CD A U.S. Environmental Protection Agency Industrial Environmental Research
l» • • » Office of Research and Development Laboratory
Research Triangle Park, North Carolina 27711
EPA-600/7-78-016
FebfUarV 1978
EPA/IERL-RTP INTERIM
PROCEDURES FOR LEVEL 2
SAMPLING AND ANALYSIS
OF ORGANIC MATERIALS
Interagency
Energy-Environment
Research and Development
Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
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were established to facilitate further development and application of environmental
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are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
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mentally-compatible manner by providing the necessary environmental data and
control technology. Investigations include analyses of the transport of energy-related
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This document is available to the public through the National Technical Information
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EPA-600/7-78-016
February 1978
EPA/IERL-RTP INTERIM PROCEDURES
FOR LEVEL 2 SAMPLING AND ANALYSIS
OF ORGANIC MATERIALS
by
J.C. Harris and P.L Levins
Arthur D. Little, Inc.
Acorn Park
Cambridge, Massachusetts 02140
Contract No. 68-02-2150, T.D. 21102
Program Element No.EHB529
EPA Project Officer: Larry D. Johnson
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, N.C. 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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ii
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TABLE OF CONTENTS
List of Tables v
List of Figures vi
Foreword vii
I. INTRODUCTION 1
A. Philosophy of the Phased Approach 1
B. Purpose of a Level 2 Study 2
C. Purpose and Scope of This Document 3
II. LEVEL 1 TO LEVEL 2 TRANSITION 5
III. LEVEL 2 SAMPLING AND ANALYSIS: TENTATIVE PROCEDURES . 9
A. Sample Types and Sampling Methods 9
B. Analysis Methods 11
1. Compounds in Predetermined Categories ... 11
2. Unknown Samples 18
IV. SAMPLING METHODS 25
A. Gases and Vapors 27
1. Gases 27
2. Vapors 32
B. Particulates 34
C. Liquids/Slurries 36
D. Solids 40
E. Fugitive Emissions 41
F. Reactive Compounds 44
V. ANALYSIS METHODS 47
A. Liquid Chromatography 47
B. High Performance Liquid Chromatography (HPLC). . 51
iii
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Table of Contents (continued)
1. Detectors 51
2. Gel Permeation Chromatography 54
3. Reverse Phase HPLC 56
4. Normal Phase HPLC 57
C. Thermal Gravimetric Analysis ......... 53
D. Gas Chromatography (GC) 59
1. Detectors 59
2. Columns 60
3. Gas Chromatographic Conditions 60
E. Gas Chromatography/Mass Spectrometry 62
1. Detector • 62
2. Columns 65
F. Mass Spectrometry (LRMS and HRMS) 65
1. Low Resolution Mass Spectrometry 65
2. High Resolution Mass Spectrometry 66
G. Infrared Spectroscopy (R) 68
H. Nuclear Magnetic Resonance Spectroscopy .... 69
I. Ultraviolet and Luminescence Spectroscopy ... 71
APPENDIX A. Expected Distribution of MEG Category Organic
Compounds in Level 1 Samples 73
APPENDIX B. Bibliography 101
iv
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List of Tables
Table Number Page
Comparison of Level 1 Data with Decision
Criteria
2 Level 2 Preferred Sampling and Sample
Treatment Methods for Various Organic
Chemical Categories 13
3 Level 2 Analysis Methods by MEG Category .... 16
4 Problematic Organic Compound Categories .... 45
5 Comparative Specifications of HPLC Detectors . . 52
6 Electronic Absorption Bands for Representative
Chromophores 53
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LIST OF FIGURES
Figure Number Pase
l.a. Level 2 Organic Analysis Scheme 20
l.b. Organic Extracts Analysis Scheme 21
2 Integrated Gas Sampling Train 28
3 Porous Polymer Vapor Sampling Method .... 30
4 Porous Polymer and Thermal Gradient
Sampling Train 31
5 XAD-2 Sorbent Trap Module 33
6 Method 5 Train Modified for Collection of
Organic Vapors 35
7 Source Assessment Sampling Schematic .... 37
8 Method 5 Particulate Sampling Train 38
9 Decision Example for "Worst Case" Site ... 43
10 Directed Level 2 LC Scheme for Analysis of
Phenols (MEG Category 18) 48
11 Directed Level 2 LC Scheme for Analysis of
Polychlorinated Biphenyls 49
12 Directed Level 2 LC Scheme for Analysis of
Polynuclear Aromatic Hydrocarbons 50
13 Guide to Selection of HPLC Analytical
Procedures 55
vi
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FOREWORD
This document constitutes an interim guide to field and
laboratory procedures for sampling and analysis of industrial effluent
and process streams. The procedures are limited to those that will
permit chemical analysis of organic species in these streams. They
are intended to provide compositional data appropriate to Level 2
in the Phased Approach to Environmental Assessment. Since experience
in this type of investigation is still rather limited, the present
document is subject to further refinement and expansion before it can
be considered complete. Additional data, including validated sampling
and analysis procedures consistent with the objectives of Level 2
Studies will be developed for incorporation into the final version of
this manual which is scheduled for completion later this year'.
vii
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vili
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I. INTRODUCTION
This Interim Procedures Manual represents a step in the develop-
ment of a final Level 2 Procedures Manual for the sampling and analysis
of organic compounds from process streams. Concepts and general guide-
lines are presented here. The final manual will contain the fully
developed concepts and, insofar as possible, validated Level 2 procedures.
A. Philosophy of the Phased Approach
The original philosophy used in the development of a phased
approach to environmental assessment is briefly reviewed to place the
purpose of a Level 2 study in context with the overall program. (1)
The Process Measurements Branch of IERL/RTP has developed a three-
tiered or phased approach to performing an environmental source assess-
ment. In this phased approach, three distinctly different sampling and
analytical activities are envisioned. (2)
The phased sampling and analytical strategy was developed to focus
available resources (both manpower and dollars) on emissions that 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.
The phased approach requires three separate levels of sampling and
analytical effort. The first, Level 1, is designed to provide enough
information about the composition of effluent and process streams to
permit them to be ranked in order of priority for probable environmental
hazard. The Level 1 assessment is intended to: 1) provide preliminary
environmental assessment data, 2) identify principal problem areas, and
3) provide the data needed for prioritization of energy and industrial
processes, streams within a process, components within a stream, and
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classes of materials, for further consideration in the overall assessment.
The second phase of sampling and analysis effort, Level 2, is designed
to provide additional information that will confirm and expand the
information gathered in Level 1. This information will be used to
define control technology needs and may, in some cases, give the probable
or exact cause of a given problem. The third phase, Level 3, makes use
of sampling and analysis methods whose precision and accuracy are
sufficient to permit quantitative monitoring of specific pollutants
identified in Level 2. Concentrations of critical components in a
stream can thus be determined as a function of time and process variation
with accuracy and precision necessary for effective control device
development.
The phased approach offers potential benefits in terms of the
quality of information that is obtained for a given level of effort and
in terms of the costs per unit of information. This approach has been
investigated and compared to the more traditional approaches and has
been found to offer the possibility 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
identified in Level 2 to provide information for control device design
and development.
B. Purpose of a Level 2 Study
The objective of a Level 2 Study will be to obtain more detailed
and accurate data about the composition of a particular process stream
than is available in the context of a Level 1 Study. The improved
i
accuracy could either be primarily quantitative in terms of establishing
a truly representative emission rate, or be primarily qualitative in
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terms of determining specific chemical composition or both. It is
expected that most Level 2 sampling and analysis studies for organic
compounds will be required to identify all of the specific chemical
species present and detectable in process streams.
Most Level 2 studies will be probably done as a result of
interpretation of data obtained from previous Level 1 studies. Level 2
inquiries are expected to be directed primarily at the identification,
quantification and confirmation of specific compounds whose presence
could be inferred on the basis of the categorical analysis of Level 1.
For these cases, a restricted set of specified procedures may be
selected. Level 2 studies may also occasionally be initiated either
on the basis of results of the bio-tests alone or on other criteria
than the Level 1 chemical analysis. Thus, the questions to be answered
by Level 2 procedures may range from highly specific, (i.e. what is
the amount and composition of polychlorinated biphenyls in the stream?)
to quite general, (i.e. what caused the positive bio-test result?).
In this latter example where Level 1 chemical analysis was apparently
not sufficiently sensitive to reveal the existence of a hazardous
composition, a comprehensive analytical effort similar to but more
exhaustive than that required for Level 1 would have to be conducted,
perhaps including detailed chemical analyses more characteristic of
Level 2.
C. Purpose and Scope of This Document
The objective of this document is to present concepts and guide-
lines to be used in consideration of Level 2 sampling and analysis
for organic compounds. This interim report focuses on concepts and
general guidelines, with suggestions for specific procedures. A
definite Level 2 Organics Procedures Manual will eventually be
published which will include the more fully developed concepts and
procedures specified as much as is possible for a wide range of
conditions.
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The Level 2 Organic Procedures Manual Is intended for use by
experienced research chemists who are presumed to be thoroughly
familiar with environmental sampling and analysis, with Level 1 pro-
cedures and with the objectives of the phased approach. The manual
will not attempt to teach the detail which is more adequately found
in other publications, but will rely heavily on reports published
previously by IERL-RTP and its contractors (1-8). A reader who is
not familiar with these documents should consult them before attempting
to use the procedures described in the Level 2 organic sampling and
analysis manual.
In addition, various standard methods such as published by ASTM,
EPA (Federal Register), NIOSH and the Intersociety Committee are relied
upon where appropriate.
The Multimedia Environmental Goals (MEG) study sponsored by IERL-
RTP has resulted in the generation of a list of categories of organic
and inorganic compounds (the MEG lists) and associated concentration
levels representing their toxicity in various media. (8) Examination of
these categories shows that they include almost all major classes of
organic compounds (with the exception of a very few such as pesticides),
and that the MEG list therefore represents a convenient means of
organizing a productive approach to organic analysis and reporting of
the results of a Level 2 inquiry. The MEG list of organic compound
categories has been used advantageously in this manual to provide a
practical basis for interpreting data and for selecting Level 2 proce-
dures. Inasmuch as the present document is by no means to be considered
final or definitive in its coverage of Level 2 needs, however, the use
of the MEG categories should be understood in the context of a reasonable
approximation which can be helpful in developing a sound approach to a
comprehensive environmental assessment process. It is emphasized that
reference to the MEG list in this report is focused on the categories
and not on the individual compounds. The MEG categories encompass
most groups for which analysis will be needed while the compound list is
quite restricted.
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II. LEVEL 1 TO LEVEL 2 TRANSITION
The current Level 1 analysis for organic species is expected to
result in the description of a number of compound categories and their
observed concentrations. Comparison of the measured concentration of
each category with an appropriate decision criterion will then establish
a basis for proceeding with and/or directing more detailed Level 2
studies. The appropriate decision criteria must be chosen with the
concurrence of the Project Officer, bearing in mind the specific objectives
of the study for which the Level 1 analysis was conducted. Decision
criteria currently under evaluation are the Level 1 0.5 mg/m^ value for
gas emissions MATE and EPC values from the MEG study, TLV's, S values,
and others.
For purposes of illustration, the decision process can be conven-
iently described using the results of a Level 1 analysis of a stack sample
collected with a SASS train, and applying two different sets of decision
criteria. Table 1 lists the compound categories found in the sample and
their calculated source concentrations.
Each of these concentrations can be compared with a consistent
set of decision criteria. In this example, the concentration for each
n
category is compared against the general 0.5 mg/m gaseous emission Level
1 criterion and against the MATE values.
i
Column 3 show that four compound categories exceeded the 0.5 mg/fa.3
concentration and further studies are indicated for fused aromatics above
and below MW 216, heterocyclic nitrogen compounds and carboxylic acids.
Column 4 lists the most stringent or "worst case" MATE values for compounds
in each of the observed categories. Column 5 gives the results of
comparing the observed concentrations with these MATE values. The
decision process becomes more complicated when using criteria such
as the MATE values because the toxicity data on which they are based are
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TABLE 1
Comparison of Level 1 Data with Decision Criteria
Compound Categories
Aliphatic HC's
Aromatics - Benzenes
Fused Aromatics <216
Fused Aromatics >216
Heterocyclic S
Heterocyclic N
Heterocyclic 0
Carboxylic Acids
Phenols
Esters
Observed Source
Concentration (mg/m3)
0.06
0.06
5.
5.
0.2
2.
0.2
2.
0.1
0.08
Exceeds Level 1
0.5 mg/m3
no
no
yes
yes
no
yes
no
yes
no
no
Worst Case MATE
(mg/m3)
200
1
30
2 x 10~5
1
0.2
590
1
2
5
Exceeds MATE
Value
no
no
no
yes
no
yes
no
yes
no
no
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for specific compounds and the only information one can expect from the
Level 1 analysis is for categories of compounds. A "worst case" approach
may be taken by using the most stringent MATE value for any compound
belonging to each category as a conservative criterion for the Level 1
comparison. This is the methodology represented in Table 1.
