PB80-146418
Status Assessment of Toxic Chemicals: Polynuclear Aromatic Hydrocarbons
Monsanto Research Corp, Dayton, Ohio
Prepared for
Industrial Environmental Research Lab-Cincinnati, Ohio
December 1979
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
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&EPA
wiiv it wi«tiiotiuJi r
Agency
December iy-/9..
Cincinnati OH 45268
Research and Development
Status
Assessment of
Toxic Chemicals
Polynuclear Aromatic
Hydrocarbons
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The nine series are:
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2. Environmental Protection Technology
3. Ecological Research ..... .
4. Environmental Monitoring
5, Socioeconomic Environmental Studies
6. Scientific and technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
:" 8:; "Special" .Reports V
9. Miscellaneous Reports .
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved .technology-required for the control and treatment
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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' TECHNICAL REPORT DATA'
(Please read Instructions on the reverse be-fore completing)
1. H-gP.ORT NO. ..-
EPA-.600/2-79-210L
'S ACCESSIO
"
4. TITLE AND SUBTITLE
Status Assessment of Toxic Chemicals: Polynuciear
Aromatic Hydrocarbons
>. REPORT:OA-TE
December 1979 issuing date
6. PERFORMING ORGANIZATION CODE
7! AUTHOH(S) : ' ' ..,-.
T.R. Blackwood, S.R, Archer
G.E. Wiltons
$. PERFORMING tSHtSAWZATIOT* RE.TORT NO.
9. PEHFORX/H-Nq ORGANIZATION NAME ANO;AC-OR4ES$ ' ' ' -' : ' v
Monsanto Research Corp Radian Corp
1515 Nichols Road 8500 Shoal Creek Blvd
Dayton, Ohio U5UOT P.O. Box 99^8
Austin, Texas T8T66
1O. PROGRAM 6X6MENT NO.
1AB60U
TV. CONTRACT/GRANT
68^03-2550
12' SPONSORING AGENCY NAME' AND ADOReSS ' :
Industrial Environmental Research Lab. T Cinn, OH
Office of Research and Development
U,S.. Environmental Protection Agency
Cincinnati, Ohio J+5268 .'
13. TVPt OF REPORT AND PERIOD'COVEREP
Task Final 11/77 - 12/77 .
14.
cooe
EPA/6.00/12,
15. SUPPUE'lvrENTARY NOTES
IER|TCi project leader'for this report is Dr. Ghar.les Frank,
16. ASST.RA'OT
This report identifies the origins ^ .applications, environmental ..
effect's,' and health effects of polynuciear- aromatic hydrocarbons.
Ways to reduce polynuciear aromatic hydrocarbon; (PNA) .emissiorisr and - ".
problems associated with PNA derived effluents in the dye industry
are discussed. 'Finally, various regulatory actions are listed
and. recommendations are made for further areas of study. ..
17.
WORDS ANQ.OOCUMENT ANALYSIS
DESCRIPTORS
^IDENTIFIERS/OPEN ENDED TERMS C. ' COSATI Field/Group
Polynuciear hydrocarbons, triphenylene,
Aromatic Polycyclic Hydrocarbons,...Aromatic
Toxic chemicals, Poly-
nuclear Aromatic Hydro--"
Hydrocarbons, Hydrocarbons, Unsaturated
Hydrocarbons, Anthracen-e, Biben-tyl, Bi-'
phenyl, Fluorenes, Methylcholanthrene, Aliihat'lc'.; pqlycyc'iic-
carbons, Aromatics, Chry-
sene " '
68A
68D
68G
Hydroca roons
Naphthalene, Phenanthrene, PolyphenyLHydro<
arbons,. Benzanthracenes,
pyrenes, stilbenes.,. terphenyls, acenaphthyienes, Unsaturated Organic
lapthacenes,
Compounds
13. DISTRIBUTION STATEMENT "
Release to Public
$. .SECURIT-Y OUASS./TVrif Repvrt>
Unclassified
2V. NO. DF
20. SECURITY Ct_ASS
Unclassified
23. PRICE
EPA Form 2230-1 (3-73)
u i oovBiiuiwr mutaeam*-. i«o-657-146/5519
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EPA-600/2-79-210L
December 1979
STATUS ASSESSMENT OF TOXIC CHEMICALS;
POLYNUCLEAR AROMATIC. HYDROCARBONS
S. R. Archer
T. R. Blackwood
Monsanto Research Corporation
Dayton, Ohio 45407
and
G. E. Wilkins
Radian Corporation.
Austin, Texas 78766
Contract No, 68rQ3-.2S50
--. ... Project Officer
.. , ' David- L. -Becker
Industrial Pollution Control Division
Industrial Environmental Research Lalporatory
, .Cincinnati, .Ohio 452-68
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI,' OHIO 45268
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DISCLAIMER
This report has been reviewed by the Industrial Environmental
Research Laboratory - Cincinnati, U.S. Environmental Protection
Agency, and approved for publication. Approval does not signify
that the contents necessarily reflect the views and policies of
the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or
recommendation for use.
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FOREWORD
When energy and material resources are extracted, processed,
converted, and used, the related pollutional impacts on our
environment and even on our health often require that new and
increasingly more efficient pollution control methods be used.
The Industrial Environmental Research Laboratory - Cincinnati
(IERL-Ci) assists in developing and demonstrating new and
.improved methodologies that will meet these needs both effi-
ciently and economically.
. . This report contains a status assessment of the air
emissions, water pollution, health effects, and environmental
significance of ,trio (2,3 dibromopropyl) pho-s^feafee. This study
was conducted to provide a better understanding of the distri-
bution and characteristics of this pollutant. Further informa-
tion on this subject may:be obtained from the Organic Chemicals
and Products Branch, Industrial Pollution Control Division. .
Status a/ssessment reports are used by IERL-Ci to communi-
cate the readily available information on selected substances to
government, /industry, and persons having specific needs and
interests. /These reports are based primarily on data from open
literature /sources, " including government reports, They are
indicative/rather than exhaustive.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
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Polynuclear aromatic hydrocarbons (PNA's) enter the environment
from natural and anthropogenic (man-made) sources. The main
PNA's of commercial significance are phenanthrene, chrysene, and
anthracene, which are refined from coal-derived chemicals. The
1974 capacity of ph«nanthren-e, anthracene, and other PNA produc-
tion facilities was 3.63 x 105 metric tons/yr.
Sources of anthropogenic PNA emissions include, combustion or
pyrolysis of fuels, processing of fuels', and manufacturing spe-
cialized organic Chemicals., The majority of PNA emissions pro-
bably arise as pyre-lysis products formed during combustion or
heating of fossil fuels or natural prbducts. Arithmetic mean
concentrations of PNA's in air have been calculated as
0.4 yg/1,000 m3 and 3 yg/1,000 m3 for nonurban and urban loca-
tions, respectively, showing that urban concentrations, tend to
be much greater than nonurban concentrations.
Reduction of atmospheric PNA emissions from combustion sources
can be achieved by proper control of combustion. Secondary com-
bustion devices.for flue gases could also reduce emissions.
Since the major mode of transportation for PNA's appears to be
adsorption onto particulates; control can be achieved by conven-
tional particulate control devices, such as mechanical collectors
or eletrostatic precipitators. indications show that chlorina-
tion and ozonation of water supplies destroys PNA's, however,
byproducts formed by chlorinatibn may result in more toxic
compounds.
Limitation of carbon monoxide and hydrocarbon emissions from
motor vehicles have simultaneously and dramatically reduced PNA
emissions. Similarly, compliance with existing regulations for
incinerators, open burning, coal combustion, and coking opera-
tions could have corresponding benefits.
PNA derivative* employed as the basic structures in a number of
important dyes and pigments represent a major source of water
pollution, large quantities of brines containing organic,
highly colored materials are produced as wastes. Further
information is needed on the magnitude of this problem and on
the most effective controls.
