United States Industrial Environmental Research EPA-600/7-80-044
Environmental Protection Laboratory March 1980
Agency Research Triangle Park NC 27711
&EPA POM Source and Ambient
Review and Analysis
Interagency
Energy/Environment
R&D Program Report
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EPA-600/7-80-044
March 1980
POM Source and Ambient
Concentration Data:
Review and Analysis
by
J.B. White and R.R. Vahderslice
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2612
Task No. 86
Program Element No. INE623
EPA Project Officer: John 0. Milliken
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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Abstract
Polycyclic organic matter (POM) is an unregulated class of pollutants
which is a potential candidate for regulatory action as outlined in
Section 122a of the Clean Air Act Amendments of 1977.
Source and ambient concentration data for POM have been reviewed and
analyzed. Based on the literature reviewed, POM data were summarized and the
sampling and analytical techniques were critiqued and evaluated against state-
of-the-art technology. The objective was to determine the scientific and
engineering credibility of a previously established POM data base by an evalu-
ation of the sampling and analytical techniques employed. POM is an unregu-
lated class of pollutants which is a potential candidate for regulatory action
as outlined in Section 122a of the Clean Air Act Amendments of 1977.
It can be concluded that sampling techniques contain uncertainties that
limit the usefulness of these data in an environmental assessment of POM.
These uncertainties include the possibility of the incomplete capture of POM
during emission sampling, the chemical degradation of the collected sample
during both emission source and ambient sampling, and the unproven reliability
of benzo(a)pyrene as an indicator of total POM from emission sources or in
ambient media.
The uncertainty may be compounded by losses during analysis. Also, since
it is not feasible to quantify all the POM which may be present in an environ-
mental sample, the number of POM reported will reflect the scope of the ana-
lytical strategy and the limitations of the analytical technique employed.
Existing POM data are sufficient, however, to document its source dependence
and variability, as well as to verify its occurrence in air, soil, and water.
11
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TABLE OF CONTENTS
Page
Abstract ii
LIST OF FIGURES v
LIST OF TABLES vi
ABBREVIATIONS AND SYMBOLS viii
ACKNOWLEDGMENTS ix
1.0 INTRODUCTION 1
2.0 SUMMARY 2
REFERENCES CITED FOR SECTION 2.0 6
3.0 SAMPLING FOR POLYCYCLIC ORGANIC MATTER 7
3.1 DIRECT EMISSION SOURCE SAMPLING 7
3.2 INDIRECT EMISSION AND AMBIENT AIR SAMPLING .... 12
3.3 WATER SAMPLING 21
3.4 SOIL SAMPLING 22
3.5 STORAGE 22
REFERENCES CITED FOR SECTION 3.0 23
4.0 ANALYTICAL TECHNIQUES 27
4.1 EXTRACTION 30
4.2 CONCENTRATION 30
4.3 ENRICHMENT 30
4.4 RESOLUTION 32
4.5 IDENTIFICATION 33
4.6 QUANTIFICATION 34
REFERENCES CITED FOR SECTION 4.0 37
iii
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TABLE OF CONTENTS (Continued)
Page
5.0 DATA SUMMARY 41
5.1 POM IN THE ATMOSPHERE 42
5.2 POM IN THE AQUATIC ENVIRONMENT 50
5.3 POM IN SOIL AND GROUNDWATER 57
5.4 POM IN THE FOOD PATH TO MAN 61
REFERENCES CITED FOR SECTION 5.0 66
APPENDIX A - LEVELS OF POM REPORTED IN AMBIENT MEDIA A-l
REFERENCES - B(a)P IN URBAN AIR A-5
REFERENCES - POM IN URBAN AIR A-18
REFERENCES - POM IN RURAL AIR A-23
REFERENCES - POM IN WATER A-30
REFERENCES - POM IN SOIL A-38
APPENDIX B - BIBLIOGRAPHY B.-|
iv
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LIST OF FIGURES
Figure Page
4-1 A Structural Comparison of 7,12-Dimethylbenz(a)anthracene,
Benz(a)anthracene, Chrysene, and Triphenylene 32
A-l Ambient Concentration of Benzo(a)Pyrene in Urban Air in
yg/1000 m A-2
A-2 Ambient Concentration of POM in Urban Air in yg/1000 m3 . . . . A-8
A-3 Ambient Concentration of POM in Rural Air in yg/1000 m3 . . . . A-21
A-4 Ambient Concentration of POM in Various Forms of Water in
yg/x, A-24
A-5 Ambient Concentration of POM in Various Soil Types in yg/kg . . A-31
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TABLE OF CONTENTS (Continued)
Page
5.0 DATA SUMMARY 41
5.1 POM IN THE ATMOSPHERE 42
5.2 POM IN THE AQUATIC ENVIRONMENT 50
5.3 POM IN SOIL AND GROUNDWATER 57
5.4 POM IN THE FOOD PATH TO MAN 61
REFERENCES CITED FOR SECTION 5.0 66
APPENDIX A - LEVELS OF POM REPORTED IN AMBIENT MEDIA A-l
REFERENCES - B(a)P IN URBAN AIR A-5
REFERENCES - POM IN URBAN AIR A-18
REFERENCES - POM IN RURAL AIR A-23
REFERENCES - POM IN WATER A-30
REFERENCES - POM IN SOIL A-38
APPENDIX B - BIBLIOGRAPHY B-l
iv
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LIST OF FIGURES
Figure Page
4-1 A Structural Comparison of 7,12-Dimethylbenz(a)anthracene,
Benz(a)anthracene, Chrysene, and Triphenylene ......... 32
A-l Ambient Concentration of Benzo(a)Pyrene in Urban Air in
ug/1000 nr .......................... A- 2
A-2 Ambient Concentration of POM in Urban Air in ug/1000 m3 . . . . A- 8
A-3 Ambient Concentration of POM in Rural Air in pg/100Q m3 . . . . A-21
A-4 Ambient Concentration of POM in Various Forms of Water in
A-24
A-5 Ambient Concentration of POM in Various Soil Types in yg/kg . . A- 31
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LIST OF TABLES
Table Page
3-1 CALCULATED EQUILIBRIUM VAPOR CONCENTRATIONS IN yg/1000 m3 FOR
POM UNDER VARYING TEMPERATURE CONDITIONS 10
3-2 COMPARISON OF TOTAL POM COLLECTION TECHNIQUES: EPA METHOD 5 VS.
MODIFIED EPA METHOD 5 EMPLOYING A SORBENT RESIN 10
3-3 B(a)P ON PARTICULATES OF VARYING SIZE 13
3-4 VAPOR PRESSURE FOR SEVERAL POM AT 25°C 13
3-5 DEGRADATION OF POM ON SMOKE SAMPLES UNDER VARIOUS TEST CON-
DITIONS (yg/100 nT) 17
3-6 VAPOR PHASE POM: COLLECTION CHARACTERISTICS OF STANDARD HIGH
VOLUME SAMPLER BACKED BY SORBENT RESINS 19
3-7 VAPOR PHASE POM: COLLECTION EFFICIENCY OF 1.0 ym FILTER BACKED
WITH A POLYURETHANE FOAM PLUG (ng/1000 m3) 19
3-8 POM LOSSES AS A RESULT OF THE STORAGE OF UNEXTRACTED SMOKE
SAMPLES 20
3-9 VARIATIONS IN POM HALF LIFE UNDER DARK CONDITIONS AT DIFFERENT
LEVELS OF ATMOSPHERIC OXIDANTS (ozone) 20
4-1 SCHEMES FOR POM ANALYSIS 28
4-2 POM ANALYSIS USING DIFFERENT ANALYTICAL TECHNIQUES 29
4-3 DETECTION DEVICES FOR POM ANALYSIS 35
5-1 ESTIMATED BENZO(a)PYRENE EMISSIONS IN METRIC TONS/YR 43
5-2 B(a)P EMISSIONS FROM HEAT GENERATION AS A CONSEQUENCE OF COM-
BUSTION EFFICIENCY 44
5-3 POM CONCENTRATIONS REFLECTING THE DOMINANCE OF A SINGLE SOURCE . 46
5-4 ANNUAL AMBIENT B(a)P CONCENTRATIONS AT NASN STATIONS (yg/m3) . . 47
5-5 VARIATIONS IN SEASONAL AVERAGES OF B(a)P CONCENTRATIONS .... 49
5-6 HALF-LIVES IN HOURS FOR DEGRADATION OF POM BY MAJOR ENVIRON-
MENTAL OXIDIZERS 49
vi
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LIST OF TABLES (Continued)
Table Page
5-7 HALF-LIVES OF SELECTED POM IN SIMULATED DAYLIGHT, SUBJECTED
TO VARYING CONCENTRATIONS OF ATMOSPHERIC OXIDANTS (ozone) ... 51
5-8 POLYCYCLIC ORGANIC COMPOUNDS IDENTIFIED IN SINGLE AMBIENT AIR
SAMPLE 52
5-9 POM IDENTIFIED IN SEVERAL U.S. SURFACE WATERS (yg/a) 54
5-10 DECOMPOSITION OF POM BY BACTERIA FOUND IN NATURAL WATER SYSTEMS 54
5-11 VARIATION OF B(a)P CONCENTRATION WITH DISTANCE FROM SOURCE
EMISSION 59
5-12 POM IDENTIFIED IN GROUNDWATER 60
5-13 POM LEVELS FOUND ADJACENT TO A STEEL WASTE SANITARY LANDFILL . 60
5-14 POM DETECTED IN A TYPICAL U.S. TOTAL DIET COMPOSITE SAMPLE . . 65
VII
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ABBREVIATIONS AND SYMBOLS
B(a)P - Benzo(a)pyrene
B(e)P - Benzo(e)pyrene
BSO - Benzene soluble organics
- Electron capture device
- Equilibrium vapor concentration
- Flame ionization detection
GC - Gas chromatography
GC/FID - Gas chromatography/Flame ionization detection
GC/MS - Gas chromatography/mass spectrometry
HPLC " High pressure liquid chromatography
LC - Liquid chromatography
MS - Mass spectrometry
PAH - Polynuclear aromatic hydrocarbons
PNA - Polynuclear aromatics
PNAH - Polynuclear aromatic hydrocarbons
POM - Polycyclic organic matter
SASS - Source analysis sampling system
- Thin layer chromatography
" Total suspended particulate
UV - Ultraviolet
~ X-ray excited optical luminescence
SL = liter
m = cubic meters
ng = nanograms
ug = micrograms
vi i i
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ACKNOWLEDGMENTS
We gratefully acknowledge the valuable contributions made to this report
by the following individuals: Dr. Charles Lochmuller, Dr. F. 0. Mixon, Dr. D.
S. Wagoner, Dr. E. D. Estes, Dr. J. M. Harden, Ms. Carrie Kingsbury, Mr. Ben
Carpenter, and Ms. Frances Scott. In particular, we thank Ms. Jocelyn Watson
who prepared the graphs.
We especially thank Dr. John Milliken, the EPA project officer, who
provided guidance and constructive comments throughout the project.
IX
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1.0 INTRODUCTION
The Clean Air Act Amendments of 1977, Section 122a, directed the Admini-
strator of the Environmental Protection Agency (EPA) to review all available
relevant information and determine whether or not emissions of "... polycyclic
organic matter into the ambient air will cause, or contribute to, air pollu-
tion which may reasonably be anticipated to endanger public health." An
affirmative determination would require POM to be listed under one of the
following sections: Section 108 (a)l, Air Quality Criteria and Control Tech-
niques, Section 112(b)(l)(a), National Emission Standards for Hazardous Air
Pollutants, or Section lll(b)(l)(a), Standards of Performance for New Station-
ary Sources.
The determination of whether to list POM and the selection of the most
suitable control option involves a thorough assessment of possible health
effects, emission sources, and ambient air levels. The procedure requires, as
a first step, a summary of the existing situation. Such an assessment should
include an evaluation of the state-of-the-art in monitoring and control tech-
nology and an estimate of the environmental impact. As pointed out by the
August 3, 1978 Science Advisory Board report on POM, the environmental assess-
ment of POM requires an in-depth analysis of the scientific credibility of the
data. It is the purpose of this report to evaluate the sampling and analyt-
ical methodologies employed in the determination of ambient levels and source
emissions of POM and to determine the utility of the data in the EPA decision-
making process.
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2.0 SUMMARY
A large source of data reflecting an international interest in the occur-
rence of polycyclic organic matter in air, soil, and water has been created
(see Appendix A). Polycyclic organic matter (POM) is a generic term applied
to a group of fused-ring organic compounds, members of whictvhave been proven
to be animal carcinogens. In general, POM refers to those organic compounds
consisting of two or more fused aromatic rings. The rings may either be
comprised totally of carbon atoms or may contain hetero atoms of nitrogen,
oxygen, and sulfur, in addition to other ring substituents.
POM is subdivided into two categories on the basis of the atomic constit-
uents of the ring structures. These categories are polycyclic aromatic hydro-
carbons and heterocyclic polynuclear aromatics. The former category contains
those compounds with all-carbon skeletons. Alternative names for this cate-
gory include polynuclear aromatic hydrocarbons (PNAH), polynuclear aromatics
(PNA), and aromatic hydrocarbons. The latter category, the least studied of
the two, includes the aza arenes, the oxa arenes, and the thia arenes.
Due to the large possible number of ring combinations and substituent
permutations, the theoretical number of POM can run into the millions. How-
ever, only 249 were listed in the 1962 Bureau of Mines Bulletin on coal car-
bonization products (1), and only approximately 100 have been identified in a
single ambient air sample (2).
Analytical techniques involved in the quantification of POM have evolved
from simple fluorescent techniques to computerized gas chromatography/mass
spectrometry (GS/MS). Most techniques have yielded conservative data which
are thought to be correct within an order of magnitude. The main advances in
analysis have been concerned with improved resolution increasing the number of
identifiable compounds.
Sampling technology has been slower to advance. Historically, sampling
for atmospheric polycyclic organic matter has been limited to the collection
of particulates on filter surfaces where losses of POM can occur through the
desorption of POM from particulate captured on the filter surface, and through
chemical rearrangement. The rate of this loss varies from compound to com-
pound and with the ambient concentrations of other oxidants. Recent studies
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have shown that benzo(a)pyrene [B(a)P] may be one of the more reactive forms
of POM (3). Its seemingly facile reaction with atmospheric pollutants as well
as with filter surfaces casts doubt on its usefulness as an indicator of total
POM.
During direct emission source sampling, losses can increase significantly
as the concentration of oxidants and temperature at which the sample is taken
increases. Emission estimates based on particulate sampling techniques have
been shown to be low by a factor of from 2 to 200 (4). Sampling techniques
employing impingers and solvent filled bubble trains offer substantial im-
provement over particulate sampling. Advanced techniques using sorbent resins
to trap the vapor phase of POM have increased accuracy by a factor of 2 to 200
over particulate sampling alone, but still do not account for POM losses
through chemical rearrangement (4). Emission estimates still may be low by as
much as a factor of 2 to 3.
Because uncertainties in sampling and analytical techniques may in some
cases have significant impact on reported data, caution should be exercised in
the interpretation and use of such data. Insufficient information concerning
geography, meteorology, distribution and type of potential sources, as well as
control technology, if any, also restricts reliable comparisons of data. In
addition, the apparent reactivity of B(a)P under normal sampling conditions
coupled with the variability of B(a)P/POM ratios in ambient mixtures and the
declining trend in the measured B(a)P concentrations makes the use of B(a)P as
a reliable indicator of total POM highly questionable. It is therefore a
conclusion of this study that historical data be viewed as being semiquanti-
tative with regard to their utility in EPA decisionmaking.
The following conclusions may also be drawn regarding POM in the environ-
ment. POM as found in the environment is largely the result of incomplete
combustion. Natural sources of POM include forest fires and volcanoes. These
sources, coupled with the possibility of bacterial synthesis, can be consid-
ered to produce a natural background of POM. Anthropogenic sources are a
consequence of the direct combustion of coal, petroleum, petroleum deriva-
tives, and wood for industrial applications, power generation, transportation,
and domestic space heating. Additional man-made sources include burning coal
refuse banks, incineration, agricultural burning, and prescribed forest burn-
ing.
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POM is emitted to the atmosphere as a component of particulate matter.
The atmosphere serves as a reservoir for storage and decomposition as well as
a medium for transport. Ultimately atomspheric POM is either decomposed or
deposited on exposed surfaces. POM deposited on soil may be decomposed, taken
up by plants, leached into the groundwater, or washed into waterways. POM
enters the aquatic environment through direct atmospheric deposition, runoff,
and industrial effluents. It may be degraded, buried in sediments, or trans-
ported to the ocean. (Measured ambient POM concentrations are contained in
Appendix A.)
POM is removed from the environment through a variety of mechanisms.
Photochemical degradation is probably the chief source of destruction of POM
in the aquatic and atmospheric environment. Chemical oxidation is significant
near the source but decreases in importance as atmospheric concentrations of
oxidants decrease. Microbial degradation appears to dominate in soil.
An evaluation of the literature indicates that efforts should be made to:
(1) determine the relative abundance of POM in the vapor state under ambient
conditions, (2) establish the rates and the mechanism by which degradation
occurs during both ambient and source sampling, and (3) establish and expand
the applicability of a single POM or a group of POM as an indicator for total
POM on a source-by-source basis.
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REFERENCES CITED FOR SECTION 2.0
1. Anderson, H. C., and W. R. K. Wu. Properties of Compounds in Coal Carboni-
zation Products. U.S. Department of Interior, Bureau of Mines, Bulletin
606.
2. Lao, R. C., R. S. Thomas, H. Oja, and L. Dubois. 1973. Application of a
Gas Chromatograph-Mass Spectrometer-Data Processor Combination to the
Analysis of the Polycyclic Aromatic Hydrocarbon Content of Airborne
Pollutants. Anal. Chem. 46(6): 908-915.
3. Katz, M., C. Chan, and H. Tosine. 1978. Relationship Between Relative
Rates of Photochemical and Biological Oxidation of Polynuclear Aromatic
Hydrocarbons and Their Carcinogenic Potential. Third International
Symposium on Polynuclear Aromatic Hydrocarbons, Columbus, OH, October 25-27.
4. Jones, P. W., R. D. Giammar, P. E. Strup, and T. B. Stanford. 1976. Effi-
cient Collection of Polycyclic Organic Compounds. Env. Sci. and Tech.
