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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                 RESEARCH REPORTING SERIES


Research reports of the Office of Research and Development, U.S. Envirq
Protection Agency, have been grouped into nine series. These nine bra
gories were established to facilitate further development and applicatic
vironmental technology. Elimination  of traditional  grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
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    1. Environmental Health Effects Research

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    4. Environmental Monitoring

    5. Socioeconomic Environmental Studies

    6. Scientific and Technical Assessment Reports (STAR)

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    8. "Special" Reports

    9. Miscellaneous Repous

This report has beqn assigned to the  INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND  DEVELOPMENT series Reports in this series  result from the
effort funded  under  the 17-agency Federal Energy/Environment Research and
Development Program. These studies  relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to  assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology  Investigations include analy-
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This report has been reviewed by the participating Federal Agencies, and approved
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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

-------
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

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      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

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              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

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    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

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           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

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      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

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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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                    REFERENCES CITED FOR SECTION 3.0

 1.   Bond, R. G., and C. P.  Straub, eds.  1972.  Handbook of Environmental
     Control.  Volume 1.  Air Pollution.  CRC Press, Cleveland, Ohio.

 2.   Benchley, David L., C.  D. Turley, and R. F. Yarmac.  1974.  Indus-
     trial Source Sampling.  Ann Arbor Science Publishers, Inc., Ann Arbor,
     MI.

 3.   Pupp, C., R. C. Lao, J. J. Murray, R. F. Pottie.  1974.  Equilibrium
     Vapor Concentrations of Some Polycyclic Aromatic Hydrocarbons, As40g
     and SeO, and The Collection Efficiencies of These Air Pollutants,
     Env.  Set, and Tech. 8:  915-925.

 4.   Commins, B.  T.  and P.  J. Lawther.  1958.  Brit. J_._ Cancer 12: 351-354.

 5.   Rondia, D.   1966.   The Protection of Metallic Conduits by Varnishes
     with Pitch and Bitumen Bases.  Tribune CEBEDEAU 19: 220-226 (French).
     Chem. Abstr. 65: 6955a.

 6.   Jones, P. W., R. D. Giammar, P. E. Strup, and T. B. Stanford.   1976.
     Efficient Collection of Polycyclic Organic Compounds.  Env. Sci. and
     Tech. 10(8): 806-810.

 7.   Feuirheller, W., et al.  1976.  Technical Manual for Process Sampling
     Strategies for Organic Materials.  EPA 600/2-76-122, April.

 8.   Adams, J.  1977.  Selection and Evaluation of Sorbent Resins for
     Collection of Organic Compounds.  EPA 600/7-77-044.

 9.   Spindt, R.  S.  1974.  Study of Polynuclear Aromatic Hydrocarbons
     Emissions from Heavy Duty Diesel Engines.  Coordinating Research
     Council, Inc.,  EPA, PB 238-688.

10.   Lane, D. A., and M. Katz.  1977.  The Photomodification of Benzo(a)
     pyrene, Benzo(b)fluoranthene, and Benzo(a)fluoranthene under Simu-
     lated Atmospheric Conditions.  Fate of Pollutants j_n the Air and
     Water Environments. Part 2, I. A. Suffet, Ed., Wiley-Interscience,
     NY.

11.   Korfmacher,  W.  A.,  D.  F. S. Natusch, and E. Wehry.  1978.  Thermal
     and Photochemical  Decomposition of Particulate PAH.  Third Interna-
     tional Symposium of Polynuclear Aromatic Hydrocarbons, Columbus, OH,
     October 25-27.

12.   Natusch, D.  F.  S.  and B. A. Tomkins.  1978.  Theoretical Considera-
     tions of the Adsorption of Polynuclear Aromatic Hydrocarbon Vapor
     onto Fly Ash in a Coal-fired Power Plant.  Chemistry, Metabolism,
     and Carcinogenesis. Vol. 3: Polynuclear Aromatic Hydrocarbons.  R.
     W.  Jones, and R. J. Freudenthal, eds., Raven Press, New York.
                                      23

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 13.   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.

