United States Office-of Water October 1982
Environmental Protection Regulations and Standards (WH-553) EPA-440/4-85-020
Agency Washington DC 20460
Water
vvEPA An Exposure
and Risk Assessment for
Benzo[a]pyrene and
Other Polycyclic
Aromatic Hydrocarbons
Volume III. Anthracene, Acenaphthene,
Fluoranthene, Flourene,
Phenanthrene, and Pyrene
-------
DISCLAIMER
This is a contractor's final report, which has been reviewed by the Monitoring and Data Support
Division, U.S. EPA. The contents do not 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.
-------
50373-101
REPORT DOCUMENTATION i- Report no. 2.
PAGE EPA-440/4-85-020
X Recipient's Accession No.
4. Tttie and Subtitle
An Exposure and Risk Assessment for Benzo[ajpyrene and Other
Polycyclic Aromatic Hydrocarbons: Volume III. Anthracene,
Acenaphthene, Fluoranthene, Fluorene, Phenanthrene, and Pyrene
3. Report Date Final Revision
October 1982
6.
7. Authortt) Byrne, M. ; Coons, S.; Goyer, M.; Harris, J.; Perwak, J.
(ADL) Cruse, P., DeRosier, R., Moss, K.; Wendt, S. (Acurex)
8. Performing Organization Rept. No.
9. Performing Organization Nam* and Address
Arthur D. Little, Inc. Acurex Corporation
20 Acorn Park 485 Clyde Avenue
Cambridge, MA 02140 Mt. View, CA 94042
10. Proiect/Task/Work Unit No.
11. ContrscttC) or Qrant(G) No.
(Q C-68-01-6160
C-68-01-6017
(CI
12. Sponsoring Organization Name and Address
Monitoring and Data Support Division
Office of Water Regulations and Standards
U.S. Environmental Protection Agency
Washineton, D.C. 20460
IX Type of Report & Period Cowered
Final
14.
IS. Supplementary Notes
Extensive Bibliographies
16. Abstract (limit; 200 word*)
This report assesses the risk of exposure to polycyclic aromatic hydrocarbons (PAHs).
This is Volume III of a four-volume report, analyzing 16 PAHs; it concerns six of
these: anthracene, acenaphthene, fluoranthene, fluorene, phenanthrene, and pyrene.
This study is part of a program to identify the sources of and evaluate exposure to
129 priority pollutants. The analysis is based on available information from
government, industry, and technical publications assembled in June of 1981.
The assessment includes an identification of releases to the environment during
production, use, or disposal of the substances. In addition, the fate of PAHs in the
environment is considered; ambient levels to which various populations of humans and
aquatic life are exposed are reported. Exposure levels are estimated and available
data on toxicity are presented and interpreted. Information concerning all of these
topics is combined in an assessment of the risks of exposure to PAHs for various
subpopulations.
17. Document Analysis a. Descriptor*
Exposure Effluents Polycyclic Aromatic Hydrocarbons Fluorene
Risk Waste Disposal Anthracene Phenanthrene
Water Pollution Food Contamination Acenaphthene Pyrene
Air Pollution Toxic Diseases Fluoranthene PAHs
b. Mmttll«fiyOp«wCMM Terms
Pollutant Pathways
. Risk Assessment
«. COSAT1 Field/Group 06F 06T
1 IS- Availability Statement
19. Security Clasa (This Report)
21. No. of Psges
Release to Public
Unclassified
158
20l Security Class (This Psge)
22. Price
Unclassified
$16.00
M AM SI—239.18) Sm instructions on fftvrtm OPTIONAL FORM 272 (4—775
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EPA-440/4-85-020
June 1981
(Revised October 1982)
AN EXPOSURE AND RISK ASSESSMENT FOR BENZO[a]PYRENE AND
OTHER POLYCYCLIC AROMATIC HYDROCARBONS:
VOLUME III. ANTHRACENE, ACENAPHTHENE, FLUORANTHENE,
FLUORENE, PHENANTHRENE, AND PYRENE
By
Melanie Byrne, Susan Coons, Muriel Goyer,
Judith Harris and Joanne Perwak
Arthur D. Little, Inc.
U.S. EPA Contract 68-01-6160
Patricia Cruse, Robert DeRosier,
Kenneth Moss and Stephen Wendt
Acurex Corporation
U.S. EPA Contract 68-01-6017
John Segna and Michael Slimak
Project Managers
U.S. Environmental Protection Agency
Monitoring and Data Support Division (WH-553)
Office of Water Regulations and Standards
Washington, D.C. 20460
OFFICE OF WATER REGULATIONS AND STANDARDS
OFFICE OF WATER
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
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FOREWORD
Effective regulatory action for toxic chemicals requires an
understanding of the human and environmental risks associated with the
manufacture, use, and disposal of the chemical. Assessment of risk
requires a scientific judgment about the probability of harm to the
environment resulting from known or potential environmental concentra-
tions. The risk assessment process Integrates health effects data
(e.g., carcinogenicity, teratogenicity) with information on exposure.
The components of exposure Include an evaluation of the sources of the
chemical, exposure pathways, ambient levels, and an identification of
exposed populations including humans and aquatic life.
This assessment was performed as part of a program to determine
the environmental risks associated with current use and disposal
patterns for 65 chemicals and classes of chemicals (expanded to 129
"priority pollutants") named in the 1977 Clean Water Act. It ircludes
an assessment of risk for humans and aquatic life and is Intended to
serve as a technical basis for developing the most appropriate and
effective strategy for mitigating these risks.
This document is a contractors' final report. Tt has been
extensively reviewed by the individual contractors end by the EPA at
several stages of completion. Each chapter of the draft was reviewed
by members of the authoring contractor's senior technical staff (e.g.,
toxicologists, environmental scientists) who had not previously been
directly involved in the work. These individuals were selected by
management to be the technical peers of the chapter authors. The
chapters were comprehensively checked for uniformity in quality and
content by the contractor's editorial team, which also was responsible
for the production of the final report. The contractor's senior
project management subsequently reviewed the final report in its
entirety.
At EPA a senior staff member was responsible for guiding the
contractors, reviewing the manuscripts, and soliciting comments, where
appropriate, from related programs within EPA (e.g., Office of Toxic
Substances, Research and Development, Air Programs, Solid and
Hazardous Waste, etc.). A complete draft was summarized by the
assigned EPA staff member and reviewed for technical and policy
implications with the Office Director (formerly the Deputy Assistant
Administrator) of Water Regulations and Standards. Subsequent revi-
sions were included in the final report.
Michael W. Sllmak, Chief
Exposure Assessment Section
Monitoring & Data Support Division (WH-553)
Office of Water Regulations and Standards
iii
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AN EXPOSURE AND RISK ASSESSMENT FOR BENZO[a]PYRENE AND
OTHER POLYCYCLIC AROMATIC HYDROCARBONS
VOLUME I
SUMMARY
1.0
2.0
VOLUME II
3.0
VOLUME III
4.0
VOLUME IV
Introduction
Technical Summary
Naphthalene
3.1 Materials Balance
3.2 Fate and Distribution in the Environment
3.3 Effects and Exposure—Humans
3.4 Effects and Exposure—Aquatic Biota
3.5 Risk Considerations
Anthracene, Acenaphthene, Fluoranthene, Fluorene,
Phenanthrene, and Pyrene
4.1 Materials Balance
4.2 Fate and Distribution in the Environment
4.3 Effects and Exposure—Humans
4.4 Effects and Exposure—Aquatic Biota
4.5 Risk Considerations
Benzo[a]pyrene, Acenaphthylene, Benz[a]anthracene,
Benzo[b]fluoranthene, Benzo[k]fluoranthene, Benzo-
[g,h,i]perylene, Chrysene, Dibenz[a,h]anthracene,
and Indeno[1,2,3-c,d]pyrene
5.0
5.1 Materials Balance
5.2 Fate and Distribution in the Environment
5.3 Effects and Exposure—Humans
5.4 Effects and Exposure—Aquatic Biota
5.5 Risk Considerations
v
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TABLE OF CONTENTS
VOLUME III
Page
LIST OF FIGURES ix
LIST OF TABLES x
ACKNOWLEDGMENTS xiii
1.0 INTRODUCTION 1-1
4.0 ANTHRACENE, ACENAPHTHENE, FLUORANTHENE, FLUORENE,
PHENANTHRENE, AND PYRENE 4-1
4.1 MATERIALS BALANCE 4-1
4.1.1 Introduction 4-1
4.1.2 Production and Use 4-1
4.1.2.1 Anthracene 4-1
4.1.2.2 Acenaphthene 4-4
4.1.2.3 Fluoranthene 4-5
4.1.2.4 Fluorene 4-6
4.1.2.5 Phenanthrene 4-7
4.1.2.6 Pyrene 4-7
4.1.3 Inadvertent Sources 4-7
4.1.3.1 Combustion 4-7
4.1.3.2 Contained Sources 4-8
4.1.4 Publicly Owned Treatment Works (POTWs) 4-14
4.1.5 Summary 4-18
4.2 FATE AND DISTRIBUTION IN THE ENVIRONMENT 4-26
4.2.1 Introduction 4-26
4.2.2 Input to Aquatic Media 4-26
4.2.3 Environmental Fate 4-23
4.2.3.1 Basic Physical/Chemical Properties 4-28
4.2.3.2 Pathways in the Aquatic Environment 4-30
4.2.3.3 Modeling of Environmental Distribution 4-47
4.2.4 Monitoring Data 4-57
4.2.4.1 STORET Data 4-57
4.2.4.2 Data From Other Sources 4-61
4.2.5 Summary of Fate and Distribution 4-63
4.3 HUMAN EFFECTS AND EXPOSURE 4-70
4.3.1 Human Toxicity 4-70
4.3.1.1 Introduction 4-70
4.3.1.2 Pharmacokinetics 4-70
4.3.1.3 Human and Animal Studies 4-71
4.3.1.4 Overview 4-73
vii
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TABLE OF CONTENTS (Continued)
Page
4.3.2 Human Exposure 4-79
4.3.2.1 Introduction 4-79
4.3.2.2 Ingestion 4-79
4.3.2.3 Inhalation 4-80
4.3.2.4 Dermal Contact 4-80
4.3.2.5 Overview 4-85
4.4 EFFECTS AND EXPOSURE—AQUATIC BIOTA 4-87
4.4.1 Effects on Aquatic Organisms 4-87
4.4.1.1 Introduction 4-87
4.4.1.2 Acute Toxicity 4-87
4.4.1.3 Chronic Toxicity 4-87
4.4.1.4 Other Toxicity Studies 4-92
4.4.1.5 Factors Affecting Toxicity 4-92
4.4.1.6 U.S. EPA Ambient Water Quality Criteria 4-92
4.4.1.7 Conclusions 4-92
4.4.2 Exposure of Aquatic Biota 4-94
4.4.2.1 Introduction 4-94
4.4.2.2 Monitoring Data 4-94
4.4.2.3 Aquatic Fate 4-94
4.4.2.4 Biosynthesis 4-95
4.4.2.5 Conclusions 4-95
4.5 RISK CONSIDERATIONS 4-97
4.5.1 Introduction 4-97
4.5.2 Humans 4-97
4.5.2.1 Statement of Risk 4-97
4.5.2.2 Discussion 4-97
4.5.3 Aquatic Biota 4-98
REFERENCES FOR 4.1 4-99
REFERENCES FOR 4.2 4-105
REFERENCES FOR 4.3 4-109
REFERENCES FOR 4.4 4-114
APPENDIX A
APPENDIX B 4-135
viii
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LIST OF FIGURES
Figure
No. Page
4-1 Computed Relationship between Depth and Average Half-Life 4- 35
for Direct Photolysis of Anthracene in the Top
35 Meters of Sea Water
4-2 Microbial Decomposition of PAH Compounds with Two and 4- 41
Three| Rings
4-3 _ Sources and Fate of Anthracene in the Aquatic Environment 4-69
ix
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LIST OF TABLES
Table
No. Page
4-1 Quantities of Select PAHs Imported and Isolated Domestically 4-2
in 1979 (kkg)
4-2 Uses of Select PAHs as Intermediates 4-3
4-3 Estimated Air Emission of PAHs by Combustion, 1978 (kkg) 4-9
4-4 Select PAHs Discharged in Used Crankcase Oil (kkg) 4-10
4-5 PAH Materials Balance: Coal Tar Production and 4-11
Distillation, 1970 (kkg/yr)
4-6 PAHs in Contained Petroleum Sources (kkg/yr) 4-12
4-7 PAH Emissions: Coke-Oven Doors 4-13
4-8 PAH Water Discharges: Timber Products, 1978 (kkg/yr) 4-15
4-9 PAH Materials Balance for Select PAHs: Municipal POTWs(kkg/yr) 4-16
4-10 PAH Concentrations in Municipal POTWs (ug/1) 4-17
4-11 Summary of Emissions Data for Select PAHs, 1973 4-19
4-12 Summary of Estimated Environmental Releases of Select 4-25
PAHs - 1978
4-13 Evaluation of Air-to-Surface Pathway for Anthracene 4-27
4-14 Physical/Chemical Properties of the Anthracene Group PAhs 4-29
4-15 Half-Lives and Quantum Yields for Photolysis of the 4-33
Anthracene Group PAIis
4-16 Bioaccumulation Data for the Anthracene Group PAHs 4-37
4-17 Biodegradation Products Reported for the Anthracene Group 4-40
PAHs
4-18 Biodegradation Rates of Anthracene Group PAHs 4-42
4-19 Kinetic Parameters of Anthracene Biotransformation 4-46
4-20 Values of Parameters used for Calculating the Equilibrium 4-48
Distribution of Anthracene Predicted by the MacKay
Fugacity Model
4-21 Equilibrium Partitioning of Anthracene, Calculated by 4-49
Using the Mackay Fugacity Model
4-22 Input Parameters for EXAMS Modeling of the Fate of 4-51
Anthracene in Generalized Aquatic Systems
4-23 Steady-State Concentrations of Anthracene in Various 4-52
Generalized Aquatic Systems Resulting from Continuous
Discharges
x
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LIST OF TABLES
(Continued)
Table
No.