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Sased upon the information presented in this report, several
items need to be considere4 for further studies. Production
quantities and sites of producer and use facilities should be
identified. Effluents from organic dye and pigment manufacturing
processes needs to be characterized and PNA concentrations
quantified to determine the most effective controls. Transport
methods in air and water should be studied so that the most
effective controls may be achieved. Effects of long-term expo-
sure of low^level PNA cpncentrations on humans should be deter-
mined and the associated population at risk identified. Finally,
chlorination and psonatioh of wastewaters should be reviewed for
control efficiencies and for identification of possible toxic
byproducts.
This report was submitted in partial fulfillment of Contract
68-rQ3-2550 by Monsanto Research Corporation under the sponsorship
of the U.S. .Environmental Protection Agency. This repc-rt covers
the period November 1, 1977 to December 31, 1977. The work was
completed as of January 20,
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CONTENTS
Foreword ..... iii
Abstract iv
Tables viii
Conversion Factors and Metric; Prefixes ...... x
Acknpwledgement. , xi;
1. Introduction. ................. ... ... 1
. .,2. Summary . . . . .', ................. ""'' -2
3." Source, Description. . , . . r . .'..-. .? r. 3
Chemical and physical properties . . ...... , . ,3
. Production and use of polynuclear aromatic hydr-o-r
- carbons 8
4. Environmental Significance arid Health Effects .... 12
Environmental significance ............ 12
Health effects . . , ,..."', ............ 24.
.5. Control Technology. 27
. . Stationary .sources . . . . . ..*.... ~. . . . . 27
Mobile 28.
6. Regulatory Action ~. 30
References . 31
Preceding page blank
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TABLES
Number
1 Polynuciear Aromatic Hydrocarbons ......... 3
2 Names and Synonyms for 12 PNA's .... ...... 6
3 Physical Properties of Six PNA's .......... 7
4 Vapor Pressure and Vapor Concentration of Selected
PNA's at 25°C . ............ ..... 7
5 Coal T-ar Resin -Producers. *";'*... ....... 8
6 Steel Companies Expanding PNA Production. ..... 11
7 Major Uses o£ Three PNA's ...... ^ ..... . 11
8 .Estimates of Annual Benzo (a)pyrene Emissions from
Various Sources . . * . ..... ....... i 13
9 Emissions of PNA From Coal-fired Plants ...... .14
10 Emissions Of PNA From Coal-fired Residential
Furnaces* . ..... . . . . . . . . . ........ . 14;.
11 Emissions of PNA From Intermediate-sized Coal-
fired Units . * i ........... ..... 14
12 Emissions of PNA. From Intermediate and Small-sized
Oil-fired Units ...... ........ ... 15
13 Emissions of PNA From Intermediate and Small-sized
-^ fired Units with Premix Burners ....... 15
14 Emissions of PNA From Incineration and Open
'Burning ...... i ......... ..... 15
15 Emissions of PNA From Motor Vehicles ........ 15
16 Emissions of PNA From Petroleum Refining ...... 16
17 Emissions of PNA From Catalyst Regeneration in
Petroleum Catalytic Cracking ........... 16
18 Concentration of PNA in Partieulates in Air Near
Steel and Coke Plant ............... 17
19 Emissions of PNA From Asphalt Blowing ....... 17
20 Emissions of PNA From Asphalt Hot^-Road Mix Plants . 18
21 Concentration of PNA in Partic-ulates in Air Near
Carbon Black Plant ..... ........... 18
viii
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TABLES (continued)
Number . Page
22 Miscellaneous Industrial Sources of PNA's 19
23 Atmospheric Concentration of PNA's in Several
Cities 20
24 Variations of PNA Concentration with Traffic. ... 20
25 PNA's in Organic Particulate Matter from Six Cities 20
26 Carcinogenic PNA Concentrations in Water Sources. . 21
27 PNA Concentrations, in Water . _.... ........... .21
28 Concentrations of PNA in Various Soils. ...... 21
29 PNA Concentrations in Cereals and Potatpes 22
30 PNA Cpncentratipns in. Vegetables and Fruits .... 23
31 PNA Concentrations in. Cooked, Smoked, and Processed
Foods . . ..',-. . , .'. '.'. ... . . '. . . . .' , . 23
32 PNA Concentrations in Beverages 24
33 Fossil Fuel and Its. Deriyative.s . . . ..... . ........ 24
34 Toxicity of Some PNA1 s. . 25
35 Automotive Benzo (a) pyrene Emission Factors 29
IX
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CONVERSION FACTORS AND METRIC PREFIXES3
CONVERSION FACTORS
To convert from ,. . ., to . . , Multiply by
Degree Celsius (°C) Degree Fahrenheit t|, = 1.8 t° + 32
Kilogram (kg) Pound-mass (pound-mass
avoirdupois) 2.204
Kilometer2 (km2). . Mile2 3.860 x 10"1
Meter3 (m3) Foot3 3.531 x.101
Meter3 (m3) ... , -Gal-Ion (U.S; liquid) 2.642 x 102
Metric ton . -Pound-mass 2.205 x 103
Pascal (Pa) : Pound-force/inch2 (psi) 1.450 x 10"1*
METRIC PREFIXES
Prefix Symbol Multiplica tjon. ;factor . Example
Kilo k 103 1 kg = 1 x 103 grams
Milli .. m . 1:0.~3. . .1 mm = 1 x 10~3 meter
Standard for Metric Practice. ANSI/ASTM Designation:
E 380-76e, IEEE Std 268-1976, American Society for Testing and
Materials, Philadelphia, Pennsylvania, February 1976. 37 pp.
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ACKNOWLEDGMENT
This report was assembled for EPA by Radian Corporation, Austin,
TX, and Monsanto Research Corporation, Dayton, OH. Mr. p. L.
lecker served as EPA Project Officer, and Dr. C. E. Frank, EPA
Consultant, was principal advisor and reviewer.
XI
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EPA 600/2-79-210L
ERRATA SHEET
2/11/80
Plaaia chatig* the ' following:
page iii, paragraph 2, line 3, from "tris(2,3i-dibr6mopropyl)'"
to "pblynuclear aromatic liydrocarbons".
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SECTION 1
INTRODUCTION
Polynuclear aromatic hydrocarbons (PNA's) enter the environment
from natural and man-made sources, including combustion or
pyrolysis of fuels, processing of fuels, and manufacturing spe-.
ciali±ed organic chemicals. Increased levels of PNA's in urban .
air, in water, and i*1 foods have caused rising concern due'to"
the carcinogenic, mutagenic, and teratbgenic properties pf
several PNA1s.
There is a need to define the various sources from which PNA's
may enter the environment, to establish consequent health and
environmental effects, and to examine possible control strategies
and current regulatory actions. This report provides a brief
overview describing these items, with emphasis on PNA emission
sources and resulting environmental levels.
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SECTION 2
SUMMARY
Polynuclear aromatic hydrocarbons (PNA's) enter the environment
from natural and man-made sources. These compounds occur natu-
rally in plants and food, and are present in coal tar and creo-
sote, which are derived from the breakdown of coal. The main
PNA's of commercial significance, which are refined from coal-
derived chemicals, are phenarithrene, chrysene, and anthracene.
Essentially all commercial PNA's are used as reagents in organic
synthesis. Table 1 highlights available information regarding
PNA's.
PNA's are high melting, high boiling solids with low vapor pres-
sures and low solubilities in water. Anthracene and phenanth-
rene can be refined from creosote, a distillation product of coal
tar. The 1974 capacity of anthracene, phenanthrene, and other
PNA production facilities was 3.63 x 10^ metric tons/yr, and
this capacity is expected to increase 10% by 1981.
Probably arising as pyrolysis products formed during combustion
or heating of fossil fuels, PNA's are found in living plant and
animal tissue, sediments, soils, air, and surface waters. Other
man-made emission sources include.processing of fuels and manu-
facturing .specialized organic chemicalsi Combustion sources are
the largest contributors to PNA emissions.
