&EPA
United S'.'
Environmental F'
Age'
Industrial En.
•
EPA/IERL-RTP
Procedures for Level 2
Sampling and Analysis
of Organic Materials
Interagency
Energy/Environment
R&D Program Report
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EPA-600/7-79-033
February 1979
EPA/IERL-RTP Procedures
for Level 2 Sampling and
Analysis of Organic Materials
by
J.C. Harris, M J. Hayes, P.L. Levins, and D.B. Lindsay
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, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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GLOSSARY OF TERMS AND ABBREVIATIONS
EPC Estimated Permissible Concentration
MATE Minimum Acute Toxicity Effluent
MEG Multimedia Environmental Goal
TLV Threshold Limit Value
amu Atomic Mass Unit
SAM Source Analysis Model
LRMS Low Resolution Mass Spectrometry
Gases Species with boiling point below 100°C
Vapors Species with boiling point above 100°C
SASS Source Assessment Sampling System
FAST Fugitive Air Sampling Train
GC/MS Gas chromatograph coupled to mass spectrometer
GC/ECD Gas chromatograph with electron-capture detector
HPLC High Performance Liquid Chromatography
HRMS High Resolution Mass Spectrometry
UV Ultraviolet
RI Refractive Index (Detector for HPLC)
GPC Gel-permeation Chromatography
PCB Polychlorinated Biphenyl
m/e Ratio of mass to charge
ii
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TABLE OF CONTENTS Page
Glossary of Terms and Abbreviations ii
List of Figures v
List of Tables vi
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 6
III. LEVEL 2 SAMPLING AND ANALYSIS: RECOMMENDED
PROCEDURES 9
A. Sample Types and Sampling Methods 9
B. Sample Recovery and Preparation 20
C. Recommended Level 2 Analysis Methods by
Compound Category 25
D. Recommendations for Analysis of Unknown Samples 56
IV. SAMPLING METHODS 63
A. Gases and Vapors 65
B. Particulates 78
C. Liquids/Slurries 80
D. Solids 82
E. Fugitive Emissions 82
V. ANALYSIS METHODS 86
A. Liquid Chromatography 86
B. High Performance Liquid Chromatography (HPLC) . 88
1. Detectors 88
continued...
iii
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Table of Contents (continued)
page
2. Gel Permeation Chromatography ^0
3. Reverse Phase HPLC 92
4. Normal Phase HPLC 93
C. Thermal Gravimetric Analysis 94
D. Gas Chromatography (GC) 95
1. Detectors 95
2. Columns 96
3. Gas Chromatographic Conditions 97
E. Gas Chromatography/Mass Spectrometry 98
1. Detector 98
2. Columns 101
F. Mass Spectrometry (LRMS and HRMS) 101
1. Low Resolution Mass Spectrometry ..... 101
2. High Resolution Mass Spectrometry .... 103
G. Infrared Spectroscopy (R) 104
H. Nuclear Magnetic Resonance Spectroscopy .... 107
I. Ultraviolet and Luminescence Spectroscopy . . . 109
J. Optical Microscopy 112
VI. BIBLIOGRAPHY 117
APPENDIX A. Expected Distribution of MEG Category
Organic Compounds in Level 1 Samples . . 121
APPENDIX B. Partition Coefficients 149
APPENDIX C. Specific Retention Volumes (Vg) for
Adsorbate Vapors on Sprbent Resins . . . 153
iv
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LIST OF FIGURES
Figure Number Page
l.a. Level 2 Organic Analysis Scheme 57
l.b. Organic Extracts Analysis Scheme 58
2 Integrated Gas Sampling Train 66
3 Porous Polymer Vapor Sampling Method 68
4 Porous Polymer and Thermal Gradient
Sampling Train 70
5 XAD-2 Sorbent Trap Module 71
6 Source Assessment Sampling Schematic 72
7 Method 5 Train Modified for Collection of
Organic Vapors * 74
8 Log Vg20 vs. Boiling Point for Individual
Adsorbate Groups on XAD-2 76
9 Method 5 Particulate Sampling Train 79
10 Decision Example for "Worst Case" Site 84
11 Directed Level 2 LC Scheme for Analysis of
Polychlorinated Biphenyls 87
12 Guide to Selection of HPLC Analytical Procedures
According to Characteristics of Species Sought. . 91
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LIST OF TABLES
Table Number
Comparison of Level 1 Data with Decision
Criteria
Sample Size and Flow Rate Comparison for
Several Sorbent Trap Designs ......... 13
Compound Categories for which Adsorption on
XAD-2 is the Recommended Level 2 Vapor
Sampling Method ................ 1*
4 Recommended Level 2 Vapor Sampling Methods
for Certain MEG Categories .......... 16
5 Distribution of Compound Categories in
LC Fractions ................. 23
6 Comparative Specifications of HPLC Detectors . . 89
vi
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I. INTRODUCTION
This Level 2 Procedures Manual for sampling and chemical analysis
of organic materials represents a step in the development of a general
methodology for chemical and biological assessment of environmental
effects of industrial effluents. Concepts and general guidelines are
presented here, together with a number of more fully developed, tested
and validated Level 2 procedures. The accumulation of experience in
sampling and chemical analysis of environmental pollutants is by no
means complete, however. The process is expected to continue for some
time, perhaps indefinitely. Users of this manual will therefore find a
number of areas in which additional research and testing is needed, and
in which present knowledge is insufficient to permit hard-and-fast
procedures to be established.
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 Measurement 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
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hazard. The Level 1 assessment is intended to: 1) provide preliminary
environmental assessment data, 2) identify principal problem areas, and
3) formulate the data needed for prioritization of energy and industrial
processes, streams within a process, components within a stream, and
classes of materials, for further consideration in the overall assessment.
The second 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
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accuracy could either be primarily quantitative in terms of establishing
a truly representative emission rate, or be primarily qualitative in
terms of determining specific chemical composition, or both. It is
expected that most Level 2 sampling and analysis studies for organic
compounds will have as an objective the identification 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 polynuclear aromatics in the stream?)
to quite general, (i.e., what caused the positive bio-test results?).
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.
This type of analysis would be characterized as Level 2.
C. Purpose and Scope of This Document
The objective of this document is to present concepts and quidelines
to be used in consideration of Level 2 sampling and analysis for organic
compounds. This report focuses on concepts and general guidelines, with
recommendations and suggestions for specific procedures. Because of the
"•imitation of present experience in conducting Level 2 investigations,
many of the procedures recommended herein have necessarily been based
on as-yet-unsubstantiated reports of work reported in the literature
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which seemed in the judgment of the authors to be reliable and applicable
to present needs. In some cases, specific tests were performed in our
laboratories to establish the adequacy of important procedures. In
other cases, advice was offered from other workers in the field of
environmental assessment. A directed effort was made to obtain such
advice from other contractor laboratories working on related projects
for EPA/IERL, and their reactions to the Interim version of this manual
were specifically sought and obtained. While the present Manual repre-
sents what we believe to be the "state of the art" in its field, the
user should be aware that new information is being developed constantly
and that further refinements of the recommended methods are to be anti-
cipated.
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
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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/m3 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
category is compared against the general 0.5 mg/m3 gaseous emission Level
1 criterion and against the MATE values.
Column 3 shows that four compound categories exceeded the 0.5 mg/m3
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 art- based are
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TABLE
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/ra3
no
no
yes
yes
no
yes
no
yes
no
no
Worst Case HATE
(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 Analysis 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.
8
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III. LEVEL 2 SAMPLING AND ANALYSIS; RECOMMENDED 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 sam-
pling 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 (?CB's) in a source. Since the Level 1 sam-
pling procedures are known to be adequate by Level 2 standards for col-
lection 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 alter-
native procedures.
Most of the organic samples retained from the Level 1 study will be
in the form of extracts in methylene chloride solution. 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.
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
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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 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
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, nitrosamines, etc.
10
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The sampling methods available for various categories of sources and
compounds are discussed in the following chapter. Review of the avail-
able methods has led to recommendation of the sampling techniques
described below for general use in Level 2 studies. The techniques are
classified according to the type of stream to be sampled - gaseous,
liquid or solid - and the state of the organic material - particulate,
vapor or gas. Because of the characteristics of the available sampling
devices, it is convenient to use a 100°C boiling point cutoff to define
the terms "gas" and "vapor." Throughout this report, species with boil-
ing points below 100°C are referred to as gases, while species with
boiling points above 100°C are referred to as vapors.
The sample size recommendations that are presented in this discus-
sion are constrained primarily by the need to acquire a sample that is
representative of the source and that is large enough for subsequent
manipulations (such as weighing and extraction of particulate). The
recommendations in this section refer to the total quantity of organic
material, except as noted, and do not reflect the analytical detection
limit expected for individual chemical species.
1. Gaseous Stack, Vent and Process Streams
The several methods described below are appropriate for sampling
of organic species present as entrained particulate, vapors and gases.
The sampling devices may be used independently if only one type of
species is sought. Alternatively, they may be combined in an integrated
sampling system, of which the SASS train is one example, to collect a
broader range of materials.
These methods were chosen to be appropriate for a concentration
3
range of about 0.1 to 50 mg/m for the individual organic species of
concern. If concentrations very much higher than this are encountered,
the capacity of the sampling device(s) may be exceeded unless especially
small samples are taken. If concentrations of the individual species of
concern are expected to be lower than 10 yg/m3, the techniques recommen-
ded for ambient air should be used to replace or supplement those
listed here.
11
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a. Particulates
A high efficiency, high purity glass fiber filter (e.g., Reeve
Angel 934AH) or quartz fiber filter (e.g., Gelman Micro-Quartz) is
recommended. If particle sizing is required to provide Level 2 infor-
mation about the distribution of organic material, one or more cyclones
should be used upstream of the filter. The temperature of the filter/
cyclone device should be controlled at 195-205°C (380-400°F) during
sampling. The volume of gas sampled must be sufficient to ensure
collection of at least 100 mg of total particulate material on a filter
and at least 500 mg of total particulate material in each cyclone, if
possible.
b. Vapors
Adsorption on XAD-2 resin is recommended for most organic categories.
The sorbent trap should be thermostatically controlled at 20 + 2°C during
sampling. The dimensions and resin capacity of the sorbent trap, and the
volume of gas to be sampled, should be varied as necessary to ensure
efficient collection of the species of interest. A procedure for estima-
T
tion of sorbent sampler design parameters from Vg values of the com-
pounds of concern is described in Chapter IV. Some illustrative data
are presented in Table 2.
The sample rate is required to be low enough to correspond to a
linear gas velocity through the sorbent bed of <43 cm/sec. The
volume of gas sampled must be sufficient to ensure collection of at
least 10 to 100 mg of total organic material on the trap.
Organic compound categories for which adsorption on XAD-2 is the
recommended vapor sampling procedure are listed in Table 3. It
should be noted that, while virtually all types of organic compounds
are represented in this list, a number of these categories include some
substances with boiling points below 100°C. The vapor sampling procedure
is not expected to be effective for those substances whose relatively
12
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Table 2. Sample Size and Flow Rate Comparison
for Several Sorbent Trap Designs
Trai
Dimensions, mm
depth diam.
Resin
Charge,
g of XAD-2
Flow
equiv to
43 cm/sec
**
Maximum Sample Size, m3
for Efficient Collection of
Octane
Benzene Phenol
SASS
70
90
130
165 Lpm
(5.9 cfm)
150
240
ADL
70
45
40
40 Lpm
(1.5 cfm)
45
0.9
74
Battelle
70
30
19
18 Lpm
(0.65 cfm)
22
0.4
35
Upper limit beyond which collection efficiency drops off.
**
Calculated from Vg for 50% breakthrough. Specified value includes a safety factor of 2.
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Table 3. Compound Categories for which Adsorption on XAD-2
is the Recommended Level 2 Vapor Sampling Method
MEG
No. Category
1 Aliphatic Hydrocarbons
2 Alkyl Halides
3 Ethers
4 Halogenated Ethers
*
5 Alcohols
6 Glycols, Epoxides
7 Aldehydes, Ketones
8C,D Amides, Esters
9 Nitriles
10 Amines
12 Nitrosamines
13B Sulfides, Bisulfides
14 Sulfonic Acids, Sulfoxides
15 Benzenes
16 Halogenated Aromatics
17 Aromatic Nitro Compounds
18 Phenols
19 Halophenols
20 Nitrophenols
21, 22 Polynuclear Aromatic
Hydrocarbons
23 Heterocyclic N Compounds
24 Heterocyclic 0 Compounds
25 Heterocyclic S Compounds
*
See also Table 4.
14
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high volatility places them in the category of gases, and which are
best sampled by the procedures described in Section C below.
Alternative vapor sampling procedures are recommended to replace or
supplement the sorbent trap for a few organic compound categories. Two
of these categories, aliphatic alcohols and aliphatic acids, include
some compounds with boiling points above 100°C that are inefficiently
sorbed by XAD-2. Note, however, that alcohols boiling above about
160°C and acids boiling above 180°C will be collected efficiently on
XAD-2. Table 4 presents the alternative methods recommended for the
collection of vapors of the lower molecular weight compounds in those
categories. Two categories of compounds that are very reactive,
hydrazines and mereaptans, also require special sampling techniques.
Table 4 presents the methods recommended for substances in all of
these categories.
c. Gases
Use of glass bulbs, fitted with high vacuum TFE stopcocks (e.g.,
Ace Glass catalog No. 8194), is the recommended sample collection
method for gases in all categories except as noted below. It is
recommended that the previously evacuated bulbs be interfaced to the
stack through a probe, glass fiber filter, and critical flow orifice
to provide a degree of time integration. (A 0.2 Lpm orifice with an
evacuated 2L bulb will give a 12 min total sample time.)
Alternatives to the gas bulb sampling approach are recommended for
both gases and vapors of two categories of reactive substances. For
hydrazines, continuous collection into bubblers containing IN aqueous
hydrochloric acid is recommended. For aldehydes, use of bubblers
containing 1% sodium bisulfite is recommended. Sampling rate should
be 21 - 28 Lpm (0.75 - 1 cfm) through the bubblers. The gas volume
sampled should be chosen to yield a final analyte concentration of at
least 10 yg/mL in the bubbler. Samples should be analyzed within five
days of collection. A third category of reactive compounds, the mercaptans,
are so reactive that sample collection by direct adsorption on Chromosorb 104,
15
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Table 4. Recommended Level 2 Gas and Vapor Sampling Methods For Certain MEG Categories
MEG. No.
Category
Method
Comment
Alcohols
Bubbler; ethylene glycol
For species with b.p.
in range ^ 100 to 160°C;
XAD-2 sorption O.K. for
less volatile.
8A,B
Carboxylic
Acids
Bubbler; 0.1 N NAOH
For species with b.p. in
range ^ 100 to 180°C;
XAD-2 sorption O.K. for
less volatile.
11
Azo Compounds
Hydrazines
Bubbler; 0.1 N HC1 .
For all hydrazines.
13A
Mercaptans
Collect on Chromosorb
104 Sorbent trap +
Sample rate *v» 30 Lpm. Select gas volume sampled to give ^ 10 - 100 mg of total organic
material per L of bubbler reagent.
Sample rate < 43 cm/sec linear velocity. Sample volume collected on Chromosorb 104 to be
< 15 L gas/g of sorbent. (Ref. 7)
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followed by thermal desorption onto a suitable GC column for prompt
on-site analysis is recommended.
2. Ambient Air
The several methods described below are appropriate for sampling of
organic species present in ambient air as particulate, vapors and gases.