Using these "worst case" MATE values, three categories are found
to exceed the relevant MATE concentration. Using these criteria, further
analysis of the lower molecular weight fused aromatics (MW < 216) is
not indicated, while detailed analysis of the fused aromatics with MW
> 216, the heterocyclic nitrogen and the carboxylic acid categories does
appear to be necessary. The decision logic described here has been used
as the underlying concept in development of the Source Assessment Models
(SAM). In some cases the selection of the "worst case" MATE value as the
basis for subjecting a particular chemical category to further scrutiny
may prove to be an unreasonably severe criterion. A more critical exam-
ination of the Level 1 data (particularly the LRMS data) may serve to
provide more reasonable and appropriate decision levels in many of those
instances. This approach is currently under evaluation.
To aid the analyst in evaluating the Level 1 data for further
action, Appendix A has been constructed to relate each of the MEG
compounds and the chemical categories to which they are assigned, to
the points at which they appear in the Level 1 analytical scheme.
Again, emphasis is placed on the use of the Appendix A categorization
as an aid in the analysis and interpretation of data, and not as a
definitive list of compounds of concern in environmental assessment.
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III. LEVEL 2 SAMPLING AND ANALYSIS: TENTATIVE PROCEDURES
A. Sample Types and Sampling Methods
The basic process sample types to be dealt with at each of the
levels of sampling and analysis are any gases which may contain suspended
liquid and/or solid particles, liquids and slurries, and solids. Level
2 analyses may be conducted either on samples freshly collected for that
purpose or on samples retained from the Level 1 sampling effort. The
choice between collecting a new sample or analyzing a retained sample or
fraction for the Level 2 data will be highly specific to the exact
question to be answered and to the nature of the chemical species to be
determined. For example, the Level 2 requirement could be to confirm the
presence of and determine the identity of each of several polychlorinated
biphenyls (PCB's) in a source. Since the Level 1 sampling procedures are
known to be adequate by Level 2 standards for collection of PCB'.s and since
PCB's do not deteriorate in storage, it would usually be sufficient to
analyze a retained Level 1 sample to provide the required data. If the
Level 2 question pertained to some reactive species or to other material
not collected well by the Level 1 methods, then a new specific sampling
and analysis effort may be called for, using alternative procedures.
Most of the organic samples retained from the Level 1 study will
be in the form of extracts in methylene chloride solution. Two exceptions
are the sorbent module wash, which at present is a methanol/methylene
chloride solution (or combined1solution/suspension), and the "grab" gas
sample. The Level 1 gas sample for determination of reactive sulfur
species and low-molecular-weight hydrocarbon species will not have been
retained, having been used for the on-site GC analysis. Some portions
of the original solid and particulate samples may be available, since
these tend to be more stable than the other samples and to be available
in larger quantities than required in the minimum Level 1 procedure.
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The Level 1 samples - mostly extract solutions - are conveniently
available for more comprehensive organic analytical characterization
using all of the techniques discussed later. However, before proceeding
to more detailed analysis of these (Level 1) samples to answer the
Level 2 question, the appropriateness of the sample for study must be
carefully evaluated. Does the sample provide a sufficiently quantitative
representation of the source? Was the sampling procedure efficient for
the species in question? Will the species to be analyzed be stable
enough to warrant more detailed analysis? Would an alternative procedure
provide a more interference-free sample for analysis? Each of these
questions requires a specific answer in each specific instance, but the
general considerations are common to all further Level 2 studies.
In many instances, the results from the Level 1 sampling and
analysis study will have triggered specific Level 2 questions. In order
to provide better guidance for the selection of specific Level 2 sampling
and analysis procedures, further studies on the retained Level 1 samples
may be warranted. These might be needed to confirm tentative identifi-
cations or to look for species that might interfere with specific methods.
However, one should remember that, at best, Level 1 samples still retain
all the inherent limitations designed into the selection of sample size,
collection methods and extraction procedures. In Level 1, not all
categories or species are collected in an optimum manner, since the
procedure is required to make certain compromises in the interest of
economy and generality. This statement is not a criticism of the Level 1
procedures but rather a reminder that a single set of procedures which
attempts to encompass all possible species cannot be expected to be
optimized for each specific species or category.
It will be necessary in many cases to collect additional samples
for Level 2 studies. The reasons for this include the arguments above
about possible limitations of the samples retained from Level 1 and
especially, perhaps, the need for providing a more accurate quantitative
10
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representation of the entire composition of an effluent or process stream.
A new Level 2 sample might also be designed to meet a requirement for
quantitative accuracy for specific compounds such as the polynuclear
aromatic hydrocarbons (PAH's) aldehydes, phenols, nitrosoamines, etc.
The sampling methods available for various categories of sources and
compounds are discussed in the following chapter.
B. Analysis Methods
This section describes specific procedures which are provisionally
recommended for Level 2 studies. Two basically different types of Level
2 studies may be carried out. In most cases, results from the Level 1
study will have providecl chemical class information which will have
directed attention to specific compound categories. In those cases a
specific sampling and analysis procedure may be selected. Recommendations
for such procedures organized , f or purposes of illustration, around the
MEG categories, are given in Subsection 1 below. In some other cases, a
need for Level 2 studies may be indicated by criteria such as a set of
positive biotest results, rather than chemical composition data. The
biotest results would not be expected to target specific chemical cate-
gories for study in Level 2. In these cases a comprehensive set of
Level 2 studies will be required, possibly using procedures with lower
detection limits than those of Level 1. It may also be necessary to
analyze for species which may originally have gone undetected because of
the procedural constraints imposed by the Level 1 economic considerations.
A general approach to analysis of these samples of unknown composition
is discussed in Subsection 2 of this section.
1. Compounds in Predetermined Categories
It is expected that most Level 2 organic analyses will be directed
towards one or more specific classes of chemical compounds that were
indicated by Level 1 analysis to exceed their respective decision-level
concentration(s). The Multimedia Environmental Goals (MEG) list (8)
11
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provides a classification of organic species into 25 chemically diferen-
tiated categories, and is therefore a convenient means of organizing
approaches to Level 2 sampling and analysis. This organizational approach
does not mean, of course, that only the particular chemical compounds
on the MEG list are to be sought for in Level 2 analyses. Furthermore,
it is recognized that there are a few kinds of organic compounds (e.g.,
pesticides, insecticides, phosphates, silicones) that do not fit logically
into any of the 25 MEG categories and that must therefore be considered
separately.
It now seems clear, nevertheless, that most Level 2 questions will
be able to be formulated in terms of determining the identity and abundance
of compounds within chemical categories that correspond fairly closely
to those of the MEG list. Sampling and analysis methods on which tentative
Level 2 procedures are based are described in Chapter IV and V of this
report. Tables 1 and 2 summarize the particular choices of sampling
and analysis methods, respectively, that can be recommended for Level 2
analyses by MEG category. The appropriate methods will, in some cases,
be described in somewhat more detail in the final Level 2 Procedures
Manual. However, because each Level 2 study is likely to be unique in
some respects, it is necessary to allow for flexibility and to leave
exact details—sample size, GC temperature program, etc.—to the discretion
of the analyst.
12
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TABLE 2
Level 2 Preferred Sampling and Sample Treatment Methods
for Various Organic Chemical Categories
Gaseous Streams
Chemical Categories
Aliphatic Hydrocarbons
Ci C7
>C7
Alkyl Halides
h.p. <100°C
h.p. >100°c
Ethers
Halogenated Ethers
b.p. <100°C
b.p. >1008C
Alcohols
b.p. <100°C (100°C
Glycols, epoxides
Aldehydes
b.p. <100°C (100°C
Ketones
b.p. <100°C (100°C
Carboxylic Acids
formic, acetic
C3 - C5
Sampling
Treatment
Aqueous Streams
Sampling Treatment
gas bulb or none, or adsorb grab
solid sorbent to concentrate
SASS
purge & trap
pentane
resin adsorbtton proportional pentane extraction
gas bulb or none or adsorb grab
solid sorbent to concentrate
purge & trap
SASS
SASS
gas bulb
SASS
gas bulb
SASS
SASS
gas bulb
SASS
SASS
SASS
SASS
resin adsorption proportional CH2Cl2extraction
resin adsorption proportional CH2Cl2extraction
none, or adsorb grab purge & trap
to concentrate
resin adsorption proportional Cf^C
none, or adsorb grab purge & trap
to concentrate
resin adsorption proportional resin adsorption
or other extraction
resin adsorption grab or none, or ether
proportional extraction
grab
purge & trap
Bisulfite none
impingers
SASS resin adsorption proportional ether extraction
none, or adsorb grab purge & trap
to concentrate
resin adsorption proportional CH2Cl2extraction
resin adsorption grab
resin adsorption grab
purge & trap
none
resin adsorption proportional CH2Cl2extraction
at pH2
13
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TABLE 2
(continued)
Chemical Categories
Amides
Cg
Esters
Nitriles
b.p. <100°C ( C2)
C6
Amines
b.p. <100°C
b.p. >100°C (C6)
Azo compounds,
hydrazine, etc.
Nitrosamines
Mercaptans
Sulfides, Bisulfides
b.p. <100°C (100°C
Sulfonic Acids,
Gaseous
Sampling
SASS
SASS
SASS
gas
(reactive)
SASS
SASS
gas bulb
SASS
SASS
special
reagent
impingers
SASS
gas bulb
and on-site
GC
gas bulb
SASS
SASS
Streams
Treatment
resin adsorption
lesin adsorption
resin adsorption
none, or adsorb
to concentrate
resin adsorption
resin adsorption
none, or adsorb
to concentrate
resin adsorption
resin adsorption
none
resin adsorption
none, or adsorb
to concentrate
none, or adsorb
to concentrate
resin adsorption
resin adsorption
Aqueous
Sampling
grab
grab
grab
grab
grab
proportional
grab
grab
grab
grab
grab
grab
grab
proportional
grab
Streams
Treatment
none
ether extraction
CH2C12 extract ion
purge & trap
none
CH2Cl2extraction
none
none
CH2Cl2extration
at pHn
none, or CH2C12
extraction at
PHn
none, or CH2C12
extraction
at pHn
none
purge & trap
CH2Cl2extraction
none
Sulfoxides
Benzene, Substituted
Benzene Hydrocarbons
b.p. <100°C gas bulb
b.p. >100°C SASS
Halogenated Aromatics SASS
none, or adsorb proportional CH2Cl2extraction
to concentrate
resin adsorption proportional CH2Cl2extraction
resin adsorption proportional CH2Cl2extraction
14
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TABLE 2
(continued)
Gaseous Streams
Chemical Categories
Aromatic Nitro
Compounds
Phenols
Halophenols
Nitrophenols
Sampling
SASS
SASS
Fused Polycyclic SASS
Hydrocarbons Fused Non-
Alternant Polycyclic
Hydrocarbons
Heterocyclic Nitrogen SASS
Compound
Heterocyclic Oxygen
Compounds
b.p. <100°C (Furan) gas bulb
b.p. >100°C
Heterocyclic Sulfur
Compounds
b.p.
.b.p.
<100°C
(Thiphene)
>100°C
SASS
gas bulb
SASS
Treatment
Aqueous Streams
Sampling Treatment
resin adsorption proportional CT^C^extraction
resin adsorption proportional none, or
or grab (for >CIQ)
ether extraction
at
resin adsorption proportional C^C^extraction
resin adsorption grab
at pHn
none, or absorb grab purge & trap
to concentrate
resin adsorption proportional CH-2Cl2extraction
none, or adsorb proportional solvent extraction
to concentrate
resin adsorption proportional solvent extraction
15
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No.
TABLE 3
Level 2 Analysis Methods by MEG Category
MEG Category/Subcategory Analysis Method
3
4
5
6
Aliphatic Hydrocarbons
b.p. < 100°C
b.p. > 100°C
Alkyl Halides
b.p. < 100°C
b.p. > 100°C
Ethers
Halogenated Ethers
Alcohols
Glycols, epoxides
7a Aldehydes
7b Ketones
8a-b Carboxylic Acids
8c Amides
8d Esters
9 Nitriles
10 Amines
11 Azo compounds
12 Nitrosamines
GC/ms or GC/FID on Porapak Q
GC/ms or GC/FID on SP-2250 (or
OV-17)
GC/ms or GC/ECD (isothermal) on
Porapak Q
GC/ms or GC/ECD (isothermal) on
SP-2250 (or OV-17)
GC/ms on SP-1000
GC/ms or GC/ECD (isothermal) on
SP-1000
GC/ms on SP-1000
GC/ms on Porapak P (direct aque-
ous injection)
1. lodometric titration of
bisulfite impingers or
2. GC/ms on SP-1000
GC/ms on SP-1000
1. Reverse phase HPLC or
2. GC/ms on SP-1000 after forma-
tion of derivative
1. Normal or reverse phase HPLC
or
2. GC/ms on SP-1000
GC/ms on SP-1000
GC/ms on Carbowax 20M-0.8% KOH
1. Normal phase HPLC or Gel Per-
meation Chromatography or
2. GC/ms on SP-1000 or Tenax
16
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TABLE 3
(continued)
_No.