10(8): 806-810.
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3.0 SAMPLING FOR POLYCYCLIC ORGANIC MATTER
The first step in determining the magnitude of a potential health or
environmental hazard is the collection of a qualitatively and quantitatively
representative sample. Regardless of the accuracy and precision of the subse-
quent analytical technique, the data generated, and ultimately, the decisions
based on those data will be no more reliable than the sample collected for
analysis. Sample collection is particularly significant when working at trace
levels such as with polycyclic organic matter.
After surveying the literature it may be concluded that:
1. Emission factors based on particulate sampling techniques incorpora-
ting sorbent resins in the sampling train are quantitatively more accurate
than those relying solely on particulate collection. Accuracy may be improved
by as much as a factor of 2 to 100 depending upon the emission source.
2. High volume samplers have been demonstrated to be an accurate method
for sampling total suspended particulates in the atmosphere. However, present
ambient particulate sampling methods do not take into consideration potential
for loss of POM in the vapor phase, the desorption of POM from particulate
matter, or molecular rearrangements of POM on the particulate surface. Conse-
quently, the accuracy of the various techniques may vary from sample to sample
by as much as a factor of 2.
3. Present water sampling methods utilizing sorbent resins appear to be
quantitatively accurate for low levels of POM.
4. No data exist by which to evaluate soil sampling techniques. How-
ever, those techniques which avoid contamination appear to be quantitatively
accurate.
3.1 DIRECT EMISSION SOURCE SAMPLING
It is widely accepted that POM results from the incomplete combustion of
organic matter in a reducing atmsophere and is found, as such, in association
with emissions from combustion sources. These emission sources are generally
categorized as either mobile or stationary (1). Mobile sources are related to
transportion. Their emissions are comprised of diesel and gasoline exhausts.
Stationary sources pertain to heat and power generation, refuse burning, and
industrial applications.
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The collection techniques employed in sampling these sources can be
categorized as either direct or indirect, depending on the characteristics of
the individual source. Mobile sources and the ducted products of large-scale
stationary sources lend themselves to direct sampling techniques. In general,
these sources are characterized by high temperature, high gas velocity, and in
some cases heavy particulate loading (2).
A number of systems have been designed for use in direct emission source
sampling. A basic component of these systems is the inclusion of a device to
trap particulates. Since the amount of particulate matter collected is a
function of design and differs from system to system, EPA Method 5 has been
adopted as a standard for particulate analysis (2) and has become the basis of
much of the POM data.
In order to obtain a representative sample by Method 5, a point must be
selected in the duct that is free of obstructions and projections that might
cause undesirable turbulence. Temperature, particulate mass distribution, and
average gas velocity are determined, and a sample is drawn at the same veloc-
ity as the gas stream being sampled, i.e., isokinetically, in order to prevent
particulate bias (2). The sample is pulled through a glass-lined, heat resis-
tant probe to a dry collection box and passed through a filter. The filter is
rated at 99.7 percent efficiency for 0.3 (jm dioctyl phthalate particles and is
relatively inert to chemical reaction. The temperature in both filter and
probe are kept above 121°C to prevent condensation. Particulate matter, and
any associated POM, is defined to be the material removed during cleanup from
the filter and from the walls of the probe and nozzle (2).
Measuring POM concentration by means of particulate sampling procedures
assumes that the POM is either in the form of condensed particulates or ad-
sorbed onto condensed particulate at the sampling temperature. However,
depending on the temperature and the nature of each source, POM at the sam-
pling point is likely to exist as a vapor or a liquid, as well as being
adsorbed onto a solid substrate. At the sampling temperature prescribed by
Method 5, the concentration of POM in the vapor phase may be significant.
PuPP et aJL (3) theorized that direct particulate sampling for flue gases and
vehicle exhausts would miss a concentration of POM equal to the equilibrium
vapor pressure concentration (EVC) of the pollutant (3). The EVC is defined
as the concentration of compound present as a vapor in equilibrium with that
8
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compound as a solid. The EVC is temperature dependent, and for a pure com-
pound it increases with increasing temperature (see Table 3-1).
Gas velocity as well as temperature may affect the vapor state of POM by
influencing the vaporization rates of the POM already trapped on the filter
surface. High temperatures increase the rate of vaporization resulting in
greater loss of POM per unit volume of emission sampled at lower gas veloc-
ities than at higher velocities (3). These factors can become significant
where POM contained in the fractionated particulate and in the material ad-
hering to the nozzle, probe, and filter surface are exposed during long peri-
ods of sampling to elution by hot exhaust gases. Losses have been recorded by
Commins and Lawther (4) for pure benzo(a)pyrene deposited on a glass fiber
filter and subjected to various flows of laboratory air at 100°C. At 0.3
liters per minute for 4 hours, approximately 60 percent of benzo(a)pyrene was
recovered from the filter surface. When the temperature of the air was eleva-
ted to 170-200°C, total loss of benzo(a)pyrene was reported after 5 minutes of
treatment.
A substantial loss of POM could, therefore, be anticipated when sampling
for long periods of time at stack temperatures or at the temperature pre-
scribed by Method 5. However, adsorption onto a solid appears to modify the
rate of loss. Rondia (5) measured the loss of several types of POM deposited
onto a granulated carbon surface and exposed to air currents at various tem-
peratures. Substantial losses of the higher weight POM occurred at 100°C, and
after 20 minutes at 130°C, only 59 percent of the total benzo(a)pyrene was
recoverable. The rate of loss increased with decreasing particulate size and
increasing temperature and air velocity.
Various attempts have been made to minimize POM losses by trapping the
vapors in impingers, solvent filled bubblers, and cold traps (1,2). The most
recent innovation was developed by Jones et al. (6). Method 5 was tested
against a modified version of Method 5 consisting of a nozzle, probe, filter
and cooled resin cartridge (TENAX) to trap organics in the vapor phase. The
results indicated that total POM as measured by Method 5 could be low by as
much as two orders of magnitude, depending on the fuel source (see Table 3-2).
The closest agreement in measurements showed Method 5 results to be low by a
factor of 2.5.
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TABLE 3-1. CALCULATED EQUILIBRIUM VAPOR CONCENTRATIONS IN
pg/1000 m3 FOR POM UNDER VARYING TEMPERATURE CONDITIONS
Pyrene
Ben7.(a)anthracene
Benz(a)pyrene
Benz(e)pyrene
Benzo(k)fluoranthene
Benzo(ghi )perylene
Coronene
-10°C
580
3.4
0.15
0.15
0.013
1.8 x 10"3
1.8 x 10"5
25°C
7.6 x 104
7.7 x 101
7.8 x 101
1.6
30°C
1.40 x 105
2.8 x 103
1.6 x 102
1.6 x 102
3.0 x 101
3.4
O.C58
50°C
9.0 x 105
1.8 x 103
1.8 x 103
48
93°C
6.3 x 107
4.3 x 105
4.3 x 105
1.8 x 104
130°C
9.4 x 108
1.4 x 107
1 .4 x 107
7.6 x 105
Reference 3
TABLE 3-2. COMPARISON OF TOTAL POM COLLECTION TECHNIQUES:
EPA METHOD 5 VS. MODIFIED EPA METHOD 5 EMPLOYING A SQRBENT RESIN
Source
Oil fired boiler
(Residual oil]
Oil fired boiler
(Residual oil)
Burner
(Natural gas)
Carbon black manufacturing
operation (effluent)
Total POM (u5/m3)
collected by Method 5 .
4.2
0.15
0.55
56.5
Total POM (ug/m3)
collected by modi-
fied Method 5
55.2
12.2
1.3
124
Reference 6 (Acaptcd)
10
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In order to accommodate the phased approach/cost effective methodology of
the EPA environmental assessment program at the Industrial Environmental
Research Laboratory, Research Triangle Park, North Carolina, a new high-
volume, particulate sampling train has been developed along the lines proposed
by Jones et aj_. (6). The Source Assessment Sampling System (SASS) employs
triple cyclones and a glass fiber filter all maintained at 205°C for particu-
late fractionation and particulate capture. This is followed by a sorbent
resin cartridge maintained at 20°C for capture of organics in the vapor
phase (7). The resin, XAD-2, has been selected for use in the SASS train
because it shows a greater volumetric and weight capacity than does TENAX (8).
POM quantifications based on SASS train sample collections are not yet
available for evaluation. Based on evaluations of the collection character-
istics of the sorbent resin alone (8), it is not unreasonable to expect quan-
titative recovery of POM in both the particulate and the vapor stages. How-
ever, potential losses as a result of chemical oxidation of POM adsorbed on
the particulate, adsorbed on the resin surface, or present in the vapor phase
have not been evaluated.
The extent of losses through rearrangement has not been clearly estab-
lished. Jones et al. (6) compared the results from POM analysis from samples
taken by Method 5 with a sorbent resin after the impinger system, and by
Method 5 with the resin situated immediately after the filter ahead of the
impinger system. EPA Method 5 with the adsorbent located after the impinger
3
system collected 1.4 pg/m of POM and the system employing a filter immedi-
ately followed by the adsorbent collected 12.2 M9/m POM. The difference of
approximately one order of magnitude between the two resin collection tech-
niques was attributed to losses via chemical reactions with oxidants produced
by the fuel.
In a series of automotive exhausts sampling validation experiments,
Spindt (9) examined several variations in the filter/sorbent resin sampling
system. In one test, using a sampling configuration similar to Jones' method,
B(a)P was both injected into the sampling line and deposited in the sorbent
trap. A sample of an automotive exhaust gas was drawn through a probe main-
tained at 176.7°C followed by a glass fiber filter and a resin cartridge at
4.5°C. Less than 50 percent of the B(a)P injected into the system and only
11
-------
20 percent of that deposited on the sorbent resin was recovered. When the
14
system was modified to include an air dilution of the sample, and C B(a)P
was injected into the system, 50 percent of the radioactive tracer was recov-
ered from the lines and filters, 2.2 percent was found in the sorbent trap,
and 21.5 percent was recovered as degraded products at various points in the
system. The remaining B(a)P was not detected. Spindt concluded that most of
the injected B(a)P reacted with constituents of the exhaust gas (9).
Factors influencing the rate of degradation appear to be the concentra-
tion of POM in the vapor phase (9), the concentration of oxidants (10), the
reactivity of the specific POM, and the spectra and intensity of electro-
magnetic radiation (11). Since limited information exists on the nature and
concentration of POM degradation products produced during a typical sampling
run, it is impossible to accurately quantify the loss of POM attributable to
chemical rearrangement. However, it appears loss can sometimes exceed
50 percent, or a factor of 2, for total POM as measured by benzo(a)pyrene.
3.2 INDIRECT EMISSION AND AMBIENT AIR SAMPLING
The physical state of POM in ambient air is determined in part by the
amount of particulate generated by the source. Natusch and Tomkins (12)
contend that the extent of POM adsorption onto particulate is proportional to
the frequency of collision of POM molecules with available surface area,
resulting in preferential enrichment of smaller diameter particulates. In
areas of high particulate concentrations, such as the stack of a fossil fuel
power plant, one would expect nearly quantitative adsorption of the POM onto
particulates. As particulate concentration decreases, as in internal combus-
tion engines, one would expect to find more POM in the condensed phase. In
general, the largest concentration of POM per unit of particulate mass will be
found in the smaller diameter aerosol particulates. As seen in Table 3-3,
tests utilizing particulate sizing techniques on urban aerosols have demon-
strated that as much as 75 percent of the total benzo(a)pyrene adsorbed onto
particulate matter can reside on particulates with diameters less than 2.3
Mm (15,16,17,18).
Sampling for POM in ambient air and from indirect emission sources has
relied heavily upon the collection of the suspended particulates. The main-
12
-------
TABLE 3-3. DISTRIBUTION OF B(a)P ON PARTICULATES OF VARYING SIZE
Ref.
15
16
17
18
Location
Green Bay, WI
wg/1000 m3
% distribution
Toronto (avg. 4 sites)
ug/1000 m3
% distribution
Ontario
ug/1000 m3
% distribution
Pittsburgh
ug/1000 m3
% distribution
Particle size in pM
<1.1 1.1 2.0 3.3 4.6 7.0 <7.0
2.9
29%
0.077
44%
1.08
85%
1.1
11%
0.047
27%
1.2 2.0 2.7
123 20% 27%
0.050
29%
0.16
15%
11.4 . 0.5
96% . 4'i
TABLE 3-4. VAPOR PRESSURE~FOR SEVERAL POM AT 25°C
Compound
Anthracene
Phenanthrene
Benzo(a)anthracene
Pyrene
Benzo(a)pyrene
Benzo(e)pyrene
Benzo(k)fluoranthene
Benzo(ghi)perylene
Coronene
Number of rings
3
3
4
4
5
5
5
6
7
Vapor pressure in Torrs
1.95 x 10"4
6.80 x 10"4
1.10 x 10"7
6.85 x 10"7
5.49 x 10"9
5.54 x 10"9
-11*
9.59 x 10 "
1.01 x 10"10
1.47 x 10"12
*Benzo(k)fluoranthene is a non-alternant compound containing a single
resonant pentacyclic ring structure.
Reference 3 (Adapted)
-------
stay of the National Air Surveillance Network (NASN) program, indirect emis-
sion sampling methods, and many individual research projects has been the high
volume sampler. The sampler consists of a filter assembly and a vacuum pump
housed under a cover shelter. Air is drawn through the filter at a flow rate
of 40 to 60 CFM (1.13 to 1.70 m3/min). Particulate matter is entrained on the
filter surface through impaction, interception, adsorption, electrostatic
deposition, or infiltration (19).
The accuracy of the high volume sampler depends upon the consistency of
the flow rate. Filter clogging can substantially reduce the flow rate and
cause as much as 50 percent deviation from the true particulate average.
However, when operated according to standard methods, the high volume sampler
has repeatedly proven its reliability. The precision of off-the-shelf sam-
plers testing the same air space has been demonstrated to be + 5 percent at
the 95 percent confidence level (20,21,22).
The high volume sampler samples with nearly 100 percent efficiency for
particulate matter greater than 0.3 (jm in diameter. When operated at the
maximum flow rate, it obtains a representative portion of the atmosphere with
a suspended particulate loading as low as 0.1 pg/m3 (19).
As in emission source sampling, the location of the sampling point is
crucial in both indirect emission and ambient sampling. A site should be
selected with regard to the spatial distribution of the emission sources, the
population density, the size of the area, the topography, and prevailing
meterological conditions (23). A sample taken from a single point cannot
necessarily be considered representative of an area (24,25). Several sites
must be selected to compensate for topography and meteorology, as well as to
delineate the geographical population variability.
The frequency of sample collection is also important. The influence of
meteorology,.the effect of topography, and the variations in the productivity
of the sources combine to determine the most desirable sampling frequency.
Daily samples yield the most accurate information. The accuracy decreases as
the time interval between samples is increased. For particulate sampling, the
minimum frequency of 24 hours once every 6 days has been recommended for an
initial air quality survey. This would yield approximately a + 90 percent
variability from the annual mean at the 70 percent confidence level (23). The
14
-------
extent to which this can be applied to POM sampling is not known. Although
POM has been shown to correlate with the benzene soluble organic fraction
(BSO) of the total suspended particulate (TSP), a correlation between the BSD
and TSP has not been established. It has not been demonstrated, therefore,
that a statistically significant particulate sampling program can yield sta-
tistically significant POM data.
The actual applicability of filter samplers in general to POM sampling is
subject to question. As in direct emission source sampling, it appears that
losses of POM might occur as a result of desorption, failure to collect vapor-
phase POM, and chemical rearrangements of POM on the filter surface. Ron-
dia (5) studied desorption and concluded that such losses were related to the
vapor pressure of the individual POM, the physical state of the POM, i.e.,
condensed liquid versus adsorbed solid, and the velocity of air and air tem-
perature during sampling.
Vapor pressures have been calculated for only a few types of POM, but
have proven to be significant (see Table 3-4). A POM mixture placed on filter
paper and allowed to stand for 30 days at room temperature showed substantial
losses of fluoranthene and pyrene, approaching 75 percent of the initial
concentration of each. Some loss of benzo(a)pyrene was recorded but no loss
was demonstrated for 1,12-benzoperylene (5).
The effect of the physical state on POM stability has received limited
attention. Volatility has been theorized to decrease as a consequence of POM
being trapped in the interior of the particulate during particulate forma-
tion (9). For pure POM mixtures adsorbed onto surfaces, volatility has been
shown to increase with increased surface area. Rondia (5) demonstrated that
for a fixed set of temperature and air flow conditions, the volatilization
decreased with increasing particulate size; higher losses were recorded for
fine smoke particulates than for granulated (100 mesh) carbon particles.
Under ambient sampling conditions, it appears that POM losses are less
dependent upon temperature variations than upon variations in the velocity of
the air passing through the sampled POM. Stenburg et al_. (26) demonstrated
that the difference in POM attributed to temperature variation when collected
from a split exhaust stream—one side cooled to 15.5°C and the other to
32°C--were well within the realm of experimental error. Rondia (5) depos-
15
-------
ited benzo(a)pyrene and 1,12-benzoperylene on a tared dish and subjected them
to temperatures ranging from 100°C to 140°C. Analyses were made every hour
for four hours and only at 140°C did losses of benzo(a)pyrene become substan-
tial. POM contained in smoke particulate was analyzed, and when all other
conditions were held constant and only the temperature was varied from "labo-
ratory conditions" to 50°C, the results showed no significant trends that
could be attributed to temperature losses (5).
Commins (27), however, demonstrated that a substantial loss of POM in a
given sample could be attributed to variations in the velocity of the air
drawn through the sample (see Table 3-5). The effect was summarized by Pupp
et al. (3). He concluded that losses occurring as a consequence of a low-
volume, long-term sampling might approach the equilibrium vapor concentration
of the respective forms of POM. Such losses would be governed by the rate of
sublimation during high volume sampling, and the total loss of POM under such
conditions would be less than that occurring during low volume sampling.
The existence of a POM vapor phase has been postulated by several re-
searchers; however, the extent to which POM is found in the vapor phase under
ambient conditions has not been conclusively determined. It has been theo-
rized by Pupp e_t al. (3), that the EVC of pure POM, such as benzo(a)pyrene, is
significant and that, barring surface adsorption effects, larger quantities of
POM could be found in ambient air than are found associated with particulate
matter.