These methods were chosen to be appropriate for a concentration range of
about 1 to 100 yg/m3 for individual organic species of concern. If
concentrations much higher than this are encountered (in a fugitive
emission sampling situation, for example) the methods described above
for stack, vent and process streams should be used to replace or supple-
ment those listed here. For concentrations much lower than 10 yg/m3,
it will generally be necessary to design and validate a sampling method
that is tailored to the particular sampling application and takes
account of the interferences suspected of being present.
a. Particulates
A high volume sampling system incorporating a high purity, high
performance glass or quartz fiber filter (e.g., Reeve Angel 934 AH or
Gelman Micro-Quartz) is recommended. The 5.2 m3/min (185 cfm) Fugitive
Ambient Sampling Train (FAST) sampling system, which incorporates a
single stage (15 urn nominal cut off) cascade impactor and a cyclone
(3 ym nominal cut off) upstream of the filter, is appropriate.
A sampling rate of 1.4 m3/min (50 cfm) for the Hi-Vol, to 5.6
m3/min (200 cfm) for the FAST system is recommended. Sample volume
should be chosen to yield at least 500 mg of total particulate material
in an 8 - 24 hour period.
b. Vapors
Adsorption on Tenax-GC resin is recommended for most organic
categories. Reasons for the choice of this sorbent for sample
collection at the low pollutant concentrations characteristic of
ambient air are presented in Chapter IV.A.2 of this report. The
sorbent trap should be small enough to allow thermal desorption of the
17
-------
entire sample into a GC/MS system. A cartridge containing 250 mg (9 cm
long by 0.5 cm I.D.) to 1 g (9 cm long by 1 cm I.D.) of Tenax - GC
is suggested. The size of the trap and the volume of gas to be
sampled should be varied as necessary to ensure complete collection
for the species of interest. A procedure for estimating sorbent
T
sampler design parameters from Vg (elution volume) values for the
T
compounds of concern is described in Chapter IV. The Vg calculations
predict that up to 50 L of air can be sampled per g of Tenax-GC with
essentially complete collection of species boiling above 100°C in all
compound categories except alcohols and carboxylic acids.
The volume of gas sampled should be sufficient to allow collection
of at least 50 - 5000 ng of each individual species of concern on the
trap, if possible. A sampling rate of 0.1 to 1 Lpm is recommended to
provide some degree of time integration.
The alternative vapor sampling procedures in Table 4 are recommended
to replace or supplement the Tenax-GC sorbent trap for the few organic
compound categories that are especially inefficiently sorbed or that
are very reactive.
c. Gases
The glass sampling bulb approach described above for stacks, vents
and process streams is recommended for ambient air sampling of gases.
This recommendation must be regarded as tentative, because its applica-
bility to organic gases at low yg/m3 concentration levels has not been
demonstrated. However, an alternative method of sample acquisition that
seems compatible with Level 2 qualitative and quantitative analysis
objectives has not been identified. (See Chapter IV.A.I of this report
for a discussion of the limitations in the use of plastic bags as
sample collectors.)
3. Aqueous Effluent and Process Streantg
Collection of samples from aqueous streams is relatively straight-
forward. The methodology used for Level 1 is suitable for use in Level 2
18
-------
as well, except that compositing to acquire a more representative sample
is recommended for Level 2 sampling. Either automatic sampling or
compositing of manually collected grab samples is acceptable for most
organic species of concern. However, samples to be analyzed for very
volatile organics (b.p. < M.OO°C) must be sealed into containers with
no headspace at the time of collection; manual collection is recom-
mended for those samples. Sampling proportional to flow is recommended
for Level 2. Time-proportional sampling is an acceptable alternative
if flow is fairly constant.
A minimum sample volume of 1 L is recommended for subsequent
extraction. A sample volume of about 50 mL is recommended for analysis
of volatiles.
4. Solids, Sludges and Slurries
Methodology used for Level 1 sampling of solids, sludges and
slurries is suitable for use in Level 2 as well, except that composit-
ing to acquire a more representative sample is recommended for Level 2.
Flow proportional compositing of manually collected grab samples
is recommended. Time proportional sampling is an acceptable alternative
if flow is fairly constant. Time proportional sampling is also accept-
able in cases where reliable flow measurements cannot be made.
A 500 g to 1 Kg sample is recommended for subsequent extraction.
19
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B. Sample Recovery and Preparation
1. Preparation of Solvent Extracts
a. Particulate, XAD-2 Resin and Solid Samples
Soxhlet extraction with methylene chloride for 24 hours is recom-
mended for each of these types of sample. Pentane is recommended as an
alternative extraction solvent if non-polar organics are the only species
of concern in a particular Level 2 study. The solvent selected must
be compatible with both the sample and the species to be extracted for
analysis. For example, solids wet with water will generally not be
effectively extracted with pentane.
The size of the Soxhlet extractor and the volume of solvent to be
used should be varied according to the quantity of solid material to be
extracted. Micro (thimble size: 10 mm dia x 50 mm) and extra-large
(thimble size: 75 mm dia x 250 mm) Soxhlet extractors are commercially
available and are recommended for quantities < 1 g and > 50 g, respectively.
Borosilicate glass thimbles with fritted glass bottoms are recommended
for use in the extractors.
Bulk solids should be crushed to a size that will pass a 60-mesh
screen before extraction. (10)
b. Aqueous Samples
Liquid-liquid extraction with methylene chloride is recommended
for most compound categories. Acceptable alternative solvents Include
pentane if non-polar organics are the only species of concern, and
15% methylene chloride/85% hexane for pesticides and PCBs.
The pH of the aqueous phase must be adjusted as necessary prior to
extraction to ensure adequate recovery of the compound categories of concern.
For extraction of organic acids, the pH of the aqueous phase should be
20
-------
adjusted to < 2 with hydrochloric acid. For extraction of organic
bases, pH should be adjusted to > 11 with sodium hydroxide. Neutral
organics will be equally efficiently extracted at any pH. Serial
extractions and back extractions at several pH's can be used to achieve
an acid-base-neutral organic fractionation in some Level 2 studies
where all three types of organic material are of interest.
Three successive extractions of each sample at each pH are recom-
mended, using 100 mL of solvent per L of sample for each extraction.
This recommended procedure can be expected to provide > 90% extraction
efficiency for individual organic species that have solvent/water
partition coefficients > 12 (log P = 1.08). Extensive listings of
partition coefficients between various solvents and water are available
(11,12), and these can be used to verify extraction efficiencies for
individual organic species of concern. Some illustrative values of
log P for heptane, chloroform and octanol are tabulated in Appendix B.
There are several categories of compounds that are not efficiently
extracted from water. These include carboxylic acids, sulfonic acids,
and glycols. Direct analysis of the aqueous sample is tentatively
recommended for those species. An alternative to liquid-liquid
extraction is also recommended for organic gases (b.p. < 100°C) in
water. A purge and trap approach is suggested below for those species.
2. Concentration of Extracts
It is recommended that Kuderna-Danish evaporators fitted with
standard three section Snyder columns be used to concentrate extracts
to a final volume of 5-10 mL. Extracts should not be concentrated
further if quantitative recovery of species with boiling points in the
100-200°C range is desired. If species with boiling points above
200°C are the only compounds of concern in a particular Level 2 study,
the extracts can be concentrated to a volume of 1 mL or less, if
necessary, to enhance analytical sensitivity. A micro Snyder column
and Kuderna-Danish graduated receiver are recommended for this further
concentration step.
21
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3. Clean-up of Sample Extracts
Clean-up of sample extracts is generally reconmended prior to
analysis by the directed Level 2 procedures, described in Section C of
this chapter. The clean-up procedures are intended to minimize inter-
ferences and are especially important when a non-selective detector,
such as GC/FID, is to be used. Recent Arthur D. Little, Inc.,
experience has indicated that sample extract pre-cleaning also
substantially increases the reliability of the more selective GC/MS
analysis. Selection of a clean-up procedure should be based upon the
sample matrix type of analysis to be performed and species to be
analyzed.
The seven-fraction, silica gel liquid column chromatographic
separation procedure (LC) used for Level 1 organic analysis (3) is
also recommended for general use in Level 2. An aliquot of the
concentrated extract equivalent to 10-100 mg of total organic material
should be taken for the LC separation. It is recommended that the LC
fractions be recombined prior to analysis, according to the category(ies)
of compounds that are being sought in a particular Level 1 study.
Table 5 indicates the LC fractions over which the various compound
categories are distributed (3). This information should be used
to guide the Level 2 recombination scheme. Note that the most
logical combinations are not mutually exclusive. In terms of polarity,
these are:
aliphatics LC 1 (or 1, 2)
aromatics LC 2, 3, 4
slightly polar organics LC 3, 4, 5
polar organics LC 5, 6, 7
When more than one compound category is to be sought, the sample can
be split to provide, for example, both an LC 2, 3, 4 and an LC 3, 4, 5
pooled sample. An alternative is to analyze both LC 2, 3, 4 and
LC 5, 6, 7 for the slightly polar organics such as the heterocyclic
0 and S compounds.
22
-------
Table 5. Distribution of Compound Categories in LC Fractions
ts)
CO
Compound Categories
Aliphatic Hydrocarbons
Alkyl Halldes
Ethers and Haloethers
Alcohols
Glycols
Epoxides
Aldehydes
Ketones
Carboxyllc Acids
Nltriles
Amines, Azo Cmpds, Nltrosamines
Mercaptans
Sulfides, Disulfides
Sulfonic Acids, Sulfoxides
Benzenes
Halo Aromatics
Nitro Aromatlcs
Phenols, Halophenols, Nitrophenols
Fused Polycyclic Aromatics
Heterocyclic N Compounds (MEG 23A, B, D)
Hererocyclic N Compounds (MEG 23C)
Heterocyclic 0 Compounds
Heterocyclic S Compounds
LC Fractions
12345
X
X X
XV *»
" '• A A
X —
X —
X X X
X X X
X —
X —
X X X
X —
X —
X X X
X —
X*y v
A A
X X X
X X X
X —
x x x
x —
X X X
X- X X
y y ,- x
6
— X —
— X —
— X —
— X —
— x —
— x —
— x —
— x —
— x —
7
X
X
— X
X
— X
— X
X
X
X
-------
Organic acids and bases behave quite similarly in the polarity-
based LC separation scheme recommended above. However, it is necessary
to separate acids from bases prior to analysis by several of the methods
recommended in Section C. These species are concentrated in LC
fractions 5, 6 and 7. The clean-up procedures described below for
LC 5, 6, 7, could also be done prior to concentration and LC separation
if a particular Level 2 study were directed towards acids or bases,
but not both. When organic acids and organic bases are both of concern,
it will be necessary to divide the fraction(s) containing the polar
organic material and clean-up separate aliquots for the subsequent
analysis. Note that the LC 5, 6, 7 solvent includes methanol, so the
volume of the organic phase will need to be adjusted by addition of
methylene chloride after clean-up with aqueous acid or base.
Extracts for GC analysis of phenols should be freed of organic
bases (which are incompatible with the recommended phenol GC column)
by shaking with three successive portions of 0.1 N aqueous hydrochloric
acid. The volume of acid solution used in each step should be 10-20%
of the volume of the extract.
Extracts for GC analysis of amines should be freed of organic
acids (which are incompatible with the recommended amlne GC column) by
shaking with three successive portions of 0.1 N aqueous sodium
hydroxide. The volume of caustic solution used in each step should
be 10-20% of the volume of the extract. Aqueous samples for direct
GC or HPLC analysis of carboxylic acids or phenols also require clean-
up to remove basic and neutral organic interferences. The pH of the
sample should be adjusted to >_ 12 (indicator paper) and the a ample
extracted with three successive portions of methylene chloride. The
organic phase can be discarded if basic and neutral compounds are not
of concern in a particular study. The pH of the aqueous solution can
be readjusted with hydrochloric acid if necessary prior to analysis.
24
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4. Recovery by Thermal Desorption of Tenax-GC
It is recommended that organic vapors collected from ambient air
onto Tenax-GC resin be recovered by thermal desorption. The sampling
device should be inserted in, or connected directly to, the injection
port of the gas chromatograph with the column oven at room temperature.
Details of the interface will vary depending on the GC instrument used.
Carrier gas flow through the trap, in a direction opposite to the sample
flow direction (backflush), is then introduced to sweep organic vapors
onto the cold GC column while the trap is rapidly heated to 200-250°C.
A 4-6 min desorb time at elevated temperature is recommended (13 ,14 ,15 )
5. Recovery by Purge-and-Trap Method for Aqueous Samples
It is recommended that organic gases be recovered from aqueous
samples by purge-and-trap techniques (16 ,17 ,18 )• A number of purge-
and-trap instruments are commercially available and are appropriate
for Level 2 use. The following conditions are recommended:
trap: 150 mm x 2.7 mm I.D. stainless steel packed with
100 mm of Tenax-GC and 50 mm of Silica Gel 15
purge cycle: 12 min at 25°C (ambient); 40 mL/min carrier flow
desorb cycle: backflush trap onto cold (ambient) GC column for
4 min at 180°C; 20 mL/min carrier flow.
C. Recommended Level 2 Analysis Methods by Compound Category
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 (9)
generated in an IERL-RTP-sponsored study provides a classification of
organic species into 25 categories which represent a convenient means
of organizing approaches to Level 2 analysis. This organizational
approach does not, of course, mean that only the particular chemical
compounds on the MEG list are to be sought for in Level 2 analyses.
25
-------
Furthermore, It is recognized that there are a few kinds of organic
compounds (e.g., pesticides/insecticides, phosphates, silicones) that
do not fit neatly into any of the 25 MEG categories and that must be
considered separately.
It is, nevertheless, clear that most Level 2 questions can be
formulated in terms of determining the identity and abundance of
compounds within particular MEG categories.
The analysis methods from which Level 2 methods have been selected
are reviewed in Section V of this report. The specific procedures that
are recommended for directed Level 2 analysis of organic species in
predetermined categories are presented on the following pages. These
methods are described in somewhat more detail than was given in the
Interim Manual published earlier (19). It is hoped that the level of
detail in the present manual will provide valuable guidance to the
analyst in selecting analysis conditions that are appropriate for
Level 2 study objectives.
Conformance to the recommended methods, to the maximum extent
possible, will maximize consistency and comparability among various
Level 2 studies. However, each Level 2 study is likely to be unique,
and it is necessary to allow for flexibility. Constraints Imposed by
a particular sample matrix, such as the nature and concentration of
potential interferences, may require variation in method details—
column liquid phase loading, GC temperatutre program, etc.—at the
discretion of the analyst. Also left to the discretion of the
analyst is the selection of appropriate Internal or external standards,
calibration procedures, and quantitative method evaluation procedures
(such as recoveries from spiked samples). It is recognized that such
analytical quality control procedures, which are critically important
in a Level 2 study, will also be uniquely constrained by the particular
circumstances of each study. These questions must, therefore, be
addressed in the program plan developed for a given Level 2 Environ-
mental Assessment.
26
-------
Detection limits stated in these methods refer to the quantity of
each individual component that the analyst can be expected to reliably
quantify in a complex environmental sample. It is recognized that
these are somewhat conservative values when compared to the ultimate
state-of-the-art of detectability (by GC/MS, for example) in a fairly
clean sample matrix.
In general, qualitative identification of specific substances is
achieved in the recommended methods by the use of mass spectrometry,
coupled wherever possible to gas chromatography (GC/MS). Accurate
compound identification is an important objective of Level 2 analysis,
and in those instances where GC/MS is either not feasible or not
recommended for other reasons, some other technique (IR, LC, LRMS,
chemical adduct formation, etc.) should be used for qualitative
confirmation.
27
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ALIPHATIC HYDROCARBONS
(MEG CATEGORY 1)
Recommended Method: GC/FID
A. Species with b.p. up to 50°C
Column: Durapak n-Octane/Porasil C, 100/120 mesh,
2mm x 2m stainless steel or glass
Conditions: Flow rate: 25 mL/min
program : 25°C isothermal (Reference A)
(Note: Reference B suggests a complementary column
if necessary.)