13
15
16
17
18
19
20
21
22
23
24
25
MEG Category/Subcategory
Mercaptans, Sulfides and
Disulfides
Sulfonic Acids,
Sulfoxides
Benzene, Substituted
Benzene Hydrocarbons
Halogenated Aromatics
Aromatic Nitro Compounds
Phenols
Halophenols
Nitrophenols
Fused Polycyclic Hydrocarbons
Fused Non-Alternant Polycyclic
Hydrocarbons
Heterocyclic Nitrogen
Compounds
Heterocyclic Oxygen Compounds
Heterocyclic Sulfur Compounds
Analysis Method
1. GC/FPD on Teflon/polyphenyl
ether/HsPOt, (in field for re-
active species) or
2. GC/ms on OV-17 or SP-1000
Ion-pair HPLC
Normal or reverse phase HPLC
GC/ms or GC/FID on SP-2250 (or
OV-17)
GC/ms or GC/ECD (isothermal) on
SP-2250 (or OV-17)
1. Reverse phase HPLC or
2. GC/ms on SP-1000 or SP-2250
1. Reverse phase HPLC or
2. GC/ms on Tenax (direct aque-
ous injection) or
3. GC/ms on SP-1000 after deri-
vative formation
1. GC/ms on Dexsil 400 or
2. Reverse or normal phase HPLC
1. GC/ms on SP-1000 or SP-2250
or
2. Normal phase HPLC
17
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2. Unknown Samples
1
Samples to be analyzed at Level 2 for which Level 1 failed to
provide a more directed analysis will generally have to be analyzed by
methods that have greater detection sensitivity for specific compounds
(i.e., lower detection limits) than those used in Level 1, and that
deal better with those areas for which Level 1 procedures are least well
suited, for instance gases and high molecular weight species. It will
be important to provide assurance that no significant portion of the
collected sample has failed to be accounted for in the analysis, and
that qualitative detail is adequate to meet the requirements of the
inquiry.
It is difficult to devise a specific scheme that will be appro-
priate for all process streams to be analyzed in this manner. This
section seeks to present some general guidance and suggestions of
procedures to be used and the sequence in which they should be used.
A general scheme that should be useful in planning a Level 2
analysis is given in Figures l.a. and l.b. Three general types of
samples are considered; (1) those that are essentially gaseous, but
may contain suspended solid or liquid aerosols; (2) those that are
essentially liquid — often aqueous — but that may contain dissolved
gases, liquids and solids as well as suspended solid particles; and
(3) those that are principally solid, and which may contain some
entrained liquids.
In terms of the sampling characteristics of the SASS train, "gases"
are defined as species with a boiling point below 100°C. "Vapors" are
defined as species whose boiling points are above 100°C (at 760 mm), and
that are present in the gas phase at partial pressures below their
saturation vapor pressures. The term "particulate" includes liquid
aerosols and solid particles. Details of some provisional sampling and
analysis procedures for these species are given in Chapters IV and V.
18
-------
Samples from the gas phase (e.g., from stacks, ducts and ambient
air) are expected to be collected principally by direct "grab" sampling,
using plastic bags, and by the SASS train or similar devices, such as,
for example, the modified Method 5 train. The "grab" samples may be
analyzed directly, using appropriate GC and/or GC/MS techniques, or they
may be pre-concentrated by adsorption at low temperature on resins such
as Tenax-GC, from which they can be thermally desorbed for GC and/or
GC/ltS analysis.
The samples collected by an atmospheric sampling train such as
SASS will pass through the cyclones and filters that are included in
those systems to remove and collect suspended solids, and will then be
led through a sorbent resin trap (XAD-2) to collect vapors of organic
compounds. Some organic vapors will be condensed on the walls of the
SASS train components and some condensate may collect in a sump below
the sorbent trap. These condensates will be added to the extract, obtained
from treatment of the sorbent resin with methylene chloride.
The particulate matter collected in the cyclones and on the filter
of the sampling train should be examined microscopically for evidence of
intact crystalline species whose identity might subsequently be obsured
or lost in the ensuing separation treatments. Optical microscopy may
be usefully combined with x-ray and/or electron diffraction and other
microscopic analysis techniques wherever the examination of individual
particles may be deemed appropriate in the general analytical scheme.
After microscopic examination, the particulate catch will be extracted
with methylene chloride or other suitable solvent and the extract, together
with that from the sorbent trap, submitted to analysis by the general
scheme outlined in Figure l.b. for organic liquids. The residue, which
may contain insoluble organic as well as inorganic components, should be
subjected to analysis by infrared (IR), thermogravimetric analysis (TGA)
and by high resolution mass spectrometry (HRMS), using a "probe" sample
insertion technique.
19
-------
N)
O
SOLID
SAMPLE
EXTRACT
EXTRACT
EXTRACT
'MICROSCOPY^
sEXTRACTIONX
|
RESIDUE
J
MICROSCOPY,
TGA, IR,
HRMS (PROBE)
.EXTRACT^ ^
.
ORGANIC EXTRACTS
ANALYSIS SCHEME
(Fig. 1.b)
FIGURE 1.Q. LEVEL 2 ORGANIC ANALYSIS SCHEME.
-------
ORGANIC EXTRACTS
SOLUTIONS, AND/OR OTHER
ORGANIC LIQUIDS
HIGH-MOLECULAR
WEIGHT FRACTION
HRMS, NMR
(FT)IR
SURVEY ANALYSIS
TGA, IR, NMR, MS, GC, MICROSCOPY
NON-VOLATILES PRESENT
POLAR, ACIDIC
FRACTION
NON-VOLATILES ABSENT
LOW-MOLECULAR
WEIGHT SUBSTANCES
COMPLEX MIXTURE
DATA FROMSIMPLE MIXTURE
SURVEY AND/*
" .LEVEL'
FIGURE l.b. ORGANIC EXTRACTS ANALYSIS SCHEME.
-------
Samples collected from liquid streams, most of which are likely
to be aqueous and destined for dilution into groundwater, may be sampled
batchwise or by continuous contact of a diverted side stream with a
solid sorbent or a continuous extractant. As shown in Tables 1 and 2,
the liquid sample may preferably be analyzed directly for some organic
components, but for most purposes, filtration (to remove suspended
solids), followed by extraction in an immissible solvent such as methylene
chloride will be the method of choice for preparing .the sample for
organic analysis. In any event a separate batch sample should be taken
initially, which will be purged with a nonreactive gas to remove and collect
low-boiling organic gases. This collected gas sample is then to be
analyzed by GC/MS, similarly to the "grab" sample taken from a gaseous
stream.
After filtration, the liquid filtrate of an aqueous sample should
be extracted with a suitable organic solvent such as rethylene chloride,
having first been adjusted to a high pH and then to a low pH to promote
extraction of partially dissociated ionic substances. Alternatively,
contact of the aqueous filtrate with a sorbent resin may prove to be a
preferable general method to remove organics which may subsequently be
desorbed by a suitable solvent. In either case, the organic extract
will then be subjected to analysis as shown in Figure l.b. above,
and the residue will be analyzed by gel-permeation chromatography (GPC)
and HRMS (probe) to detect and identify any organics that were not able
to be extracted or sorbed. Any solid residue that remains after filtra-
tion of a principally liquid sample, will be analyzed in the same way
as particulates removed from a gaseous stream, i.e., by microscopy,
extraction with an organic solvent, and TGA, IR and HRMS analysis of the
non-extractable residue.
Solid samples, which are likely to be particulate, and which may
contain small amounts of entrained liquids, will be analyzed in the same
manner as the solid particulate fractions removed by filtration, from
gaseous samples and liquid samples. The organic extracts of these samples
22
-------
can be expected to dissolve and remove any entrained organic liquids as
well as the soluble portion of the solids themselves. These extracts
will then be analyzed in the same manner as all other organic extracts.
The general analytical scheme for organic extracts rinse solutions
and other organic liquids is shown in Figure l.b. When the information
sought is not limited to a specific question about one or a few components,
but requires instead a broad-ranging examination of the entire organic
composition of the sample, an initial survey analysis should be performed
prior to the application of various chromatographic separation techniques.
Data may be obtained from TGA, IR, MS, GC and microscopic examination of
residues remaining upon evaporation of the solvent (typically methylene
chloride or similar low-boiling solvent) at a temperature not above 40°C.
These data, in combination with NMR, which requires that a portion of
the sample be redissolved in an appropriate solvent (aprotic for proton-
NMR; -"-^c-depieted for I^C-JJMR, etc), will serve to show what the general
composition of the sample is, whether it is especially complex or
limited to a relatively small number of components, and whether -it
contains high-molecular-weight and/or non-volatile organic species which
might not be seen in a TCO assay. Any other relevant data, including
that from a prior Level 1 study should be considered here, in the interest
of developing the most efficient and productive plan for the subsequent
separation and identification scheme.
On the basis of the survey analysis, a decision can be made as
to whether a significant fraction of the sample appears to be of such
low volatility that it will not be susceptible to analysis by GC/MS. If
so, the entire sample should first be subjected to gel-permeation
chromatography (GPC) to separate the high-molecular weight fraction,
which is likely to contain many or all of the non-volatiles, from the
relatively low-molecular-weight substances. A break-point of M.W. = 300-
500 is likely to be satisfactory for the GPC separation. The high-
molecular weight, non-volatile fraction is likely to be analyzed most
successfully by a combination of NMR and IR (both Fourier-transform-
23
-------
assisted) and perhaps by HRMS, using a solids probe for sample insertion.
If the low-molecular-weight and relatively more volatile fraction
from GPC (or the entire sample if GPC was not required) appears to be a
mixture of only a few substances, as suggested by the survey data, GC/
MS may be sufficient to provide all the identification and quantification
required. If not, then an LC separation, using silica gel, alumina or
Florisil, as appropriate, will be necessary to resolve the mixture into
more manageable fractions, as well as to assist in characterizing
chemical composition. Chapter V of this manual provides a more detailed
discussion of liquid chromatographic techniques that will be most
appropriate to this operation.
Non-polar and aromatic fractions of the LC eluate may be submitted
directly to GC/MS. Those that are more polar and acidic may benefit
from a more discrete resolution of their components by means of high
performance liquid chromatography (HPLC). The choice of a favorable
combination of column packing, mobile phase and detector will depend in
part on information available to the analyst about the sample at this
point in the process and partly on the analyst's own experience and
preference. Since HPLC techniques are often capable of resolving
individual chemical substances, discrete fractions may be collected for
subsequent analysis by HRMS, (FT) NMR, and/or (FT) IR, or by GC/MS.
More detailed descriptions of these analytical techniques, with particular
reference to their applicability to environmental assessment studies,
are provided in Chapter V of this manual.
24
-------
IV. SAMPLING METHODS
Sampling methods for use in Level 2 may in many cases be the same
as those used in Level 1. It may be possible in some cases where a
specific measurement is sought to use simpler procedures than those
prescribed for Level 1. In some cases, alternative procedures will
be desirable to measure species not represented well by the Level 1
scheme and/or especially reactive compounds, such as certain reactive
olefins, hydrazines, etc.
The available sampling methods have been described in detail in
several sources. All of the Level 1 sampling methods and procedures
are described in the "IERL-RTP Procedures Manual: Level 1 Environmental
Assessment". (3) A companion document, "Technical Manual for Process
Sampling Strategies for Organic Materials", (4) gives further details on
Level 1 methods and additional methods that may be appropriate to
Level 2 and Level 3 studies. Many specific methods are detailed in
various ASTM documents, and the Federal Register contains descriptions
of standardized EPA methods. The reference "Standard Methods for the
Examination of Water and Wastewater", (16) and the EPA publication, "Hand-
book for Monitoring Industrial Wastewater" (17) are excellent resources
for water sampling and analysis methods. Fugitive sampling method-
ology has recently been addressed in several EPA publications. (7a,
7b, 7c). The reader should refer to these and similar sources for
i
detailed descriptions and discussions of specific methods. Those
procedures which seem to be most appropriate for Level 2 studies will
be reviewed briefly in this chapter. The orientation in selection of
methods for consideration was influenced by the existing Level 1
procedures and the chemical categories represented in the MEG list of
organic compounds.
