EPA-600/2-77-115
June 1977
Environmental Protection Technology Series
ENVIRONMENTAL ASSESSMENT
SAMPLING AND ANALYSIS:
PHASED APPROACH AND TECHNIQUES
FOR LEVEL 1
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental Protection
Agency, have been grouped into five series. These five broad categories were established to
facilitate further development and application of environmental technology. Elimination of
traditional grouping was consciously planned to foster technology transfer and a maximum
interface in related fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION TECHNOLOGY
series. This series describes research performed to develop and demonstrate instrumenta-
tion, equipment, and methodology to repair or prevent environmental degradation from point
and non-point sources of pollution. This work provides the new or improved technology
required for the control and treatment of pollution sources to meet environmental quality
standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily reflect the views and
policy of the Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
This document is available to the public through the National Technical Information Service,
Springfield, Virginia 22161.
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EPA-600/2-77-115
June 1977
ENVIRONMENTAL ASSESSMENT
SAMPLING AND ANALYSIS:
PHASED APPROACH AND TECHNIQUES
FOR LEVEL 1
by
James A. Dorsey, Larry D. Johnson,
Robert VI. Statnick, and Charles H. Lochmuller
Environmental Protection Agency
Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
Program Element No. INE624
Prepared for
U.S, ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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CONTENTS
Figures iv
Tables iv
I. Historical Development and Overview of the
Phased Approach 1
Introduction 1
Information Effective Strategies 4
Cost Effectiveness—Direct and Phased
Approaches 5
Sampling Programs in a Phased Approach 7
Level 1 Sampling 7
Level 2 Sampling 9
Level 3 Sampling . . . 10
Analytical Methodology in a Phased Approach .... 11
Level 1 Analysis 11
Level 2 Analysis 13
Level 3 Analysis 14
II. Level 1 Methodology and Components 16
Introduction 16
Level 1 Sampling Effort 18
Sample Acquisition 18
Manpower Associated with Sample Acquisitions . 22
Laboratory Analysis 23
Physical Characterization 24
Chemical Characterization 24
Determination of Biological Hazards 29
Further Use of Level 1 Samples 31
Reporting 32
Cost Information 33
iii
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FIGURES
Number Page
1 Flow Chart of an Environmental Assessment
Program 2
2 Source Assessment Sampling System Train 20
3 Flow Chart of Level 1 Scheme 25
4 Liquid Chromatographic Fractions vs Class
Types 28
TABLES
Number Page
1 E.qtimated Total Costs of Direct vs Phased
2
3
4
5
Analytical Chemical Techniques Applicable
in Level 2 Following Level 1 Survey of
Requirements for Stream Sampling ........
Fupitive Emissions Sampling Techniques
Ms.rtpower Associated with Sample Acquisition . . .
_/
15
21
22
23
iv
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SECTION I
HISTORICAL DEVELOPMENT AND OVERVIEW
OF THE PHASED APPROACH
INTRODUCTION
A sampling and analytical approach has been developed for
conducting environmental source assessments of the feed, product,
and waste streams associated with industrial and energy processes.
The primary intent of this document is to present an overview of:
the historical development of the strategy, the concepts employed,
the measurement techniques applied, and the costs of program imple-
mentation (see Cost Information, page 33). No attempt will be made
to list the myriad details that must be considered: these guidelines
will be supported by a series of forthcoming technical and pro-
cedural manuals.
Before discussing the basic concepts, it seems appropriate to
first outline the components of an environmental source assessment
program. As used in this document and supporting manuals, an environ-
mental source assessment contains: (1) a systematic evaluation of the
physical, chemical and biological characteristics of all streams associ-
ated with a process; (2) predictions of the probable effects of those
streams on the environment; (3) prioritization of those streams rela-
tive to their individual hazard potential, and; (A) identification
of any necessary control technology programs. These components are
depicted schematically in Figure 1. An environmental source assessment
program addresses, to the maximum extent possible, the identification
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STREAM
CHARACTERIZATION
BV
SURVEY METHODS
IDENTIFY CONTROL
TECHNOLOGY PROGRAMS
HEALTH AND
ECOLOGICAL
EFFECTS
KNOWN
PROCESS
CHEMISTRY
STREAM
CHARACTERIZATION
DATA SUFFICIENT ?
CONTROL
TECHNOLOGY
NEEDED ?
PLAN AND EXECUTE
STREAM-SPECIFIC
CHARACTERIZATION
EXISTING
TECHNOLOGY
ADEQUATET
CONTROL
DEVELOPMENT
PRIORITIZE
STREAMS
Figure 1. Flowchart of an environmental assessment process,
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of all potential air, water, and terrestrial problems, both for
pollutants for which specific standards have been set and for
pollutants that are suspected to have deleterious effects on
the environment and that may be subject to future regulations. The
ultimate goal of an environmental source assessment is to ensure:
(1) that the streams from a given processing scheme will be
environmentally acceptable, or (2) that adequate control technology
either exists or can be developed.