B. Species with b.p. in the range 0 - 200°C
Column: 3% SP 2100 on 100/120 Supelcoport
2nm x 3m glass or stainless steel
Conditions: Flow rate: 20 mL/min
Program: 5Q°C (Reference C)
6°C/min
r
200°C
C. Species with b.p. greater than 200°C
Column: 3% Dexsil 400 on 100/120 Supelcoport
2mm x 3m glass or stainless steel
Conditions: Flow rate: 20mL/min
Program: 150°C
I 8°C/min
400°C
Detection Limit: 5 ng injected
SUGGESTED ALTERNATIVE METHODS
1. For resolution of very complex mixtures the following capillary
column can be used: Sp 2100, 50 me tars, 50 °C
Flow rate 20 cm/sec. Helium. 1 2°C/min
200° C
2. GC/MS can be used for confirmation
3. For separation of very high boiling species, 1% Dexsil 400 on
100/120 Supelcoport, 18" long, glass or stainless steel.
28
-------
4. GC/MS will give detection limits of about 100 - 500 ng injected.
Note: In addition to the general columns above, Reference B also
describes a number of columns giving more specific selectivities.
References:
~k.Supelco Catalogue No. 12^ p. 28, Supelco, Inc., Bellefonte, PA.
B. Saha, N.C., S.K. Jain and R.K. Dua, "A Generalized and Easily
Adaptable Gas Chromatographic Method for the analysis of Gaseous
Hydrocarbons", J. Chromatograph Science. 16, 323, (1978)
C. "Separation of Hydrocarbons", Bulletin 745B, Supelco, Inc.,
Bellefonte, PA.
29
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ALKYL HALIDES
(MEG CATEGORY 2)
Recommended Method: GC/MS
A. For b.p. 20 - 200°C
Column: 0.1% SP 1000 on Carbopack C 80/100 mesh
2mm x 2m Glass or stainless steel
Conditions: Flow Rate: 20mL/min (Reference A)
Program: 175°C isothermal
Expected Retention Times (Reference A)
Carbopack C
0.1% SP-1000
Chloroalkanes 175°C
Methylene chloride 0.50
1,1-Dichloroethane 0.65
Chloroform 0.70
1,2-Dichloroethane 0.75
1,1,1-Trichloroethane 1.00
Carbon Tetrachloride 0.95
Trichloroethylene 1.28
1,1,2-Trichloroethane 1.40
Perchloroethylene 2.25
1,1,1,2-Tetrachloroethane 3.1
l,l,2,2,<-Tetrachloroethane 3.3
B. For b.p. greater than 150°C
Column: 3% SP 2250 on 100/120 Supelcoport
2mm x 2m glass or stainless steel
Conditions: Flow Rate: 20mL/min
Program: 100°C isothermal
Detection Limit: 50 ng injected
SUGGESTED ALTERNATIVE METHODS;
1. The useful range of the above columns can be extended if required.
The SP 1000 column has a temperature limit of 225°C isothermally or
250°C when programmed. The SP 2250 has a limit of 350°C.
2. GC/ECD is an alternative detector for Interference free samples.
Reference:
A. "Carbopack, Graphitized Carbon Black", Supelco Bulletin 738 B,
Supelco, Inc., Beliefonte, PA.
30
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ETHERS AND HALOETHERS
(MEG CATEGORIES 3 and 4)
Recommended Method: GC/FID
Column: 3% SP 1000 on 100/120 Supelcoport
2mm x 2m glass or stainless steel
Conditions: Flow Rate: 30 ml/min
Injector: 250°C
Program: 60°C (2 min)
8°C/min
250°C
Detection Limit: 50 ng Haloethers; 500 ng Ethers
Expected Retention Times (Min) (Reference A)
2-chloroethyl vinyl ether 2.68
Bis (2-chloroethyl) ether 8.35
Bis (2-chloroethoxy) methane 13.02
4-chloro phenyl phenyl ether 19.34
4-bromo phenyl phenyl ether 21.08
SUGGESTED ALTERNATIVE METHODS;
1. Chemical ionization mass spectroscopy can be used for qualitative
identifications.
2. Haloethers may be determined by GC/MS with a 50 ng detection limit.
3. For haloethers free from interferences:
A. The Hall Electroconductivity detector can be used
Conditions: Furnace temperature 850°C
Hall Electrolyte flow: 5 mL min, 24 mL/min l
Hall electrolyte makeup: 50 mL/min l H2.
B. The electron capture detector can be used.
Reference;
A. Levins, Philip L., and Kathleen E. Thrun, "Analytical Methods
Recommendations for Organic Priority Pollutants for the Chemicals
and Plastics Industry Category Verification Study", Submitted as
part of monthly progress report No. ADL 79347-23, EPA Contract
No. 68-02-2150, May, 1978.
31
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ALCOHOLS
(MEG CATEGORY 5)
Recommended Method: GC/FID
A. For b.p. up to 200°C
Column: .1% SP 1000 on Carbopack C
2mm x 2m Glass.
Conditions: Flow rate: 20 mL/min
Program: 100°C
8°C/min
225°C
Expected Retention Times (Reference A)
Methyl alcohol .6 min
Ethyl alcohol .8 min
Isopropyl alcohol 1.2 min
Isobutyl alcohol 2.8 min
n-Butyl alcohol 3.8 min
B. For b.p. greater than 200°C
Column: 3% SP 2100
on 100/120 mesh Supelcoport (Reference B)
2mm x 3m glass
Conditions: Flow Rate: 20 mL/min
Program: 225°C isothermal
Detection Limit: 50 ng injected
SUGGESTED ALTERNATIVE METHODS:
1. Chemical ionization mass spectroscopy detection may be applicable
to this category
References:
A. "Solvent Mixtures and Determination of Water in Solvents", Supelco
Bulletin 747C, Supelco Inc., Beliefonte, PA.
B. Supelco Catalog No. 12, p. 5, Supelco Inc., Bellefonte, PA.
32
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GLYCOLS. EPOXIDES
(MEG CATEGORY 6)
At this time no satisfactory general method has been found for
analysis of this category, although the 3% SP 1000 column may be
suitable for some compounds.
33
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ALDEHYDES AND KETONES
(MEG CATEGORY 7)
A. Aldehydes
The recommended method for this category is the 5-Methyl-2
Benzothiazolone Hydrazone (MBTH) method for total aldehydes
in air. Sample air is bubbled through an aqueous solution of
MBTH, allowed to react for 1 hour after sampling is stopped,
an oxidizing agent is added and the absorbance measured at
628 nm. The detection limit is approximately 1-10 ppb
in air. (Reference A)
B. Ketones
Recommended Method: GC/MS
Column: 3% SP 2250 on 100/120 Supelcoport
2mm x 2m, glass
Conditions: Flow Rate: 20 mL/min
Program 60°C
I
6°C/min
200°C
Detection Limit: 50 ng injected
SUGGESTED ALTERNATIVE METHODS;
None recommended.
Reference:
Hauser, Thomas, R. and Rodney L. Cummins, "Increasing Sensitivity
of 3-methyl-2-Benyothiayolone Hydrazone Test for Analyses of
Aliphatic Aldehydes in Air", Analytical Chemistry. 56, 679 (1964)
34
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CARBOXYLIC ACIDS
(MEG CATEGORY 8a-b)
(Note: The methods proposed for all substances In this category must
be regarded as tentative, pending demonstration of their effec-
tiveness for environmental assessment.)
A. Formic, acetic acids,
Mono-acids to C5
Recommended Method: GC/MS
Column: Carbopack B/3% Carbowax 20 M/0.5% H3POH,
30" (76cm) x 4mm I.D. glass
Conditions: Flow Rate: 60 mL/min
Program: 160°C isothermal
Detection Limit: 50 ng injected
Expected Retention Times (Reference A)
formic <1 min.
acetic 1 min.
propionic 1.6 min.
isobutyr.ic 3.6 min.
n-butyric 5 min.
n-valeric 15 min.
B. Dicarboxylic acids, aromatic acids, aliphatic acids >C5, and
acids with additional functional groups
Recommended Method: Reverse Phase HPLC (Reference A)
Column: MicroPak-CH (octadecylsilane), yBondapak/Cjs
30cm x 4mm I.D., or equivalent
Mobile phase: water, acidified to pH 2.5 with HClOi^ and operated at
60°C for MicroPak-CH; Water Hethanol mixtures for
yBondapak C18; ^ 2mL/min.
Detector: UV, (variable wavelength) at 210nm for aliphatic acids,
and 254nm for others.
Detection Limit: 1 - 100 vg/mL, (50pL injected.)
SUGGESTED ALTERNATIVE METHODS;
1. For samples in which known interferences are absent:
Determination of acids as methyl or methylsilyl esters,
35
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with detection by GC/FIO.
Ion-exchange liquid chromatography, using either:
(1) cation-exchange resins (Dowex 50W-X4 or Aminex 50W-4X)
with 0.001N or 0.01N HC1 eluent, or;
(2) Strongly basic anicn-exchange resins (e.g. Dowex 1-X8), with
0.2M NaOAc and HOAc as eluents. Detection by RI or UV at
210nm or 254nni as appropriate. (Reference B).
References:
A. Supelco Catalog No. 13, p. 3, Supelco, Inc., Beliefonte, PA.
B. Richards, M., "Separation of Mono and Dicarboxyllc Acids by
Liquid Chromatography", Journal of Chromatographv. 115, 259 (1975)
36
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AMIDES
(MEG CATEGORY 8C)
Recommended Method: GC/MS
Column: 3% Dexsil 400 on 100/120 mesh Supelcoport
2mm x 3m glass
Conditions: Flow Rate: 20mL/min
Program: 150°C
I 8°C/min
300°C
Detection Limit: 50 ng injected.
37
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ESTERS
(MEG CATEGORY 8D)
Note: (The following tentative method was developed primarily for species
such as phthalate esters but is expected to be applicable to a
wide range of esters.)
Recommended Method: GC/MS
Column: 3% SP 2250 on 100/120 mesh Supelcoport
2mm x 2m glass
Conditions: Carrier: 20 mL/min
Program: 100°C
I 6°C/min
280°C
Detection Limit: 50 ng injected
38
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NITRILES
(MEG CATEGORY 9)
Recommended Method: GC/MS
Column: 3% SP 1000 on 100/120 Supelcoport
2mm x 2m glass
Conditions: Flow Rate: 30 mL/min
Program: 100°C
8°C/min
250° C
Detection Limit: 50 ng injected
SUGGESTED ALTERNATE METHODS:
1. Flame lonization Detection can be used for interference-free samples.
39
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AMINES
(MEG CATEGORY 10)
Recommended Method: GC/MS
Column: 4% Carbowax 20 M on Carbopack B + .8% KOH
2mm x 2m Glass
Conditions: Flow Rate: 20 mL/min N2
Program: 100°C
8°C/min
200°C
Expected Retention Times (Reference A)
Amine 125°C 175°C
Methyl 0.65 min - min
Dimethyl 0.95
Ethyl 1.0
Trimethyl 1.15
Isopropyl 1.65 0.75
n-Propyl 2.05 0.85
t-Butyl 2.75 1.
Diethyl 3.55 1.2
sec-Butyl 3.9 1.3
Isobutyl 4.2 1.35
n-Butyl 5.45 1.6
Isoamyl 12.3 3.
n-Amyl - 3.45
Diisopropyl 11. 2.70
Triethyl - 2.8
Dipropyl - 4.7
Ethylenediamine 4.5 1.5
Piperidine 8.3 2.25
Pyridine 10.2 2.55
Morpholine 11.3 2.75
1,3-Propanediamine - 2.95
Piperazine 16.4 3.7
Cyclohexyl 25. 5.1
1-4- Butanediamine
Detection Limit: 50 ng injected
40
-------
SUGGESTED ALTERNATIVE METHODS:
1. For High boiling amines:
10% Carbowax 20 M - 2% KOH on 80/100 Chromosorb W AW,
2mm x 2m glass, column temperature 200°C,
Flow Rate: 20 mL/min-1, RT for nicotine is approximately
3.2 min. (Reference A.)
2. For Non-volatile amines:
HPLC can be used. Young and McNair (Reference B) have separated a
wide variety of high-MW amines using several different silica gel
columns.
3. An alternate detector for preliminary GC evaluation is the FID.
References.
A. "Amine Analysis", Supelco Bulletin 737B Supelco Inc., Bellefonte, PA.
B. Young, Philip R., and Harold M. McNair, "High Pressure Liquid
Chromatography of Aromatic Amines", Journal of Chromatography,
119 (1978) 569-579.
41
-------
AZO COMPOUNDS AND HYDRAZINES
(MEG CATEGORY 11)
The recommended method for this category is an approved NIOSH
method for phenylhydrazine and 1,1 -dimethyIhydrazine and is expected to
be general for all hydrazines. (Reference A)
The collected sample is reacted with phosphomolybdic acid to form
a complex with a strong adsorption maximum at 750 nm. The detection limit
is approximately 5 mg/m3 in air.
Reference;
A. NIOSH Manual of Analytical Methods* Second Edition, Method
No. S160.
42
-------
Nitrosamines
(MEG CATEGORY 12)
Recommended Method: GC/MS
Column: 3% SP 2100 on 100/120 Supelcoport
2mm x 3m Glass
Conditions: Flow rate: 20 mL/min
Program: 90° isothermal
Expected Retention Times (Reference A)
N-Nitrosodimethyl amine 1.3 min
N-Nitrosodipropyl amine 11 min
Detection Limit: 50 ng injected.
SUGGESTED ALTERNATIVE METHODS:
1. An alternative column is a 4% Carbowax 20 M -H 0.8% KOH
2mm x 2m glass (see amine analysis)
2. Alternate detectors are
a. Alkali flame ionizatinn detector
H2 - 6 mL/min-1
b. Hall (electroconductivity)
c. ECD
3. For non-volatile species the following HPLC columns can be used:
a. v Porasil 30cm x 4mm
5% acetone/95% isoactane 2 mL/min
b. y Bondapack-C/V 30cm x 4mm I.D.
1.5% acetonitrite, 98.5% isooctane
1.5 mL/min, detection is either by UV at 254 nm or
with a thermal energy analyzer.
Reference;
A. Levins, Philip L., and Kathleen E. Thrun, "Analytical Methods
Recommendations for Organic Priority Pollutants for the Chemical
and Plastics Industry Category Verification Study", Submitted as
part of monthly progress report No. ADL 79347-25, EPA Contract
No. 68-02-2150, May, 1978.
43
-------
MERCAPTANS. SULFIDES. DISULFIDES
(MEG CATEGORY 13)
Recommended Method: GC/MS
A. For b.p. 6-60°C
Due to the difficulty of storing species such as Methyl Mercaptan,
these should be analyzed by on-site G.C. using the column specified
by the Level 1 procedure.
B. For b.p. greater than 60°
Column: 3% SP 1000 on 100/120 Supelcoport 2ran x 2m glass
Conditions: Flow Rate: 20 mL/min
Program: 100°C
6°C/min
200°C
Detection Limit: 50 ng injected
SUGGESTED ALTERNATIVE METHODS
1.
The following column has been used to separate low molecular weight
compounds in this category; Chromasil 330, 2mm x 2 m Teflon,
Flow Rate: 20 mL/min, Temperature 65°C (retention of N-butyl
mercaptan = 8 min, methyl disulfide 9 min.) (Reference A)
2. Flame photometric (Reference B) or flame ionization detection can
be used for interference-free samples.
References:
A. "Analysis of Sulfur Gases", Supelco Bulletin 722F, Supelco Inc.,
Beliefonte, PA.
B. Stevens, R.K., and A.E. O'Keefe, Analytical Chemistry, 42 142-A
(1970).
44
-------
SULFONIC ACIDS, SULFOXIDES
(MEG CATEGORY 14 a-b)
Note: (The methods proposed for all substances in this category
must be regarded as tentative, pending demonstration of their
effectiveness for environmental assessment.)
