United States
Environmental Protection
Agency
Environmental Monitoring Systems
Laboratory
Research Triangle Park NC 27711
Research and Development
EPA-600/S4-83-027 Aug. 1983
Project Summary
Technical Assistance Document
for Sampling and Analysis of
Toxic Organic Compounds in
Ambient Air
R M. Riggin
The objective of this project is to
develop a Technical Assistance Docu-
ment (TAD) for sampling and analysis
of toxic organic compounds in ambient
air. The primary users of this document
are expected to be regional, state, and
local environmental protection person-
nel who need to determine ambient air
quality for regulatory or information-
gathering purposes.
The TAD consists of the following
four sections:
(1) Introduction
(2) Regulatory Issues Related to Toxic
Organic Monitoring
(3) Guidelines for Development of a
Monitoring Plan
(4) Sampling and Analysis Tech-
niques
A topical index is included to assist
the reader in locating pertinent subjects
within the document.
This Project Summary was developed
by EPA's Environmental Monitoring
Systems Laboratory, Research Triangle
Park. NC, to announce key findings of
the research project that is fully doc-
umented in a separate report of the
same title (see Project Report ordering
information at back).
Introduction
The objective of this project was to
develop a Technical Assistance Document
(TAD) to aid technical and program man-
agement personnel within regional, state,
and local environmental protection organiza-
tions in analyzing toxic organic compounds
in ambient air. The scope of the document
is broad enough so that others may use it
for designing monitoring programs.
The TAD Is not intended to be a single
source of technical information but should
be used as an overview document, with
the user consulting referenced information
in the TAD as required
Federal, state, local, and regional regula-
tions concerning the control of toxic organic
chemical emissions have resulted in moni-
toring programs for toxic organic chemicals
in ambient air. Unfortunately, adequate
information about sampling and analysis
of such compounds in ambient air is not
readily available. Also, many technical
difficulties encountered in such monitoring
programs have not been adequately docu-
mented. Therefore, the purpose of the
TAD is to detail regulatory issues, monitor-
ing strategies, and sampling and analysis
methods.
Structure of the TAD
Figure 1 shows the four major sections
and associated subsections of the TAD.
The first section is an introduction. The
second section deals with regulatory policy
and public issues. Special emphasis is
given to regulatory or public objectives as
they relate to the technical design and
implementation of monitoring programs.
The third section presents a set of
detailed guidelines for developing an
ambient air monitoring program. The
procedure for defining objectives, compil-
ing existing information, selecting samp-
ling and analysis methods, selecting a
sampling strategy, specifying QA and safe-
ty procedures, and defining data format is
-------
General Topic of Interest*
Regulatory
Issues
Monitoring
Strategies
\ \
Section 2 Section 3
—Monitoring Objectives,
pp. 8-14
—Sources of Monitoring
Information, pp. 14-18
—Selection of Sampling &
Analysis Methods, pp. 18-24
—Sampling Strategy (e.g..
site selection), pp. 24-26
—Quality Assurance
Considerations, pp. 27-35
—Data Format, p. 35
—Safety, p. 35
—Sources of Sampling &
Analysis Methods, p. 18
—Sources of Monitoring
Data, p. 14
—Meteorological
Considerations, p. 17
—Method Performance Data
for Sampling & Analysis
Methods, p. 18
Specific Information
Concerning Sampling and
Analysis Techniques
\
Section 4
—Sampling Methods.
Overview, pp. 37-47
—Analytical Methods.
Overview, pp. 47-74
—Screening Methods,
Field, pp. 49-56
—Screening Methods,
Laboratory, pp. 56-58
—Compound Specific
Methods (GC. HPJLC.
GC/MS, etc.), pp. 58-74
—Compound Classes.