Miguel and Friedlander (28) attempted to verify this by sampling 6 m of
an urban aerosol (Pasadena, California) with a high volume glass fiber filter
backed by two cold traps in series. Although calculations based upon the EVC
for benzo(a)pyrene indicated that 165 times as much of this POM would be
contained in the vapor phase than in the annual geometric average reported for
Los Angeles, California, none was detected. Since the detection limit of the
thin layer chromatography/spectrophotofluorometric analysis technique employed
in this experiment was 0.05 ng, it was estimated that the amount of B(a)P
3
escaping collection was less than 0.08 ng/m .
Vapor-phase benzo(a)pyrene was also tested for by Commins and Lawther (4)
3
by drawing 81.6 m of filtered urban air over a 30 day period through a Dre-
schel bottle containing pure paraffin as a solvent. Tests for fluorescence at
16
-------
TABLE 3-5. DEGRADATION OF POM ON SMOKE SAMPLES UNDER
VARIOUS TEST CONDITIONS (yg/100 m3)
POM
Fluoranthene
Phenanthrene
Benzo(e)pyrene
Pyrene
Benzo(ghi)perylene
Benzo(a)pyrene
Anthanthrene
Initial
analysis
30.9
14.0
5.8
23.7
6.6
20.0
2.3
Analysis after
3 week
19.5
5.9
7.1
15.6
6.0
19.1
2.5
3 week @
0.3 £/min
7.4
4.1
3.9
3.2
6.3
19.0
1.6
3 week @ 0.3 ,
£/min & 50°CQ
7.2
2.9
5.6
3.4
5.5
16.6
2.0
Reference 27 (Adapted)
Initial analysis of POM contained in smoke sample.
Analysis of unextracted smoke sample after three weeks storage under
laboratory conditions.
Analysis of POM contained on smoke sample held at laboratory temperatures
after 3 weeks of exposure to 0.3 £/min of clean air.
Analysis of POM contained in smoke sample held at 50°C after 3 weeks
exposure to 0.3 £/min of clean air.
17
-------
regular intervals did not produce any evidence of benzo(a)pyrene. Bunn et
aK (29) sampled an urban aerosol using a sorbent resin column in parallel
with a standard high volume sampler. Laboratory analysis of the sample frac-
tion showed that substituted as well as unsubstituted dicyclic POM were col-
lected on the resin, but tricyclic POM and greater were found only in the
particulate fraction (see Table 3-6). In addition, Pellizzari et aJL (30)
using a TENAX column especially designed to sample vapor phase organics re-
ported no forms of POM larger than naphthalene in the vapor phase when sam-
pling urban air.
A distinction should be made between POM in a true vapor state and POM
contained in the smaller diameter aerosol particulates. Krstulovic et a_L
(31) sampled three areas in Rhode Island using a filter backed with a poly-
urethane foam plug. The filter was rated at 98 percent efficiency for par-
ticles £ 1.0 urn. Since efficiency for collecting smaller particulates
decreases with decreasing particulate diameters, significant amounts of POM
were found on the polyurethane plug (see Table 3-7). The results of the test
were inconclusive for demonstrating the presence of POM in the vapor phase.
DeWeist and Rondia (32) sampled for benzo(a)pyrene in a coking region of
Belgium and found substantial seasonal variations even though there was no
apparent change in the productivity of the source. In a series of wintertime
experiments with filters heated from -2°C to 28°C, they were able to duplicate
the seasonal trends in B(a)P. They concluded that those trends were probably
due to volatilization and/or chemical reactions catalyzed by trace metals.
Since the loss of vapor phase POM appears to be negligible when sampling
ambient air at high velocities and at ambient temperatures, the most likely
explanation for the losses appears to be via chemical rearrangement. Lane and
Katz (10) experimented with POM under varying conditions of illumination and
ozone concentrations. Under conditions of zero illumination, which would
duplicate the illumination levels encountered inside a high volume sampler,
the half-life of three POM was found to decrease substantially with increasing
concentrations of ozone (see Table 3-8). Benzo(a)pyrene, which has been used
as the indicator for total POM showed particularly significant losses. The
initial rate of disappearance was extremely rapid and was theorized to be
dependent on the exposed surface area. Multilayering on the particle and the
accumulation of POM in the interstices of the particulates modified the rate
of disappearance to 1.5 percent per hour after the initial rapid reaction.
18
-------
TABLE 3-6. VAPOR PHASE POM: COLLECTED CHARACTERISTICS OF STANDARD
HIGH VOLUME SAMPLER BACKED BY SORBENT RESINS
Compound
Naphthalene
Methyl naphthalene
Anthracene
Fluoranthene
Pyrene
Benzofluorene
Methyl chrysene
Benzofluoranthene
Benzpyrene
Tenax-GC
X
X
ND
ND
ND
ND
ND
ND
ND
XAD-2
X
X
ND
ND
ND
ND
ND
ND
ND .
Hi-Vol Participate
ND
ND
X
X
X
X
X
X
X
Reference 29
X - POM detected.
ND - POM not detected.
TABLE 3-7. VAPOR PHASE POM: COLLECTION EFFICIENCY OF 1,0 ym FILTER
BACKED WITH A POLYURETHANE FOAM PLUG (ug/1000 nT)
Compound
Naphthalene
Phenanthrene
Fluoranthene
Benzo(a)pyrene
1 ,2,3,4-Dibenz-
anthracene
Providence3
Filter Plug
248
337.7
1,249.8
29.7
806.4
100.7
5.6
281.3
-
3,709.2
Kingston
Filter Plug
31.1
46.6
-
-
102.5
27.9
4.9
165.4
3.5
-
Narragansett Bayc
Filter Plug
3.18
4.9
159.4
4,2
-
4.91
6.4
-
-
29.7
Reference 31
aProvidence, RI - industrialized area
Kingston, RI - urban area
cNarragansett Bay, RI - remote area
19
-------
TABLE 3-8. VARIATIONS IN POM HALF LIFE UNDER DARK CONDITIONS
AT DIFFERENT LEVELS OF ATMOSPHERIC OXIDANTS (Ozone)
Ozone ppm
0.19
0.70
2.29
B(a)P
0.62
0.4
0.3
B(b)F
52.7
10.8
2.9
B(k)F
34.9
13.8
3.3
Reference 10 (Adapted)
TABLE 3-9.
POM LOSSES AS A RESULT OF THE STORAGE OF
UNEXTRACTED SMOKE SAMPLES
Compound
Fluoranthene
Pyrene
Benzo(a)pyrene
Benzo(e)pyrene
Anthanthrene
Benzo(ghi)perylene
Coronene
Concentration (yg/g ot smoke;
Initial
225
328
111
71
70
252
142
1 yr later
18
38
76
55
55
226
140
Percent loss
92
88
32
23
21
10
1
Reference 27 (Adapted)
20
-------
Later work by Katz et al_. (33) using simulated smog conditions in which
S0x and N0x were drawn through a filter using benzo(a)pyrene, demonstrated
that the degree of degradation was greater with NO than it was with SO . The
X X
rate was greater still when the two pollutants were combined in the presence
of ozone.
It appears possible, therefore, for the chemical decomposition during
ambient sampling to exceed 35 percent over a 24-hour period (10). Korfmacher
et al_. (11) showed that such losses for benzo(a)pyrene might run as great as
50 percent. The rate could be higher depending upon the substrate surface and
the ambient oxidant concentration. Consequently, it is not unreasonable to
expect sample concentrations to be low by as much as a factor of 2 due to
chemical reactions involving POM entrained on the filter.
3.3 WATER SAMPLING
POM is found in water in both solid and liquid fractions. Sampling
techniques for water-borne POM have varied from grab sampling to the use of
sorbent resins. Grab samples must be viewed with suspicion due to the adsorp-
tion of POM onto container surfaces. The POM loss under these conditions is
dependent on the POM concentration and composition of the container. Losses
as high as 77 percent for benzo(ghi)perylene in glass have been reported (34).
Sorbents such as TENAX-GC (35), XAD-2 (36,37), and polyurethane foam
(34,38) have been tested and shown to be capable of quantitative recovery for
B(a)P and other forms of POM at low concentrations spiked into water samples.
A field monitoring unit has been proposed by Basu and Saxena (34) that employs
polyurethane foam plugs. The monitor consists of a pumping unit, a thermo-
static water circulator, polyurethane foam columns, a temperature sensor, and
a flow meter. When operated at 62 + 2°C and at a flow rate of 240 m£/min, it
has demonstrated an ability to quantitatively recover POM in distilled water,
tapwater, and raw river water (38).
3.4 SOIL SAMPLING
POM in soil is found in association with decaying organic matter, micro-
organisms, or bound to mineral surfaces. Typically samples are collected with
coring or spading techniques. There are no indications that special tech-
niques other than those which prevent sample contamination are required.
21
-------
Although it is not possible to accurately evaluate soil sampling methodologies
at this point, it would appear that current soil sampling allows quantitative
recovery of POM. Errors, however, could be anticipated in the extraction of
POM tightly bound to soil particles prior to analysis.
3.5 STORAGE
Organic compounds in general are subject to losses due to photodecompo-
sition, adsorption, vaporization, thermal decomposition, and chemical reaction
during storage (39). Substantial losses have been demonstrated for POM when
held for a year prior to analysis (see Table 3-9). In order to minimize such losses,
has been recommended that samples be extracted and stored in the dark in glass
containers and at subzero temperatures (39).
22
-------
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Laboratories, Columbus, Ohio,.
37. Thomas, R. S. et al. 1976. Trace Analysis in Aqueous Systems Using
XAD-2 Resin and Capillary Column Gas Chromatography and Mass Spec-
troscopy, Carcinogenesis, Vol. !_: Polynuclear Aromatic Hydrocarbons,
Chemistry, Metabolism. Carcinogenesis. R. J. Freudenthal and R. W.
Jones, Eds., Raven Press, N.Y.
25
-------
38. Saxena, J., J. Kozuchowski, and D. K. Basu. 1972. Monitoring of
Polynuclear Aromatic Hydrocarbons on Water Extraction and Recovery
of Benzo(a)pyrene with Power Polyurethane Foam. Env. Sci. and Tech.
11(7) 682-685.
39. Wise, S. A., S. N. Chesler, H. S. Hertz, L. R. Hilpert, and W. E.
May. 1978. Methods for Polynuclear Aromatic Hydrocarbon Analysis
in the Marine Environment. Carcinogenesis. Vol. 3, Metabolism. Chem-
istry, and Carcinogenesis. P. Jones and R. E. Freudenthal, eds.,
Raven Press, N.Y., pp. 175-182.
26
-------
4.0 ANALYTICAL TECHNIQUES
A variety of analytical techniques are currently being used to determine
POM concentrations in environmental samples. A review of the literature would
indicate that:
1. Hundreds of POM compounds may be present in environmental samples.
The number of POM compounds reported for a given sample may vary substan-
tially, thus reflecting the limitations of the specific analytical technique
used.
2. Agreement between POM concentrations obtained using different ana-
lytical techniques can be expected to be no better than an order of magnitude.
3. Quantitative data for POM concentrations will generally be less than
actual concentrations.
Quantitative analysis of an environmental sample for POMs can be accom-
plished in a variety of ways. Two currently used techniques for POM analysis
are outlined in Table 4-1 (1,2). These examples represent two of the hundreds
of methods for POM analysis found in the literature. Basically all methods
for POM analysis share a common format of six distinct steps: (1) extraction,
(2) concentration, (3) enrichment, (4) resolution, (5) identification, and
(6) quantification. There is, however, no standard technique for POM analy-
sis, and significant variations in methods exist for each of these six steps.
Few studies have been published comparing the effectivenes of different
techniques for POM analysis. Establishing the effectiveness of any one method
is therefore difficult. Results from both intralaboratory and inter!aboratory
studies indicate that POM concentrations obtained using different techniques
can generally be expected to agree within an order of magnitude (3,4,5,6,7).
In one intralaboratory study, food and soot samples were analyzed. For most
POM compounds, results agreed within a factor of five, but reports varied sub-
stantially in the number of POMs found in the sample. Other inter!aboratory
comparisons indicate that results can be expected to agree within a factor of
two for POM test mixtures. Test mixtures are solutions containing POM stan-
dards and do not approach the complexity of environmental samples (8,9). For
intralaboratory comparisons of two methods for POM analysis, agreement within
a factor of two is common (see Table 4-2).
27
-------
TABLE 4-1. SCHEMES FOR POM ANALYSIS
New Method for B(a)P Analysis
for National Air Surveillance Network
Samples
Method Used by National Bureau of
Standards for POM Analysis in the
Marine Environment
l~4\ I
I
SAMPLE
I Soxhlet extraction with
y cyclohexane
EXTRACTED ORGANICS IN DILUTE SOLUTION
Kuderna Danish
Concentrator
CONCENTRATED SOLUTION
Thin layer chromatography on
20% acelated cellulose developed
with ethanol/CH2C!2
PARTIALLY RESOLVED POMs
Perkin-Elmer MPF-3
Fluorescence spectrophotometer
Scan at excitation wavelength:
388 nm for B(a)P
434 nm for anthracene
IDENTIFICATION OF B(a)P AND ANTHRACENE
Read at emission wavelength:
430 nm for B(a)P
470 nm for anthracene
QUANTITATIVE DATA ON B(a)P AND ANTHRACENE
98.9 ± 5% recovery reported for
samples spiked with B(a)P
SEAWATER OR MARINE SEDIMENT
1 Dynamic headspace sampling
NONVOLATILE ORGANICS
Liquid chromatography
Precolumn coupled to a
viBondapak CIS analytical
column
POM SEPARATED FROM MATRIX
High pressure liquid chroma-
tography
uBondapak NH2 solid phase
RESOLVED BY RING NUMBER
Reversed phase high pressure
liquid chromatography
ALKYL HOMOLOGUES RESOLVED
UV absorption and fluorescence
emission spectroscopy
Gas chromatography/mass spec-
trometry
POM
I
POM
I
I
IDENTIFICATION AND QUANTIFICATION
OF NUMEROUS POM
Reference 1
Reference 2
28
-------
TABLE 4-2. POM ANALYSIS USING DIFFERENT ANALYTICAL TECHNIQUES
Reference
number
3
4
5
e.
1
Techniques compared
Thin layer chromatography/
fluorescence
Gas chroma tography/f lame
ionization detector
High pressure liquid chromatog-
raphy/ultraviolet absorption
Gas chroma tography/f lame
ionization detector
Gas chromatography/flame
ionization detector
Column chromatography/ultra-
violet absorption
Seven different thin layer
chromatography methods
Gas liquid chromatography/
flame ionization detector
Column chromatography/ultra-
violet absorption-fluorescence
Gas chromatography/ultra-
violet absorption
Gas chromatography/mass
spectroscopy
Sample
medium
Water
Pitch
Air
Filter
Hi !«• +•
LJUSt
Standards
in
solvent
Spiked
ai r
a I r
samples
Spiked
soot
Results
B(a)P
42.7 ng/X,
77.1 ngA-
53 yg/x,
45 yg/£
74.5 yg/2. av
59 yg/£ av
5.35 yq/q
6.05 yg/g
(% Recovery)
90.0%
80.5%
55.8?:-100.4% av
82 . 5%
75.6% av
92°:
105%
Other POM
137.5 ng/X, av
154.9 ng/x, av
9.2 yg/g av
6.8 ug/g av
(% Recovery)
91 . 7%
77.7%
95. 58 av
110.5% av
29
-------
4.1 EXTRACTION
Thorough extraction of POM from a sample is necessary if the amount of
POM available for analysis is to represent the quantity sampled. Air and
water samples contain POM tightly bound to particulate matter, and in samples
of vegetation or food, POM may be complexed with protein (10). Only a per-
centage of the POM concentration will be reported unless a rigorous extraction
procedure is used. The most commonly employed method has been Soxhlet extrac-
tion. The sample is placed in a Soxhlet apparatus with organic solvent and
refluxed for several hours. Benzene and cyclohexane have achieved widespread
use, but other solvents have also been used, including methanol, methylene
chloride, acetone, tetrahydrofuran, hexane, pentane, ether, isooctane, chloro-
form, and mixtures of two or more of these solvents. However, the effective-
ness of some of these solvents in achieving good POM recovery may be question-
able (11,12).
Ultrasonic extraction, an alternative to using the Soxhlet apparatus,
involves mechanical disruption of the sample with ultrasonic vibrations
(13,14). This method allows for faster extraction than with the Soxhlet
apparatus, although there is controversy over which is the more effective.
4.2 CONCENTRATION
After extraction of a sample, the POM is contained in a dilute solution.
Usually, the solution must be concentrated before further analysis is possi-
ble. Although evaporative methods, such as the use of Kuderna-Danish appara-
tus, rotary evaporator, or nitrogen stream, can concentrate the solvent mix-
ture effectively, significant quantities of POM may be lost if evaporation is
not done carefully. This applies especially to the more volatile tricyclic
and tetracyclic POM compounds (9).
Two extraction methods do not employ large quantities of solvents, making
a concentration step unnecessary: thermal stripping, a method in which POM is
removed from the sample by heating it to 300°C, and vacuum sublimation, in
which samples are heated under reduced pressure. These methods may offer good
results but have not yet achieved widespread use (15).
4.3 ENRICHMENT
A typical laboratory sample contains less than 2 percent polycyclic
organic matter. An enriched mixture containing a higher percentage of POM is
30
-------
obtained by concentrating the POM separated from other compounds using either
chromatographic techniques or solvent partitioning.
Liquid chromatography (LC) has achieved widespread use for the separation
of POM from other components. A variety of LC techniques have been used
differing in the choice of solvents (mobile phase), column packings (solid
phase), and number of stages. Numerous solvents and solvent mixtures have
been employed, including pentane, hexane, cyclohexane, isooctane, benzene,
chloroform, methylene chloride, ether, isopropanol, toluene, methanol, and
water. Alumina or silica gel are generally used as column packings.
Thin Layer Chromatography (TLC) has also been used for enriching POM in a
sample. As with LC, a variety of organic solvents have been used for the
mobile phase. Silica gel, alumina, and acelated cellulose are commonly used
solid phases. In addition to enriching a sample, initial resolution of the
individual POM compounds can also be accomplished with TLC; for example,
Daisey and Leyko separated POM from a sample and obtained three POM fractions.
Effective separation of the B(a)P and B(e)P isomers was achieved, making
subsequent resolution of the individual forms of POM relatively easy (16).