Since an environmental source assessment study must characte-
rize the total pollution potential of all waste streams, the sampling
program must be much more extensive than those generally conducted
for the acquisition of process or control engineering data. The
assessment sampling is more complete in that all waste streams
must be sampled, and no attempt is made to limit sampling to a se-
lected number of process streams. The sampling is also more
comprehensive in that all substances of potential environmental
concern must be detectable above some minimum level of concern.
This comprehensiveness is in direct contrast to the more narrowly
defined lists of major stream components utilized for process
engineering measurement programs. These requirements of complete-
ness and comprehensiveness call for a strategy of approach where
philosophy and structure ensure the maximum utilization of
available resources.
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Information Effective Strategies
Two clearly distinct strategies of approach to an environ-
mental assassment sampling and analysis program which would satisfy
the requiranents for comprehensive information are the direct and
phased approaches. In a direct approach, all streams would be care-
fully sampled and the samples subjected to complete detailed analysis
for all detactable components at an overall accuracy of + 50 per
cent. In a phased approach, all streams would first be surveyed
using simplified, generalized sampling and analytical methods which
would permit their ranking on a priority basis (Level 1) i.e., very
hazardous streams would be distinguished from those less hazardous
or relatively innocuous in nature. Level 1 information is antici-
pated to be accurate to a factor of - 2. Detailed sampling and analysis
(Level 2) would then be applied first to streams ranked in the highest
priority by the Level 1 survey, and other streams would be addressed
in descending order of potential hazard. Another phase, initiated
after consideration of Level 1 and 2 results, would involve the con-
tinuous monitoring of "key" indicator materials to evaluate long-
term process variability (Level 3).
It should be clear that any partially direct approach (e.g.,
the use of predetermined lists of significant compounds) violates
the completa and comprehensive requirements of either the direct
or the phased environmental assessment philosophy and therefore is
not an alternative to either approach. Similarly, a priori
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judgements based on process chemistry, thermodynamics, etc. are
not acceptable practices in this context.
Cost Effectiveness — Direct and Phased Approaches
Since both the direct and phased (Level 1, 2, 3) approaches
offer, at least in principle, equal promise for ultimate success
(i.e., comprehensiveness and complete characterization), it is worth-
while to examine their relative resource requirements. Studies
were conducted by the staff of the Process Measurements Branch of
EPA's IERL-RTP with the objective of comparing the costs of direct
and phased (with elimination of low priority streams) sampling and
analysis approaches. Details of these studies will be reported
elsewhere, but it is interesting to consider the final estimates
for two unit operations — a limestone wet scrubber and full-scale
low-BTU coal gasifier. The scrubber involved seven feed or waste
stream sampling sites. The gasifier contained a total of 70 iden-
tifiable stream sampling points. A comparison of the total estimated
costs for both processes by both approaches is shown in Table 1.
Table 1. ESTIMATED TOTAL COSTS OF DIRECT
VS PHASED APPROACHES TO SAMPLING
AND ANALYSIS
Process
Limestone Wet Scrubber
Coal Gasifier
Phased (Total 1,2)
$ 350,000
$ 725,000
Direct
$ 500,000
$1,450,000
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In bc>t.h cases, the phased approach was found to be more
cost effective than the direct approach even though the scrubber
and coal g,asifier differ markedly in size, complexity, basic
technology, and total cost of sampling and analysis. The cost
advantages of the phased sampling and analysis approach were
found to be approximately proportional to the complexity of the
process being sampled. The phased approach resulted in a 50 per-
cent reduction in costs over the direct approach for the gasifier
(70 streairs), and the corresponding savings for the wet limestone
scrubber were 30 percent (7 streams). Within the phased approach,
the initial (Level 1) sampling and analysis costs were shown to be
10 percent of the total cost of the phased effort. Thus, many
qualitative judgements, including whether or not a full-scale
endeavor is at all necessary, can be made at low cost before a
commitment is made to initiate a detailed (Level 2) assessment.
This actual resource savings is only one aspect of justification
for the phased scheme. As the result of information developed in
Level 1, a significant improvement in sampling can be anticipated
at Level 2. It is doubtful that equal data could actually be
acquired in a direct approach due to the lack of the very necessary
learning processes involved in difficult source sampling and
analytical projects.
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SAMPLING PROGRAMS IN A PHASED APPROACH
Based on the results -of the studies mentioned, the most
cost-effective approach clearly is one in which detailed sampling
is performed only on those streams demonstrated to be potentially
hazardous by a generalized survey program. Further, it has been
noted that it is not sound practice to attempt to define a detailed
sampling program until: (1) the general characteristics of the
stream in question have been evaluated, and (2) the nature of any
unfavorable sampling system/sample interactions has been considered
(e.g., chemical reaction, volatility loss). Hence, an effective
sampling program involves a series of reiterative tests in which
each iteration enhances the source assessment by focusing resources
and efforts on the pollutants and streams of concern. At the end
of each refinement and before further resources are expended, the
output can be compared for equivalency to the goals of the overall
program itself.