4-24 The Fate of Anthracene in Various Generalized Aquatic 4-53
Systems
4-25 The Persistence of Anthracene in Various Generalized 4-55
Aquatic Systems after Cessation of Loading
4-26 Comparison of Results from tlackay's Equilibrium Model 4-56
and EXAMS for Anthracene in a Pond System
4-27 The Number and Ranges of Observations in STORET for 4-53
the Anthracene Group PAHs
4-28 Distribution of Observed Ambient and Effluent Concentra- 4-59
tions of Anthracene Group PAHs in STORET
4-29 Distribution of Observed Sediment and Tissue Concentra- 4-60
_ tions of Anthracene Group PAHs in STORET
4-30 Fluoranthene Levels Detected in Wastewater and Effluents 4-62
4-31 Concentrations of Pyrene in Tissues of Edible Marine 4-64
Species
4-32 Automotive and Coking Source Concentrations of Fluoranthene 4-65
in Air
4-33 Concentrations of Anthracene Group PAHs Detected in the 4-66
Urban Atmosphere
4-34 Average Concentrations of Pyrene and Anthracene in the 4-67
Air of Selected U.S. Cities
4-35 Results of Carcinogenicity Studies with Anthracene 4-72
4-36 Results of Carcinogenicity Studies with Fluoranthene 4-73
4-37 Results of the Screening of Anthracene, Phenanthrene, 4-74
and Pyrene for Tumor-Initiating Activity
4-38 Tumor Initiation by Apparently Noncarcinogenic Poly- 4-75
cyclic Aromatic Hydrocarbons
4-39 Summary of Mutagenic Activity for PAH Compounds Comprising 4-77
the Anthracene Group
4-40 Estimated Human Exposure to the Anthracene Group PAHs 4-81
via Drinking Water
4-41 Levels of Anthracene Group PAHs in Food and Estimated 4-82
Exposure via Ingestion of Food
4-42 Estimated Exposure to Anthracene Group PAHs Due to 4-84
Inhalation of Ambient Air
xi
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LIST OF TABLES
(Continued)
Table
No. Page
4-43 Estimated Human Exposure to Anthracene Group PAHs 4-86
4-44 Acute Toxicity of Anthracene Group PAHs for Freshwater 4-83
Species
4-45 Acute Toxicity of Anthracene Group PAHs for Marine 4-89
Invertebrates and Fish
4-46 Toxicity of Anthracene Group PAHs for Freshwater and 4-90
Marine Plants
4-47 Chronic Toxicity of Anthracene Group PAHs for Marine 4-91
Species
xii
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ACKNOWLEDGMENTS
The major contributors to the Exposure and Risk Assessment for
the PAHs in the Anthracene Group were Melanie Byrne (Aquatic Effects
and Exposure), Susan Coons (Environmental Fate, Risk Considerations),
Muriel Goyer (Human Effects) and Joanne Perwak (Human Exposure);
Judith Harris provided significant input to several chapters of this
report. In addition, Kate Scow contributed to the discussions of
biodegradation and aquatic effects, and Janet Wagner performed the
environmental modeling tasks. Documentation of this report was done
by Nina Green; Jane Metzger and Paula Sullivan were responsible for
editing and final report production.
The Materials Balance for the PAHs in the Anthracene Group
(Section 4.1) was produced by Acurex Corporation, under Contract
No. 68-01-6017 to the Monitoring and Data Support Division (MDSD),
Office of Water Regulations and Standards (OWRS), U.S. Environmental
Protection Agency. Patricia Cruse was the task manager for Acurex,
Inc.; other contributors include Robert DeRosier, Kenneth Moss and
Stephen Wendt. Patricia Leslie was responsible for report production
on behalf of Acurex, Inc.
John Segna and Michael Slimak were the EPA project managers for
this assignment.
xiii
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1.0 INTRODUCTION
The Office of Water Regulations and Standards (OWRS), Monitoring
and Data Support Division, of the U.S. Environmental Protection Agency
is conducting a program to evaluate the exposure to and risk of 129
priority pollutants in the nation's environment. The risks to be
evaluated include potential harm to human beings and deleterious effects
on fish and other biota. The goals of the program under which this
report has been prepared are to integrate information on cultural and
environmental flows of specific priority pollutants, to estimate the
likelihood of receptor exposure to these substances, and to evaluate the
risk resulting from such exposures. The results are intended to serve
as a basis for estimating the magnitude of the potential risk and
developing a suitable regulatory strategy for reducing any such risk.
This report, comprised of four separate volumes, provides a summary
of the available information concerning the releases, fate, distribu-
tion, effects, exposure, and potential risks of the 16 priority pollu-
tants that are polycyclic aromatic hydrocarbons (PAHs). The chemical
structures of these compounds are shown in Figure 1-1.
The number of chemicals considered in this exposure and risk
assessment is appreciable. The possibility of preparing 16 separate
exposure and risk assessment documents was considered and rejected
because it would lead to considerable redundancy and because so little
information was available on some of the individual PAHs. As an
alternative, the 16 PAHs were organized at the onset of the work into
three groups, as indicated in Figure 1-1.
The rationale for the organization into these three specific groups
included considerations of materials balance, chemical properties
related to fate and environmental pathways, and health effects, as
described briefly below.
• Naphthalene is the only one of the 16 PAHs with substantial
U.S. commercial production and with a significant potential
for direct exposure to consumers of a commercial product
(mothballs). It is significantly more volatile and more water
soluble than any other PAH. It was not anticipated to have
carcinogenic effects in humans.
o Anthracene, acenaphthene, fluorene, fluoranthene, phenanthrene
and pyrene are all imported in rather small quantities for
special commercial uses. These compounds are three- and
four-ring PAHs, with moderately low volatility and water
solubility. The question of their possible carcinogenicity
was expected to require careful review. Most of the informa-
tion pertaining to this group is specific to anthracene.
1-1
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THE ANTHRACENE GROUP
I
N>
Anthracene
Acenaphthene
Fluorene
Phenantlvene
Pyrene
Fluoranthene
Benzo [a] pyrene Acenaphthylene Benz [a] anthracene
Chrysene
Benzo[b) fluoranthene
Dibenz [a,h I anthracene
Benzo[k| fluoranthene
Benzo (g,h,t) perylene
Indeno [ 1,2,3-c,d 1 pyi ene
FIGURE 1-1 STRUCTURES OF THE PRIORITY POLLUTANT
POLYCYCLIC AROMATIC HYDROCARBONS
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• Benzo[a]pyrene (BaP) and the eight other PAHs in the third
group have no commercial production or use, except as research
laboratory standards. They are released to the environment
inadvertently by combustion sources. With one exception
(acenaphthylene), the chemicals in this group have very low
vapor pressures and water solubilities. Several of the PAHs
in the BaP group had been identified as carcinogens. Much of
the information regarding this group of compounds is for BaP.
The exposure and risk assessment for each of the three groups of
PAHs was treated in a separate chapter of a multivolume report; Chapter
3.0 (Volume II) concerns naphthalene; Chapter 4.0 (Volume III) concerns
the anthracene group PAHs; and Chapter 5.0 (Volume IV) concerns the
benzo[a]pyrene group PAHs. These chapters are bound separately.
Potential waterborne routes of exposure are the primary focus of
these exposure and risk assessments because of the emphasis of OWRS on
aquatic and water-related pathways. Inhalation exposures are also
considered, however, in order to place the water-related exposures into
perspective. Each chapter contains major sections discussing the
following topics:
• Information on environmental releases of the subject PAHs,
including the form and amounts released and the receiving
medium at the point of entry into the environment (materials
balance);
• Description of the fate processes that transform and/or
transport the compounds from the point of release through
environmental media until exposure of humans and other recep-
tors occurs, and a summary of reported concentrations detected
in the environment, with a particular emphasis on aquatic
media;
• Discussion of the available data concerning adverse health
effects of the subject PAHs on humans, including (where known)
the doses eliciting those effects and an assessment of the
likely pathways and levels of human exposure;
• Review of available data concerning adverse effects on aquatic
biota and the levels of environmental exposure; and
• Discussion of risk considerations for various subpopulations
of humans and other biota.
Two comments regarding the materials balance section are appropri-
ate. First, these sections were based in large part on draft material
prepared by Acurex Corporation, under EPA Contract 68-01-6017, and
provided to Arthur D. Little, Inc. by EPA. Second, the phrase "mater-
ials balance" is somewhat inappropriate when applied to chemicals such
as the PAHs that are produced primarily as byproducts of combustion
1-3
-------
processes. Since most PAH production is inadvertent rather than
deliberate commercial production, the conventional approach of trying to
balance production versus use and environmental release is not strictly
applicable to these chemicals. Therefore, the materials balance sec-
tions of these exposure and risk assessments are focused on estimates of
releases from major sources such as combustion; considerable uncertainty
is associated with most of these estimates.
After an initial review of the three exposure and risk assessments
covering all 16 priority pollutant PAHs, it was determined that one
chemical, benzo[a]pyrene, was of appreciably greater interest to OWRS
than were the other 15 compounds studied. This interest reflects the
more extensive data base available for assessment of environmental fate
and exposure and also the existence of some, although limited, dose-
response data to which various extrapolation models can be applied for
estimation of potential human carcinogenic risk from ingestion of BaP.
For the other PAHs considered, data on carcinogenic or other long-term
effects were generally limited, nonquantitative, and/or did not indicate
statistically positive results. Table 1-L presents a summary of the
hazard of the 16 priority pollutant PAHs in terms of carcinogenicity,
based on qualitative review of available information.
For these reasons, the technical summary presented in Volume I is
organized somewhat differently than the rest of the report (Chapter 3.0-5.0)
(Volumes II-IV). The summary is focused on benzo[a]pyrene as the PAH of
greatest interest. The estimated releases to the environment, environ-
mental fate, monitoring data, human effects and exposure, biotic effects
and exposure, and risk considerations concerning BaP are presented in
expanded summary form. Abbreviated summaries are then provided for
naphthalene, anthracene group PAHs, and the other PAHs considered.
Included in the summary volume are critical data and references to
the literature so that this volume may be read and understood by itself
without reference to the separately bound Chapters 3.0-5-0. The latter
volumes contain more extensive compilations of data, more detailed
discussions of the available information and of the interpretations
drawn, and more complete documentation of the multiple literature
sources that were reviewed in the course of this work.
1-4
-------
TABLE 1-1. SUMMARY OF EVIDENCE FOR CARCINOGENICITY OF
PRIORITY POLLUTANT PAHs
PAH
Benzo[a]pyrene
Dibenzta,h]anthracene
Benz[a]anthracene
Benzo[g,h,i]perylene
Benzo[h]fluoranthene
Chrysene
Indeno[1,2,3-c,d]pyrene
Pyrene
Fluoranthene
Benzo[k]fluoranthene
Phenanthrene
Basis
Positive oral carcinogen with
other positive carcinogenic
data.
Positive oral carcinogen with
other positive carcinogenic
data.
Positive oral carcinogen with
other positive carcinogenic
data.
Not tested orally, other posi-
tive carcinogenic or co-car-
cinogenic data.
Not tested orally, other posi-
tive carcinogenic or co-car-
cinogenic data.
Not tested orally, other posi-
tive carcinogenic or co-car-
cinogenic data.
Co-carcinogen or initiator
with negative carcinogen or in
vivo mutagen.
Co-carcinogen or initiator
with negative carcinogen or in
vivo mutagen.
Co-carcinogen or initiator
with negative carcinogen or in
vivo mutagen.
Negative in a single carcino
genie study.
Several negative carcinogenic
and mutagenic studies but not
tested orally.
1-5
-------
TABLE 1-1. SUMMARY OF EVIDENCE FOR CARCINOGENICTY OF
PRIORITY POLLUTANT PAHs (Continued)
Anthracene Negative studies, tested
orally.
Naphthalene Negative studies, tested
orally.
*
No data for evaluation of carcinogenicity were available for
acenaphthene, acenaphthylene, or fluorene.
1-6
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4.0 ANTHRACENE, ACENAPHTHENE, FLUORANTHENE,
F1UORENE, PHENANTHRENE, AND PYRENE
4.1 MATERIALS BALANCE
4.1,1 Introduction
This section reviews both published and unpublished data
concerning the production, use, and disposal of anthracene and
related PAHs in the United States. Information from the available
literature has been reviewed to present an overview of major
sources of environmental releases of these compounds. Tables
have been included to aid data evaluation. The Section is
organized such that the text (Section 4.1.2) discusses the
various uses, production sources, and attendant environmental releases
of each of the six PAHs covered herein (anthracene, acenaphthene,
fluoranthene, fluorene, phenanthrene, and pyrene), separately. Within
each chemical-specific section, both major and miscellaneous sources
of the compound are discussed. Sources of inadvertent releases of
this group of PAHs are covered in Section 4.1.3, and PAHs in publicly-owned
treatment works (POTWs) are discussed in Section 4.1.4." The tables,
both in the section itself and in Appendix A, are structured
to allow comparison of all of these PAHs resulting from the various
sources and processes for which data were available.
4.1.2 Production and Use
4.1.2.1 Anthracene
Overview
Among the PAHs, anthracene is second in commercial importance to
naphthalene. In 1979, approximately 280 kkg of anthracene were
imported into the U.S. (U.S. Department of Commerce 1980, see
Table 4-1). Also, more than 100 kkg were recovered domestically from
creosote oil (Ritchie 1980, Hagman 1980, see Note 2, Appendix A for
further details). Therefore, >380 kkg of anthracene are assumed to
have been consumed in the U.S. during 1979.
Anthracene was used as an intermediate in the synthesis of various
end products (see Table 4-2).. It is assumed that most of the anthracene
used domestically was incorporated into anthraquinone, which in turn was
used to synthesize a wide variety of dyestuffs (Henley Company 1980,
LaPine Scientific 1980, and Chung 1978). If one assumes that 1% is
released to the environment, approximately >4 kkg of anthracene were
released to the environment in 1979. This release is assumed, for
lack of data, to be divided equally among the aquatic, atmospheric, and
terrestrial environments.
4-1
-------
Table 4-1. Quantities of Select PAHs Imported and Isolated Domestically in 1979 (kkg)a
Acenaphthene Anthracene Fluoranthene Fluorene Phenanthrene Pyrene
Imported
250
280
100
<1
<1
90
Recovered
100c
I
ro
-------
Table 4-2. Uses of Select PAHs as Intermediates
Uses
Acenaphthene Anthracene Fluoranthene Fluorene Phenanthrene Pyrene
Soapa
X
X
X
X
X
X
Pharmaceutical sb
X
X
X
X
X
X
Food Processing0
X
X
X
X
X
X
Photographic Fluoras^
x<
X
X
X
X
Pigments and Dyes
xeg
X e
xf
X9
xf
xh
Pyrotechnics
X*
x"
Insecticides
xe9
X
X
Fungicides
xe9
Plastics
xe9
Herbicides
X9j
Office Copiers
x1
V
Miscellaneous
X
X
X
X
X
X
a) Based on assumption (Analabs 1980).
b) Unidentified use 1n pharmaceuticals industry, (Lachat Chemicals [nc 1980; Eastman Kodak Company 1980;
Baker Chemical Company 1980; Columbia Organic Chemicals 1980, and Fisher Scientific 1980).
