EPA-600/2-76-160a
June 1976
Environmental Protection Technology Series
IERL-RTP PROCEDURES MANUAL:
Level 1 Environmental Assessment
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
i. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade
names or commercial products constitute endorsement or
recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/2-76-160a
June 1976
IERL-RTP PROCEDURES MANUAL:
LEVEL 1
ENVIRONMENTAL ASSESSMENT
by
J.W. Hamersma, S.L. Reynolds, and R.F. Maddalone
TRW Systems Group
One Space Park
Redondo Beach, California 90278
Contract No. 68-02-1412, Task 18
ROAPNo. 21AAZ-015
Program Element No. 1AB013
EPA Project Officer: Robert M. Statnick
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
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 recommend-
ed the implementation of a phased sampling and analytical strategy for
Environmental Assessment Programs. The first phase, Level 1, 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 soecify the exact sampling and
analysis procedure for every possible circumstance. When situations
arise where alternative Level 1 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.
If this document 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
-------
TRW Document No.
24916-6040-RU-OO
ABSTRACT
This manual gives Level 1 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 1 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 slurries),
and solids. The analytical section is divided into three chapters:
inorganic, organic, and bioassays.
IV
-------
ACKNOWLEDGEMENT
This work was conducted under the direction of Dr. R. M. Statnick,
EPA Task Order Manager, 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. Loch-
miiller of the EPA during the course of this task order. The extensive
editorial and technical assistance provided by S. C. Quinlivan is also
appreciated.
The many helpful comments, suggestions, and criticisms from the follow-
ing PMB/IERL-RTP Term Level of Effort contractors is also appreciated:
Arthur D. Little, Inc., Sampling and Analysis of Organic Materials,
Dr. P. L. Levins, project manager; Research Triangle Institute, Develop-
ment of Environmental Assessment Control Technology Quality Assurance
Programs, Dr. F. Smith, project manager; Aerotherm/Acurex Core., Measure-
ment Techniques for High Temperature/High Pressure Processes, Inc., Mr.
F. E. Moreno, project manager; Southern Research Institute, Particulate
Sampling Suoport, Dr. W. B. Smith, project manager; and TRC, Inc., 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.
-------
CONTENTS
Page
INTRODUCTION xiii
CHAPTER I. STRATEGY AND GENERAL INFORMATION 1
1.1 Definition of Strategies 1
1.1.1 The Phased Approach 1
1.1.2 Strategy of the Phased Approach 2
1.1.2.1 Definition of Level 1 Sampling
and Analysis 3
1.1.2.2 Definition of Level 2 Sampling
and Analysis 4
1.2 Multimedia Sampling Procedures 6
1.2.1 Classification of Streams for Sampling Purposes 6
1.2.2 Phased Approach Sampling Point Selection
Criteria 8
1.2.3 Stream Prioritization Using the Phased Approach 11
1.3 Data Requirements and Pre-Test Planning 13
1.3.1 Process Data Needs 13
1.3.2 Pre-Test Site Survey 14
1.3.3 Pre-Test Site Preparation 15
1.4 Analysis of Samples 16
1.5 Accuracy and Precision of Results 17
CHAPTER II. GAS AND VAPOR SAMPLING METHODOLOGY 20
2.1 Introduction ., 20
2.2 Sampling Test Preparation 20
2.3 Gas Sampling Techniques 21
2.3.1 High Pressure Line Grab Samples 22
2.3.2 Slight Positive Pressure Grab Purge Sampling 22
2.3.3 Negative Pressure Evacuated Bulb Sampling 26
2.3.4 General Considerations 26
2.4 Sampling Procedures 27
2.4.1 Process Streams, Flues and Ducts 27
2.4.2 Vents 28
2.5 Sample Handling 28
vi
-------
CONTENTS (Continued)
Paqe
CHAPTER III. GASEOUS STREAMS CONTAINING PARTICULATE MATTER 29
3.1 Introduction 29
3.2 Particulate Matter Sampling Methodology 34
3.3 Preparing for Sample Collection 35
3.3.1 Pre-Site Survey 35
3.3.2 Personnel Requirements 35
3.3.3 Equipment Preparation for Sample Collection 36
3.3.3.1 Precleaning Procedures for the SASS
Train and Sample Containers 36
3.3.3.2 Apparatus Checkout 37
3.4 Series Cyclone Sampling Procedure 38
3.5 Sample Handling and Shipment 40
3.6 Opacity Measurements 41
3.7 Data Reduction 46
CHAPTER IV. FUGITIVE EMISSIONS SAMPLING 47
4.1 Introduction 47
4.2 Airborne Fugitive Emissions 49
4.2.1 Preparation for Sample Collection 49
4.2.1.1 Pre-test Site Survey 49
4.2.1.2 Measurement Equipment 50
4.2.1.3 Personnel Requirements 54
4.2.2 Sampling Procedures 55
4.2.2.1 High Volume Sampler Applications 55
4.2.2.2 SASS Train Sampler Applications 57
4.2.2.3 Gas Samples 58
4.2.3 Decision Aid for Appropriate Category Selections 58
4.2.4 Sample Handling and Shipment 59
4.2.5 Data Reduction for Airborne Fugitive Emissions 59
4.3 Waterborne Fugitive Emissions 60
4.3.1 Preparation for Sample Collection 60
4.3.1.1 Pre-test Site Survey 60
4.3.1.2 Measurement Techniques 60
4.3.1.3 Personnel Requirements 61
vii
-------
CONTENTS (Continued)
Page
4.3.2 Sampling Procedures 61
4.3.3 Decision Aid 61
4.3.4 Sample Handling and Shipment 63
4.3.5 Data Reduction for Waterborne Fugitive Emissions 63
CHAPTER V. LIQUID AND SLURRY SAMPLING 65
5.1 Introduction 65
5.2 Preparing for Sample Collection 66
5.2.1 Pre-test Site Survey 66
5.2.2 Personnel Requirements 67
5.2.3 Equipment Preparation 67
5.2.3.1 Sample Containers 57
5.2.3.2 Apparatus 68
5.3 Sampling Procedures °9
5.3.1 Heat Exchange Sampling Systems for High
Temperature Lines by
5.3.2 Tap Sampling 70
5.3.3 Dipper Sampling 72
5.4 Liquid Sample Handling and Shipment 73
CHAPTER VI. SOLID SAMPLING 76
6.1 Introduction 75
6.2 Pre-test Site Survey 76
6.3 Solids Sampling Procedures 77
6.3.1 Shovel Grab Sampling 77
6.3.2 Boring Techniques 78
6.4 Sample Collection and Storage 79
CHAPTER VII. LEVEL 1 INORGANIC ANALYSIS TECHNIQUES 81
7.1 Introduction 81
7.2 Level 1 Analysis Methodology 84
7.2.1 Elemental Analysis by Spark Source Mass
Spectrometry 85
7.2.2 Wet Chemical Analysis for Hg, As, and Sb 87
7.2.3 Gas Chromatographic Analysis of Gaseous
Components 89
7.2.4 Analysis of Nitrogen Oxides 91
vi ii
-------
CONTENTS (Continued)
Page
7.2.5 Analysis of teachable Material 91
7.2.6 Analyses Specific for Aqueous Samples 91
CHAPTER VIII. LEVEL 1 ORGANIC ANALYSIS TECHNIQUES 93
8.1 Introduction 93
8.2 Level 1 Organic Analysis Methodology 93
8.3 Sample Preparation 96
8.3.1 Aqueous Solutions 97
8.3.2 'Solids, Particulate"Matter"and Ash 97
8.3.3 Sorbent Trap 97
8.4 Analysis of Samples for Organics 98
8.4.1 Gas Chromatographic Analysis of C1 - Cg Range 98
8.4.2 Gas Chromatographic Analysis of C7 - C,2 Range 100
8.4.3 Liquid Chromatographic Separation 101
8.4.4 Infrared Analysis 102
8.4.5 Low Resolution Mass Spectrometry 102
CHAPTER IX. PARTICLE MORPHOLOGY AND IDENTIFICATION 104
9.1 Introduction 104
9.2 Particle Characterization 105
9.2.1 Handling Particles for Microscopic Examination 105
9.2.2 Photomicrography and Particle Sizing for
Fugitive Emissions 105
9.2.3 Visual Identification 107
CHAPTER X. BIOLOGICAL TESTING 108
10.1 Introduction 108
10.2 Health Effects Bioassays 109
10.2.1 Acute Toxicity (In-vitro) Test 109
10.2.2 Mutagenicity (Carcinogenicity) Screening Test 109
10.2;3 LD5Q Screening Test 110
10.3 Ecological Effects Bioassays 110
10.3.1 Aquatic Effects 110
10.3.2 Terrestrial Effects 110
REFERENCES 112
IX
-------
CONTENTS (Continued)
Page
APPENDIXES
A Design and Preparation of a Field Testing Unit 118
A.I Advantages 118
A.2 Components and Layout 119
B Process Data Needs 123
C Liquid Chromatography Separation Procedure 127
C.I Procedure for Column Preparation 127
C.2 Preparation of the Sample 127
C.3 Loading Sample on the Column 128
C.4 Chromatographic Separation into 8 Fractions 129
D Preparation of XAD-2 Resin 130
-------
ILLUSTRATIONS
Page
1. Multimedia Sampling Approach Overview 7
2. Basic Level Sampling and Analytical Scheme for
Particulates and Gases 9
3. Basic Level 1 Sampling and Analytical Scheme for
Solids, Slurries, Liquids 10
4. Typical Process Flow Diagram for Limestone Venturi
Spray Tower System 12
5. High Pressure Line Grab Purge Sampling Apparatus 23
6. Low Pressure Grab Purge Sampling Apparatus 24
7. Evacuated Grab Sampling Apparatus 25
8. Source Assessment Sampling Schematic 30
9. Cyclones and Water Cooled Probe 31
10. XAD-2 Sorbent Trap Module 32
11. Flue Gas Sampling Flow Diagram 33
12. Sample Handling and Transfer - Nozzle, Probe, Cyclones
and Filter 42
13. Sample Handling and Transfer - XAD-2 Module 44
14. Sample Handling and Transfer - Impingers 45
15. Sampling Categories for Level 1 Airborne Fugitive
Emissions 48
16. Decision Example for "Worst Case" Site 51
17. Expanded View of Connections of XAD-2 Cartridge to High
Volume Sampler 53
18. Sampler Flow Rate Settings for Dust 56
19. Plug Collector for Fugitive Water Samples 62
20. Level 1 Water Runoff Fugitive Emissions Characterization 64
21. Sampling Methods as a Function of Stream Type 65
22. Sampling Apparatus for HPHT Lines 71
23. Field Handling Scheme for Liquid/Slurry Samples 74
24. Multimedia Analysis Overview 82
25. Level 1 Inorganic Analysis Flow Scheme 83
26. Sample Preparation for SSMS Elemental Analysis 86
27. Hg, Sb, As Sample Preparation and Analysis 88
28. Multimedia Organic Analysis Overview 94
29. Level 1 Organic Analysis Flow Diagram 95
30. Particle Characterization Flow Scheme 106
31. Level 1 Multimedia Mobile Laboratory 120
xi
-------
TABLES
Page
1. Recommended Sample Sizes and Detection Limits 19
2. SASS Train Impinger System Reagents 39
3. List of Analyses to be Performed on Liquid/Slurry
Samples 75
4. Decision Matrix for Solid Sampling 78
5. Recommended Gas Chromatographic Parameters for 90
Analysis of Inorganic and Organic Species
6. Solvents Used in Liquid Chromatographic Separations 101
7. Level 1 Mobile Van Equipment 122
8. Process Data Needs for Phased Environmental Assessment 124
9. Liquid Chromatography Elution Sequence 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 pro-
gram. 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 by the methods delineated in
Chapters II through VI. For those samples which are analyzed as part of
the sampling 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 1.