High pressure liquid chromatography (HPLC) is the newest chromatographic
method to be applied to POM analysis. HPLC is very versatile partly because
of the availability of numerous solid and mobile phases. Certain HPLC columns
have been shown to effectively enrich the POM and resolve the POM mixture into
individual compounds, and may significantly reduce the time needed for analy-
sis.
With any technique, some loss of POM from the sample can be expected to
occur during enrichment. POM may bind irreversibly to chromatographic sur-
faces or undergo chemical photooxidative decomposition, if the sample is
exposed to light.
Another technique for enrichment is liquid -liquid extraction, i.e.,
solvent partitioning. This method has not been used as much as TLC or LC but
offers some advantages. Multistep partition schemes involving extraction with
nitromethane, cyclohexane, and dilute acid and base solutions have been shown
to enrich samples while dividing POMs into acid, basic, and neutral frac-
tions (17). The literature is not conclusive on which solvents are best
suited for solvent partitioning. Dimethylformamide and dimethylsulfoxide have
been reported to be superior solvents for this method (15).
31
-------
4.4 RESOLUTION
Once the POM mixture has been separated from the matrix, the individual
POM compounds must be resolved. Many POM compounds exist as isomers having
the same number of fused rings and possessing similar chemical properties
which makes them difficult to isolate. Since different isomers can exhibit
very different biological effects, their resolution is extremely important.
For example, benzo(a)pyrene is an active carcinogen and its isomer benzo(e)-
pyrene is nonactive. Other isomers that can be difficult to separate include
benz(a)anthracene, chrysene and triphenylene, benzo(b)fluoranthene and benzo-
(k)fluoranthene, and benzo(ghi)perylene and anthanthrene (18).
Resolution of POM with methyl substitutions from parent compounds is also
difficult. Since each parent compound may have numerous possible substitution
sites, the number of possible derivatives is enormous, particularly if disub-
stituted and polysubstituted structures are considered. For example, benz(a)-
anthracene can be difficult to separate from numerous similar compounds,
including chrysene, triphenylene, 12 possible methyl derivatives, and 66
possible dimethyl derivatives (see Figure 4-1).
CH
CH,
Benz(a)anthracene
Chrysene
7-12 Dimethylbenz(a)anthracene
Triohenylene
Figure 4-1. A structural comparison of 7,12-dinethylbenz(a)anthracene
benz(a)anthracene, chrysene, and triphenylene
Once again, separation is especially important because of the different bio-
logical effects these compounds may have. Although 7,12-dimethylbenz(a)an-
thracene is a highly active carcinogen, other methyl substituted benz(a)an-
thracenes are only moderately active or nonactive.
32
-------
In experiments concerned only with quantifying 8(a)P or a limited number
of POM compounds, LC or TLC methods are also used for resolution. Many meth-
ods including those employing LC and TLC for separating and resolving POMs
have been proposed as tentative standard methods for air pollution analyses.
However, other techniques are capable of greater resolution of POM mixtures
into individual compounds.
Gas chromatography (GC) is the most effective method for resolving POM.
Resolution of air and cigarette smoke samples into over a hundred POM com-
pounds can be achieved with GC methods. Both capillary and packed GC columns
have achieved extensive use for POM analysis. Capillary columns are consid-
ered more effective than packed columns for resolving POM, but early problems
with column fabrication, coating, and short column life made packed columns
easier to use (15).
HPLC is rapidly becoming a popular method for POM analysis. Resolution
of POM compounds can be accomplished relatively quickly and cheaply using
HPLC, but may be incomplete. Mass spectral analyses of single HPLC fractions
can indicate the presence of more than one type of POM (17). However, HPLC is
the most powerful tool for the resolution of high molecular weight POM com-
pounds possessing volatilities too low for GC application (19).
4.5 IDENTIFICATION
Initial identification of POM compounds can be made based on LC, TLC, or
GC retention values. For LC, POM identification is based on elution order.
POM compounds on a TLC plate have a characteristic color and migration index
(Rf). Identification using GC is based on retention times. Confidence in the
identification is enhanced when an internal standard is run and retention
values are measured relative to the standard.
Detection devices measuring UV absorption, UV fluorescence, or mass
spectra (MS) are used to identify or verify identifications of POMs. UV
absorption is a commonly used method. Each POM compound has a unique spectra
making positive identification of POM compounds possible in principle. How-
ever, significant overlap exists between the spectra for many POM compounds.
With limited instrumental resolution, identification may not be possible in
practice.
33
-------
UV fluorescence offers advantages in sensitivity over UV absorption.
Identification of picogram quantities of POM has been claimed. Also, differ-
ences in absorption and emissions wavelengths can be used, to identify POM
(15).
Mass spectra are extensively used for POM identification. Capillary
GC/MS is generally accepted as the most powerful tool for the identification
of trace levels of POM. Even with this technique, however, identification of
each component in a sample containing hundreds of POM compounds is not feasi-
ble. Some unknown compounds may be identified by analyzing POM standards and
comparing results. Presently, standards can be purchased for some priority
pollutant ROMs including 1,2-benzanthracene, benzo(a)pyrene, 3,4-benzofluor-
anthene, 11,12-benzofluoranthene, and chrysene (20). The lack of standards
has limited the ability of researchers to elucidate the POM components of a
sample.
4.6 QUANTIFICATION
Once a POM compound has been identified, quantitative data can be ob-
tained. The accuracy of such data is dependent on the efficiency of each step
of the analysis procedure. Care must be taken to minimize loss of POM during
analysis. Confidence in the analytical technique is also enhanced when sam-
ples are spiked with known amounts of POM and good recoveries are reported.
Many methods are available for quantifying POM concentrations (see
Table 4-3). UV absorption, UV fluorescence, flame ionization detection (FID),
and mass spectroscopic (MS) methods are the most commonly used techniques for
POM quantification. Results obtained by these methods appear comparable (see
Table 4-2) (2,9,21,22,23,24,25,26).
Originally the most commonly employed technique, UV absorption continues
to be popular for POM analysis. The method is familiar and available to many
investigators. Problems can develop, however, due to significant overlap of
spectra between POM compounds. A new method for the analysis of POM absorp-
tion spectra may aid in interpreting data by producing more distinct spectral
peaks. This method treats the spectrum as a curve and plots the second deriv-
ative of the expression for the curve. Further experimentation with second
derivative analysis will determine its applicability to POM analysis (27). UV
absorption methods do not offer the sensitivity achieved with UV fluorescence.
34
-------
TABLE 4-3. DETECTION DEVICES FOR POM ANALYSIS
Detection Method
UV Absorption
UV Fluorescence
Flame lonization
Detector (FID)
Electron Capture
Detector (ECD)
Mass Spectrometry
(MS)
Shpol'skii Effect
X-ray Excited Optical
Luminescence (XEOL)
Synchronous Lumines-
cence
Sensitized Fluorescence
Advantages
Familiar method useful for
routine analysis.
Excellent sensitivity.
Possess the widest r?nge
of linear response
B(a)P response distin^
guishable from B(e)P.
The most sophisticated
tool for POM quantifica-
tion.'1
Increased selectivity over
room temperature fluorescence.6
Require no resolution once the
POM fraction is isolated.'9'"
Requires no expensive equipment
or special training.1
Limitations
Overlap between POM
spectra can make
quantification dif-
ficult.3
Nonselective response.
Good resolution
necessary.
Sample must be free of
impurities.
Expensive for routine
analysis.
Relatively new methods
which have not achieved
widespread use.
Limited estimation of
total POM.
Reference
3Reference
"Reference
Reference
i
"Reference
Reference
'Reference
Reference
Reference
15 (Adapted)
21 (Adapted)
2 (Adapted)
9 (Adapted)
22 (Adapted)
23 (Adapted)
24 (Adapted)
25 (Adapted)
26 (Adapted)
35
-------
Fluorescence detectors have shown the capacity for detecting POM in picogram
to nanogram quantities. UV absorption and fluorescence methods were the major
choices for POM quantification until the application of GC for the resolution
of POM mixtures.
Flame ionization detectors (FIDs) can be coupled to GC for POM analysis.
GC/FID is well suited to analysis of environmental samples for POM, since it
gives both good sensitivity and a wide range of linear response. GC/FID
allows for accurate POM quantification over a range of- seven orders of magni-
tude (21). FID response, however, is nonselective, and accurate data are
dependent on complete GC resolution. A more selective response can be
achieved with electron capture devices (ECDs). ECDs are rarely used for
environmental POM analysis since the relatively weak POM response can be
completely obscured by sample contaminants such as organosulfur (4). GC-mass
spectrometers are the most sophisticated devices used for POM analysis.
Because MS data can be extremely complex, computer analysis of results can aid
in the interpretation and quantification of POM data.
The above methods are best suited to POM analysis once POM compounds have
been resolved. Because of the difficulties involved with resolution, methods
employing X-ray Excited Optical Luminescence (XEOL), Shpol'skii fluorescence
effects, and synchronous luminescence are being developed to give quantitative
POM data without prior resolution.
A fluorescence spot test has been developed for the estimation of POM
concentrations. This method requires no sophisticated equipment. It is based
on the sensitization of the inherent fluorescence of POM. POM fluorescence
can be greatly enhanced, i.e., sensitized, in the presence of trace amounts of
naphthalene. The fluorescence of a sample extract plus naphthalene can be
compared visually under an ultraviolet lamp to the fluorescence of naphthalene
and the sample alone, and total POM concentrations can then be deduced. This
-12
method can be used for detection of POM in picogram (10 g) quantities and
is reported to be accurate within a factor of ten. This method may provide a
useful screening method for environmental samples to determine if more spe-
cific and elaborate analysis is warranted (26).
36
-------
REFERENCES CITED FOR SECTION 4.0
1. Swanson, D., C. Morris, R. Hedgecoke, R. Jungers, R. Thompson, and
J. Bumgarner. 1978. A Rapid Analytical Procedure for the Analysis
of Benzo(a)pyrene in Environmental Samples. Trends in Fluorescence
1(2): 22-27.
2. Wise, S. A., S. N. Chesler, H. S. Hertz, L. R. Hilpert, and W. E.
May. 1978. Methods for Polynuclear Aromatic Hydrocarbon Analysis
in the Marine Environment. Carcinogenesis, Vol. 3, Metabolism.
Chemistry, and Carcinogenesis. P. Jones and R. E? Freudenthal,
eds., Raven Press, N.Y., pp. 175-182.
3. Basu, D. K., and J. Saxena. 1978. Polynuclear Aromatic Hydrocarbons
in Selected U.S. Drinking Waters and Their Raw Water Sources. Env.
Sci. Tech. 12: 795-98.
4. Burchill, P., A. A. Herod, and J. G. James. A Comparison of Some
Chromatographic Methods for Estimation of Polynuclear Aromatic Hydro-
carbons in Pollutants. Polynuclear Aromatic Hydrocarbons: Chemistry,
Metabolism, and Carcinogenesis. Vol. 3_._, P. Jones and R. J. Freudenthal,
eds., Raven Press, N.Y., pp. 35-45.
5. Liberti, A., G. Morozzi, and L. Zoccolillo. 1975. Comparative De-
termination of Polynuclear Hydrocarbons in Atmospheric Dust by Gas
Liquid Chromatography and Spectrophotometry. Annali dj_ Chimica 65:
573-580.
6. Sawicki, E., T. W. Stanley, W. C. Elbert, J. Meeker, and S. McPherson.
1966. Comparison of Methods for the Determination of Benzo[a]pyrene
in Particulates from Urban and Other Atmospheres. Atmos. Environ.
1: 131-145.
7. Perry, P., R. Long, and J. R. Major. 1970. The Use of Mass Spec-
trometry in the Analysis of Air Pollutants. Second International
Clean Air Congress of the Int. Union of Air Pollution Prevention
Assoc., December 6-11, Washington, D.C.
8. Bjorseth, A., and B. Olufsen. 1978. Results from a Nordic Round
Robin Test for PAH Analysis. Nordic PAH-Project, Report No. 1, Sep-
tember 1978.
9. Hertz, H. S., W. E. May, B. A. Wise, and S. A. Chester. 1978. Trace
Organic Analysis. Anal. Chem. 50(4): 428a-435a.
10. Grimmer, G., and H. Boehnke. 1975. Polycyclic Aromatic Hydrocarbons
Profile Analysis of High-Protein Foods, Oils, and Fats by Gas Chroma-
tography. Journal of the Assoc. of Agric. Chem. 58(4): 725-733.
11. Adamek, E. G. 1976. A Two-Year Survey of Benzo(a)pyrene and Benzo(k)
fluoranthene in Urban Atmosphere in Ontario. Ontario Ministry of
the Environment, March 1976.
37
-------
12. Hill, H. H., K. W. Chan, and K. F. Karasek. 1977. Extraction of
Organic Compounds from Airborne Particulate Matter for Gas Chroma-
tographic Analysis. J. Chromatogr. 131: 245-252.
13. Seizinger, D. E. 1978. Automated LC Fluorescence Measurement of
Benzo(a)pyrene Levels in Diesel Exhaust. The Third International
Symposium on PAH, Columbus, OH, October 25-27.
14. Jackson, James 0., and James 0. Cupps. 1978. Field Evaluation and
Comparison of Sampling Matrices for PAHs in Occupational Atmosphere.
Carcinogenesis, Vol. 3_._, P. W. Jones and R. J. Freudenthal, eds. ,
Raven Press, N.Y., pp. 183-192.
15. Herod, H. and R. Janes. 1978. A Review of Methods for the Estima-
tion of Polynuclear Aromatic Hydrocarbons with Particular Reference
to Coke Oven Emissions. J_._ Inst. Fuel. September 1978, pp. 164-177.
16. Daisey, J. M., and M. A. Leyko. 1979. Thin Layer Gas Chromatographic
Method for the Determination of Polycyclic Aromatic and Aliphatic
Hydrocarbons in Airborne Particulate Matter. Anal. Chem. 51(1):
24-26.
17. Novotny, M., M. Lee, and D. Bartle. 1974. The Methods for Fraction-
ation, Analytic Separation, and Identification of Polycyclic Aromatic
Hydrocarbons in Complex Mixtures. vL. Chromatogr. Sci. 12: 606-612.
18. Syracuse Research Corporation. 1978. Draft Report on Health Assess-
ment Document for Polycyclic Organic Matter. Office of Research and
Development. Environmental Protection Agency, Washington, D.C.
May.
19. Thomas R., and M. Zander. 1976. On the High Pressure Liquid Chrom-
atography of Polycyclic Aromatic Hydrocarbons. Anal. Chem. 282:
443-445.
20. U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory. 1977. Sampling and Analysis Procedrues for
Screening of Industrial Effluents and Priority Pollutants. USEPA,
Cincinnati, OH.
21. Katz, Morris, (ed.). 1977. Methods of Air Sampling and Analysis.
2nd Edition. American Public Health Association.
22. Colmsjo, A., and U. Stenburg. 1979. Identification of Polynuclear
Aromatic Hydrocarbons by Shpol'skii Low Temperature Fluorescence.
Anal. Chem. 51(1): 145-150.
23. Woo, G. S., A. P. D'Silva, V. A. Fassel, and G. Oestreich. 1978.
Polynuclear Aromatic Hydrocarbons in Coal. Identification by X-ray
Excited Optical Luminescence. Env. Sci. and Tech. 12(2): 173-174.
38
-------
24.
25.
26.
27.
D'Silva, A. P. 1978. X-ray Excited Optical Luminescence of Poly-
cyclic Aromatic Hydrocarbons—Analytical Applications. The Third
International Symposium on PAH, Columbus, Ohio, October 25-27.
VoOinh, T., R. B. Gammage, A. R. Gammage, A. R. Hawthorne, and J. H.
Thorngate. 1978. Synchronous Spectroscopy for Analysis of Polycyclic
Aromatic Hydrocarbons. Env. Sci. and Tech. 12(12): 1297.
Smith. E. M., and P. L. Levins. 1978. Sensitized Fluorescence for
the Detection of Polycyclic Aromatic Hydrocarbons. Available from
the National Technical Information Service, Springfield, VA, EPA-600/
7-78-182.
Gammage, R. B., T. VoDinh, A. R. Hawthorne, and J. H. Thorngate.
1978. A New Generation of Monitors for Polynuclear Aromatic Hydro-
carbons. Carcinogenesis. Vol. 3.. P. Jones and R. I. Freudenthal,
Eds., Raven Press, N.Y., pp. 155-174.
39
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40
-------
5.0 DATA SUMMARY
There exists a large data base dealing with POM in air, water, and soil
which reflects the international interest in POM over the past 25 years (see
Appendix A). The accuracy of this data base is not known. It is generally
considered to be semiquantitative, with the measured POM concentrations best
categorized as being high, medium, or low.
In order to grasp the semiquantitative nature of the data, a useful
approach might be to consider it with respect to the recommended phased sam-
pling and analytical strategy proposed by Process Measurements Branch of IERL
at RTP (1). At Level 1 of this 3-phase approach, no special emphasis is
placed on obtaining a statistically representative sample. The sampling and
analysis are designed to show within broad general limits the presence or
absence of a pollutant and its approximate concentration. The target accuracy
is specified to be within a factor of 3. In order to give that accuracy, both
sampling and analytic methods must have a precision better than a factor of 2.
After reviewing the literature it can be concluded that POM emission
factors and POM emission estimates based on particulate collection techniques
alone do not fall within the bounds of a Level 1 assessment. SASS train
analysis is thought to give an order of magnitude increase in accuracy in some
cases but still does not consider POM losses arising from chemical rearrange-
ments on the filter surface and in the gas phase eluted from the particulate.
Thus, while the available data are inadequate to demonstrate the efficiency of
the method, indications are that the SASS train data will give comparable
Level 1 accuracy when sampling for POM
Ambient POM estimates based on particulate sampling also contain a high
degree of uncertainty. Assuming losses arising from failure to collect the
vapor phase and from desorption to be negligible, the chief source of error
apparently lies in chemical degradation of POM on the filter surface. The
extent to which this occurs is a function of the filter composition and the
oxidant concentrations in the ambient air, the physical characteristics of the
POM and its carrier substrate, and the individual chemical characteristics of
the POM under investigation (see Section 5.1). The accuracy of the estimate
can also be expected to decrease when using a single POM such as benzo(a)-
41
-------
pyrene as an indicator for total POM. Ambient estimates of POM concentrations
appear to be less accurate than specified for a Level 1 evaluation.