Although it is possible and desirable to specify a restricted set
25
-------
of procedures for Level 1 studies, the Level 2 situation is not analogous.
The objectives of studies at Level 2 may cover a wide range and may vary
from the need for better process (flow) data to compound-specific
emission or composition data. A set of methods must be put together
for the Level 2 study which are most appropriate for each specific task.
Generally speaking, it should be possible to choose from the sampling
methods described in this Manual, although it may be desirable in some
cases to make modifications of the procedures. Methods for some species
are not yet well developed and will need to continue to evolve as the
state-of-the art advances.
Sources to be sampled may be organized by procedures into:
a) fixed sources: process and effluent streams, vents
and stack emissions, and
b) fugitive emissions.
The sources will yield the basic sample types described as:
gas/vapor
particulate
liquid/slurry
solid
For the purposes of this Manual, particulates will be treated
separately from the gases and vapors, although "particulate" refers
to solid or liquid materials entrained in gaseous streams. Fugitive
sources of particulates and vapors/gases are treated separately.
Level 2 procedures for reactive compounds are also treated in a
separate section.
26
-------
A. Gases and Vapors
1. Gases
The Level 1 procedure for gases involves sampling (in a bulb)
followed by on-site GC analysis. Gases are considered to be those
species with a boiling point range similar to those of the C^ - 67
hydrocarbons, i.e., -160°C to 100°C. Special provision is also made
to measure the reactive reduced sulfur species on the on-site GC,
using the FPD.
The disadvantage of the Level 1 procedure for the low-boiling
materials is that qualitative chemical information cannot be obtained
beyond that which might be inferred from the retention time data.
Exoneration of a source on the basis of such limited information would
require a risky assumption in many environmental assessment studies
of sources of unknown composition. As an alternative, most compounds
in the low boiling range, with the exception of certain reactive
species, may be readily and reliably identified and quantitatively
estimated by GC/MS analysis methods. The question then is of the
most appropriate method for collecting the gas sample for the GC/MS
study. At this point, it should be noted that experience with the
Level 1 procedures — both in terms of materials collected efficiently
on the XAD-2 module and those lost in sample treatment steps — suggests
that all species boiling in the range of -160°C to 100°C (Ci~ C7
hydrocarbon equivalent) should be treated as gases.
*
In terms of the analysis method detection limits, it will be
sufficient for Level 2 purposes in most cases to analyze the equivalent
of 0.1 - 1.0 L of gas sample. It may be possible to collect grab or
time-integrated samples in inert bags, as suggested by Figure 2.
The bag could then be returned to the laboratory where it may be analyzed
either directly or by preliminary concentration of the species on a
material such as Tenax GC and subsequent thermal desorption. There are
27
-------
AIR-COOLED
CONDENSER
oo
PROBE
RIGID
CONTAINER
Figure 2 Integrated gas sampling train (Solid lines showing
normal arrangement, Dotted lines - alternate arrangement,
evacuating chamber around bag).
Source:EPA-600/2-76-122, April 1976 p.60
-------
reports of the successful use of this method. The need to concentrate
the samples will be set by the concentration of the species present in
the sample and the detection limits of the analytical instrumentation.
The major uncertainty with this approach is of the stability of samples
in "inert" bags, a topic still under investigation.
An alternative method for sampling these low molecular weight
materials is the use of porous polymers. Two materials in particular,
XAD-2 and Tenax-GC, have been used successfully for this purpose. The
choice of methodology depends on the sampling temperature, trap size
and the elution volume (Vg - the volume of gas in which the compound
"breaks through" the trap) of the compound. If the higher-boiling
end of the volatile range (e.g. B.P.- 0°C - 100°C) is being examined,
or if the concentration of volatiles is high (allowing, therefore,
lower volumes of sample to satisfy the analytical detection limits),
then a simple sampling system as shown in Figure 3 could be used.
Tenax-GC would be the adsorbent of choice in this sampler because its
higher thermal stability would facilitate direct thermal desorption
and analysis. In order to obtain adequately representative quantita-
tive data for the stream, several 0.1 - 1.0 L samples should be
collected. Larger samples may be needed if greater sensitivity is
demanded.
If the Vg value for solid sorbent sampling is too low at ambient
(20°C 1 5°C) temperatures, then an approach using the Kaiser tube
thermal gradient on a porous polymer might be used, as shown in
Figure 4. While this approach has great promise from a theroetical
viewpoint, preliminary field treatments have met with limited success,
due to difficulty in maintaining a uniform, high temperature gradient
across the Kaiser tube.
No good procedures for concentration of sufficient quantities
of gaseous species for biotesting have been identified. The best
29
-------
STAINLESS STEEL PROBE
SOURCE
OJ
o
POLYMER
PACKED
TUBE
D
ROTOMETER
GAS METER
FLEX HOSE
Figure 3 Porous polymer vapor sampling method
Source: EPA-600/2-76-122, April 1976 p.66
-------
u>
TEMPERATURE GAUGE
PRESSURE GAUGE
V
/THERMOCOUPLES
HEATED SECTION
POLYMER PACKED TUBE
VACUUM PUMP
STAINLESS STEEL PROBE CONDENSER
EVACUATED CYCLINDER
LI QUID NITROGEN DEWAR
COMPRESSED NITROGEN
Figure 4 Porous polymer and thermal gradient sampling train
Source: EPA-600/2-76-122, April 1976 p. 28
-------
procedure currently available is the collection of the 3 x 500-liter
bag samples, which is the sampling method required for the "stress
ethylene" test.
2. Vapors
In the context of this report, vapors are defined as compounds
with boiling points above about 100°C (or a CQ normal hydrocarbon
equivalent) that exist as gaseous species in the stream or environment
to be sampled because they are present below their equilibrium vapor
pressure concentration. When these same species are present at
concentrations above their vapor pressures they would, of course,
exist as aerosols and be sampled as particulate. Most of the compounds,
in the vapor range are sampled efficiently by the XAD-2 sorbent module
(Figure 5) in the SASS train (see Figure 7)• For those compounds
with low Vg values (e.g., boiling points below 20'JC), it may be necessary
to sample less than 30 cubic meters (the Level 1 volume) to ensure
quantitative collection. These constraints are discussed in detail
in the EPA report, "Selection and Evaluation of Sorbent Resins for
the Collection of Organic Compounds". (6)
The preferred Level 2 sampling procedure for organic (and organo-
metallic) vapors is the use of XAD-2 or Tenax GC. Alternative methods
should only be used when there are data to show an established prefer-
ence over these materials. The resins can be used with the sorbent
module of the SASS train alone (no particulates, no impingers) when
sufficient quantities are required for biotests. XAD-2 is the preferred
resin when solvent extraction procedures are to be used in sample
preparation. If thermal desorption is to be used, Tenax GC is the
sorbent of choice. Thermal desorption methods should generally be
reserved for small-scale sampling apparatus. While XAD-2 and Tenax-GC,
have comparable Vg characteristics at 20°C, XAD-2 has generally slightly
better volumetric capacity and has substantially greater (10X) weight
capacity than Tenax-GC.
-------
U)
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 5 XAD-2 Sorbent Trap Module
Source: EPA-600/2-76-160a, June 1976 p. 32
-------
In many Level 2 cases it will be possible to use simpler sampling
methods than the SASS train when only organic vapors are to be measured.
In earlier studies reported in the literature, impingers and bubblers
using toluene, xylene, isooctane or ethylene glycol have been used to
sample, for instance, PCB's and pesticides. NIOSH methods use
activated petroleum-base charcoal and activated coconut-base charcoal
for a wide range of compounds. Many other resins related to XAD-2 and
Tenax GC have also been studied. (6)
Smaller scale versions of the SASS sorbent module have been success-
fully operated on modified Method 5 trains as with the Battelle Sampler
(9) and in recent studies of incinerator emissions (10) in which the
version shown in Figure 6 was used. Sufficient quantities of vapors
for analysis may frequently be obtained by the simple version of a
train previously shown in Figure 3.
Normal care (as specified in Federal Register Method 5) should be
taken in both gas and vapor sampling to obtain a representative sample.
There is no explicit Level 2 requirement for isokinetic sampling of
gaseous species, but samples should either be taken across the cross
section of the duct or in a well mixed portion of the stream.
B. Particulates
Particulates consist of solids and liquid aerosols; both are
collected efficiently by appropriate combinations of cyclones and
filters. Other special purpose particulate collectors such as.electro-
static precipitators have found limited application in the collection
of samples for environmental assessment studies related to chemical
composition.
There is a wide variety of trains and configurations that can be
used to characterize particulate emissions. A complete discussion of
these can be found in the EPA reports.
34
-------
To Control
j Module
Silica Gel
Figure 6 Method 5: Train Modified for Collection of Organic Vapors
Source: "Destroying Chemical Wastes in Commercial Scale Incinerators1'. Facility Report No. 5
EPA Contract No. 68-01-2966 TRW Systems Inc., Subcontract No. A82870 DNB-L,
Arthur D. Little, Inc. July 1977 p. 14
-------
For chemical characterization studies and to provide samples for
biotesting, the SASS train shown in Figure 7 is used for Level 1
studies. The SASS is capable of providing particulate sample in the
following size ranges:
> 10 ym cyclone
3 - 10 ym cyclone
1 - 3 ym cyclone
< 0.5 ym filter
The first two and last two size ranges are each combined to yield
only two particulate fractions for analysis in Level 1 but can be
maintained separately for Level 2 studies. Interest in analysis of
each of the size fractions might be related to the relative distribu-
tion of the trace metals or pesticides or other species of interest.
For simple quantitative measurement of total particulate emission
levels, or if smaller quantities of particulate are required, the
Method 5 train (Figure 8) as described in the Federal Register may
be adequate.
C. Liquids/Slurries
The general considerations given in the Level 1 Procedures Manual
still pertain for Level 2 sampling of liquid and slurry streams. Stream
homogeneity and flow rate are important factors to consider in collect-
ing a representative sample and may be accomplished by a number of well
established methods (4).
Grab samples, such as collected in the Level 1 Procedure, may
also be used for Level 2 studies. Grab samples will be adequate if the
primary Level 2 objective is more complete qualitative chemical or
biological characterization than provided in Level 1. However, it is
expected that most Level 2 studies will also require better quantitative
data and for this purpose proportional sampling should be used.
36
-------
U)
STACK T.C.
">_
V
HEATER
CON-
TROLLER
SS PROBE
1
CONVECTION
OVEN
FILTER
, GAS COOLER
"A
I ^^_
GAS
TEMPERATURE
T.C. /
XAD-2
CARTRIDGE
TRACE ELEMENT
COLLECTOR
CONDENSATE
COLLECTOR
DRY GAS METER ORIFICE METER
CENTRALIZED TEMPERATURE
AND PRESSURE READOUT
CONTROL MODULE
" 10 CFM VACUUM PUMP
Figure 7 Source Assessment Sampling Schematic
Source: EPA 600/2-76-160a, June 1976 p.30
-------
oo
Figure 8 Method 5: Particulate Sampling Train
Source: 40 CFR 60, Appendix A - Government Printing Office, Washington B.C., July 1976
-------
Sampling may be done proportional to either time or flow, and the
choice will have to be dictated by the process characteristics and the
measurement objectives. It is possible to obtain samplers which
provide the substance in a composite or separate sequential mode.
Sampling with this type of equipment whould be restricted to streams
with low or no visible solids. Slurries should be sampled by grab
techniques.
For aqueous streams, grab sampling combined with solvent extraction
of organics is a tedious procedure and does not always lead to quanti-
tative extraction. Continuous extraction/concentration techniques used
in conjunction with a proportional sampler offer significant promise
for obtaining a quantitative time-averaged sample from aqueous liquid
streams.
The Carbon Adsorption Method (CAM) has previously been used by EPA
in a large number of water and wastewater sampling studies. While the
CAM has apparently good extraction efficiency, quantitative recovery of
some compounds is poor. Recent studies in the laboratory of EPA (11) and
ERDA (12) indicate that XAD-2, XAD-8 and combinations of these resins
are good sorbents for the extraction and recovery of ppb-level materials.
A program is currently underway on the design of a XAD-2 sampler for use
in the field collection of samples.
For high concentrations of organics in water (> 10 ppm) solvent
extraction procedures are still recommended. The resins have limited
mass capacity and are probably inferior to solvent extraction at high
concentration levels.
For Level 2 studies, it is recommended that a separate liquid
sample be collected for the analysis of volatile constituents. These
volatile species, or "purgeables" have been the subject of recent EPA
studies, (13) and this class has been shown to contain many compounds
suspected as carcinogens. A number of the compounds on the MEG list would
be detected as purgeables in a water sample.