 14.   Corn,  M.,  T.  L.  Montgomery,  and N.  A.  Esmen.   1971.   Suspended Par-
      ticulate  Matter:   Seasonal Variations  in Specific Surface Areas and
      Densities.   Env. Sci.  and Tech.  5:155-158.

 15.   Starkey,  R.,  and J. Warpinski.   1974.   Size  Distribution of Particu-
      late  Benzo[a]pyrene.   «L_  Env.  Health.  Mar/Apr:  503-505.

 16.   Katz,  M.,  and R. C. Pierce.   1976.   Quantitative  Distribution of
      Polynuclear  Aromatic Hydrocarbons  in Relation  to  Particle Size of
      Urban  Particulates.  Carcinogenesis, Vol.  L_  Polynuclear Aromatic
      Hydrocarbons:  Chemistry.  Metabolism, and Carcinogenesis.   R.  J.  Freud-
      enthal and P.  W. Jones, eds.,  New  York,  Raven  Press,  pp.  413-429.

 17.   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.

 18.   DeMaio, L.,  and  M. Corn.   1966.  Polynuclear Aromatic Hydrocarbons
      Associated with  Particulates  in  Pittsburgh Air.   J_._ Air  Pollut.  Con-
      trol Assoc.  16:  67-71.

 19.   Katz,  Morris,  (ed.).   1977.  Methods of Air  Sampling  and Analysis.
      2nd Edition.   American Public  Health Association.

 20.   Lee, R. E. , J. S.  Caldwell, and  G.  B.  Morgan.   1972.   The Evaluation
      of Methods for Measuring  Suspended  Particulate  in Air Atm.  Env.  6:
      543-662.

 21.   McKee, H.  C.,  R. E. Childers,  0. Saenz,  Jr., T. W. Stanley,  and J.
      H. Margeson.  1972.  Collaborative Testing Method  to Measure  Air
      Pollutants 1.  The High Volume Method  for Suspended Particulate
      Matter J^  Air  Pollut.   Control  Assoc. 22(5):  342-347.

 22.   National Research Council Subcommittee  on Airborne Particles.   1977.
      Airborne Particles.  National  Academy  of Sciences, Washington,  D.C.

 23.   Committee  on the Challenges of Modern  Society.  1972.  Air  Pollution:
      Guidelines to  Assessment  of Air  Quality  (Revised)  SO  , TSP,  CO,  HC,
      NO , and Oxidants N.6, A  Report  by  the  NATO  CCMS  Air  Pollution  Pilot
     I1W , 
-------
26.  Stenburg,  R.  L.,  D. J. von  Lehmden,  and  R.  P.  Hangebrauck.  1961.
     Sample Collection Techniques  for  Combustion Sources  -  Benzopyrene
     Determination Am. Int. Hyg. Assoc. J_._  22:  271-275.

27.  Commins, B. T.   1962.  Interim  Report  on the Study of  Techniques for
     Determination of  Polycyclic Aromatic Hydrocarbons in Air.   Nat. Can-
     cer  Inst.  Man.  9:225-233.

28.  Miguel, A. H.,  and  S.  K.  Friedlander.  1978.   Distribution  of  Benzo(a)
     pyrene and Coronene with  Respect  to  Particulate  Size in  Pasadena
     Aerosols in the Submicron Range.   Atmos.  Env.  12: 2407-2413.

29.  Bunn, W. W.,  E. R.  Dean,  D. W.  Klein,  and R.  D.  Kleopper.   1975.
     Sampling and  Characterization of  Air for Organic Compounds.  Water
     Air  Soil Pollut.  4(3-4):  367-380.

30.  Pellizzari, E.  D.,  0.  E.  Bunch, R. G.  Benchley,  and  J. McKee.   1976.
     Determination of  Trace Organic  Vapor Pollutants  in Ambient  Atmos-
     pheres by  GC/MS Computer.   Anal.  Chem. 48(6):  803-807.

31.  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.