There are many compounds derived from PNA's manufactured as
specialty chemicals for Use in organic dye and pigment manufac-
ture. Although specific effluent rates are unknown for this
industry, a problem exists in the area of liquid waste disposal
since large quantities of brines containing organic, highly
colored materials are produced as waste. In plants manufacturing
PNA-based dyes, some of the organic materials present in the
waste brines are probably PNA compounds.
PNA's seem to be transported in water and the atmosphere adsorbed
on particulates and bacteria. Urban concentrations of PNA's in
air tend to be 10 to 100 times greater than nonurban concentra-
tions, with arithmetic mean concentrations of 0.4 yg/1,000 m3
for nonurban locations and 3 yg/1,000 m3 for urban locations.
Essentially insoluble in water, PNA's may exist in water in
association with other organic matter or colloids, such as those
formed by detergents.
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TABLE 1. POLYNUCLEAR AROMATIC HYDROCARBONS
Extent of problem
Emission source
Air emission
quantity3
(metric tons/yr)
Population exposed
Control method
Regulatory action
Combustion
Coal 376.1
Oil 1.4
Gas 1.1
Refuse burning 18.5
Catalytic cracking of petroleum 17.1
Asphalt road mix 9.07 x 10'6
Asphalt air blowing <4.35 x 10~5
Motor vehicles 16.7
bye and pigment manufacture -
Indication of widespread
exposure because PDA's
exist in all phases of the
environment. Urban con-
centrations are 10 to 100
times.greater than non-
urban concentrations.
Persons working with or
using fossil fuel-derived
products are exposed to
high PNA levels.
PDA's from combustion
sources may be controlled
by .increasing air-to-fuel
ratios or ..using secondary
combustion devices on flue
gases. Conventional
..particulate control methods
could help reduce PNA
transport.
Chlorination and ozoaation
Of water supplies are
believed .to destroy PNA's
but mote toxic byproducts
could be formed.
Compliance with existing
regulations for inciner-
ators, open burning, coal
combustion and coking
operations could
significantly reduce emis-
sions. Specific control
regulations are not believed
to be warranted or practical.
One-hundred and twenty-nine
chemicals including 13 PNA's
have recently been-designated
priority pollutants under the
Federal Water Pollution Con-
trol Act.
Emissions given in metric tons/yr of benzo(a)pyrene.
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Air emissions of PNA's from combustion sources can be reduced by
increasing air-to-fuel ratios, or with secondary combustion
devices for flue gases. Particulate matter, which appears to a
method of 'transport for PNA's in the environment, may be con-
trolled by conventional methods, such as mechanical collectors or
electrostatic precipitators, thus aiding in reducing PNA emis-
sions. Indications are that chldrination and ozonation of water
supplies destroys PNA's; however, byproducts much more toxic than
the original compounds may be produced in chlorination.
Limitation of carbon monoxide and hydrocarbon emissions from
motor vehicles has simultaneously and dramatically reduced PNA
emissions from these sources. Control regulations designed
specifically for PNA's are not considered practical, but compli-
.ance with existing regulations for incinerators, open burning,
coal combustion, and coking operations could significantly
reduce emissions* Consideration is being given to establishing
revised standards for coke oven emissions under the Clean Air
Act. Documentation of physical and chemical behavior, health
and environmental effects, and sources ahd environmental levels
for 65 chemicals and classes* including PNA's, was scheduled to
be published by July 1977. Subsequently, appropriate water-
quality criteria, effluent guidelines, toxic pollutant standards,
and/or pretreatment requirements will be established under the
Federal Water Pollution Control Act in accordance with a court-
approved schedule.
Based upon the information presented in this report, the follow-
ing items need to-be considered for future studies:
* Production quantities and locations of user and manufac-
turer facilities should be identified for all major PNA's.
Effluents irom Organic dye and pigment manufacturing pro-
cesses should be characterized and PNA concentrations
quantified to determine the most effective controls.
PNA transport methods should be studied so that efficient
emission and effluent pollutant control may be realized.
Human health effects of long-term, low-level exposure
should be determined.
Population risking exposure to PNA's should be quantified.
Chlorination and bzbnation of wastewaters should be
reviewed for control efficiencies and for identification of
possible toxic byproducts.
PNA atmosphere and environmental persistence.
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SECTION 3
SOURCE DESCRIPTION
Polynuclear aromatic hydrocarbons (PNA's) enter the environment
from natural and anthropogenic (man-made) sources. EN-A's are
not manufactured as synthetic organic chemicals.' These compounds
occur naturally in plants.and food,'and are present in coal tar
and creosote,.which are derived from the breakdown of coal.
Since the form of PNA's in coal is unclear, it is not known
whether it is .anthropogenic or natural..in- origin. Phenanthrene,
chry.sene, and anthracene, which are refined from coal derived
chemicals, are. the main PNA's of commercial significance.
Essentially all commercial PNA's are us.ed as reagents in- organic
synthesis.
CHEMICAL AND PHYSICAL PROPERTIES
Chemical nomenclature for 12 selected PNA.'s is .listed ,in Table 2 ,
(1, 2). Polynuclear aromatic hydrocarbons are all high melting,
high boiling solids. Tables 3 and 4 summarize specific proper-
ties of selected PNA's (3-9) .. As shown in Table 4, vapor
(1) Radding, S. B., T. Mill, C. W. Gould, D. H. Liv, H. L. John-
son, D. C. Bomberger and V. C. Fpjo. The Environmental Fate
of Selected Polynuclear Aromatic Hydrocarbons. EPA 560/5-
75-009,'U.S. Environmental Protection Agency, Washington,
D.C., February 1976.' 131. pp. .
(2) Patterson, A. M., L. T. Capell, and D. F. Walker. The Ring
Index. A List of Ring Systems Used in Organic Chemistry.
American Chemical Society, Washington, D.C., 1960. 1425 pp.
(3) International Agency for Research on Cancer, "Monograph on
the Evaluation of Carcinogenic Risk of the Chemical to Man:
Certain Polycyclic Aromatic Hydrocarbons and Heterocyclic
Compounds," World Health Organization, Geneva, Switzerland,
1973, 'Volume 3. !
.(.4) Hansch, ..C... . (1975) , private communication, Pomona College,
Pomona, California. -
(5) Fieser, L.'F, and A. M. Seligman (1935), "The Synthesis of
Methycholanthrene," J. Amer. Chem. Soc. 57, 942-46.
(6) "Handbook .of Chemistry and Physics," 45th Ed., Chemical
5 (continued)
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TABLE 2. NAMES AND SYNONYMS FOR 12 PNA's (1, 2)
Common name
Synonyms
Benzo (a) pyrene
Benzo (a)anthracene
CoTSToT
Methylcholanthrene
3,4-Benzpyrene
BP
BAP
3,4-Benzopyrene
1,2-Benzanthracene
Benzanthrene
Benzo(b)phenanthrene
2,3-Benzophenanthrene
Tetraphene
1,2-Benz(a)anthracene
Cholanthrene, 3-roethyl-
20-MC
MC
3-MC
20-Methylcholanthrene
3-Methylcholanthrene
1,2-Benzphensnthrene
Paranaphthalene
None
Benzole)pyrene
Benzo(ghi)perylene
Fluoranthene
4,5-Benzopyrene
1,2-Benzopyrene
Dibenz(de,kl)anthracene
1,12-Benzoperylene
Dibenzo(def,mno)chrysene
Dibenzolcd,jk)pyrene
Dibenzo(ghi,pgr)perylene
Benz(a)acenaphthylene
1,2-Benzoacenaphthylene
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TABLE 3. PHYSICAL PROPERTIES OF SIX PNA's
Mol.