A. Sulfonic acids
Recommended Method: reverse-phase ion-pair liquid partition
chromatography (Reference A)
Column: LiChrosorb SI 60 silanized or Bondapak Cis/Porasil B coated
with 10% tri-n-octylamine; 185 - 300mm x 3mm I.D.
Mobile Phase: Tetrabutylammonium in aqueous phosphate buffer,
pH 7.4; or aqueous perchloric acid in pH ^2-6.
Maintained at 25° Eluted at 0.7 - 2.5 mm/sec.
Detector: UV at 254 run
Detection Limit: 10 - 50 ng injected
B. Sulfoxides
Recommended Method: GC/MS
Column: 3% SP 1000 on 100/120 Supelcoport
2m x 2mm glass
Conditions: Carrier: 30mL/min
Program: Isothermal 165°
Detection Limit: * 50 ng injected (each component)
SUGGESTED ALTERNATIVE METHODS;
None Recommended.
Reference;
A. Kraak, J.C. and Huber, J.F.K. J. Chromatography 102 (1974)
333-351; Wahlund, K.G. ibid. 115 (1975) 411-422.
45
-------
BENZENE AND SUBSTITUTED BENZENE HYDROCARBONS
(MEG CATEGORY 15)
Recommended Method: GC/MS
A. For boiling point range: 80 - 200 °C
Column: .1% SP 1000 on 80/100 mesh carbopack C
2mm x 2m glass or stainless steel (Reference A)
Conditions: Flow Rate: 20 mL/min
Program: isothermal at 225°C
Detection Limit:
Expected Retention Times (Reference A)
200 °C 225°C
n-Hexane
n-Heptane
n-Octane
n-Nonane
Benzene
Toluene
Ethylbenzene
Isopropylbenzene
m & p-Xylene
o-Xylene
n-Propylbenzene
1,3,5-Trimethylbenzene
1,2,4 Trimethylbenzene
1,2,3-Trimethylbenzene
tert-Butylbenzene
sec-Butylbenzene
Isobutylbenzene
n-Butylbenzene
B. For boiling point range > 110°C
Column: 3% SP 2250 or equivalent on 100/120 mesh supelcoport
2mm x 2m glass or stainless steel. (Reference A)
Conditions: Carrier 20 mL/min
Program: 70 °C
10°C/min
300°C
46
-------
Fample Chromatogram (Reference A)
Expected Retention Times
1,3,5-trimethylbenzene 9.2 min.
1,2,4-trimethylbenzene 10.9 min.
1,2,3-trimethylbenzene 13.9 min.
1,2,4,5-tetramethylbenzene 22.0 min.
1,2,3,5-tetramethylbenzene 23.5 min.
1,2,3,5-tetramethylbenzene 29.1 min.
SUGGESTED ALTERNATIVE METHODS;
1. GC/FID is an alternative for samples
free of interferences.
2. An alternate column for low boiling aromatics is a .2% Carbowax
1500/ Carbopack C 2mm x 2m glass or stainless steel.
Conditions: Flow Rate: 20 ml/min
Program: 60°C (3 min)
I 8°C/min
160°C
Retention of ethylbenzene is 20 min. (References B,C)
References.
A. "Separation of Hydrocarbons", Bulletin 743 B, Supelco Inc.,
Beliefonte, PA.
B. "Carbopack", Bulletin 738 B, Supelco Inc., Beliefonte, PA.
C. "Water Pollution Analysis and Standards" Bulletin 775, Supelco, Inc.
Beliefonte, PA.
47
-------
HALOGENATED AROMATIC COMPOUNDS
(MEG CATEGORY 16)
Recommended Method: GC/MS
Column: 3% SP 2250 on 100/120 Supelcoport
2mm x 2m Stainless steel or glass
Conditions: Flow Rate: 30 mL/min
Program: 75°C
8°C/min
260°C (for 15 min)
Detection Limit: 10 ng injected
Retention Times for 1% SP 2250 (Reference A)
1,3 Dichlorobenzene 6.8 min
1,2,4 Trichlorobenzene 10.6 min
4,4' ODD 25.8 min
Hexachlorobenzene 19.4 min
SUGGESTED ALTERNATIVE METHODS:
1. GC/ECD is an alternative detection system.
References.
A. "Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants," U.S. EPA, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio, March 1977 (Revised April
1977).
48
-------
AROMATIC NITRO COMPOUNDS
(MEG CATEGORY 17)
Recommended Method: GC/MS
Column: 3% SP 2250 on 100/120 Supelcoport
2mm x 2m glass or stainless steel (Reference A)
Conditions: Flow Rate: 30 mL/min
Program: 100°C
10°C/min
350°C
Detection Limit: 10 ng injected
SUGGESTED ALTERNATIVE METHODS;
1. GC/FID or BCD is an alternative detection system for preliminary
evaluation, for interference free samples.
2. An alternate column is 1.5% SP 2250 + 1.95% SP 2401 on
100/120 Supelcoport, 2mm x 2m,
80°C
8°C/min
300°C (Reference B)
References.
A. Goerlitz, D., F., L.M. Law, "G.C. Method for the Analysis of TNT
and RDX Explosives Contaminating Water and Soil Core Material",
U.S. Department of the Interior, Geologic Survey, Water Resources
division, Report 75-182 (1975).
B. Jones, Peter W., Anthony P. Graffeo, Ralph M. Rigger and Paul E.
Strup, "Development of Methods for Analysis Benzidines, PAHs,
Nitrobenyenes and Isophorone in Industrial Wastewater", Monthly
Progress Report, Battelle, Columbus Labs, Contract No.
68-03-2624, March, 1978.
49
-------
PHENOLS, NITROPHENOLS. HALOPHENOLS
(MEG CATEGORIES 18, 19, 20)
Recommended Method: GO/MS
Column: 1% SP 1240 DA on 100/200 Mesh
Supelcoport; 2m x 2mm glass
Conditions: Carrier: 30 mL/min
Program: 85°C (4 min)
10°/min
200 °C
Detection Limit: 50 ng injected
Expected Retention Times
o-chlo ropheno1
o-nitrophenol
phenol
2,4-dimethylphenol
2,4,6-trichlorophenol
2,4-dinitrophenol
pentachlorophenol
SUGGESTED ALTERNATIVE METHODS:
1 m
Column
1.7 min
2.1 min
3 min
min
min
min
min
(Reference A)
2 m
Column
4
6
10
12
3.9
5.1
6.9
8.8
12
16
17
1. For samples free of interferences:
GC/FID; same chromatographic conditions as above. Detection
Limit: 1-10 ng injected
2. For non-volatile phenols (e.g., hydroxy-BaP) and/or direct
analysis of phenols in aqueous samples:
HPLC, Reverse phase
Column: y Bondapak-Cig, 4 mm x 300 mm
Mobile Phase: water: ethanol:: 60:40
40 mL/hr
Detector: UV at 254 nm
Detection Limit: 10-50 ng injected
Reference;
A. Levins, Philip L., and Kathleen E. Thrun, "Analytical Methods Recom-
mendations for Organic Priority Pollutants for the Chemicals and
Plastics Industry Category Verification Study", Submitted as part of
monthly progress report No. ADL 79347-23, EPA Contract No. 68-02-2150,
May, 1978.
50
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POLYNUCLEAR AROMATICS
(MEG CATEGORIES 21, 22)
Recommended Method: GC/MS
Column: 3% Desil 400 on 80/100 mesh Supelcoport
2mm x 3m, glass or stainless steel
Conditions: Flow Rate: 30 mL/min
Program: 10U°C (2 min)
8°C/min
375°C (Reference A,B)
Detection Limit: 10 ng injected
SUGGESTED ALTERNATIVE METHODS;
1. GC/FID is an alternate detection system.
2. For very complex samples requiring greater separating power or for
resolution of Benz(a)pyrene and Benz(e)pyrene the following
capillary column can be used:
Column: .25mm x 20m SE-52 glass capillary
Conditions:
Program: 150°C
5°C/min
275°C (Reference C)
The following reverse phase HPLC method has been used to analyze
18 PNA's from napthalene to indeno (1,2,3-cd) pyrene with detection
limits from 0.01 to 1.0 ppb. Perkin Elmer HC-ODS column, 40%
acetonitrile in water, isocratic for 5 min.; then gradient elution
to 100% acetonitrile in 25 min. Flow rate: 0.5 ml/min.
References;
A. Lao, R.C., R.S. Thomas, H. Oja, L. Dubois, "Application of a GC/MS/
Data Processing System Combination in the Analysis of the Poly-
cyclic Aromatic Hydrocarbon Content of Airborn Pollutants"
Analytical Chemistry, pp. 45, 908, (1973).
B. Cautreels, W., K. Van Cauivenberlke, "Fast Quantitative Analysis
of Organic Compounds in Airborn Particulate Matter by Gas Chromato-
graphy with Selective MS Detection", J. Chromatography, pp. 151,
253 (1977).
51
-------
C. Strup, Paul E., Jo Ann E. Wilkinson, and Peter W. Jones, "The Trace
Analysis of Polycyclic Aromatic Hydrocarbons in Aqueuous Systems using
XAD-2 Resin and Capillary Column GC/MS Analysis," Battelle Columbus
Labs, Columbus, Ohio.
D. Personal Communication: Battelle Columbus Laboratories to Arthur D.
Little, Inc., RFP No. RJ-4253, December 7, 1978.
HETEROCYCLIC NITROGEN COMPOUNDS
(MEG CATEGORY 23)
Recommended Method: GC/MS
Column: 3% Desil 400 on 100/120 mesh Supelcoport
2mm x 3m glass or stainless steel
Conditions: Flow Rate: 60 mL/min
Program: 160°C
i: 16
8°C/min
300°C (Reference A)
Detection Limit: 10 ng injected
SUGGESTED ALTERNATIVE METHODS:
1- GC/AFID or GC/FID for samples free from interferences.
2. For complex ramples requiring greater separating power:
Column: SE-52 glass capillary - average phase thickness: .29p
25mm x 20 M
Conditions:
Program: 100°C
2f
4°C/min
°°c (Reference B)
52
-------
Heterocyclic Nitrogen Compounds (MEG Category 23) (Continued)
References:
* » .
A. Dong, Michael W., David C. Locke and Dietrich Hoffman, "Characteriza-
tion of Aza Arenes in Basic Organic Portion of Suspended Particulate
natter Environmental Science and Technology. 11, 612 (1977)
B. Lee, M.L., K.D. Bartle and M.V. Novotny, "Profiles of the PN-1
Fraction from Engine Oils Obtained by Capillary Column G.C. and
Nitrogen Selective Detection", Analytical Chemistry. 47, 540 (1975)
HETEROCYCLIC OXYGEN COMPOUNDS
(MEG CATEGORY 24)
Recommended Method: GC/MS
Column: 3% SP 1000 on 100/120 Supelcoport
2mm x 2m
Conditions: Flow Rate: 30 mL/min
Program: 100°C
10°C/min
250°C
Detection Limit: 10 ng injected
SUGGESTED ALTERNATIVE METHODS:
1. GC/FID for preliminary evaluation or samples free of interferences.
2. Additional Resolution may be obtained using the alternate column
described for category 23.
53
-------
HETEROCYCLIC SULFUR COMPOUNDS
(MEG CATEGORY 25)
Recommended Method: GC/MS
A. For b.p. range 80 - 200°C (Purge-and-trap or organic extract)
Column: 0.1% SP 1000 on Carbopack C 80/100 mesh
2mm x 2m Glass or stainless steel.
Conditions: Flow Rate: 30 mL/min
Program: isothermal at 225°C
B. For b.p. range > 110°C
Column: 3% SP 2250 on 100/120 mesh supelcoport
2mm x 2m Glass or Stainless Steel.
Conditions: Carrier:
Program: 70°C
10°C/min
350°C
Detection Limit: 10 ng injected
SUGGESTED ALTERNATIVE METHODS;
1. GC/Flame Photometric detection or GC/FID for preliminary evaluation
or for samples free of interferences.
2. The SE-52 capillary column described for category 23 can be used if
resolution is a problem. (Reference A)
Reference.
A. Lee, M.L., and Ronald Kites, "Characterization of Sulfur Containing
Polycyclic Aromatic Compounds in Carbon Blacks." Analytical
Chemistry, Vol. 48, 1890 (1976).
54
-------
PESTICIDES AND PCS*8
Recommended Method: GC/MS
The following method is used by U.S. EPA (Reference A),
Column: 1.5% SP 2250 and 1.95% SP 2401 on
100/120 Supelcoport 4 mm X 2m glass.
Conditions: Flow Rate: 70 mL/min
Program : 200°C isothermal
Expected Retention Times
Group 1
Pesticides
a-BHC
3-BHC
5-BHC
Heptachlor-
epoxide
DDE
(Aldrin=l) RT'
.56 1.35
.79 1.90
.90 2.15
1.46 3.50
2.14 5.13
Group 2
Pesticides
a-BHC
Heptachlor
Aldrin
Endosulfan I
Dieldrin
RRT
.71
.83
1.00
1.87
2.27
RT
1.70
2.00
2.40
4.50
5.45
DDP 3.26 7.83 Endrin 2.73 6.55
DDT 3.92 9.40 Endosulfan II 3.33 8.00
Detection Limit: 50 ng injected
SUGGESTED ALTERNATIVE METHODS:
1. The SP 2250 column described for Halogenated Aromatics (MEG
Category 16) can also be used for this group.
2. BCD is an alternative detector.
Reference;
A. Federal Register Vol.38, Number 125, part II, pp. 17318 - 17323,
Friday, June 29, 1973.
55
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D. RECOMMENDATIONS FOR ANALYSIS OF UNKNOWN SAMPLES
In some cases, a need for Level 2 studies may be indicated by
criteria other than the results of Level 1 chemical analysis. Such
criteria might include, for example, a set of positive biotest results,
rather than chemical composition data. The biotest results would not
target specific chemical categories for study in Level 2. In these cases
a comprehensive set of Level 2 studies will be required using procedures
with lower detection limits than 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 considera-
tions. A general approach for these unknown samples is discussed in
this section.
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
56
-------
Ul
SOLID AND
LIQUID
PARTICLES
ORGANIC EXTRACTS
ANALYSIS SCHEME
(Fig.l.b)
1
NON-
EXTRACTABLE
RESIDUE
EXTRACT
FIGURE 1.Q. LEVEL 2 ORGANIC ANALYSIS SCHEME.
-------
ORGANIC EXTRACTS
SOLUTIONS, AND/OR OTHER
ORGANIC LIQUIDS
in
00
HIGH-MOLECULAR
WEIGHT FRACTION
HRMS, NMR
(FT)IR
TGA,
SURVEY ANALYSIS
IR. NMR. MS. GC. MICROSCOPY
DATA FROM
LEVEL 1
NON-VOLATILES PRESENT /OKTA FROM\ NON-VOLATILES ABSENT
^SURVEY AND >
\LEVEL L, '
POLAR, ACIDIC
FRACTION
LOW-MOLECULAR
WEIGHT SUBSTANCES
-COMPLEX MIXTURE ^/DAW FRQMX SIMPLE MIXTURE
L C >•• V SURVEY MO/>
LEVEH. "
H GC/MS
FIGURE l.b. ORGANIC EXTRACTS ANALYSIS SCHEME.
-------
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.
Samples from the gas phase (e.g., from stacks, ducts and ambient
air) are expected to be collected principally by direct "grab" sampling,
using glass bulbs, 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/ItS analysis.
The samples collected by an atmospheric sampling train such as
SASS pass through the cyclones and filters that are included in those
systems to remove and collect suspended solids, and are then led
through a sorbent resin trap (XAD-2) to collect vapors of organic
compounds. Some organic vapors condense on the walls of the SASS
train components and some condensate may collect in a sump below
the sorbent trap. These condensates should 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 obscured
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
59
-------
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.