39
-------
The EPA Cincinnati protocol for purgeables should be adopted
for Level 2. This requires collection of a special grab sample sealed
with a Teflon faced septum and no head space. The sample should be
analyzed by the "purge and trap" procedure of Bellar and Lichtenberg. (14)
When solvent extraction procedures are to be used, it is recom-
mended that several extractions be carried out at. each of the two pH
extremes. Extraction is suggested at pH 2 and pH 11. Methylene chloride
has been found to be effective for many compounds, but other solvents
such as diethyl ether may offer advanatages in certain cases„ The ex-
traction sequences of — base/neutrals then acids, or — acid/neutrals
then bases — have both been evaluated and found successful in certain
cases. The former sequence is currently used in the EPA/Cincinnati pro-
tocol. The sequence of choice would appear to be affected by problems
such as emulsion formation and should therefore be left to the discretion
of the individual sampler/analyst and his project officer.
D. Solids
Level 1 procedures call for the use of a shovel or borer to obtain a
sample for biotesting and to determine composition. Level 2 procedures
should more systematically address the method of obtaining a representative
sample. There are two basic types of solid samples - a bulk sample and a
moving sample. Bulk samples include coal piles, sludge disposal areas,
etc. Moving samples come from transport systems such as conveyor belts
or transfer points. A number of ASTM procedures describe acceptable
means of collecting each of these sample types.
For bulk samples, ASTM D346-35, "Standard Method of Sampling Coke
for Analysis", describes the basic techniques for shovel, coning and
quartering methods and locating sampling points. ASTM D-1799-65, "Sampling
Packaged Shipments of Carbon Black", provides a method for bagged or
cartoned materials. ASTM C183-71, "Sampling Hydraulic Cement", describes
40
-------
discharge point sampling and a slotted tube sampler for hopper sampling.
ASTM D-2013-72, "Preparing Coal for Analysis", describes several mechanical
sample dividers and riffles which can be used in preparing a fraction of
the sample for analysis.
Moving samples may be collected by several procedures. A "stop
belt" method involves stopping periodically and removing a standardized
portion of the stream, taking care to obtain a complete cross section, since
settling will occur. A cutter device, as described in ASTM D 2234-72,
removes a portion of the stream by a traverse at a uniform speed. Samples
from discharge points may be collected by moving a pan across the entire
cross section of the discharge.
E. Fugitive Emissions
Fugitive emissions are all those emissions discharged to the environ-
ment by a source other than a well-characterized stack or stream. They
may include particulate, vapor, gas and water samples or species. Fugitive
emissions can be considered to be dilute source samples at ambient conditions.
The dilution factor requires special consideration in sample volumes required
for collection. The fact that fugitive emission species are defined only
as being present in the ambient environment poses special sampling strategy
problems for sampler choice and location,,
The general characteristics of fugitive emissions and sampling method-
ology have been described in recent IERL-RTP reports. (7a, b, c.)
Airborne fugitive emissions may generally be described in terms of:
Site Source
Specific Source: Category 1
Specific Source: Category 2
41
-------
Several examples of these are described in a worst case site description
in Figure IV-8. A "site source" is a general emission contributed to by
many individual sources. Sampling such a source requires an upwind/down-
wind strategy. Some specific diffuse sources, Category 1, can be sampled
by placing a sampler directly downwind if it has minimum confusion by other
sources. Other specific sources, Category 2, are less diffuse, such as
hearth or coke oven vents, and may be sampled using point source sampling
methods.
Particulate samples from site sources and Category 1 specific
sources may be sampled using a Hi-Vol sampler. If size fractionation
is desired, a Hi-Vol impactor stage may be added. For Category 2 specific
sources, the same choices for stack methods described in Section IV.B. are
applicable. Primary emphasis in a level 2 study may be on better quanti-
tative data which will required collecting a large number of samples with
associated meteorological and source data.
By operating at about 50 cfm the Hi-Vol sampler is generally capable
of collecting sufficient fugitive particulate sample for study (chemical
analysis). There is no analagous equipment or method for sampling fugi-
tive gases and vapors. The ambient/fugitive concentrations are 100 -
10,000 times lower than source levels, but the currently available method-
ology will not allow flow rate scaling to collect large quantities. Al-
though there has been only limited testing, it is believed that the general
bag and sorbent (Tenax GC) procedures described in Section IV A for source
levels will provide sufficient sample for chemical analysis studies of
fugitive vapors and gases. However, use of these methods for this purpose
requires further careful validation.
The same procedures described for Level 1 fugitive water sampling
are recommended for Level 2 studies, if required.
42
-------
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
DOWN V.'IND
PILE
DO./N v-IND SIR SOURC-'
SAMPLERS
CATEGORY I HIGH VOL.
DOWN '.VINO FROM COAL
PILES
CATEGORY I HIGH-VOl.
DOWN WIND FROM
LIMESTONE BINS
\
CATECOSY I HlGH-^'Ol.
DOV.'N V IMD FROM ON-. IT;
ORt TfUAJIMC, OPERATION'.-
UPWIND SITE - SOURCE
SAMPLER
CATEGORY I HIGH-VOL.
DOWN WIND FROM QUENCH-
TOWER AND COKE GRINDING
CATEGORY i HIGH-VOL.
DOV/N '.VINO FROM COKt
OVEN BYPRODUCT RECOVERY
COKE OVEN BANK
CATEGORY 2 SASS TRAIN
Figure 9 Decision Example for "Worst Case" Site
Source: EPA 600/2-76-160a, June 1976 p.51
-------
F. Reactive Compounds
There are many specific compounds which are reactive and would
not persist in a general sampling and analysis scheme long enough for
quantitative and possibly even qualitative determination. For example,
examination of the MEG list of organic compounds (8) shows several species
or categories which will need special attention if the need should arise
to determine them. (See Table 3).
For some compounds, there are relatively straightforward solutions.
For instance, the low FID response of the alkyl halides can be overcome
by using an ECD detector. The reactive mercaptans can be analyzed by
GC on-site (as in Level I). However, the compounds which pose a problem
because of very high reactivity represent a more difficult case. Specific
methods will have to be used for each of these cases0 In some cases, as
for the aldehydes, methodology exists in the form of a specific bisulfite
collection followed by iodometric titration or GC analysis. Some other
species, such as the dienes, will require development of special sampling
and analysis methods. It may be possible to modify a colorimetric pro-
cedure to measure the level of azo compounds and hydrazines.
Each of the compounds or categories listed in Table 3 (and
perhaps others) represents a special case which must be handled on an
individual basis.
44
-------
TABLE 4
Problematic Organic Compound Categories
Category Problem
Alkynes reactive
Haloforms low response to F.I.D.
Halogenated Dienes reactive
Ralogenated Ethers (some) reactive
Aldehydes reactive
Methyl Methacrylate reactive
Acrylonitrile reactive
Azo compounds, Hydrazine reactive
and derivatives
Mercaptans reactive (on-site GC)
Dicyclopentadiene reactive
45
-------
46
-------
V. ANALYSIS METHODS
A. Liquid Chromatography
In Level 2 organic analysis, as in Level 1, it will usually be necessary
or desirable to perform some sample fractionation prior to analysis. One
approach to sample fractionation is liquid column chromatography (LC) on
media such as silica gel, alumina, or Florisil. An LC separation on
silica gel is often useful as a method for separating a sample into a
small number (i.e., 4-8) of fractions prior to bioassay or chemical
characterization. An eight-fraction scheme of this type is used in Level
1 organic analysis and in some cases it may be possible to use those same
eight fractions for further, Level 2 analysis. In the more general case,
in which discrete Level 2 samples have been collected, alternative
fractionation procedures are likely to be attractive.
A number of different LC schemes will be used in Level 2, depending on
which categories of compounds are of concern. Furthermore, since Level 2
analysis will ordinarily be directed towards only one or a few specific
categories of compounds identified in Level 1, a simple two- or four-
fraction LC separation may suffice. One example is shown in Figure 10
for Level 2 analysis of phenols.
Other LC procedures that are of value in Level 2 organic analysis are
separations on alumina or Florisil to remove interferences in the analy-
sis of selected substances. An example, shown in Figure Us is tne
Florisil column pre-cleaning procedure used to remove interfering
substances prior to analysis of polychlorinated biphenyls (PCB's) in
industrial effluents (15). Another example of possible application of
LC in Level 2 organic analysis is shown schematically in Figure V-3. In
this example, a silica gel LC procedure to isolate aromatics is followed
by an alumina LC procedure to separate polynuclear aromatics into classes
by ring number.
47
-------
©
Pentane
Organic
Extract
LCOn
Silica
Gel
Methylene
Chloride/
Pentane
*0r Fraction 6 From Level 1 LC Scheme
50% Methanol/
Methylene Chloride
GC/MS For Phenols
FIGURE 10. DIRECTED LEVEL 2 LC SCHEME FOR ANALYSIS OF
PHENOLS
48
-------
Organic Extract
0
LCOn
Florisil
Fats, Lipids
c
Chlorob
(A)
Aromatics
LCOn
Silica
Gel
) ©
snzenes
GC/MS For RGB's
FIGURE 11. DIRECTED LEVEL 2 LC SCHEME FOR ANALYSIS
OF POLYCHLORINATED BIPHENYLS
-------
0
Pentane
Organic Extract
LCOn
Silica Gel
Methylene Chloride/
Pentane
LCOn
Alumina
Benzenes Naphthalenes
Anthracenes 4-Ring 5-Ring
& Aromatics Aromatics
Phenanthrenes
*0r combined Level I LC Fractions 2, 3 and 4.
FIGURE 12. DIRECTED LEVEL 2 LC SCHEME FOR ANALYSIS OF POLYNUCLEAR
AROMATIC HYDROCARBONS
50
-------
B. High Performance Liquid Chromatography (HPLC)
HPLC is a separation technique with applications in quantification, iso-
lation and identification. HPLC is differentiated from other LC methods
by high speed, high sensitivity and high resolution comparable to that of
gas chromatography. These improvements have been achieved by columns
using microparticle packings with small diameter (5-50 micrometers) and
high surface area (approximately 300 m2/g particles. Separations may be
achieved by differences in molecular size, number or type of functional
groups, steric configuration, polarity, etc.
1. Detectors
The two most commonly used methods of detection of sample components in
HPLC effluents are ultraviolet (UV) absorbance detectors and refractive
index (RI) detectors. Features of these two types of detectors are sum-
marized in Table 4. High sensitivity and specificity are achievable
using a UV detector at fixed (e.g., 254 nm) or variable (200-800 nm) wave-
length. Lower limits of detection in the nanogram range have been reported
for strongly absorbing sample species (i.e., molar absorbtivity ^ 14,000.
Table 5 presents some molecular absorbtivity data to illustrate the
range of detection limits that can be expected for the UV detector. The
differential refractometer detector has lower sensitivity and less speci-
ficity than the UV detector. The RI detector responds to essentially all
sample components and is a potential "universal" detector for HPLC, but
lower limits of detection are in the microgram range. Furthermore, gener-
ality of the RI detector response requires matching of solvent system
refractive indices during gradient elution HPLC; this is difficult to
achieve in lab practice. Other types of HPLC detectors, such as the moving
wire flame ionization detector and the fluorescence detector, do not
appear to offer any special advantages for Level 2 organic analysis
compared to the UV and RI detectors. The fluorescence detector might be
applied in some specific cases, such as analysis of polynuclear aromatic
hydrocarbons.
51
-------
TABLE 5
Comparative Specifications of HPLC Detectors
Range of Application
Destructive or Non-
destructive
Gradient Compatible
Detectability
Min. Physical Change
Minimum Concentration
Minimum Det. Sample
Linear Range
Short Term Reproduci-
bility
Peak Shape
Peak Spreading
Norn. Response Time
Cell Void Volume
Experimental Upper Limit
Flow Sensitivity (b.l.
shift 0-90 raL/hr)
UV
Selective
Nondes tructive
Yes
2 x lO' Abs.
4 x 10~9 g/mL
2 x 10
3000
"11
g/sec
Less than 1%
deviation
Positive only
1 second
8 microliters
46 microliters
12% f.s.
RI
Universal
Nondestructive
~7
1 x 10 RI units
7 x 10~7 g/mL
3 x 10
3000
9
g/sec
Less than 1%
deviation
Positive or
Negative
1 second
6 microliters
20 microliters
^25% f.s.
