L., 

"Technical Manual for Process Sampling Strategies for Organic 

Materials," EPA-600/2-76-122, U. S. Environmental Protection Agency, 

Research Triangle Park, N. C., April 1976. 

46. Gould, R.F., ed., "Coal Science," Advances in Chemistry Series 55, 

American Chemical Society, Washington, D.C., 1966, Sections Ill, 

IV and VI. 

47. Anderson, W.W. in "Standard Method of Chemical Analysis," 6th ed, 

F. Welcher, Ed., D. Van Nostrand Co., Inc., Princeton, N.J., 1963, 

pp 28-38. 

48. ASTM Comittee D-3, D-5 and D'22, "Plastics-Specifications, Methods 

of Testing Pipe, Film, Reinforced and Cellular Plastics," 1974 

Annual Book of ASTM Standards, Part 26, D2234'72, American Society 

for Testing and Materials, Philadelphia, Pa., 1974, pp 482-498. 

49. Leonard, J.W., and Mitchell, D.R., "Coal Preparation," 3rd ed., The 

American Institute of Mining, Metallurgical, and Petroleum Engineers, 

Inc., New York, N.Y., 1968, Chapters 6, 7 and 8. 

50. Lowry, H.H., ed., "Chemistry of Coal Utilization," Suppl. Vol. 1019, 

John Wiley and Sons, New York, N.Y., 1963,.1142 pp. 

51. Jones, P., Graffeo, A., Detrick, R., Clarke, P.• and Jacobsen, R., 

"Technical Manual for Analysis of Organic Materials in Process 

Streams," EPA-600/2-76-072, U. S. Environme•ital Protection Agency, 

Research Triangle Park, HI. C., 1976. 

52. Nicholls, G. D., Graham, A., Williams, E., and Wood, M., Anal. Chem. 

3•9, 584 (1967). 

53. Attari, A., "Fate of Trace Constituents of Coal During Gasification," 

EPA-650/2-73-O04, U. S. Environmental Protection Agency,Research 

Triangle Park, N. C., August 1973. 

54. Ahearn, A., ed., "Trace Analysis by Mass Spectrometry," Ist ed, 

Academic Press, New York, N. Y., 1972, 460 pp. 

55. Javorskii, F. F., Anal. Chem. 46, 2080 (1974). 

56. Von Lehmden, D., Jungers, K., .and Lee, R. Jr,, Anal• Chem. 46, 239 

(1974). 

115 
57. Kessler, T., Sharkey, A., and Friedel, R., "Spark Source Mass Spectrometer Investigation of Coal Particles and Coal Ash," Bureau of Mines 

Technical Progress Report 42, P#ttsburgh, Pa., 1971, 15 pp. 

58. Jacobs, M.L., Sweeney, S.L., and Webster, C.L., in "Keystone Coal 

Industry Manual," 1975 ed., G.F. Nielson, Ed., McGraw-Hill Mining 

Publications, New York, N.Y., 1975, pp. 243-245. 

59. 

60. 

Brown, R., Jacobs, M.L., and Taylor, H.E., American Laboratory 4, 

29 (1972). 

Brown, R., and Taylor, H.E•,."The Application of Spark Source Mass 

Spectrometry to the Analysis of Water Samples," Proceedings of the 

American Water Symposium No. 18, American Water Resources Association, 

Urbana, I•., 1974, p 72. 

61. Bringham, K.A., and Elliott, R.M., Anal. Chem. 43, 43 (1971). 

62. Guidoboni, R.J.; Anal. Chem, 45, 1275 (1973). 

63. Dean, J.A., and Rains, T.C., "Flame Emission and Atomic Absorption 

Spectrometry in Components and Techniques," Vol. 2, Marcel Dekker, 

Inc., New York, N.Y., 1971, Chapter 10. 

64. Angino, E.E., and Billings, G.K., "Atomic Absorption Spectrometry in 

Geology," Elsevier Publishing Co., New York, N.Y., 1967, 144 pp. 