32.  DeWiest, F.,  and  D. Rondia.   1976.   On the Validity  of Determinations
     of Benzo[a]pyrene in  Airborne Particles  in the Summer  Months.   Atmos.
     Environ. 10(6): 487-489.

33.  Katz, M.,  C.   Chan,  and H. Tosine.  1978.   Relationship Between Rela-
     tive Rates of Photochemical and Biological  Oxidation of  Polynuclear
     Aromatic Hydrocarbons  and Their Carcinogenic Potential.   Third Inter-
     national Symposium  on  Polynuclear Aromatic Hydrocarbons,  Columbus,
     OH,_October 25-27.

34.  Basu, D. K.,  and  J. Saxena.   1978.   Polynuclear  Aromatic  Hydrocarbons
     in Selected U.S.  Drinking Waters  and Their Raw Water Sources.   Env.
     Sd. Tech. 12: 795-98.

35.  Burnham, A. K., G.  V. Calder, J.  S.  Fritz,  G.  A. Jink, H. J. See,
     and R.  Willis.  1972.  Identification  and  Estimation of Neutral
     Organic Contaminants  in Potable Water.   Anal.  Chem.  44(1):   139-142.

36.  Grosser, Z. A. , J.  C. Harris, and P. L.  Levins,  Quantitative Extrac-
     tion of PAH and Other Hazardous Organic  Species  From Process Streams
     Using Macroreticular  Resins.  1978.  Third International  Symposium
     on Polynuclear Aromatic Hydrocarbons,  Oct.  25-27, Battelle-Columbus
     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

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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

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                           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

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                      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

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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

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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

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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

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   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

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      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

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                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

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                   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

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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

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                               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

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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

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                             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

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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

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   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

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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

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      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

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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

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     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

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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

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     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

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         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

-------
     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

-------
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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     Med.  68(7): 1136-1141.

46.   Graf, W.,  and W.  Nowak.   1966.   Promotion  of Growth in Lower and
     Higher  Plants  by  Carcinogenic  Polycyclic Aromatics.  Arch.  Hyg.  Bakt.
     150:  513-28.   ORNL/tr-4111.

47.   Mallet,  L., A. Perdriau,  and  J.  Perdriau.   1963.   The  Extent of  Pollu-
     tion  of BP-type  Polycyclic  Hydrocarbons  of the  Western Region of the
     Artie Ocean.   C^ R._ Acad. Sci.  (Paris) 256(16):  3787-3489.

48.  Hettche, H. 0.   1971.   Plant  Waxes as Collectors of PCAH in the  Air
     of  Polluted Areas.  Staub.  31:  72-76; Chem. Abstr.  74, 145943.

49.  Cherepanova,  A.  J.  1971.   Levels of Polycyclic Hydrocarbons in  Feeds
     and Mineral Supplements and Their Possible Buildup in  Tissues,  Organs,
     Eggs, and  Milk.   Zap.  Leningrad.  Selshokhoz Inst.  141:  97-106.

50.  Gorelova,  N.  D.,  and P.  P.  Dikun.   1958b.   BP  in Smoked Sausage and
     Bologna.   Vop. Onkol.  4:  405-408 (Russian). Chem.  Abstr.  (1959)  53:
     6468e.

51.  Tilgner, D. J. and H.  Daun.   1969.  Polycyclic Aromatic Hydrocarbons
     (Polynuclears) in Smoked Foods.   Residue Reviews 27: 19-41.
                                       69

-------
52.  Forest, J. C., E, D. Aberle, H. B. Hedrick, M. D. Judge,  and  Rob
     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.

b.   Basu, D. K., and J. Saxena.  1978.   Polynuclear  Aromatic Hydrocarbons
     in Selected U.S. Drinking Waters and Their Raw Water Sources.  Env.
     Sci. and Tech.  12: 795-98.

c.   Dikun, P. P. and A. I. Makhinenko.   1963.  Detection of BP  in the
     Schistose Plant Resins, in Its Effluents and  in  Water  Basins After
     Discharge of Effluents.  Gig, i. Sanit. 28:(1):  10-12  (Russian).
     Chem. Abstr.. 1963, 59, 3640g.