Samples collected from liquid streams, nost 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 immiscible 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 r»ethylene 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.
60
-------
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
can be expected to dissolve and remove any entrained organic liquids as
well as the soluble portion oj 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; l^C-depleted ^°r ^^-NMR, etc^» wm 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
61
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relatively low-molecular-weight substances. A break-point of M.W. - 300-
500 is likely to be satisfactory this 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-
assisted) and perhaps by HRMS, using a solids probe for sample insertion.
If the low-molecular-weight and relatively more volatile fraction
from the GPC separation (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 Florlsil, 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.
62
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IV. SAMPLING METHODS
Sampling methods for use in Level 2 may in many cases be the same
as those used in Level 1. In some cases where a specific measurement
is sought, it may be possible 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", (20) and the EPA publication, "Hand-
book for Monitoring Industrial Wastewater" (21) are excellent resources
for water sampling and analysis methods. Fugitive sampling method-
ology has recently been addressed in several EPA publications. (8a,
8b, 8c). The reader should refer to these and similar sources for
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
63
-------
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.
64
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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 having boiling points within a range similar to those of the
G! - C7 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 (C^ 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
65
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ON
PROBE
r.
I!
AIR-COOLED "
CONDENSER
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 the
bag samples.
A comparative study of gas storage stability in two types of
sample bags and glass bulbs carried out under the Arthur D. Little, Inc.
program (22) indicates that glass bulbs are the best overall choice.
Reactive and highly-polar materials were preferentially lost in the
sample bags. Relatively simple (unreactive) gases were quite stable
in the sampling bags and the bags are recommended for these type of
species. In using sampling bags care should be taken to note the
possible need for conditioning of the surfaces. Collection of high
concentrations (> 1%) of organic gases in bags will usually lead to
contamination which will adversely affect any of those bags.
An alternative method for sampling low molecular weight organic
gases 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. (See discussion in next section, "2. Vapors," for criteria
in using sorbent resins.)
67
-------
STAINLESS STEEL PROBE
SOURCE
00
POLYMER
PACKED
TUBE
ROTOMETER
o
VALVE
GAS METER
Figure 3 Porous polymer vapor sampling method
Source: EPA-600/2-76-122, April 1976 p.66
-------
If the Vg value for solid sorbent sampling Is too low at ambient
(20°C t 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 theoretical
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
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 (equivalent to a CQ normal
hydrocarbon) that exist as gaseous species in the stream or environment
to be sampled because they are present below their equilibrium vapor
pressure concentrations. 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 (Figure 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 be used only when there are data to show an established prefer-
ence over these two 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
69
-------
TEMPERATURE GAUGE
PRESSURE GAUGE
THERMOCOUPLES
TC,
VACUUM PUMP
HEATED SECTION
POLYMER PACKED TUBE
EVACUATED CYCL NDER
STAINLESS STEEL PROBE CONDENSER
LIQUID NITROGEN DEWAR
COMPRESSED NITROGEN
Figure 4 Porous polymer and thermal gradient sampling train
Source: EPA-600/2-76-122, April 1976 p. 28
-------
HOT GAS
FROM OVEN
LIQUID PASSAGE
GAS PASSAGE
GAS COOLER
CONDENSATE «^
RESERVOIR
3-WAY SOLENOID VALVE
- TO COOLING BATH
— FROM COOLING BATH
COOLING FLUID
RESERVOIR
IMMERSION
HEATER
LIQUID PUMP
TEMPERATURE
CONTROLLER
Figure 5 XA0"2 Sorbent Trap Module
Source: EPA-600/2-76-160a, June 1976 p. 32
-------
to
. CONVECTION
/ OVEN
FILTER
GAS COOLER
'71
/
PROBE^f—I-
F s
./
*'
GAS
TEMPERATURE
T.C.
OVEN
T.C.
XAD-2
CARTRIDGE
IMP/COOLER
TRACE ELEMENT '
COLLECTOR
CONDENSATE
COLLEaOR
DRY GAS METER ORIFICE METER
CENTRALIZED TEMPERATURE
AND PRESSURE READOUT
CONTROL MODULE
10 CFM VACUUM PUMP
Figure 6. Source Assessment Sampling Schematic
Source: EPA 600/2-76-160a, June 1976 p. 30
\
IMPING ER —
T.C.
-------
have comparable collection characteristics at 20°C, XAD-2 has generally
slightly better volumetric capacity and has substantially greater (10X)
weight capacity than Tenax-GC.
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
(23) and in recent studies of incinerator emissions (24) in which the
version shown in Figure 7 was used. Sufficient quantities of vapors
for analysis may frequently be obtained by the simple version of a
train previously shown in Figure 3.
The characteristics of XAD-2 and Tenax-GC for use in collection of
vapors and quantitative data describing their collection efficiency and
capacity are given in two EPA reports, "Selection and Evaluation of
Sorbent Resins for the Collection of Organic Compounds" (6) and
"Characterization of Sorbent Resins for use in Environmental Sampling."
(7) For any given sampling situation, the quantity of resin to
be used, volume to be samplefl, operating temperature, etc., should be
selected using the background provided in these reports.
Two basic factors control the quantitative behavior of
these resins in a sampling system, their weight capacity and
the volumetric capacity (Vg) for each compound with its specific
volatility (boiling point) and polarity. If the resins are to
be used for streams with high concentrations of pollutants
(>> 100 mg/m3), the capacity of the resin for the pollutant is a complex
73
-------
To Control
Module
Silica Gel
Figure 7. Method 5 Train Modified for Collection of Organic Vapors
Source: "Destroying Chemical Wastes In Commercial Scale Incinerators". 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
-------
function of pollutant concentration, volalitity and polarity. Gen-
erally speaking, XAD-2 will have an upper weight sorption capacity
of 1 - 10% of the resin weight. Tenax-GC weight capacity is generally
about 10% of that of XAD-2 or 0.1 - 1% of the resin weight.
Most environmental assessment studies involving the collection of
vapors will represent situations where the pollutant concentration is
quite low (e.g. 1 - 100 mg/cu m). In these cases, the principal char-
acteristic influencing resin quality and sampling conditions is the
volumetric capacity (Vg) for the specific pollutant. The volumetric
capacity (Vg) describes the breakthrough capacity of the resin (in units
of mL/g) and is the maximum volume of sample stream which can be
pulled through the resin while still quantitatively retaining the
pollutant.
A summary of the Vg values obtained for a large number of pollutants
in the work described in Ref. 7 are given in Appendix C. The
general behavior of the resin-pollutant interaction can be conveniently
summarized in terms of an empirical correlation observed between elution
volume (actually log Vg) and boiling point as shown in Figure 8.
As is indicated in the Figure, good correlations were observed between
log Vg and the boiling point within each compound category studied.
There are some significant differences in Vg values for compounds that
have the same boiling point but are in dissimilar compound categories.
These data can be used in two basically different ways starting
with either the resin quantity or the volume to be sampled as the
fixed quantity. The following examples describe the procedures used
in designing the sampling approach.
Suppose a source were to be sampled for chlorobenzene and a
typical set of Method 5 conditions were to be used, i.e., 28 Lpm for
1 hr. The Vg for chlorobenzene (Appendix C) on XAD-2 is 2.4 x 10s
mL/g. Since total volume of 1680 L is to be collected, a minimum of
7 g of XAD-2 would be required for complete collection.
75
-------
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
Amines
'Phenols
Aliphatic*
Aliphatic Acids
Alcohols
50
100 150
Boiling Point (°C)
200
FIGURE 8. LOG v|° VS. BOILING POINT FOR INDIVIDUAL ADSOR3ATE GROUPS ON XAD-2
-------
Another question might be whether or not the SASS train under
standard conditions will quantitatively collect, for instance, benzyl
amine. The sorbent cartridge in the SASS train contains about 130 g
of XAD-2 and a 30 m3 sample is normally collected. These values can
be used to calculate a "cutoff" Vg value for the SASS train of 2.3 x
105 mL/g or log Vg - 5.4. This value is indicated by the dashed line
in Figure 8. In order for a compound to be collected completely
by the sorbent module its Vg would have to be greater than 2.3 x 105.
The Vg for benzylamine is 7.9 x 106 and it would thus be completely
collected. A comparison of several sampling trains relative to vapor
collection was given in Table 2.
The compound categories studied as represented in Figure 8 cover
each of the different types to be encountered well enough so that
one can estimate a Vg (log Vg) value for any new compound by careful
interpolation and extrapolation.
Two cautions are given when using the Vg data to estimate sampling
requirements or to estimate efficiencies. The Vg values were obtained
under laboratory conditions and any estimates for purposes of sampling
system design should be decreased by about a factor of two as a safety
margin. The Vg values have a normal temperature dependence and careful
temperature control is necessary when operating near the boundaries
of the trap limit. The Vg values given in Appendix C and Figure 8 are
all for 20°C, the design temperature of the SASS sorbent module. A
10°C change in sorbent module temperature will result in a change in
Vg value of about a factor of two.
"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 sampling should either be taken
across the cross section of the duct or in a well-mixed portion of
the stream.
77
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B. Particulates
Particulates consist of solid and liquid aerosols; both are
collected efficiently by appropriate combinations of cyclones and
filters. Other special purpose particulate collectors such as
electrostatic 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. Many of these have
been summarized and reviewed in the EPA report, "Technical Manual:
A survey of Equipment and Methods for Particulate Sampling in
Industrial Process Streams" (10). The SASS train is described
in detail in the EPA report, "Source Assessment Sampling System:
Design and Development." (25).
For chemical characterization studies and to provide samples for
biotesting, the SASS train shown in Figure 8 is used for Level 1
studies. The SASS is capable of providing particulate sample in the
following size ranges:
> 10 wm cyclone
3 - 10 urn 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 *$ as described in the Federal Register may
be adequate.
78
-------
Figure 9 Method 5: Particulate Sampling Train
Source: 40 CFR 60, Appendix A - Government Printing Office, Washington D.C., July 1976
-------
Particle sizing studies may be done with both impactors and
cyclones. Most previous studies have been done with impactors of the
Anderson and Brink type. Present evidence indicates that cyclones
are preferred for particle sizing devices because they are less
subject to operator errors than impactors and provide sufficient
sample of sized particles for analysis. A five-stage series cyclone
system has been designed which allows in-stack sampling.
A small electrostatic precipitator is under development and may
prove useful as a replacement for the backup filter used in sizing
devices. These devices could allow longer sampling times in situations
where rapid buildup of material on the filter would otherwise require
premature conclusion of sampling.
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 quantita-
tive data and for this purpose proportional sampling should be used.
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 would be restricted to streams
with low or no visible solids. Slurries should be sampled by grab
techniques.
80
-------
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 laboratories of EPA (26) and
ERDA C27) 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, (28) 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.
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. (17)
81
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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 proce-
dures 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 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 Emmlssions
Fugitive emissions are all those emissions discharged to the
environment by a source other than a well-characterized stack or stream.
They may include particulate, vapor, gas and water samples or individ-
ual species. Fugitive emissions can be considered to be dilute source
samples at ambient conditions. The dilution factor requires special
82
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consideration in sample volumes required for collection. The fact
that fugitive emissions 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
methodology have been described in recent EPA reports. (8, b, c.)
Airborne fugitive emissions may generally be described in terms of:
Site Source
Specific Source: Category 1
Specific Source: Category 2
Several examples of these are described in a worst case site descrip-
tion in Figure 10. A "site source" is a general emission contributed
to by many individual sources. Sampling such a source requires an
upwind/downwind 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 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 quantitative data which
will require 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 analogous equipment or method for
sampling fugitive gases and vapors. The ambient/fugitive concentrations
are 100 - 10,000 times lower than source levels, but the currently
83
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OPfN HI ARIM HIBMACt. INIIHNAI PIUMJ SIMILAR ID
COM OVEN. IMIMIU H> AIMt.SI'lllvl THROUGH OPEN
MDIS ANDROol. (.AUC.ORY 7 SAV. IRAIN
CAHGORY I HIOH-VOl.
DOWN WIND FROM BLAST
FURNACI AND SINTERING
/ OPfRAIIONS
CATEGORY I HIGH-VOl.
DOWN /-IND FROM COM
PILE
DO. N V INO Sill >O
CAT1OORV I HIGH VOL.
DOWN WIND FROM COAL
rats
00
UP.VINO SIH - SOlftCE
SAMPLCR
CATEGORY I HIGH-VOl.
DOWN WIND FROM
LIMESTONE BINS
CAHOOir, I MlGM-vOl.
DOVN '. IMO FRC"Ct4-.ll!
OBI
vL, OP[R-'k"'ti
CATEGORY I HIGH-VOL.
DOWN WIND FROM QUENCH-
TOWIR AND COKE GRINDING
CATEGORY I HIGH-VOl.
DOV/N V/IND FROM COM
OVEN BYPRODUCT RECOVERY
COKE OVEN BANK
CATFCOMY 2 SASS TRAIN
Figure 10. Decision Example for "Worst Case" Site
Source: EPA 600/2-76-160a, June 1976 p.51
-------
available methodology will not allow flow rate scaling to collect large
quantities. Although 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.
A very high volume fugitive air sampling train (FAST) is currently
under development at the Research Corporation for use in special
studies. The FAST train is designed to operate at 6 cu m/min (180 cfm)
for 8 hours. Particulate will be collected in the 0-3 ym and 3-15 ym
size range and vapors will be collected in an XAD-2 module.
The same procedures described for Level 1 fugitive water sampling
are recommended for Level 2 studies, if required.
85
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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 chroma-
tography (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. A seven-fraction scheme of this type is used
in Level 1 organic analysis and in many cases it may be possible to use
those same seven fractions for further, Level 2 analysis. In other cases,
in which discrete Level 2 samples have been collected, alternative frac-
tionation 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.
Other LC procedures that are of value in Level 2 organic analysis
are separations on alumina or Florisil to remove interferences in the
analysis of selected substances. An example, shown in Figure 11, is the
Florisil column pre-cleaning procedure used to remove Interfering sub-
stances prior to analysis of polychlorinated biphenyls (PCB's) in
industrial effluents (29). Another example of possible application of
LC in Level 2 organic analysis is the use of Sephadex-LH, a gel permea-
tion chromatography medium, which can be used for chemical class separa-
tion in a number of modes: lipophilic-hydrophilic partitioning, molecular
size separation, and aliphatic-aromatic separation (30). For example,
recent unpublished studies at Arthur D. Little, Inc., have indicated
that Sephadex LH is superior to Florisil/alumina for clean-up of extracts
prior to GC/ECD analysis of pesticides.
86
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0
Organic Extract
LCOn
Florisil
Fats, Lipids
Aromatics
LCOn
Silica
Gel
O
Chlorobenzenes
GC/MS For PCB's
FIGURE 11. DIRECTED LEVEL 2 LC SCHEME FOR ANALYSIS
OF POLYCHLORINATED BIPHENYLS
87
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B. High Performance Liquid Chromatography (HPLC)
HPLC is a separation technique with applications in quantification,
isolation 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 6. High sensitivity and specificity are achievable
using a UV detector at fixed (e.g., 254 nm) or variable (200-800 nm)
wavelength. Lower limits of detection in the nanogram range have been
reported for strongly absorbing sample species (i.e., molar absorptivity
- 14,000).
The differential refractometer detector has lower sensitivity and
less specificity than the UV detector. The RI detector responds to es-
sentially all sample components and is a potential "universal" detector
for HPLC, but lower limits of detection are in the microgram range.
Furthermore, generality 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.
An HPLC-MS combination might be of interest in some Level 2 appli-
cations. However, these systems are not in common use because of the
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TABLE 6
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 mL/hr)
UV
Selective
Nondestructive
Yes
2 x 10"^ Abs.
4 x 10"9 g/mL
2 x 10"n g/sec
3000
Less than 1%
deviation
Positive only
1 second
8 microliters
46 microliters
12% f.s.