PNA formula
Benzo (a) pyrene czoHl2
Benzo (a) anthracene Ci3H12
Methylcholanthrene C21H15
Chrysene C18Hu
Anthracene CII»HI
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pressures are extremely low. Solubilities of PNA's in water
generally.appear to be less than 10*10 molar. These compounds
undergo the reactions Of. simple aromatics, in addition to some
reactions peculiar to PNA's as a class. They are subject to
oxidation and yield quinones, diols, peroxides, and ring cleav-
age products. Alkylated PNA's are more reactive toward electro-
philic agents, with reactivity increasing with ring number (1).
PRODUCTION-AND USE OF POLYNUCLEAR AROMATIC HYDROCARBONS
Anthracene is the only PNA of.commerce refined from fossil fuel
sources. While quantities refined were not found, several coal
tar resin producers, who may refine anthracene, are presented in
Table 5 (10).
TABLE 5. COAL TAR RESIN PRODUCERS (10)
Chemfax, Inc. Gulfport, MS
The Goodyear Tire & fcubber Co.
Chem. Div. Beaumont, TX
Hercules, Inc.
Organic* Dept. Baton Rouge, LA
. Clairton, PA
West Elizabeth, PA
Neville Chem. Co. Anaheim, CA
Neville Island, PA
Northwest Indust., Inc.,
Velsicoi Chem. ...Corp.,
subsidiary Marshall, IL
Reichhold ChemS., Ihc*
Newport Div. . Gulfport, MS
Schenectady Chems., Inc. Rotterdam Junction, NY
Anthracene and phenanthrene can be refined from creosote, which
is produced by distillation of coal tar. A number of distillate
oils are produced in the distillation of coal tar and creosote
is a mixture of these oils. Creosote production may be repre-
sented by the schematic shown in Figure 1 (11). Creosote is
(10) 1977 Directory of Chemical Producers. Stanford Research
Institute, Menlo Park, California. 1977. p. 782.
(11) von Rumker, R*, E. W. Lawless, and A. F. Meiners. Produc-
tion, Distribution, Use and Environmental Impact Potential
of Selected Pesticides (PB 238 795). Council on Environ-
mental Quality, Washington* D.C., March 1974. 439 pp.
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AMMONIA
COAL GAS
CARBOLIC OIL
NAPHTHALENE OIL
LIGHT OIL (OTHER PRODUCTS)
COAL TAR
WATER
DISTILLATION
CREOSOTE-
PITCH
COKE
Figure 1. Production schematic for creosote (11). .
then washed with water, and solid crude anthracene is separated.
in filters and centrifuges as shown i:n Figure 2 (12). The crude
product is then recrystallized from furfural. Solids separation
and drying steps produce refined anthracene product.
In 1974, the capacity of phenanthrene, anthracene, and other PNA
production facilities was 3.63 x 10s metric tons/yr and this
capacity is expected to'increase 10% by 1981 (13). Actual cur-
rent production data were -not. available. However, since the
majprity of PNA's are produced at steel making facilities, eight
steel companies planning to expand s.te-el production by 1981 at
11 sites are listed in Table. 6 (13) .
(12) Development Document for Effluent Limitations Guidelines and
New Source Performance Standards for the Major Organic Pro-
ducts Segment of the Organic Chemicals Manufacturing Point
Source Category, EPA 440/l-r74-<-OQ9-a, U.S. Environmental
Protection Agency, Washington, D.C.., 1?74.
(13) Cooper, F. D. Coke and Coal Chemicals. In: Minerals Year-
. book 1974, Volume 1. Metals, Minerals, and Fuels. U.S.
Government Printing Office, Washington, D.C., 1976.- p 447.
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CREOSOTE
WATER
DIRECT CONTACT
t
3
-
e
j
1
'
1
Oil
- 1
CENTR
WASTEWATER
REFINED
ANTHRACENE
WASTEWATER
WASTEWATER
Figure 2. Anthracene refining flow diagram (12).
-------
TABLE 6. STEEL COMPANIES EXPANDING PNA PRODUCTION (13)
Company
Location
Approximate
start-up
date
Armqo Steel Corp.
Bethlehem Steel Corp.
Inland Steel Co.
Jone? & Laughlin steel Corp
Lykes-Youngstown Corp.
Republic Steel Corp.
United States Steel Corp,
Wheeling-rPittsbvurg Steel Corp.
Middletown, OH
Bethlehem, PA
East Chicago, IN
Ali<3uippa, PA
Aliquippa, PA
Indiana Harbor,
Cleveland, OH
Warren, OH
Gary, IN
Gary, IN
Foilansbee, WV
July 1976
Mid-1975
1978 '
Mid-1975
Not contracted
Mid-1977
1976
1978
Late 1975
Late 1976
Mid-1977
Table 7 presents a partial list of uses for three of the .most
important PNA's (14).
TABLE 7. MAJOR USES OF THREE ENA's (14)
Compound
Uses
Anthracene
Dyes; alizarin;' phenahthrene;
carbazole; anthraquinone; calico
printing; component of smoke screens;
scintillation counter crystals; reagent
in organic semiconductor research
Organic synthesis
Dye stuffs;, explosives;, drug synthesis;
biochemical research.; phenanthrene-
quinone
Chyrsene
Phenanthrene
(14) Hawley,,. Qessaer, G, , Ed./' The Condensed Chemical Dictionary,
..- 8th'Ed.', New York, Van ;Nostrand Reinhqld Co., 1971.
11
-------
SECTION 4
ENVIRONMENTAL SIGNIFICANCE AND HEALTH EFFECTS
ENVIRONMENTAL SIGNIFICANCE
PNA's are widely distributed in the environment. They are found
in living plant and animal tissue, sediments, soils, air, and
surface waters. The majority of PNA's probably arise as pyroly-
sis products formed during combustion or heating of fossil fuels.
The major environmental transport mode is as particulate in air
or water, due primarily to low vapor pressures and virtual
insolubility in water. Presently used methods of analysis for
estimating airborne concentrations of PNA's however, may seri-
ously underestimate the concentrations of some relatively vola-
tile PNA's such as pyrene, anthracene, and benzo(a)anthracene (1)
Sources
PNA's enter the environment from natural and anthropogenic
sources. Anthropogenic PNA emissions may occur from combustion ,
or pyrolysis of fuels, processing of fuels, and manufacturing of
specialized organic chemicals.
Several potential sources of PNA emissions have been monitored.
Emission estimates for these sources are presented in Table 8
(15). Combustion sources are the largest contributors to PNA
emissions. Sampling and analysis data for these combustion
sources are presented in .Tables 9 through 15 (15).
PNA emissions from petroleum refining .sources have been studied;
sampling and analysis results are presented in Table 16 (16).
Table 17 lists emissions of PNA from catalytic regeneration in
petroleum catalytic cracking (15).
(15) Hangebirauck, R. P., et al. , Sources of Polyniiclear Hydrocar-
bons in the Atmosphere, 999-AP-33, Public Health Service,
1967.
(16) Samedov, i. G. and A. S* Kurbanov, "Pollution of the Air
with Carcinogenic Substances by Baku Petroleum Refineries,"
Azerbaydzhanskiy Medit. Zh. 28 (11), 62-67 (1971) .
12
-------
TAPLE 8. ESTIMATE? OF ANNUAL BEN?O(a)PYRENE
EMISSIONS- FROM VARIOUS SOURCES (15)
Source
£gtimated annual
emission
(metric tons)
Coal combustion
Residential
Hand stoked
Underfeed
Commercial
Industrial
Power plants
Oil combustion
Gas combustion
Refuse burning
Municipal incineration
Commercial incineration : -
Open burning-municipal
Grass, leaves
Auto components
Catalytic cracking of petroleum.
FCC - no carbon monoxide boiler
FCCu r with carbon monoxide boiler
HCC T no carbon monoxide boiler
HCC - with carbon monoxide boiler
TCC -r air lift * no carbon monoxide
boiler
TCC - air lift T with carbon
monoxide boiler
TCC f bucket lift - no carbon
monoxide boiler
Asphalt road mix
AsphaLt air blowing
Motor vehicles
Gasoline automobiles
Gasoline tr-ucks
Diesel
362.9
8.8
2.5
0.5
1.4
1.1
0.1
4:4
4.4
4.4
5.2
0.19
0.010
5.1
0.0022
'11.8
<0.0026
0.0037
9.07 x lO'6
<4.35 x 10-5
7.8
1.8
Fluid catalytic cracking.