Level 1 Sampling
Level 1 sampling stresses the concept of completeness by
presuming that any and all streams leaving the process will be
sampled unless empirical data equivalent to Level 1 programmatic
output already exists. Further, Level 1 sampling is not predicated
on a priori judgements as to the composition of streams. The
techniques utilized presume that whatever prior knowledge is
available, at best, is incomplete. Predictive and extrapolative
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techniques employed during source assessments serve as a check
on the empirical data and not as a replacement for it.
Level 1 sampling systems are therefore envisioned to permit
collection of all substances in the stream at a reasonably high
level of efficiency. They do not necessarily produce information
as to specific substances or their chemical form. For example,
if sulfur-containing gases are in the gas stream, Level 1 sampling
will separate and retain all particulates and vapor-phase organic
and inorganic sulfur compounds, and the distinction between parti-
culate and gaseous forms can be made. Although Level 1 is not
designed to preserve the specific sulfur compound identity, in many
cases a reasonable specific compound identification may result.
However, conceptually, the identification is not necessary in
judging the success of Level 1.
Further, Level 1 sampling programs are designed to make
maximum use of existing samples and stream access sites. While
some care 'nust be exercised to ensure that the samples are not
biased, the commonly applied concepts of multiple point, isokinetic
or flow proportional sampling are not rigidly adhered to. Normally
a single sanple of each stream should be collected under average
process operating conditions or, alternatively, under each condition
of interest. These samples should be time-integrated over one or
more process cycles. When a series of discrete samples result, they
are combined to produce a single "average" for analysis, and the
average is considered as representative of the total process cycle.
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Level 2 Sampling
Level 2 sampling programs are directed toward a more de-
tailed representation of stream composition. They are not as
"inclusive" as Level 1 in that resources are expended to improve
information only on streams of a critical nature. Additional
sampling of other streams is deferred because Level 1 information
has indicated a less significant level of environmental impact.
Level 2 sampling is optimized for specific compounds or classes
of compounds contained in the streams sampled. It also provides
a more quantitative description of the concentrations and mass
flow rates of the various substances in the stream.
Level 2 sampling must be considerably more refined than
Level I since it is being conducted on streams which have already
been identified by Level 1 results as having potentially adverse
environmental effects. One primary refinement will be the need
for more rigorous attention to selection and preparation of
sampling sites. Additionally, adherence to procedures for acquir-
ing a representative sample must be incorporated into the test
procedures. Level 2 sampling should also provide for replication
of samples in order to further improve accuracy and be more
representative.
In many cases, Level 2 sampling will require not only more
care in use but also modifications of Level 1 equipment and/or the
application of entirely new methods. Such cases result from the
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necessity to identify more definitively the materials which
produce the adverse environmental problems. For example, if
Level 1 has; indicated a high concentration of sulfur-containing
species, Level 2 sampling must be specifically designed to
provide isolation of the sulfur-containing materials into appro-
priate fractions which can be analyzed for individual compounds
or compound, classes.
Level 3 Sampling
At Level 3, emphasis is placed on the variability of stream
composition with time and process or control system parameters.
Having determined at Level 1 that a stream is environmentally
unacceptable and at Level 2 what the unacceptable components
are, it is now necessary to define accurately the range of values
to be expected and the effectiveness of a control process if control
equipment is installed. An effective Level 3 sampling program
is designed to monitor a limited number of selected compounds or
compound classes.
Level 3 sampling is designed to provide information over
a long period of time. To be cost effective, such programs must
be tailored to the specific requirements of each stream being
monitored. Based on the information developed at Level 2,
specialized sampling procedures can be designed to track key
indicator materials at frequent intervals. If at all possible,
Level 3 should also incorporate continuous monitors where appropriate.
10
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During Level 3 programs, it is anticipated that Level 2
sampling will be conducted at predetermined intervals to check
the limited Level 3 information. Further, recommended procedures
for compliance testing should be introduced into the program at a
time appropriate to the status of the process or control technology
development.
ANALYTICAL METHODOLOGY IN A. PHASED APPROACH
During an environmental source assessment, the analytical
methods applied will vary from relatively simple, manual wet chemistry
to highly complex instrumental techniques. Analyses proceed from
general, broadly applicable, survey methods to more specialized
techniques tailored to specific component measurements. This very
broad range requirement has been structured to adhere to the same
level concept described for the sampling program. At each phase
of the analytical program, the depth and sophistication of the
techniques are designed to be commensurate with the quality of the
samples taken and the information required. Hence, expenditure
of analytical resources on screening type samples from streams of
unknown pollution potential is minimized.
Level 1 Analysis
Level 1 sampling provides a single set of samples acquired to
represent the average composition of each stream. This sample
set is separated, either in the field or in the laboratory, into
solid, liquid, and gas-phase components. Each fraction is
11
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evaluated with survey techniques which define its basic physical,
chemical, and biological characteristics. The survey methods
selected ace compatible with a very broad spectrum of materials
and have sufficient sensitivity to ensure a high probability of
detecting environmental problems.