Source: Basic Liquid Chromatography, Varian Instrument Company
52
-------
Chromophore
Ether
Thioether
Amine
Thiol
Bisulfide
Bromide
Iodine
Nitrile
Acetylide
Sulfone
Oxime
Azido
Ethylene
Ketone
Thioketone
Esters
Aldehyde
Carboxyl
Sulfoxide
Nitro
Nitrite
Azo
Nitroso
Nitrite
Benzene
Diphenyl
Naphthalene
Anthracene
Pyridine
Quinoline
Isoquinoline
TABLE 6
Electronic Absorption Bands for
Representative Chromophores
System
-0-
-S-
-NH2
-SH
-S-S-
-Br
-I
-C=N
-C=C-
-S02-
-NOH
>C=N-
-C=C-
>C=0
>C=S
-COOR
-CHO
-COOH
>S-K)
-NO 2
-ONO
-N=N-
-N=0
-ONO 2
X Max
185
194
195
195
194
208
260
160
175-180
180
190
190
190
195
205
205
210
200-210
210
210
220-230
285-400
302
270
e Max X Max e
1000
4600 215 1
2800
1400
5500 255
300
400
-
6000
-
5000
5000
8000
1000 270-285
strong
50
strong 280-300
50-70
1500
strong
1000-2000 300-400
3-25
100
12
Max
,600
400
18-30
11-18
10
X Max e Max
(shoulder)
-(C=C) 2-210-2 30 21,000
(acyclic)
-(C=C)3- 260 35,000
-(C=CX- 300 52,000
-(C=C) 330 118,000
-(C=cr2- 230-260 3000-8000
(alicyclic)
C=C-CHC 219 6,500
C=C-C=N 220 23,000
C=C-C=0 210-250 10,000-20,000
C=C-N02
229
184
220
252
174
227
218
9,500
46,700
112,000
199,000
80,000
37,000
80,000
202
246
275
375
195
270
266
6,900
20,000
5,600
7,900
6,000
3,600
4,000
300-350
255
312
251
314
317
weak
170
175
1,700
2,750
3,500
Source: Basic Liquid Chromatography, Varian Instrument Company
53
-------
An HPLC-MS combination might be of interest in some Level 2 applications.
However, these systems are not in common use because of the formidable
problems in designing an interface to remove carrier (solvent) prior to
MS analysis. Similarly, the FTIR detector offers great promise when and
if it becomes fully developed for this application.
HPLC methods are likely to be used in two different modes in Level 2
organic analysis. First, some HPLC separations by Gel Permeation, normal,
or reverse phase chromatography are useful ways of achieving a preliminary
coarse fractionation of the sample according to molecular weight range
and polarity. Secondly, some normal or reverse phase chromatographic
procedures may be selected as the quantitative analytical finish for
sample components that have high molecular weight, poor thermal stability,
and/or high polarity. A guide to selection of an analytical HPLC method
is summarized in Figure 13. In practice, of course, the use of such a
guide would require that determination be made at each decision point to
provide information required for the choice. The types of HPLC separations
most useful in Level 2 organic analysis are discussed briefly below.
2. Gel Permeation Chromatography
This technique is based on separation by molecular size, which is closely
related to molecular weight. Large molecules may be excluded from some
or all of the pores in the column packing material, due to their hydro-
dynamic volume in solution. Therefore, large molecules elute from the
column before smaller molecules which permeate the pores. Columns are
available in a variety of nominal pore sizes, and a number of columns are
usually used in series to ensure adequate resolution.
Column packings used with non-aqueous mobile phases (for example, tetra-
hydrofuran, toluene, dimethylfortnamide and methylene chloride) include
polystyrene (e.g., Styragel®), spherical silica (e.g., Porasil®) and
irregularly shaped silica (e.g., Merkogel® Si). Packings suitable for
use in aqueous GPC include Dextran gels (e.g., Sephadex®) and controlled
pore-size glass (e.g., CPC®).
54
-------
01 Sample.
Water
Insoluble
MW<1000
Water Soluble
MW> 1000
Hexane
Soluble
(Non-Polar)
Alcohol
Soluble
Polar
HPLC Mode
Reverse Phase
Normal Partition
__ Adsorption
Ion Exchange
Solvent System
Water/Methanol
Water/Acetonitrile
Hexane/Chloroform
Methylene Chloride
Chloroform, Hexane
Aqueous
Buffers
Gel Permeation
Adapted from Literature of DuPont Instruments, Scientific and Process Division Wilmington, Delaware
THF, Chloroform
(Non-Polar)
Water, Alcohol
(Polar)
FIGURE 13. GUIDE TO SELECTION OF HPLC ANALYTICAL PROCEDURES
-------
GPC may be used to achieve initial sample fractionations on a fairly large
scale, since 150 to 200 mg of material may be handled by y-Styragel columns.
Even higher loading capacities can be achieved by using larger particle
sizes (macro-Styragel) and column diameters.
For purposes of Level 2 organic analysis, GPC will probably be most use-
ful as a technique to separate samples into two molecular size ranges,
with a molecular weight of about 500 as the dividing point. The species
with molecular weight < 500 can then be analyzed by gas chromatography or
GC/MS, although some small and very polar or thermally unstable molecules
(amino acids, etc.) may require derivativization or alternative treatment.
The sample components in the >500 mw cut will require analysis by methods
not involving GC. These might include mass spectrometry (LRMS or HRMS)
or Fourier transform IR or NMR.
3. Reverse Phase HPLC
This technique is based on separation by polarity differences in the mobile
phase vs. stationary phase. The stationary phase is prepared by using
long-chain alkyl silylating reagents to produce a hydrophobic layer on a
silica solid substrate. Non-polar solutes have a higher affinity for the
stationary phase than do polar solutes. The mobile phase is generally
programmed in a continuous gradient elution scheme from polar to non-
polar solvents. Water/methanol and water/acetonitrile are binary solvent
systems frequently employed. In reverse phase HPLC, polar sample compo-
nents elute first.
In Level 2 organic analysis, reverse phase HPLC may be applied to low
molecular weight range sample components to separate the polar materials,
which would require derivative formation prior to gas chromatographic or
GC/MS analysis, from the non-polar materials suitable for direct gas
chromatography or GC/MS. Reverse phase HPLC is also an attractive possi-
bility for ultimate quantitative analysis of some classes of compounds,
such as phenols and carboxylic acids.
56
-------
4. Normal Phase HPLC
This technique, like reverse phase HPLC, is based on separation by polarity.
In normal phase separations, the stationary phase is more polar than the
mobile phase. Gradient elution systems from non-polar to polar solvents
are used, and non-polar solutes elute first. In Level 2 organic analysis,
normal phase HPLC may be used as a quantitative analytical finish for
some classes of compounds. The choice between normal and reverse phase
systems for this purpose would be based on several considerations.:
(1) Quantity of solute to be isolated for qualitative identi-
fication by NMR, IR, etc.
(2) Solute class solubility in the mobile phase.
(3) Column capacity for solutes in general.
(4) Ease of solvent removal after HPLC.
The first point is amply illustrated by considering the separation of poly-
cyclic aromatic hydrocarbons. Excellent separations between these solutes
is accomplished using H20/MeOH isocratic and gradient mixtures as solvents.
With these solvent systems and a Ci8-silylated silica support, even the
isomeric pair of phenanthrene and anthracene can be partially separated.
However, despite the excellent thermodynamic selectivity of this HPLC
system, it is limited in the quantity of solute which can be chromato-
graphed. This is in part due to the lower capacity of reverse phase
packings, the normal loss in resolution with sample overload, but pri-
marily due to the solubility limit of the hydrocarbon moiety in polar
solvents. Using a hydrocarbon solvent in conjunction with a silica sup-
port (normal phase system) 'allows larger quantities of this particular
class to be isolated (larger capacity of support, higher solubility, etc.)
although the resolution is diminished. It should be noted that sample
solubility in the mobile phase is of prime consideration in preparative
chromatography, particularly when mild gradients (water to methanol, n-
hexane to methylene chloride) are used in reverse or normal phase systems.
57
-------
If HPLC is to be used to isolate large quantities of material, the column
capacity becomes a factor. For example, semi-preparative reverse phase
columns have a typical capacity of 5 mg while a micro-particulate silica
gel for normal phase LC has a capacity of 1000 mg. It is therefore not
always possible to simply scale-up an analytical reverse phase HPLC sepa-
ration to achieve a preparative procedure.
It should also be noted that subsequent analytical procedures to be ap-
plied to HPLC fractions will possibly necessitate the removal of solvent
from the collected fractions. Water/methanol eluents can be more diffi-
cult to remove than a volatile hydrocarbon and may result in the loss of
some of the analyte. From this point of view, normal phase would seem to
offer some advantages.
C. Thermal Gravimetric Analysis (TGA)
The techniques which are used for the ultimate qualititative and quanti-
tative Level 2 analysis will depend on the volatility of the sample com-
ponents. Analytical procedures based on gas chromatography (GC), including
GC/MS, are suitable for volatile components. Sample components that are
non-volatile (because of high polarity and/or high molecular weight) must
be separated and analyzed by other techniques. Thermal Gravimetric
Analysis (TGA) is a rapid instrumental method for quantitatively determi-
ning the volatility of a sample as a function of temperature.
In a TGA analysis, the weight of a small sample (1-10 mg) is continuously
recorded as a function of time (isothermal operation) or temperature
(temperature programmed operation). The water content in mixtures, for
example, m?y be determined by TGA due to the well-defined weight loss at
its boiling point. In addition, isothermal TGA can be used to determine
residue on ignition on a micro scale by isothermal operation at high
temperature. For sample characterization studies, temperature programmed
i
operation is more normally used. The sample atmosphere (nitrogen, air,
may be controlled to aid in the study, for instance, of decomposition of
non-volatile samples.
58
-------
An example of the applicability of TGA to Level 2 organic analysis would
be the determination of whether the "aromatic1' material indicated as
present in a source by Level 1 analysis is more suited to separation and
analysis by GC/MS or by HPLC.
D. Gas Chromatography (GC)
Gas chromatography is a very powerful tool for separation of complex mix-
tures of organics with appreciable volatility. GC is also an exceedingly
valuable technique for quantitative analysis of sample components. How-
ever, qualitative analysis by GC is limited to inferences drawn from
retention times of individual peaks and known detector selectivities.
(The combination of mass spectrometric detection with GC to give quali-
tative data is discussed in a separate section).
1. Detectors
A considerable variety of detection principles have been utilized for
*
gas chromatography purposes. Of the detectors available, there are three
which are potentially of interest in Level 2 organic analysis.
The flame ionization detector (FID) is the most versatile general purpose
device. The FID responds to any substance that will burn in the air/
hydrogen flame to produce ions. Most organics, except for highly halo-
genated species, give strong FID responses. The lower limit of detection
for organic species is on the order of one nanogram per microliter (ppm)
of injected solution, and the dynamic range of the detector spans four or
more orders of magnitude.
(
The electron capture detector (ECD) is specific for species that contain
electronegative atoms or groups—halogens, phosphorus, sulfur, and nitro-
groups. The high selectivity of the ECD has been used to good advan-
tage in analyses of pesticides and polychlorinated biphenyls (PCB's).
The lower limit of detection is as much as 1000 times lower than that
of the FID, but the dynamic range is generally smaller. The magnitude
of the ECD response is sensitive to analyte structure, as well as to
59
-------
concentrations, since different species have different electron capture
cross sections. The detector response is also temperature dependent,
so that an BCD cannot usefully be employed in temperature programmed GC.
All of these factors combine to support the conclusion that GC/ECD is not
a technique with wide applicability in Level 2 organic analysis, but
one which may be used for snmp snecific ratfi<*ories of analvtes.
The flame photometric detector (FPD) is specific for species that contain
sulfur or phosphorus. Its specificity, detection limits, and sensitivity
are comparable to those of the BCD, although a completely different prin-
ciple of detection is involved. When operated in the sulfur mode, the
FPD response is logarithmic, rather than linear, with concentration. The
FPD may be utilized in Level 2 organic analysis of organophosphorus pesti-
cides and some sulfur species (including on-site analysis of reactive
sulfur gases, as in Level 1).
2. Columns
The number of potential choices of column type for Level 2 organic analy-
sis is staggering. Columns may be packed, support coated open tubular
(Scot) or wall-coated capillary column of stainless steel, glass, or
Teflon. An enormous range of stationary phases is available, including
porous polymers and liquids coated onto solid substrates. Highly
®
specialized columns include the polyphenylether/phosphoric acid on Teflon
matrix used for sulfur gases and the recent nematic phase liquid crystal
packings used to achieve resolution of isomeric polynuclear aromatic
hydrocarbons. These types of columns may be required in special Level 2
situations.
However, it appears that a set of five or six GC columns can be specified
that will cover most Level 2 analysis requirements and would maximize
comparability of data acquired in different EA programs. A suggested
set of columns for general purpose Level 2 work is the following:
60
-------
For volatiles - Porapak Q (2 mm x 2 m stainless steel). This
porous polymer column can separate hydrocarbons boiling
between -161°C and 68°C in a single temperature programmed
run. Fairly high resolution within a narrower boiling range
can be achieved by isothermal operation.