65. "Products for Water Analysis," Hach Chemical Co., Catalog No. 11, 

Ames,la., 1974, p 50. 

66. 

67. 

"A New Concept in Water Analysis," Bausch and Lomb Analytical Systems 

D•vision, Catalog No. 33-6070, Rochester, N.Y.; 1976, p II. 

Czernikowski, 0., American Laboratory 7, 52 (1975). 

68. 

69. 

Patton, W.F., and Brink, A. Jr., J. Air Pollut. Control Assoc. 13, 

162 (1963). 

Dominick, D. D., "Methods for Chemical Analysis of Water and Wastes," 

EPA-625/6-74-O03, U. S. Environmental Protection Agency,Cincinnati,., 

Ohio, 1974. 

.70. Levins, P. L., Ca•agay, A. B., Thrun, K. E., Stauffer, J. L., and 

Guilmette, L., "Evaluation of Alternative Level I Organic Analysis 

Methods," Draft Report on EPA Contract No. 68-02-2150; U. S. Environmental Protection Agency, Research Triangle Park, N. C. June 1976, 

pp 1-8. 

71. Leibrand, R.J., Applications Laboratory Report 1006, Avondale, Pa., 

Mar 1966. 

72. "Liquid Phase and Solid Support Applications to Chromatographic 

Separation," Hewlett-Packard Applications Laboratory, Avondale, Pa., 

1970, 67 pp. 

73. Snyder, L.R., Anal. Chem. 33, 1527 (1961). 

116 
74. "Compilation of Gas Chromatographic Data," ASTM Data Series, 

Publication No. DS25A, American Society for Testing and Materials, 

Philadelphia, Pa., 1967. 

75. ASTM Committee D-2, "Petroleum Products-LPG, Aerospace Materials, 

Sulfonates, Petrolatum, Wax," 1971 Annual Book of ASTM Standards, 

Part 17, D2887-70T, American Society for Testing and Materials, 

Philadelphia, Pa,, 1971, pp 1072-1081. 

76. Rao, C.N.R., "Chemical Applications of Infrared and Raman Spectroscopy," 

Ist ed• Academic Press, London, England, 1963, 683 pp. 

77. Colthup, N.B., Lawrence, H.D., and Wiberley, S•E., "Introduction to 

Infrared and Raman SpectrascQpy,".Ist ed, Academic Press, London, 

England, 1964, 511 

78. Cross, A.D., "An Introduction to Practical Infrared Spectroscopy," 

Ist ed, Butter•orth, Inc., Washington, D. C., 1964, 86 pp. 

79. Kendall, D.N., "Applied Infrared Spectroscopy," Ist ed, Reinhold 

Publishing Corporation, New York, N.Y., 1966, 560 pp. 

80. Reed, R.I., "Applications of Mass Spectrometry to Organic Chemistry," 

Ist ed, Academic Press, New York, N•Y., 1966, 256 pp. 

81. Budzikiewicz, H., Djerassi, C., and Williams, D., "Mass Spectrometry 

of Organic Compounds," Ist ed, Holden Day, Inc., San Francisco, Ca., 

1976, 690 pp. 

82. Imperial Chemical Industries, Ltd., "Eight Peak Index of Mass Spectra," 

Ist ed, Mass Spectrometry Data Center, Alder Maston, Reading, United 

Kingdom, 1970. 

83. "Selected Mass Spectral Data," API Research Project No. 44, Texas 

A&M University, College Station, Tx., 1975. 

84. McCrone, W.C., Drafty, R., and Dilly, J.C., "The Particle Atlas," 

Ist ed, Ann Arbor Science Publishers, Ann Arbor, Mi., 1967, 406 pp. 

85. west, P.W., The Chemist Analyst 34, 76 (1945). 

86. West• P.W., The Chemist Analyst 35, 4 (1946). 

87. Herdon, G., "Small Particle Statistics," 2nd ed, Academic Press, New 

York, N.Y., 1960, 520 pp. 