RI
Universal
Nondestructive
1 x 10~7 RI units
7 x 10"7 g/mL
3 x 10~9 g/sec
3000
Less than 1%
deviation
Positive or
Negative
1 second
6 microliters
20 microliters
f.s.
Source: Basic Liquid Chromatography, Varian Instrument Company
89
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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, 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 12. 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 hydrodynamic 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,
tetrahydrofuran, toluene, dimethylformamide and methylene chloride) in-
clude 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 con-
trolled pore-size glass (e.g., CPC ).
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VO
Water
Insoluble
MW < 1000
Water Soluble
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
MW>1000
Gel Permeation
Adapted from Literature of DuPont Instruments, Scientific and Process Division Wilmington, Delaware
THF, Chloroform
(Non-Polar)
Water, Alcohol
(Polar)
FIGURE 12. GUIDE TO SELECTION OF HPLC ANALYTICAL PROCEDURES ACCORDING TO CHARACTERISTICS OF SPECIES SOUGHT
-------
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, gel permeation chromatography
(GPC) will probably be most useful as a technique to separate samples into
two molecular size ranges, with a molecular weight of about 300-500 as the
dividing point. The species in the lower molecular weight range 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
derivation or alternative treatment. The sample components in the higher
range will require analysis by methods not involving GC. These might
include mass spectrometry (LRMS or HRMS) or Fourier transform infrared
(FT/IR) or nuclear magnetic resonance (FT/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 solid silica substrate. Non-polar solutes have a higher af-
finity 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 components 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 chromato-
graphic or GC/MS analysis, from the non-polar materials suitable for
direct gas chromatography or GC/MS. Reverse phase HPLC is also an at-
tractive possibility for ultimate quantitative analysis of some classes
of compounds, such as phenols and carboxylic acids.
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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 analy-
tical 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
identification 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 polyeyelie aromatic hydrocarbons. Excellent separations between
these solutes is accomplished using H20/MeOH isocratic and gradient
mixtures as solvents. With these solvent systems and a Cis-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 chromatographed. This is due in part to the lower capacity
of reverse phase packings, the normal loss in resolution with sample
overload, but it is due primarily to the solubility limit of the hydrocarbon
moiety in polar solvents. Using a hydrocarbon solvent in conjunction
with a silica support (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.
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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 there-
fore not always possible to simply scale-up an analytical reverse phase
HPLC separation to achieve a preparative procedure.
It should also be noted that subsequent analytical procedures to be
applied to HPLC fractions will possibly necessitate the removal of sol-
vent from collected fractions. Water/methanol eluents can be more dif-
ficult 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 qualitative and quanti-
tative Level 2 analysis will depend on the volatility of the sample com-
ponents. Analytical procedures based on gas chromatography (GC), in-
cluding 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 quantita-
tively determining the volatility of a sample as a function of tempera-
ture.
In a TGA analysis, the weight of a small sample (1-10 mg) is con-
tinuously recorded as a function of time (isothermal operation) or
temperature (temperature programmed operation). The water content in
mixtures, for example, may be determined by TGA by virtue of 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 operation is more normally used. The sample
atmosphere (nitrogen, air, etc.) may be controlled to aid in the study,
for instance, of decomposition of non-volatile samples.
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An example of the applicability of TGA to Level 2 organic analysis
would be the determination of whether "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 mixtures of organics with appreciable volatility. GC is also an
exceedingly valuable technique for quantitative analysis of sample com-
ponents. However, qualitative analysis by GC is limited to inferences
drawn from retention times of individual peaks and known detector selec-
tivities. (The combination of mass spectrometric detection with GC to
give qualitative 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
halogenated species, give strong FID responses. The lower limit of
detection for organic species is on the order of one nanogram per micro-
liter (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
advantage 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
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concentrations, since different species have different electron capture
cross sections.
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 principle 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 pesticides 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
analysis is staggering. Columns may be packed, support-coated, open
tubular (Scot) or wall-coated capillaries of stainless shell, 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 environment assess-
ment programs. A suggested set of columns for general purpose Level 2
work is the following:
96
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• For volatiles - Qxypropionitrile/Porasll C (2 mm x
2 m glass). This column can separate hydrocarbons boiling
between -16l°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 Supelcoport or equivalent
2 mm x 2 m glass.) 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
Supelcoport or equivalent, 2 mm x 2 m glass). Dexsil 400 is
a carborane-methyl phenyl silicone that is stable at tempera-
tures up to 500°C. Like OV-17, Dexsil 400 is basically a
boiling point column. It is useful for analyzing 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) (3% on Supelcoport, 2 mm x 2 m glass or
stainless steel). Polyethylene glycol (Carbowax 20M) modified
with a terephthalic 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.
In addition to these general purpose columns with broad applicability,
unique, specially deactivated columns are required for Level 2 analysis
of phenols and amines. Also, in some particular Level 2 studies it may
be desirable to take advantage of the very high resolving power afforded
by capillary column GC.
3. Gas Chromatographic Conditions
Details of gas chromatographic conditions, such as carrier gas and
97
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temperature 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/DS)*
The combination of gas chromatographic (GC) separation methdds 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
quantitative 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 suffi-
ciently 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 compounds
that elute simultaneously from the GC. Lower limits of detection for
conventional (non-capillary) column GC are typically 30-100 ng/u L 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
parameters 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
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.
98
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in considerable fragmentation of the parent molecule. This fragmentation
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 or
impossible to detect, making specific Identification impossible. CI
provides a much gentler mode of ionization, yielding fewer fragment ions
and substantially larger parent ions. It is the method of choice for
those classes that given no El parent ion, such as the higher mass
alcohols, or for those that give very small parent ions with less frag-
mentation; however, less structural information is provided, although
some is available and may be of a unique type. Reactions with the CI
reagent gas complicate 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 prc-
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
99
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analyses, sufficient information will be available about the sample compo-
sition and/or the components of particular interest to allow one to scan
a more limited mass range. For example, the mass scan could be limited
to the range of m/e 100 to 300 if polynuclear aromatic hydrocarbons 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 instead of scan-
ning a continuous wide mass range. The extreme case of limited mass
scanning would be to monitor a single ion continuously, if only one com-
pound 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 acquisition.
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
objectives 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 chromato-
grams," in which only the abundance of selected ions, with m/e values
corresponding to specific sample components, is considered. The mass
chromatogram approach 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 qualita-
tive identification of the component producing the chromatographic peak(s)
The confirmation of identity should be achieved by performing an initial
100
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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.
In interpreting the GC/MS results it is also important to consider
retention 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,
absolute, as well as relative, retention times (RRT) can be used in
interpreting GC/MS data. It is frequently beneficial to use internal
standards, such as p,p'-DDI, 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 four basic columns—Oxypropionitrile/Porasil C, SP-2250
or OV-17, Desil 400 and SP-1000, —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 exten-
sively 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
differences in mass on the order of 1 part per thousand. This is equi-
valent 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 ordinarily used as a detector in GC/MS systems.
101
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The use of LRMS data to determine the structure of single compounds
is the mode of mass spectrometry that is most familiar in organic
chemistry. As discussed in Section E (above), electron impact ionization,
which leads to extensive fragmentation of parent (or molecular) ions is
ordinarily used to generate spectra for comparison with library reference
spectra. The library spectra may be in hard copy, fe.g., "Eight Peak
Index of Mass Spectra," 1st Ed., Imperial Chemical Industries, Ltd.,
Mass Spectrometry Data Center, Alder Maston, Reading, United Kingdom,
1970) or in computerized 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 ion-
ization or low voltage electron impact ionization. These techniques
minimize fragmentation 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 poly-
nuclear 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 in-
trinsic 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 temperatures, sample decomposition can occur; this is frequently
indicated by the reappearance of material with low molecular weights at
probe temperatures inconsistent with their volatility.
102
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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
unit. Data from the HRMS analysis are reported to four decimal places
in m/e. The high accuracy and precision makes it possible to take ad-
vantage 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 elements corresponding to a given mass. The theoretical and measured
masses are then compared and a "match" 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 suf-
ficient to calculate the exact theoretical mass expected for C2oHi2 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 yg is more realistic.
These detection limits are typical ones for HRMS instruments utilizing
electrical detection. With photographic (photoplate) detection 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
*Limits for determining "plausible" combinations are set by the user in
each application.
103
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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 compositions
into classes according to heteroatom composition and degree of hydrogen
unsaturation (rings plus double bonds or R 4- DB). An alternative approach
is to compare the set of measured masses with theoretical masses calcu-
lated for a list of reference compounds. The utility of these reference
compound file searching procedures is obviously dependent 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 environmental assessments 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 identi-
fication of organic compounds. Absorption in the IR range is due to
vibrational energy transitions and virtually all organic compounds (and
many inorganic species) have 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
transmittance) 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
104
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accuracy (3 cm"1 at 3000 cm-1). Most are equipped with ordinate expansion
capability and some are specifically designed for interfacing with auto-
matic data processing systems for spectral subtraction and other data
manipulations. Dispersive IR instruments are by far the most common
types available. 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 micropellet in an instrument equipped with a beam condenser and/or
ordinate expansion capability.
Individual sample components amounting to <5-10% of the total sample
are likely to remain undetected.
Fourier transform infrared systems differ from conventional dis-
persive infrared spectrophotometers in that conventional infrared spec-
troscopy uses a monochromater to generate the spectral information, whereas
an interferometer is used for this purpose in Fourier transform infrared
spectroscopy (FTIR). The use of an interferometer to generate spectral
information in the form of an interferogram (light intensity versus time)
necessitates a second difference between the types of infrared spectros-
copy. This difference is that FTIR systems use a dedicated digital
computer to obtain the Fourier transform of the interferogram, converting
it to a conventional infrared spectrum (light intensity versus wavelength
or frequency). These two differences lead to two major advantages of
FTIR over conventional infrared spectroscopy.
Using an interferometer results in a substantial gain in energy or
light throughput as compared to a monochromator. This gain in energy
results from the fact that all wavelengths of light are examined
simultaneously at an interferometer and no energy is lost (as in a dis-
persive instrument by examining the light one wavelength at a time).
This additional energy can be used in one of several ways: (a) for
faster scan speeds (as fact as 0.6 sec.), (b) for up to a 30-fold in-
crease in signal-to-noise ratio or (c) for 102 - 103 greater sensitivity.
105
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The availability of a dedicated computer offers several major data
handling advantages. Not only can spectra be ratioed against each other
to remove absorption bands due to background materials, but the computer
can be used to perform spectral arithmetic. Thus, spectra can be added
or subtracted from each other and also multiplied or divided. In this
way, the spectra can be adjusted in size, and unwanted components can be
removed from the spectra without the necessity of chemical separation.
This ability to utilize a computer is not unique to Fourier transform
spectroscopy, i.e., in theory a computer could be attached to a conven-
tional dispersive infrared spectrophotometer. However, in practice,
this is rarely done, whereas all Fourier transform systems use a computer.
Thus, from a practical standpoint, the use of a computer is a major
advantage in FTIR systems.
Recent papers have described the identification of less-than-nanogram
amounts of materials and the union of FTIR with GC (41,42). In the former, the
method of sample preparation is a key element of the analysis. NaCl
plates are cleaved to extremely thin sections, the samples are applied
using microscopes for observation, and still with the aid of a microscope,
the plates are centered in 50 or 100 ym apertures and oriented in an 8X
beam condenser. The sample is then scanned until a recognizable signal
can be differentiated from background. The authors claim this has been
successful with subnanogram quantities, e.g., of cellulose acetate, in
less than two hours. In the case of the GC/FT-IR system, the paper
describes a commercial system ("Chemigram") for on-the-fly analysis of
vapors separated by GC.
IR spectra, whether conventional or FT-IR, will be a major tool in
the characterization of non-volatile organic species in Level 2. In the
general case, when the sample is a fairly complex mixture of compounds,
the IR spectrum is primarily useful as an indicator of functional groups
present in the sample. It will usually not be possible to determine how
these functional groups are combined into various compound classes. In
those specific instances where one or only a small number of components
106
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are present (as, for example, in an HPLC fraction) it may be possible to
interpret the IR spectrum in terms of compound structure. If it is pos-
sible to identify a one-to-one match between bands in the sample spectrum
and those in a reference spectrum of a known material, this is convincing
evidence of compound identify.
H. Nuclear Magnetic Resonance Spectroscopy (NMR)
Nuclear magnetic resonance spectroscopy (IHOU as an organic analysis
technique has many similarities to IR spectroscopy in the type of in-
formation provided and in the potential applicability to Level 2. The
NMR spectrum arises when nuclei with magentic dipoles, or non-zero spin
number, undergo radiofrequency transitions in the presence of an external
magnetic field. Common nuclei with spin number 1/2 whose NMR spectra
are useful in organic analysis are: 1H, 19F, 13C and 31P. The utility
of NMR in organic analysis is increased because the transition frequency
(chemical shift) of a given nucleus depends not only of 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 abundance of 1H 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,
milligram (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.
107
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Determination of 13C NMR spectra in samples with natural abundance
of 13C (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-NMR. The chemical
shift range of 13C is about thirty times greater than that of 1Hf so
considerably greater resolution is possible in 13C NMR spectra.
It is anticipated that NMR spectroscopy will be a valuable tool in
characterizing 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 cases, however, there may be sufficient sample to also
acquire 13C FT-NMR spectra. The combination of 1H and 13C spectra com-
bined with IR data will probably provide the best method of characterizing
high molecular weight, non-volatile species in Level 2 organic analysis.
108
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I. Ultraviolet-Visible (UV-Vis) and Luminescence Spectroscopy (LS)
a. Ultraviolet-Visible Spectroscopy
Ultraviolet-Visible (UV-VIS) Spectroscopy is the measurement of
molecular absorption of light of various wavelengths in the spectral
region extending from the ultraviolet through the visible by a substance.
The spectra usually are plots of the wavelength of frequency or absorption
versus absorption intensities, but they may also be presented as plots of
wavelength versus molar absorption, e, or log e. The spectra are
dependent on the electronic structure of the molecular species,
specifically the electronic or binding energy. Energy absorbed produces
electronic transitions within a molecule, generally from the electronic
ground state that is in the zero vibration level to an excited state
of multiple vibration levels. Structures in which electronic transi-
tions can take place with the absorption of minimum energy absorb at
relatively long wavelengths; structures that require high energy for
electronic transitions absorb at shorter wavelengths.
Two factors tend to reduce the effectiveness of absorption
Spectroscopy as a qualitative tool for the identification of unknown
species. Spectrometric measurements of substances in solution tend to
produce boardened, and therefore rather non-specific, absorption bands
as a result of the presence of both vibrational and rotational energy in
the excited state. Of greater import, however, are the spectral overlaps
contributed by functional groups which broaden the spectral bands even more.
The use of UV-VIS Spectroscopy for qualitative identification of
substances in environmental assessment will be of greatest value when the
analyte is known and spectra can be compared to those of standard solutions.
Adequate spectra for such identifications can generally be made at con-
centrations on the order of micrograms per milliliter. For quantitative
measurements, when the identify of the analyte is known and interferences
are absent, the technique is of proven value. Adding to that value are
the extensive compilations of reference spectra including those of nearly
all the known carcinogenic urban air pollutants.
109
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b. Luminescence Spectroscopy
Luminescence Spectroscopy (LS) results from the same absorption of
electromagnetic radiation as occurs in UV-Vis Spectroscopy, but measures
also the intensity of radiation emitted by luminescing species in
returning from the excited electronic state to the ground state. Two
spectra can be obtained for any luminescing compound, the emission
spectrum and the excitation spectrum (which corresponds to all or part of
the absorption spectrum of the material). The sensitivity of LS is 100
to 1000 times greater than that of UV-Vis absorptiometry primarily because
of the method of detecting the signal of interest. In the absorption mode,
the signal at any wavelength is the difference between the intensity of
the source and the intensity after passing through the analyte. In LS,
the intensity of the luminescence emission is measured against an essentially
zero background. Good descriptions of the instrumentation available are
to be found in the textbook of Guilbault (31).