d.   Woidich, H., W. Pfannhauser, and G.  Blaicher.  1976.   Analysis of
     Polycyclic Aromatic Hydrocarbons in  Drinking  and Technically Used
     Water.  Lebensmittelchemie Und Gerichtliche Chemie 30(8): 141-160.

e.   Basu, D. K., and J. Saxena.  1977-78.  Analysis  of Raw and  Drinking
     Water Samples for Polynuclear Aromatic Hydrocarbons, EPA P.O. No.
     CA-7-2999-A, and CA-8-2275-B, Exposure Evaluation Branch, HERL,  Cin-
     cinnati, OH.

f.   Siddiqi, I., and K. H. Wagner.   1972.  Determination of 3,4-Benzpyrene
     and 3,4-Benzofluoranthene in Rain Water, Ground  Water, and  Wheat.
     Chemosphere 1(2):  83-88.

g.   Borneff, J.  1977.  Fate of Carcinogens in Aquatic Environments.
     Fate of Pollutants jm the Air and Water Environments,  Part  2, I. A.
     Suffet ed., New York, Wiley-Interscience.

h.   Niaussat, P., and C.  Auger.  1970.   Distribution of Benzo!apyrene
     and Perylene In Various Organisms of the Clipperton Lagoon  Ecosystem.
     Compt. Rend. Ser.  D_._ 274:  2702-2705.

i.   Gilbert, J. A.  S.  and A. J. Lindsey.  1955.   The Determination of
     the Amount and  Distribution of Atmospheric Smoke Pollution  by Analy-
     sis of Snow.  Chemy.  Ind.  33: 1439-1440.

j.   Cooper, R.  L.,  and A. J. Lindsey.  1955.  3:4-Benzpyrene and Other
     Polycyclic Hydrocarbons in Cigarette Smoke.   Brit. «h_  Cancer 9:
     304-309.
                                       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.

-------
                        REFERENCES -  POM  IN  SOIL

a.   Borneff, J., and H. Kunte.   1963.  Carcinogenic  Substances  in Water
     and Soil.   XIV.  Further  Investigation  Concerning  Polycyclic Aromatic
     Hydrocarbons in Soil Samples.  Arch. Hyg.  147: 401-409.

b.   Hites, R. A., R. E. LaFlamme, and J. W.  Farrington.   1977.  Sedimentary
     Polycyclic  Aromatic Hydrocarbons:  The  Historical  Record.   Science
     198: 829-831.

c.   Matshushita, H., K. Arashidani,  and  M.  Koyano.   1977.   Simple Analysis
     of Polycyclic Aromatic Hydrocarbons  in  Soil.  Taiki Osen  Kenkyu  11(4):
     352-359.

d.   Mallet,  L., and C. Scheider.  1964.  Presence of Polybenzene Hydro-
     carbons  of  the Benzo-3,4-pyrene  Type in Geological and  Archeological
     Levels.  Compt. Rend. 259(3): 675-76.

e.   Harrison, R. M., R. Perry, and R. A. Wellings.   1975.   Polynuclear
     Aromatic Hydrocarbons in  Raw, Potable and  Waste  Waters.   Water  Res.
     9: 331-346.

f.   Medve, E.,  and K. Herman.  1977.  Natural  3,4-Benzopyrene Content of
     Soil Plant  Samples of a Self-Supporting Ecosystem.  Egesxsegtudomany
     21(1): 76-79.

g.   Mallet,  L., and M. Heros.  1961.  Investigations on the Fixation of
     BP-type  PH  by Micro-organisms and Their Role as  Vectors of  Carcino-
     genic Substances.  C_._ £._  Acad. Sci.  (Paris) 253: 587-589  (French).

h.   Binet, L.,  and L. Mallet.  1963.  Diffusion of PH  in  the  Animated
     Environment.  Gaz. Hop. (Paris), 135: 1142 (French).  Chem. Abstr.,
     1964, 60: 2282c.