88. Orr, C., and Dalla Valle, J.M., "Fine Particle Measurement, Size, 

Surface and Pore Volume," Ist ed, Macmillan Publishing Co., New York, 

N.Y., 1960, p 83-91. 

89• Ames, B.W., Gurney, ELG., Miller, J.A. and Bartsch, H., Proc.•Nat. 

Acad. Science 69:3Z28 

90. Ames, B.W., Lee, F•D. and Durston, W.E., Prec. Nat. Acad. Science 70: 

782 (1973). 

91. Ames, B.W., Durston, W.E., Yamasaki, E. and Lee, F.D., Prec. Nat. 

Acad. Science 70:2281 (1973). 

117 
APPENDIX A 

DESIGN AND PREPARATION OF A FIELD TESTING UNIT 

(REFERENCES 1, 3, 6) 

Mobile laboratories in the form of vans or trailers have been used 

very effectively for a variety of source assessment efforts such as stack 

sampling,, ambient air sampling and water quality measurements. Because 

the use of a van as a mobile laboratory for on-site analysis is very 

desirable for the Level I effort, this appendix is included to aid those 

contractors interested in outfitting their own vans. 

A.I ADVANTAGES 

In order to sample a proposed site in a timely and efficient manner, 

it is desirable to fabricate a field testing unit which is completely outfitted with all necessary equipment required for Level I sampling and 

on-site analysis. In addition to the obvious advantages Kith respect to 

sampling, a major advantage of such units lies in the fact that many samples 

may be or are unstable, and delaying the analysis could result in erroneous 

conclusions. In addition, the results for a given sample are often quite 

unexpected and the presence of an on-site laboratory allows the immediate 

re-analysis of a check sample and/or modification of the experimental plan 

on a real time basis, which allows the saving of time, effort and cost. 

In the phased sampling effort for environmental assessment, many 

effluent parameters must be determined on-site due to their unstable nature. 

In addition, the philosophical aims of Level• 1 testing in the phased 

approach can be enhanced greatly with an on-site laboratory. A wellequipped laboratory will allow additional Level I or "Semi-Level 2" samples 

to be taken so that the final Level 2 effort can be focused in greater 

detail, with a resultant decrease in cost for the Level 2 effort. Finally, 

unanticipated problem areas can be identified in greater detail for the 

Level 2 effort. 

Most sampling efforts will require the rental of a van or trailer to 

transport needed equipment, tools and reagents from the laboratory to the 

sampling source. Driver and mileage rates must also be figured into the 

overall cost. Since the above costs are incurred as a natural outgrowth 

of most sampling efforts, the cost effectiveness of a mobile laboratory 

118 
unit is greatly enhanced since these normally incurred costs may be 

applied to the mobile laboratory unit. An additional advantage is that 

sampling equipment assembly, sample transfer and equipment clean-up are 

facilitated by the additional work space made available in the mobile 

laboratory unit for all phases and types of sampling operations. 

A.2 COMPONENTS AND LAYOUT 

This section describes the components and layout of a Level 1 sampling 

and on-site analysis room. A van was chosen as the room because of the 

versatility and mobility of the van compared to a trailer, particularly 

when many sites must be visited. The discussion below, however, also 

applies to the outfitting of a trailer. 

Basic furnishings of the Level I vans should include: 

• A refrigerator for storing ice and preserving water 

samples. 

An ice maker to provide a continuous and convenient 

supply of ice for cooling down the SASS train 

i mpl ngers. 

Cabinets, drawers and shelves for storage of sampling equipment, tools, hardware, spare parts, glassware, sample bottles, reagents, etc. 

• Work surfaces for assembling equipment and performing analyses. 

• Lockers for storage of rain gear, goggles, overalls, 

etc. 

• .A desk and 2,drawer file for storage of data, notebooks 

and instrument and equipment manuals. 

A laminar flow bench for performing.operations such 

as sample transfers (particularly those for trace 

analyses and toxicity testing) that are susceptible 

to ambient contamination. 