In its simplest form, LS is applied to solutions of materials in
solvents that are usually non-absorbing in the region of the excitation
wavelength. In the case of single luminescing components, uncorrected
spectra are usually sufficient to determine the compound present;
quantitative data may be generated only with dilute solutions—1 yg/L
to 1 ngXL—when a calibration curve is employed. In the case of
mixtures, it is often possible to determine the components by selective
excitation of the luminescence of each material present. Where the
complexity of mixtures prevents selective excitation, a technique first
described by Lloyd (32) has been useful In gaining improved resolution.
In this technique, the emission and excitation monochromators of the
spectrophotomer are scanned synchronously at a fixed wavelength
difference, e.g., with the excitation wavelength 25 nm less than the
emission wavelength.
110
-------
With very complex mixtures, as well as those of only a few
compounds, LS of chromatographed fractions, especially on TLC plates,
can be used to Identify the compounds present, as first reported by
Sawicki, e_t al. (33). Spectra can be obtained with nanogram quantities
of luminescing compounds. More recently, use of sensitized fluorescence
to detect trace amounts (< nanogram) of polynuclear aromatic hydro-
carbons has been reported 04 , 35).
Ill
-------
J. Optical Microscopy
1. General
One of the most valuable tools available to the analytical chemist
for use in environmental assessment studies is the optical microscope.
The fact that its value has failed to be widely appreciated in an era
dominated by more specialized Instruments should not discourage any
practicing chemist from obtaining at least some rudimentary data by
techniques that are as simple and rapid as many of them can be. More
sophisticated techniques, involving optical measurements on single
crystals, using polarized light and other esoteric phenomena, may be
left to the few experts in chemical microscopy to whom those methods
are truly familiar, but much useful information can be obtained by
even a neophyte if he will acquire a few basic skills.
Figure la, "Level 2 Organic Analysis Scheme," shows several points
at which "microscopy" is suggested for examination of collected samples
and extracts that may contain particulate solids. Figure Ib, "Organic
Extracts Analysis Scheme," includes "microscopy" as one of several
techniques recommended for qualitative and semi-quantitative analysis
of the extracts, solutions and other liquids. In the latter instance
the primary purpose of the microscopic examination is to detect, and
possibly to identify, crystalllzable solutes in those liquids. In the
former instance, the primary purpose will be to detect and characterize,
or possibly to identify, pre-existing particulate matter which may
contain insoluble and/or inextractable organic matter as well as
inorganic solids. These Initial examinations will require only
rudimentary observations and descriptions of the solid substances found
in the sample. The data reported will generally be used in an auxilliary
or confirmatory manner, and as a means of checking on the general
reasonableness and completeness of the data produced by other techniques.
112
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2. Apparatus
The basic equipment needed to obtain the kinds of chemical
information obtainable by microscopic technique are as follows:
1) A stereobinocular microscope, equipped for both incident and
transmitted illumination, and capable of magnification to
at least SOX.
2) An inexpensive monocular compound microscope, equipped for
transmitted illumination with magnification to 100X, and
with a fixed stage, suitable for use with electrically-
heated auxiliary hot stage.
3) A standard petrographic microscope (rotatable stage),
equipped for illumination with incident and transmitted
polarized light, and with magnification to 1000X.
4) Hot stage capable of achieving temperature to 350°C.
5) Immersion liquids with refractive index (n^ 25°) of 1.44,
1.52 and 1.66. For positive identification of various
organic crystalline substances, a set of immersion fluids
with n_ 25° ranging from 1.4 to about 1.7 in increments of
.002 will be useful.
6) Miscellaneous small tools (probes, droppers, needles),
slides, cover-slips and assorted solvents.
7) Tables of data on solubility, melting point, and optical
properties of crystalline organic compounds
8) Reference samples (or photomicrographs) of commonly occurring
particulate substances such as flyash from various kinds
of sources, pollen particles, vegatable fibers, etc. (With
experience, the analyst will acquire a personal memory-bank
of color, shape and size of these kinds of particulate
contaminants, and will be able to identify many of the
components of environmental samples at sight. At the outset,
reference samples and pictures will be essential, however,
and will always be helpful in conveying this kind of infor-
mation to the uninitiated (36)).
113
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3. Procedures
Gas sampling trains such as SASS generally separate any entrained
solid and/or liquid particles in cyclones and filters. Microscopic
examination of the "catches" of these devices should be done Initially
with the low-power stereo-binocular and subsequently with the petro-
graphlc microscope, using magnifications up to about 100X. Initial
examination, using a measuring reticle, will show whether the desired
size fractionation produced by the cyclones is satisfactory. It will
also reveal some general morphological evidence; whether the particles
are generally spherical (Implying either that they are liquid or that
they were formed as liquids and then solidified without crystallizing
when cooled), whether some portion of the particles appear to be crystalline,
or metallic or vegetable fibers, and whether some fraction of the "catch"
appears to be liquid. Rough estimates can be made of volume fractions
of each type of particle or phase seen. (36,37)
Application of a drop of methylene chloride or other proposed
extractant to the sample under examination will show what proportion
can be dissolved (and therefore subsequently extracted). Water-
solubles and hexane-solubles can also be estimated In this way. By
allowing the extract to evaporate to dryness, and examining it for
crystal formation in the process, a further check on the quantity of
extractables can be made.
The residue after extaction (to remove organics) can be re-
examined for evidence of non-extractable organics. For example,
cellulosic fibers as well as certain organic salts may be found in the
residue. The microscope offers a convenient test-point for application
of other extractive solvents.
Immersion of non-extracted particles, In each of the three Immersion
fluids (Up25 " 1.44, 1.52 and 1.66) will reveal the proportion of
low-electron-density solids to those of higher electron density.
Generally speaking, organic compounds without heavy-atom substitution
114
-------
(i.e., atoms such as S, Cl, I), and without aromatlcity and with little
or no conjugated unsaturation will have quite low refractive indices.(37)
Inorganic solids of low average atomic weight and appreciable water-
solubility will also have low refractive indices, but will exhibit
different solubilities in organic solvents, all of which effects are
visible microscopically.
Particulate solids obtained from filtration of liquid samples may
be treated similarly to those obtained from gaseous samples, with micro-
scopic examination, using test-solvents and refractive index liquids
before and after extraction of organics. Solid samples should be
examined directly, prior to extraction and again after extraction.
General morphology and size distribution can be recorded to complete
the qualitative and rough quantitative data obtained in this way.
Quantitative estimates of proportions of identifiable particulate
matter should be made by visual examination, and can be expected to
be good to about one significant figure (i.e., one part In ten).
Extracts should be examined microscopically for crystalline (or
other) residues remaining after evaporation of the extractant from an
individual sample of about 10 yL on a microscope slide. (A single cubic
crystal, 10 ym in each dimension, having specific gravity =1.0 and
therefore weighing 1 ng, is readily visible at 100X magnification and
readily identifiable by optical measurements such as refractive index.)
Residues that crystallize readily and completely on evaporation suggest
the absence of long-chain aliphatics and of non-rigid molecular structures
whose presence generally Inhibits crystallization. Residues that are
predominantly polycrystalline, consisting of mats of very small crystals
that form quickly as the last vestiges of solvent evaporate, suggest
the presence of a number of different crystallizable components.- (38,39)
An Important tool for the chemical microscopist In the analysis of
organic compounds is the hot-stage microscope (40). Samples in which
Individually visible crystals as small as a few micrometers in each
dimension occur can be tested to determine melting points of individual
115
-------
solid components in a physical mixture. The presence of volatile
components can also be detected, and their condensation as liquid
droplets or as sublimed crystals can be observed. Mixtures of organic
and Inorganic particles are often resolvable by virtue of the lower
melting points of the organlcs. By visual estimation of the fraction
of a mixed sample that changes phase, from solid to liquid and/or to
vapor at elevated temperature, the analyst can provide both quantitative
and qualitative data to augment and support the data obtained from
other sources.
Finally, in some instances, positive qualitative identifications
can occasionally be made on individual crystals which contain no more
than a nanogram of material, by use of easily determinable optical
properties or by fusion with a test crystal of known composition on
the hot stage. Both isotropic and birefringent crystals can be
identified unequivocally by refractive index matching, a process that
requires only a few minutes' time and minimal observational and
manipulative skill. Compound identity determinations by fusion with
known substances are equally simple and rapid when performed with the
polarizing microscope and the hot stage. (36)
In summary, the use of the optical microscope, even at a level
that would be considered quite primitive by skilled practitioners,
since it makes use of only the simplest and most easily interpreted
aspects of the technique, offers the analyst an abundance of data,
both qualitative and quantitative, to support, extend and confirm the
information he obtains from other methods. The information provided
by the microscope and its accessories will often serve to guide the
analyst in the choice of the most appropriate methods for separation
of mixtures and identification of components. It will serve as a
check on the validity of other observations, and it can provide a
quick, easy and unequivocal confirmation of the identity of most
organic compounds.
116
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BIBLIOGRAPHY*
1. Dorsey, J.A., C. H. Lochmuller, L. D. Johnson, R. M. Statnick,
Guidelines for Environmental Assessment Sampling and Analysis
Programs—Historical Development and Strategy of a Phased Approach.
EPA Draft Report (March 9, 1976).
2. Environmental Assessment Sampling and Analysis: Phased Approach
and Techniques for Level 1: EPA-600/2-77-115, PB 268-563/AS
(June 1977).
IERL-RTP Procedures Manual: Level 1 Environmental Assessment;
EPA-600/2-76-160a, PB 257-850/AS (June 1976).
,4. Technical Manual for Process Sampling Strategies for Organic
^ Materials; EPA-600/2-76-133, PB 256-696/AS (April 1976).
5. Technical Manual for Analysis of Organic Materials in Process
Streams; EPA-600/2-76-072, PB 259-299/AS (March 1976)
6. Selection and Evaluation of Sorbent Resins for the Collection of
Organic Compounds; EPA-600/7-77-044, PB 268-559/AS (April 1977).
7. Characterization of Sorbent Resins for Use in Environmental Sampling,
Report No. EPA-600/7-78-054, PB 284-3147/AS, March 1978.
8. Technical Manual for the Measurement of Fugitive Emissions:
a. Upwind/Downwind Sampling Method for Industrial Emissions;
EPA-600/2-76-089a, PB 253-092/AS (April 1976).
b. Roof Monitor Sampling Method for Industrial Fugitive Emissions;
EPA-600/2-76-089b, PB 257-847/AS (May 1976).
c. Quasi-Stack Sampling Method for Industrial Fugitive Emissions;
EPA-600/2-76-089c, PB 257-848/AS (May 1976).
9. Cleland, J. G. and G. L. Kingsbury, "Multimedia Environmental Goals
for Environmental Assessment," Vol. I. EPA-600/7-77-136a,
PB 276-919/AS (November 1977).
10. Technical Manual: A Survey of Equipment and Methods for Particulate
Sampling in Industrial Process Streams, Report No. EPA-600/7-78-043,
PB 282-501/AS (March 1978).
*Citations included in this list are those referenced by number in the
text of this report. References supporting the recommended analytical
procedures in Chapter IIC are cited individually for each procedure and
are NOT repeated in this list.
117
-------
11. Leo, Albert, Corwin Hansch and David Elklns, "Partition Coefficients
and Their Uses." Chemical Reviews 71, 525 (1971).
12. Seidell, A., "Solubility of Organic Compounds," Vol. II, 3rd Ed.,
Van Nostrand, Princeton, New Jersey (1941).
13. Parsons, James S. and Stanley Mitzner, "Gas Chromatographic Method
for Concentration and Analysis of Traces of Industrial Organic
Pollutants in Environmental Air and Stacks," Environmental Science
& Technology, 9(6), pp. 552 (1975).
14. Pellizzari, Edo D., John E. Bunch, Ben H. Carpenter and Eugene
Sawicki, "Collection and Analyses of Trace Organic Vapor Pollutants
in Ambient Atmospheres."
15. Pellizzari, E. D., J. E. Bunch, Perkley and J. McRae, "Collection
and Analyses of Trace Organic Vapor Pollutants in Ambient Atmospheres.
The Performance of a Tenax GC Cartridge Sampler for Hazardous Vapors,"
Analytical Letters 9(1), 45 (1976).
16. Novak, J., J. Zluticky, V. Kubelka and J. Mostecky, "Analysis of
Organic Constituents Present in Drinking Water," J_. Chromatog., 76,
45-50 (1973).
17. Bellar, T. A., and J. J. Lichtenberg, "Determining Volatile Organics
at Microgram-per-Litre Levels by Gas Chromatography," Journal AWWA,
739-744 (1974),
18. Grob, K., "Organic Substances in Potable Water and Its Precursor,
Part I," _J. Chromatog., 84, 255-273 (1973).
19. EPA/IERL-RTP Interim Procedures for Level 2 Sampling and Analyses
of Organic Materials, EPA-600/7-78-016, PB 270-212/AS (Bebruary 1978).
20. "Standard Methods for the Examination of Water and Wastewater," 13th
Edition (1976), APHA, New York.
21. "Handbook for Monitoring Industrial Wastewater," U.S. EPA Technology
Transfer (August 1973).
22. Gas Storage Stability Study: Arthur D. Little, Inc., EPA Contract
No. 68-02-2150, unpublished results.
23. "Efficient Collection of Polycyclic Organic Compounds from
Combustion Effluents," ES&T 10, 806 (1976).
24. "Destroying Chemical Wastes in Commercial Scale Incinerators,"
Final Report, EPA Contract No. 68-01-2966 (June 1977).
25. Source Assessment Sampling System: Design and Development, Report
No. EPA-600/7-78-018, PB 279-757/AS (February 1978).
118
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26. Webb, R. B., "Isolating Organic Water Pollutants: XAD Resins,
Urethane Foams, Solvent Extractions," EPA-660/4-75-003 (June 1975).
27. Junk, G. A., et al., J. Chromat. 99, 745 (1974), and other papers
by Junk and Svec.
28. "Sampling and Analysis Procedures for Survey of Industrial Effluents
for Priority Pollutants," U. S. EPA Environmental and Support
Laboratory, Cincinnati, Ohio. IFB No. Wa-77-B133, Appendix B
(April 1977).
29. U. S. Federal Register, 38_, No. 75, Part 2.
30. Jones, A. R., M. R. Guerin and B. R. Clark, "Preparative Scale
Liquid Chromatographic Fractionation of Crude Oils Derived from
Coal and Shale," Anal. Chem., 49_, 1766-72 (1977).
31. Guilbault, G. E., Practical Fluorescence; Theory, Methods, and
Techniques. Marcel Dekker, Inc., New York (1973).
32. Lloyd, J. B. F., ±. Forensic Sci. Soc., 11, 83 (1971).
33. Sawicki, E., T. W. Stanely, W. C. Elbert, and J. D. Pfaff, Anal.
Chem.. 36, 497 (1964).
34. Smith, E. M., P. L. Levins, EPA Report No. 600/7-78-182 (September 1978)
35. Hornyak, I., Mickochimica Acta, _23 (1978).
36. McCrone, W. C. and J. G. Delly, "The Particle Atlas," Edition III;
Volume I, "Principles and Techniques"; Volume II, "The Light
Microscopy Atlas"; Volume IV, "The Particle Analyst's Handbook";
Ann Arbor Science Publishers, Inc., Ann Arbor, Michigan (1973).
37. Schaeffer, H. F., "Microscopy for Chemists," Van Norstrand, New
York, 1953; reprinted by Dover Publications, New York (1966).
38. Winchell, N. A., "The Optical Properties of Organic Compounds,"
Academic Press, New York (1954).