For moderate volatility, non-polar species - Methyl Phenyl
Silicone (SP 2250 or OV-17). (3% on Chromosorb WHP or equivi-
lent, 2 mm x 2 m stainless steel.) This stationary phase
separates analytes primarily on the basis of volatility (boiling
point) and can be used at temperatures up to 375°C. The liquid
phase is a 50% phenyl silicone.
For high boiling, non-polar species - Dexsil 400 (3% on
Chromosorb WHP or equivalent, 2 mm x 2 m stainless steel).
Dexsil 400 is a carborane-methyl phenyl silicone that is
stable at temperatures up to 500°C. Like OV-17, Dexsil 400
is basically a boiling point column. It is useful for
analysing species such as the polynuclear aromatics. It
does not function well much below 80°C.
For moderately volatile and moderately polar species - Modified
Carbowax 20M (SP 1000) (10% on Chromosorb W, 2 mm x 2 m glass or
stainless steel). Polyethylene glycol (Carbowax 20M) modified
with a terephthalalic acid, as in SP-1000, is a liquid phase
suitable for analysis of a variety of moderately polar species
including ethers, carbonyl compounds and alcohols. It can be
used at temperatures up to 275°C.
For moderately volatile and highly polar species - Tenax GC (2 mm
x 2 m, glass). This porous polymer is a recommended medium for
general GC analysis of phenols and carboxylic acids. It has high
thermal stability up to 375°C. (Note that in Level 2 organic
analysis, very polar analytes will be analyzed by HPLC, rather
than GC, in most cases.)
61
-------
3. Gas Chromatographic Conditions
Details of gas chromatographic conditions, such as carrier gas and tem-
perature regimes, will vary depending upon the compound categories of
interest. In general, temperature programming will probably be required
for Level 2 analyses.
E. Gas Chromatography/Mass Spectrometry (GC/MS/PS)*
The combination of gas chromatographic (GC) separation methods with mass
spectrometric (MS) detection coupled with an automated data system (DS)
is an extremely powerful tool for analysis of organic compounds. The
GC/MS technique differs from other GC procedures discussed earlier in
that GC/MS can provide specific qualitative information as well as quan-
titative data about sample components.
1. Detector
The detector in GC/MS is a dedicated low resolution mass spectrometer. This
has the unique benefit of being both highly compound specific and having
substantially uniform response to all components that are sufficiently
volatile to pass through the gas chromatograph. Furthermore, under normally
favorable circumstances, the MS/DS can discriminate among and often provide
discrete quantitative data for two or more components that elute simulta-
neously from the GC. Lower limits of detection for conventional (non-
capillary) column GC are typically 30-100 ng/yl of solution injected, and
lower for capillary column GC.
The GC/MS combination has available a range of operating conditions that
significantly affect the performance of the system. The operating param-
eters chosen must be appropriate to the objectives of each particular
analysis if the optimum results are to be obtained.
The most significant choices concern the mode of ionization, and the
format for mass scanning. Two classes of ionization mode are generally
i
available: electron impact (El) and chemical ionization (CI). El pro-
vides energy in excess of that required for simple ionization, resulting
* In this discussion, the term GC/MS is intended to imply also the
existence of an automated data handling system which is a virtual
necessity for Level 2 organic analysis.
62
-------
in considerable fragmentation of the parent molecule. This fragmenta-
tion provides structural information and a characteristic signature for
a given compound or compound class. Since reference spectra generally
available are of the El type, this ionization mode facilitates direct
matching of spectra for species identification. For some compound types
the fragmentation is so extensive that the parent ion is difficult cr
impossible to detect, making specific identification impossible. CI pro-
vides a much gentler mode of ionization, yielding fewer fragment ions and
substantially larger parent ions. It is the method of choice for those
classes which give no El parent ion, such as the higher mass alcohols,
or for those which give very small parent ions with less fragmentation;
however, less structural information is provided, although some is avail-
able and may be of a unique type. Reactions with the CI reagent gas com-
plicate the spectrum somewhat.
A range of adjustments is available for both El and CI, offering some
intergradation of features. By varying the reagent gas composition, CI
spectra can be made to approach the fragmentation pattern obtained in
El; reducing the electron beam energy in El can simplify the fragmenta-
tion pattern of that mode. El is somewhat more universal in application,
as it provides a more consistent sensitivity from species to species,
but CI can provide unique information that is sometimes necessary for
identification. Both techniques can be used for the same material pro-
vided sufficient sample and time are available for multiple analyses.
The adjustable parameters in selection of a GC/MS mass scanning format
are the range of the scan (or number of masses monitored) and the dwell
time on each ion. These must combine to give a fast enough scan to
yield several scans per GC peak; each complete scan must therefore last
a few seconds at most. One alternative is to scan the entire (i.e., m/e
12 to m/e 600) mass spectrum of material eluting from the column at a
frequency of about one scan every three seconds. However, the option
of scanning the entire available mass range is normally chosen only if
absolutely nothing is known about the sample. In virtually all Level 2
analyses, sufficient information will be available about the sample
composition and/or the components of particular interest to allow one to
scan a more limited mass range. For example, the mass scan could be
63
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limited to the range of m/e 100 to 300 if polynuclear. aromatic hydro-
carbons were the only compounds of concern. If a specific GC/MS analysis
for PCB's was desired, a few selected clusters of masses corresponding
to the di-, tri-, tetra-, etc., chlorobiphenyls could be monitored in-
stead of scanning a continuous wide mass range. The extreme case of
limited mass scanning would be to monitor a single ion continuously,
if only one compound were of interest. Reducing the range of the mass
scan allows an appreciably longer dwell time on each ion and this is
used to improve the signal to noise ratio. A limited mass scan also
enhances sensitivity by reducing background. The background elimination
can also be effected in the data processing phase, but the dwell time
for each ion is a real time parameter which is fixed during data acqui-
sition.
The improvement in effective sensitivity can be as much as three orders
of magnitude between the extremes of a complete mass scan and single ion
monitoring. Limited mass range scanning of selected ions or clusters can
approach the sensitivity of single ion monitoring.
The selection of the appropriate mass scan range will depend on the ob-
jectives of each particular Level 2 analysis. The presentation of the
data accumulated in the GC/MS scans can also be varied according to the
requirements of the analysis. One can print out a "reconstructed gas
chromatogram" in which the sum of ions of all mass numbers for each scan
is plotted versus mass spectrum scan number (a measure of retention time).
A second alternative is to plot the data in the form of "mass chromatograms",
in which only the abundance of selected ions, with m/e values corresponding
to specific sample components, is considered. The mass chromatogram ap-
proach is especially useful for quantitative analysis of known components.
In all cases, however, the quantitative data obtained from the selected
ion mass chromatogram(s) must be supported by qualitative identification
of the component producing the chromatographic peak(s). The confirmatiqn
of identity should be achieved by performing an initial GC/MS run using a
broad mass range scan (i.e., m/e 40 through the molecular weight of the
component) and directing the data system to print out the mass spectrum
of the scan(s) corresponding to the GC peak in question.
64
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In interpreting the GC/MS results it is also important to consider reten-
tion time data as well as the mass spectra. If the MS data appear to show
benzpyrene eluting ahead of phenanthrene from a Dexsil 400 column, it is
reasonably certain that at least one of these compound assignments is
incorrect. If reference samples of known components are available, abso-
lute, as well as relative, retention times (RRT) can be used in interpre-
ting GC/MS data. It is frequently useful to use internal standards, such
as p,p'-DDE, for the purpose of establishing RRT's.
2. Columns
The discussion of gas chromatographic columns, which was presented above
in the discussion of GC (Section D.2), holds equally well for GC/MS. The
same five basic columns—Porapak Q, SP-2250 or OV-17, Dexsil 400, SP-1000,
and Tenax GC—are expected to be used for the bulk of Level 2 GC/MS work.
F. Mass Spectrometry (LRMS and HRMS)
There are two principal mass spectrometric techniques, in addition to GC/
MS discussed above, that are applicable to Level 2 organic analysis.
These are low resolution mass spectroscopy (LRMS) and high resolution
mass spectroscopy (HRMS). Both of these techniques may be used extensively
for analysis of non-volatile materials not amenable to GC. HRMS may also
have application to various volatile materials as well.
1. Low Resolution Mass Spectroscopy
A low resolution mass spectrometer is typically capable of resolving dif-
ferences in mass on the order of 1 part per thousand . This is equivalent
to measuring individual m/e'values to within +0.1 to 0.5 mass units for
the normal range of organic ions. An LRMS instrument is the type usually
used as a detector in GC/MS systems.
The use of LRMS data to determine the structure of single compounds is
the mode of mass spectrometry which is most familiar in organic chemistry.
As discussed in section E (above), electron impact ionization, whirl-
leads to extensive fragmentation of parent (or molecular) ions is usually
used to generate spectra for comparison with library reference spectra.
The library spectra may be in hard copy (e.g., "Eight Peak Index of Mass
65
-------
Spectra," 1st ed.> Imperial Chemical Industries, Ltd., Mass Spectrometery
Data Center, Alder Maston, Reading, United Kingdom, 1970) or in computer-
ized data bases (e.g., EPA/NIH MSSS file or STIRS). The use of LRMS
data in interpreting spectra of mixtures of compounds as in complex
environmental samples, in addition relies on chemical ionization or low
voltage electron impact ionization. These techniques minimize fragmen-
tation and facilitate the identification of various sample components
by their respective molecular ions. Particular features of the El mass
spectrum, such as the intense double ionization of polynuclear aromatic
hydrocarbons, also aid in interpreting LRMS spectra of mixtures.
Samples may be introduced into the LRMS instrument via either the batch
inlet or the direct insertion probe. The batch inlet is used for samples
with fairly volatile components that would be lost if the solvent were
evaporated. The lower limit for reliable detection of individual sample
components for batch inlet spectra is on the order of 1 yg. This requires
a concentration of about 500 ppm in the concentrated sample extract, since
only 1-2 yL of solvent is routinely injected. The direct insertion probe
is used for moderately volatile components. The absolute quantity of
sample taken is between 1 ng and 1 yg, but there is no intrinsic limit on
the volume of solution that can be dried onto the probe. The temperature
of the direct insertion probe can be programmed to drive progressively
more non-volatile species into the analyzer. At very high probe tempera-
tures, sample decomposition can occur; this is frequently indicated by
the reappearance of material with low molecular weights at probe tempera-
tures inconsistent with their volatility.
For complex environmental samples, such as fractions from preliminary
LC or HPLC separations, LRMS can indicate molecular weight ranges and
probable chemical class assignments (aliphatic, aromatic, alkylphenols,
etc...). Individual chemical compound identifications on the basis of
LRMS may not be possible, to any high degree of certainty, for many of
these complex mixtures.
2. High Resolution Mass Spectrometry
A high resolution mass spectrometer is capable of measuring masses of
ions in the spectrum with an accuracy of better than 0.001 atomic mass
66
-------
unit. Data from an HRMS analysis are reported to four decimal places in
m/e. The high accuracy and precision makes it possible to take advantage
of the mass defect characteristic of atoms and use their exact masses to
compute elemental composition assignments for the observed ions. The
theoretical mass can be calculated for all plausible* combinations of ele-
ments corresponding to a given mass. The theoretical and measured masses
are then compared and a "match11 is identified when they agree to within a
specified value, typically 0.002 or 0.003 amu.
In the simple case where HRMS is being used to confirm or deny the presence
of a particular sample component, such as benzopyrene, it is sufficient to
calculate the exact theoretical mass expected for C2oH12 and see if there
is a measured m/e value in the sample spectrum within 0.002 or 0.003 amu
of the calculated value. This type of static peak matching to preset
values (equivalent to the selected ion monitoring mode of LRMS) has a
realistic detection limit on the order of 1 ng. For dynamic peak
matching or scanning of the HRMS, a limit of about 1 ug is more realis-
tic. These detection limits are typical ones for HRMS instruments
utilizing electrical detection. With photographic (photoplate) detec-
tion of ions, HRMS spectra can be recorded for samples on the order of
1 ng.
There are a number of other ways in which HRMS data may be of value in
the Level 2 analysis of complex organic samples. These involve the use
of computer software systems to aid in interpretation of the large
quantity of data (500-2000 precisely determined masses of ions with
estimated abundances) that is accumulated in an HRMS run. One approach
to interpreting these data is to sort the assigned elemental composi-
tions into classes according to heteroatom composition and degree of
hydrogen unsaturation (rings plus double bonds or R + DB). An alternative
approach is to compare the set of measured masses with theoretical
masses calculated for a list of reference compounds. The utility
* Limits for determining "plausible" combinations are set by the user
in each application.