i.   Kolar, L.,  R. Ledvina, J. Ticha, and R.  Hanus.   1975.   Contamination
     of Soil, Agricultural Crops, and Vegetables by 3,4-Benzpyrene  in the
     Vicinity of Ceska Budjovice.  Cesk Hyg.  20(3): 135-139.

j.   Shabad,  L.  M., and G. A.  Smimov.  1972.  Aircraft  Engines as a  Source
     of Carcinogenic Pollution of the Environment-Benzo[a]pyrene Studies.
     Atmos. Environ. 6: 153.

k.   Shabad,  L.  M., Y. L. Cohan, A. Ya. Khessina, H.  P. Schubak, and G.
     A. Smirnov.  1969.  The Carcinogenic Hydrocarbon Benzo[a]pyrene in
     the Soil.   J. Nat. Cancer Inst.  47:  1179-1191.

1.   Blumer, M., and W. W. Youngblood.  1975.   Polycyclic  Aromatic  Hydro-
     carbons  in  Soils and Recent Sediments.   Science  188:  53-55.

m.   Shabad,  L.   M.  1967.  .Studies in the U.S.S.R. on the  Distribution,
     Circulation, and Fate of  Carcinogenic Hydrocarbons in the Human Envir-
     onment and  the Role of Their Deposition in Tissues in Carcinogenesis:
     A Review.   Cancer Res. 27: 1132-1137.
                                      A-38

-------
n.   Mallet, L.  1966.   Investigation  on  the  Presence  of  BP-type  PH  in
     the Deep Sediments  Underlying the Seine  Bed  Downstream  from  Paris.
     Gaz. Hop. (Paris) 138(2): 69-70 (French).  Chem.  Abstr.  1966, 64,
     19234b.                                    	

o.   Giger, W. and M. Blumer.  1974.   Polycyclic  Aromatic Hydrocarbons  in
     the Environment:  Isolation and Characterization  by  Chromatography,
     Visible, Ultraviolet and Mass Spectrometry.  Anal. Chem. 46:  1663.

p.   Bourcart, J., and L Mallet.  1965.  Marine  Pollution of the Shores
     of the Central Region of the Tyrrhenian  Sea  (Bay  of  Naples)  by  BP-type
     PH.  C^ R^ Acad. Sci. (Paris) 260: 3729-3734 (French).   Chem. Abstr.
     1965, 62, 15004b.	

q.   Suess, M. J.  1972.   Polynuclear  Aromatic  Hydrocarbon Pollution of
     the Marine Environment.  Marine Pollution  and Sea Life.  Ed.  M.  Ruivo,
     pp. 568-70.   London:  Fishing News (Books) Ltd.

r.   Mallet, L.,  A. Perdriau, and J. Perdriau.  1963.   The Extent of Pollu-
     tion of BP-type Polycyclic Hydrocarbons  of the Western  Region of the
     Artie Ocean.  C.. R^. Acad. Sci. (Paris) 256(16): 3787-3489.

s.   Bourcart, J., and L. Mallet.  1965.  Marine  Pollution of the Shores
     of the Central Region of the Tyrrhenian  Sea  (Bay  of  Naples)  by  BP-type
     PH.  C^ R.. Acad. Sci. (Paris) 260: 3729-3734 (French).   Chem. Abstr.
     1965, 62, 15004b.                                        	

t.   Blumer, M.  1977.  Polycyclic Aromatic Hydrocarbons  in  Soils of a
     Mountain Valley:  Correlation with Highway Traffic and  Cancer Incid-
     ence.  Env.  Sci. and Tech. 11(12) 1082-1084.
                                      A-39

-------
A-40

-------
                           APPENDIX  B  -  BIBLIOGRAPHY


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 Adamek, E. G.   1976.   A Two-Year Survey of Benzo(a)pyrene and Benzo(k)
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 Adams,  J.   1977.   Selection and Evaluation of Sorbent Resins for Collec-
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 Aizenshtat,  Z.   1973.  Perylene and Its Geochemical  Significance.  Geochim
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 Bartle,  K. D.,  M. L.   Lee,  and M. Novotny.   1976.  An  Integrated  Approach
 to the Analysis of Air-pollutant Polynuclear Aromatic  Hydrocarbons.   Proc.
Analyst Div. Chem. Soc.. Oct.: 304-307.                               	