The purpose of this initial effort is to obtain preliminary environmental
assessment information, identify problem areas, and provide the basis for
the prioritization of streams, components and classes of materials for
further 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 1 sampling activities that can be found in most industrial
comolexes: gas and vapor samnles, gaseous streams containing particulate
matter, fugitive emissions sampling, liquid and slurry sampling, and solids
xiii
-------
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 samoles for shipment.
Chapters VII specify a Level 1 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 1 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 1 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,
xiv
-------
CHAPTER I
STRATEGY AND GENERAL INFORMATION
The Process Measurements Branch of IERL/RTP has developed a three-
tiered 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 des-
cribed in Section 1.1, this procedures manual focuses on the Level 1 sam-
pling and analysis effort.
This manual describes for an experienced professional a set of sampling
and analytical procedures which are compatible with the information require-
ments of a comprehensive Level 1 environmental assessment. This manual is
not intended for use by inexperienced personnel. A comprehensive environ-
mental 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 1n Chapters VII
through X. The overall sampling and analysis effort is designed to be
quantitative in nature with an overall accuracy of a factor of ±2 to 3.
1.1 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 information-
cost 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
analytical effort. The first level utilizes quantitative sampling and
analysis procedures accurate within a factor of 2 to 3 and: 1) 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 with-
in 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 prob-
lem. 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 per-
centage of the sampling or analysis effort to be repeated.
There is a possibility that many streams or even the entire installa-
tion 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, con-
siderable savings could result in both time and furids.
A second possibility is that budgetary limitations may require pri-
oritizing 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.
-------
The phased approach offers potential benefits 1n 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. 1) 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 1 identifies the questions
that must be answered by Level 2, and Level 3 monitors the problems identi-
fied in Level 2 to provide information for control device design and deve-
lopment. For example, if a Level 1 test indicated that polycyclic organic
material (POM) might be present in significant amounts and gave a positive
mutagenicity test, Level 2 sampling and analysis would be designed to
determine the exact quantities of organic constituents, the percentage of
POM, and the identity of as many specific POM compounds present as eco-
nomically possible. In addition, using the Level 1 data and any available
Level 2 results, the sample would be retested for cytotoxicity and muta-
genicity in order to confirm and expand the total bioassay information. A
test for cardnogenicity 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 1 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 site-
specific, neither a general approach nor sampling and analysis methodolo-
gies can be specified and for this reason, Level 3 will not be discussed
further.
1.1.2.1 Definition of Level 1 Sampling 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.
-------
For this reason, no special procedure 1s employed in obtaining a statisti-
cally representative sample and the chemical, physical, and biological test-
ing has survey and/or quantitative accuracy consistent with the character-
istics of the sample.
At this level, the sampling and analysis is designed to show within
broad general limits the presence or absence, the approximate concentra-
tions, 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 addi-
tional testing among a series of energy and industrial sources, streams
within a given source, and components within streams. Level 1 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 1
technique Involves the application of slightly more sophisticated pro-
cedures 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 Sampling 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 1 for
maximum cost and schedule efficiency. Consequently, Level 2 sampling and
-------
Tnalysis 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 1, it will not always
be true that a Level 2 effort at a given site will be more manpower inten-
sive 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 qas source where volatile organic components were
the only materials found in a sample which were of environ-
mental 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 ele-
ments of environmental interest. On Level 2, a repre-
sentative sample would be taken and accurately analyzed
only for the elements of interest.
• A fugitive emissions problem which can be defined by con-
ventional 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.
t A source where trace inorganic elements are found at gener-
ally 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 1 procedure described in this manual can be utilized to
acquire process samples, effluent samples, and fead stock samples. The
Level 1 environmental assessment program must, at a minimum, acquire a
sample from each 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 pro-
cedures 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 1n
Figure 1 has been organized around the five general types of sampling found
in industrial and energy producing processes rather than around the analy-
tical procedures that are required on the collected samples. This facili-
tates the complex and difficult task of organizing the manpower and equip-
ment necessary for successful field sampling and establishing meaningful
units of cost.
The five sample types are:
• Gas/Vapor - These are samples for light hydrocarbon and
inorganic gas analysis. They include samples from input
and output process streams, process vents, and ambient
ai r.
t 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. Non-
flowing pastes are considered solids.
-------
MULTIMEDIA SAMPtING
APPROACH OVERVIEW
COAl PILE AND/
OK RAW MATERIALS
1 GENERAL
•OUNDARY
ASSESSMENTS
Isrccric
l«iOCESS
APPLICATIONS
Figure 1. Multimedia Sampling Approach Overview
-------
0 Solids — These include a broad range of material sizes
from large lumps to powders and dusts, as well as non-
flowing wet pastes. Because the distinction between solids
and slurries can become blurred, the reader should consult
both Chapters V and VI when in doubt.
• Particulate or Aerosol Samples — This involves sampling in
contained streams such as ducts or stacks.
• Fugitive 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 III) by using a probe nozzle which is
specifically selected for isoklnetic 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 ensure a sample representative of
the actual effluent. The recommendations in this manual are restricted
to Level 1 sampling and analysis criteria only.
8
-------
ELEMENTS AND
SELECTED ANIONS
PHYSICAL SEPARATION
ORGANiCS ! INTO FRACTIONS,
ELEMENTS AND
SELECTED ANIONS
PHYSICAL SEPARATION
INTO FRACTIONS
LC/IR/MS
NOX CHEMILUMINESCENCE
CHROMATOGRAPHY OR
BIO ASSAY SEE CHAPTtR X
APPROVED ALTERNATIVE
MATERIAL > C6 | (AS NECESSARY)
PHYSICAL SEPARATION
INTO 8 CLASSES
CHROMATOGRAPHY
ALIQUOT I'ORGAS
CHROMATOGRAPHIC
ANALYSIS
PHYSICAL SEPARATION
INTO FRACTIONS,
LC/IR/MS
*WEIGH INDIVIDUAL CATCHES
Figure 2. Basic Level 1 Sampling and Analytical
Scheme for Particulates and Gases
-------
LEACHABLE
MATERIALS
QA PHYSICAL SEPARATDN
INTO FRACTIONS LC/IR/MS
ELEMENTS AND
SELECTED AN IONS
-. ORGANICS
SELECTED ANIONS
PHYSICAL SEPARATION
INTO FRACTIONS
INORGANICS StS«N!?.AND
SELECTED ANIONS
ELEMENTS AND
SELECTED ANIONS
SELECTED
WATER
TESTS
(AQUEOUS)
se& SECTION 7.2.6,
CHAPTER VII
PHYSICAL SEPARATION
INTO FRACTIONS
LC/IR/MS
PHYSICAL SEPARATION
INTO FRACTIONS,
LC/IR/MS
ALIQUOT FOR GAS
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
containers 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 be relaxed con-
siderably for Level 1 site selection.
In the case of solids sampling, the standard procedures used in sam-
pling 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 sampling procedure.
In most cases, Level 1 sampling methods 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 sampling philosophy. These modifications include:
1) 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 1 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 Prioritization 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
-------
- GAS STREAM
LIQUOR STREAM
O LEVEL 1 SITES
O LEVEL 2 SITES (MEETS ALL EPA METHOD 5 AND ASTM CRITERIA)
O LEVEL 1 AND LEVEL 2 SITES
O GAS COMPOSITION
8 PARTICULATE COMPOSITION & LOADING
» SLURRY OR SOLIDS COMPOSITION
OVERFLOW
THE POWER PLANT IS NOT INCLUDED FOR THE PURPOSES OF THIS REPORT.
Figure 4. Typical Process Flow Diagram for Limestone Venturi Spray Tower System
-------
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 prioritization studies and of the preliminary selection process based
on the site selection criteria of a given program, and on the data require-
ments 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 require-
ments as well as any anticipated problems. The following paragraphs pre-
sent 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 asso-
ciated 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 partic-
ularly important to know that detailed relevant process data are necessary
for the sampling and analysis effort as well as for the overall environ-
mental 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 interrelationships among
process variables permits extrapolation to condi-
tions in other sizes of the system being assessed,
and
6) Detailed process data are the basis from which con-
trol 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 1 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 appro-
priate data that may be collected. It is expected that professional
sampling and analysis personnel in conjunction with the EPA Project
Officer and PMB-IERL-RTP will select the appropriate data requirements for
a given industry.
1.3.2 Pre-test Site Survey
After establishing the necessary process data needs and selecting a
tentative set of sampling points, a pre-test site survey should be per-
formed. 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 missing data. Using this information, the survey
team will then proceed to select the actual sampling sites with the follow-
ing criteria in mind:
t 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.
t 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 1
sampling).
14
-------
• The sampling site must have a reasonably favorable
working environment. The survey personnel must con-
sider 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 the 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 manpower will 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 VII through X specify analysis schemes and procedures that
will provide data relatable to all existing EPA standards and those addi-
tional data requirements specified above for Level 1 environmental assess-
ment. These schemes identify accepted methods of analysis, anticipated
output, and the estimated level of effort required to implement the analy-
sis scheme.
There are seven categories of analysis:
• Organic Analysis - Survey techniques are used to
identify compound classes by functional group.
t 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 - Includes microscopic examina-
tion 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 Chromatoqraphic Analysis -Consists of on-site analy-
sis of gaseous and/or low boiling organic and inorganic
species.
• 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.
16
-------
Table 1 shows the recommended sample volumes that must be collected
which will result in the listed sensitivities when the recommended analy-
sis method is used. These sensitivities have been selected by PMB-IERL-RTP
for both inorganic and organic components 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 proce-
dures which have been selected for this Level 1 manual are adaptations of
standard EPA, ASTM, API, etc., methods which have a accuracy and/or pre-
cision factor of ±10-20 percent or better. These requirements, however,
have been reduced to fit the economic and philosophical constraints for a
Level 1 environmental assessment. In order to determine emissions from a
given site to within a factor of ±2 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 analy-
ses both had a precision within a factor of 2, then the overall precision can
be calculated on the basis of equation (1).
Oj.-*..-, - "W0-—I*-- + °
2 2
total \°sampling analysis
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 0.5X to 2X. Substituting these values into equation (1)
gives a range from 0.3X to 3.8X for the precision of the final value which
is to be used for the environmental assessment. (For the lower limit
°total = X " °-5x2 = °-3x and for tne uPPer 11mit' 0total = X
17
-------
Table 1. Recommended Sample Sizes and Detection Limits
Sample Source
Sample Type
Inorganic Organic
Stack 30m ?