67
-------
of these reference compound file searching procedures is obviously de-
pendent on maintaining a relevant and appropriately comprehensive library
of listed compounds and masses. If the list were as extensive as, for
example, the MSSS file of LRMS spectra, the potential usefulness of HRMS
file-matching in Level 2 organic analysis would be great indeed. This
approach has the advantage that data interpretation can be made identical
from laboratory to laboratory, and thus results of different EA's can be
more readily compared.
HRMS methods are expected to be widely used in Level 2 analysis of non-
volatile polar components separated by LC and HPLC methods.
G. Infrared Spectroscopy (IR)
Infrared Spectroscopy was once the most widely used tool for identifica-
tion of organic compounds. Absorption in the IR range is due to vibra-
tional energy transitions and virtually every organic species (and many
inorganic species) has at least one absorption band in the normal IR
frequency range (4000 to 400 cm 1). The fact that various functional
groups absorb characteristic IR frequencies, rather independently of other
portions of the molecular structure, is one of the distinctive features
of IR Spectroscopy.
In conventional, dispersive IR Spectroscopy, a monochromator is used to
scan vibrational frequencies and generate a plot of absorption (or trans-
mittance) versus frequency. Modern, dispersive IR instruments, suitable
for Level 2 organic analysis, utilize grating monochromators to achieve
high resolution (<1.5 cm'1 at 3000 cm 1) and high wavelength accuracy
(3 cm at3000 cm ). Most are equipped with ordinate expansion capa-
bility and some are specifically designed for interfacing with automatic
data processing systems for spectral subtraction and other data manipula-
tions. Dispersive IR instruments are by far the most common types avail-
able. Sample size requirements for dispersive IR are on the order of
1 mg for a KBr macropellet or salt plate or about 100 yg for a KBr micro-
pellet in an instrument equipped with a beam condenser and/or ordinate:
expansion capability.
68
-------
Individual sample components amounting to <5-10% of the total sample
are likely to remain undetected.
A considerable improvement in sensitivity is made possible by the use
of Fourier 'transform infrared spectroscopy (FT-IR) in which an interfer-
ometer is used to generate the spectral information. The dedicated com-
puter system that is an integral part of an FT-IR instrument facilitates
procedures such as subtraction of "background" spectra. Sample sizes in
the range of 1 to 10 ug can be used in FT-IR, which has lower detection
limits for individual components on the order of 0.1-1 pg (10%). The
FT-IR instruments are not yet widely available; an estimated 75 units
were in use worldwide in 1976 compared to more than 50,000 dispersive
units. Nevertheless, the potential usefulness of FT-IR in Level 2
organic analysis seems clear.
IR spectra, whether conventional or FT-IR, will be a major tool in the
characterization of non-volatile organic species in Level 2. In th
-------
of NMR in organic analysis is increased because the transition frequency
(chemical shift) of a given nucleus depends not only on the magnitude of
the applied, external magnetic field, but also on the local magnetic
field generated by adjacent nuclei.
Proton NMR has been most widely investigated for organic analysis, since
most organic species have an abundande of *H nuclei. In the NMR spectra
of mixtures, inferences about functional groups present in the sample
may be drawn from the absence or presence and intensity of peaks in these
varying shift ranges. In those special cases where only one or a few
components are present in the sample (as in an HPLC fraction), the fine
structure (spin-spin coupling) in the proton NMR spectrum can also aid
in interpretation. For conventional, continuous wave proton NMR, milli-
gram (5-50) quantities of sample are required. A time averaging
computer can be used to reduce the lower detection limit by about a factor
of ten, at the expense of a considerable increase in analysis time to
20-30 hours/sample. The use of pulsed Fourier transform (FT) NMR techniques
can dramatically improve the sensitivity to a lower detection limit of
about 10 yg of sample by decreasing the scan time per spectrum.
Determination of 13C NMR spectra in samples with natural abundance of l3C
(i.e., 1.1% of total carbon) are done almost exclusively in the Fourier
transform mode of operation. Because of the low natural abundance,
milligram quantities of sample are required for 13C FT-IR. The chemical
shift range of 13C is about thirty times greater than that of 1H, so con-
siderably greater resolution is possible in 13C NMR spectra.
It is anticipated that NMR spectroscopy will be a valuable tool in charac-
terizing materials that are not sufficiently volatile for GC analysis or
mass spectroscopy in Level 2. in many cases, sample size limitations may
restrict the use of NMR to proton Fourier transform methods. In other
i
cases, however,"there may be sufficient sample to also acquire 13C FT-NMR|
spectra. The combination of 1E and 13C spectra combined with IR data will
probably provide the best method of characterizing high molecular weight,
non-volatile species in Level 2 organic analysis.
70
-------
I. Ultraviolet (UV) and Luminescence Spectroscopy (LS)
Both ultraviolet (UV) and luminescence Spectroscopy (LS) are primarily
quantitative tools to be used for the measurement of the amount of a
species present either directly, after separation, or through color de-
velopment with a suitable reagent. UV is still considered by many to
be the only unequivocal method for distinguishing the various polynuclear
aromatic hydrocarbon carcinogens, after they have been isolated by LC,
HPLC, TLC or GC. The value of this technique is enhanced by the existence
of extensive compilations of reference spectra, including those of
nearly all the known carcinogenic urban air pollutants.
LS is a qualitative and quantitative tool for determination of compounds
which exhibit fluorescence or phosphorescence. It is especially useful
for analysis of polynuclear aromatic hydrocarbons which are strongly
fluorescent. The method is sensitive to impurities, to light scatter, a
and to side reactions such as photodecomposition of the analyte and
quenching of luminescence by oxygen. It has, nevertheless, found wide
acceptance in PAH analysis.
In Level 2 organic analysis it is probable that GC/MS and/or HPLC methods
will be used in most cases as an alternative to quantitative analysis by
UV or LS methods.
71
-------
72
-------
APPENDIX A
Expected Distribution of MEG Category Organic Compounds
In
Level 1 Sampling and Systems Procedures
73
-------
Appendix A
Expected Distribution of MEG Category Organic Compounds In
Level 1 Sampling and Systems Procedures
Each compound in the MEG list of organic compounds (8) has been review-
ed to estimate where that sample would be collected in the Level Sampling
and Analysis procedure. The attached charts reflect those estimates
based on the information currently available. The revised Level 1
procedure has been used as the basis for the review. The estimates
for many of the compounds are somewhat speculative, having been derived
by analogy to known compounds, rather than being based upon actual
experimental data.
Some additional data, such as molecular weight (MW), elemental composition
(COMP) and boiling point (BP) were included to assist in studies of these
compounds. The health effects-related MATE values for air and water
were also included where available.
A compound was defined as a gas to be analized with the field GC if the
boiling point was less than 100°C. Volatile compounds analyzed by
the TCO procedure are those which have boiling points in the range of
100 to 300°C. The non-volatile materials analized by the GRAV procedure
are those with boiling points greater than 300°C.
74
-------
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Ethane
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Octanes
Nonanes
Alkanes (C > 9)
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and Dienes
Ethylene
Propylene
Butyl enes
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Chlorobenzene
Brano and dlbromobenzenes
Bronochloro benzenes
1 .2-d1chlorobenzene
1 ,3-dichlorobenzene
1 ,4-dlchlorobenzene
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1,2-dihydroxybenzene
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Nitrogen Compounds
A. Pyrldlne and Substituted
Pvrldlnes
Pyridine
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Methyl quInoHnes. methyl 1 SOT
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and Fused Ring DeHva-
lives of Pyrrole
Pyrrole
Indole
Methvllndoles
Carbazole
Methyl carbazol es
Benzo(a
Dlbenzo
Dlbenzo
Dlbenzo
karbozole
a,g)carbozole
a,i Jcarbozcle
c,g)carbozole
D. Nitrogen Heterocvcles cental n-
Ina additional Heteroatoms
Ben7ath1azole
Methyl
benzothlazoles
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Furan
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Dlbenzofuran
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Thioohene
Methyl thiophenes
Dimethvlthloohenes
Trimethvl;and tetramethyl
thiophenes
2.2'-B1thioi>hene
BenzoFbl thlophene
D1benzoth1ootane
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A. Alkyl or Aryl OrganometalHcs
Trlmethyl arslne
Alkyl lead frELl
Alkyl mercury/t>Mi»j}
Organotln
Oraanooermanes
B. Sandwich Type OrganometalHcs
Ferrocene
Nlckelocene
D1 benzene chromium
C. Hetal Porohvrlns and Other
Chelates
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Nickel
Copper
Iran
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-------
Appendix B
BIBLIOGRAPHY
j_t J. A. Dorsey, C. H. Lochmuller, L. D. Johnson, R. II. Statnick,
Guidelines for Environmental Assessment Sampling and Analysis
Programs - Historical Development and Strategy of a Phased
Approach. EOA Draft Report, Harch 9, 1976.
2. Environmental Assessment Sampling and Analysis: Phased
Approach and Techniques for Level 1: June 1977,
EPA-600/2-77-115.
3. IERL-RTP Procedures Manual: Level 1 Environmental Assessment;
June 1976, EPA-600/2-76-160a, PB 257-850/AS.
4. Technical Manual for Process Sampling Strategies for Organic
Materials; April 1976, EPA-600/2-76-122, PB 256-696/AS.
5. Technical Manual for Analysis of Organic Materials in
Process Streams; March 1976, EPA-600/2-76-072, PB 259-299/AS.
6. Selection and Evaluation of Sorbent Resins for the Collection
of Organic Compounds; April 1977, EPA-600/7-77-044.
7. Technical Manual for the Measurement of Fugitive Emissions:
a. Upwind/Downwind Sampling Method for Industrial Emissions;
April 1976, EPA-600/2-76-089a, PB 253-092/AS
b. Roof Monitor Sampling Method for Industrial Fugitive
Emissions; May 1976, EPA-600/2-76-089b, PB 257-847/AS
c. Quasi-Stack Sampling Method for Industrial Fugitive
Emissions; May 1976, EPA-600/2-76-089C, PB 257-848/AS
8. Cleland, J.G. and Kingsbury, G.L., "Multimedia Environmental
Goals for Environmental Assessment", Vol. I.
EPA-600/7-77-136a. Nov. 1977.
9. "Efficient Collection of Polycyclic Organic Compounds from
Combustion Effluents", ES&T 1(), 806, 1976.
10. "Destroying Chemical Wastes in Commercial Scale Incinerators",
Final Report, EPA Contract No. 68-01-2966, June 1977.
101
-------
BIBLIOGRAPHY
(Continued)
11. Webb, R. G., "Isolating Organic Water Pullutants: XAD Resins,
Urethane Foams, Solvent Extractions", EPA-660/4-75-003, June 1975,
12. Junk, G. A., et al, J. Chromat. 9JJ, 745 (1974) and other papers
by Junk and Svec.
13. "Sampling and Analysis Procedures for Survey of Industrial
Effluents for Priority Pollutants". USEPA Environmental and
Support Laboratory, Cincinnati, Ohio. April 1977; IFB No. Wa-
77-B133, Appendix B.
14. Bellar, F. A. and Lichtenberg, J. J., Journal AWWA, p. 739-744,
Dec. 1974..
15. U.S. Federal Register 38, No. 75, part 2.
16. "Standard Methods for the Examination of Water and Wastewater",
13th Edition (1976), APHA, New York.
17. "Handbook for Monitoring Industrial Wastewater", USEPA Technology
Transfer (August 1973).
102
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse bcjore completing)
. REPORT NO.
EPA-600/7-78-016
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
EPA/IERL-RTP Interim Procedures for Level 2
Sampling and Analysis of Organic Materials
S. REPORT DATE
February 1973
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
J.C. Harris and P.L. Levins
3. PERFORMING ORGANIZATION NAME AND ADDRESS
Arthur D. Little, Inc.
Acorn Park
Cambridge. Massachusetts 02140
10. PROGRAM ELEMENT NO.
EHB529
11. CONTRACT/GRANT NO.
68-02-2150, T.D. 21102
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: 6-12/77
14. SPONSORING AGENCY CODE
EPA/600/13
15.SUPPLEMENTARY NOTES IERL-RTP project officer is Larry D. Johnson, Mail Drop 62.
919/541-2557.
is. ABSTRACT
interim report presents concepts and guidelines to be used in consider-
ing Level 2 sampling and analysis for organic compounds. It suggests specific pro-
cedures. (The final Level 2 organics procedures manual will include more fully devel-
oped concepts and procedures , specified as much as is possible for a wide range of
conditions. ) The report is intended for experienced research teams , thoroughly famil-
iar with environmental sampling and analysis , Level 1 procedures , and the phased
approach. It does not attempt to teach the detail which is more adequately found in
other publications , but relies heavily on reports published previously by IERL-RTP
and its contractors.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Organic Compounds
Sampling
Analyzing
Ppllution Control
Stationary Sources
13E
07C
14B
13. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
115
20. SECURITY CLASS (ThispageJ
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
103
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