Unidentified use in food processing (Baker Chemical Company 1980); used as an intermediate in the
manufacture of a green food dye (Henley Company 1980).
d) Based on assumption (Lachat Chemicals Inc. 1980).
e) The Merck Index 1976.
f) Used as an Intermediate to make a fluorescent pigment used in leak detection, clothing and road
equipment (Henley Company 1980).
g) Eastman Kodak Company 1980.
h) Hagman 1980; Chung and Farrls 1979.
1) Henley Company 1980.
j) Intermediate used in herbicide manufacture, all of which is exported (Henley Company 1980).
k) To include biochemical research laboratory standards and reagents and microbiological stains (Hawryluk,
1980: Aldrich Chemical Company 1980; Analabs 1980; Baker Chemical Company 1980; and Columbia Organic
Chemicals 1980).
-------
Pharmaceutical and Photographic Industries
Anthracene is consumed by the pharmaceutical and photographic
industries, where it is assumed to be used only in select, specialized
processes due to its low detection frequency and low concentration in
wastewaters from those industries (EPA 1980e, EPA 1980f, see also
Table 4-2). In a comprehensive pharmaceutical industry profile, only
one of 212 plants reported that anthracene was used as a raw material,
while one other plant responded that they used this compound in their final
product (see Table A-l, Appendix A). Further, when the wastewaters (influent
and effluent) of 26 plants were analyzed, with a detection limit of 10 yg/1,
anthracene was found only once and at a very low concentration (14 yg/l, See
Table A-2). The estimated quantity of anthracene contained in influent
wastewaters generated by the pharmaceutical industries for 1979 is <1 kiq>
(see Table A-2). After in-plant treatment, anthracene was not detp.rtpd -fn
effluent wastewaters; and upon removal was either injected into deep
wells or discharged to lagoons (EPA 1980e, see also Notes 4 and 5,
Appendix A for further details). Also, anthracene was not detected
in effluents of 112 plants in the photographic industry (EPA 1980f,
Klobukowski 1980).
Miscellaneous Uses
The quantities of anthracene used in the soap, food processing,
and pyrotechnic industries are unknown but assumed to be small (i.e.,
<1 kkg). No information could be found on such uses, either in a compre-
hensive literature search or through contacts with 10 different
anthracene distributors in the U.S. Furthermore, because anthracene
is used as an intermediate in the above industries, <1 kkg is estimated
to have been released from these industries combined (Henley Company
1980, Baker Chemical Company 1980).
4.1.2.2 Acenaphthene
Overview
Approximately 250 kkg of acenaphthene were imported and used in
the United States in 1979 (see Table 4-1; see also Note 1,
Appendix A for further details). In all cases, acenaphthene was
used as an intermediate in the synthesis of other end products
(see Table 4-1). It is assumed that the majority of this compound
was used in the synthesis of four pigments, since data on other uses
could not be found (see Note 3, Appendix A).
Because acenaphthene is used largely as an intermediate in
multistep synthesis, it appears likely that <1% of the total quantity
used (i.e., <2.5 kkg/yr) is released to the environment. In the
absence of specific information, any acenaphthene so released is
assumed to be equally divided among the aquatic, atmospheric, and
terrestrial environmental compartments.
4-4
-------
Pharmaceutical and Photographic Industries
Acenaphthene is consumed by the pharmaceutical and photographic
industries, where it is assumed to be used only in select,
specialized processes due to its low detection frequency and low
concentration in wastewaters from those industries (EPA 1980f, see
also Table 4-2). In a comprehensive pharmaceutical industry profile,
only one of 212 plants indicated that acenaphthene was used in the final
product, and only three of 26 plants generated wastewaters that
contained acenaphthene (EPA 1980e, see also Tables A-l and A-2,
Appendix A). The estimated quantity of acenaphthene contained in
influent wastewaters generated by the pharmaceutical industry was
<1 kkg. Furthermore, after in-plant treatment, acenaphthene was not
detected in effluent wastewaters; the small quantity that was removed
was reportedly injected into deep wells or discharged to waste
lagoons (EPA 1980e and see also Notes 4 and 5, Appendix A).
In a comprehensive study of the photographic industry
(EPA 1980f), acenaphthene was not detected in effluents from 112
photographic industry facilities (Klobukowski 1980).
Miscellaneous Uses
The quantities of acenaphthene used in the soap, food processing,
insecticide, fungicide, and plastics industries are unknown but are
thought to be small (i.e., <1 kkg). No information could be found on
domestic use, either in a comprehensive literature search or through con-
tacts with the eight different distributors of acenaphthene in the U.S.
Furthermore, because acenaphthene is used as an intermediate, it is
assumed that <1 kkg would have been released to the environment from
all of these industries combined (Eastman Kodak Company 1980,
Baker Chemical Company 1980).
4.1.2.3 Fluoranthene
Overview
Nearly 100 kkg of fluoranthene were imported and used in the U.S.
in 1979 (see Table 4-1 and Note 1, Appendix A for further details).
The only available information on fluoranthene use was obtained from
its distributors (Lachet Chemical Inc., Henley Company, and Baker
Chemical Company). In all cases, fluoranthene was reported to be
used as an intermediate in the synthesis of other end products (see
Table 4-2). One distributor indicated that the major use of
fluoranthene was in the synthesis of fluorescent pigments employed
for the detection of industrial leaks and for coating materials to
make them glow in dim light [such as traffic directors' vests and
municipal road equipment, (Henley Company 1980)]. However, the
quantity of fluoranthene used in synthesis of fluorescent pigments
is unknown.
4-5
-------
Pharmaceutical and Photographic Industries
Fluoranthene is assumed to be used by the pharmaceutical and
photographic industries, but only in select, specialized processes,
due to its low detection frequency and low concentration in
wastewaters from those industries (see Tables A-l and A-2,
Appendix A ). In an industry profile, only one of 212 pharmaceutical
plants reported that fluoranthene is used in their final products,
and fluoranthene was not detected in any of the wastewaters from 26
plants surveyed (EPA 1980e, see also Appendix A}_.
In a comprehensive survey of the photographic industry (EPA 1980f),
fluoranthene was not detected in effluents from 112 photographic industry
facilities (Klobukowski 1980}.
Miscellaneous Uses
The quantity of fluoranthene used in the soap and food processing
industries is unknown but is thought to be small (i.e., <1 kkg). No
information could be found on domestic uses of fluoranthene, either in
a comprehensive literature search or through contact with seven U.S.
distributors of fluoranthene. Furthermore, because fluoranthene is
used as an intermediate, it is estimated that less than 1 kkg would have been
released to the environment from the two industries listed above
(Analabs 1980, Henley Company 1980).
Due to the role of fluoranthene as an intermediate in the
synthesis of various products, it is assumed that 992 of the
fluoranthene imported and used in the U.S. (i.e., 100 kkg) is
consumed/converted into end products. Therefore, approximately 1 kkg
would be released to the environment; it is assumed, for lack of data,
that this release is equally distributed among the aquatic, atmospheric,
and terrestrial environmental compartments.
4.1.2.4 Fluorene
Very small quantities of fluorene (i.e., <1 kkg) were imported
into the U.S. in 1979 (U.S. Department of Commerce 1980, see also
Table 4-1). Furthermore, no domestic fluorene producers could be
found, and two distributors for this chemical indicated that all
the fluorene used domestically for that year was imported (Henley
Company 1980, McKenzie Chemical Works of Louisiana 1980).
Fluorene has diverse uses (see Table 4-2), however, because it
is used as an intermediate in the synthesis of other compounds.
Only about 1 kkg was used nationwide in 1979^ total environmental
releases to water, air and land must have been <1 kkg.
4-6
-------
4.1.2.5 Phenanthrene
Import and USITC data indicate that domestic commercial use of
phenanthrene was very limited in 1979 (<1 kkg was consumed, U.S.
Department of Commerce 1980, USITC 1979, and see also Table 4-1).
Phenanthrene is thought to be used by many industries in small
quantities for a variety of purposes; however, because <1 kkg was used
in 1979, far less than that quantity would have been released to the
environment.
4.1.2.6 Pyrene
According to the U.S. Department of Commerce (1980), approximately
90 kkg of pyrene were imported into the U.S. in 1979 (see Table 4-1).
Also, there did not appear to be any domestic production of pyrene
in 1979 (see Note 1, Appendix A).
In the absence of information concerning other uses, it is
assumed that the majority of pyrene used domestically in 1979 was
converted into dye intermediates (i.e., dibenzoylpyrene and
pyrene-1,3,6,8-tetrasulfonic acid, see Note 6, Appendix A for
further details).
Pyrene is also assumed to be used in the pharmaceutical industry
(Baker Chemical Company 1980). However, pyrene was not detected in
wastewater samples from 26 pharmaceutical plants (see Tables A-l and
A-2, and Note 5, Appendix A).
Pyrene has also been linked to uses as synthesis intermediates
in the soap, food processing, and photographic industries (see
Table 4-2). However, because no information could be found on
specific uses of pyrene in these industries (either in the
literature or from seven domestic pyrene distributors), the quantity
of pyrene used in this manner is assumed to be small (<1 kkg). For
the photographic industry, a comprehensive EPA report (1980f) does not
list pyrene as a constituent of any of the effluent wastewaters
collected at 112 photographic plants.
Since pyrene was used mainly as an intermediate in the multistep
synthesis of the aforementioned dyes and other products (see Table 4-2),
it is likely that less than 1% of the total quantity used (90 kkg) was
released to the environment. Therefore, <1 kkg of pyrene may have
been released to the environment, divided equally among the aquatic,
atmospheric, .and.terrestrial environments.
4.1. 3 Inadvertent Sources
4.1.3 .1 Combustion
As is true of all PAHs, the chief source of the anthracene
group PAHs is combustion. Quantities of these PAHs released from
4-7
-------
this source are estimated in Table 4-3. Combustion of wood for
residential heating generates Che largest amount of PAHs. Anthracene
and phenanthrene account for 75% of the total anthracene group emissiors
from residential wood burning. (Supplemental data concerning PAHs fror
combustion sources are given in Appendix A, Notes 8 through 15.)
As a byproduct of combustion, PAHs may be found in crankcase oil
and may be released to either land or water if the oil is disposed of
haphazardly. Table 4-4 shows estimates of the PAHs contained in these
releases. (See Appendix A, Note 13 and Table A-12.)
4.1.3.2 Contained Sources
This section presents information, primarily in tabular format,
on amounts of anthracene group PAHs contained in coal tar and petro-
leum. Delineation of all such potential "inadvertent sources"
of PAH release is a monumental task, since petroleum- and
coal-derived oils, fuels or solvents that contain at least small
amounts of PAHs are omnipresent. The major sources discussed here
are summarized in two tables: Coal Tar Production and Distillation
(Table 4-5) and Petroleum Sources (Table 4-6)» supporting data and
related information are presented in Tables A-3 to A-7, Appendix A.
It is important to comment on the quality of available data in
this section. Specifically, concentrations of the various PAHs in
crude oils, coal, or coal and petroleum products are highly
variable, depending upon the place or origin and method of
processing. Furthermore, as subsequent calculations are based on
these concentrations, they can be considered as rough estimates
only, at the order of magnitude level of reliability.
Coal Tar
Coal tar is the heavy distillate fraction from the destructive
distillation (coking) of coal. The distribution of coke-oven tar
production in the U.S., PAH concentrations, and environmental
releases (Tables 4-7, A-3, -4, and -5"> have been combined to provide
the information presented in Table 4-5. Naphthalene (see Section 3.1),
present in the largest concentration in coal tar, is the only PAH
compound warranting recovery and isolation in large amounts.
Anthracene is also isolated, but to a lesser extent and usually in
crystals that form during creosote oil recovery. Creosote oil is
used in the wood preserving industry. Information on PAH
4-8
-------
Table 4-). CitUuled A1r tottsloa of FAm by Coabustlon. 19/6 (Ug)
3 Prliiry Auxiliary
Residential Residential Residential Coal
Cot I 3 Wood Wood ^Refuse
Cocbuitlon Fireplaces Heating Heitlng Cigarettes Piles
a b
Prescribed
Burning
a j e utility f
Cirtou® lire (j Agricultural A Bollert
, Black Uear Burning Gasoline Coil —" GlI
J]
Utility anJ Gas- and 1.
g Industrial Oil- FirM
Incinerators 1C Lnytnes Residential
Sources
Acenaptithene
300
4
so
70
1
30
Anthracene
70
30
500
700
neg
1
90
SO
neg
neg
30
4
7
Huoranthene
40
5
100
200
neg
neg
200
100
neg
3
70
70
3
20
nee
Fluorene
200
n£J
100
100
neg
* wo
Phenanthrene
70
30
soo
700
neg
t
90
SO
neg
neg
30
30
1
20
neg
1 20
Pyrene
40
&
100
100
neg
neg
200
100
1
10
60
100
3
a
Total
720
74
1,350
1.870
ne9
2
HO
300
2
13
190
204
7
48
neg
I S7
Note 8 and Note 13 Blanks Indicate data not available, negligible • <1 kkg.
Note 9
Note 10
Note II.
Note 12.
Note/ 1 L
a) See Appendix A
b) See Appeodlx A
c| See Appendli a
d) See Appendix A
e) See Appendix A
fj See Appendix A
g) See Appendix a
h) (PA 1979b
I) CPA 1979c.
-------
Table 4-4. Select PAHs Discharged in Used Crankcase Oil (kkg)
PAH
Discharge3
Anthracene
neqb
F1uoranthene
9
Fluorene
3
Phenanthrene
20
Pyrene
10
Total
42
9
a) Based upon 2x10 1 oil disposed of annually. Releases go presumably
to POTWs and landfills. No recycling is assumed.
I
b) Negligible is <1 kkg.
Source: Peake and Parker 1980 and Tanacredi 1977, see Note 13,
Appendix A.