39. Hartshorne, N. H. and A. Stuart, "Crystals and the Polarizing
Microscope," 4th Edition, Edward Arnold, London (1970).
40. McCrone, W. C., "Fusion Methods in Chemical Microscopy," Inter-
science, New York (1957).
41. Cournoyer, R., J. C. Shearer, and D. H. Anderson, "Fourier Transform
I. R. Analysis Below the One Nanogram Level," Anal. Chem., 49, 2275
(1977).
42. Coffey, P., D. R. Mattson, and J. C. Wright, American Laboratory,
10, 126 (1974).
119
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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.
121
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Nonanes
AUanes (C > 9)
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and Oienes
Ethylene
Propylene
Butadienes
Pentenes
CycloDCfltadienes
Hixfnes
Cvclobexene
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2.X2
aai
ilk.
278
278
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ru
mo*
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3HD
am
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_Sft?
"435
.43ft.
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i i •
t t
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' t -r
-t -t-
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4-U'
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4*
n-Ti-U-'
tL
JL.
t
\
, ,--(-
^ft
1 t -\-
iU:^:
fJJtf
T-
-f-
1- 1 > -1 f
-------
22
Fused Non-Alternant Polycycllc
Hydrocarbons
Indent and derivatives
Dlcvclopentadlene
Fluorene and derivatives
CvclopentanoMphthalene
?,t.hMiTnrlunr»n*
Ftuorantnene; tetrahydrofluoran-
tfwnc
1 ,2-benzof luorene
4-H-cyc1oDenta(def)phenanthrene
Benzol k ) fl uoranthene
Benzol e 1 fl uoranthene
Benzo(J)fluoranthene
1 .2:S.6-d1henzof luorene
3-«ethvl cholanthrene
Indeno (1.2.3.c.d)nyrene
TniRcne trlbeniylene benzene)
i
i , ,>
IUII
A.1
•LffA
Lfc£4
9-oe>i
LbES
\nf.?
kVSE3
|.3E«1
a.eeo
LbE^
~
••M*
tSE^
2.4 Ei
4tfc
2-SEM
Ui£Ji
tfr^l
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* -»• *iiin» »^*im ••»•»» •• ••* *
4 t.HAV ft'
-------
u.t^ryeUe Hltnyn Ccapoundt
A. Purloin Mid Substituted
51
0.
-------
24
HeterocycHc tayotn
• •MGC
ICC
ICO* CIUV* HI..1— .
Furtn
mhnmrfurui
Hrttoldlharoofurans
lUBhthefurant
PI»ii.imim[Q.11UhTfiir«i
JS
Ui
-iie_
itt.
JLlfi.
Jl
LiyiLO
••0
.0
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lt
I -1
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1 it
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-4-
n4
1 f 1 4 S b /
IT
:;.t
trr
l:it
* 1
t i-
1 ,-
t
1 ICO W100
« CNAV Vf '• TOff.
-------
Htttrocycltc Sulfur
ten* t.«*v*
DlBBthvlthlMlMMS
titrwcUlvl
UkfOPlMIMft
zoMnhtlMtMDhcM
»M_/*f in') >
12.314
XJE4&SU.
•t
f
.li:
> no •» io> >o^c
t- '- » - •»«
-------
OwnoBBta 1 1 1 cs
A. Alkyl or Aryl OrgwecUlllcs
Trtecthyl mine
Alkvl lead (TEL)
Alkyl Mercury ftiMfO
Organotln
thmr"""-"in«i
B. Sandwich Type Organaectaiiicj
FemceM
Mlek*in£Mie
Dlbtnnne '.*\ri~'^
C. fetal PanhvrlM and Other
ChelatM
CoaBlexed Vanadlu*
Nickel
Im
Tin
Zinc
/ . .1
•All
IOEJ-
LOCI
9ZK*4
L.OC4
s.se-5
^OF^
SO
•SfcA
LfitS
S.I Ell
j e«i
•^
110
*i3
life
lBb_
(M
JLOb.
. __
»
SL.
9aft
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—
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CtMT
"*te.wA
TL(f ILlL
j. (puP
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fi(C
9
0
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J_. ; -> >f
-------
APPENDIX B
Partition Coefficients
The following table lists Logio partition coefficients for a
wide range of species, tabulated according to MEG categories. The
octanol data were taken from the work of Leo, et al., and the values
for heptane and chloroform were calculated by the method described
in that paper. The chloroform values are Intended to approximate the
values for methylene chloride, as it was not possible to calculate
values for that solvent. The heptane values are given as appoximations
of the pentane partition coefficients.
*Leo, Albert, Corwin Hansch and David Elkins, "Partition Coefficients
and their Uses," Chemical Review 71, 525 (1971).
149
-------
Appendix B*
Partition Coefficients for Sample MEG Compounds
No. Category
1 Aliphatic Hydrocarbons
2A Saturated Alkyl Halides
2B Unsaturated Alkyl Halides
3 Ethers
4 Halogenated Ethers
5A Primary Alcohols
5B Secondary Alcohols
5C Tertiary Alcohols
6A Glycols
6B Epoxides
7A Aldehydes
7B Ketones
8A Carboxylic Acids
8B Carboxylic Acids
with addnl.
functional groups
8C Amides
9 Nitriles
10A Primary Amines
Compound
1-Chlorobutane
Propyl Ether
___ /
1-Butanol
1-Pentanol
2-Butanol
2-Pentanol
t-Butanol
t-Pentanol
Ethylene Glycol
Decamethylene
Glycol
Acetaldehyde
Prop ionaldehyde
Butyraldehyde
Acetone
2-Butanone
"2-Hexanone
Acetic Acid
Valeric Acid
Hexanoic Acid
Decanoic Acid
Phenylvaleric
Acid
'Laurie Acid
6-Phenylcaproic
Acid
Phthalic Acid
Suberic Acid
Azelaic Acid
Ace t amide
Valeramide
N,N-Diethyl-
valeramide
Acetonitrile
Aery loni tr ile
Benzonitrile
Ethylamine
Butylamine
Amylamine
Hexylamine
Aniline
-0.33
large
2.01
1.53 2.76
similar to ethers
-1.88
-1.28
-2.13
-1.44
-2.32
-1.40
-4.84
-1.51
similar
-1.43
-1.52
-0.04
—
-1.71
0.33
—
-1.37
—
1.47
-0.43
1.58
—0.32
-2.56
-2.11
-1.19
— —
-2.51
-0.88
-3.21
-2.75
-1.20
-1.89
-0.67
-0.21
1.47
—
0.37
1.0
0.15
0.86
-0.07
0.89
-2.67
0.78
to ethers
0.72
0.66
1.68
0.38
0.52
1.93
-1.55
0.30
1.94
3.25
1.23
3.30
1.36
-1.02
-0.55
0.41
-1.25
-0.26
1.44
-1.0
-0.50
1.10
0.39
1.23
1.55
2.69
1.30
LogP
oct
2.39
2.03
0.43
0.38
1.18
0.275
1.38
1.4
4.09
2.29
4.20
2.40
0.28
0.70
1.57
0.32
1.87
-0.34
0.10
1.56
0.18
0.84
1.09
~2
*See Section IIB-1 for application
150
-------
No. Category
10B Secondary Amines
LogP,
hept
IOC
11
12
13A
13B
14A
Tertiary Amines
Azo Compounds,
Hydrazine, and
Derivatives
Nitrosoamines
Mercaptans (Thiols)
Sulfides, Disulfides
Sulfonic Acids
14B
U4C)
15
16A
16B
17
ISA
18B
18C
19
Sulfoxides
Sulfonic Acid
Salts (Detergents)
.32
Benzene/& Subst'd. benzene
Hydrocarbons
Ring-subst. Halogenated
Aromatics
Aromatics w/Halogenated
Alkyl Side Chains
Aromatic Nitro Cmpds.
Monohydric Phenols
Dihydric & Polyhydric
Phenols
Fused Ring Hydroxy
Compounds
Halophenols
Appendix B
Compound
Diethylamine
Methylbutylamtne
Dipropylamine
Triethylamine
Hydrazine
Butyl tercaptan
Methyl Disulfide
Benzenesulfonic
Acid
Paraiodobenzene-
sulfonic Acid
Naphthalenesulfonic
Acid
Dimethylsulfoxide -4
Potassium dodecyl-
benzene Salfonate -2
Sodium dodecylben—
zene Sulfonate
Benzene
Toluene
Chlorobenzene
1,2-Dichloro-
benzene
1,3-Dichloro-
benzene
1,4-Dichloro-
benzene
a-Chlorotoluene
Nitrobenzene
Phenol
Methylphenols
(cresols)
Ethylphenols
Dimethylphenols
1,2-Dihydroxy-
benzene
1,3-Dlhydroxy-
benzene
1,4-Dihydroxy-
benzene
1,2,3-Trihydroxy-
benzene
a-Napthol
S-Napthol
2-Chlorophenol
Chlorinated Cresols 0.40
LogP
CHC13
LogP
-2.00
oct
-1.30
0.23
0.97
0.44
0.05
0.84
1.87
2.38
2.00
1.35
0.5
1.33
1.73
1.44
1.23
1.99
1.05
-5.24
-4.19
-4.57
-4.99
3.07
0.43
-3.88
-2.76
-3.20
-2.85
2.28
1.77
-2.26
-1.27
-1.63
-2.03
-0.36
-3.33
1.38
2.54
3.03
4.02
4.04
4.04
2.03
1.21
-1.30
-1.05
-0.32
-0.42
-1.87
-2.13
-2.38
-2.58
0.30
-1.09
-0.42
5 0.40
-1.11
2.66
3.46
3.79
4.47
4.47
4.49
1 3.11
2.54
0.30
0.56
1.30
1.30
-0.30
-0.58
-0.85
-1.40
2.00
0.27
1.30
2.11
-0.45
1.95
2.58
2.84
3.38
3.38
3.39
2.30
1.86
1.47
1.7
2.4
2.3
0.93
0.68
0.45
0.26
2.98
1.67
2.3
3.08
151
-------
No.
20
21
22
23A
23B
23C
23D
24
25
26
Category
Nitrophenols
Fused Polycyclic
Hydrocarbons
Fused Non-Alternant
Hydrocarbons
Pyridlne & Subst.
Pyridines
Fused 6-membered ring
Heterocyclic N Cpds.
Pyrrole & Fused Ring
Derivs.
Nitrogen Heterocycles
Contg. Addnl. Heteroatoms
Heterocyclic Oxygen
Compounds
Heterocyclic Sulfur
Compounds
Or ganomet allies
Appendix B
Compound
1,2-Nitrophenol
1,3-Nitrophenol
1 , 4-Nitrophenol
Dinitrophenol
Trinitrophenol
Naphthalene
Indene
Pyridine
Chloropyr idine
Quinoline
Acridine
Pyrrole
Benzothiazole
Fur an
"nHrrnhln^
LogPhept
1.20
-0.74
-0.83
-1.05
-1.40
3.84
3.17
-1.02
0.20
1.29
3.97
-0.84
1.51
2.71
1.12
LogPCHCL,
2.53
0.90
0.81
0.58
0.20
4.36
4.89
1.00
1.84
2.60
4.30
1.11
2.75
3.58
2.48
LogP fc
6 oct
1.85
2.0
1.91
1.71
1.37
3.28
2.92
0.65
1.31
3.35
0.75
2.02
2.67
1.81
no data found
152
-------
APPENDIX C
Specific Retention Volumes (Vg)* for Adsorbate Vapors
on Sorbent Resins (20 °C)
Adsorbate
n-Hexane
n-Octane
n-Decane
n-Dodecane
Benzene
Toluene
p~Xylene
Ethylbenzene
n-Propylbenzene
1 , 2-Dichloroe thane
Fluorobenzene
1,1, 2- trichloroethy lene
Chlorobenzene
Bromobenzene
1 , 4-Dichlorobenzene
2-Butanone
2-Heptanone
4-Heptanone
Cyclohexanone
3-Me thy 1-2-butanone
3 , 3-Ditne thy 1-2-butanone
2 , 6-Dime thy 1-4-hep tanone
Acetophenone
n-Butylamine
n-Araylamine
n-Hexylamine
Benzylamine
Di-n-butylamine
Tr i-n-buty lamine
Tenax-GC
2.58 x 10*
1.89 x 105
3.08 x 106
2.19 x 108
6.09 x 10*
7.88 x 10s
3.81 x 10s
8.36 x 105
1.53 x 106
2.32 x 10*
8.82 x 10*
8.82 x 10*
2.36 x 106
8.41 x 106
1.73 x 107
2.21 x IQk
5.55 x 106
3.22 x 106
1.36 x 106
6.46 x 10*
—
^^
1.23 x 107
2.67 x 10*
1.96 x 10s
7.35 x 10s
1.58 x 106
1.91 x 106
4.85 x 10s
XAD-2
7.53 x 104
2.29 x 106
2.09 x 107
5.24 x 10*
2.58 x 10s
9.05 x 10s
5.64 x 105
4.61 x 106
1.96 x 101*
3.13 x 10**
3.06 x 101*
2.43 x 10s
6.39 x 105
2.33 x 106
4.39 x 103
1.49 x 106
1.52 x 106
£
3.66 x 105
•t
2.53 x 101*
8.59 x 10*
1 61 x 107
^ • \J ^ *v AW
£
7.70 x 106
1.80 x 10*
_ c
1.29 x 10s
4.80 x 10s
7.87 x 106
6.90 x 106
""
153
-------
Specific Retention Volumes (Vg)* for Adsorbate Vapors
on Sorbent Resins (20°C)
Adsorbate Tenax-GC
Ethanol 9.08 x 102
n-Propanol 5.71 x 103
n-Butanol 4.34 x 101*
2-Butanol 1.86 x 101*
2-Methyl-2-propanol 7.08 x 102
2-Methyl-l-propanol 2.88 x 101*
Phenol ' 2.47 x 106
o-Cresol 1.00 x 107
p-Cresol 1.40 x 107
m-Cresol 1.18 x 107
Acetic Acid 3.20 x 103 7.07 x 103
Propionic Acid 1.73 x 101* 4.00 x lO4
n-Butanoic Acid 1.04 x 10s 7.74 x 101*
n-Pentanoic Acid 5.53 x 105 2.89 x 105
*
In units of nL/g.
154
-------
TECHNICAL REPORT DATA
(Please read Instructions on the revene before completing)
1. REPORT NO.
EPA-600/7-79-033
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
EPA/IERL-RTP Procedures for Level 2 Sampling
and Analysis of Organic Materials
5. REPORT DATE
February 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
J.C.Harris,M.J.Hayes, P.L.Levins, and
D.B.Lindsay
8. PERFORMING ORGANIZATION REPORT NO.
9. 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; 6/77-12/77
14. SPONSORING AGENCY CODE
EPA/600/13
16.SUPPLEMENTARY NOTES JERL-RTP project officer is Larry D. Johnson, MD-62, 919/541-
2557.
16. ABSTRACT
The manual, giving Level 2 procedures for sampling and chemical analysis
of organic materials, represents a step in the development of a general methodology
for chemical and biological assessment of environmental effects of industrial efflu-
ents. It presents concepts and general guidelines, together with a number of more
fully developed, tested, and validated Level 2 procedures. The accumulation of ex-
perience in sampling and chemical analysis of environmental pollutants is by no
means complete, however. The process is expected to continue for some time,
perhaps indefinitely. Users of the manual will therefore find a number of areas in
which additional research and testing is needed, and in which present knowledge is
insufficient to permit hard and fast procedures to be established.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Sampling
Chemical Analysis
Organic Compounds
Industrial Wastes
Effluents
Pollution Control
Stationary Sources
Level 2 Procedures
13B
14B
07D
07C
21. NO. OF PAGES
161
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (TUt Report)
Unclass if ied
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
155
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