Definition, pp. 76-80
—Specific Sampling &
Analysis Methods, pp. 80-94
—Methods for Determining
Compounds Listed in
Table 1. pp. 88-94
—Quality Assurance, pp. 94-102
Nitrobenzene
Nitrosomorpholine
Perchloroethylene (tetrachloroethylene)
Phenol
Phosgene
Polychlorinated biphenyls
Propylene oxide
Toluene
Trichloroethylene
Vinylidene chloride (1,1-dichloroethylene)
o-, m-,p-Xylene
Figure 1. Topical flowchart for technical assistance document. *
"Consult Index for specific topics.
presented. The intended purpose of this
section is to give the reader an appreciation
for the factors to be considered in designing
a monitoring program at each stage of
development The development process
is actually iterative, and conflicts between
overall objectives and sampling and analysis
limitations must be resolved through modi-
fication or technical refinement
The final section reviews sampling and
analytical techniques and describes screen-
ing and specific methods. Also, physical
and chemical properties of compounds used
to select appropriate methods are dis-
cussed. This aspect of the document is
very important because methods for deter-
mining certain compounds have not been
devised Analyzing several compounds
with one method is less costly than moni-
toring each compound by a specific method.
The TAD also details specific methodology
that may be used to analyze the compounds
presented in Table 1. These compounds
are currently being considered for regula-
tion under the Clean Air Act This method-
ology might also be used to analyze chemi-
cals similar to those listed in Table 1.
Table 1. Organic Compounds Being
Considered for Regulation Under
Clean Air Act Amendments
Acetaldehyde
Acrolein
Acrylonitrile
Ally I chloride
Benzyl chloride
Carbon tetrachloride
Chlorobenzene
Chloroform
Chloroprene
o-,m-,p-Cresol
p- Dichlorobenzene
Dimethyl nitrosamine
Dioxin (2,3,7,8 tetrachlorodibenzodioxin)
Epichlorohydrin
Ethylene dichloride
Ethylene oxide
Formaldehyde
Hexachlorocyclopentadiene
Maleic anhydride
Methyl chloroform (1,1,1 trichloroethane)
Methylene chloride (dichloromethane)
-------
R. M. Riggin is with Battelle-Columbus Laboratories. Columbus, OH 43201.
L. J. Purdue and H. G. Richter are the EPA Project Officers (see below).
The complete report, entitled "Technical Assistance Document for Sampling and
Analysis of Toxic Organic Compounds in Ambient Air," (Order No. PB 83-239
020; Cost: $14.50, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield. VA 22161
Telephone: 703-487-4650
The EPA Project Officers can be contacted at:
Environmental Monitoring Systems Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
irUS GOVERNMENT PRINTING OFFICE- 1983-659-017/7159
-------
-*";* Postage and
United States Center for Envih3rttti#rtal Research Fees paj(j
Environmental Protection Information. ;•-£•*£.- Environmental
Agency Cincinnan^W-^aBB Protection
-.'"'. Agency
EPA 335
Official Business
Penalty for Private Use $300
RETURN POSTAGE GUARANTEED j g FfoVlR PROTECTION AGENCY
REGION 5 LIBRARY
230 S DEARBORN STREET
CHICAGO IL 60604
-------
United States
Environmental Protection
Agency
Environmental Monitoring Systems
Laboratory
Research Triangle Park NC 27711
Research and Development
EPA-600/S4-83-026 Sept. 1983
4>EPA Project Summary
A Summary of the 1981 EPA
National Performance Audit
Program on Source
Measurements
E. W. Streib, R. G. Fuerst, and M. R. Midgett
In the spring and fall of 1981, the
Quality Assurance Division (QAD) con-
ducted its semi-annual National Audits
for certain Stationary Source Test
Methods. The audit materials consisted
of: a critical orifice for Method 5 (dry
gas meter only), five simulated, liquid
samples each for Method 6 (SO2) and
Method 7 (NOX), and two coal samples
for Method 19. Industrial laboratories,
contractors, universities, foreign la-
boratories, and local, state and Federal
agencies participated.
For the Method 5 spring audit, the
mean for all participants differed by
13.6% from the true (EPA) value. For
the fall audit, participants' mean was
4.3% from the true value. In the two
Method 6 audits, the median values
measured for 9 of 10 samples differed
by less than 1 % from the true value,
whereas the median values for all 10
samples used in the two Method 7
audits were within 2% of the true
value. This was the first coal audit
conducted by QAD. For the sulfur, ash,
and moisture analysis, the participants'
accuracy was consistently better for
the higher concentration samples than
for the lower concentration samples.
This Project Summary was developed
by EPA's Environmental Monitoring
Systems Laboratory, Research Triangle
Park, NC, to announce key findings of
the research project that is fully doc-
umented in a separate report of the
same title (see Project Report ordering
information at back).