4-10
-------
Table 4-5. PAH Materials Balance: Coal Tar Production and Distillation, 1978 (kkg/yr)d
Environmental Releases
Tar h
Used By Producers^
Sold for
Refining''
Coal-Tar
Coal -Tar
Air
^ Land
Watere
Production"
Refining/ fuel
Others
Quantity
On liana
P1tchc
Creosote
P0TU Surface
Total
Topping
Dec. 31
0ild
Acenaphthene
26,000
6,200
4,500
400
15,000
2,200
14,000
Anthracene
23,000
5,500
3,900
350
13.000
2,000
6.900
8
8
F1uoranthene
15,000
3,600
2,600
' 230
8,600
1,300
14,000
10
7
8 10
35
F1uorene
26,000
6,200
4,500
400
15,000
2,200
10,000
4
2
3 4
13
Phenathrene
77,000
18,000
13,000
1,200
44,000
6,600
35,000
Pyrene
7,700
1,800
1,300'
< 120
1 '
4,400
660
10,000
8
5
6 8
27
Total
30
14
17 22
83
a) All production values rounded to two significant figures, environmental releases to one figure; blank spaces = data not
available. Totals may not add due to rounding.
b) See Tables A- 3 and A-4 for tar production/distribution totals and concentrations of PAHs, respectively. Density of
Coal tar = 1.223 kg/1.
c) See Table A- 4 for PAH concentrations; total based on 790 x 1(P kkg pitch produced 1n 1978 (USITC 1979).
d) See Table A- 4 for PAH concentrations; total based on 3.3 x 10° 1 creosote oil produced in 1978 (USITC 1979). Density
of creosote oil = 1.06 kg/1.
e) See Table A- 5 for coke plant effluent discharge factors. Distribution of discharge: 33% - direct, 25% - POTWs, 2* deep
well. 40% quenching (20% - land, 20% - a 1r) (EPA 1979d). All values rounded to one significant figure. See Table 4-7 for
f) Includes emissions from coke-oven doors (see Table 4-7 K
-------
Table 4-6. PAHs in Contained Petroleum Sources, (kkg/yr)a
b Environmental Releases
Input Petroleum
PAH Crude Oild Gasol1ne6 Diesel Fuel' Oil Spills Gasoline Spills Refinery Wastes
Water Land Water Land Alrh Water Land
Acenaphthene
ND
neg 3
neg
Anthracene
trace
90
ne
-------
Table 4-7. PAH Emissions: Coke-Oven Doors
Emission Rate
(mg/hr/oven)a
Yearly Emission
(kkg/yrj5
F1uorene
Anthracene
Pyrene
Fluoranthene
30
120
58
71
2
8
4
4
a) EPA 1977c
b) Based on 1300 kkg coke produced per typical coke oven battery of 58
ovens; 160,000 kkg/day typical capacity for total by-product coke-
making industry (resulting in a total of 123 batteries); 365 day,
24 hour operation; emission data in first column, EPA 1979d.
4-13
-------
concentrations in creosote oil and wastewater discharges during use
is presented in the previously mentioned tables and Table 4-8,
respectively. Of a total of 224 wood preserving plants responding to
EPA's data collection protocol, two reported direct discharge, 47
reported discharge to POTWs, and the remainder reported self-
contained no-discharge operations [mostly evaporation, with some
soil irrigation or treated effluent recycle (EPA 1979e)].
Besides creosote, other principal tar products containing PAHs
are pitch and refined tar, used in a variety of applications ranging
from road materials and electrodes to shampoos. Coal tar and tar
products are also used as fuel (see Table 4-5), either by producers
(e.g., iron and steel plants) or distillers.
Petroleum Sources
The other fossil fuel source containing appreciable amounts of
1 PAHs is petroleum. The concentration and emissions data in
Tables A-6 and A-7 have been combined for use in the summary
Table 4-6.
Only spills and petroleum refinery environmental releases are
presented here. As mentioned previously, the type of crude feedstock
determines its chemical composition and, therefore, the composition
of specific waste streams. Other variables include pollution controls,
level of technology of the processes used, and operational
practices and control. The air emissions listed in Table 4-6 are
specifically from petroleum catalytic cracking, which accounts for
over 50% of the annual oil feed to refineries (Oil and Gas Journal
1979); the remainder is used for catalytic reforming, for which
emissions factors were not available.
4.1.4 Publicly Owned Treatment Works (POTWs)
Input of PAHs to POTWs is largely dependent upon variations in
industrial discharges feeding the POTWs and the types of industry in
a particular municipality. A recent EPA study of 20 urban POTW
facilities with secondary treatment and varying feed conditions
produced a materials balance of PAHs shown in Table 4-9.
The materials balance in Table 4-9 was constructed using a total
POTW flow of approximately 10^^ 1/day (EPA 1978c) and the average
concentrations of the various PAHs in influent, effluent and sludge,
presented in Table 4-10. It is assumed for purposes of these
calculations that influent and effluent flow rates are equal, i.e.,
that water losses from sludge removal and evaporation are small
compared with influent flows. When these assumptions are used, 70 kkg
of all PAHs were discharged from POTWs in 1978, while there was an
4-14
-------
Table 4-8. PAH Water Discharges: Timber Products, 1978 (kkg/yr)
Raw Discha
rge
Treated
Di scharge "
PAH
Input3
Concentration^
Quantity0
Concentration'5
Quantityc
(mg/1)
(mg/1)
Acenaphthene
14,000
5.03
40
2.10
20
Anthracene
6,900
3.45
20
2.07
20
Fluoranthene
14,000
3.84
30
2.13
20
F1uorene
10,000
4.35
30
1.83
10
Phenanthrene
35,000
3.45
20
2.07
20
Pyrene
10,000
2.66
20
1.21
10
a) See Table 4- 5, coal-tar creosote,
a) Source: EPA 1979e.
c) Based, on 56% of 476 total plants using creosote or mixture thereof, 350 day/yr, 75,500 liters/day/plant.
d) Assumed\to go to POTW (see text).
-------
Table 4-9. PAH Materials Balance for Select PAHs: Municipal POTWs (kkg/yr)a
Environmental Releases
PAH Inputb Airc Waterd Lande
Anthracene
120
63
22
35
Phenanthrene
120
63
22
35
Pyrene
37
18
7.3
12
Fluoranthene
15
4.1
3.7
7.2
F1uorene
11
8.4
NDf
2.6
Acenaphthene
3.7
3.7
ND
3.8
a) All values rounded to two significant figures.
bj Based on influent concentrations shown in Table 4-10, 1011
liters per day total POTW flow,
c) Difference between input and water and land,
dj Based on secondary effluent concentrations shown in Table 4-10,
1011 1/day total POTW flow.
e) Based on wet sludge concentrations shown in Table 4-10, 6x106
metric tons dry sludge generated/yr, wet sludge 95% water (by
weight).
f) Not detected.
4-16
-------
Table 4-10. PAH Concentrations in Municipal POTWs (pg/l)a
PAH
Influent
2° Effluent
Raw Sludge
Anthracene
3.3
0.6
295
Phenanthrene
3.3
0.6
295
Pyrene
1.0
0.2
101
Fluoranthene
0.4
0.1
60
F1uorene
0.3
ND
22
Acenaphthene
0.1
ND
32
a) Average values.
Source: EPA 1980d.
4-17
-------
input of 590 kkg. Of that total, 55 kkg of anthracene group PAH were
discharged to water.
PAHs discharged in sludge can be estimated from the PAH •
concentrations in sludge and the quantity of dry sludge produced
annually, 6.0 x 10 kkg (EPA 1970g). Wet sludge is assumed to be 95%
water by weight. As ocean dumping of sludge is mandated to cease by
1981 and if more stringent air quality standards further curb
incinerator use (EPA 1979h), the 150 kkg of PAHs contained in sludge
may be assumed to be discharged to land. Anthracene group PAHs
accounted for 96 kkg (64£ of the total).
PAHs released to the atmosphere may be estimated by the difference
between the loading in influent and the loading in effluent and sludge
according to the following assumptions: (1) PAHs recycled within the
activated sludge process will eventually be "wasted"; and (2) PAHs are
lost to the atmosphere by mechanical stripping^ or aeration.
These assumptions yield an estimate of 390 kkg of PAHs released
to the atmosphere from POTWs in 1978. Approximately 160 kkg (41% of
the total) are attributed to anthracene group PAHs.
4.1.5 Summary
Table 4-11 summarizes the production and use and estimated releases
for the anthracene group PAHs. Of the group, anthracene, acenaphthene,
fluoranthene, and pyrene are imported, and anthracene is recovered from
creosote oil. Otherwise, these compounds are produced and used in the
United States only in very small quantities. The releases are primarily
from inadvertent production in the combustion of wood and fossil fuels.
Most of these releases are estimated to originate from household heating
with wood, although both prescribed burning and wildfire appear to be
important sources. Residential coal combustion is also an important
source, particularly for acenaphthene and fluorene.
Table 4-12 summarizes the estimated environmental releases by
media for the compounds in this group. It can be seen that releases
to the atmosphere predominate. The only releases to surface waters
generally identified were those from POTWs.
4-18
-------
Table 4-11. Summary of Emissions Data for Select PAHs - 1978
Quantity
{kkg/.yr)
Estimated Environmental Releases (kkq)
Water
Air
Land
Surface
POTW
Total
Anthracene
Production
Imported
Recovered
from creosote oil
280
>100
Uses
Synthesis of dye stuff
Pharmaceutical Industry
Photographic Industry
Soap, food processing,
pyrotechnic
Inadvertent Sources
Combustion
Coal Tar Production &
Wsti llation
Contained Petroleum iburces
(Spills and Refinery Wastes)
Timber products (use of creosote)
Used Crankcase Oil
POTW
most of supply 1
1
<1
1
<1
<1
<1
1482
8
<1
63
<1
<1
35
<1
20
<1
22
4
<1
<1
<1
1482
8
<1
20
<1
120
-------
Table 4-11. Summary of Emissions Data for Select PAHs - 1978 (Continued)
Quantity
(kkq/.yr)
Air
Estimated Environmental Releases (kkq)
Water
Land
Surface
POTW
Total
Acenaphthene
Production
Imported
Recovered
250
<1
Uses
Intermediate in Synthesis
of dye
Pharmaceutical Industry
Photographic Industry
Soap, food processing,
pesticides, plastics
Most of supply
<1
<1
<1
<1
<1
<1
<1
<1
<1
<2.5
<1
<1
<1
Inadvertent Sources
Combustion
Coal Tar Production &
Di stillation
Contained Petroleum Sources
(Spills and Refinery Wastes)
Timber Products (use of creosote)
Used Crankcase Oil
455
<1
<1
<1
20
455
<1
<1
20
POTW
4 4
<1
8
-------
Table 4-11. Summary of Emissions Data for Select PAHs - 1978 (Continued)
Quantity
(kkg/yr)
Air
Estimated Environmental Releases (kkg)
Water
Land
Surface
POTW
Total
F1uoranthene
Production
Imported
Recovered
100
<1
Uses
Intermediate in pigment
Pharmaceutical Industry
Photographic Industry
Soap, food processing industry
Inadvertent Sources
Combustion
Coal Tar Production &
Distillation
Contained Petroleum Sources
(Spills & Refinery Hastes)
Timber Products (use of creosote)
Used Crankcase Oil
POTW
<1
811
10
<1
<1
7
<1
4.5
7
<1
<1
<1
10
1
20
4.5
<1
<1
<1
811
35
1
20
9
15
-------
Table 4-11. Summary of Emissions Data for Select PAHs - 1978 (Continued)
F1uorene
Production
Imported
Recovered
Uses
Intermediate
Inadvertent Sources
Combustion
Coal Tar Production &
Di stillation
Contained Petroleum Sources
( Spills and Refinery Wastes)
Timber Products (use of creosote)
Used Crankcase Oil
POTW
Estimated Environmental Releases (kkq)
Quantity Water
(kkg/yr) Air Land Surface POTW Total
<1
<1
<1
<1
<1
<1
<1
<1
400 400
4 2 4 3 13
3 3
10 10
1.5 1.5 3
8 3 <1 11
-------
Table 4-11. Summary of Emissions Data for Select PAHs - 1978 (Continued)
Quantity
(kkq/yr)
Estimated Environmental Releases (kkg)
Water
Air
Land
Surface
POTW
Total
Phenanthrene
Production
Imported
Recovered
<1
<1
Uses
Miscellaneous
<1
<1
<1
<1
<1
<1
Inadvertent Sources
Combustion
Coal Tar Production &
Distillation
Contained Petroleum Sources
(Spills and Refinery Wastes)
Timber Products (use of creosate)
Used Crankcase Oil
POTW
1523
10
10
63 35
20
10
22
1523
11
20
20
120
-------
Table 4-11. Summary of Emissions Data for Select PAHs - 1978 (Continued)
Quantity
(kkg/.yr)
Estimated Environmental Releases (kkg)
Mater
Air
Land
Surface
POTW
Total
Pyrene
Production
Imported
Recovered
90
<1
Uses
Dye Intermediate
Pharmaceutical Industry
Photographic Industry
Soap and Food Processing
Inadvertent Sources
Combustion
Coal Tar Production &
Distillation
Contained Petroleum Services
(Spills and Refinery Wastes)
Timber Products (use of creosote)
Used Crankcase Oil
POTW
<1
<1
747
8
<1
<1
18
5
12
<1
<1
<1
<1
8
1
<1
10
5
<1
<1
<1
<1
747
27
10
10
37
Source: See text.
-------
Table 4-12. Summary of Estimated Environmental Releases of Select PAHs - 1978
Environmental Release (kkq/.year)
Compound Air Land Surface Water POTW
Anthracene
1560
40
20
20
Acenaphthene
460
4
<1
20
F1uoranthene
830
20
20
30
F1uorene
410
10
10
10
Phenanthrene
1600
40
20
30
Pyrene
780
20
20
20
Source: See text.
4-25
-------
4.2 FATE AND DISTRIBUTION IN THE ENVIRONMENT
4.2.1 Introduction
This section characterizes the fate processes that determine the
ultimate distribution of the anthracene group PAHs in the aquatic
environment and, therefore, the opportunities for water-borne exposure
of humans and other biota. Much of the information presented pertains
specifically to anthracene; however, since the properties and fate
characteristics of this compound are representative of those of the
other compounds.in the group, the behavior of anthracene in the environ-
ment is believed to be a good model for the entire group.
Section 4.2.2 presents an overview of the environmental loading of
aquatic media with anthracene, from both direct releases to surface water and
physical transport (deposition from the atmosphere). In Section 4.2.3,
physical/chemical properties of anthracene are summarized in order to
identify the processes that transform and transport the chemical upon its
release to the environment (Section 4.2.3.1). Section 4.2.3.2 discusses
the interplay of fate- processes that determines the major pathways of
anthracene in aquatic environmental media. Modelling efforts were under-
taken based upon environmental loadings estimated from Section 4.1, in order
to characterize the fate and distribution of anthracene in specific
environmental scenarios; these are discussed in Section 4.2.3.3. Monitoring
data from STORET and a limited number of other surveys are summarized in
Section 4.2.4 to provide indications of concentrations of anthracene group
PAHs actually detected in aquatic media. Finally, Section 4.2.5 summarizes
those aspects of the fate and ultimate environmental distribution of
anthracene having the greatest significance for the water-borne exposure
of humans and other biota.