In Level 1, the analytical techniques and instrumentation
have been kept as simple as possible in order to provide an
effective level of information at minimum cost. Each individ-
ual piece of data developed adds a relevant point to the overall
evaluation,, Conversely, since the information from a given analysis
is limited;, all the tests must be accomplished to provide a valid
assessment: of the sample.
Physical analysis of solid samples is incorporated into Level 1
because the. size and shape of the particles have a major effect on
their behavior in process streams, control equipment, atmospheric
dispersions and the respiratory system. In addition, some materials
have characteristic physical forms which can aid in their identifica-
tion. Chemical analyses to determine the types of substances present
are incorporated to provide information for predicting: control
approaches, atmospheric dispersion/transformation, and potential
toxicity of the stream. Finally, because prediction of hazard
based on physical and chemical analyses alone is subject to many
uncertainties, biological assay techniques are incorporated ag a
measure of the potential toxicity.
12
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Level 2 Analysis
The analytical procedures applied at Level 2 may be extensions
of the Level 1 procedures. In most cases, however, information
developed at Level 1 will provide background for selection and
utilization of more sophisticated sampling and analysis techniques.
Since these techniques will require a major investment in equipment
and a well-trained staff, Level 2 analyses will probably be most
effectively accomplished by a limited number of selected labora-
tories.
Because Level 2 analyses must positively identify the
materials in sources which have already been defined as causing
adverse environmental effects, these analyses are the most
critical of all three levels. It is equally important, however,
that the analyses be conducted in an information-effective manner.
This is because increasing specificity and/or accuracy result in
cost escalations which are, at best, exponential rather than
proportional. Due to the multiplicity of analytical techniques
required and the potential for unnecessarily high expenditures,
Level 2 analyses should be managed and interpreted by experienced
analytical personnel working in well-equipped laboratories. Further-
more, the analyses must be conducted with a full awareness of the
information requirements of an environmental assessment program.
It is evident from the preceding comments that Level 2 analyses
cannot be conducted via a prescribed series of tests. Each sample
13
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will recuire the analyst to select appropriate techniques based
on the information developed in Level 1 and the information re-
quirements of the assessments. Several attempts have been made
to formulate a generalized scheme which proceeds through a complex
series of logical "if-then" steps; however, no optimized approach
is presently available. Whatever scheme is utilized for Level 1, it
must contain physical, chemical, and biological analyses. In the
absence oŁ a general scheme, Table 2 indicates the types of analyses
which are applicable at Level 2.
Level 3 Analysis
The analytical procedures for Level 3 are specific to
the stres.m components being monitored, and it is not possible to
define the exact form they may take. Level 3 analyses are
oriented toward the time variation in the concentrations of key
indicator materials. In general, the analysis will be optimized
to a specific set of stream conditions and will therefore not be
as complex or expensive as the Level 2 methods. Both manual and
instrumental techniques may be used, provided they can be implemented
at the process site. At Level 3, continuous monitors for selected
pollutants should be incorporated in the analysis program as an aid
in interpreting the data acquired through manual techniques.
The Level 3 analysis program should also include the use of
Level 2 analysis at selected intervals as a check on the validity
of the key indicator materials to reflect process variability.
14
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Table 2. ANALYTICAL CHEMICAL TECHNIQUES APPLICABLE
IN LEVEL 2 FOLLOWING LEVEL 1 SURVEY OF STREAM CONTENTS
Category A
Wet Chemical Methods
(e.g., S04, N03, F,
total phenolics )
Elemental Analysis
Spark-Source Mass Spectrometry
Atomic Absorption Spectrometry
Arc and Spark Emission Spectrometry
Neutron Activation Analyses
X-Ray Fluorescence
Organic Materials
Infrared Spectrometry
G. C. - Mass Selective Detector
G. C. - Selective Detector
(e.g., Flame lonization, Flame
Emission, Electron Capture)
Chemi-Ionization Mass Spectrometry
Category B
Separation Techniques
High-Performance Liquid
Chromatography
Gas Chromatography
Ion Exchange
Solvent Extraction
Structure Elucidation
Nuclear Magnetic Resonance
High-Resolution Mass Spectrometry
Photoelectron/Inner Shell Electron
Spectrometry (Surface Inorganics)
Infrared Spectrometry
Quantitative Measurement
If not achieved in Separation
or Structure Elucidation,
utilize Category A.
This is not an all inclusive or an exclusive list. Choice of
the most cost/information effective methods will vary from
sample to sample.
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SECTION II
LEVEL 1 METHODOLOGY AND COMPONENTS
INTRODUCTION
In Section I, a three-level phased approach to a cost and
information-effective measurement program for environmental assessment
studies was presented. In general, the intent of each phase is
the measurement of the mass flow rates of primary pollutant classes —
either out of the envelope containing the process or out of the
plant of x;hich the process is one part. The strategy which has
been developed includes characterization of feed streams to provide
a rough n^.terial balance and to determine if feedstock modification
is an effective control approach. The characterization also extends
to the product streams whenever they may directly affect the environment
at the next step of usage.