Thework areas of the vans will be separated into two general areas: 

one for "clean" operations which will be away from the door and separated 

by curtains, and one for "dirty" operations. A layout design for the 

furnishings listed above is shown in Figure 31. Along with the basic 

floor plan, cutaway views of the two side walls are. also presented. 

119 
PARTfTION GAS 

CHROMATOGRAPH 

\GENERATOR 

•ARTITION CURTAIN HOUSING 

CUTAWAY V IEW SHOW NG RI GHT S DE 

R FT 

WINDOW 

WINDOW 

WINDOW 

LEFT SIDE 

32 FT 

RIGHT SIDE DOOR 

STORAGE 

CABINET 

ICE REFRIGERATOR 

MAKER 

TOP VIEW 

GAS CHROMATOGRAPH, 

AND CARRIER AND 

CALIBRATION GASES 

PARTfflON 

CURTAIN 

CUTAWAY VIEW SHOWING LEFT SIDE 

PARTITION 

r/CURTAIN 

Figure 31. Level 1 Multimedia Mobile Laboratory 

120 
Several important criteria dealing with functionality and structural 

strength are incorporated in the design of the field test vans shown in 

Figure 31. These criteria are: 

Functionality 

• Maximize work surfaces and storage spaCe. 

• Separate clean work areas from dirty work areas. 

• Place related supplies, equipment and work areas 

in close proximity. 

Structural Strength and Safety 

• Distribute weight evenly from side to side. 

• Place heaviest load between axles. 

• Avoid installing items that would require bolts 

into housing over a generator. 

Figure 31 shows an 8' x 32' van with a 15 KW generator to supportthe 

basic van systems such as air conditioning, lights, refrigerator, ice maker, 

and gas chromatograph. For a completely independent power supply to suPport all van and sampling (SASS train) systems, a 30 KW towable.diesel 

generator is required• Items shown in the: layout are all flexible in size 

and design and can be chosen and assembled to make maximum usage of the 

space inside the vanL For example, the work bench and storage cabinet at 

the rear of the van can be adjusted to the same height as the generator 

housing sheif to provide a continuous, level work surface with wall cabinets 

providing additional storage. Good use can also be made of the areas over 

the wheel wells since certain items can be built around.or over the wells. 

Equipment for the Level 1 mobil• test van is shown in Table 7. 

Additional equipment which would be used for Level 2 source assessments 

consists of high-accuracy, continuous monitors for particulate matter and 

individual gases (i.e.• CO, NO x, SOx, 02, and C02); automatic, compositing 

water samplers with flow monitors; high-accuracy water analysis instruments; 

and other special capital equipment appropriate for field use. This Level 2 

sampling and analysis equipment can be carried in the vans when space and 

121 
Table 7. Level 1 Mobile Van Equipment 

Gas Sampling 

SASS Train 

Hi-Vol Ambient Samplers 

Glass bulbs with a diaphragm vacuum pump for evacuation 

Gas Analysis 

Multiple column and detector gas chromatograph for CO, SO x, N 2, CO 2, 02 C I C 6 hydrocarbons, NH3, HCN, (CN)2 

Water Sampling 

Portable Hach Sampling Kit 

Positive displacement pump and hoses 

Portable flow monitoring devices 

Water Analysis 

Electrodes and meters to measure pH, conductivity, turbidity, 

and dissolved oxygen 

Portable water analyzer to perform alkalinity, hardness and 

COD analysis 

Portable Hach Analysis Kit 

weight capacities permit. The excess can be drop-shipped or placed in a 

separate trailer as appropriate. However, the cost, bulk and weight of the 

equipment along with the infrequency of its use make permanent installation in the vans impractical. 

122 
APPENDIX B 

PROCESS DATA NEEDS 

Table 8 delineates the process data needs for a phased environmental 

.assessment. These needs are subcategorized for plant characterization, 

plant operating conditions, plant stream conditions, and sampling/analysis. 

123 
124 
125 
126 
APPENDIX C 

LIQUID CHROMATOGRAPHY SEPARATION PROCEDURE 

Column: 200 mm x 10.5 mm ID, glass with teflon stopcock. 