Houdriflow catalytic cracking.
Thermofor catalytic cracking.
13
-------
TABLE 9. EMISSIONS OF PNA FROM COAL^FIRED PLANTS (15)
Emissions in ug/103 j
Type of unit
Benzo(a)-
pyrene Pvrenc
Beneo(e)- Pery-
pyrene lene
Benzolghi)- Anthan- Phenan- Fluoran-
perylene threne Coronene threne thene
Pulverized coal (vertically-fired,
dry-bottom furnace)
Pulverized coal (front-wall-fired,
dry-bottom furnace)
Pulverized coal (tangentially-
fired, dry-bottom furnace)
Pulverized coal (opposed-, down-
ward inclined burners; wet
bottom furnace)
1-8 - 123 70 - 216
16 - 20 152 - 190
123
133
52
80
67
Crushed coal (cyclone-fired,
wet-bottom furnace)
Spreader stoker (traveling
grate) <14 - S3
20 - 133 37 - 1-14 68 - 398
72 - 351 237 - 1,706 104 - 645 32
20 - 56
SB
79 80 - 389
13 190 12 - 152
142 4.6 6.7 30 370
142 - 1,042 7.7-88 52 - 199
34 - 341 10 42 - 104
9.0
NOTE: Blanks indicate data not available.
20 - 56
TABLE 10. EMISSIONS OF PNA FROM COAL-FIRED
RESIDENTIAL FURNACES (15)
. Emissions, uq/loS J fuel
Firing
Underfeed
method
stokers
Benzo(a)-
pyrene
3,600 - .
76,780
Pvrene
7,300 -'
284,360
Benzole )-
pyrene
5,120.- ..
55,920
Pere-
lene
407 -
7,490
Benzol ghi )-
perylene
550 -
57,800
Anthan-
threne
1,230 -
5,780
Coronene
1,140 -
3,690
Anthra-
cene
1,230 -
66,350
Phenan-
threne
. 27,500 -
578,200
Fluoran-
thene
44,550 -
312,800
Hand stoked
379,150 - 568,720 - 94,800 - 56,870 -
3,127,960 8,625,600 1,421,800 331,750
284,360 - 85,300 - 28,440 - 379,150 - 947,900 - 947,900 -
2,085,300 464,500 91,950 2,748,800 7,109,000 10,426,500
NOTE: Blanks indicate data not available.
TABLE 11. EMISSIONS OF PNA FROM INTERMEDIATE-
. SIZED COAL-FIRED UNITS (15)
. . . Emissions ,. uo/109 J fuel
Firing method
Pulverized
Chain grate stoker
Spreader stoker
Underfeed stokers
Benzo(a)-
py*«ne.
30
35
25
114 -
9,200
Benzole )' Fere- B«nzo(ghi)- Anthan-
pyrenc. Byxene. lent pervlene : threne
227
370
560
1,610 -
15,160
87
123
330
216 - 1,516 4,260 275
7,500
Anthra- Phenan- Pluoran-
Coronene cene threne thene
350
25
313 805 948
9,480
645
340
3,030 -
36,000
NOTE: Blanks indicate data not available.
14
-------
TABLE 12. EMISSIONS OF PNA FROM INTERMEDIATE AND
.SMALL-SIZED OIL-FIRED UNITS (15)
' 'Emissions,
J -fuel
Firing method
BenzoU)- 'Sense (ghi) ? V '"' , ' Anihan- 'Shenan-
pyrene Pyrene perylene Coronene threne threne thene
Steao atomized «19-45 46-284
Low pressure air Atomized 853 5,780
Pressure atomized <38-<57 14-1,700
Vaporized <95 1,140
1.700 53-256
285 1,990 3,700 3.320 1,800
3,440 72-4,470
14,200
NOTE: Blank? indicate data not available.
TABLE 13. EMISSIONS OF PNA FROM INTERMEDIATE AND SMALL-SIZED
GAS-FIRED UNITS WITH PREMIX .BURNERS (15)
Emissions, yg/109' J fuel
Ben2o(a)r ''; ;\
pryene Pyrene
pyrene
perylene
threne,
;. . Flu- Anthan-' -. ftathra- Phenan- Pluoran-
of vehicle pyrene Byrene pyrane lane parylene threna Coronena ,cena threne thene
Automobiles
Trucks
1.8 -
.,20.8
>1.6 -
TO .
8.0 -
212
2.9 *
19.6
255 - >2.2 .-
930 65
0.17 - 4.2 - 90 0.19 -
2.2 2.83
0.52- - 5-7 T 300 0 - 73
: 12
2.S - 0.65 -
39.7 7.9
24 -
ISO
4 - US
2.7 -
57
162 -
640
4.2 -
145
137 -
610
15
-------
TABLE 16. EMISSIONS OF PNA FROM PETROLEUM REFINING (16)
, : . Process. . ..:
Straight run distillation
Pyrolysis
Asphalt production
Petroleum coke production
Petroleum products
purification
Emissions
Benzo(a)-
. , pyrene
0.015
0.30-
0.74
25.5
0.024
, vg/ioo m3a
Benzo ( ghi ) -
perylene
0.11
0.170
1.58
0.4
h
Mean values of multiple samples.
Not available.
TABLE 17. EMISSIONS OF PNA FROM CATALYST REGENERATION
IN PETROLEUM CATALYTIC CRACKING (15)
Type of unit
rcc:8
Regenerator outlet
Carbon monoxide boiler outlet
HCCrb
Regenerator outlet .
TCC = C
Air lift, regenerator outlet
TCCi
Brucket lift, regenerator outlet
NOTE: Blanks indicate data not tm
. - F1"* qeione , uc/»3 oil charges
Benxo(a)- Benzole)- Pery- Benxo(ghi)- ftnthan- _ Anthra- Phenan- Fluoran-
pyrene -Pyrene pyrene> lene- pervlene threne ~coronene cene threne thene'
0.7 - 73 6.4 - 1.7 - 572 24 - 67 63.560 7.0 - 3,180
4,450
1.7 - 3.4 3.9 - 26 2.9 - 3.3 6.8 330 3.2 - 13
.32,600- 20,700- 20,800- 5,400 47,700- 2,380- 1,780- '146- 3,340-1,320-
36,700 20,800 60,400 60,400 2,860 4,130 318 4,600 1,810
8.900 - Jl.OOO - 8,900 - 875 - 7,000 - 205 - 57 1,640 - 52,500 - 1,685 -
19.100 41,300 19,100 1,590 11,450 700 1,685 56.000 4,610
5 46 - 57 IS 9-17
lilfble.
bHoudriflow catalytic cracking.
CThen»for catalytic cracking.
PNA's, in the form of partieulates, can be emitted to the atmos-
phere from coking operations. Particulate matter collected from
the air in the vicinity of a coke oven and steel mill has-been
analyzed and the results are shown in Table 18 (15). The major
sources of atmospheric emissions from the coke and steel industry
are slot-type coke ovens and oxygen-lanced open hearth furnaces.
Beehive ovens have higher emission rates, but they are seldom
used in the industry. PNA's are also found in coal tars (17).
(17) Lowry, H. H., Ed., Chemistry of Coal Utilization, 2 Vols.
and supplementary volume, N.Y., Wiley, 1945, 1963 (supple-
mentary volume).
16
-------
TABLE 18, CONCENTRATION OF PNA IN PARTICULARS IN
AIR NEAR'STEEL AND COKE PLANT (15)
'"-"'' ^ v ;.-== - ^Concentration,
Compound g/1,000 m3 air
Benzo(a)pyrene 8.6
Pyrene 6.6
Benzo(e)pyrene 4.1
Perylene 1.0
Benzo(ghi)perylene 7.1
Anthanthrene .0.83 . .