(1,060ft3)
Gas d) 3 liters
Ambient Air 480m3
(17,000ft3)
Liquid 10 liters
(2.5 gal)
Solid 1 kg
(2.2 Ib)
a) Particulate Matter . O.Olyg/rri3
b) Sorbent Trap, >Ci2 b| O.Olyg/m3
c) Sorbent Trap, 65-012°' —
a) General Components
b) Sulfur Compounds 9)
a) Particulate Matter
b) Sorbent Trap, >Cj2
c) Sorbent Trap, C5~Ci2
2yg/m3
2yg/m3
1 mg/m
lyg/m3
O.Olyg/m:
O.Olyg/m;
O.Olyg/m-:
lyg/1 h)
1 mg/g
100yg/m3
Iyg/m3
30yg/m3
lyg/m3
10yg/md
lOyg/1
100 ng/g
f)
a) At STP
b) The analysis is terminated for organic material if less than 15 mg
(0.5 mg/m3) of organic components are extracted from the total sample.
c) Assumes that the XAD extract is 2 liters and a 1 yl sample is injected
into a G.C. with a flame ionization detector with a 0.1 ng detection
limit.
d) A maximum sample size of 10 ml is assigned for all cases.
e) Detection limit is approximately 1 ppm.
f) Detection limit is approximately 0.1 ppm.
g) Detection limit is approximately 1 ppb.
n
h) Assuming a 0.1 ml sample for SSMS electrode formation and a 10 g
instrument sensitivity.
18
-------
From this explanation, it can be seen that when it is stated that the
results are accurate with a factor of three, it means that actual value
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.
19
-------
CHAPTER II
GAS AND VAPOR SAMPLING METHODOLOGY
2.1 INTRODUCTION (References 1, 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 pur-
pose 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 pro-
cess cycle (see Chapter I).
This chapter discusses the sampling methodologies applicable to the
following stream types:
t 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. Con-
sequently, 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-CQ
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.
Fugitive gaseous 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 1, 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 famil-
iar with the characteristics of each sampling location, A pre-test
Level 1 site survey of process streams and vents for sampling gaseous com-
ponents involves the following six steps:
1) 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 system must be conducted to uncover any
undocumented output sources or unrecorded equipment
modifications.
3) Locating and itemizing process vents.
4) Locating and itemizing stacks and flares.
5) 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 dis-
covered, then a full-scale Level 2 analysis will be
initiated to quantify the problem. Thus, the selec-
tion of representative Level 1 sampling sites should
reflect this philosophy of obtaining the type of a
sample for analysis rather than typical compliance
testing criteria.
21
-------
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 guide-
lines regarding parameters of interest may be found in
Appendix B.
Aside from these general considerations, there are two specific require-
ments for gas and vapor sampling:
1) 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, 16, 17, 18)
As stated in Section 2.1, a single grab sample of each stream in
question is sufficient for Level 1 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 suf-
ficient pressure reduction for effective bulb purge. The sampling bulb
is the dual valve positive displacement type and is 3 liters in volume.
The bulb must be purged with approximately ten volumes of the stream
gas before the sample is isolated.
A small 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
-------
ro
to
PYREX
WOOL
PLUG
STYROFOAM
PROTECTOR
Figure 5. High Pressure Line Grab Purge Sampling Apparatus
-------
rv>
PYREX
WOOL
PLUG
STYROFOAM
PROTECTOR
Figure 6. Low Pressure Grab Purge Sampling Apparatus (for Less Than 2 Atmospheres Pressure)
-------
ro
on
TEFLON TUBE TO ACT AS NOZZLE
PYREX WOOL PLUG
STYROFOAM
PROTECTOR
EVACUATED
3 LITER
VESSEL
Figure 7. Evacuated Grab Sampling Apparatus (for Subatmospheric Pressures)
-------
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 pres-
sure is slight. Since the pressure is slight, however, a side-bloed is
not required for pressure reduction. Figure 6 shows the apparatus con-
figuration 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 1/4 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 pre-
vent 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 con-
tainer with dilute hydrochloric add followed by distilled water.
26
-------
After use, containers should be thoroughly cleaned. A 2:1 mix of
Alconox or abrasive cleaner and water may be used followed by a tap water
rinse. The container is then rinsed with a 1:1 mixture of HySQ. and
HN03, followed by a tap water rinse of the acid, followed by a final flush-
ing 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, flues and ducts, and vents.
2.4.1 Process Streams. Flues and Ducts
A process 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 Sec-
tion 2.3.1. Streams under only slight positive pressures and streams
under negative pressures will require the apparatus described in Sec-
tions 2.3.2 and 2.3.3 respectively.
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 sys-
tems 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-line 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 nozzle 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 (this 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 regu-
lated 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-liter evacuated bomb (Figure 7). The important considerations in
obtaining vent gas samples are:
t The sample must be taken while the vent cycle 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.
28
-------
CHAPTER III
GASEOUS STREAMS CONTAINING PARTICULATE MATTER
3.1 INTRODUCTION
Stationary source participate 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, 19). In
addition, health effects data indicate that an adequate assessment of the
collected partlculate matter requires size fractionation into at least
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 10)
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 particu-
late matter size-classified into three ranges: a) >10 jim, b) 3 p.m to 10 urn,
and c) 1 |o.m to 3 fim. Together with a standard 142 mm filter, a fourth cut,
<1 jxm 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 sys-
tem 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 10-cfm high volume vacuum
Manufactured by Aerotherm Corporation, 485 Clyde Avenue, Mountain View,
Ca., 94042, Tele. (415) 964-3200.
29
-------
CO
o
CONVECTION
OVEN
FILTER
STACK T.C.
GAS COOLER
GAS
TEMPERATURE
T.C.
CONDENSATE
COLLECTOR
DRY GAS METER ORIFICE METER
CENTRALIZED TEMPERATURE
AND PRESSURE READOUT
CONTROL MODULE
IMP/COOLER
TRACE ELEMENT
COLLECTOR
TO CFM VACUUM PUMP
Figure 8. Source Assessment Sampling Schematic
-------
Figure 9. Cyclones and Water Cooled Probe
-------
CO
HOT GAS
FROM OVEN
LIQUID PASSAGE
GAS PASSAGE
GAS COOLER
XAD-2 CARTRIDGE
CONDENSATE
RESERVOIR
3-WAY SOLENOID VALVE
TO COOLING BATH
FROM COOLING BATH
COOLING FLUID
RESERVOIR
IMMERSION
HEATER
LIQUID PUMP
TEMPERATURE
CONTROLLER
Figure 10. XAD-2 Sorbent Trap Module
-------
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, 1s shown 1n Figure 11. Details of the sample handling
and transfer procedures are presented in Section 3.5.
Knowledge of the 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 matter fraction
will deposit in close 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 1 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 iso-
kinetic conditions when the test is initiated. For the accuracy require-
ments of Level 1, this flowrate is allowed a slippage of from -30 percent
to +50 percent of the specified Isokinetic rate. Conditions existing out-
side of the above specified margin must result 1n 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 a 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:
1) Clogging of the probe nozzle, and
2) Clogging of the backup filter.
•33
-------
FLUE \ J OPACITY BY
SOURCE _j "RINGELMANN
1
1
PARTICULAR
t * * * r
F
GASES "SAMPLED
PROBE AND , , __ ,
R,NCsE°NE W&HT 'vKi ^cm W^GHT IMP'NGERS
i '
COMBINE COMBINE ELEMENTS
•• t 1 i 1
CO "l '
•**!• EXTRAOION ASH BIO ASSAY ANIONS MORPHOIOG
,, 1 r
i r
t
(JKJjANICS INORCANIC5
XAD-2
HOMOGENIZE
AND DIVIDE
ASH FOR 1
INORGANICS |
•
'
EXTRACT FOR
ORGANICS
1
' (CHAPTER ID
1 4
XAD-2
ADSORPTION
AND GAS
CONDITIONER
ON-SITE
G.C.
H
ORGANICS
C1-C6
INCLUDING
N, S, 0 AND
HALOGEN
COMPOUNDS
i •
C
CONDENSATE CH-><
:H2CI2 EXTRACTION CON
* *
CH2CI2
EXTRACT
INORGANICS
ON AQUEOUS
PHASE
| ACIDIFY | | BASIFY |
|
NOX
CHEWI-
LUMINESCENCE
|
5H/CH2Cl2 GAS
DITIONER WASH
TOTAL ORGANICS IN THE
XAD MODULE
Figure 11. Flue Gas Sampling Flow Diagram
-------
The only possible solution 1n both cases requires SASS train shutdown and
concomitant probe nozzle cleaning or filter replacement.
3.3 PREPARING FOR SAMPLE COLLECTION
3.3.1 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 1 sampling as
described in Section 1.3 and 3.2).
0 The sampling site must have a reasonably favorable working
environment. The survey personnel will consider the tempera-
ture 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 suffici-
ently 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 1n 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 correla-
tions 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. 1, 6, 24).
The acquisition of a Level 1 sample using a SASS train generally requires
two and in some cases, three persons for equipment assembly and disassembly.
After assembly the train 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 parti oil ate matter samples required to characterize the site in question~7
the time required for the acquisition of each sample (determined as a func-
tion 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 discuss the equipment preparation required for
the SASS train, including cleaning procedures of the train components and
sample containers, and apparatus checkout. The SASS train schematic and
other parts of the train Ire^ "shown~TnTigures~87~9"andTOT
3.3.3.1 Precleaning 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 generalized cleaning procedure cannot be estab-
lished. Two primary cleaning methodologies are required. The first
methodology, described 1n 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 1n preparing the sampling train and sample containers
for sample collection is prepasslvatlon with a nitric add solution. All
surfaces in the sampling train which come in contact with sample, as well
as all sample containers and containers for the impingers, should be
prepassivated by a one-hour standing contact with 1:1 (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
36
-------
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 or dry
nitrogen and inspected throughly for any sign of contaminating residue,
scale, rust, etc. A contaminated train component may not 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 clean-
room 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 "clearrodm grade nylon has been
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:
1) 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 allowable leak rate for the SASS train is 0.05 cfm
37
-------
at a pressure of 20 Inches tif 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 1 sample may be taken as follows (Ref. 6):
1) Assemble sampling 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 1n
the XAD-2 Module. Under most conditions 15 to 30 minutes
are required for preheating. The oven and probe should be
maintained at 205°C UOO°F). The temperature of the cartridge
should be kept at 20°C (680F).
3) Measure the stack temperature, moisture content, and velocity
profile. Determine the position in the stack which corresponds
to the average stack velocity.
4) Leak test the system. As mentioned earlier 1n Section 3.3.3.2,
the equipment should be thoroughly leak-checked prior to site
arrival. If this has been done properly, the on-s1te leak test
should simply be a precautionary formality to ensure that all
fittings are properly tightened.
5) 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 1n the proper
position in the duct, as determined 1n (3).
8) To initiate the sampling run, turn on the vacuum pump and
throttle the intake valve to achieve the flowrate determined
1n (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.
38
-------
Table 2. SASS Train Impinger System Reagents
IMPINGER
REAGENT
QUANTITY
PURPOSE
#1
12
#3 J
6 M H202
0.2 M (NH4)2S2Og
+0.02 M AgN03
0.2 M (NH4)2 S208
+0.02 M AgN03
Drierite (Color Indicating)
750 ml
750 ml
750 ml
750 g
Trap reducing gases such as
SO^ to prevent depletion of
oxidative capability of trace
element collecting impingers
2 and 3.
Collection of volatile trace
elements by oxidative
dissolution.
Collection of volatile trace
elements by oxidative
dissolution.
Prevent moisture from
reaching pumps.
-------
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 can-
not 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:
o
• At least one process cycle and 30 standard m (1060 scf)
of the process effluent are to 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 repre-
sentative 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 pro-
gress 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 con-
tamination 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 terms 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.
40
-------
At the conclusion of the sampling run, the train is disassembled and
transported to the mobile lab unit or prepared work area as follows:
1) Open the cyclone oven to expedite cooling, disconnect
the probe and cap off both ends.