Level 1, the principal subject of this section, is structured
to produce a cost-effective information base for prioritization of
streams aid for planning any subsequent programs. It seeks to
provide rrput data to support evaluation of the following questions:
a. Do streams leaving the processing unit have a finite
probability of exceeding existing or future air, water,
or solid waste standards or critieria?
b. Do any of the streams leaving the processing unit contain
Łny classes of substances that are known or suspected to
have adverse environmental effects?
16
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c. Into what general categories (classes) do these
adverse substances fall?
d. What are the most probable sources of these
substances?
e. Based on the adverse effects and mass output
rates, what is the priority ranking of streams?
f. For streams exhibiting potential environmental
effects, what is the basic direction that control
strategies are likely to follow?
The Level 1 measurement program provides information on the
physical characteristics, chemical composition, and biological
effects of a given stream.
These pfogram components produce data which permit both the
identification of existing problems and the evaluation of the
possible adverse environmental effects of the streams. The
measurement techniques do not; attempt the quantitative determination
of compliance with existing standards; however, they do provide re-
sults that can be used both for semiquantitative evaluation of process
compliance and for planning subsequent sampling and analysis programs.
It is desirable that the Level 1 measurement methods be
designed to ensure comparability of information from a wide range
of processes. Present indications are that a reasonably specific
set of procedures can be defined for Level 1 studies. The proposed
methodology is applied to all streams from a given source during a
17
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single, comprehensive field test period. This approach is sound
and reasonable since it ensures comparability and internal con-
sistency in ievel 1 data by removing bias due to measurement proce-
dures and to feedstock or process variations that might occur over ex-
tended sampling periods. The following discussions are a general
description of the techniques applied. A more detailed procedures
manual is being prepared to provide specific information on each
aspect of Level 1.
Level 1 Sampling Effort
The ^oal of the Level 1 sampling effort is to acquire for subse-
quent analysis, a sample from each process feedstock stream, each pro-
cess waste stream, and each process product stream. In addition to sample
acquisition, sufficient process data must be acquired to permit cal-
culations such as mass emission rate and mass emission rates per unit
of product. These data must be acquired during the sample acquisition
phase, and the test program should establish the flow rate of each
stream sanpled. The quality of these data needs only to be comparable
to the stripling error and can be obtained from direct measurements,
from operator log sheets, or from indirect approaches such as fan and
pump curves.
Sample Acquisition
It is consistent with the philosophy of an environmental assess-
ment at Level 1 that the sampler should not prejudge the chemical
and/or physical nature of any stream. For example, a flue gas stream
18
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is always assumed to contain inorganic and organic gases as well
as inorganic and organic entrained particulates. The subsequent
physical and chemical analyses will then be used to establish
the presence or the absence of any constituent.
To provide this type of unbiased sampling, the acquisition
of gas samples requires the use of a sampling train designed
specifically for environmental assessment sampling. The Source
Assessment Sampling System (SASS) (shown schematically in Figure 2)
will be used to sample at 90-150 1pm (3-5 scfm) and collect both
solids and vapors. The entrained particulates are fractionated
into four sizes: > 10 urn, 3-10 ym, 1-3 ym, and < 1 urn. Vapor-
phase organic materials are adsorbed on a solid sorbent, and the
inorganic vapors are retained in the chemically active impinger
solutions.
Because it is impossible to predict the concentration
of a constituent in the gas stream at the start, sampling is
based on the minimum volume of gas necessary to provide detection
3 3
of materials in the analytical scheme. A minimum of 30 m (1000 ft )
is sufficient to ensure detection of materials at approximately
3
1 mg/m . Utilizing the 90-150 1pm SASS train will require a sampling
time of 3.5 to 5.5 hours.
The solid sorbent used in the SASS train does not collect,
quantitatively, materials whose boiling points correspond to those
of the less than C,-hydrocarbons with optimum efficiency. Therefore,
19
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Convection
oven
Filter
Stack T.C.
Gas cooler
Gas
temperature
T.C.
S-type pi tot
Stack velocity
magnehelic gauges
Condensate
collector
Sorbent
cartrld
Imp/cooler
trace element
collector
Implnger
T.C.
Coarse adjustment
valve
Vacuum pumps
Orifice
magnehelic gauqe
Vacuum
gauge
Dry test meter
Figure 2. Source assessment sampling system train.
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a gas sample is acquired in addition to the SASS samples from
each gas stream. These gas samples are analyzed in the field
by gas chromatography utilizing multiple column/detector
methodology.
For solids and liquids, the sampling methodologies are also
kept at a minimum level compatible with the Level 1 analyses.
Liquid samples are acquired from existing taps in lines or with
simple, dippers from open streams. Solid sampling is effected
with coring devices for piles and with a shovel for moving
streams. General requirements are listed in Table 3.