4.2.2 Input to Aquatic Media
Data presented in Section 4.1 indicate that although anthracene
(as well as the other PAHs in this group) is produced and used commercially
in the U.S., direct releases to surface water appear to be very low.
Anthracene group PAHs are rarely observed in final industrial effluents.
Direct discharges^of anthracene to surface waters totalled ^2 kkg in 1978; in
contrast discharges to POTWs were 20 kkg, and atmospheric emissions were
almost 1560 kkg. However, anthracene may be transported indirectly from
the atmosphere to aquatic systems via wet and/or dry deposition.
The air-to-surface pathway has been evaluated and that analysis is
presented in Appendix B of this report. The results for anthracene are
summarized in Table 4-13. Under ambient conditions typically encountered
in either urban or rural areas, anthracene is expected to partition pre-
ferentially to the vapor phase. Less than 10% of the airborne anthra-
cene is likely to be adsorbed onto ambient aerosols. However, in the
plume from a combustion source smokestack, where aerosol concentrations
are much greater, as much as 97% of the anthracene may be adsorbed. As
a result of the preferred association with the vapor phase, dry deposition
of anthracene under ambient conditions is expected to be a slow process,
with a characteristic velocity of less than 0.1 cm/sec; in contrast, dry
deposition velocity near a combustion source would be 1.0 cm/sec.
4-26
-------
TABLE 4-13. EVALUATION OF AIR-TO-SURFACE
PATHWAY FOR ANTHRACENE
Rural
Urban
Near Combustion
Source
Adsorbed Fraction
of Airborne Mass
0.002
0.06
0.97
Dry Deposition Velocity
(cm/sec)
0.02
0.08
Precipitation Scavenging
Ratio
[ng/1 (water)"1
lag/m-^air)
130
3.6x10"
1.2x10"
Percent of Atmospheric
Emissions Deposited: Rural
- dry deposition 1
- wet deposition <1
- total 1
Urban
4-19
1-7
5-26
Source: See Appendix B.
4-27
-------
The vapor/aerosol partitioning also affects the precipitation scavenging
ratio [rainfall concentration (ng/1) divided by air concentration (ug/m^)].
The estimated scavenging ratio for anthracene is sensitive to the assumed
aerosol concentration, ranging from 130 for typical rural conditions to
1.2 x 105 for rainfall passing through the plume of a major combustion
source.
Taking into account the observed concentrations of anthracene in
both rural and urban areas, as well as the chemical degradation rates,
it is estimated that only about 1% of emitted anthracene is deposited in
rural areas. On the other hand, 5% to 26% of the anthracene emitted
in major urban areas (100 square miles) is likely to be deposited there.
More than 75% of the total deposition is expected to be due to dry
deposition processes, including fallout, impaction of particles with
adsorbed anthracene, and dissolution of gaseous anthracene by surface
moisture.
On the basis of the atmospheric emissions data given in Section 4.1
(1560 kkg/yr) and the range of percent deposition of atmospheric emissions
given in Table 4-13 (5-26%), 75-400 kkg/yr can be expected to be deposited
on the surface of the United States. If one assumes that approximately 2%
of the total area of the continental United States is inland surface water
(U.S. Bureau of Census 1980), 1.5-8.0 kkg/yr may land directly on water.
The remainder of the fallout would be deposited on the surface of dry
land. A fraction of that amount could be transported ultimately to
aquatic systems by surface runoff. However, there are insufficient data
to allow a reasonable estimate of the extent of this pathway.
The above discussion of the air-to-surface pathway clearly indicates
that a significant amount of airborne anthracene near combusion sources
may be removed and deposited on the land or water surfaces. A water
body near a combustion source could receive large quantities of
anthracene group PAHs by this pathway.
4.2.3 Environmental Fate
4.2.3.1 Basic Physical/Chemical Properties
The physical/chemical properties of anthracene and related PAHs
(Table 4-14) suggest a number of important pathways for this chemical
in the aquatic environment. Anthracene and its related compounds have
relatively high octanol:water partition coefficients and low water solu-
bilities which suggest that adsorption to sediments may be important
in determining their transport and fate. The vapor pressures and Henry's
Law constants for this group, although intermediate for PAHs, are still
quite low; therefore, volatilization is likely to be of minimal
importance as a removal mechanism in aquatic systems.
Removal pathways, as well as the chemical and biological fate
processes of anthracene and the related PAHs, are discussed in the fol-
lowing sections.
4-28
-------
TABLE 4-14. PIIYSILAL/CIIQIICAL PRUPEKTIES OF THE ANTHRACENE CHOUP PAHs
hornula
M W.
Accnaphthene
Anthracene
Pluornnthcnc
Phennnchrene
1*4.21
C«H10
178.24
202.26
Cli'lO
166.23
J 78.24
Pyrenc
202.26
Ki-firunceq
Hoasc (1974)
Vapor Pressure
(lorr)
Saturated Vapor
Concentration ot
(25T.) (g/mJ)
10~3-10"2<20'C)
] ,(i*10-3(25°C)
] ,3*lO-2
1•95xiO?^{20°C)
2.4*10 (25°C>
2.3*10-3
10~6-10~4(20"C)
5x10""6(25*C)
5.4xI
2.Sx10-6<25°C)
2.7x10
Callahan et dl^ (1979)
SRf (1960J
Cjilculjicd HV«nRT
Wo Cor Solubility
(¦fi/i)
3.42
0.045
0.073
0.2b
1.69
1.98
1.00
1. 29
0.14
0.132
Callalvm ejt o_l (1979)
4>
I
ro
MuUJng Ft.
et >
Boiling Pr.
(°C)
279
216.2
216.4
340
(corrected)
^375
293-295
156
(corrected)
393
Wedst (1974)
Ucatit (L974)
1°R *-a
log K
3.72
4.45
5. 33
4.64
3.65
4, 2fl
5.32
4.64
Cd 11 d lion c L u J. (1979)
SRI <1980)
llcnry*s Uav
consume
| lit IB Dl^l
[ molo J
9.33x10
I.25x10
5.12x10
-6
1.29x10
2.25x10
4.75x10
Calculated vapor pressure
water solubility
-------
4.2.3.2 Pathways in the Aquatic Environment
Introduction
This section examines the pathways of anthracene in the aquatic
environment. The processes for actual removal from the water column
are reviewed first, i.e., volatilization and sedimentation; the
chemical transformation and degradation pathways for anthracene in
solution are described; and finally, biodegradation and its role in
the ultimate fate of PAHs is considered.
Volatilization and Atmospheric Fate
The actual rate of volatilization in the environment is dependent
upon the wind velocity, temperature, and the amount of air/water mixing.
Southworth (1979) measured a half-life of ^300 hours for anthracene at
a depth of 1.0 m under rapidly stirred laboratory conditions of ^0.04 m/
sec wind, and 0.1 m/sec water current. Increases in both wind and cur-
rent velocity decreased the measured half-life; a four-fold decrease in
half-life was observed with a ten-fold increase in both wind and current
velocity. Although extrapolating these data to environmental conditions
is difficult, it is likely that, except under the rare conditions of
high temperature, high winds, and shallow depths, the volatilization of
anthracene will be insignificant. The Henry's Law constant is a good
measure of the tendency of a solute to escape from water. The values
of this parameter for the other PAHs in the anthracene group indicate
that volatilization will be unimportant for these compounds as well.
The portion of these PAHs that does volatilize is expected to be
degraded by photooxygenation to oxygenated compounds, including quinones
(Radding e£ jil. 1976). Radding al. (1976) estimated a half-life of
10 hours for hydroxy radical photolysis of anthracene, phenanthrene
and pyrene, indicating that this process may be important in the fate
of airborne PAHs. The reaction with singlet oxygen, although occurring
with a shorter half-life (\5 hours for anthracene), is not likely to be.
important since the availability of singlet oxygen in air is low.
Adsorption and Sedimentation
Due to anthracene's limited water solubility and high octanol:water
partition coefficient, as shown in Table 4-14, much of the anthracene
in the aquatic system can be expected to be found adsorbed onto particu-
late matter. Anthracene is likely to be adsorbed onto both organic and
non-organic particulate materials.
Adsorption and concentration of PAHs in the presence of various
inorganic substrates such as activated carbon, calcareous material,
silica, glass, soil particles, and organic particles have been cited
by numerous authors as summarized in Neff (1979). From studies by
Herbes (1977) on autoclaved yeast cells, it has been predicted that a
significant fraction (0.15-0.65) of anthracene in the aqueous system
4-30
-------
would be associated with both detrital and living organic matter in
natural waters with only moderate amounts of suspended solids. The
role of mineral particulate material may be far less significant with
respect to PAH adsorption than the role of organic particulates.
The importance of organic adsorption is supported by the observa-
tion that 72% of anthracene in solution was adsorbed by yeast cells
(Herbes 1977), whereas only 22% was adsorbed by bentonite clay (Meyers
and Quinn 1973). In a similar experiment with autoclaved yeast cells
and anthracene (Southworth 1977), a partition coefficient (solid:water)
of 25,000 was observed. In another study, a particition coefficient of
1600 was reported for adsorption onto inorganic particulates (Versar
1979).
Solubilization of PAHs via micellar mechanisms involving surface
active species such as detergents, biopeptides and alkaloids is discus-
sed by several authors (Eisenbrand 1971, Elsworthy £t _al. 1968). How-
ever, these laboratory-observed solubilizations may be much less important
in natural waters where solubilizer concentrations are likely to be much
lower than particulate concentrations (Radding fet_ al^. 1976).
The actual amount and rate of PAHs adsorbed onto particulates under
environmental conditions seem to be governed by an equilibrium exchange
between adsorbed and soluble PAHs (Smith 1978, Lewis 1975). Lewis (1975)
analyzed five PAHs, including fluoranthene, in both the particulate and
soluble phases from river samples. PAHs were found in both phases, with
soluble PAHs accounting for 2-16 percent of the concentration of particu-
late PAHs. Fluoranthene, the most soluble of the PAHs analyzed in that
study, was found at the highest concentration in solution. Pyrene's
solubility and partition coefficients are similar to those of fluoranthene
and should follow the distribution observed for fluoranthene. Anthracene
has a lower solubility and higher partition coefficient than fluoranthene,
and should be found in the water column at lower concentrations. The other
compounds in this group, i.e., fluorene, acenaphthene, and phenanthrene,
have higher solubilities and lower partition coefficients, thus should be
found in the water column at somewhat higher levels than fluoranthene.
The ultimate fate of PAHs that have been adsorbed onto particulates will
depend partially upon the amount of sedimentation in the environmental system.
Sedimentation occurs as particulates gradually settle out of the water
column; flocculation of suspended clay-sized particles (as occurs in
the increasing salinity gradient of an estuary) will increase the rate
of deposition (Neff 1979). Once deposited in sediment, PAHs are much
less liable to be degraded photochemically; furthermore, biodegradation
in sediments is not very rapid, especially under anaerobic conditions
(see discussion on Biological Fate).
For anthracene, Southworth (1977) estimated the rate of removal
from solution based on adsorption onto particulates and subsequent sedi-
mentation. Using a sedimentation rate of 8.4 cm/year, a removal rate
of 7.2 x 10 ~3 hours-1 (tj/2 = 96 hours) was calculated for clay
particles and 1.44 x 10-3 hours-1 (t1/2 = 481 hours) for silt particles.
Whether these rates will be competitive with other removal processes
4-31
-------
depends upon the actual hydrologic conditions. Removal by sedimentation
is expected to occur more slowly than the degradation pathway but will be
competitive with volatilization in some aquatic systems.
The actual accumulation of anthracene in sediments occurs
not only due to sedimentation, but also due to adsorption directly onto
the sediments; so adsorption rates are expected to be higher than those
calculated on the basis of sedimentation alone. In another study
(Armstrong jet al. 1977), the concentrations of PAHs in sediments and
seawater were monitored in a Texas bay receiving a brine effluent.
Nearly all the aromatics were found to be at much higher concentrations
in sediment than in the overlying water columns. At a distance of 15 m
from the dune outfall, higher weight aromatics (including anthra-
cene) were found in the sediments, but were undetectable in the water
column (detection limit 0.1 yg/1). For all but the most soluble, low
molecular weight PAHs, concentrations in sediments are expected to be
greater than concentrations in solution by a factor of more than
1000.
To the extent that sedimentation is controlled by flow rate, PAHs
would be expected to accumulate in placid lakes and reservoirs. Much
of river-borne particulate PAHs would eventually be carried to the ocean,
where deltas and estuaries have been shown to be traps for suspended
matter (White and Vanderslice!1980). Onshore and alongshore currents
combine to restrict suspended matter in the ocean to continental shelf
areas. Gross (1970) has estimated that 90% of river-borne particulates
accumulate in this region of the ocean, where they are subject to resus-
pension and wave/current transport.
Chemical Degradation
PAHs have high absorptivities at wavelengths above the solar cut-
off (300 nm). For this reason, direct photochemical degradation (ini-
tiated by absorption of light by the PAHs, rather than an intermediate)
is expected to be a significant fate process in water despite the inef-
ficient nature of photochemical reactions (quantum yields in the range
of 0.001 to 0.01) (Smith et^ al. 1978). Table 4-15 presents the half-
lives calculated for photolysis reactions and quantum yields for some of
PAHs in the anthracene group.
Anthracene and pyrene have fairly low half-lives, and quantum yields
in the middle of the range for PAHs, indicating that photooxidation of
these two PAHs in aquatic environments is likely to be an important pro-
cess. Phenanthrene has a longer half-life (an effect usually seen in
"bent" compounds, i.e., those in which the rings are not arranged
linearly), and is expected to photolyze more slowly. Fluoranthene is an
anomolous compound, exhibiting an unusual dependence of quantum yield
on wavelength, as well as peculiar excited-state behavior. This be-
havior is probably related to the fact that fluoranthene, unlike the
other PAHs studied, is a nonalternate aromatic hydrocarbon (i.e., con-
tains a cyclopenta-ring and has only limited resonance) (Zepp and
4-32
-------
TABLE 4-15. HALF-LIVES AND QUANTUM YIELDS FOR PHOTOLYSIS OF THE
ANTHRACENE GROUP PAHs
Compound
Anthracene
Disappearance Quantum Yield Photolysis Half-Life (hours)
0.003 (at 366 nm) 0.75
Phenanthrene
0.010 (at 313 nm)
8.4
Pyrene
0.002 (at 313 nm)
0.0022 (at 366 nm)
0.68
0.68
Fluoranthrene
0.00120 Cat 313 nm)
0.2x10 ^ (at 366 nm)
21
Source: Zepp and Schlotzhauer (1979)
4-33
-------
Schlotzhauer 1979). Nagata and Kondo (1977) studied the rate of photo-
degradation of several PAHs in mixed acetone-water or carbon tetrachloride-
water solvents. Under laboratory conditions, the PAHs do seem to be photo-
sensitive. After 10 hours, approximately 65% of the anthracene and phen-
anthrene in the solution had been photodegraded; about 10% of the pyrene
and fluorene had been photodegraded in the same time period.