2) Disconnect the line joining the cyclone oven to the XAD-2
module at the exit side of the filter and cap off
a) the entrance to the 10y cyclone, 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 1:1 mixture
of methylene chloride (CH2C12) 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 1s presented in the following series of flow diagrams (Figure 12
to Figure 14). It 1s suggested that these diagrams be placed in an easily
visible location 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
Ringelmann technique which involves the 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 1 purposes, this require-
ment has been waived.
41
-------
PROBE AND
NOZZLE
CH2CI2 : CH3OH
RINSE INTO AMBER
GLASS CONTAINER
ADD TO 10p
CYCLONE RINSE
i
10 M CYCLONE
STEP!: TAP AND BRUSH
CONTENTS FROM WALLS
AND VANE INTO LOWER
CUP RECEPTACLE
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL ON WALLS AND VANE
INTO CUP (CH2CI2 : CHgOH)
REMOVE LOWER CUP
RECEPTACLE AND
TRANSFER CONTENTS
INTO A TARED NALGENE
CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER (CH2CI2 : CHjOH)
INTO PROBE RINSE CONTAINER
[CO Ml
i
INJ
STEP 1: TAP AND BRUSH CON-
TENTS FROM WALLS INTO
LOWER CUP RECEPTACLE
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL WITH CH-CI, : CH_OH
INTO CUP ^ 2 3
STEP 3: RINSE WITH CH2CI2:CH3OH
INTERCONNECT TUBING JOINING
10,. TO 3M INTO ABOVE CONTAINER
»
REMOVE LOW
TACLE AND T
TENTS INTO >
GENE CONI7
ER CUP RECEP-
RANSFER CON-
\ TARED NAL-
UNER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
AN AMBER GLASS CONTAINER
./COMBINE)
COMBINE
ALL RINSES
FOR SHIPPING
i AND ANALYSIS
Figure 12. Sample Handling and Transfer-Nozzle, Probe, Cyclones and Filter
-------
CYCLONE
STEP 1: TAP AND BRUSH
CONTENTS FROM WALLS
INTO LOWER CUP RECEP-
TACLE
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL WITH CH0CL:CH,OH
INTO CUP i I *
STEP 3: RINSE WITH CH2CI2:CH3OH
INTERCONNECT TUBING JOINING
3/-TO IM INTO ABOVE CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
A TARED NALGENE CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
AN AMBER GLASS CONTAINER
-P.
CO
FILTER
HOUSING
STEP 1: REMOVE FILTER AND
SEAL IN TARED PETRI DISH
STEP 2: BRUSH PARTICULATE FROM
BOTH HOUSING HALVES INTO A
TARED NALGENE CONTAINER
STEP 3: WITH CH2CI2:CH3OH
RINSE ADHERED PARTICULATE
INTO AMBER GLASS CONTAINER
STEP 4: WITH CH2CI2:CH3OH
RINSE INTERCONNECT TUBE
JOINING IM TO HOUSING
INTO ABOVE CONTAINER
NOTES: ALLCH2C12:CH3OH
MIXTURES ARE 1:1
ALL BRUSHES MUST HAVE
NYLON BRISTLES
ALL NALGENE CONTAINERS
MUST BE HIGH DENSITY
POLYETHYLENE
Figure 12. Sample Handling and Transfer-Nozzle, Probe, Cyclones and Filter (Continued)
-------
STEP NO. 1
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 CART-
RIDGE. EMPTY RESIN INTO WIDE
MOUTH GLASS AMBER JAR
STEP NO. 2
CLOSE CONDENSATE RESERVOIR VALVE
RELEASE UPPER CLAMP AND
LIFT OUT INNER WELL
WITH GOTH UNITIZED WASH BOTTLE
(CH2CI2:CH3OH) RINSE INNER WELL
SURFACE INTO AND ALONG CON-
DENSER WALL SO THAT RINSE RUNS
DOWN THROUGH THE MODULE AND
INTO CONDENSATE COLLECTOR
WHEN INNER WELL IS CLEAN,
PLACE TO ONE SIDE
REPLACE SCREEN ON CARTRIDGE, RE-
INSERT CARTRIDGE INTO MODULE.
JOIN MODULE BACK TOGETHER.
REPLACE CLAMP.
OPEN CONDENSATE RESERVOIR
VALVE AND DRAIN AQUEOUS
CONDENSATE INTO A 1 LITER
SEPARATORY FUNNEL. EXTRACT
WITH CH2CI2.
AQUEOUS PHASE
ORGANIC PHASE
BASIFYONEHALF
s PH 12
ACIDIFY ONE HALF
PH LESS THAN 2
RINSE ENTRANCE TUBE INTO MODULE
INTERIOR, RINSE DOWN THE CONDEN-
SER WALL AND ALLOW SOLVENT TO
FLOW DOWN THROUGH THE SYSTEM
AND COLLECT IN CONDENSATE CUP
i
RELEASE CENTRAL CLAMP AND
SEPARATE THE LOWER SECTION
(XAD-2 AND CONDENSATE CUP)
FROM THE UPPER SECTION (CON-
DENSER)
THE ENTIRE UPPER SECTION IS NOW
CLEAN.
RINSE THE NOW EMPTY XAD-2 SEC-"
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 Transfer - XAD-2 Module
44
-------
ADD RINSE FROM
CONNECTING LINE
LEADING FROM XAD-2
MOD TO FIRST IMPINGER
IMPINGER NO. 1
TRANSFER TO
NALGENE
CONTAINER
RINSE WITH 1:1 IPA/
DIST. H2O AND ADD
IMPINGER NO. 2
TRANSFER TO
NALGENE
CONTAINER
RINSE WITH 1:1 IPA/
DIST. H2O AND ADD
fc
85
IMPINGER NO. 3
TRANSFER TO
NALGENE
CONTAINER
RINSE WITH 1:1 IPA/
DIST. H20 AND ADD
COMBINE AND
MEASURE TOTAL
VOLUME FOR
SINGLE ANALYSIS
IMPINGER NO. 4
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 dis-
cussed in detail in Chapter I; however, certain aspects specific to SASS
train samples are briefly presented here.
After the laboratory analyses have been performed for a specific sam-
ple, 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 condi-
tions 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 meas-
ured. 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 func-
tion 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 con-
ducted 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 air or receiving surface and ground waters with-
out 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 pol-
lutants 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 1 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 over-
all 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. Fig-
ure 15 summarizes the sampling categories for Level 1 airborne fugitive
emissions.
47
-------
AIRBORNE FUGITIVE
EMISSIONS
SITE SOURCE
SPECIFIC SOURCE
CATEGORY 1
£
UPWIND/
DOWNWIND
SAMPLING
1
F
I
SPECIFIC SOURCE
CATEGORY 2
DOWNWIND
SAMPLING
FREE PLUME
SAMPLING
1
EVACUATED GRAB
SAMPLE FOR
GASES
HIGH VOLUME
SAMPLER WITH
XAD-2TRAP
EVACUATED GRAB
SAMPLE FOR
GASES
HIGH VOLUME
SAMPLER WITH
XAD-2TRAP
I
EVACUATED GRAB
SAMPLE FOR
GASES
SASS TRAIN FOR
ALL COMPONENTS
AS PER CHAPTER ffl
Figure 15. Sampling Categories for Level 1 Airborne Fugitive Emissions
-------
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 water-
borne 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 1n order to avoid confusion. The
first part considers airborne fugitive emissions while the second considers
fugitive emissions as they relate to waterborne contaminants. The dis-
cussions include technique descriptions, equipment requirements, 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.
4.2.1.1 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 1n 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:
1) 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.
49
-------
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 decision must hinge on the likelihood of the emission's migra-
tion beyond the site boundaries. If uncertainty exists concerning specific
source significance criteria, disregard the source under the assumption
that 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 upwind-
downwind 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 deta'il 1n 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 1 sampling consists of three primary components:
1) A commercially available, high volume filter device
for partlculate matter identification,
2) An XAD-2 absorbent trap for>Cg organlcs, and
3) A 5-cfmpump for the XAD-2 cartridge.
50
-------
OPEN HEARTH FURNACE, INTERNAL PLUME SIMILAR TO
COKE OVEN, EMITTED TO ATMOSPHERE THROUGH OPEN
SIDES AND ROOF; CATEGORY 2 SASS TRAIN
CATEGORY I HIGH-VOL.
DOWN WIND FROM BLAST
FURNACE AND SINTERING
OPERATIONS
CATEGORY I HIGH-VOL.
DOWN WIND FROM COKE
PILE
DOWN WIND SITE SOURCE
SAMPLERS
CATEGORY I HIGH VOL.
DOWN WIND FROM COAL
PILES
CATEGORY I HIGH-VOl.
DOWN WIND FROM
LIMESTONE BINS
CATEGORY I HIGH-VOL.
DOWN WIND FROM ON-SITE
ORE TREATING OPERATIONS
UPWIND SITE - SOURCE
SAMPLER
CATEGORY I HIGH-VOL.
DOWN WIND FROM QUENCH-
TO WER AND COKE GRINDING
CATEGORY I HIGH-VOL.
DOWN WIND FROM COKE
OVEN BYPRODUCT RECOVERY
COKE OVEN BANK
CATEGORY? SASS TRAIN
Figure 16. Decision Example for "Worst Case" Site
-------
In most common types of high volume filters, a high speed
vacuum-cleaner type motor 1s 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 commerciany available and may be utilized
interchangeably if the following general specification can be met:
• Flowrate - This should be variable between 0.57m3/min
and 1.7m3/min (20 to 60 cfmj.This variability is needed
in order to compensate for differences in particulate
density.
t Filter size - 20.3cm x 25.4cm (8"xlO") 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 con-
trol is recommended to promote accurate, unattended
flow control.
• Construction - Lightweight and durable, capable of all-
weather 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 3.5y and a back-up filter is recommended.
Grab sampling of gases may be accomplished using 3-liter 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 III. A similar trap (equal in
volume but with different end fittings) is connected as an integral part
of this system as indicated in Figure 17.
52
-------
1/4 INCH
SWAGELOK
BULKHEAD
COPPER
TUBING
WALL
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 1s to be
used to sample Category 2 specific sources which generate plumes 1s presented
1n Chapter III. 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 1, 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 activa-
tion 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 1 purposes; long
elevating poles or platforms are not required. After activation, sampler
operation is automatic and does not require supervision. Manpower require-
ments for the hi-vol sampling matrix may then be estimated as a function
of the anticipated number of sampler locations.
As indicated in Chapter III, 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 1s held within the
emissions plume. Obtaining the required amount of sample (see Table 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
-------
period will depend on the density of the plume and the frequency of the
cycle (assuming the process is cyclic). The decision to place a specific
source 1n Category 2 for cost effectiveness reasons must not be made
lightly. Figure 16 can again be used to clarify the general process
magnitudes applicable to specific sampling types.
4.2.2 Sampling Procedures (References 27, 28. 29, 30, 31)
4.2.2.1 High Volume Sampler Applications
The modified high volume sampler, as described in Section 4.2.1.2, will
be used in all first category specific sources (see Section 4.2.1.1) 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 Level 1
sampling matrix. The design of the system 1s influenced by such factors
as source complexity and size, site geometry and prevailing meteorological
conditions. Generally, only one upwind device is required in order to
supply background data and one or more downwind samplers are needed depend-
ing on the above stated factors. Downwind site-source samplers are to be
removed as far as possible from any process operation since the objective
1n this case Involves the collection of a measured portion of a homogeneous
cloud as it passes beyond the plant boundary.