Adsorbent: Davison Silica Gel, 60-200 mesh, Grade 950, (Fisher Scientific 

.Company). This adsorbent is activated at 110oc for two hours 

just prior to use. Cool in a desiccator. 

C.1 PROCEDURE FOR COLUMN PREPARATION 

Dry pack the chromatographic column, plugged at one end.with glass 

wool, with 6.0 grams,.of freshly activated sili•a gel. A portion of properly activated silica gel weighing 6.0 ±0.2 g occupies 8 ml in a I•0 ml 

graduated cylinder. Vibrate the column for a minute to compact the gel 

bed. Pour pentanei•tO the solvent reservoir positioned above the cO'l•mn 

and let the pentane flow into the silica gel bed until the column is 

homogeneous throughout and free of any cracks and trapped ai• bubbles*. 

The total height of the silica bed in this packed column is 10 cm. The 

solvent void volume of the column is 2 to 4 ml. When the column is fully 

prepared, allow the pentane level in the column •o drop to the top of the 

silica bed so that the sample can be loaded for subsequent chromatographic 

elution. 

C.2 PREPARATION OF THE SAMPLE 

At room temperature evaporate the solvent from an aliquot of solution 

containing at least 20 to 500 mg of sample. The preferred sample weight is 

lO0.mg. Weigh this sample in a glass weighing funnel. In order to facilitate transfer of the sample, add 0.5 to 1.0 g of activated silica gel to 

the sample and carefully mix this with the sample using a micro-spatula. 

A convenient device for the elimination of gel bed cracks and air bubbles 

is acetone coolant, which is subsequently referred to as the ACE B method. 

It consists of a paper towel wound loosely around the glass column along 

the region of the crack or bubble; the paper towel is periodically 

moistened with acetone. The acetone evaporation cools the region and 

dissipates the bubble or crack. 

127 
Table 9 shows the sequence for the chromatographic elution. In 

order to ensure adequate resolution and reproducibility, the column elution 

rate is maintained at I ml per minute. 

Table 9. Liquid Chromatography Elution Sequence 

No. Volume 

Fraction Solvent Composition Collected 

I Pentane 25 ml 

10 ml 

10 ml 

20% Methylene_. chloride in pentane • 

•'wv(L50% Met•de in pentane 

Methylene chloride 10 ml 

20% Methanol in methylene chlorid.; • • 10 ml 

50% Methanol in •thylene chloride T•IO ml 

C.3 LOADING SAMPLE ON THE COLUMN 

Quantitatively transfer the sample into the Column via the weighing 

funnel used for sample preparation; a micro-spatula can be Used to aid in 

the sample transfer. Rinse the funnel* with a few ml of pentane to complete the quantitative sample transfer. (Note: Do not rinse with methylene 

chloride because this solvent will cause the aromatics to elute width the 

paraffins.) Add the solvent slowly to minimize disturbing the gel bed and 

eliminate the trapped air bubbles, particularly in the zone of the samplecontaining silica gel, by using the ACE B approach (see footnote, preceding 

page). The chromatographic system is now ready for sample fractionation. 

Save this weighing funnel, for subsequent additional rinsing with the 

solvents used at interim fractions up to methylene chloride. 

128 
C.4 CHROMATOGRAPHIC SEPARATION INTO 8 FRACTIONS 

The volume of solvents shown in Table 9 represents the solvent volume 

collected for that fraction. If the volume of solvent collected is |ess 

than volume actually added due to evaporation, add additional solvent as 

necessary. In all cases, however, the solvent level in the column should 

be at the top of the gel bed, i.e.,the sample-containing zone, at the 

end of the col|ection of any sample fraction.. 

After the first fraction is collected, rinse the original sample 

weighing funnel with a few ml of the Fraction Number 2 solvent (20% 

methylene chloride/pentane) and carefully transfer this rinsing into the 

column.. Repeat as necessary for Fractions 3 and 4. 