Water sampling using resins and soil sampling appears to be accurate
within a factor of 2. At low concentrations of POM quantitative errors in the
extraction and analytical portion of the determinations are probably the
largest source of uncertainty. Water and soil values, however, can be con-
sidered to meet Level 1 requirements.
Although the direct application of these data to the EPA decisionmaking
processes should be restricted, they can serve to trace out the route of POM
through the environment.
5.1 POM IN THE ATMOSPHERE
Polycyclic organic matter in the atmosphere originates as pyrolysis
products formed during combustion. It can be concluded that:
1. Normal background ambient air concentrations for POM in remote areas
3
appear to be £0.2 nanograms/m . Urban atmospheric levels may be 10 to 100
times higher.
2. Atmospheric POM concentrations as indicated by ambient B(a)P appear
to be declining and are considered significantly less than the levels recorded
10 years ago.
3. Chemical and photochemical oxidations function to remove POM from
the atmosphere. The rate of removal is a function of light intensity and
duration, concentration of atmospheric oxidants, chemical properties of the
individual POM, and interaction with the carrier substrate.
4. Neither long- nor short-term studies using benzo(a)pyrene as an
indicator of total POM are reliable for quantitative estimates. Underestima-
tions of total POM result from the failure to consider B(a)P's apparent rapid
decomposition rate as well as the variable B(a)P/POM ratios in ambient air.
The quantity of POM generated by a source varies with the efficiency of the
combustion process and the quantity of fuel used (2).
In general, it is thought that combustion efficiency is the primary
factor. Inefficient combustion sources such as residential space heaters tend
to emit higher amounts of POM than do the better controlled, more efficient
sources such as utility boilers. These factors are reflected by B(a)P emis-
sion estimates based on emission factors (see Table 5-1). The concentration
42
-------
TABLE 5-1 . ESTIMATED BENZO(a)PYRENE EMISSIONS IN METRIC TONS/YR
Source
Coal -Fired Power Plants
Coal -Fired Industrial Boilers
Coal -Fired Residential
Furnaces
Other Solid Fuel Burning
Sources
. Domestic Stoves
. Residential Fireplaces
Oil -Fired Intermediate Boilers
. Industrial Boilers
. Commercial/Institutional
Boilers
Oil-Fired Residential
Furnaces
Gas-Fired Intermediate Boilers
. Industrial Boilers
. Commercial/Institutional
Boilers
Gas-Fired Residential
Furnaces
Petroleum Catalytic Cracking
. Fluid Catalytic Cracking
. Thermofor Catalytic
Cracking
. Hondriflow Catalytic
Cracking
Coke Production
Asphalt Production
. Saturators
. Air Blowing
. Hot Road Mix
Other Industrial Processes
Iron and Steel Sintering
. Chainlink Fence
Lacquer Coating
. Carbon Black Production
Incinerators
. Municipal
. Commercial
Minimum
0.31
0.047
0.096
52
0.23
0.89
0.12
0.000022
0.0000015
0.0044
0.050
0.00035
0.0014
0.022
0.039
0.0031
0.98
Intermediate
0.46
0.057
26
73
0.37
19
0.98
0.021
0.61
0.43
0.00023
0.0012
0.0048
110
0.0044
0.0044
0.0012
0.63
0.087
0.027
2.1
Maximum
0.77
19
740
110
0.68
2.0
1.5
0.0024
0.035
0.0048
300
0.017
0.025
0.013
41
0.087
0.24
4.7
Date
1974
1973
1972
1975
1973
1973
1973
1973
1973
1973
1977
1977
1977
1975
1976
1976
1976
1977
1976
1974
1972
43
-------
TABLE 5-1 . (Continued)
Source
Agricultural & Forest Fires
. Bagasse Boilers
. Forest Fires
Burning Coal Refuse Banks
Mobile Sources
. Automobile (gasoline)
. Automobile (diesel)
. Trucks (diesel)
. Rubber Tire Wear
. Motorcycles
Minimum
9.5
280
1.5
0.0064
0.075
0
Intermediate
2.7
0.013
0.13
5.6
Maximum
0.0061
127
310
3.3
0.031
6.2
11
Date
1973
1976
1972
1975
1975
1975
1977
1975
Reference 3. Range of estimates based on multiplying the B(a)P emissions factor
times the most recent national production or consumption figures.
TABLE 5-2. B(a)P EMISSIONS FROM HEAT GENERATION AS A FUNCTION
OF COMBUSTION EFFICIENCY
Source
Residential furnaces
<210,000 Btu/hr
Intermediate and industrial
boilers
<30 x 10 Btu/hr
Wood
(ug/kg)
17,000
-
Coal
(ug/kg)
3,500
0.93
Oil
(ug/0
2.2
1.1-32
Gas,
(yg/mj)
2
0.6-7.6
Reference 3
44
-------
of POM inherent in the composition of the fuel is of lesser importance.
Although fossil fuels have been shown to possess substantial amounts of POM as
a consequence of formation or processing techniques, the combustion of coal,
gas, or oil do not necessarily produce a higher POM level than wood (see
Table 5-2).
POM is emitted to the atmosphere as a liquid-solid particulate suspen-
sion, i.e., an aerosol. The chemical composition is a complex mixture reflec-
ting combustion characteristics of each individual source or the dominance of
a single type of source such as the coking ovens of Birmingham, Alabama, or
the vehicular traffic of Los Angeles, California (see Table 5-3). As the
mixture moves through the air, its composition may be altered by mixing,
dilution, and chemical reactions. The transport through the atmosphere is
governed by the aerosol's residence time and windspeed. The residence time is
dependent on the size of the particulate and has been reported to be on the
order of 35 to 80 hours in winter and 100 to 200 hours in summer (5). POM
from emission sources is generally contained within the lower 2 km of the
atmosphere, and POM concentrations can generally be expected to decrease with
distance from the source (5). For benzo(a)pyrene the decrease has been report-
ed to be best described by a double logarithmic function curve (6).
Those conditions that favor reduced residence times in winter, e.g.,
decreased vertical mixing, also tend to favor long-range transport of aero-
sols. Monitoring studies by Lunde and Bjorseth (7) have shown that POM can be
transported up to 1000 km. A 20-fold increase in local concentrations in
Norway was measured in the winter when winds were from the direction of indus-
trial Western Europe. The phenomenon was not detected during the summer.
Given the possibility of long-range transport, it is not surprising,
then, that nonzero atmospheric POM levels have been found in remote areas.
Since it is impossible to separate the contributions of natural sources from
those originating from the dispersal of anthropogenic aerosols, it is reason-
able to accept the remote levels as being indicative of background concentra-
tions (see Table 5-4).
Urban and industrial centers are characterized by much higher levels of
POM, which for a specific site may run as much as 10 to 100 times as great as
remote levels. Urban POM levels as measured by B(a)P have been shown not to
45
-------
TABLE 5-3. POM CONCENTRATION REFLECTING THE DOMINANCE OF A SINGLE SOURCE
POM Concent
Compound
Pyrene
Benz(a)anthracene
Benzo(e)pyrene
Benzo(a)pyrene
Fluoranthene
Benzo(ghi)perylene
Coronene
rations in Los Angeles Air (nq/m ): Automotive Source
Site 1
2.0
1.1
3.0
1.1
1.9
9.2
6.4
Site 2
1.4
0.8
1.8
0.5
0.8
4.2
3.2
Site 3
3.8
3.1
3.2
3.5
3.4
7.1
2.8
Site 4
0.16
0.04
0.09
0.03
0.12
0.21
0.20
Average
1.8
1.3
2.0
1.3
1.6
5.2
3.2
Reference 4
POM Concentrations in Birmingham, Alabama Air (nq/m3): Cok
Compound
Pyrene
Benz(a)anthracene
Benzo(e)pyrene
Benzo(a)pyrene
Fluoranthene
Benzo(ghi)perylene
Coronene
Site 1
4.6
5.3
7.6
9.0
4.9
9.5
2.7
Site 2
10.8
21.2
26.1
35.8
11.2
22.4
3.8
Site 3
9.1
14.5
15.0
20.5
10.8
15.3
3.5
Site 4
2.5
3.4
5.6
6.0
2.6
7.9
2.7
ng Source
Average
6.8
11.1
13.6
17.8
7.4
13.8
3.2
Reference 3
46
-------
TABLE 5-4. ANNUAL AMBIENT B(a)P CONCENTRATIONS AT NASN STATIONS
(ng/M3)
Honolulu
Chicago
Montgomery
New Orleans
Baltimore
Detroit
New York
Youngstown
Bethlehem
Philadelphia
Chattanooga
Average for NASN
urban stations
Average for 3 NASN
remote stations
1966a
-
-
-
-
-
-
-
-
-
-
-
4.6
0.5
1970a
-
-
-
-
-
-
-
-
'
-
-
2.2
0.2
1976b
0.02
0.53C
0.26
0.24
0.51
1.1
1.0
1.4
0.33
0.98
0.27
0.5a
O.la
1977b
0.05
0.21C
0.04C
0.18
0.32
0.42C
0.47C
1.2
0.15
0.45
0.66
0.28b
-
Reference 3
Reference 8
cBased on 3 quarters reported
47
-------
relate to city size, but rather to the nature and degree of industrial and
public activities, types and relative quantities of fuels consumed, degree of
regulation exercised by authorities over emissions, volume of vehicular traf-
fic, and extent to which photochemical and other reactions occur (9).
These levels are a product of large-scale and/or massed combustion sourc-
es, and have been observed to coincide with the presence of an inversion
layer, steady winds from the direction of the combustion source, and the onset
of winter. Temperature inversions limit the movement of air masses and pre-
vent the dispersal of atmospheric pollutants. Adamek (10) found benzo(a)-
pyrene levels to be 117 to 350 percent higher than average during inversions.
Gordon (11) demonstrated that B(a)P levels would vary inversely with the
height of the inversion layer and found a linear relationship between the two.
As in long range transport, wind direction will also have an important
effect on local POM levels. Adamek compared wind direction and atmospheric
B(a)P levels and found B(a)P to increase when the wind was from the direction
of urban centers. Unlike wind direction, windspeed does not appear to exert
any significant effects on POM levels. In three separate studies comparing
windspeed and B(a)P concentrations, no significant correlation was detected
(10,11,12).
Two pronounced trends have been observed to occur in POM concentrations.
The first is the pronounced seasonal variation in POM concentrations, which
has been demonstrated in many areas (see Table 5-5). Higher levels of benzo-
(a)pyrene occur in winter coinciding with increased particulate concentration
and increased particulate surface area (14). The effect is assumed to be a
result of increased combustion of home space heaters and local meteorology.
The second trend has been a long-term decrease in ambient benzo(a)pyrene.
Between 1966-1976 an approximate 84 percent decrease from an annual average
3 3
median concentration of 3.2 ng/m to 0.5 ng/m was reported for 32 of the
reporting NASN urban stations. The decrease has been characterized by a
lessening of the seasonal variations in urban POM levels and a decline in
remote POM levels. This has been attributed to the decrease in the residen-
tial usage of coal for space heating and restrictions on outdoor incineration.
As long as particulate is suspended in the atmosphere, POM adsorbed onto
its surface will be degraded. Degradation pathways include photooxidation by
ultraviolet light and chemical oxidation by ozone, peroxides, NO or SO (see
X A
48
-------
TABLE 5-5. VARIATIONS IN SEASONAL AVERAGES OF B(a)P CONCENTRATIONS
(ug/1000 m3)
Reference
13
3
3
3
3
10
10
3
Location
Toronto
Belfast
Dublin
Oslo
Helsinki
Canada—average of
10 towns
Well and, Canada
URBAN USA—average of
10 NASN sites
Yr.
1972-73
1962-63
1962-63
1962-63
1962-63
1971-72
1972-73
1971-72
1972-73
1958-59
Summer
12.6
9
3
36
42
0.50
1.2
6.0
5.53
1.96
Winter
17.1
51
23
103
53
0-71
0.85
11.6
4.76
24.6
TABLE 5-6. HALF-LIVES IN HOURS FOR DEGRADATION OF POM
BY MAJOR ENVIRONMENTAL OXIDIZERS
Anthracene
Dimethyl anthracene
Phenanthrene
Pyrene
Perylene
Benzopyrene
Benzanthracene
Dimethyl benzanthracene
Di benzanthracene
Di methyl di benzanthracene
DO "
r\vj/5
3.8 x 104
2 x 108
2.4 x 105
3.8 x 104
2.4 x 105
Singlet.
oxygen
5
.05
5
10
<5
<5
0.02
Ozone
(water)
0.68
1.05
0.45
0.42
0.17
Ozone
(air)
5.6 x 102
0.7 x 102
3.7 x 102
3.4 x 102
<1.4 x 102
Chlorine6
All
have
half-
1 ives
<.5 hr
H02f
All
have
half-
life
of
approxi-
mately
10 hr
JSame for air. Alkyl peroxy radical.
3Same for air.
C10"4 M.
d2 x 10"9 M.
e!0'5 M.
Hydroperoxy radical.
Reference 15.
49
-------
Table 5-6) (15). Laboratory simulations of POM degradations give conflicting
results depending upon the concentration of atmospheric oxidants and the light
source used for illumination. Lane and Katz (16) took great care in simula-
ting both illumination and ambient pollutant levels, and determined that
benzo(a)pyrene was more rapidly degraded in both light and dark conditions
than benzo(k)fluoranthene and benzo(b)fluoranthene (see Table 5-7).
The quantity of POM contained in ambient atmosphere is of great interest.
Lao et al_. (17) identified over 100 compounds in a single air sample (see
Table 5-8). Obviously, an analysis of the total POM in an atmospheric sample
is prohibitively time-consuming and much too costly to be employed on a rou-
tine basis. An estimate of the total POM based on routinely analyzed B(a)P,
however, does not consider B(a)P's facile reactivity with atmospheric pollut-
ants and sunlight. Neither does it consider the variation in B(a)P to POM
ratios from source to source and with the application of source specific
control technology. These factors become extremely important in trying to
interpret the significance of the declining trend of B(a)P from 1966 to
1976 (18).
5.2 POM IN THE AQUATIC ENVIRONMENT
Conclusions about POM in the aquatic environment are general in nature
due to limitations in the available data base. It may be concluded, however,
that:
1. POM enters the aquatic system from four major sources: (a) atmo-
spheric deposition; (b) urban and rural runoff; (c) industrial and municipal
effluent; and (d) oil seeps and spills.
2. POM is only slightly soluble in water. Consequently a significant
percentage of POM in the aquatic system would be found adsorbed onto particu-
late matter.
3. Natural water systems act as a reservoir for POM. POM is trans-
ported through these reservoirs as particulates or adsorbed onto sediment and
can be expected to accumulate in areas of biological significance, e.g.,
lakes, reservoirs, and estuaries.
4. Primary removal of POM from the aquatic environment is through
photochemical reactions and bacterial degradation.
50
-------
TABLE 5-7. HALF LIVES IN HOURS OF SELECTED POM IN SIMULATED DAYLIGHT,'
SUBJECTED TO VARYING CONCENTRATIONS OF ATMOSPHERIC OXIDANTS (ozone)
Ozone
0.0
0.19
0.70
2.28
Benzo(k)fluoranthene
14.1
3.9
3.1
0.9
Benzo(a)pyrene
5.3
0.58
0.20
0.08
Benzo(b)fluoranthene
8.7
4.2
3.6
1.9
Reference 16
aQuartzline lamp,
51
-------
TABLE 5-8- POLYCYCLIC ORGANIC COMPOUNDS IDENTIFIED IN SINGLE AMBIENT AIR SAMPLE
Biphenyl
Octahydro-phenanthrene and
octahydro-anthracene
Dihydro-fluorene
Dihydro-fluorene
Methyl-biphenyl
Methyl-biphenyl
Benzindene
Benzindene
Fluorene
Dihydro-phenanthrene
Di hydro-anthracene
2-Methyl-fluorene
1-Methyl-fluorene
9-Methyl-f1uorene
Phenanthrene
Anthracene
Benzoquinoline
Benzoquinoline
Acridine
Fluorene carbonitrile
Fluorene carbonitriled
Methyl-phenanthrene
Methyl-anthracene
Ethyl-phenanthrene and
dimethyl-phenanthrene
Ethyl-phenanthrene and
ethyl-anthracene
Ethyl-anthracene and
dimethyl anthracene
Octahydro-f1uoranthene
Octahydro-pyrene
Di hydro-f1uoranthene
Dihydro-pyrene-
Fluoranthene
Dihydro-benzo[a]fluorene and
dihydro-benzo[b]fluorene
Pyrene
Dihydro-benzo[c]fluorene
Dihydro-benzo[c]fluorene
Benzo[a]fluorene
Benzo[b]f1uorene and
benzo[c]fluorene
Methyl-fluoranthene
Methyl-pyrene
Methyl-pyrene
Trimethyl-fluoranthene and
trimethyl-pyrene
Trimethyl-fluoranthene and
trimethyl-pyrene
Di hydro-benzo[c]phenanthrene
Di hydro-benzo[c]phenanthrene
Benzo[c]phenanthrene and
hexahydro-chrysene
Benzo[ghi]fluoranthene
Dihydro-benzo[a]anthracene,
dihydro-chrysene, and
d1 hydro-tri phenylene
Dihydro-benzo[a]anthracene
dihydro-chrysene, and
di hydro-tri phenylene
Benzo[a]anthracene, chrysene,
and triphenylene
Tetrahydro-methyl-benzo[a]anthracene,
chrysene, and triphenylene
Di hydro-methyl-benzo[ghi]
fluoranthene
Methyl-benzo[a]anthracene
Methyl-triphenylene
Methyl-chrysene
6,8'-Binaphthyl
Dihydro-methyl-benzo[kSb]
fluoranthenes and
di hydro-methyl -benzo
[a&e]pyrenes
Methyl-s.6'-binaphthyl
Dimethyl-benzo[a]anthracene
and triphenylene
Dimethyl-chrysene
Benzo[j]fluoranthene
Benzo[k]fluoranthene and
benzo[b]fluoranthene
Methyl-benzo[k]fluoranthene and
methyl-benzo[b]f1uoranthene
Benzo[a]pyrene, benzo[e]pyrene
Perylene
3-Methyl-cholanthrene
Methyl-benzo[a]pyrene and
methyl-benzo[e]pyrene
o-Phenylene-fluoranthene
Dimethyl-benzo[k]f1uoranthene and
dimethyl-benzo[b]f1uoranthene
Dimethyl-benzo[a]pyrene and
dimethyl-benzo[e]pyrene
1 ,2,3,4-Dibenzanthracene
2,3,6,7-Dibenzanthracene
Benzo[b]chrysene and
o-phenylenepyrene
Picene and benzo[c]tetraphene
Benzo[qhi]perylene and
anthanthrene
Methyl-o-phenylene-fluoranthene
Methyl-di benzanthracene
Methyl-benzo[b]cyrysene and
methyl-benzo[c]tetraphene
Methyl-o-phenylene-pyrene
and methyl-picene
Methyl-benzo[qhi]perylene
and methyl-anthanthrene
Coronene
Dibenzpyrene
Reference 17
52
-------
POM can enter the aquatic systems via a number of routes. Surface waters
near a source of urban and industrial aerosols will receive a substantial
amount of POM through atmosphere fallout and precipitation. Runoff following
heavy rains will result in POM-containing soils, road and tire dust, exhaust
condensation, and other materials containing POM being washed into storm
sewers and ditches (19). Municipal and industrial effluents discharging into
waterways will further increase POM loadings (20)(see Table 5-9). Concen-
trations of benzo(a)pyrene as high as 27,000 ug/£ have been found in some
untreated industrial effluent (21). In addition, oil seeps, spills, and dis-
charges add to the POM concentration. Sullivan (22) estimated that 10 to 20
metric tons of B(a)P entered the oceans each year as a result of petroleum
discharges.