First category specific source samples need only be taken on the down-
wind side of the source. These samples are all taken external to the source
and should be placed within the actual cloud if possible. 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 specific source.
Subjective estimates of existing cloud densities may be applied to the
curves provided 1n Figure 18 as a general guideline for time versus flow-
rate settings.
55
-------
130
120
§ 110
u_
O
0100
2
6 8°
o
o 70
UJ
Q
IU
UJ
Z 60
O
Z
i 50
u. 40
O
§ 30
x
20
10
.13MJ/MINFLOW
(40 CFM)
_L
J_
_L
J 1
10 15 20 25 35
100 200 300 200
PARTICULATE/M3 IN AMBIENT AIR
300
400 500 700 900 1100
FLOW RATE CURVE TO BE USED
WHEN DUST CONCENTRATIONS ARE
ARE NOT VISIBLE
CLEAR-
-*• VERY LIGHT HAZE
FLOW RATE CURVE TO BE USED
UNDER HAZE CONDITIONS
LIGHT HAZE-
-*• HEAVY HAZE
FLOW RATE CURVE TO BE USED
WHEN DUST CONCENTRATIONS
ARE VISIBLE
HEAVY HAZE •
THICK DUST
Figure 18. Sampler Flow Rate Settings for Dust
56
-------
4.2.2.2 SASS Train Sampler Applications
Fugitive emissions falling Into the second specific source category
(see Section 4.2.1.1) are sampled with the SASS train. The minimum sample
quantities per run, as shown in Table 1, apply here as well.
No two second category specific sources will ever have the same (or
even similar) site geometry. Plume characteristics (temperature, area,
velocity, density, composition, cyclic frequency, etc.) will also vary
markedly depending on process type, size, meteorological conditions and
the existence or nonexlstence 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
position 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 to whatever distance
the process geometry demands. If the arrangement is such that room for the
probe only exists, the entire remainder of the system must be placed in a
57
-------
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 nozzle. 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 1s presented 1n detail 1n Chapter II.
4.2.3 Decision Aid for Appropriate Category Selections
As previously stated, the sampling matrix for airborne fugitive emission
characterization results from the choke of three available options: site
source samples, Category 1 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 t>e classified
Into Categories 1 or 2, are not as easily Identified as the site source.
For this reason, a worst-case model 1s presented (Figure 16) 1n which a
wide variety of specific sources are known to exist. The model, which
represents an Integrated steel plant 1s not Intended to be viewed as a
specific case representation, but provides an example of many of the
specific sources found Individually 1n smaller and less complex operations
grouped together as an integrated unit.
As Indicated 1n 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 coke oven" bank, and an open hearth
furnace.
58
-------
4.2.4 Sample Handling and Shipment (References 3, 4, 6, 25)
Quantitative transfer of the samples from the 3.5y ; size fractionating
head and the filter 1s necessary 1n order to determine existing participate
densities. The > 3.5v catch can be removed from the head by tapping the
head and carefully brushing any adhering material into a tared high
density Nafgene shipping container. The glass fiber filter must be
transferred into a petrf dish and sealed without particulate matter loss.
During the sampling process, the filter materials 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 (Referencei "2.
24. 27) ~ L
When the sampling program has been completed and the samples have been
analyzed to yield qualitative pollutant concentrations in such terms as
mlcrograms per cubic meter 1n 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) at the 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:
1) 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 topo-
graphic 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 1
characterization of waterborne fugitive emissions is surface runoff
sampling.
This method 1s utilized for sources that can be Identified as contri-
butors to the pollution of water at an industrial site and whose runoff dur-
ing 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 con-
centration 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 rela-
tively 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 appro-
priate intervals depending upon runoff intensity. The collector contents
are measured and analyzed for pollutants as discussed 1n 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 carefully studied by
those individuals responsible for this activity. Key areas to identify are:
• 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
-------
GROUND WATER
SEEPAGE
SURFACE WATER
ENTRANCE
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, Imd
• 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 sam-
ples 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.
62
-------
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 sepa-
ration scheme indicated 1n Figure 23 (Chapter V). The only digressions
from the Figure 23 flow plan are:
1) BOD and COD analysis are not performed, and
2) A 10-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 rain-
falls. 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 1 assessment programs described in this section.
63
-------
WATERBORNE FUGITIVE
EMISSIONS
ISOLABLE
SOURCES
SURFACE RAINWATER
RUNOFF
RAINFALL
MEASUREMENT
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 methods 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 1 sampling of liquids and slurries are heat exchange, tap sampl-
ing 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 VII and
LIQUID PROCESS STREAMS
1
LIQUIDS CONTAINING MISCIBLE
AND IMMISCIBLE PORTIONS,
WITHOUT SOLIDS
B,C
SUPERHEATED LINES
MOLTEN SOLID
LINES
A,B*
SLURRIES
B,C
SAMPLING METHODS
A - HEAT EXCHANGE
B - TAP SAMPLE
C - DIPPER SAMPLE
M*TB BETAKEN IN LINES OF THIS NATURE ONLY IF THE MATERIAL 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 loss, 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 homo-
geneity. 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
66
-------
stream line is flushed with 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. There are conditions, however, where addi-
tional manpower wifflTe 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 CH2C12 extractions, must be placed in
amber glass bottles to inhibit sample degradation. These amber glass
bottles are cleaned by:
a) Strong soap solution,
b) Liberal tap water rinse,"
c) Distilled water rinse,
d) Methanol rinse,
e) Methylene chloride rinse, and
f) Drying a clean, hot air stream or by placing in an oven
at 400C (140°F).
67~
-------
After the apparatus has been cleaned and dried, 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 Al79.
• 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:
t Steel (suitable for fusion welding up to 850°F) - ASTM
Designation A216
• Steel (carbon forged) - ASTM Designation A105
t Steel (alloy steel castings for use up to 1100°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 Fig-
ure 21, three specific methods are applicable; they are:
a) Heat exchange,
b) Tap sampling, 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
sample presents no problem. At near atmospheric pressures, special
means must be provided to establish sample flow. This problem can be over-
come by using either a small pump to deliver the sample to the sample con-
tainer or an evacuated sampling vessel. Prior to sample acquisition, all
new sampling lines should be purged with line fluid to 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 10-liter
sample is required to perform the analyses identified in Chapters VII
and VIII.
5.3.1 Heat Exchange Sampling Systems for High Temperature Lines
The majority of industrial systems utilize steam for a variety of
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 character!zable
69
-------
as reaction products. The sampling techniques described in this section
pertain to all of the 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 constitu-
ents will to some degree dissolve any substance contacted. For this reas.on,
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 sampl-
ing 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 character-
istics, such as stratification. A flowing stream containing particulate
matter will be stratified. A tank sample may also be stratified but in
the static sense rather than in the fluid sense. Moving streams are tradi-
tionally sampled using a technique 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
technique called tap sampling.
70
-------
COOLING COILS
TO
SAMPLE
COLLECTION
COOLING COILS
RESERVOIR
PROCESS LINE
NATURAL CIRCULATION SAMPLING SYSTEM
(HIGH PRESSURE, HIGH TEMPERATURE)
PROCESS LINE
FORCED INJECTION SAMPLING SYSTEM
(SUBATMOSPHERIC PRESSURE, HIGH TEMPERATURE)
Figure 22. Sampling Apparatus for HPHT Lines
-------
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 7a~thoroughly
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 Sampling
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 free-
flowing 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 tech-
niques are too sophisticated for Level 1 application, the lack in uniformity
often found in thick or stratified slurries may require special considera-
tion 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 bounds 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 handling scheme for liquid/slurry samples. This
scheme has been modified (Ref. 45) to handle suspended particulate matter.
Figure 23 shows the worst case (Aqueous/Organic/Solid), but is also appli-
cable 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
for inorganic, organic and biological preservation, 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.
73
-------
AQUEOUS/ORGANIC/SOLID
10 LITER SAMPLE
1
1 LITER - TRANSFER
CAREFULLY TO AVOID AIR
ENTRAINMENT-BOD, COD
SEE TABLE 3 FOR SAMPLE
PRESERVATION AND
CHAPTER VII FOR INOR-
GANIC MATERIAL ANALYSIS
Figure 23. Field Handling Scheme for Liquid/Slurry Samples
74
-------
Table 3. List of Analyses
on Liquid/Slurry
to be Performed
Samples.
Analysis
Acidity
Alkalinity
Conductivity
BOD
COD
Suspended Solids
Total Dissolved Solids
Hardness.
Water & HC1 Leachable Anions
Trace Cations
pH
K1 '
Organic Material
Methyl ene Chloride Extracts
Cyanides
Ammonia Nitrogen
Field
Analysis
V
V
V
V
V
V
J
V
V
Lab
Analysis
V
V
V
V
V
V
Fraction
Untreated
Untreated
Untreated
Untreated
Acidify
Untreated
Untreated
Untreated
Basify
Aci di fy
Untreated
Untreated
Untreated
Untreated
Untreated
Preservation
Cool 4°C
Cool :4°C
Cool 4°C
Cool 4°C
H2S04 to pH <2
None Required
None Required
Cool 4*C
NaOH to pH12
HN03 <2
Run
Immediately
None Required
Non Required
Cool 4°C
Cool 4°C
Holding
24 hrs
24 hrs
24 hrs
6 hrs
7 days
-
-
7 days
Depends on
An ion
38 days
38 days
7 days
7 days
24 hrs
24 hrs
-------
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. Further-
more, 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 1 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 1. In most cases, the_ _differ-
ence between the Level 1 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
established in the pre-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 sys-
tem (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 1 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 pre-
test 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 show-
ing the appropriate sampling technique as a function of physical character-
istics 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 Sampling (References 20, 22, 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.
77
-------
Table 4. Decision Matrix for Solid Sampling
PHYSICAL NATURE
OF SAMPLE
FINE POWDER
COARSE POWDER
COARSE GRAIN
LUMP
BELT
CONVEYORS
N/A
N/A
CROSS
STEAM CUT,
ONE
SHOVEL
CROSS
STEAM CUT,
ONE
SHOVEL
LADDER TRAY
CONVEYOR
SHOVEL
GRAB FROM
ONE TRAY
SHOVEL
GRAB FROM
ONE TRAY
SHOVEL
GRAB FROM
ONE TRAY
N/A
SCREW
CONVEYOR
ONE SHOVEL
FROM POINT
OF EXIT
ONE SHOVEL
FROM POINT
OF EXIT
N/A
N/A
DUCT
SAMPLE
ONE SHOVEL
FROM EXIT
IF ENCLOSED,
FROM TOP IF
OPEN
ONE SHOVEL
FROM EXIT
IF ENCLOSED,
FROM TOP IF
OPEN
ONE SHOVEL
FROM EXIT
IF ENCLOSED,
FROM TOP
IF OPEN
N/A
OPEN
PILES
PIPE OR
THIEF
PIPE,
THIEF OR
AUGER
AUGER
FOUR
SHOVELS,
ONE FROM
EACH
SIDE
STORAGE BINS
OR SILOS
PIPE OR
THIEF
PIPE, THIEF OR
AUGER
AUGER
SHOVEL OR
AUGER
Screw conveyors transfer sludge-type materials (such as ash effluents)
and are usually enclosed systems. The optimum 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, thief or auger (Section 6.3.2).