                                    B-l

-------
 Basu,  D.  K.,  and J.  Saxena.   1977-78.   Analysis of Raw and Drinking Water
 Samples for  Polynuclear Aromatic Hydrocarbons, EPA P.O.  No.  CA-7-2999-A,
 and CA-8-2275-B, Exposure Evaluation Branch,  HERL, Cincinnati, OH.

 Basu,  D.  K.,  and J.  Saxena.   1978.   Monitoring of Polynuclear Aromatic
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 Basu,  D.  K.,  and J.  Saxena.   1978.   Polynuclear Aromatic Hydrocarbons in
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 Begeman,  C. R.  and J.  M.  Colucci.   1968.   Benzo(a)pyrene in  Gasoline Par-
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 Begeman,  C. R., and  J.  M.  Colucci.   1970.   Polynuclear Aromatic Hydrocar-
 bon Emissions  from Automotive Engines.   SAE Paper 700469.   Detroit:   Soci-
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 Beine,  H.  1970.  The Level  of 3,4-Benzopyrene in the Waste  Gases of Do-
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 Benchley,  David L.,  C.  D.  Turley,  and  R.  F. Yarmac.   1974.   Industrial
 Source Sampling. Ann Arbor Science  Publishers,  Inc.,  Ann Arbor, MI.

 Bentley,  H. R.  and J.  G. Burgan.   1958.   Polynuclear  Hydrocarbons in Tobacco
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 Bentley,  H. R.,  and  J.  G.  Burgan.   1960.   Polynuclear Hydrocarbons  in
 Tobacco and Tobacco  Smoke.   Part II.   The  Origin of 3:4-Benzopyrene  Found
 in  Tobacco and  Tobacco  Smoke.   Analyst 85:  723-727.

 Bergmann,  E. D. , R.  Ikan,  and J.  Kashman.   1964.   The Occurrence  of  Pery-
 lene in Huleh  Peat.   Israel  vh_ Chem. 2:  171-172.

 Biernoth, G.,  and H.  E. Rost.   1967.   The  Occurrence  of  PAH  in Coconut
 Oil  and Their  Removal.  Chemy.  Ind.  45:  2002-2003.

 Biernoth, G. ,  and H.  E. Rost.   1968.   The  Occurrence  of  PAH  in Edible
 Oils and Their  Removal.  Arch.  Hyg.  (Berl). 152:  238-250 (German)

 Binet,  L., and  L. Mallet.  1963.  Diffusion of  PH in  the Animated Environ-
 ment.   Gaz. Hop. (Paris),  135:  1142  (French).   Chem.  Abstr..  1964,  60:
 2282c.

 Bingham, E., A. W. Horton, and  R. Tyre.   1965.   The Carcinogenic  Potency
 of Certain Oils.  Arch. Environ. Health  10: 449-451.

 Bjorseth, A.   1978.   Analysis  of Polycyclic Aromatic  Hydrocarbons in Envi-
 ronmental Samples by Glass Capillary/Gas Chromatography.   Carcinogenesis,
Vol. 3. P. Jones and R. I. Freudenthal,  eds.,  Raven Press, NY  75-83.
                                      B-2

-------
Bjorseth, A., and B. Olufsen.  1978.  Results from a Nordic Round Robin
Test for PAH Analysis.   Nordic PAH-Project. Report No.  1, September 1978.

Blumer, M.   1975.  Curtisite, Idrialite and Pendletonite, Polycyclic Aro-
matic Hydrocarbon Minerals: Their Composition and Origin.  Chem.  Geol.
16: 245-56.

Blumer, M.   1977.  Polycyclic Aromatic Hydrocarbons in Soils of a Mountain
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                                      B-27

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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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