The effect of POM in the aquatic world is determined by its solubility:
the more soluble the POM the better the chances of its being incorporated into
biological systems. The solubility will vary depending upon the POM in ques-
tion, but it is generally quite low. Solubilities in water of most POM con-
sisting of three or more rings is reported to be less than 10 M (15).
Theoretically, solubility can be enhanced through micellular mechanisms
involving surfactants such as detergents, biopeptides, and alkaloids. The
extent to which such enhancement occurs in nature is not known. However, it
is generally felt that major environmental transport will be in the form of
condensed particulate or adsorbed onto particulate. McGinnes and Snoe-
yink (23) studied two representative POMs, benzopyrene and benzanthracene, and
proposed that POM would not occur significantly in solution but would be
either adsorbed onto a surface or in the form of a condensed particle. In the
latter case, it would adsorb onto the first available surface and remain there
until decomposed, biologically assimilated, or dissolved in an organic non-
polar solvent.
In an adsorbed state, transport through the aquatic environment is gov-
erned by the physical laws of sedimentation. Since sedimentation and resus-
pension occur as a function of flow rate, an accumulation of POM would be
expected to occur in placid areas such as lakes and reservoirs. The river-
borne particulate, however, would eventually work its way to the ocean where
deltas and estuaries have proven to be efficient traps for suspended matter.
Particulate retention in these areas is enhanced by inshore and alongshore
53
-------
TABLE 5-9. POM IDENTIFIED IN SEVERAL U.S. SURFACE WATERS
Source
Monongahela @ Pittsburgh, PA
Ohio River @ Huntington, WV
Ohio River @ Wheeling, WV
Delaware River @ Philadelphia, PA
Lake Winnebago @ Appleton, WI
B(a)P
0.04
0.006
0.21
0.04
0.0006
Total POM
0.60
0.058
1.59
0.35
0.007
Reference 20
TABLE 5-10. DECOMPOSITION OF POM BY BACTERIA FOUND IN NATURAL WATER SYSTEMS
Nonarowth
POM
Growth
substrate
Nongrqwth POM percent
remainino after 4 weeks
Pyrene
Benzo(a)pyrene
1,2-Benzanthracene
1,2,5,6-Dibenzanthracene
Naphthalene
Phenanthrene
Naphthalene
Phenanthrene
Naphthalene
Phenanthrene
Naphthalene
Phenanthrene
36.7
47.2
83.5
38.3
58.3
33.8
92.7
32.9
Reference 29
-------
currents which combine to restrict suspended matter into continental shelf
areas. It has been estimated that 90 percent of the river-borne particulates
accumulate in this region where they can undergo continuous resuspension and
transport via wave action and currents (24).
POM has been shown to follow the same general trends. Sedimentation has
been demonstrated by high POM levels which have been measured in lake beds.
River-borne concentrations of POM have been shown to increase following rain-
fall events indicating that scouring of sediments may be occurring as a result
of increased river flow. The possibility of containment of POM on the conti-
nental shelf is shown by Mallet who has identified POM in coastal waters both
adjacent to and remote from human areas and habitats (25). Additional work by
DeLima-Zanghi (26) showed that coastal plankton contained significant amounts
of B(a)P, whereas those plankton taken from the high seas were not contami-
nated.
Removal processes of POM from the aquatic world include evaporation,
photochemical oxidation, sedimentation, and microbial oxidation. Evaporation
appears to remove dicyclic POM and, to a limited extent, tricyclic POM. It
has been demonstrated to be effective with naphthalene, but less so with
anthracene and fluoranthene which are significantly less volatile (27).
Photochemical oxidations of POM in water occur as a result of direct photoly-
sis involving oxygen and photosensitized reactions via intermediate sub-
stances. Sensitivity varies from compound to compound and appears to be a
function of molecular weight, ring structure, and physical state. Half-lives
have been shown to increase with increasing molecular weights, and linear
polycyclics are more sensitive than their bent isomers (28). In general,
photochemical oxidations in water systems appear slower than in air because of
the presence of fewer types of oxidizing species. The primary oxidizers in
natural water have been identified as alkylperoxy and hydroperoxy radicals as
well as singlet oxygen (15).
The effect of the physical state on decomposition was studied by McGinnes
and Snoeyink (23). Benzo(a)pyrene as a condensed particulate was shown to
decompose rapidly under normal daylight conditions; the rate of decomposition
and endpoint were governed by the size of the particle. For particles of
1.5 Mm in diameter, the reaction exhibited first order kinetics until 55 to
55
-------
65 percent of the total B(a)P was decomposed at which point the process
ceased, leaving a residual. The residual was not affected by an increase in
radiant energy. Apparently the decomposition products formed a protective
barrier around the residual B(a)P preventing it from reaction. It was postu-
lated that a residual would remain in particulate greater than 0.4 pm in
diameter.
Particulate benz(a)anthracene did not exhibit this effect. Although it
did require a threshold value of sunlight, once the threshold value was at-
tained, the particulate decomposed completely. No residual was detected,
presumably due to the solubility of the decomposition product.
The adsorption of POM onto a surface can modify the rate of reaction.
Adsorption onto Kaolinite clay, a particulate commonly found in natural water
systems, was shown to enhance the rate of decomposition presumably by increas-
ing the surface area. In addition, the reaction proceeded to completion for
both benzo(a)pyrene and benzo(a)anthracene.
In an experiment using an ecosystem enclosure treated with POM-enriched
14
crude oil, Lee et a]_. (27) determined that as much as 50 percent of C benzo-
(a)pyrene might be degraded via photochemical reactions. The rate of degrada-
tion was postulated to be dependent upon the intensity of the ultraviolet
radiation, the duration of exposure, and physical state. McGinnes and Snoe-
yink (23) stated that sufficient ultraviolet energy is produced on a cloudy
day to decompose benzo(a)anthracene and benzo(a)pyrene in turbid streams. Lee
et aj. (27) concluded that the first five meters depth is the most important
region of photochemical reactions. Other studies have shown that the ultra-
violet radiation zone can extend to a depth of 25 to 30 meters in clear water
and to a depth of 18 cm in highly turbid rivers (28).
The duration of POM exposure to sunlight is also important in the decom-
position of POM. In estuarine waters, the duration of exposure is partially a
function of particulate sedimentation and resuspension. It has been estimated
that sediment a few millimeters deep is recycled through the water column on a
daily basis and that sediment approximately 2 cm deep is recycled annually.
Particulates less than 0.5 |jm in diameter have been estimated to reside in the
water column between 200 and 600 years. It has also been estimated to take
500 to 1000 years to bury a single layer of particulate, and, consequently,
any associated POM on the continental shelf (24).
56
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Degradation of POM in water can also occur by bacterial action. Bacteria
may act directly upon POM contained in a sediment or upon a metabolite pro-
duced by marine fauna. Such metabolites typically contain trans-diols substi-
tuted on intact polynuclear rings. The rate and degree of decomposition by
bacteria is apparently influenced by the degree of solubility, membrane perme-
ability, and enzyme specificity (29). Mixed bacterial cultures taken from
natural water systems have been shown to grow on naphthalene, phenanthrene,
and to a limited extent, anthracene. POM with larger ring structures could
not be utilized directly as a growth substrate. Benzo(a)pyrene, pyrene,
1,2-benzanthracene, and 1,2,5,6-dibenzanthracene were slowly decomposed over a
4-week period only in the presence of naphthalene and phenanthrene (see
Table 5-10) which served as a carbon source (29).
Although restricted by the ring size and the degree of alkylation, bacte-
rial degradation presents the ultimate means of removing POM from the environ-
ment. POM is attacked forming cis-diol products and eventually results in
ring cleavage and the generation of CO- and water (30).
5.3 POM IN SOIL AND GROUNDWATER
Polycyclic organic matter has been identified in soil and in underlying
groundwater. Conclusions are:
1. The preponderance of POM in soil probably results as a consequence
of atmospheric deposition from both natural and anthropogenic combustion
sources.
2. A natural background has been hypothesized to exist and may origi-
nate in part from bacterial synthesis.
3. POM contained in soil can be taken up by plant tissues.
4. POM can be incorporated into groundwater by leaching. Sanitary
landfills might be a major source of future contamination.
5. POM in soil is decomposed by photochemical and microbial action.
Bacterial processes appear to be the most important.
POM in soil originates from the deposition of atomspheric aerosols of
both anthropogenic and natural combustion sources. As many as 30 different
POM have been identified in soil samples (31). Studies of airports (32,33)
oil refineries (34), highways (35), and process works (34) have demonstrated
that concentrations of POM resulting from anthropogenic activities decrease
57
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with the distance from the source and with the soil depth (see Table 5-11).
Highest levels have been found on the surface within 50 m of the source, and
elevated concentrations have been measured as far away as 5 km. In areas
remote from man, the relationship appears to be different. In these remote
areas, concentrations of POM appear to be independent of soil depth (36).
The extent to which natural sources such as forest fires and volcanic
activity contribute to POM levels is unknown. It is believed that these
sources combined with a postulated bacterial biosynthesis account for an
apparent background of 1-10 M9/kg benzo(a)pyrene in soil (34).
POM in the soil may be incorporated into the food path by adsorption into
vegetative and plant matter, leached into groundwater, buried in sediments, or
degraded. The quantity of POM absorbed by plant tissues has been found to be
less than, but parallel to, the POM concentration in contiguous soils. Food
crops such as carrots and potatoes have been observed to contain benzo(a)-
pyrene when grown in contaminated soil (37,38). The highest concentrations
were found in the first few millimeters of the root's surface. In addition,
both carrots and potatoes demonstrated the capability of absorbing POM through
the roots and translocating it to other tissues (39).
POM has been identified in groundwater and as such may constitute a
natural background for surface waters (see Table 5-12). It has been postu-
lated that POM levels in groundwater are a consequence of atmospheric deposi-
tion and bacterial synthesis during groundwater formation, infiltration from
already contaminated surface waters, and leaching from solid waste disposal
sites (see Table 5-13).
Removal of POM from soil occurs through photolytic oxidation and bacte-
rial degradation. Pyrene adsorbed onto garden soil and exposed to ultraviolet
radiation at 32°C has been shown to undergo chemical rearrangements resulting
in the formation of diones and diols (44). As in water, the ultimate removal
of POM is through microbial actions (29). The rate of destruction is depen-
dent on the size of the ring structure, the degree of condensation, and the
number of and location of ring substituents. For POM greater than 4 rings, an
alternate carbon source is required for co-metabolism. Bacterial cultures
using phenanthrene as a carbon source were shown to degrade more than 50 per-
cent of the B(a)P, 30 percent of the pyrene, and 27 percent of the 1,2-benz-
58
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TABLE 5-11. VARIATION OF B(a)P CONCENTRATION WITH DISTANCE FROM SOURCE EMISSION
(ygAg)
Reference Location
33 Airport*
34 Oil refinery
35 Highway* (in town)
(rural )
Distance from source in meters
Source
400
12,000
176
120
< 50
64
100
51-250
45
6
251-500
17
1,200
21
15
501-1500
1.3
120
5
*Total POM yg/kg
tMaximum values
VARIATION OF B(a)P CONCENTRATION IN SOILS NEAR EMISSION SOURCES AS A FUNCTION OF DEPTH
Reference
35
34
33
34
34
Location
Hungary - forest soil*
Oil refinery* - USSR
500 m from refinery*
1,500 m from refinery*
Airport - USSR*
Farmland - USSR*
Soils treated with sha
tar - USSR*
Depth in cm.
0-10
3.5
11,900
1,200
120
64.3
8.2
e
238
n-3o
2.5
14,530
1,120
190
32.0
5.0
25
31-50
2.0
13,530
81
8
-
-
-
51-150
1.6
540
2
.5
-
-
-
*Maximum values
59
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TABLE' 5-12. POM IDENTIFIED IN 6ROUNDWATER (ug/£)
Reference
20
20
20
40
41
42
Location
Champaign, IL
Elkhart, IN
Fair born, OH
Germany
(maximum values)
Germany
(average at 12 locations)
Germany
(average of 3 locations)
B(a)P
Not detected
0.004
0.0003
0.0007
0.0004
0.02
Total POM
0.007
0.02
0.003
0.013
0.04
TABLE 5-13. POM LEVELS FOUND ADJACENT TO A STEEL WASTE SANITARY LANDFILL (ppb)
Location
POM concentration (ppb)
Well at highest elevation of landfill
Well at below landfill
Surface water at site
Downstream, surface water
Seepage spring
3
<3
11
<3
3-30
Reference 43.
60
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anthracene contained in a test solutions over a 4-week period (29). In other
laboratory studies, microfauna have been shown to destroy as much as 70 per-
cent of the benzo(a)pyrene in a soil sample (45). In soils containing as much
as 30,000 mg/kg of B(a)P, bacterial degradation has been credited with 50 to
70 percent removal (34).
Bacterial decomposition appears to be restricted to the upper portions of
the soil. Under anerobic conditions such as may occur below the soil's sur-
face, degradation may not occur (45). Benzo(a)pyrene has been identified at
depths of 17 m below the surface, corresponding to a geologic age of 100,000
years.
5.4 POM IN THE FOOD PATH TO MAN
There are numerous studies in the international literature dealing with
POM concentrations in food for human consumption. Caution is advised when
attempting to generalize such data from one country to the next. While simi-
larities exist, the principal dietary constituents, growing conditions and the
processing and preparation techniques may differ substantially enough to cause
misinterpretation of the data. A review of the literature leads to the fol-
lowing conclusions:
1. POM may be introduced into food at several points along the food
path. In general, microorganisms, plants, and invertebrates tend to accum-
ulate higher levels of POM than do vertebrates. Although POM is lipid soluble
and is readily incorporated into a biological system, no evidence of irrever-
sible bioaccumulation in fatty tissues has been documented.
2. POM levels in ambient air and to a lesser extent POM levels in soil
contribute to the total POM found in and on crops. POM levels in water are
amplified in some foods derived from aquatic systems.
3. Variations in industrial control techniques, degree of urbanization,
growing conditions, processing procedures, and preparation methods will affect
POM contained in food.
Due to the high lipid solubiity and increased aqueous solubility via
lipids and molecules, POM appears to be readily incorporated into biological
systems. It can therefore be expected to enter the food chain at any trophic
level. In aquatic environments, POM may enter through absorption and/or
61
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ingestion. Algae and other organisms have demonstrated the ability to absorb
POM directly from the surrounding waters (46). In turn, algae and particulate
matter containing POM may be ingested by filter feeders. Mollusks, especially
mussels, have demonstrated high POM concentrations when grown in contaminated
water. Significant levels of benzo(a)pyrene have been identified in mussels
found in remote areas the Greenland coast (47). In areas where measurable
amounts of POM have been identified in the water, concentrations in algae and
invertebrates are found to be as much as 200 times higher than that recorded
in the water (15).
In terrestrial plants, POM levels appear to be a function of ambient POM
concentration, length of exposure, and surface characteristics of the plant.
In root vegetables, benzo(a)pyrene has been identified in carrots grown in
soil containing a known amount of benzo(a)pyrene and in potatoes grown in soil
treated with shale oil for erosion control (34). High levels in above ground
crops have been linked with ambient air concentrations (grain, kale), large
surface areas (kale), waxy surface (plum), and length of growing season (toma-
toes) (38,48).
POM may enter higher trophic levels, i.e., vertebrates, through inhala-
tion and ingestion. The extent to which it may concentrate has not yet been
adequately documented. In one study cows, pigs, chickens, and ducks were fed
a daily diet of 10 mg benzo(a)pyrene for an unspecified period of time. Less
than 0.26 ug/kg of B(a)P was found in the muscle fat and liver, 0.007 ug were
found in eggs, and cow's milk contained 0.10ug/£ (49). Gorelova and Di-
kun (50) could find only traces of B(a)P after the administration of an un-
specified amount in these same test animals.
Polycyclic organic matter may also be added to food during some proces-
sing and preparation steps. Heat treatment with smoke, sterilization in the
canning process, fumes from grain dryers, food additives, and cooking can all
contribute to increased POM levels in food.
The smoking process can result in substantial increases in POM levels in
meat and fish. This is particularly important in Europe where up to 40 per-
cent of the meat products and 15 percent of the fish catch are smoked (51).
In America where the trend is toward chemical preservation and liquid smoke
flavoring, smoking is rarely used for food preservation (52). The Food and
62
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Drug Administration (FDA) has tested liquid smoke for benzo(a)pyrene and found
none to be present. However, B(a)P can be found in the residue from which
liquid smoke is distilled in concentrations up to 3,800 ug/g (53).
Since food additives have numerous applications in the food processing
industry, they are a potential source of POM. Food additives include chemical
residuals which may or may not be added directly to the food itself. Hydro-
carbon solvents are a potential additive when used in the extraction of vege-
table oil. European workers have reported POM in technical grade hexane (54).