6.3.2 Boring Techniques (References 22. 46. 50)
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 to 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 ends) 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 particu-
larly true if the sample has a wide particle size distribution. Stored
containers or heaped beds of material tend to settle, segregating the par-
ticles 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 interior 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.
79
-------
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 pre-
cipitators. 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 col-
lection hopper or 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 VII
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 1 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. To
achieve this goal, the analytical results must have an accuracy of -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 multi-
media 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 1 inorganic gas analysis. Viewed independently,
a variety of alternative techniques will provide satisfactory Level 1 data
for inorganic gases; yet within the integrated Level 1 analysis format,
the GC can also be used for organic gases and consequently becomes the
optimum choice.
81
-------
LEVEL 1 SAMPLE
GASES
LIQUIDS
00
ro
INORGANIC
• GC-S02/ H2S, COS, CO,
C02, 02/ NH3, HCN,
(CN)2
•NOy- CHEMI-
A LUMINESCENCE
• IMPINGERS
- SSMS
- WET CHEMICAL
ORGANIC
• GCFORC1-C6
» XAD-2 EXTRACT
- GC FOR C6-C12
- IR
- LC/IR/LRMS
INORGANIC
ELEMENTS
- SSMS
- WET CHEMICAL
SELECTED ANIONS
AQUEOUS - SELECTED
WATER TESTS
SOLIDS
1
INORGANIC
ELEMENTS
- SSMS
- WET CHEMICAL
LEACHABLE MATERIAL
REGULATED BY EPA -
REAGENT TEST KITS
ORGANIC EXTRACTS
• GCFORC.-C,,
O \£.
• IR
• LC/IRARMS
ORGANIC
EXTRACT AQUEOUS
SAMPLES WITH
GC FOR C,-C,
O I
IR
LC/IR/LRMS
Figure 24. Multimedia Analysis Overview
-------
LEVa 1
INORGANIC ANALYSIS
GASES
LIQUIDS
SOLIDS
CO
CO
SSMS
ELEMENTAL
ANALYSIS
OF SORBENT
TRAP
GCFOR:
CO, C02/ S02,
H2S.
COS
NH3, HCN, (CN)2
NOXBY
CHEMILUMINESCENCE
SSMS ELEMENTAL
ANALYSIS
WET
CHEMICAL
ANALYSIS
FOR Hg, Sb, A.
WET
CHEMICAL
ANALYSIS
FOR Hg, Sb, As
WATER ANALYSIS
pH, ACIDITY,
ALKALINITY, BOD,
COD, DISSOLVED
OXYGEN,
CONDUCTIVITY,
DISSOLVED AND
SUSPENDED SOLIDS,
SPECIES ANALYSIS
SSMS
ELEMENTAL
ANALYSIS
tEACHABLE MATERIAL SSMS
ELEMENTAL ANALYSIS
REAGENT ANALYSIS KITS-
SPECIES ANALYSIS
WET
CHEMICAL
ANALYSIS
FOR Hg, Sb, As
Figure 25. Level 1 Inorganic Analysis Flow Scheme
-------
Level 1 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 1 inorganic analysis
is designed to detect:
• Inorganic elements in all influent and effluent streams,
• S02, NOX, CO, 02, C02, N2, H2S, COS, NHs, 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 anigns frpm_samples which are solids
( parti cul ate 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 1 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). 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 photo-
graphic 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, followed by a series of exposures with a refer-
ence 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 1 ug/1 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
85
-------
SAMPLE FOR
ELEMENTAL
ANALYSIS
WATER AND
NON-ORGANIC
SOLUTIONS
XAD-2
SORBENT
ORGANIC*: LIQUID
OR SOLID
PARTICULATE
MATTER, ASH
OR NON-ORGANIC
SOLIDS
SLURRY ALIQUOT
WITH GRAPHITE AND
EVAPORATE
CO
HOMOGENIZE
AND DIVIDE
PARK BO MB
COMBUSTION
OVER HN03
PARR BOMB
COMBUSTION
OVER HNO3
2a.
PARK BOMB
COMBUSTION
OVER HNO,
EXTRACT
FOR
ORGANICS
SLURRY ALIQUOT
WITH GRAPHITE AND
EVAPORATE
SLURRY SOLUTION
AND RESIDUE WITH
GRAPHITE AND
EVAPORATE
SLURRY SOLUTION
AND RESIDUE WITH
GRAPHITE AND
EVAPORATE
5
•z.
FORM ELECTKOOE
FORM ELECTRODE
FORM ELECTRODE
FORM ELECTRODE
SSMS
SSMS
SSMS
SSMS
Figure 26. Sample Preparation for SSMS Elemental Analysis
-------
extensive preparations consisting of reducing the organic material content of
the matrix. This matrix reduction step consists of ashing the sample by Parr
bomb combustion of the sample over HN03- 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,. The inorganic elements are then
o
determined by SSMS, and the remainder of the sample is then used for organic
analysis (Chapter VIII.)
7.2.2 Wet Chemical Analysis for Hg. 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 absorption 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 pre-
sents 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 accomplished with well known analysis schemes. In the XAD-2 analy-
sis, the samples are treated as fuels and bomb combusted. These analyses
have few interferences. ,...„,«
87
-------
SAMPLE TYPE
00
CO
WATER AND
NON-ORGANIC
LIQUIDS
PARTICULATE MATTER.
ASH, AND NON-ORGANIC
SOLIDS
XAD-2
SORBENT
ORGANICS -
LIQUID
OR SOLID
PARR BO MB
COMBUSTION
OF 2g ALIQUOT
OVERHNO
PAffi COMBUSTION
IOMB OVER HNO,
SAMPLE ANALYSIS
Hg
-»
SnClj
REDUCTION
COLD VAPOR
ATOMIC
ABSORPTION
SPECTROSCOPY
Figure 27. Hg, Sb, As Sample Preparation and Analysis
RHODAMINEB
COLORIMfrtlC
METHOD
Ai
ARSINE EVOLUTION
USING Ae-DtETHYL-
DITHKDCASBAMATE
METHOD
-------
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 com-
pounds to several percent for C02 and water in stack gas effluents.
Because many of the samples which are taken, especially those which con-
tain 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 chrornatography 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, Tracer and others expand the scope of analysis to include
virtually all gaseous species without having a van full of gas chromato-
graphic units. It is recommended that a multidetector unit capable of
detecting sulfur compound at the ppb level be purchased for an environ-
mental 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 condi-
tions 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
-------
Table 5. Recommended Gas Chromatographic Parameters
for Analysis of Inorganic and Organic Species
Species of Interest
Sensitivity
Column
Temperature
Detector
C02, CO, 02, N2,
H20, SO®, H2Sa
NOX
H2S, S02, COS,
CH3SH, CH3CH2SH,
1 ppm
a,b
• C6H13SH
j-Cg Hydrocarbons
C,-C-|2 Hydrocarbons
C-j-Cg Chlorocarbons,
Pesticides
0.1 ppm
0.1 ppm
0.1 ppm
6 feet SS, Molecular
Sieve 5A
6 feet glass,
3% OV-1 on Chromosorb
W, 100/120 mesh
6 feet SS, Poropak Q
6 feet SS,
1.5% OV-101 on Gas
Chrom Q, 100/120 Mesh
6 feet SS,
1.5% OV-17/2.0%
OV-210 on silanized
Chrom W, H.P. or Gas
Chrom Q 100/120 mesh
Isothermal at 40°C Thermal Conductivity
Isothermal at 60°C Flame Photometric
Isothermal at 50°C
Isothermal at 50°C
for 5 min; program
at 10°C/min to 150°C
CrC6 120°C
Pesticides 200°C
Flame lonization
Flame lonization
Electron Capture
NH
3, HCN, Cyanogen >
1 ppm
6 feet SS, Poropak Q Isothermal at 40°C Thermal Conductivity
a) Concentrations greater than 25 ppm only. For survey work and lower concentrations, the flame
photometric detector system must be used.
b) Concentrations greater than 25 ppm only. For survey work and lower concentrations, the
chemiluminescent method must be used.
c) A spectral Teflon-coated and glass system is necessary for these analyses.
-------
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 N02) are not measured
routinely on a gas chromatograph. The Level 1 analysis of N0/N02 concen-
trations 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-liter 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 per-
cent, -50 percent) be performed.
7.2.5 Analysis of Leachable Material (Reference 25)
The analysis of water and HC1 Teachable 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 fol-
lowing analyses must be performed on all aqueous samples:
© Acidity
e Alkalinity
o pH
o BOD
o COD
91
-------
Conductivity
Total dissolved solids
Anion analysis for S04 =, N02"/N03", and CO/
Total suspended solids
Dissolved oxygen
Ammonia
HCN
All these analyses can be performed either in the field or the labora-
tory 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 modi-
fied and simplified version of standard methods. The reagents are encap-
sulated and stored in small plastic pillows in pre-measured quantities
until opened for analysis. Upon addition of the reagent or reagents to
the sample, component concentrations are determined colorimetrically or
turbidimetricany 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 1 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.
t 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 laboratory for analysis of leachables,
they provide quick, inexpensive analyses for the
required data.
92
-------
CHAPTER VIII
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 compre-
hensive analysis, the objective of these Level 1 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 1 analysis. In addi-
tion, 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 Chap-
ters II through VI will be either gases, liquids, or solids. The multi-
media analysis flow scheme presented in Figure 28 shows how each of the
sample types is split for organic analysis.
8.2 LEVEL 1 ORGANIC ANALYSIS METHODOLOGY
An overview of the methodology to be used for the Level 1 organic
analysis is shown in Figure 29. This methodology deals with the prepara-
tion 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 C^Cg 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
proceed without complication. The analysis of organic extract or organic
93
-------
SAMPLES FOR ORGANIC ANALYSIS
GAS £?LUUT°ra$NS CYANIC
OA:> EXCEPT LIQUIDS
IMPINGERS (FUELS)
METHYLENE
CHLORIDE
EXTRACTION
SOLIDS
METHYLENE
CHLORIDE
EXTRACTION
1. GC, Cj-C^ i. GC. C7<,2 ,
GC, C,-C6 2. TOTAL SAMPLE 2. TOTAL SAMPLE
3. LC FRACTIONATE 3. LC FRACTIONATE
SAMPLE - IRARMS SAMPLE - IRARMS
PARTICULATE
OR ASH
METHYLENE
CHLORIDE
EXTRACTION
. TOTAL SAMPLE 1.
-IR
. LC FRACTIONATED 2.
SAMPLE
-IRARMS
XAD-2
SORBENT
TRAP
HOMOGENIZE
AND DIVIDE
PENTANE
^^fT!0^ PORTION FOR
IN SOXHLET, INORGANIC
PLUS XAD-2 ANALYSIS
MODULE RINSES
1/1
' 1 '
SASS m
TRAIN
RINSES
TOTAL SAMPLE
-IR
LC FRACTIONATED
SAMPLE
-IRARMS
1. GC, C^-C^ 1.
2. TOTAL SAMPLE
-IR 2.
3. LC FRACTIONATE
SAMPLE - IRARMS
| PREPARATION
TOTAL SAMPLE „.