Table 3. REQUIREMENTS FOR STREAM SAMPLING
Stream
Gas
Liquid
Sample Size
30 m3
10 liter
Location
Ducts, stacks
Lines or tanks
Sampling Procedure
SASS train
Tap or valve samplinj
Solids
1 kg
Open free-flowing
streams
Storage piles
Conveyors
Dipper method
Coring
Full stream cut
A further sampling category included in Level 1 is fugitive emissions,
A fugitive emission is any solid, liquid, or gaseous emission which is not
released through ducts, pipes, stacks, etc. of a regular cross-sectional
area. General techniques that are applicable to such emissions are listed
in Table 4.
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Table 4. FUGITIVE EMISSIONS SAMPLING TECHNIQUES
Sampling Technique Applicable to Description
SASS Gases, Dusts Sample at emission point
Upwind/Downwind Gases, Dusts Establish a sampling network
upwind and downwind of the
source
Plug Reservoir Liquids Establish network around
source to sample runoff
In many cases, the upwind/downwind technique may also be used to
isolate a specific process from the general plant background. This
requires mobile units which can be kept downwind of the fugitive
source.
Manpower Associated with Sample Acquisitions
The acquisition time per sample — which includes equipment
setup time, sample acquisition time, and equipment tear-down and
cleanup time — has been estimated as a function of sample type
and is given in Table 5. These estimates do not include site
preparation times or travel. The estimated level of effort per
stream is based upon the use of an experienced field sampling
team.
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Table 5. MANPOWER ASSOCIATED WITH SAMPLE ACQUISITION
Particulate & Gases
Liquid
Solid
Fugitive Particulate
Manhours /Stream
12
1
1
15
Cost*
$ 360
30
30
450
*
Assuming $30/mhr
LABORATORY ANALYSIS
The information that will be available for the prioritization
of process streams will come from analyses carried out on samples
collected via the previously described methods. Some of the analyses
will be performed as part of the sampling team effort (e.g., on-site
gas chromatography); others require laboratory conditions that could
be achieved in the field only at high, unwarranted expense. The
general analysis scheme is divided into three stages (physical and
chemical characterization, and biological hazards) that have been
designed to yield a maximum amount of useful complementary infor-
mation at reasonable cost. The scheme yields relevant information
on all pollutants including those covered by emission standards.
The first stage involves the physical characterization of solid
and particulate matter, including such items.as morphology and particle
size distribution. The second deals with the chemical characterization
23
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of samples and sample extracts and includes the determination
of elemental distribution from both qualitative and semi-quantitative
•viewpoints. Organic material is separated into fractions that can
be assayed on a weight basis. The third stage involves the deter-
mination of biological hazards in the form of in vitro measurement
of cytotoxicitys mutagenicity, and ecological effects in the form
of selected plant and animal responses. Figure 3 shows flow charts
of the analysis scheme and the estimated cost of each analysis scheme
of field samples.
Physical Characterization
Level 1 physical characterization of solids suspended in gas
streams is carried out initially in the field utilizing the cyclone
system in the SASS train. The solids are weighed in the laboratory
and then combined into a > 3 um fraction and a < 3 um fraction. Optical
photomicroscopic examination is then performed on the two fractions.
In solids from piles, storage bins, etc., the size distribution
is determined using a Coulter Counter. Optical photomicroscopy
evaluation of these samples is also performed to determine particle
morphology.
Chemical Characterization
In Level 1, it is important that no assumptions be made about
the composition of the samples obtained in the field. The recommended
analytical procedures are, therefore, designed to be generally
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FIELD
SAMPLES
PHYSICAL
SOLIDS MORPHOLOGY
INORGANIC
ELEMENTAL ANALYSIS
(SPARK SOURCE MASS
AND ATOMIC ABSORPTION
SPECTROMETRY)
ORGANIC
LIQUID CHROMATOGRAPHY
INFRARED AND LOW
RESOLUTION MASS SPECTROMETRY
BIO ASSAY
in vitro CYTOTOXICITY,
BACTERIAL MUTAGENICITY;
ECOLOGICAL TESTING;
in vivo TOXICITY
REPORT
INPUT TO
IMPACT
ANALYSIS
Figure 3. Flow chart of level I scheme.
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applicable and to yield information appropriate to the needs
of the. stream prioritization strategy. Since the c.osts of chemical
analysis increase in proportion to the demand for increased quali-
tative differentiation and quantitative precision, the Level 1
procedures do not seek to identify particular chemical compounds
as such. The results of the analysis schemes to be outlined in
this section are combined with the analyses performed by the field
sampling team to form the chemical information output.
It Is convenient to divide analytical schemes into the classical
subdivisions of inorganic and organic analyses, despite the fact
that such chemical classes as the organometallics (or metallo-
organics" can be considered in either subdivision. In Level 1
chemical analysis: inorganic analysis involves determination of
elemental composition; organic analysis is the separation of organic
solvent soluble material, by gas and liquid chromatography, into
defined fractions that include the general classes of organic com-
pounds. Ko classes of compounds or elements have been excluded;
however, no deliberate attempt has been made to optimize any
specific compounds or elements.