Coronene 0.44
Anthracene 2.4
Fluoranthene 3.2
Processing of coal tar could result in PNA emissions in both
gaseous and liquid or semi-liquid form.
Asphalt blowing and hot-mix asphalt plants are potential PNA
emission sources.. The results of a sampling and analysis program
for these two sources are shown in Tables 19 and 20 (15). Carbon
-black plants are also potential emitters of PNA1s (15, .18).
Table 21 .presents an analysis of collected particulate matter in
the vicinity of a carbon black "plant (15).
TABLE 19. EMISSIONS OF PNA FROM ASPHALT BLOWING (15)
'' ::;-'!:' '""' Emissions, ug/1,000 m^
Compound (211.1°C, 1 x 105 Pa)
Pyrene 3,100/000
Benzo(a)pyrene <4/000
Anthracene 220,000
(18) Todd, Robert G., Direct Identification of Polycyclic Aro-
matic Hydrocarbons from Carbon Black, Masters Thesis, Uni-
versity of Oklahoma, Norman, Oklahoma, 1970.
17
-------
TABLE 20. EMISSIONS OF PNA FROM ASPHALT HOT-ROAD MIX PLANTS (15)
Emissions, pg/1,000 m3
. Compound .. (.211.1°C,-.l, x. .105 Pa)
Pyrene 3,000
Ben-zo (a-) pyren-e
-------
TABLE 22 r MISCELLANEOUS INDUSTRIAL SOURCES OF PNA'S
-! ' " ..- - ... .... : ...- Refer-*
Industry Emissions enc.e
Foundry (casting 1 -r 3 mg BaPa/103m3 19
operations)
Aluminum plant 10 kg BaPa/day 20
0.26 mg BaPa/m2-?day
Fiberbpard works-pitch 0.2. mg BaPa/103m3 on premises 21
boiling plant 0.1 mg BaPJ|/103m3 at 100 ra
0.05 mg BaP /103m3 at 500 m
Carborundum 0.08 mg BaP /103m3 21
Vinyl phonograph records . 5'. 2 mg BaP /103m3 21
plant . . . . .'
Rubber products plant 0.05 r 0.02 mg BaPa/103m3. 21
(dependent on distance)
Benzo(a)pyrene '.
Environmental Levels
Air
Urban concentrations of PNA's in air tend, to be 10 to 100 times
greater than nonurban concentrations. An arithmetic mean concen-
tration has been 'determined: 6.4 yg/1,000 ra3 for nonurban loca-
tions, 3 yg/1,000 m3 for urban locations (20). winter levels are
usually higher than summer levels. This phenomenon may be due to
both lower photo-oxidation rates and increased use of fossil
fuels for space heating. Table 23 contains some data for atmos-
pheric levels of PNA's as a function of season (3, 20). Traffic
variations also cause variations in PNA concentrations. The
range .in values corresponding to traffic variations is shown in-
Table' 24 (3).' Traffic contributes from 5% to 42% to the level
o.f PNA's in air (22) .
.(continued)
(21) "Basic Industrial Sources of the Carcinogenic Hydrocarbon;
BenzotaJpyrene," Med. Zh. Uzb. No. 11, 51-4.
(22) Sawicki, E. (1967), "Airborne Carcinogens and Allied
pounds," Arch. Environ. Health 14 (.1) , 46-53.
19
-------
TABLE 23. ATMOSPHERIC CONCENTRATION OF PNA'S IN SEVERAL CITIES
Benzo(a)pyrene
Chyrsene
Benz (a) anthracene
Winter ,
yg/1,000 .m3
0.6 - 104
26
(14 U.S. Cities)
20 - 361
94
(Siena)
361
(Bochun)
Summer,
..... ug/1,000 m3
0.03 - 4
1.9
(14 U.S. Cities)
2.5 - 3.6
1.6
(Siena)
136
(Pittsburgh)
Refer-
ence
3
20
3
3
TABLE 24. VARIATIONS OF PNA CONCENTRATION WITH TRAFFIC (3)
.... . ... PNA ,. , . ..
Benzo (a) pyrene
Chrysene
Benz (a) anthracene
Concentration ,
yg/1,000 -in3
2.5
1.8
0.6
- 6.5
- 13.3
- 13. -7
PNA's seem t6 be transported in the atmosphere adsorbed on
particulates and bacteria. An analysis of particulate matter
from six cities is given in Table 25 (3)>
TABLE 25* PNA'S IN ORGANIC PARTICULATE MATTER FROM SIX CITIES (3)
Concentration,
.PNA
Behio(a)pyrene
Chrysene
Benz(a)anthracene
110 - 670
150 - 490
43 - 280
Water"
PNA's are essentially ihsoluble in water. They may exist in
water in association with other organic matter or colloids, such
as those formed by detergents. They are probably transported to
the waterways adsorbed on particles or bacteria. Table 26 pre-
sents concentrations of carcinogenic PNA'S found in water systems
(23). Another study of water contamination by three specific
PNA's resulted in the data shown in Table 27 (3).
20
-------
26. CARCINOGENIC PNA CONCENTRATIONS IN WATER SOURCES (23!
' ' '''';:'-''-'"'' Sguree ' : ' ..."'''"'.'' mg/m3
Ground water 0.001 -r 0.1
Treated river and lake water 0.01 -r 0.025
Surface water 0.025 - 0.100
Surface water/ strongly contaminated >0.100
TABLE 27. PNA CONCENTRATIONS IN WATER (3)
: ''" ^""'Orinking water,'" 'Surface water,
PNA mg/m3 mg/m3
Benzo(a)pyrene 0,0-001 - 0,023 0.0006 - 0.114
Chrysene ' '' ' -a 0.0118 - 0.038
Ben?(a)anthracene 0.001 - 0.023 0.0043 7 0.185
aNpt available. .
Soils-»- ...-.,... - . . '
Levels of three PNA's found in soils from different locations are
presented in Table 28 (3). The PNA compounds may settle on the
soil where they are absorbed by microorganisms or plants or are
decomposed-by bacteria. There is a natural background level of
PNA's in soil, probably due to production by plants and micro-
organisms ,
TABLE 28. CONCENTRATIONS OF PNA IN VARIOUS SOILS (3)
(yg/kg)
Soil source
Forest
Nohindustrial
Towns and vicinities
Soil near traffic
Near oil refinery
Near airfield
Polluted by coal tar. pitch
V '..-. . . : - .- i ; - -.
Data not 'available.
Benzo(|i) f
pyrene
<1,300
0 - 127
0 -r 939
<2,000
200,000
785
650,000
Chrysene
a
a
a
"a
a
"a
600,000
Benz'(a)r
anthracene
5 - 206
a
a
1,500
_a
"a
2,500,000
(23) Andelman, J. B., M. J. Suess (1970), "Polynuclear Aromatic
Hydrocarbons in the Water. Environment," World Health Organi-
zation 43, 479-5081 '
21
-------
Plants > Food, and Beverages-*
The concentration of benzo (a) pyrene is 10 yg/kg to 50 yg/kg in
plants, 2 yg/kg to 10 yg/kg in dried bacteria, and 103 yg/kg to
270 yg/kg in tobacco leaves (1) .
PNA's have been determined in many foods; some of the concentra-
tions found are listed in Tables 29, 30, and 31 (3, 23-28).
Table 32 contains concentrations of PNA's as determined in
beverages (3, 25) .
TABLE 29. PNA CONCENTRATIONS IN CEREALS AND POTATOES
(yg/kg)
_ PNA ... . _ Cereals _ Potatoes _ ence
Benz (a) anthracene In general .a 3
0.4 - 6.8
Chyrsene In general a 3
0.8 - 14.5
Benzo (a) pyrene In general Peelings 0.36 24
0.25 - 0.84 Tubers 0.09
Barley, Wheat, Rye . 25
0.2 - 4.1
Not available.