-IR z
LC FRACTIONATED >
SAMPLE !<
-IR/LRMS £
Figure 28. Multimedia Organic Analysis Overview
-------
G.C.,
ALIQUOT
FOKC
HYDRO-
CARBONS
INFRARED
ANALYSIS
G.C.,
ALIQUOT
FOR HYDRO-
CARBONS
TOC,2
CONCENTHAIE
AUQUOI FOR
GRAVIMETRIC
AND IR
•ON FRACTIONS EXCEEDING
THRESHOLD CRITERIA,
SECTION B.4.5
INFRARED
ANALYSIS
IOW RESOLUTION
MASS SPECTRA
ANALYSIS
Figure 29. Level 1 Organic 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 Cy-Cio hydro-
carbons (100-200°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 determina-
tion of the types of functional groups present. A low resolution mass
spectrum (LRMS) is also obtained on all fractions which exceed the con-
centration threshold criteria in order to determine the principal compound
types present in each fraction. For the sample streams identified in the
Level 1 scheme, these concentrations, computed back to the source, are:
q
• Gas (particulate, sorbent trap, etc.) 0.5 mg/m
• Solids 1 mg/kg
• Solutions 0.1 mg/1
Care must be taken in this computation to correct for those C^-C^
compounds that were analyzed 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 analysis. The best possible laboratory pro-
cedures 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 proce-
dure 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 for direct gas chromatographic analysis of.materials in
96
-------
the C7-C12 boiling range. It is necessary to obtain the total weight of
organics in the solvent extract, to obtain an IR on a portion from this
extract, and to concentrate the extract for the LC separation. The appro-
priate 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 recommended to have at least 10 mg of sample for
the gravimetric analysis. Prior to the LC analysis step, it is recom-
mended that the solvent solutions be concentrated to 1 to 10 ml. The
Kuderna-Danish apparatus 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 stop-
cock. 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-liter samples should be
sufficient.
8.3.2 Solids, Parti oil ate 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 pre-
viously 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-liter 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 precipit-
ate 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 OR6ANICS
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 C,-Cg range (up to 70°C);
and the volatile materials in the C7-C12 range (100-200°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 Ci - Cfi Range (Ref. 71 through 75)
The on-site gas Chromatographic requirements for analysis of the
C, - Cg 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 GI - Cg n-paraffin mixture.
The conditions recommended for this analysis are:
Column: Porapak Q, 100/120 mesh, 6'
Detector: Flame lonization
Temperature: Isothermal at 100°C
98
-------
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 compounds. The boiling points of the C, - Cg
hydrocarbons are:
Gas BP (°C)
Methane, C^ -161
Ethane, C2 -88
Propane, C3 -42
Butane, C. 0
Pentane, C5 36
Hexane, Cg 69
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 chromatogram be reported
as present in the ranges given below:
Range BP (°C)
A .-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 Cj - Cg hydrocarbons, the basis of the data may
be reported as such and the chromatogram peaks assigned accordingly.
99
-------
8.4.2 Gas Chromatoqraphic Analysis of C? - CIP 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 Cy - C,2 hydrocarbons which
would otherwise be lost by evaporation can be analyzed in a manner similar
to that described above for the Cj - Cg 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: 1.535 OV-101 (or SE-30) on GasChrom Q, 100/120 mesh,
1/8" OD x 6' SS
Detector: Flame ionization
Temperature Program: Isothermal at 50°C for 5 min., then
program at 10°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 C7 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 Cj - Cg gases. The boiling points of the hydrocarbons and recommended
reporting ranges are:
Vapor BP (°C) Range BP (PC)
Heptane, C? 93 7 90 to 110
Octane, Cs 126 8 110 to 140
Nonane, Cg 151 9 140 to 160
Decane, CIQ 174 10 160 to 180
Undecane, Cn 196 11 180 to 200
Dodecane, Ci2 216 12 200 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
100
-------
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.
Table 6. Solvents Used in Liquid
Chromatographic Separations
Fraction No. Solvent Composition
1 Pentane
2 20% Methylene Chloride in Pentane
3 50% Methylene Chloride in Pentane
4 Methylene Chloride
5 5% Methanol in Methylene Chloride
6 20% Methanol in Methylene Chloride
7 50% Methanol in Methylene Chloride
8 5/70/30, Cone. 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. Frac-
tions 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.
101
-------
Fractions 5 through 7 will contain the polar species including phenols,
alcohols, phthalates, amines, ketones, aldehydes, amides, etc. The distribu-
tion of class type between Fractions 5 through 7 will be a function of their
polarity and affinity for the silica gel. Some weak acids 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).
8.4.4 Infrared Analysis
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 is 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 the IR 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:
3
Gas - SASS train samples 0.5 mg/m
3
- Ambient air - particulate 1 ug/m
- Ambient air - Sorbent trap 0.5 mg/m
Solids 1 mg/kg
Aqueous solutions 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 inlet. 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
obtained 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 separa-
tion scheme, the IR spectra, and other information about the source. Data
are grouped by homologous series based on a most probable structure assign-
ment. 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 1 particle morphology and identification use techniques
designed to study the physical (including structure) and chemical prop-
erties 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 collect-
ing fugitive emissions. An important part of the morphological examina-
tion 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 con-
trol 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 pre-
liminary 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 identification) -
Using polarized light (Ref. 84, 85, 86), the particu-
late matter is viewed under a microscope; particles
down to 0.5p can be identified by physical appearances.
Although the procedures described in this chapter are straightforward,
they do require a degree of skill, experience and the ability to make con-
sistent subjective evaluations on the part of the personnel performing the
work. Component identification should be carried out by a trained tech-
nician and/or microscopist either internally or in a commercial laboratory
3104
-------
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 1 or as specified by the project officer 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 fig-
ure 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 (l-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 Photomicrography 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
-------
PARTICLE MORPHOLOGY
AND IDENTIFICATION
FIELD
WEIGHT
PHOTO-
MICROGRAPHY
PARTICLE SIZE
DISTRIBUTION
FUGITIVE
EMISSIONS
i
VISUAL
IDENTIFICATION
SHAPE
CLEAVAGE
STRUCTURE
COLOR
Figure 30. Particle Characterization Flow Scheme
-------
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 photo-
graphic 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 projected 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 color, 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
10.1 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 incor-
porated 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 test-
ing 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 com-
pletely 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 1 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 (1n-vitro) test, a mutagenic screening test, and a LD5Q
screening test. Although these tests do not provide a directly correla-
table 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 ofjthe 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,~1.e., Tiving
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 1 to 2 man-days per series.
10.2.2 Mutagenicity (Carcinoqenicity) 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 "typh'imurim 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 dimethyl-
sulfoxide (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 require-
ments are approximately 2 man-days per series.
10.2.3 LD5Q Screening Test
The LD[.n 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 LDcn value. The test procedure requires 14 days and 15 grams of
ou
sample. Manpower requirements are approximately 1 man-day. 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 metabo-
lites 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 procedures will utilize selected species of animals and plants to
provide an indication of 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
110
-------
exposed to air pollutants has been used successfully to assess the health
hazards of some pollutants. This test requires 4 hours and takes approxi-
mately 2 man-hours. Measurement of the 02 consumption and C02 production
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 con-
taining 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 ^ to 4 man-days per system.
Ill
-------
REFERENCES
1. Hamersma, J. W and Reynolds, S. L., "Field Test Sampling/Analytical
Strategy and Implementation Cost Estimates; Coal Gasifixation and
Flue Gas Desulfurization," EPA-600/2-76-093b, U. S. Environmental
Protection Agency, Research Triangle Park, N. C., April 1976.
2. Dorsey, J., C. Lockmuller, L. Johnson, and R. Statnick. "Guidelines
for Environmental Assessment Sampling and Analysis Programs -Level 1 "
U. S. Environmental Protection Agency, Research Triangle Park, N. C.
Mar 1976, 35 pp.
3. 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.
4. 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.
5. 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.
6. Clausen 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.
• 7. 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. 58-02-1882, U. S. Environmental Protection Agency, Research
Triangle Park, N. C., 1975.
8. Application of El Paso Natural Gas Co. before U. S. Federal Power
Commission, Docket No. CP73-131, El Paso, Tx., Aug 1972.
9. Danielson, J. A., "Air Pollution Engineering Manual," 2nd ed, Air
Pollution Control District, County of Los Angeles, Los Angeles,
Ca., 1973, p 987.
10. Shaw, H., and Magee, E. M., "Evaluation of Pollution Control in
Fossil Fuel Conversion Processes in Gasification", EPA-650/2-74-009-C,
U. S. Environmental Protection Agency, Research Triangle Park,
N. C., July 1974.
11. ASTM Committee D-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971
Annual Book of ASTM Standards, Part 19, D1145-53, American Society
for Testing and Materials, Philadelphia, Pa., 1-971, pp 1208-1213.
12. 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. ASTM Committee D-3 and D-5, "Gaseous Fuels; Coal and Coke," 1971
Annual Book of ASTM Standards, Part 19, D1247-54, American Society
for Testing and Materials, Philadelphia, Pa., 1971, pp 222-231.
14. Leithe, W., "The Analysis of A1r Pollutants," 1st ed, Ann Arbor-
Humphrey Science Publishers, Ann Arbor, Mi., 1970, p 150.
15. U.S. Environmental Protection Agency, Federal Register 36. 24876
(1971). '
16. Intersociety Committee, "Methods of Air Sampling and Analysis," 1st ed,
American Public Health Association, Washington, D.C., 1972, p 480.
17. Mueller, P.K. , Chairman, "Methods in Air Pollution and Industrial
Hygiene Studies," 12th Conference, University of California, Los
Angeles, Ca., 1971, p 170.
18. American Conference of Governmental Industrial Hygienists, "Air
Sampling Instruments," 4th ed, ACGIH, Cincinnati, Oh., 1972, pp S-l
to S-50.
19. Lapson, W.F., Dehne, H., and Harris, D.B., presented to 67th Annual
Air Pollution Control Association meeting, Denver, June 1974.
20. Silver-man, L., Bill Ings, C., and First, M., "Particle Size Analysis
3J,Jnd!£jrial Hy9iene»" ls* 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," 1st ed
Plenum Press, New York, N.Y. , 1973, 384 pp.
22.
Flegal, C. A., Starkovich, J. A., Maddalone, R. F. , Zee, C., and Kraft
EPA ^ntraTNo^a^ iS?8?, *««««"*• Trace inorganic ^1
T
..'' 1St ed' ^ ™« «d Sons,
25-
< AnlualTokTf A°^M ^d ^ "Wateri At^Pheric Analysis," 1971
^
2 7' wn/w/oa"? t *•"?* of Fug1t1ve
Research Triangle Park.NC/ 1976 / Environmental Protection Agency,
113
-------
28. Vandergrift, A., Shannon, L. , Lawless, E., Borman, P., Sailee, E.,
and Reichel, M., "Particulate Pollutant System Study, Volume III -
Handbook of Emission Properties," EPA Contract No. 22-69-104,
U. S. Environmental Protection Agency, Durham, N. C., 1971, p 629.
29. 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.
30. U. S. Environmental Protection Agency, Federal Register 36, 22384
(1971).
31. Seeley, J. L., and Skogerboe, R. K. , Anal. Chem. 46, 415 (1974).
32. Midwest Research, 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.
33. "Handbook for Monitoring Industrial Wastewater," U. S. EPA Technology
Transfer Series, U. S. Environmental Protection Agency, Washington,
D. C., 1973.
34. McCoy, J. W., "Chemical Analysis of Industrial Water," 1st ed,
Chemical Publishing Co., New York, N. Y., 1969, pp 175-176.