Level 1 inorganic analysis utilizes the Spark Source
Mass Spectroscopic technique to achieve qualitative and semi-
quantitative .elemental analyses on all solids, particulates,
filterable solids from liquid streams, and evaporated residues
of liquid samples. This technique is used because of its:
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general multielement capability, acceptable detection limits,
speed, and cost. An accuracy of a factor of - 2 and a detection
limit of 1 ppm for all elements analyzed are specified. Since
spark-source mass spectrometers are quite complex (fairly expen-
sive instruments that require highly trained operators), the
estimated cost of a Level 1 elemental analysis is $300.
The Level 1 organic analysis achieves a semi-quantitative
estimate of the predominant classes of organic compounds present
in samples taken from process streams. Classes of organic compounds
include: paraffins, aromatic hydrocarbons, alcohols, ketones,
aldehydes, carboxylic acids, and amines. While it is possible
to fractionate complex mixtures into these classes, it is difficult
and costly. The Level 1 strategy is to isolate well-defined frac-
tions by conventional liquid chromatography rather than isolate
specific classes. Under controlled conditions, the contents of a
chromatography fraction (in terms of class types) are predictable.
An example of the relation between organic class and chromatographic
fraction is illustrated in Figure 4.
Organic extracts of > C.„ materials are resolved into eight
fractions by liquid/solid chromatography on silica gel, utilizing
a prescribed series of eight solvent mixtures as elutants. The
fractions are evaporated to constant weight by methods that minimize
evaporative loss of the constituents of interest. The weight of
each fraction is determined to - 0.5 mg. As an aid to identification
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Paraffins
Aromatic
Hydrocarbons
Polyaromatic
Hydrocarbons
00
'Heterocyclic
Sulfur Compounds
'Esters, Alcohols,
-Ketones
Phenols,. Amides .-.
Carboxylic Aqids
Sulfonates
Figure 4. Liquid chromatographic" fractions vs class types.
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of the constituents of each fraction, an infrared (IR) adsorption
spectrum is obtained and interpreted. For those fractions whose
mass exceeds a minimum level of concern for source concentration
(i.e., 0.5 mg/nm for stack gases), further analysis is performed
by Low Resolution Mass Spectrometry (LRMS). The total cost of a
Level 1 organic analysis is approximately $500.
Organic analysis of C7~C1„ materials which might be lost
during evaporation is conducted using gas chromatographic techniques.
This is done on the sorbent trap extract prior to concentration for
liquid chromatographic separation. The separation is essentially
by boiling point, and compounds are grouped into classes by boiling
point range.
The required level of operator training is that of skilled
technicians capable of following the Level 1 technical and procedural
manual. Interpretation of the infrared and low resolution mass
spectra will require a senior technician trained and experienced
in such tasks.
Chemical analysis of inorganic gases and of low-molecular weight
organic gases is conducted in the field using gas chromatographic
techniques. Nitrogen oxides are also determined using chemiluminescence.
All other analyses are performed in the laboratory.
Determination of Biological Hazards
Biological tests included in the Level 1 analysis scheme are
intended to indicate potential biohazards independently
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of chemical analysis. This environmental assessment tool is an
important aspect since chemical information, as mentioned earlier,
is an anbiguous predictor of biological activity. Level 1 chemical
analysis .is a search for danger signals; bioassay provides additional
indicators. This aspect of the. Level 1 analysis strategy is still
in development, and the methods described are examples of present
thought. The bioassay component is anticipated to extend to methods
which assess the terrestrial and aquatic effects of certain process
waste sf.reams and fugitive emissions.
Like the chemical analysis, Level 1 bioanalysis must remain
relatively simple and inexpensive. For this reason, in vitro or
test tube methods are highly advantageous for the first level.
The selected methods discussed in this section provide an estimation
of acute cellular toxicity and of certain types of mutagenic activity.
In addition to being of direct interest, mutagenic behavior is an
effective screening indicator for carcinogenic activity, Although
not all nutagens are carcinogenic, nearly all carcinogens cause
mutagenesls.
An estimate of the acute cellular toxicity is determined by
means of the rabbit alveolar macrophage procedure. Although the
system presents opportunities for considerably more sophisticated
studies, only cell mortality compared to controls has been utilized
as part of Level 1. Particulate samples are added, in weighed
quantities, to the culture medium and incubated before adding the
30
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test cells. After a second incubation, the number of dead and •
living cells is determined by dye exclusion techniques. Appro-
priate tests for water samples and other liquid materials are
under consideration.
The recommended test for mutagenesis is carried out using a
B. Ames type procedure with selected strains of microorganisms.
At Level 1, only one solvent system is employed. Solid samples
are dissolved as completely as possible in dimethyl sulfoxide,
filtered, and added to the test system. Liquid samples are added
to dimethyl sulfoxide and then to the test system.