(24) Shabab, L. M. and V. L. Cohan (1972), "Contents of Benzo(a)-
pyrene iii Some Crops," Arch. Geschwulstforsch. 40 (3), 237-43.
(25) Grimmer, G. (1968), "Carcinogenic Hydrocarbons in the Human
Environment," Deut. Apoth.-Ztg. 108 (16),529-33.
(J>6) Grimmer, G. , A. Hildebrandt (1965b) , "Content of Polycyclic
Hydrocarbons in Different Vegetables. III. Hydrocarbons in
the Human Surroundings," Deut. Lebensm.-Rundschau 61(8), 237-9.
(27) Gorelova, N. D., P. P. Dikun, L. D. Kostenko, 0. P. Gret-
skaya, and A. V. Emshanova (1971) , "Detection of the Possible
Presence of 3,4-benzopyrene in Fresh Fish," Novosti Onkol.,
8-12.
(28) Wierzchowski, j. and R. Gajewska (1972) , "Determination of
3,4-benzopyrene in Smoked Fish," Bromatol. Chem. Toksykol.
5(4), 481-6.
22
-------
TABLE 30. PNA CONCENTRATIONS IN VEGETABLES AND FRUITS
(yg/kg)
PNA Cabbage
Benz (a) anthracene
Chyrsene
BenzoU)pyrene 24.5 (26)
Kale
43.6 -
230
58.5 -
395
12.6 r
24.5 (25)
12.6 r
48.1 (3)
Spinach
16.1 (3)
28.0 (3)
7.4 (23)
7.4 (3)
iettuoe Tomatoes
0.3 (3)
0.5 (3)
2.8 - 0.22 (25)
12.8 (23)
0.2 (3)
Otber
Fruits Salad
4.6
15.
5.7
26.
2-8 (3)
2.8
5.3
,.
4 (3)
-
5 (3)
-
(3)
NOTE: Blanks indicate data not available.
TABLE 31- PNA CONCENTRATIONS IN COOKED,
. ' ' SMOKED,'AND PROCESSED FOODS
(yg/kg)
PNA
Benzp ( a ) py rene
Cbrysene
Benz (a) anthracene
Refined oils
or fats
0.9 - 15 (3)
Margarine
0.2 - 6.8 (3)
Coconut oil
43.7 (3)
Coconut fat
62 (3)
0.5 - 129 13)
0.5 - 13.5 (3)
Coconut oil
98 (3)
Coconut fat
125 (3)
Fresh fish"' ' '
frozen gr Broiled meat
salted or fish
<0.1 (.27) Meat and
Sausages (3)
0.17 - 0.63
BBQ meat (3)
2.6 - 11.2
Pish 0.9 (3)
8.7 - 27.2 (29)
Ham (3)
0.5 - 2.6
Pish 4.3 (3)
Heat and
.sausages (3)
0.5 r 2.6
BBQ meat (3)
0.6 - 25.4
Meat and
sausages (3)
0.2 - 1.1
Charcoal
broiled (3)
1.4 - 31
Smoked meat
Smoked fish sausages
1.0 - 78.0 (23) 0.02 - 107 (3)
37 (23)
0.1 - 0.8 (25)
Traces - 2.1 (3)
0.3 - 173 (3)
Ham <12 (.3)
0.02 - 189 (3)
NOTE: 'Blanks indicate data not available.
(29)- Shirotori, 1972.
23
-------
TABLE 32. PNA CONCENTRATIONS IN BEVERAGES
(mg/m3)
: PNA. .
Benzo (a)pyrene
Roasted coffee
0.3 -
0.1 -
0.5 (25)
4 (3)
3.7
3.9
Teas
- 3.9 (25)
- 21.3 (3)
Whiskey
0.04 (3)
*
Chrysene
Green teas (3)
0.5 - 16
0.6 - 19.1 (3) 4.6 - 6.3 (3)
Benzta)anthracene 0.5 - 14.2 (3)
0.04 - 0.06 (3)
0.04 - 0.08 (3)
aData not available.
Fossil Fuels--
Levels of PNA's occurring in some fossil fuels and fuel fractions
are shown in Table 33 (3). PNA's are more concentrated in fuel
byproducts formed under high temperature conditions.
Population Exposed
There is indication of widespread exposure to PNA's from natural
and anthropogenic sources. They occur in all phases of the
environment. PNA's are more concentrated in urban areas where
large population densities exist. Persons working with or using
products derived from fossil fuels are potentially exposed to
very high levels of PNA's. .
TABLE 33. FOSSIL FUEL AND ITS DERIVATIVES (3)
: (vg/kg)
PNA
Benio(a)pyrene
Chrysene
Benz (a ) anthracene
Coal
300 - 1*000
«*
'**,
Coal tar .
30,000
<2,860
<6.980
Coal tar Petroleum
pitch asphalt
12,500 0.1 - 27
<10,000 <0.4 - <34
<12,500 <35
Creosote
, ...oil '
0.00014 -
0.0002
<1,340
<2,940
Data hot available.
HEALTH EFFECTS
PNA's are part of a group of known carcinogens that are present
in the particulate phase of polluted air. The extent of the con-
tribution of these agents to the incidence of human lung cancer,
however, is unknown (30). The majority of health effects data
(30) Committee of Biologic Effects of Atmospheric Pollutants,
National Research Council. Particulate Pdlycyclic Organic
Matter. ISBN 0-309^02027-1 (PB-212 940), National Academy
of Sciences/ Washington, D.C., August 1972. 375 pp.
24
-------
regarding PNA's is concerned with their carcinogenicity, muta-
genicity and teratogenicity. Table 34 summarized the low toxic
doses of selected PNA's (31) . :
TABLE 34, TOXICITY OF
PNA's (31)
Combound'
Anthracene
Benzo(a)pyrene
Chrysene
Phenanthrene
Benz (a)anthracene
3-methycholanthrene
Benzo(k)fluoranthene
Pyrene
2,3-o-phenylenepyrene
1,2,5,6-dibenzanthracene
("route, anjmal,~
18 g/kg, oral, rat, carcinogenic
3,300 rag/kg, subcutaneous, rat, neoplastic effects
2 ug/kg skin, mouse, carcinogenic
250 ug/kg, subcutaneous, rate, neoplastic effects
200 mg/kg, subcutaneous, mouse, carcinogenic
99 mg/kg for 31 weeks, intermittent, skin, mouse, neoplastic
700 mg/kg, oral, mouse, LD50
71 mg/kg, skin, mouse, neoplastic
240 mg/kg for 5 weeks, skin, mouse, carcinogenic
2 mg/kg, subcutaneous, mouse, carcinogenic
10 mg/kg, intraveneous, mouse, lowest lethal dose
3 mg/kg, parenteral, mouse, carcinogenic
80 mg/kg, implant, mouse, carcinogenic
280 mg/kg, oral, rat, carcinogenic
34 mg/kg fpr 25 weeks,,, intermittent, skin, fat, neoplastic '.
18 mg/kg, subcutaneous, rat, carcinogenic .
39 mg/kg for $ days, intraveneously, rat, neoplastic
3 mg/kg, parenteral, rat, carcinogenic
100 mg/kg for 5 weeks, intermittently, intratracheal, rat, carcinogenic
800 ug/kg, implant, rat, carcinogenic
40 mg/kg for 20 days of pregnancy, oral, mouse, neoplasties
2,300 mg/kg for 90 days continuously, oral, mouse, carcinogenic
13 mg/kg for 42 weeks, intermittently, skin, mouse, carcinogenic
100 mg/kg for intraperitoneal, mouse, lowest lethal dose
1,600 mg/kg for 20 weeks intermittently, intraperitoneal, mouse, neoplastic
312 ug/kg, subcutaneous, mouse, carcinogenic
120 mg/kg for week, intermittently, intratracheal,' mouse; carcinoienic
80 mg/kg, implant, mouse, neoplastic
40 mg/kg, implant, dogt, neoplastic .