The importance of photooxidation will vary with the actual environ-
mental conditions and the location of the compound in the water column.
In one experiment, Southworth (1977) observed a photolysis half-life of
35 minutes in distilled water under midday sun, in midsummer at 35°N
latitude. Using the procedure of Southworth (1977), Zepp and Cline (1977)
predict a photolytic half-life of 4.8 hours under average winter solar
conditions, and 1.6 under summer conditions in shallow waters. A 19-
fold increase in the photolytic half-life of anthracene in a turbid
water system containing ^50 mg/1 of clay suspension supports the pre-
diction that adsorption of light by dissolved and suspended matter will
greatly reduce photolysis (Southworth 1977). Zepp and Schlotzhauer
(1979) further demonstrate the effect of light attentuation on PAHs.
Figure 4-1 shows the depth dependence of direct photolysis for anthra-
cene during summer. The data show photolysis half-lives for anthracene
of 6 hours in mid-Gulf water, and 1.2 days in the coastal environment.
The difference is primarily attributable to the greater attentuation of
light in the biologically active, productive coastal zone.
An important factor limiting photolysis in the environment is the
tendency for anthracene and other PAHs to partition to sediments where
no light is present (Zepp and Schlotzhauer 1979). For surface PAHs
(e.g., oil slicks), however, photodegradation is expected to be quite
significant. Lee et al. (1978) report qualitatively from model ecosys-
tems that photochemical oxidation seems to be an important process in
the destruction of oil slicks that contain fluoranthene.
Chlorine and ozone, used in water purification processes, are
strong oxidants that react with PAHs to form quinones. Several studies
report various half-lives for the reaction of PAHs with chlorine, gen-
erally less than 0.5 hours. Data summarized by Radding al. (1976)
indicate that though the reactivities of the PAHs do vary, the half-lives
are generally <0.5 hours when exposed to 10-SM solutions of chlorine
under the standard conditions for water purification. Smith £t al.
(1977) identified several polychlorinated aromatics during chlorination
of biphenyl and naphthalene, in addition to the quinones; some of these
polychlorinated aromatics may be highly toxic and persistent in the en-
vironment.
4-34
-------
I-
<
(E
111
>
I-
<
_l
LLI
CC
0.01
DEPTH, meters
FIGURE 4-1 COMPUTED RELATIONSHIP BETWEEN DEPTH AND AVERAGE
HALF-LIFE FOR PHOTOLYSIS OF ANTHRACENE IN THE TOP
35 M OF SEAWATER :
Note: Data for Naphthalene (solid line) included for comparison (A) mid-Gulf
and (B) coastal water.
Source: Adapted from Zepp and Schlotzhauer (1979).
4-35
-------
Ozone is also frequently used for water treatment. Radding et al.
(1976) reported that PAHs generally will react with ozone. Il'natskie
et al. (1968) measured the amounts of PAHs after treating 0.0067 mg/1 of
PAH with 40 mg/1 of ozone for 1 minute at 25°C. From these data, Radding
et al. (1976) calculated a half-life of 41 minutes for the reaction of
pyrene with ozone. The data suggest that in urban water supplies treated
with ozone, the lifetimes of PAHs would be quite short if the ozone does
not evaporate or become consumed more rapidly by other organics and
organisms.
Biological Fate
Introduction
Very little information is available on the biological fate of
this PAH group except for anthracene. Bioconcentration data from labora-
tory studies are presented in Table 4-16. The transport, bioaccumula-
tion and biodegradation of anthracene in aquatic ecosystems have been
studied fairly extensively.
Bioaccumulation
Bioaccumulation studies of anthracene have so far been limited to
invertebrates. No measurements were available for any fish species.
Uptake by filter-feeding organisms may constitute a major pathway
of entrance of PAHs
-------
TABLE 4-16. BIOACCUMULATION DATA FOR ANTHRACENE
Organism
Cladoceran
Daphnia magna
Compound
Anthracene
Exposure
Time
(hr)
1
BCF'
200
Reference
Herbes (1976)
Cladoceran
Daphnia pulex
Anthracene
24
760
Herbes and
Risi (1978)
Mayfly
Hexagenia sp.
Anthracene
28
3500
Herbes (1976)
a) BCF = Bioconcentration factor.
4-37
-------
. ^ The rate of PAH uptake is more rapid than the rate of metabolism
£ in Daphnia, which results in bioaccumulation by factors of several
< hundred-fold. A potential exists for exposure of fish through feeding
^ ^ on zooplankton; therefore, water column concentration alone may not
V provide enough information to indicate the potential for adverse effects
to fish populations. This exposure pathway to fish has not been
investigated.
Microbial Biotransformation
The anthracene group of PAHs is subject to microbial breakdown;
the rate and extent of degradation within the class of compounds is
variable. Structural factors such as ring number and type of ring
fusion influence biodegradation. Other environmental fate processes
such as adsorption, solubility, vaporization, and other competitive
transformation reactions also affect biodegradation of PAHs. Most
biodegradation studies are laboratory investigations, commonly conducted
in simplified systems with the goal of eliciting biodegradation. Under
environmental conditions, persistence may be considerably longer than in
the laboratory. This section describes the biodegradability of the anthra-
cene group of PAHs, based upon laboratory and field studies, including
rate and metabolic product data, and discusses environmental variables
that influence the rate of reaction.
Microorganisms act on PAHs by removing one cyclic unit at a time
(Alexander 1977) . This is supported by an observed inverse relationship
between ring number and degradation rate.1 Tricyclics, such as anthra-
cene, are reduced to dicyclic intermediates which, in turn, are oxidized
to catechol, gentisic acids, etc. (Alexander 1977). Figure 4-2 shows
this more expanded metabolic pathway.
Not all microorganisms are capable of using PAHs as sole carbon
sources; thus cometabolism may play a role in degradation (Alexander
1977). Fungi, especially, may add hydroxyIs to the aromatic ring but
be unable to break the ring. These transformations may create a problem
greater or equal to the presence of the parent compound due to the possible
production of harmful intermediates rather than complete mineralization
to C02 and H20 (Alexander 1977) .
Presented in Table 4-17 are a number of reported biodegradation
products derived from anthracene. They are primarily intermediates in
the multistep pathway of reactions leading to eventual complete mineral-
ization.
It must be mentioned, however, that other factors such as substituent
type and size, interfere with this relationship so it is not always
evident. Malaney did not find a direct relationship between ring num-
ber and biodegradability (Malaney al. 1967).
4-33
-------
Rates of Biodegradation
The rate of biodegradation of PAHs is quite variable across this
chemical group. Table 4-18 presents quantified rates of biodegradation
reported for the anthracene group in soil and freshwater systems. Marine
bacteria have also been reported capable of degrading phenanthrene, an-
thracene, and fluorene (Dean-Raymond 1975). One study on estuarine pop-
ulations is presented. Due to the variety of test methods, analytical
techniques, microbial species and data analyses used in biodegradation
studies, it is difficult to compare the results from the different tests
reported in Table 4-18.
Some general trends in PAH biodegradability are illustrated by the
results in Table 4-18. Anthracene, for which the most data were avail-
able, is readily degradable in"acclimated)cultures; however, half-lives
are quite variable, ranging from on the order of hours to weeks. Degrada-
tion is slower in previously unexposed populations (Giddings £t^ a^L. 1979).
No data were available for acenaphthene. One study each on fluorene and
fluoranthene reported significant degradation in one week at a 5 mg/1
concentration of PAHs in water and a much lower percentage degraded at
10 mg/1 (0% in the case of fluoranthene) (Quave et al. 1980). The
results for phenanthrene seem to be contradictory. One study found
the compound to be the most readily degradable of 17 PAHs tested (22-46%
of theoretical oxygen demand removed) (Malaney et al. 1967); another
study reported a mean degradation rate of 80% in one month (Sherrill and
Sayler 1980); and a third study found 0% degradation in one week (Quave
et al. 1979). The studies on pyrene generally indicated a lower rate
of degradation than for anthracene and phenanthrene, with the removal of
pyrene apparently enhanced by the presence of other PAHs (McKenna and
Heath 1976).
The Gardner et al_. (1979) study on biodegradation of anthracene
and fluoranthene in estuarine sediment populations was not continued long
enough to estimate a half-life for persistence. The results did indicate
that the presence of polychaete worms increased the rate of degradation
of fluoranthene. This may have been due to the role of the worms in
sediment mixing or their own metabolism of the substances. The results
for anthracene showed no difference when worms were present. Degradation
was greatest in populations in large grain-size sediment and higher in
the surface than in the subsurface sediment layers.
The turnover time and transformation rate of PAHs in both accli-
mated and unacclimated stream populations (Herbes and Schwall 1978)
provide a good estimation of the environmental persistence of these com-
pounds, as well as the importance of microbial adaptation (see Table 4-19).
The turnover time in the non-acclimated populations was 167 days. How
applicable these aquatic turnover times are for soil is unknown. How-
ever, the acclimated population turnover time could be comparable to
a well-acclimated soil population.
4-39
-------
TABLE 4-17. BIODEGRADATION PRODUCTS REPORTED FOR THE ANTHRACENE CROUP PAHs
PAH
Anthracene
Degradation ProducLs
2,3-djhydroxynaphthalene via trans-1,2-
dihydro-1, 2-dihydroxyanthracene,
1,2-dihydroxyanthracene and 2-hydroxy-
3-naphthoic acid.
Reference
Evans _et al.
(1965)
Phenanthrene
l-hydroxy-2-naphthoic acid, salicylic
acid, catechol.
Kaneko et al.
(1968, 196 9~
Phenanthrene
1,2-dihydroxynaphtha]ene via trans-3-4-
dihydro-3,A-dihydro xy-phenanthrene; 3,4-
dihydroxyphenanthrene; and l-hydroxy-2-
naphthoic acid.
Colla j2t al.
(1959)
-------
OH
COOH
OH
1-Hydroxys-
naphthoic
acid
Naphthalene
Phenanthrene
OH
Anthracene
3-Naphthol
1,2-Dihydroxynaphthalene
' f
COOH
-OH
COOH
3-Hydroxy- Salicylic acid
2-naphthoic acid
OH
OH
Gentisic
acid
Catechol
Source: Alexander (1977).
FIGURE 4-2 MICROBIAL DECOMPOSITION OF PAH COMPOUNDS WITH TWO AND THREE RINGS
4-41
-------
TABLE 4-18. BIODEGRADATION RATES OF ANTHRACENE GROUP PAHs
Test Type/Population Origin
Static flask
(wastewater culture)
Compound Tested
Anthracene
Results
92% lost at 5 mg/1 and 51% at
10 mg/1 at 1 week in acclimated
culture.
Phenanthrene
Fluorene
Fluoranthene
Pyrene
Freshwater Aquatic Anthracene
Soil population from near Anthracene
an oil drilling site
Sediment from oil-contaminated Anthracene
stream and uncontaminated
stream
0% lost at 5 and 10 mg/1 at 1 week in
non-acclimated culture
77% lost at 5 mg/1 and 45% at 10 mg/1
at 1 week in acclimated culture
100% lost at 5 mg/1 and 0% at 10 mg/1
at 1 week in acclimated culture
100% lost at 5 mg/1 and 0% at 10 mg/1
at 1 week in acclimated culture
80% degraded over 12 weeks due to both
photolysis and biodegradation
90% conversion in 90 min. (no conc.)
tl/2 = 12 days for exposed population,
tl/2 = ^20 days for unexposed
Freshwater populations Anthracene
1st order rate constant of 0.055
day for days 0 to 15 (t^/2 = 13 days);
0.007 day~l for days 20 to 64 (t^/2 =
99 days) (tested 84 days). Not all due
to biodegradation.
Source
Quave et al.(1980)
Quave et^ al. (1980)
Quave ej: jQ. (1980)
Quave ^_t al^. (1980)
Quave et al. (198)
Giddings jat al.
( 1979)
Ciddings al.
( 1979)
Giddings jet al.
(1979)
Giddings jet al.
( 1979)
-------
TABLE 4-18. BIODEGRADATION RATES OF ANTHRACENE GROUP PAHs (Continued)
Test Type/Population Origin
14
CO2 evolution from
stream sediment populations
from petroleum contaminated
area
Warburg O2 consumption, non-
acclimated sludge population
14
CO2 evolution from sea
water population from
treated area
14
CO2 evolution from
contaminated stream
sediment population
Shake flasks with
natural water
populations
Static flasks with
natural water populations
from contaminated and
uncontaminated sites
Compound Tested
14
C-anthracene
Phenanthrene
Anthracene
Anthracene
14
C-anthracene
Pyrene
Phenanthrene
Results
14
C-anthracene approximately 60% of
total PAH transformed at 120 hours
22-46% of TOD degraded. Most
degradable of 17 PAH compounds tested.
2-13% of TOD degraded.
0.02 pg/l/day
-3
2.5 x 10 /hr (rate reduction
occurred at >1 Mg/g)
Negligible degradation for compound
alone; with naphthalene = 36.7%
remaining at 4 wks; with phenan-
threne = 47.2% remaining
50% to 100% degradation in 1 month
over the year at different sites
(80% = mean)
Source
Schwall and Herbes
(1978 )
Malaney et al (1967)
Malaney ejt a^l (1967)
Lee ej: al.
(1978)
Herbes and Schwall
(1978)
McKenna and Heath
(1976)
Sherrill and Sayler
(1980)
Static flasks with
natural water populations
from contaminated and
uncontaminated sites
Pyrene
0% to 57% degradation in 1 month
over the year at different sites
(15% = mean)
Sherrill and Sayler
(1980)
-------
TABLE 4-18. BIODEGRADATION RATES OF ANTHRACENE GROUP PAHs (Continued)
Test Type/Population Origin
Compound Tested
Results
Source
Coastal estuary sediment
populations (3 types) with
and without presence of
polychaete worm
Capitella capitata
I
¦P-
Anthracene
Fluoranthene
Experiment
Fine sand
Fine sand &
C^. capitata
Medium sand
Medium sand &
C^. capitata
Marsh sediment
Marsh sediment &
C^. capitata
% removed
in 1 week
Anth. Fluor.