129 
APPENDIX D 

PREPARATION OF XAD-2 RESIN 

The XAD-2 resin to be used in the SASS train sorbent trap must be 

cleaned prior to use. The resin as obtained from Rohm and Haas is soaked 

with an aqueous salt solution. This salt solutionplus residual monomer 

and other trace organics must be removed before the resin can be used for 

sampling trace organics. 

Transfer the resin to a large Soxhiet extractor with a 1.5-1iter 

dumping Volume. This requires 2 to 2.5 liters of solvent in the 3-1iter 

supply flask. The XAD-2 resin is then extracted in sequence with the 

following Solvents and times: 

• Water 22 hrs, 

• Methanol 22 hrs; 

• Anhydrous ether 8 hrs, 

o Pentane 22 hrs. 

The water removes the salt solution and any water soluble organic 

material. Methanol removes the residual water from the resin and ether 

removes the majority of the polar organic material. Pentane is used as 

the final stage because it is the solvent used in the actual extraction 

of Collected material from the resin. 

After the final pentane extraction, transfer the XAD-2 resin into a 

clean flask and dry it under a vacuum for 18 hrs using mild heat from a 

heat lamp. 

130 
tt':CHNICAL REPORT DATA 

E pA-.600/2-76-160a 

IERL-RTP Procedures Manual: Level 1 Environmental 

Assessment 

}. RECIPIENT'SACCESSIOP•ND. 

$. REPORT DATE 

TRW Systems Group 

lOne Space Park 

Redondo Beach California 90278 

June 1976 

PERFORMING ORGANIZATION CODE 

AUTHOR{S) J.W. Hamersma, S.L. Reynolds • and s. PERFORMING ORGANIZATION REPORT NO 

R.F. Maddalone 24916-6040-RU 00 

10, PROGRAM ELEMENT NO. 

lAB013; ROAP 21AAZ-015 

11. CONTRACT/GRANT NO. 

68-02-1412, Task 18 

13: TYPE OF REPORT AND PERIOD COVERED 

_T_ask Final; 2-5/76 

14. SPONSORING AGENCY CODE 

EPA, Office of Research and Development 

Industrial Environmental Research Laboratory 

Research Triangle Park, NC 27711 EPA-ORD 

•S. SUPPLEMENTARY NOTES• IERL-RTP project officer for this m,•mual is R.M. Statnick, Mail Drop 62, (919) 549-8411, Ext 2557. 

,•. ASSTRAC• The manual gives Level 1 procedures (recommended by Industrial Environ- mental Research Laboratory--Research Triangle Park) for personnel experienced in coIlecting and analyzing samples from industrial and energy producing processes. 

The phased environmental assessment strategy provides a framework for determining industry, process, and stream priorities on the basis of a staged samplingand analy- 3is technique. (Level 1 is a screening phase that characterizes the pollutant potential af process influent and effluent streams. ) The manual is divided into two major !sections: sampling procedures and analytical procedures. The sampling section is further divided into five chapters: fugitive emissions, gases, aerosols, liquids (including slurries), and solids. The analytical section is divided into three chapters: inorganic, organic, and bioassays. 

L DESCRIPTORS 

Pollution 

•ampling 

•nalyzing: 

Industrial Processes 

Energy Conversion 

BG.as Sampling 

lOassay 

Unlimited 

KEY WORDS AND DOCUMENT ANALYSIS 

EPA Form 2220,1 (9-73) 

b. IDENTIFIERS/OPEN ENDED TERMS 

Pollution Control 

Stationary Sources 

Environmental Assessment 

Energy Processes 

Fugitive Emissions 

19. SECURITY CLASS 

Unclassified 

c. COSA]I |:icld/Gmup 

13B 07D 

14B 

llG 

131 

Aerosols 

Liquids 

Slurries 

Solids 

Inorganic Compounds Organic Compounds 

20. SECURITY (:LASS (l'hispage) 

Unclassified 

21. NO. OF PAGES 

145 

13H 

10A, 10B 

07B 

D6A 07C