100 mg/kg for 9 weeks, intermittently, intrapleural, rabbit, neoplastic
132 mg/kg for 12 weeks, intermittently, intratracheal, rabbit, carcinogenic
4 mg/kg intraperitoneal, guinea pig, carcinogenic
40 mg/kg for 15 days, subcutaneous, guinea pig, carcinogenic
36 mg/kg, intraveneously, guinea pig, neoplastic
2,075 mg/kg for 17 weeks, intermittently, oral, hamster, carcinogenic
3,320 ug/kg for 40 weeks, skin, hamster, neoplastic
4,150 gg/kgr subcutaneous, hamster, neoplastic
58 mg/kg, implant, hamster, carcinogenic
4,500 ug/kg for 8 weeks, intermittently, intraperitoneal, chicken, carcinogenic
27 mg/kg, intratracheal, duck, carcinogenic
11 mg/kg, intrarenal, frog, lowest lethal dose
72. mg/kg for 9 weeks, «kin, mouse, carcinogenic
10 ug/kg for 3 weeks, intermittently, skin, mouse, neoplastic
72 mg/kg for 9 weeks, intermittently, subcutaneously, mouse, carcinogenic
500 ug/kg, subcutaneous, rat, carcinogenic
360 mg/kg for 22 .weeks, continuously, oral, mouse, carcinogenic
6 ug/kg, skin, mouse, neoplastic
76 ug/kg, subcutaneous, mouse, carcinogenic
10 mg/kg, intraveneously, mouse, lowest lethal dose
80 mg/kg, implant, mouse, neoplastic
30 mg/kg, intraveneously, guinea pig, neoplastic
11 mg/kg, intramuscularly, pigeon, carcinogenic
8 mg/kg, intrareneally, frog, carcinogenic
Some observed doses are expressed as dependent on time.
(31) Christensen, Herbert E., Ed., Registry of Toxic Effects of
Chemical Substances, 1976 Edition, Rockville, Md., U.S.
Department of Health, Education and Welfare, 1976. 1245 pp.
25
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The American Conference of Governmental Industrial Hygienists has
adopted an eight hour work day limit of 200 pg/m3 for coal tar
pitch volatiles (benzene fractions containing compounds such as
anthracene, benzo(a)pyrene, phenanthrene, acridine, chrysene, and
pyrene) (1). The World Health Organization has recommended
0.2 mg/m3 of PNA's as a maximum permissible concentration for
human consumption. This is calculated a-s the sum of six com-
pounds. The recommended benzo(a)pyrene limit for the sum was
0.0075 mg/m3, and the recommended limit for all PNA's was
0.03 mg/m3 (1).
26
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SECTION 5
CONTROL TECHNOLOGY
Indications are that chlori.na.tion and ozonation of water supplies
destroy PNA's (1); however, byproducts may be produced that are
much more toxic when they are "destroyed" by chlorination. An
assessment of the degradation products formed and their toxicity
appears to be mandatory.
Emissions of PNA's from combustion sources can be reduced by.
increasing airrto-fuel ratios. Secondary combustion devices for
flue gases would also reduce emissions. Paxticulate matter seems
to be'a method of transport for PNA's in.the environment; thus,
particulate controls should help in reducing emissions-
STATIONARY SOURCES
Benzo(a)pyrene (BaP) is chosen to be a typical PNA emission for
the purposes of this section, since BaP emissions represent the
most completely characterized PNA emission. The most important
contributors of BaP emissions in heat and power generation are
hand-fired coal furnaces and wood burning; thus, the preferred
choice of control would be by alternative fuel sources. One
might argue that substitution is the only means of control for
these two sources., as neither is amenable to better engineering
controls.
In regard tp refuse burning., efficient incinerators are being
installed for municipal, commercial, industrial, and apartment
building sources. Relative contributions from these sources are
diminishing in comparison to coal refuse banks. Existing burn-
ing began spontaneously. Federal regulations have been proposed
for all burning coal refuse piles which will eliminate most
emissions as these regulations are implemented.
BaP emissions from catalytic cracking in the petroleum industry
apparently are receiving necessary action through utilizing car-
bon monoxide (CO) waste boilers for effective control (see
Table 8). From Table 8 it is clear that CO waste-heat boilers
have significant beneficial effects on BaP emissions and, thus,
on other PNA emissions.
Much of the BaP produced at byproduct coke ovens quite likely
could be removed in the byproduct stream, except for that
27
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escaping from a leaky system. However, BaP emissions from most
coke processing still appear to be quite high, whether they
originate from charging or leaks or directly from the gas stream.
Some possible approaches to controlling BaP from coke ovens are
under investigation by EPA and industry groups; two demonstration
_.projects _for particulate control ..fromcoke o-vens -are .in- progress,
and BaP sampling is being done simultaneously (32).
Sampling results indicate that about 90% control of particulates
is achieved (32) . With this level of particulate control, a
similar degree of reduction in BaP emissions was expected. Pre-
liminary evaluation of the BaP fraction of the particulate from
the controlled versus the noneontrolled larry car (vehicle that
drops coal into the oven) indicates that approximately 85% to 90%
control is achieved (32). If these results are obtained for
other types of particulate control, a reduction of PNA's should
result. These results confirm previous expectations of control
engineers that particulate control will significantly reduce BaP
emissions. . .
MOBILE
Before the current concern for reducing vehicle emissions was
instigated by the Clean Air Act, most vehicles operated with
fuel-rich carburetion to .-promote smooth performance and quick
power response. Preliminary modifications prior to the 1970
Clean Air Amendments resulted in leaner fuel-aix mixtures and
lower BaP. emissions*
Emission control devices will affect control of BaP concomitantly,
as indicated in Table 35. Data to support this view are based
on current exhaust sampling techniques. If such a high degree
of control is achieved in actual practice, mobile source pollu-
tion caused by BaP will assume a much less significant role. At
any rate, one may logically expedt a reduction of BaP emissions
from light-duty vehicles as a result of the EPA motor vehicle
control activityi A higher degree of uncertainty exists for
other transportation sources; e.g., buses, heavy diesel trucks,
or aircraft.
(32) Preferred Standards Path Report for Polycyclic Organic
Matter. Draft report, U.S. Environmental Protection Agency,
Durham, North Carolina, October 1974. 107 pp.
28
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TABLE 35. AUTOMOTIVE BENZO(a)PYRENE EMISSION FACTORS (32)
" ' ' "" '"""' ; ' ". '"" Benzo
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SECTION 6
REGULATORY ACTION
Limitation of carbon monoxide and hydrocarbon emissions from
motor vehicles has simultaneously and dramatically reduced the .
emissions of PNA's. A 1974 analysis of stationary source pro-
blems concluded that control regulations designed specifically
for benzo(a)pyrene or polynuclear aromatic hydrocarbons were not
warranted or practical. It did note that compliance with exist-
ing regulations for incinerators> open burning, coal combustion,
and coking operations cbuld significantly reduce emissions.
Additional efforts to document stationary source emissions,
atmospheric chemistry, and human exposure have been initiated
on a limited scale. Consideration is being given to establish
revised standards for doke oven emissions under the Clean Air
Act.
One hundred and twenty-nine chemicals including 13 polynuclear
aromatic hydrocarbons, have recently been designated as priority
pollutants for study. Physical and chemical behavior, health
and environmental effects, and sources and environmental levels
are to be documented. Appropriate water quality criteria, efflu-
ent guidelines, toxic pollutant standards, and/or pretreatment
requirements will be established under the Federal Water Pollu-
tion Control Act in accordance with a court-approved schedule
(33).
(33) Identification Of Selected Federal Activities Directed to
Chemicals of Near-Term Concern. EPA 560/4-76-^007, U.S.
Environmental Protection Agency/ Washington, D;C.,
September 1976. 21 pp.
30
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33
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