2.0 1.9
2.3 3.3
2.4 2.4
3.2 3.5
2.6 2.0
2.7 2.6
Gardner _et al,
(1979)
-------
In another study using microbial populations from pristine and
PAH-contaminated areas, phenanthrene biodegradation was significantly
greater (3 to 4 times) in the previously exposed cultures than in those
from the pristine area (Sherrill and Sayler 1980).
As noted in Section 3.2.3.4, environmental factors such as avail-
ability of oxygen, soil solution pH and the presence of natural humic
polymers may influence the rate of biodegradation.
A regression analysis was performed in order to determine the de-
pendency of the phenanthrene degradation rate on numerous environmental
variables (Sherrill and Sayler 1980). Approximately 46% of the total
variation in the rate was attributed to environmental characteristics,
the presence of acclimated bacteria, and the total viable microbial cell
count. Less important were dissolved oxygen, suspended sediment levels,
and nitrate-nitrogen levels, accounting each for 5% of the variability.
Phenanthrene degradation was found to be influenced significantly
by incubation temperature (Sherrill and Sayler 1980). Virtually no
degradation was detected at 5° and 45°C; between 15° and 37°C, the rate
increased by a factor of 9 (from 10% to 90% in one month).
One study measured a very poor correlation (r = 0.07) between sus-
pended sediment load and phenanthrene biodegradation rate (Sherrill and
Sayler 1980). This contrasts with prevailing theory and indicated
that adsorption onto sediment had little effect on microbial degradation.
In conclusion, the anthracene group of PAHs is intermediate in its
biodegradability when compared with higher and lower ringed class mem-
bers. Half-lives were on the order of 1-2 weeks under laboratory con-
ditions. Anthracene itself was usually readily degradable following a
period of acclimation. No information was available specifically con-
cerning the biodegradation of acenaphthene and only limited information
on fluorene and fluoranthene.
4-45
-------
TABLE 4-19. KINETIC PARAMETERS OF ANTHRACENE BIOTRANSFORMATION
a b
Rate Constant k (1/h) Turnover Time Transformation Rate (pg/g/hr)
Compound Contaminated Uncontaminated Contaminated Uncontaminated Contaminated Uncontaminated
Anthracene 2.5 x 10~3 2.5 x 10~4 7 days 167 days 8.5 x 10~3 <3 x 10~6
a
Turnover Time = 1/k
^Transformation Rate = k x concentration
Source: Schwall and Herbes (1978)
-------
A.2.3.3 Modeling of Environmental Distribution
Introduction
Very limited monitoring data are available to describe the extent
of anthracene group PAH contamination in the environment. Several model-
ling efforts were undertaken in order to estimate the distribution of
anthracene in the environment and to describe the important aspects of
the behavior of anthracene in selected environmental settings. Since
all of the physiochemical properties (solubility, KQw, etc.) for the
chemicals in this group are similar, only anthracene was modelled and
the results were assumed to be representative of the behavior of all
chemicals in this group.
The Mackay equilibrium model was used to predict the partitioning
of anthracene among environment compartments in equilibrium (Mackay
1979). The EXAMS (Exposure Analysis Modeling System) developed by the
U. S. EPA (U.S. EPA 1980a) was used to study the fate of anthracene in
several environmental scenarios. '
Mackay Equilibrium Partitioning Model
The Mackay model (described previously in Volume II) was used to
predict the partitioning of anthracene among environmental compart-
ments. The chemical-specific parameters given as input for the model
are presented in Table 4-20. The total amount of anthracene in the sys-
tem was taken to be 0.69 kg. Details of the calculation methods are
provided elsewhere (Mackay 1979) and are not repeated here.
The results obtained for anthracene are presented in Table 4-21.
The vapor pressure of anthracene is in the middle of the range of vapor
pressures among the PAHs. Thus when only equilibrium processes are
considered, a measurable amount of partitioning to air is expected to
occur. Since anthracene's partition coefficient (KqW =2.8 x 10^) is
high, sorption to sediments and biota is also likely to be significant.
The Mackay model confirms these expectations with the prediction that 58%
of the anthracene will be found in the air and 41% in the sediment. The
different fractions of material in the suspended solids and sediments
are a result of the different sizes and densities of the compartments
of the model; the concentrations in these compartments are the same.
Within the water column (water, aquatic biota, and suspended solids),
the largest mass of anthracene is dissolved in the water, although
the concentrations in the other phases are much higher. Again, this
result occurs because the volume of water allowed by the model is
considerably larger than the volume of either aquatic biota or suspended
solids.
4-47
-------
TABLE 4-20. VALUES OF PARAMETERS USED FOR CALCULATING THE EQUILIBRIUM
DISTRIBUTION OF ANTHRACENE PREDICTED BY THE MACKAY FUGACITY
MODEL
CHEMICAL-SPECIFIC PARAMETERS (25°C)
3 -3
Henry's Law Constant (m -atm/mole) 1,25x10
Adsorption coefficient
suspended solids (.OlxK ) 158.50
sediment (.OIxKqc) 0C 158.50
biota (.2xKqW) 5640
Total Amount in System 0.69 kg
COMPARTMENT-SPECIFIC PARAMETERS (25°C)
Air; ^ 2
area 1x10- m
depth 3x10 m
Water: 4 2
area 1x10 m
depth 2 m
biomass content 12.9 mg/1
suspended sediment 30 mg/1
Sediment:
area
depth
biomass content
wet sediment density
sediment dry weight
1x10^ m^
• 5m ,
50.01 g/mf
1.85 g/cm
(100 x wet wt)/137
4-43
-------
TABLE 4-21, EQUILIBRIUM PARTITIONING OF ANTHRACENE, CALCULATED BY USING
THE MACKAY FUGACITY MODEL
Compartment
Air
Water
Suspended Solids
Sediment
Aquatic Biota
Sediment Biota
Moles
2.2
0.03
1.4x10
1.6
2.1x10
2.2x10
Partitioning at Equilibrium
-4
-4
-3
Concentration
0.013 mg/m^
2.7x10 ^ mg/l
4.2x10 ^ mg/kg
_2
4.2x10 mg/kg
1.5 mg/kg
1.5 mg/kg
Percent
57.88
0.770
0.004
41.28
0.006
0.056
Total in System
3.86 moles (.690 kg)
100%
4-49
-------
EXAMS Model
Calculations based on EXAMS (described in Volume II) were done
for anthracene. All six EXAMS environments (pond, eutrophic lake,
oligotrophic lake, river, coastal plain river, and turbid river) were
modelled using the ecosystem parameters that are provided with the
model. The values entered for the chemical-specific parameters are
given in Table 4-22. Any input variables not in the table were set
to zero; the physical processes associated with these other variables
(such as hydrolysis) either were not considered important for anthracene
or were calculated by the model from other input data.
A loading rate of 0.1 kg/hour was initially specified for the anthra-
cene calculations. However, in the more static systems with low volumes
of water flow, a 0.1 kg/hour discharge into the input streams would ex-
ceed the maximum solubility limit. If this solubility limit is exceeded,
non-equilibrium conditions (which EXAMS cannot model) occur. Thus in
order to maintain equilibrium conditions, the loading rate was adjusted
to 0.017 kg/hour for the lakes and 0.0007 kg/hour for the pond. The
materials balance (Section 4.1) suggests that 0.1 kg/hour is repre-
sentative of a maximum loading from industrial discharge.
Table 4-23 summarizes the anthracene concentrations predicted for
the simulated environments under steady-state conditions. In the rela-
tively static pond and lakes, the concentrations of anthracene dissolved
in water are similar (2.3 x 10Jt - 7.2 x 10-1+ mg/1), when the anthracene
is present in the input streams at close to maximum solubility levels.
In the rapidly flowing rivers, the dissolved concentrations are lower
due to dilution and physical transport, even though the loading rate was
higher for the rivers. These aqueous concentrations are all well below
the 0.045 mg/1 aqueous solubility of anthracene; therefore, these results
may be extrapolated for higher inputs of anthracene as long as the
solubility limits of the input streams are not exceeded. Sediment con-
centrations are all higher than the water concentrations in the same
environmental systems; biota concentrations are even higher than those
of the sediments.
Table 4-24 presents the EXAMS data relative to the fate and distri-
bution of anthracene in the same aquatic systems. Examination of the
distribution data reveals the importance of environmental conditions in
the partitioning of anthracene between water and sediments. In the
static pond and lake systems, over 84% of the anthracene is lost by
chemical transformation (photolysis). In the rapidly flowing river
systems, other processes such as transport beyond the boundaries of
the system account for most of the anthracene removal. In the slower
coastal plain river, both transport and photolysis are important.
Volatilization accounts for removal of about 8% of the anthracene in the
pond, eutrophic lake, and coastal plain river. Volatilization is some-
what less important in the oligotrophic lake, because the lack of biota
in the water column allows sunlight to penetrate this system and thus
chemical transformation predominates. Biological transformation is
significant only in the biota-rich eutrophic lake.
4-50
-------
TABLE 4-22. INPUT PARAMETERS FOR EXAMS MODELING OF THE FATE OF
ANTHRACENE IN GENERALIZED AQUATIC SYSTEMS
Explanation
Molecular wt. (g/mole)
Ratio of volatilization
to reareation rate
Aqueous solubility (mg/1)
Partition coefficient
biomass:water (ug/g)/(mg/1)
Henry's Law Constant
(atm mole"-'-)
Partition coefficient
octanol:water
Second order bacterial
degradation rate constant in
water and sediment (ml/cell/hr)
Increase in bacterial degradation
rate per 10°C change in
temperature
First-order photolysis rate
constant (hr~l)
Reference latitude for
photolysis rate constant
Loading rate (kg/hr)
Input
Value Reference
178.2 Weast (1979)
.4240 SRI (1980)
.045 Callahan £t al_. (1979)
4650 SRI (1980)
i.25xl0~3 Table 4-14
(calculated)
28,840 Callahan et al. (1979)
3xl0"9 SRI (1980)
2 SRI (1980)
0.924 Zepp and Schlotzhauer
(1979)
35.00 Zepp and Scholtzhauer
(1979)
0.1 Section 4.1
4-51
-------
TABLE 4-23. STEADY-STATE CONCENTRATIONS OF ANTHRACENE IN VARIOUS GENERALIZED AQUATIC SYSTEMS RESULTING FROM
CONTINUOUS DISCHARGES
Maximum Concentrations
Total
System
Loading
Rate
(kg/hr)
Dissolved
Water
(mg/1)
Total
Water
(mg/1)
Pore
Water
(mg/1)
Sediment
Deposits
(Mg/1)
Plankton
(pg/1)
Benthos
(pg/g)
Steady-State
Accumulation
(kg)
Total
Daily Load
(kg/day)
Pond
0.0007
2.3x10"*
2.6xl0~4
2.3xl0~4
0.43
1.1
1.1
0.29
0.017
Eutrophic Lake
0.017
7.2xl0~4
8.9xl0~4
6.2x10 4
0.44
3.3
2.9
3.0
0.408
Oligotrophic Lake
0.017
7.1xl0-4
8.8xl0"4
3.4xl0~5
0.062
3.3
0.16
0.47
0.408
River
0.1
9.4xl0-5
l.OxlO-4
2.1xl0~5
0.025
0.44
0.097
0.46
2.4
Turbid River
0.1
8.3xl0-5
l.OxlO-4
4.1xl0~5
0.015
0.39
0.19
0.35
2.4
'Coast Plain River
0.1
8.0xl0~4
8.4x10 4
2.0xl0~4
0.49
3.7
0.92
8.1
2.4
All data simulated by EXAMS (U.S. EPA 1980a) model (see text for further Information).
-------
TABLE 4-24. THE FATE OF ANTHRACENE IN VARIOUS GENERALIZED AQUATIC SYSTEMS'
Percent Distribution
Percent Lost by Various Processes After Cessation of Loading
Transformed
System
Pond
Eutrophlc Lake
Oligotrophic
Lake
River
Turbid River
Coastal Plain
River
Residing in
Water at
Steady-State
1.79
20.38
54.46
19.16
25.37
7.76
Residing in
Sediment at
Steady-State
98.21
79.62
45.54
80.84
74.6J
92.24
Transformed
by Chemical
Processes
90.89
84.75
95.70
5.51
3.69
34.46
by
Biological
Processes
0.15
6.65
0.00
0.09
0.08
0.64
Volatilized
8.04
8.44
4.27
1.11
0.99
8.08
Lost
by Other b
Processes
0.92
0.16
0.02
93.30
95.24
56.82
Time for
System Sell-
Purification1
316 days
432.5 days
258 days
73.4 days
62.2 days
93.5 days
•i) All data simulated by the EXAMS (U.S. EPA, SERL, Athens, Ga. 1980a) model (see text for further information)
b) Including loss through physical transport beyond system boundaries.
c) Estimate for removal of ca. 97% of the compound accumulated In system (5 apparent system half-lives). Estimated
from the results of the half-lives for the compound in bottom sediment and water columns, with overall cleansing
time weighted according to the pollutant's initial distribution.
-------
In all environments, except for the oligotrophic lake, over 75% of
the anthracene present at steady-state is residing in the sediments.
The oligotrophic lake has very little suspended matter, and very little
sedimentation; thus, the anthracene at steady-state is almost evenly
divided between the sediment and the water column.
The rapidly flowing rivers, where physical transport dominates the
removal processes, are the fastest systems to cleanse themselves of anthra-
cene after loading has stopped, requiring less than 100 days for self-
purification. In the lakes and ponds, where the slower process of
photolysis dominates, the self-purification times are higher (250-430
days).
On the basis of the distribution and fate data, and the rates spe-
cified for the various removal and degradation processes, the persistence
of anthracene can be estimated for each of the aquatic systems. These
data are presented in Table 4-25. In all of the systems, the anthra-
cene is removed more rapidly from the water column than from the sedi-
ments. This persistence in sediments occurs because of the strong ad-
sorption of anthracene onto the sediments, and also because the major
fate processes such as photolysis and volatilization do not occur to
any appreciable degree in the sediments. In the rapidly moving river and
turbid river where physical transport occurs, over 99% of the anthracene
is lost from the water column within half a day. In the other systems,
where the removal processes (photolysis, biodegradation, etc.) are
slower, the anthracene will persist for longer periods. Anthracene
is most persistent in the relatively static pond, where the high content
of particulate matter inhibits sunlight penetration; the model predicts
that after 24 days only 24% of the anthracene will have been removed
from this system.