35. Lager, J. A., and Smith, W. A., "Urban Stormwater Management and
Technology - An Assessment," EPA-600/2-75-065, U. S. Environmental
Protection Aqency, Cincinnati, Ohio, December 1974.
36. 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.
37. 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.
38. Sridharan, N., and Lee, G. F., J. of Water Pollution Control Assoc. 46,
684 (1974).
39. 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.
40. 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.
41. 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, D1192-64, 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. Faeirheller, R., Marn, P. J., Harris, D, H., and Harris, D. L.,
"Technical Manual for Process Sampling Strategies for Organic
Materials," EPA-6QO/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 III,
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 Conmittee 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. Environmental Protection Agency,
Research Triangle Park, N. C., 1976.
52. Nicholls, G. D., Graham, A., Williams, E., and Wood, M., Anal. Chem.
39, 584 (1967).
53. Attari, A., "Fate of Trace Constituents of Coal During Gasification,"
EPA-650/2-73-004, U. S. Environmental Protection Agency,Research
Triangle Park, N. C., August 1973.
54. Ahearn, A., ed., "Trace Analysis by Mass Spectrometry," 1st 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 Spectro-
meter Investigation of Coal Particles and Coal Ash," Bureau of Mines
Technical Progress Report 42, Pittsburgh, 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. Brown, R., Jacobs, M.L., and Taylor, H.E., American Laboratory 4.
29 (1972).
60. 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, II., 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. "A New Concept in Water Analysis," Bausch and Lomb Analytical Systems
Division, Catalog No. 33-6070, Rochester, N.Y.; 1976, p 11.
67. Czernikowski, 0., American Laboratory 7, 52 (1975).
68. Patton, W.F., and Brink, A. Jr., J. Air Pollut. Control Assoc. 13.
162 (1963).
69. Dominick, D. D., "Methods for Chemical Analysis of Water and Wastes,"
EPA-625/6-74-003, U. S. Environmental Protection Agency,Cincinnati,,
Ohio, 1974.
70. Levins, P. L., Caragay, A. B., Thrun, K. E., Stauffer, J. L., and
Guilmette, L., "Evaluation of Alternative Level 1 Organic Analysis
Methods," Draft Report on EPA Contract No. 68-02-2150, U. S. Environ-
mental 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 JLR., "Chemical Apj?li_ca_t1pn_s_.cif Infrared and Raman Spectroscopy,"
1st edi7 Academic Press, London, England, 1963, 683 pp.
77. Colthup, N.B., Lawrence, H.D., and WJMrley., S.E., "Introduction to
Infrared and Raman Spectroscopy," 1st ed, Academic Press, London,
England,"1964. 511 pp.
78. Cross, A.D., "An Introduction to Practical Infrared Spectroscopy,"
1st ed, Butter-worth, Inc., Washington, D. C., 1964, 86 pp.
79. Kendall, D.N., "Applied Infrared Spectroscopy," 1st ed , Reinhold
Publishing Corporation, New York, N.Y., 1966, 560 pp.
80. Reed, R.I., "Applications of Mass Spectrometry to Organic Chemistry,"
1st ed, Academic Press, New York, N.Y., 1966, 256 pp.
81. Budzikiewicz, H., Djerassi, C., and Williams, D., "Mass Spectrometry
of Organic Compounds," 1st ed, Hoi den Day, Inc., San Francisco, Ca.,
1976, 690 pp.
82. Imperial Chemical Industries, Ltd., "Eight Peak Index of Mass Spectra,"
1st 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,"
1st ed, Ann Arbor Science Publishers, Ann Arbor, Ml., 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," 1st ed, Macmillan Publishing Co., New York,
N.Y., 1960, p 83-91.
89. Ames, B.W., Gurney, E.G., Miller, J.A. and Bartsch, H., Proc. Nat.
Acad. Science 69: 3128 ,(1972). 7"~ ~
i •'
90. Ames, B.W., Lee, F.D. and burston, W.E., Proc. Nat. Acad. Science 70- '
782 (1973). •—"•
91. Ames, B.W., Durston, W.E., Yamasaki, E. and Lee, F.D., Proc. 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 1 effort, this appendix is included to aid those
contractors interested in outfitting their own vans.
A.1 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 out-
fitted with all necessary equipment required for Level 1 sampling and
on-site analysis. In addition to the obvious advantages with 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 (nodification 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 alms of Level 1 testing in the phased
approach can be enhanced greatly with an on-site laboratory. A well-
equipped laboratory will allow additional Level 1 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 1 vans should include:
• A refrigerator for storing ice1 and preserving water
samples.
• An ice maker to provide a continuous and convenient
supply of ice for cooling down the SASS train
impingers.
• Cabinets, drawers and shelves for storage of sampl-
ing equipment, tools, hardware, spare parts, glass-
ware, sample bottles, reagents, etc.
• Work surfaces for assembling equipment and perform-
ing analyses.
0 Lockers for storage of rain gear, goggles, overalls,
6 tC •
•
•
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
JH I^K" ?nd toxicity testing) that are susceptible
to ambient contamination.
The work 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
-------
7-1/2FT,
PARTITION
^CURTAIN
MULTIPLE
DETECTOR
GAS
CHROMATOGRAPH
PARTITION CURTAIN
CUTAWAY VIEW SHOWING RIGHT SIDE
GENERATOR
HOUSING
ICE
MAKER
TOP VIEW
REFRIGERATOR x INSTRUMENT STORAGE,
GAS CHROMATOGRAPH,
AND CARRIER AND
CALIBRATION GASES
REAR
7-1/2 FT
CUTAWAY VIEW SHOWING LEFT SIDE
FRONT
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 support the
basic van systems such as air conditioning, lights, refrigerator, ice maker,
and gas chromatograph. For a completely independent power supply to sup-
port 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 van. 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 shelf 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 mobile 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, NOX> S0x, 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, SOV,
N2, C02, 02, C1 - Cfi,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 installa-
tion 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
-------
Table 3. Process Data Needs for Phased Environmental Assessment
IV)
Type of industry
Industrial sub-category
Geographical location
Plant boundaries
Plant access
Products
Waste products
Patent situation
Potential health hazards
Designed plant capacity
Current operating load
Maximum plant capacity
Plant start-up
Plant Characterization
Metallurgical, petro-chemical, etc.
Type of process used
Urban, rural, population center, etc.
Diagram of plant and property lines showing equipment
locations
Rail, road and water connections
Marketable results of plant operation
By-products or process control wastes
To avoid sampling in sensitive areas
Follow OSHA and FDA guidelines
Plant Operating Conditions
Output at design load
Percentage of design load
Potential maximum capacity
Time required to reach optimum conditions and change in
stream composition during this period
-------
Table 8. Process Data Needs for Phased Environmental Assessment (Continued)
Plant shutdown
Cyclic nature of process
Process flow diagram
Raw material streams
Product streams
Waste streams
Control equipment
Physical parameters
Special materials or construction
Streams to be sampled
Potential sampling sites
Availability of process
instrumentation
Plant Operating Conditions
Time required to shut down and effect on-stream
compositions
Process condition changes (temperature, pressure and
composition) with time
Plant Stream Conditions
—r "L - — ~- — /
Overall relation of streams
Location, composition, physical characteristics
Location, composition, physical characteristics
Location, composition, physical characteristics
Type and location
Temperature, pressure and flowrate
Need for specialized sampling equipment
Sampling/Analysis
Select representative streams
Select potential sites on basis of above information
Find on-site equipment and note condition
-------
Table 8. Process Data Needs for Phased Environmental Assessment (Continued)
Sampling/Analysis
Availability of utilities Electrical and water requirements for sampling and
analysis equipment
Available equipment On-site sampling or analysis equipment
On-site laboratory support Analytical capabilities
ro
-------
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 11QOC for two hours
just prior to use. Cool in a desiccator.
C.I PROCEDURE FOR COLUMN PPxEPARATION
Dry pack the chromatographic column, plugged at one end with glass
wool, with 6.0 grams of freshly activated silica gel. A portion of prop-
erly activated silica gel weighing 6.0 +0.2 g occupies 8'ml in a 10 ml
graduated cylinder. Vibrate the column for a minute to compact the gel
bed. Pour pentane into the solvent reservoir positioned above the column
and let the pentane flow into the silica gel bed until the column is
homogeneous throughout and free of any cracks and trapped air 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 to 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
100 mg. Weigh this sample in a glass weighing funnel. In order to facili-
tate 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 1 ml per minute.
Table 9. Liquid Chromatography Elution Sequence
No.
Fraction
1
2
3
4
5
6
7
8
Solvent Composition
Pentane
20% Methyl ene chloride in pentane
50% Methyl ene chloride in pentane
Methylene chloride
5% Methanol in methyl ene chloride
20% Methanol in methyl ene chloride
50% Methanol in me thy! ene chloride
Cone. HCl/Methanol /Methyl ene
chloride (5+70+30)
Volume
Collected
25 ml
10 ml
10 ml
10 ml
10 ml
10 ml
10 ml
10 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 com-
plete the quantitative sample transfer. (Note: Do not rinse with methylene
chloride because this solvent will cause the aromatics to elute with the
paraffins.) Add the solvent slowly to minimize disturbing the gel bed and
eliminate the trapped air bubbles, particularly in the zone of the sample-
containing 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 less
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 collection 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 solution plus 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 Soxhlet extractor with a 1.5-liter
dumping volume. This requires 2 to 2.5 liters of solvent in the 3-liter
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,
0 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
-------
I TCHNICAl. REPORT DATA
(Please read fiwtniclifiii? on tlu' reverse befur? completing)
. HtPORT NO.
E PA- 600/2 -76-160a
4. TITLE AND SUBTITLE
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE ANP sun F i i uc
IERL-RTP Procedures Manual: Level 1 Environmental
Assessment
5. REPORT DATE
June 1976
0. PERFORMING ORGANIZATION CODE
.AUTHORS j w Hamersma, S.L. Reynolds, and
R. F. Maddalone
8. PERFORMING ORGANIZATION REPORT NO.
24916-6040-RU 00
i. PERFORMING ORGANIZATION NAME AND ADDRESS
TRW Systems Group
One Space Park
Redondo Beach, California 90278
10. PROGRAM ELEMENT NO.
1AB013; ROAP 21AAZ-015
11. CONTRACT/GRANT NO.
68-02-1412, Task 18
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final: 2-5/76
14. SPONSORING AGENCY CODE
EPA-ORD
. SUPPLEMENTARY NOTES IERL_RTP proiect officer for this
Mail Drop 62, (919) 549-8411, Ext 2557.
manual is R. M. Statnick,
16. ABSTRACT
The manual gives Level 1 procedures (recommended by Industrial Environ-
mental 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 analy-
sis technique. (Level 1 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
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.
17.
1.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDF.NTIFIERS/OPEN ENDED TERMS
c. COSATi Field/Group
Pollution
Sampling
Analyzing
Industrial Processes
Energy Conversion
Gas Sampling
Bioassay
13. DISTRIBUTION STATEMENT
Aerosols
Liquids
Slurries
Solids
Inorganic Com-
pounds
Organic Compounds
Pollution Control
Stationary Sources
Environmental Assess
ment
Energy Processes
Fugitive Emissions
13B
14B
13H
10A,10B
06A
07D
11G
Unlimited
19. SECURITY CLASS (Ttiis Report)
Unclassified
07B
07C
21. NO. Ot- PAGES
145
20. SECURITY "CLASS (This page)
Unclassified
72. PRICE
EPA Form 2220-1 (9-73)
131
------- |