Introduction
In 1 977 the Environmental Monitoring
Systems Laboratory (EMSL) of EPA estab-
lished a performance audit program to
evaluate the performance of organizations
that conduct source testing using EPA
Reference Methods. By participating in
this free and voluntary program, users of
these methods can compare their per-
formance to other laboratories conducting
similar measurements.
Laboratories participating in the audits
sent their data to the Source Branch and
later received a written report comparing
their results to EPA's. The participants had
eight weeks to return data to EPA At the
end of this period, all data were statistically
analyzed to determine the participants'
precision and accuracy.
Audit Materials
In the Method 5 audit procedure, partici-
pants use a critical orifice to check the
calibration of the dry gas meter in their
EPA Method 5 meter box. This device
allows a participant to compare his mea-
sured volume to EPA's expected volume.
Asummaryof the 1981 Method5audit
shows that 76% of the 350 laboratories
that requested samples returned data for
the spring and fall audits. The Code of
Federal Regulations requires that the dry
gas meter be calibrated to an accuracy of
within 2 percent, so this was used as the
criterion for accuracy. Only 42% of the
reporting laboratories in the 0381 audit
and 44% in the 0981 audit obtained this
accuracy.
For the Method 6 audit, a sample set of
five different dilutions of sulfunc acid was
prepared. This audit checks the partici-
pant's ability to analyze a Method 6 sample
for S02.
A summary of the 1981 Method6audit
shows that 70% of the 311 laboratories
-------
requesting samples returned data for the
spring and fall audits. Two percent was
chosen as the criterion for accuracy. Of all
the data retu rned an average of 5 596 of the
participants achieved an accuracy within
2%.
For the Method 7 audit, a sample set of
five concentrations of potassium nitrate
was prepared. This audit checks the
participant's ability to analyze a Method 7
sample for NOX.
Asummaryofthe 1981 Method7audit
shows that 6696 of the 250 laboratories
requesting samples returned data for the
spring and fall audits. Three percent was
chosen as the criterion for accuracy. Of all
the data returned, an average of 3596 of
the participants achieved an accuracy of
3% for both audits.
The first coal audit by the Quality Assur-
ance Division was conducted in 1981.
This audit made use of two 60-mesh coal
samples. Participants analyzed each coal
sample for BTU content and percent sulfur,
moisture, and ash.
A summary of the 1981 coal audit
results shows that 83% of the 77 labora-
tories that requested samples returned
data. Five percent was chosen as1 the
accuracy criterion for each of the four
parameters. For the high concentration ef
sulfur and moisture, 61% and 80%, re-
spectively, of the analyses were within 5%
of the expected value. However for the low
concentration of sulfur and moisture, only
1 6% of the analyses were within the 5%
criterion. The data for the gross calorific
analysis were better, with 92% of the low
values and 85% of the high values within
5% of the expected value.
Recommendations
The Quality Assurance Division of the
Environmental Monitoring Systems La-
boratory maintains a repository of audit
samples for EPA Methods 6 and 7, and for
coal. These stable samples are available to
any laboratory having a need for them,
such as for training new personnel and
conducting quality control checks of the
laboratory. Since the expected values for
these samples are included with the
analysis instructions there is no require-
ment for the data to be returned to EPA.
We recommend that participants make
use of this sample repository, to help
increase their overall analytical skills.
The EPA authors E. W. Streib (also the EPA contact, see below). R. G. Fuerst, and
M. P. M/dgett are with the Environmental Monitoring Systems Laboratory,
Research Triangle Park, NC 2771 1.
The complete report, entitled "A Summary of the 1981 EPA National
Performance Audit Program on Source Measurements," fOrder No. PB 83-
252 502; Cost: $10.00, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, V'A 22161
Telephone: 703-487-4650
E. W. Streib can be contacted at:
Environmental Monitoring Systems Laboratory
U.S. Environmental Protection Agency
Research Triangle Park. NC 27711
iVUS GOVERNMENT PRINTING OFFICE 1983-659-017/7177
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Postage and
Fees Paid
Environmental
Protection
Agency
EPA 335
Official Business
Penalty for Private Use $300
PS 0000329
U S ENVIR PROTECTION AGENCY
REGION 5 LIBRAHY
230 S DEARBORN STREET
CHICAGO IL 6060a
------- |