Since hydrocarbon solvents are a potential food additive when used in the
extraction of edible oils, they have been examined by the Food and Drug Ad-
ministration. In a survey of commercial grade hexane from 11 plants involved
in the processing of edible oils and related products, of the 15 solvents
tested only nine solvents contained traces of pyrene, fluoranthene, anthra-
cene, and phenanthrene and at levels of less than 0.35 ug/£ (53).
Mineral oils, when used in the canning of meats and in the manufacture of
bread, may also become a food additive. Concentrations of mineral oil in
bread can go as high as 1500 ppm. Analyses of mineral oils by the Food and
Drug Administration have shown that the oils conform to the current standards
that restrict total POM at such levels to less than 0.05 ug/£ (53).
POM has also been identified in carbon black stabilized polyethylene
plastics and petroleum-based waxes (54,55,56). To determine the possibility
of POM migration into food from paraffin waxes, the Food and Drug Admini-
stration has analyzed 290 different waxes. Approximately one-fifth of the
samples contained POM above 0.01 ug/g, but none were carcinogenic (53).
Canned food may contain POM as a result of the heat sterilization pro-
cedure during processing. The contents are heated to at least 120°C to insure
sterilization, but higher temperatures are reached next to the surface of the
can and may promote POM production (57).
At temperatures greater than 400°C, fatty acids, glycerides, cholesterol,
carotenes, and other compounds found in food can form POM. Temperature depen-
dent effects on benzo(a)pyrene production have been demonstrated by heating
starch in the absence of air at two different temperatures. At 370°-390°C,
7 ug of B(a)P/g of starch were formed as opposed to 1700 ug B(a)P/g of starch
at 650°C (58). These temperatures are commonly reached during cooking where
63
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the surface of bread can reach 400°C while baking, and boiling fats reach
400-600°C (59).
Fumes from the heat source may contain POM which may be deposited on food
surfaces. Bread baked in wood stoves show elevated POM levels over bread
baked in an electric oven. Elevated POM levels are also seen in charbroiled
meat, where POM is produced by pyrolysis of grease drippings and is subse-
quently deposited on the surface of the meat through smoke condensation
(60,61)
Preparation of food items can also be responsible for decreased levels of
POM in fresh produce. Washing fruits and vegetables can lower B(a)P concen-
trations as much as 10 percent and peeling has been shown to reduce B(a)P
levels in potatoes (37).
Work has been done by the FDA to determine the amount of POM in a total
diet composite sample (see Table 5-14). Typically a composite contains 82
items of food and drink in a quantity sufficient to provide a two-week intake
of food for a 16-19 year-old boy. The composite is prepared in the following
manner: About 25 items from a typical market basket require such processing
as frying, boiling, peeling, trimming, or washing. Bones, peelings, stems,
and other nonedible portions are discarded, but meat drippings are saved and
included in the composite. Those foods normally eaten raw are divided into
portions, and part are prepared and part are left uncooked. After prepara-
tion, weight adjustments are made for losses during processing and the foods
are weighed in predetermined proportions before homogenization and analy-
sis (62).
Using European data, Borneff estimated the yearly intake of POM through
food to approach 4.15 mg. This represents a 3 to 4 mg of POM intake from
fruits, vegetables and bread, 0.10 mg from fats and oils, and 0.05 mg from
meat and drinking water (19). These estimates are significantly higher than
the USFDA estimates, possibly reflecting national differences in environmental
conditions and in food preparation.
64
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TABLE 5-14. POM DETECTED IN A TYPICAL U.S. TOTAL DIET COMPOSITE SAMPLE
Category
POM detected
Quantity of POM
(yg/kg)
Yearly Intake
(pg/kg)
MEATS, FISH, POULTRY
Roast beef, ground beef,
pork chops, pork sausage,
chicken, fish, canned .
fish, luncheon meat,
liver, eggs, frank-
furters - 3,916 g
ROOT VEGETABLES
Carrots, onions - 383 g
DAIRY PRODUCTS
Fresh milk, evaporated
milk, nonfat dry milk,
ice cream, cottage
cheese, processed cheese,
natural cheese,
butter - 12,403 g
OILS, FATS, AND SHORTENINGS
Shortenings, peanut
butter - 539 g
BEVERAGES
Tea, coffee, cocoa,
soft drinks, water •
16,855 g
Pyrene, fluoran-
thene
Pyrene, fluoran-
thene
Pyrene, fluoran-
thene
Pyrene fluoran-
thene, benzo(a)-
pyrene, benzo(k)-
fluoranthene,
benzo(b)fluoran-
thene, benzo(e)-
pyrene, benzo(ghi)-
perylene, benzo(a)-
anthracene, phenan-
threne
Pyrene, fluoran-
thene
<2
<204
<2
<2
<646
<0.5
<7
<2
Reference 59
65
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Merkel. 1975. Principles of Meat Science, W. H. Freeman, Co., Pub-
lishers, San Francisco.
53. Haenni, H. 0. Analytical Control of Polycyclic Aromatic Hydrocarbons
on Food and Food Additives. Residue Rev. 25: 41-78.
54. Fritz, W. 1971. Extent and Sources of Food Contamination with Car-
cinogenic Hydrocarbons. Ernahrungs forschung 16(4): 547-557.
55. Fritz, W., and H. Noggim. 1973. Migration of Carcinogenic Hydro-
carbons from Carbon Black Stabilized Plastics on Food. Zeitschrift
furdie Gesamte Hygiene und ihre Grenzgebiete 19(5): 349-352.
56. Swallow, W. H. 1976. Survey of Polycyclic Aromatic Hydrocarbons in
Selected Foods and Food Additives Available in New Zealand. New
Zealand J^ Sci. 19(4): 407-412.
57. Achman, W., and W. G. Tenning. 1977. Effect of Heating Time on
Composition of Canned Pork Meat. Food Chemistry 2(2): 135-143.
58. Davies, W., and 0. R. Wilmshurst. 1960. Carcinogens Formed in the
Heating of Food Stuffs. Formation of 3,4-Benzopyrene from Starch at
370-390C. Brit. J._ Cancer 14: 295-299.
59. Howard, J. W., T. Fazio, R. H. White, and B. A. Khmeck. 1968. Ex-
traction and Estimation of Polycyclic Aromatic Hydrocarbons in Total
Diet Composites. J_._ Assoc. Off. Agric. Chem. 51: 129.
60. Lijinsky, W. and P. Shubik. 1965a. PH Carcinogens in Cooked Meat
and Smoked Food. Industr. Med. Surg. 34: 152-154.
61. Lijinsky, W. and P. Shubik. 1964. BP and Other PH in Charcoal-
broiled Meat. Science 145: 53-55.
62. Cummings, J. G. 1966. Pesticides in the Total Diet. Residue
Review 16: 30-45.
70
-------
APPENDIX A
Appendix A is comprised of five sets of bar graphs presenting POM concen-
trations measured in air, water, and soil. The graphs are a compilation of
the data gathered during the review phase of this project. They are inter-
national in scope. No effort has been made to screen the data on the basis of
the sampling and analysis technique employed for collection. They are in-
tended only to demonstrate the range and variability of POM occurring in the
environment. Each value is referenced enabling the user to return to the
original reference for data of particular interest.
All the graphs are similar in construction. The end point of each bar
indicates the concentration of a specific POM as reported in the reference
indicated by a lower case alphabetic character. Diagonal cross hatching is
used when the POM concentrations have been converted to common units of mea-
2
sure to facilitate comparison. Standard units are ug/1000 m for air, ug/£
for water, and ug/kg for soil. The structures of the individual POM compounds
have been included for convenience.
The first three graphs contain air data categorized as urban or rural.
(The individual references should be consulted for a more exact definition of
urban and rural.) Due to the large number of benzo(a)pyrene determinations,
urban 8(a)P has been separated from the other urban POM reading.
Water data are contained in the fourth series of graphs. POM levels
identified in river, lake, ground, and marine waters are included.
The fifth set of graphs give POM levels in soil. The soil categories
include rural, urban, and industrial soil.
A-l
-------
0.01
Benzo(a)pyrene
BENZO(a)PYRENE CONCENTRATIONS IN /ig/1000 m3
_10 too
T
T
"•"* ** r*r f*i g
Ezzzzzzzzzzzzzzzzzzzzzzzzzzzna h
OZZZZ2ZZZZ
cant.
\
3m
3)
2223,
ftfffffffl \
3P
zzzzzzzzza |
1000
Figure A-l. Ambient concentration of benzo(a)pyrene in urban air
in ng/1000 m . Each line represents specific reported
values. Diagonal lines indicate ranges.
-------
0.01
BENZO(a)PYRENE CONCENTRATIONS IN /^g/1000 m3
0.1 1 10 100
Benzo(a)pyrene
cont.
cont.
I I
"""*'"""*-" fff**ff ""*"***
i r
• i
f-fff*r" S
^fff'ffffff S
~~^~* "™~"^~"™™^"~' ^^^*^~ • I
Ij
li
nj
+ *-rrfm U
\***litirrrrri'm v
v////////li
***rm\ s
ij
li
*f~"f~"f'i S
\/t////t///M\
i*»f**ttttf*ff*rrrrr»rrttfn w
' i^Aia
~"
•P
«z
trtjjijffffmt
-If-f-fff^"* r r 1 S
«P
\iriruiriiiimrrtrrtrrf tt\ v
1000
Figure A-l. Ambient concentration of benzo(a)pyrene in urban air
3
in yg/1000 m . Each line represents specific reported
values. Diagonal lines indicate ranges.
-------
0.01
Benzo(a)pyrene
cont.
BENZO(a)PYREIUE CONCENTRATIONS IN /xg/1000 m3
0.1 1 10 100
T
T
'* r rf "
• *f'r'r"f""f S
• * •*••*•' * *•** y
ft * s
1000
Figure A-l. Ambient concentration of benzo(a)pyrene in urban air
in yg/1000 m3. Each line represents specific reported
values. Diagonal lines indicate ranges.
-------
REFERENCES - B(a)P IN URBAN AIR
a. Kertesz-San'nger, M., E. Meszaros, and T. Varkonyi. 1971. On the
Size and Distribution of Benzo[a]pyrene Containing Particles in Urban
Air. Atmos. Environ. 5: 429-431.
b. Pierce, R. C., and Katz, M. 1975. Determination of Atmospheric
Isomeric Polycylic Arenes by Thin-layer Chromatography and Fluoresc-
ence Spectrophotometry. Anal. Chem. 47(11): 1743-48.
c. Colucci, J. M., and C. R. Begeman. 1971. Carcinogenic Air Pollutants
in Relation to Automotive Traffic in New York. Env. Sci. Tech. 5:
145-150.
d. Kotin, P., H. L. Falk, and M. Thomas. 1954. Aromatic Hydrocarbons.
II. Presence in the Particulate Phase of Gasoline-engine Exhausts
and the Carcinogenicity of Exhaust Extracts. A. M. A. Arch. Ind.
Hyg. Occup. Med. 9: 164-177.
e. Colucci, J. M., and C. R. Begeman. 1965. The Automotive Contribu-
tion to Airborne Polynuclear Aromatic Hydrocarbons in Detroit. vh_
Air Pollut. Control Assoc. 15: 113-122.
f. King, R. B., A. C. Antoine, J. J. Fordyce, H. E. Neustadter, and H.-
F. Leibecki. 1977. Compounds in Airborne Particulates: Salts and
Hydrocarbons. vL_ Air Pollut. Control Assoc. 27(9): 867-871.
g. Gordon, R. J. 1976. Distribution of Airborne Polycyclic Aromatic
Hydrocarbons throughout Los Angeles. Env. Sci. and Tech. 10:
370-373.
h. Colucci, J. M., and C. R. Begeman. 1970. Polynuclear Aromatic Hydro-
carbons and Other Pollutants in Los Angeles. Presented at the 2nd
International Clear Air Congress, Washington, D. C., December 6-11.
i. Sawicki, E., W. Elbert, W. T. Stanley, T. R. Houser, and F. T. Fox.
1960. The Detection and Determination of Polynuclear Hydrocarbons
in Urban Airborne Particulates I. vh_ Int. Air Pollut. 2: 273-282.
j. Sawicki, E., T. R. Hauser, W. C. Elbert, F. T. Fox, and J. E. Meeker.
1962. Polynuclear Aromatic Hydrocarbon Composition of the Atmosphere
in Some Large American Cities. Am. Ind. Hyg. Assoc. J^ 23: 137-144.
k. Faoro, R. B. 1975. Trends in Concentrations of Benzene Soluble
Suspended Particulate Fraction and Benzo[a]pyrene. JL_ Air Pollut.
Control Assoc. 25: 638-640.
1. Gordon, R. J., and R. J. Bryan. 1973. Patterns in Airborne Poly-
nuclear Hydrocarbon Concentrations at Four Los Angeles Sites. Environ.
Sci. Tech. 7(11): 1050-1053.
A-5
-------
m. Cleary, G. J. 1962. Discrete Separation of Polycyclic Hydrocarbons
in Airborne Particulates Using Very Long Alumina Columns. J_._ Chromatogr.
9: 204-215.
n. Fox, M. A., and S. W. Staley. 1976. Determination of Polycyclic
Aromatic Hydrocarbons in Atmospheric Particulate Matter by High Pres-
sure Liquid Chromatography Coupled with Fluorescence Techniques.
Anal. Chem. 48(7): 992-998.
o. Stocks, P., and J. M. Campbell. 1955. Lung Cancer Death Rates Among
Nonsmokers and Pipe and Cigarette Smokers. An Evaluation in Relation
to Air Pollution by Benzpyrene and Other Substances. Brit. Med. J_._
2: 923-939.
p. Sawicki, E. 1967. Airborne Carcinogens and Allied Compounds. Arch.
Env. Health 14: 46-53.
q. Commins, B. T., and L. Hampton. 1976. Changing Pattern in Concentra-
tions of Polycyclic Aromatic Hydrocarbons in the Air of Central London.
Atmos. Env. 10: 561-562.
r. Tokiwa, H., K. Morita, H. Takeyoshi, K. Takahashi, and Y. Ohnishi.
1977. Detection of Mutagenic Activity in Particulate Air Pollutants.
Mutation Research, El sevier/North-Holland, Bitnedical Press.
s. Sawicki, E. 1967. Airborne Carcinogens and Allied Compounds. Arch.
Env. Health 14: 46-53.
t. Louw, C. W. 1965. The Quantitative Determination of Benzo[a]pyrene
in the Air of South African Cities. Amer. Industr. Hyg. Assoc. J_._
26: 520-526.
u. Takatsuka, M., T. Tsujikawa, K. Yoshida, and M. Murata. 1973. The
Measurement Method for the Atmospheric Carcinogens and Conditions in
Mie Prefecture. Mie Ken Kogai Senta Nenpo (Mie Prefect. Pub. Nuisance
Center Annu. Rep.TT: 60-70.
v. Sullivan, J. L., and G. J. Cleary. 1964. A Comparison of Polycyclic
Aromatic Hydrocarbon Emissions from Diesel-and Petrol-Powered Vehicles
in Partially Segregated Traffic Lanes. Brit. J^_ Ind. Med. 21: 117-123.
w. Rao, A. M. Mohan, and K. G. Vohra. 1975. The Concentrations of
Benzo[a]pyrene in Bombay. Atmos. Environ. 9(4): 403-408.
x. Dautov. F. F. 1977. Sanitary Evaluation of Air Pollution with 8enz[a]
pyrene and Toxic Compounds in Ethylene Oxide Production. Gig. j_.
Sanit. 6: 85-87.
y. Stocks, P., B. T. Commins, and K. V. Aubrey. 1961. A Study of Poly-
cyclic Hydrocarbons and Trace Elements in Smoke in Merseyside and
Other Northern Localities. Int. J. Air Water Pollut. 4: 141-153.
A-6
-------
z. Hettche, H. 0. 1971. Plant Waxes as Collectors of PCAH in the Air
of Polluted Areas. Staub. 31: 72-76; Chem. Abstr. 74, 145943.
aa. Commins, B. T. 1958. Polycyclic Hydrocarbons in Rural and Urban
Air. Int. J. Air Pollut. 1: 14-17.
bb. Arceivala, S. J. 1973. A Review of Environmental Pollution Studies
in Turkey. Preprint, Middle East Technical Univ., Environmental
Engineering Dept., 74 pp.
A-7
-------
00
0.01
Naphthalene
Acenaphthene
OOO Anthracene
Phenanthrene
Benz(a)anthracene
Triphenylene
POM CONCENTRATIONS IN /xg/1000 m3
0.1 1 10 100
* * * * * * *• I
I in
'I
3 i)
1000
zrt
Figure A-2. Ambient concentration of POM in urban air in ug/1000 m . Each
line represents a reported value. Diagonal line indicates ranges
-------
<£>
0.01
Chrysene
Pyrene
cunt.
POM CONCENTRATIONS IN /ig/1000 m3
Q=L_ i 10 100
T
iq
iq
I c
lb
K
iq
•rfffrrffffT-K I
'f'rfflffrrrrr.
T
1000
Figure A-2. Ambient concentration of POM in urban air in pg/lOOO m . Each
line represents a reported value. Diagonal line indicates ranges.
-------
I
o
0.01
Pyrene
cont.
Benzo(e)pyrene
POM CONCENTRATIONS IN /
-------
0.01
Perylene
Naphthojl, 2.3.4-def Jchrysene
Anthanthrene
cont.
POM CONCENTRATIONS IN /ig/1000 m3
01 i _ 10
T
rrm^ |
*ff*f* "\ 0
""*f*f**f
+rr"ffff*
•fffff'ffrf
a q
iq
iq
ZZZZZ23 k
za q
31 q
100
1000
Figure A-2. Ambient concentration of POM In urban air in pg/1000 m . Each
line represents a reported value. Diagonal line indicates ranges
-------
ro
0.01
Anthanthrene
cont.
Naphtho(2,1,8-qra)naphthacene
Dibenzo(b,def)chrysene
Benzo(rst)pentaphene
Benzo(ghi)perylene
cont.
POM CONCENTRATIONS IN ,/g/IOOO m3
0.1 1 10 100
T
•'''•r"-"*-"***
Id
•'""" j
•fffflVt
•ifitna
zza Q
ZZZIk
1000
Wffl \
Figure A-2. Ambient concentration of POM in urban air in pg/1000 m . Each
line represents a reported value. Diagonal line indicates ranges.