Skilled technicians, under close supervision of a professional
cytologist and bacterial geneticist, are required for the cytoxicity
and mutagenicity testing, respectively. Experienced personnel must
interpret the test results. To avoid health hazards to the test personnel,
laboratories must be x^ell equipped and carefully managed to prevent
chemical or biological contamination of samples. For these reasons,
this work must be conducted in laboratories .approved by EPA health
effects programs.
FURTHER USE OF LEVEL 1 SAMPLES
Level 1 samples are anticipated to be used during the
early stages of Level 2 sampling and analysis strategy planning.
While analysis of the samples by Level 2 methods cannot be
considered as a substitute for Level 2, the analysis can provide
useful, additional information for Level 2 program development.
31
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For example, if the Level 1 organic analysis suggests the
presence of oxygenated hydrocarbons which may include phenols
and if other tests indicate, the sample is toxic, then a direct
analysis for phenolic compounds as a class may be desirable prior
to Leve.L 2. This confirmation of phenols would aid in optimizing
sampling for these species. However, because Level 1 sampling,
sample handling, and storage are not optimized, the data cannot be
used to accurately quantify materials detected.
REPORTING
The output from Level 1 testing must provide a basis for the
decision to proceed with Level 2 sampling and analysis and must
also provide direction to the design of the Level 2 test program.
The essential data for this purpose are:
a) Concentration of. elements in streams sampled. (This
information is derived from SSMS analysis and appropriate volumetric
measurements.) Mass emission rates are also necessary for all
effluent streams.
b) Weight percentage of total organics found in each chroma-
tographic fraction. (These should also be expressed as mass emission
rates foi total organics and organics in each fraction.)
c) Preliminary identification of organic species from IR/LRMS.
d) Photomicrograph and description of morphology. .
e) Particle size data, if applicable.
f) Gas chromatographic data from field portable unit. In
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addition, the presence and estimation of concentration of volatile
materials need to be determined.
g) Estimation of potential acute toxicity and mutagenicity
characteristics of all streams subjected to bioanalysis.
h) Volumetric flow rates;, production rates, and other
appropriate process data at the time of sampling.
Calculations, using Level 1 data, of the quantities of
output should be made well in advance of the sampling visit to
ensure that essential information is not overlooked.
COST INFORMATION
Estimated costs are summarized below for Level 1 sampling,
analysis, and reporting.
a. Site preparation (per site.) $ 250
b. Travel (3-man crew) and shipping 2,650
c. Sampling by stream type .(per sample):
Fugitive Dust 450
Liquid. 30
Particulate & Gases 360
Solid 30
d. Analysis by sample (per sample):
Gas 1,600
Liquid. . . 2,600
Particulate ...'..' 4,600
Solid 1,400
e. Data reduction and reporting 2,500
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4. TITLE AND SUBTITLE
7. AUTHOR(S)
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT NO.
EPA-600/2-77-115
2.
Environmental Assessment Sampling
and Analysis: Phased Approach and Techniques for
Level 1
Jaraes A.Dorsey, Larry D.Johnson,
Robert M.Statnick, and Charles H. Lochmuller
3. RECIPIENT'S ACCESSION-NO.
5. REPORT DATE
June 1977
6. PERFORMING ORGANIZATION.CODE
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
(Same as Block 12, below.)
10. PROGRAM ELEMENT NO.
1NE624
11. CONTRACT/GRANT NO.
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
Phase Final: 4/7B-4/77
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES This ^ ^ TŁRL-RTP inhouse report. J. Dorscy's Mail Drop is 62;
his phone is 919/549-8411 Ext 2557.
16. ABSTRACT
The report discusses a three-level approach to sampling and analysis, and
gives details of a Level 1 sampling and analysis phased approach for an environmental
source assessment. A research program was initiated to develop a sampling and
analytical approach for conducting environmental source assessments of the feed,
product, and waste streams associated with industrial and energy processes. An
environmental source assessment identifies potential air, water, and terrestrial
problems for both regulated (specific standards exist) and unregulated pollutants
(future regulations may be necessary). The three-level sampling and analysis
approach resulted from this program. Level 1 is a complete survey of all streams,
using simplified, generalized sampling and analytical methods which permit priority
ranking; i.e. . hazardous streams are distinguished from those less hazardous or
relatively innocuous in nature. Level 2 is detailed sampling and analysis of the
streams ranked in the highest priority by the Level 1 survey. Other streams may then
be addressed according to potential hazard. Level 3 involves continuous monitoring
of 'key' indicator materials to evaluate the effect on emissions of process variability.
17
KEY WORDS AND DOCUMENT ANALYSIS
a.
DESCRIPTORS
Pollution
Sampling
Analyzing
Measurement
Industrial Processes
Energy
Process Variables
Toxicity
Bioassay
Hazards
Ranking
b.lDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Source Assessment
Process Streams
Hazard Potential
Prioritization
c. COSATI Field/Group
13B 07A,13H
14B 06T
06A
13H 12B
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report}
Unclassified
21. NO. OF PAGES
38
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
34
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