-------
0.01
Benzo(ghi)perylene
cont
Coronene
cont.
POM CONCENTRATIONS IN /ig/1000 m3
_PJ i 10 100
3Q
zzzzzzzzzzaq
rrtitltrrrittjtfn (
r t\r\
zzzzzzzzzai
ZZZZZZZZiq
zzae
\rrrrrmtfi\e.
Zl e
a q
»q
iq
Z29
HZZZZZZZZjq
Vlliuiurrrmmrrn)).
1000
Figure A-2. Ambient concentration of POM in urban air in pg/1000 HI . Each
line represents a reported value. Diagonal line indicates ranges
-------
POM CONCENTRATIONS IN ,
-------
0.01
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(j)fluoranthene
Benz(mno)fluoranthene
lndeno(1.2,3-cd)pyrene
POM CONCENTRATIONS IN /tg/1000 m3
0.1 1 10 100
T
T
at 9
31
is
iq
aq
2ZZZZZZJ P
iq
Figure A7?.
T
1000
concentration of POM In urban air in ug/1000 m3. Each
hfe l-epre^nts a reported value. Diagonal line indicates ranges.
-------
>
CTl
0.01
Quinoline
Isoquinoline
Methylquinolines
Ethylquinolines
Ethylisoquinolines
Dimethylquinolines
2,6 Dimethylquinoline
Dimethylisoquinolines
3C quinolines
Acridine
Phenanthridine
Benzo(f)quinoline
4 Azapyrene
POM CONCENTRATIONS IN /tgllOOO m3
o.i
10
100
1000
w """
Ibb
3iaa
IDaa
|aa
laa
Figure A-2. Ambient concentration of POM in urban air in pg/1000 m . Each
line represents a reported value. Diagonal line indicates ranges
-------
COO
0.01
Benzacridine
1 Aza fluoranthene
2 Methylindole
Carbazole
Benzothiazole
POM CONCENTRATIONS IN /ig/1000 m3
0.1 1 10 100
T
T
1000
abb
Ibb
Figure A-2. Ambient concentration of POM in urban air in ^g/1000 m . Each
line represents a reported value. Diagonal line indicates ranges
-------
REFERENCES - POM IN URBAN AIR
a. Krstulovic, A. M., D. M. Rosie, and P. R. Brown. 1977. Distribution
of Some Atmospheric Polynuclear Aromatic Hydrocarbons. Amer. Lab.
(July 1977) pp. 11-18.
b. Cleary, G. J. 1962. Discrete Separation of Polycyclic Hydrocarbons
in Airborne Particulates Using Very Long Alumina Columns. J. Chrom-
atogr. 9: 204-215.
c. Stocks, P., and J. M. Campbell. 1955. Lung Cancer Death Rates Among
Nonsmokers and Pipe and Cigarette Smokers. An Evaluation in Relation
to Air Pollution by Benzpyrene and Other Substances. Brit. Med. J.
2: 923-939.
d. Hettche, H. 0. 1971. Plant Waxes as Collectors of PCAH in the Air
of Polluted Areas. Staub. 31: 72-76; Chem. Abstr. 74, 145943.
e. Stocks, P., B. T. Commins, and K. V. Aubrey. 1961. A Study of Poly-
cyclic Hydrocarbons and Trace Elements in Smoke in Merseyside and
Other Northern Localities. Int. J^ Air Water Pollut. 4: 141-153.
f. Kertesz-Saringer, M., E. Meszaros, and T. Varkonyi. 1971. On the
Size and Distribution of Benzo[a]pyrene Containing Particles in Urban
Air. Atmos. Environ. 5: 429-431.
g. Gordon, R. J. 1976. Distribution of Airborne Polycyclic Aromatic
Hydrocarbons throughout Los Angeles. Env. Sci. and Tech. 10: 370-373.
h. Colucci, J. M., and C. R. Begeman. 1971. Carcinogenic Air Pollutants
in Relation to Automotive Traffic in New York. Env. Sci. Tech. 5:
145-150.
i. King, R. B., A. C. Antoine, J. J. Fordyce, H. E. Neustadter, and H.
F. Leibecki. 1977. Compounds in Airborne Particulates: Salts and
Hydrocarbons. J_._ Air Pollut. Control Assoc. 27(9): 867-871.
j. Colucci, J. M., and C. R. Begeman. 1970. Polynuclear Aromatic Hydro-
carbons and Other Pollutants in Los Angeles. Presented at the 2nd
International Clear Air Congress, Washington, D. C., December 6-11.
k. Gordon, R. J., and R. J. Bryan. 1973. Patterns in Airborne Poly-
nuclear Hydrocarbon Concentrations at Four Los Angeles Sites.
Environ. Sci. Tech. 7(11): 1050-1053.
1. Sullivan, J. L., and G. J. Cleary. 1964. A Comparison of Polycyclic
Aromatic Hydrocarbon Emissions from Diesel-and Petrol-Powered Vehicles
in Partially Segregated Traffic Lanes. Brit. J_._ Ind. Med. 21: 117-123.
m. Tokiwa, H., K. Morita, H. Takeyoshi, K. Takahashi, and Y. Ohnishi.
1977. Detection of Mutagenic Activity in Particulate Air Pollutants.
Mutation Research. El sevier/North-Holland, Bimedical Press.
A-18
-------
n. Colucci, J. M., and C. R. Begeman. 1965. The Automotive Contribu-
tion to Airborne Polynuclear Aromatic Hydrocarbons in Detroit. vh_
Air Pollut. Control Assoc. 15: 113-122.
o. DeMaio, L., and M. Corn. 1966. Polynuclear Aromatic Hydrocarbons
Associated with Particulates in Pittsburgh Air. J^ Air Pollut. Con-
trol Assoc. 16: 67-71.
p. Dautov. F. F. 1977. Sanitary Evaluation of Air Pollution with Benz
[a]pyrene and Toxic Compounds in Ethylene Oxide Production. Gig. i_.
Sam't. 6: 85-87.
q. Sawicki, E., T. R. Hauser, W. C. Elbert, F. T. Fox, and J. E. Meeker.
1962. Polynuclear Aromatic Hydrocarbon Composition of the Atmosphere
in Some Large American Cities. Am. Ind. Hyg. Assoc. «L_ 23: 137-144.
r. Fox, M. A., and S. W. Staley. 1976. Determination of Polycyclic
Aromatic Hydrocarbons in Atmospheric Particulate Matter by High Pres-
sure Liquid Chromatography Coupled with Fluorescence Techniques.
Anal. Chem. 48(7): 992-998.
s. Commins, B. T. 1958. Polycyclic Hydrocarbons in Rural and Urban
Air. Int. J. Air Pollut. 1: 14-17.
t. Pierce, R. C., and Katz, M. 1975. Determination of Atmospheric
Isomeric Polycylic Arenes by Thin-layer Chromatography and Fluoresc-
ence Spectrophotometry. Anal. Chem. 47(11): 1743-48.
u. Commins, B. T., R. L. Cooper, and A. J. Lindsey. 1954. Polycyclic
Hydrocarbons in Cigarette Smoke. Brit. »L_ Cancer 8: 296-302.
v. Bartle, K. D., M. L. Lee, and M. Novotny. 1976. An Integrated
Approach to the Analysis of Air-pollutant Polynuclear Aromatic Hydro-
carbons. Proc. Analyst Div. Chem. Soc., Oct.: 304-307.
w. Rost, H. E. 1976. Influence of Thermal Treatments of Palm Oil on
the Content of Polycyclic Aromatic Hydrocarbons. Chem. Ind. 14:
612-613.
x. Kertesz-Saringer, M., E. Meszaros, and T. Varkonyi. 1971. On the
Size and Distribution of Benzo[a]pyrene Containing Particles in Urban
Air. Atmos. Environ. 5: 429-431.
y. Campbell, J. M., and A. J. Lindsey. 1956. Polycyclic Hydrocarbons
Extracted From Tobacco: The Effect Upon Total Quantities Found in
Smoking. Brit. J_._ Cancer 10: 649-652.
z. Gordon, R. J. 1976. Distribution of Airborne Polycyclic Aromatic
Hydrocarbons throughout Los Angeles. Env. Sci. and Tech. 10: 370-373.
aa. Dong, M. W. and Locke, D. C. 1977. Characterization of Aza-Arenes
ia Basic Organic Portions of Suspended Particulate Matter. Env.
Sci. and Tech. 11(6): 612-618.
A-19
-------
bb. Brocco, D., A. Cimmino, and M. Possanzini. 1973. Determination of
Aza-heterocyclic Compounds in Atmospheric Dust by a Combination of
Thin-layer and Gas Chromatography. .L_ Chromatogr. 84: 371-377.
A-20
-------
r -
0.001
COO
Naphthalene
Anthracene
Phenanthrene
Pyrene
III
Dibenzo(a,c)anthracene
I
Benzo(a)pyrene
POM CONCENTRATIONS IN /
-------
>
ro
0.001
Benzo(e)pyrene
Benzojghilperylene
Coronene
Fluoranthene
POM CONCENTRATIONS IN /xg/1000 m3
0.01 0.1 1 10
Figure A-3.
Ambient concentration of PGM in rural air in ng/1000 m .
Each line represents a specific reported value. Diagonal
lines indicate ranqes.
-------
REFERENCES - POM IN RURAL AIR
a. Krstulovic, A. M., D. M. Rosie, and P. R. Brown. 1977. Distribu-
tion of Some Atmospheric Polynuclear Aromatic Hydrocarbons. Amer.
Lab. (July 1977) pp. 11-18.
b. Stocks, P., and J. M. Campbell. 1955. Lung Cancer Death Rates Among
Nonsmokers and Pipe and Cigarette Smokers. An Evaluation in Relation
to Air Pollution by Benzpyrene and Other Substances. Brit. Med. J.
2: 923-939.
c. Stocks, P., B. T. Commins, and K. V. Aubrey. 1961. A Study of Poly-
cyclic Hydrocarbons and Trace Elements in Smoke in Merseyside and
Other Northern Localities. Int. J._ Air Water Pollut. 4: 141-153.
d. Commins, B. T. 1958. Polycyclic Hydrocarbons in Rural and Urban
Air. Int. J. Air Pollut. 1: 14-17.
e. Sawicki, E. 1967. Airborne Carcinogens and Allied Compounds. Arch
Env. Health 14: 46-53.
f. Colucci, J. M., and C. R. Begeman. 1965. The Automotive Contribu-
tion to Airborne Polynuclear Aromatic Hydrocarbons in Detroit. J
Air Pollut. Control Assoc. 15: 113-122. ~~
A-23
-------
RIVER WATER o.oooi
Benz(a)anthracene
ro
~
Chrysene
Benzo(a)pyrene
Perylene
Db
0.001
POM CONCENTRATIONS IN /
-------
ro
en
RIVER WATER cont. o.oooi
Benzo(ghi)perylene
Fluoranthene
Benzo(b)fluoranthene
POM CONCENTRATIONS IN /
-------
POM CONCENTRATIONS IN
ro
cr>
RIV/FR WATFH™-t o.oooi o.ooi 0.01 0.1
Benzo(k)fluoranthene
r-i
A
Benzo(j)fluoranthene
A
lndeno(1,2,3-cd)pyrene
$£>
— k^y\/
3 b
na
1 a
— -la
• 1 a
rah
1 a
Figure A-4. Ambient concentration of POM in various forms of water in ng/£.
Each line represents a specific reported value. Diagonal lines
indicate ranges.
-------
ro
LAKE WATER
0.0001
Pyrene
Benzo(a)pyrene
I Benzo(ghi)perylene
Fluoranthene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(j)fluoranthene
Indenopyrene
MARINE
Perylene
o.ooi
POM CONCENTRATIONS IN /tg/l
0.01 0.1 1
I
10
Figure A-4. Ambient concentration of POM in various forms of water in
Each line represents a specific reported value. Diagonal llines
indicate ranges.
-------
ro
DO
GROUND WATER o.ogoi
Benz(a)anthracene
POM CONCENTRATIONS IN /(g/l
0.001 0.01 0.1
Pyrene
Benzo(a)pyrene
Perylene
Benzo(ghi)perylene
Fluoranthene
Benzo(b)fluoranthene
Benzo(j)fluoranthene
Indenopyrene
T
** * » d
rff rrfrf * ' * ~ n\ to
323d
_ui d
** * * * 0
nzzzi j
Figure A-4. Ambient concentration of POM in various forms of water in
Each line represents a specific reported value. Diagonal lines
indicate ranges.
10
-------
POM CONCENTRATIONS IN
i
r\i
10
PRECIPITATION
Benz(a)anthracene
xCQ Pyrene
\x^^
Benzo(a)pyrene
OTX) Pe'v|ene
Benzo(ghi)perylene
Fluoranthene
^s ^/
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(j)fluoranthene
Inrf onnnurono
IIUCIIU|jyi CMC
00001 0.001 0.01 0.1 1 10
' ^o'
r^Vri
k^x^-x^— x
-r-rW
CXXJ
rW
^xr
rv^r^r^i
"rrrrrr" \JJL-U
r^VrYi
Q/l1^^^
^v^x ^x1
Figure A-4.
Ambient concentration of POM in various forms of water in
Each line represents a specific reported value. Diagonal lines
indicate ranges.
-------
REFERENCES - POM IN WATER
a. Harrison, R. M., R. Perry, and R. A. Wellings. 1975. Polynuclear
Aromatic Hydrocarbons in Raw, Potable and Waste Waters. Water Res.
9: 331-346.
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A-30
-------
POM CONCENTRATION IN
I
CO
RURAL SOIL °-°l
Benz(a)anthracene
o.i
Pyrene
Benzo(a)pyrene
conl
'frfrrfrff^r
ZZ3 b
10
3 a
3 *
3 e
******I
je
39
100
1000
Figure A-5. Ambient concentration of POM in various soil types in pg/kg.
Each line represents a specific reported value. Diagonal lines
indicate ranges.
-------
POM CONCENTRATION IN /xg/kg
CO
cant.
0.01
Benzo(a)pyrene
Benzo(ghi)perylene
Fluoranthene
con).
0.1
10
100
3d
a
d
I m
36
D e
3 e
3 e
3 a
Figure A-5. Ambient concentration of POM in various soil types in yg/kg.
Each line represents a specific reported value. Diagonal lines
indicate ranges.
1000
-------
POM CONCENTRATIONS IN /ig/kg
com. 0-01
Benzo(b)fluoranthen
Benzo(k)fluoranthene
lndeno(1.2,3 cdjpyrene
oo
Co
0.1
10
~r
100
1000
Figure A-5.
Ambient concentration of POM in various soil types in pg/kg.
Each line represents a specific reported value. Diagonal lines
indicate ranges.
-------
POM CONCENTRATIONS IN /
CO
URBAN SOIL
Benz(a)anthracene
Chrysene
Pyrene
1000
10000
100000
Benzo(a)pyrene
Benzo(e)pyrene
Perylene
Anthanthrene
Benzo(ghi)perylene
Fluoranthene
Benzo(k)fluoranthene
Figure A-5.
Ambient concentration of POM in various soil types in yg/kg.
Each line represents a specific reported value. Diagonal li
indicate ranges.
ines
-------
POM CONCENTRATIONS IN /ig/kg
cont. 1
Benzo(a)pyrene
Benzo(e)pyrene
Perylene
Anthanthrene
cont.
10
100
1000
10000
m
11
TTTtq
DO
DP
aq
14
IP
100000
Figure A-5. Ambient concentration of POM in various soil types in ng/kg.
Each line represents a specific reported value. Diagonal lines
indicate ranges.
-------
POM CONCENTRATIONS IN /Aglkg
INDUSTRIAL SOIL
Benzo(a)pyrene
MARINE SEDIMENTS
Anthracene
CO
cr>
Phenanthrene
Benz(a)anthracene
Chrysene
Pyrene
cant.
10
100
10000
~r
10000
100000
•*"** C
ceo
Mffrfrrrrrrr.
JO
JO
Ik
:m
Figure A-5. Ambient concentration of POM in various soil types in yg/kg.
Each line represents a specific reported value. Diagonal lines
indicate ranges.
-------
POM CONCENTRATIONS IN /tg/kg
cont.
10
1000
3=»
CO
Benzo(ghi)perylene
Coronene
Fluoranthene
10000
100000
Figure A-5. Ambient concentration of POM in various soil types in yg/kg.
Each line represents a specific reported value. Diagonal lines
indicate ranges.
-------
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A-39
-------
A-40
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TECHNICAL REPORT
(Please read Instructions on the reverse
DATA
before completing)
1. REPORT NO.
EPA-600/7-80-044
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
POM Source and Ambient Concentration Data:
Review and Analysis
5. REPORT DATE
March 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
J.B. White andR.R. Vanderslice
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
INE623
11. CONTRACT/GRANT NO.
68-02-2612, Task 86
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; 9/78 - 1/80
14. SPONSORING AGENCY CODE
is. SUPPLEMENTARY NOTES IERL-RTP project officer is
919/541-2745.
EPA/600/13
John O. Milliken, Mail Drop 63,
ACT The report gives results of an analysis of source and ambient concentration
data for polycyclic organic matter (POM). Based on the literature reviewed, POM
data were summarized and the sampling and analytical techniques were critiqued
and evaluated against state-of-the-art technology. The objective was to determine
the scientific and engineering credibility of a previously established POM data base
by an evaluation of the sampling and analytical techniques employed. (POM is an
unregulated class of pollutants which is a potential candidate for regulatory action as
outlined in Section 122a of the Clean Air Act Amendments of 1977.) It was concluded
that sampling techniques contain uncertainties that limit the udesfulness of these data
in an environmental assessment of POM. The uncertainties include the possibility of
the incomplete capture of POM during emission sampling, the chemical degradation
of the collected sample during both emission source and embient sampling, and the
unproven reliability of benzo(a)pyrene as an indicator of total POM from emission
sources or in ambient media. The uncertainties may be compounded by losses during
analysis. Also, since it is not feasible to quantify all the POM which may be present
in an environmental sample, the number of POMs reported will reflect the scope of
the analytical strategy and the limitations of the analytical technique employed.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution Pyrenes
Polycyclic Compounds
Organic Compounds
Sampling
Analyzing
Assessments
Pollution Control
Stationary Sources
Polycyclic Organic Mat-
ter
Benzo(a)pyrene
13 B
07C
14B
8. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
147
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Perm 2220-1 (1-73)
B-28
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