Comparison of Mackay and EXAMS Models
The EXAMS pond environment is the most appropriate system to com-
pare with the Mackay models since there is very little transport across
system boundaries in the pond. The Mackay model calculates partitioning
between compartments, while EXAMS models the fate of pollutants within
a compartment and transport out of that compartment. Since the under-
lying assumptions of the models are different, the quantitative results
may be different. The pollutant load for the Mackay model was chosen
so that the anthracene mass in the water and sediments would be equal
to the total steady-state accumulation in the pond, predicted by EXAMS
(0.29 kg).
Table 4-26 summarizes the concentration and distribution data from
both models. The EXAMS concentrations and those predicted by Mackay for
the water column agree to within an order of magnitude. Both models also
predict that the highest concentrations will be in the sediments, and the
lowest concentrations will be in the water. The ratios of the amount of
dissolved anthracene to the amount adsorbed are also in agreement; both
models predict that 50 times more anthracene will be found in the sediments
than in the water column.
4-54
-------
TABLE 4-25. THE PERSISTENCE OF ANTHRACENE IN VARIOUS GENERALIZED AQUATIC
SYSTEMS AFTER CESSATION OF LOADING
System
Pond
Eutrophic Lake
Oligotrophia
Lake
River
Turbid1 River
Coastal Pond
Time
Period
(days)
24
10
1.5
0.5
0.5
4.5
% Lost
from Water
85.95
79.59
92.89
99.59
99.69
93.62
% Lost
from Sediment
22.83
6.25
.92
1.89
2.06
14.32
%
from
Total
System
23.96
20.99
51.01
20.61
26.83
20.48
All data simulated by the EXAMS (U.S. 1980a) model. See text for further
information.
4-55
-------
TABLE 4-26. COMPARISON OF RESULTS FROM MACKAY'S EQUILIBRIUM MODEL AND EXAMS
FOR ANTHRACENE IN A POND SYSTEM
EXAMS Results
(0.0007 kg/hr loading,
0.29 kg steady state accumulation)
Maximum Concentration
Water
Aquatic Biota
Sediment Biota
Sediment
2.6x10 ^ mg/1
1.1 mg/kg
1.1 mg/kg
.43 mg/kg
Accumulation
% in water 1.79
% in sediment 98.21
Mackay Results
(.69 kg in system)
Concentration
2.7x10 ^ rag/1
1.5 mg/kg
1.5 mg/kg
.042 mg/kg
Percent of Chemical per Compartment"
0.77%
41.28%
a) 57.88% of the initial load was partitioned to the atmosphere.
-------
4.2.4 Monitoring Data
4.2.4.1 STORET Data
Introduction
The anthracene group PAHs have been monitored in all environmental
media. The highest concentrations for compounds in this group appear
in urban and industrial areas.
STORET monitoring data (U.S. EPA 1980b) for PAHs in the anthracene
group reflect sampling activities in thirty-one states and Puerto Rico.
Over 90% of the observations for each compound are remarked, indicating
that pollutant levels do not exceed a specified reporting (detection)
limit. Table 4-27 presents the number and ranges of observations
in ambient and effluent waters and in sediment for this compound group;
Tables 4-28 and 4-29 give the distribution of concentrations in ambient
and effluent waters, sediment, and tissues.
Ambient Water
Observations of anthracene and related PAHs in ambient waters were
primarily remarked; of 2304 total observations, 64 values, or 2.8%, were
unremarked and, therefore, represent concentrations actually detected.
There were only two unremarked observations of anthracene reported.
Of the 64 unremarked values approximately 65% were less than 100 ug/1.
Effluent Water
The total number of observations for the anthracene group PAHs in
effluent water was 3130; of these, 88 values, or 2.8% were unremarked.
Fluoranthene was detected most often (34 observations) and acenaphthene
least often (7 observations). Sixty-six of the 88 unremarked values
were less than 100 Mg/1; there were 11 observations between 100.1 and
1000 Mg/1 and 11 observations greater than 1000 pg/1.
Sediment
These PAHs were detected less frequently in sediment than in water,
but a greater percentage of the values were unremarked. Of 738 total
sediment observations, 128 or 17% were unremarked. Thirty-six percent
of these, or 46 observations, were at concentrations greater than 100
Mg/kg. Phenanthrene was detected most frequently (30 observations) and
fluorene least often (11 observations).
Fish Tissue
As shown in Table 4-29, all observations in STORET for the
anthracene group PAHs in fish tissue are remarked with one exception;
4-57
-------
TABLE 4-27. THE NUMBER AND RANCES OF OBSERVATIONS IN STORET FOR
THE ANTHRACENE GROUP PAHs
Anthracene
Acenaph thene
Fluoranthene
F1uorene
Phenanthrene
I
00
Ambient Mater (ug/Z.)
Total Observations
Unremarked
Remarked
Maximum Detection Limit
Range of Unremarked
Observac ions
Effluent Water3 (wg/J£)
Total Observations
Unremarked
Remarked
Maximum Detection Limit
Range of Unremarked
Observa t ions
Sedlment (pg/kg-dry wt.)
Total Observations
Unremarked
Remarked
Maximum Detection Limit
Range of Unremarked
Observa tions
254
2
252
50
1-27
341
8
333
2500
0.4-6200
121
n
94
10000
0. 7-2000
417
10
407
560
0.1-880
567
7
560
2500
1.5-3600
131
13
118
10000
2.3-97
414
17
397
400
0.4-1100
685
34
651
2500
0.01-2500
125
26
99
10000
0 1-1150
424
8
416
400
0.3-390
577
11
5b6
2500
0.6-6400
129
11
118
1000
3.6-145
382
12
370
600
1-630
394
14
380
2500
0.5-36000
116
30
86
5000
2.9-1100
SOURCE: STORET Water Quality System (U.S. EPA 1980b) as of November 20, 1980.
aEffluent data as of April 9, 1981.
Prvene
413
15
398
400
0.3-960
566
14
552
2500
0.5-11000
116
21
95
10000
0.03-2500
-------
TABLE 4-28. DISTRIBUTION OF OBSERVED AMBIENT AND EFFLUENT CONCENTRATIONS
OF ANTHRACENE GROUP PAHs IN STORET
No. Ambient Observations
Remarked
Unremarked
Cone, (ug/1)
Cone.
(m g/l)
Compound
Total
1.1-10 10.1-100 100
1-1000
Total
si
1.1-10 10
.1-100
loo.i-iooo -lu:"'
Anthracene
252
48
179 25
2
1
1
Acenaphtliene
407
36
308 56
7
10
3
3
1
3
F1 uoranthene
39 7
40
325 32
17
1
7
1
6 2
Fluorine
416
39
318 55
4
8
1
1
4
2
Phenanthrene
370
37
307 22
4
12
1
2
4
5
P> rene
398
9
82 9
15
3
5
2
5
STORET data as or Novonb^r 20, 1980.
Antnracene
Acenaphtliene
riuoranthene
1Luorene
I'lienancluene
Pvrene
No. Efflufinf-
1hsprvar(nns
Remarked
Ilnrpmarkprf
Cone, (wg/1)
Cone.
(Mg/1)
Total
1000
Total
<1 1
1-10 10
.1-100
lOO.l-LOilO
> luOO
333
186
137
10
8
2
2
3
1
560
185
358
17
7
5
1
1
651
276
335
40
34
25
3
2
3
1
566
187
362
17
11
3
3
2
1
2
380
194
171
15
14
6
1
1
3
3
552
186
340
26
14
3
5
3
3
blOUhl data as o: April 9, 19 31
-------
TABLE 4-29. DISTRIBUTION OF OBSERVED SEDIMENT AND TISSUE CONCENTRATIONS
OF ANTHRACENE GROUP PAHs IN STORET
No. of Sediment Observations
¦p-
t
O
An c!i racene
Aconaphthene
t1unranthene
hluorene
Plionanthrene
fs rone
Remarked
Unremarked
Compound
Total
si
Cone. (Mg/kg
1.1-10 10.1-100
- dry wt.)
100.1-1000
>1000
Total
Cone,
il 1
(Mg/kg -
1-10 10
dry wt
. 1-100
)
100.1-1000
An thracene
94
19
1
17
57
27
1
5
10
9
¦\cenjpiithene
118
33
1 2
17
65
1J
5
7
Fluoranthene
99
20
1 2
11
65
26
2
3
10
8
Fluorene
US
32
2 2
17
65
11
6
3
2
Plienaiiclirene
86
15
1
16
54
30
2
15
in
I'v rene
95
17
2 1
16
59
21
1
2
9
9
LL-_x»
2
3
3
Reiuai k
J
[o._ of Fish-Tiasue-Ohaervatious
Total
73
73
68
73
72
72
<1
10
10
7
10
10
20
1.1-10
63
63
61
62
62
52
Cone, (mg/kg - wet wt.)
10.1-100 100.1-1000 >1000
Unremarked
Total
0
0
0
1
0
0
Cone, (mg/kg - wet wt.)
<1 1.1-10 10.1-100 100.1-1000
>1000
SOURCE: STORET data as of November 20, 1980.
-------
there is one unremarked observation of fluorene no higher than 1 mg/kg.
The distribution indicates that roughly 10% to 15% of the samples were
analyzed with detection limits not exceeding 1 mg/kg, and about 85% of
the detection limits are between 1.1 and 10 mg/kg.
4.2.4.2 Data from Other Sources
Drinking Water
Kim and Stone (1979) have analyzed public water system wells for
levels of organic chemicals. Thirty-nine wells were tested for anthracene/
phenanthrene levels; of these 7 (18%) were positive. The maximum level
of anthracene/phenanthrene detected was 21 ug/1-
Levins et^ _al. (1980) reported that none of the anthracene group
PAHs were found (at 10 yg/1 reporting limits) in tap water samples from
Cincinnati, St. Louis, Atlanta, and Hartford.
Municipal Wastewater
The U. S. EPA (1980d) has measured levels of fluoranthene in sewage
water and found that concentrations were elevated after heavy precipita-
tion. On a dry day, sewage water concentration of fluoranthene was 0.352
Ug/1; a concentration measured after a heavy rain was 16.3 ug/1, approxi-
mately 50 times greater. Levins et ail. (1980) found that anthracene
group PAHs were absent (at 10 ug/1 reporting limits) in municipal waste-
water from Cincinnati, St. Louis, Atlanta, and Hartford.
Industrial Effluents
Water samples from industrial effluents and industrial sewage efflu-
ents, in particular, indicate that industrial input will raise the level
of fluoranthene found in the surrounding water (U.S. EPA 1980d). Fluor-
anthene concentrations in industrial sewage effluents ranged from 2.6 ug/1 to
3.4 yg/1. Other results reported for fluoranthene levels in industrial
and domestic effluents are given in Table 4-30.
Soils and Sediment
White and Vanderslice (1980) have reported levels of pyrene and
fluoranthene in urban soils. Concentrations of both compounds ranged
from 5000-1^0,000 yg/kg in urban soils. Levels in marine sediments have
also been reported by White and Vanderslice (1980). The maximum pyrene
concentration in marine soil was 1000 yg/kg; fluoranthene levels reached
a maximum of 900 yg/kg. These results were found at Buzzard's Bay,
Massachusetts. The average ranges for pyrene and fluoranthene were
9-90 yg/kg and 10-100 yg/kg, respectively.
4-61
-------
TABLE 4-30, FLUORANTHENE LEVELS DETECTED IN WASTEWATER
AND EFFLUENTS
Type of
Sample
Domestic Effluent
Domestic Effluent
Factory Effluent
Sewage
Industry
Domestic
Domestic (heavy rains)
Concentration
(ug/1)
2.4
0.273
2.2
2.6-3.4
0.35
16.3
Comment
From runoff and atmospheric
washout
Man-made sources
From natural and industrial
sources (i.e., detergents,
atmospheric washout)
SOURCE: U.S. EPA 1980d.
4-62
-------
Food
Pancirov and Brown (1977) have studied concentrations of pyrene in
edible marine tissue. These measurements, which were taken at a variety
of locations, reported levels ranging from <0.2 pg/kg (crab) to 58 ug/kg
(oyster). The highest level (58 ug/kg) was taken from a polluted harbor
area on Long Island Sound. Table 4-31 provides a complete listing of the
pyrene levels reported by Pancirov and Brown. No other data were found
concerning the levels of anthracene group PAHs in food.
Air
The anthracene group PAHs have been detected in the air of urban
and industrial areas (U.S. EPA 1980c, 1980d). Table 4-32 presents con-
centrations of fluoranthene found in automotive air samples in Los
Angeles. An average fluoranthene concentration from four sites was 1.6
ng/m3 (0.18 ppt). Table 4-32 also summarizes fluoranthene concentrations
taken from air samples near a coking source in Birmingham, Alabama. The
average of four site readings was 7.4 ng/m3 (0.822 ppt) (U.S. EPA 1980d).
Other air levels of fluoranthene have been measured by Fox and Staley
(1976) and Hoffman and Wynder (1977) (Table 4-33). An average concentra-
tion range found in U. S. cities was 0.10-4.1 ng/m3 (0.01-0.45 ppt).
Phenanthrene levels in Providence, Rhode Island, have been measured by
Krstulovic et^ al. (1977). The concentration range for this compound,
which can be found in Table 4-33, is 0.011-0.340 ng/m3 (0.001-0.04 ppt).
Table 4-33 also presents the concentration range of pyrene levels found
in urban air. These levels ranged from 0.18-5.2 ng/nr (0.02-0.57 ppt)
(Fox and Staley 1976, Gordon and Bryan 1973). The U. S. EPA (1980c) has
reported concentrations of pyrene in urban air samples over a summer-
winter period (Table 4-34). The average pyrene concentration of the
seven cities reported was 7.6 ng/m3 (0.84 ppt). Anthracene levels de-
tected in this study were lower than those of pyrene, as shown in Table
4t34. The average concentration from the seven urban areas sampled was
0.6 ng/m3 (0.07 ppt). Table 4-34 shows that the range of pyrene concen-
trations found was 1.0-19.4 ng/m3; the lowest concentration was measured in
San Francisco and the highest in Detroit, a more industrialized city.
The anthracene concentration ranges follow a similar pattern; they range
from 0.1 ng/m3 to 1.3 ng/m3.
4.2.5 Summary of Fate and Distribution
The environmental release data indicate that most of the discharges
of the PAHs in the anthracene group are to the atmosphere. Atmospheric
deposition (from both wet and dry processes) may remove 5-26% of the atmospheric
load of anthracene in urban areas, accounting for 75-400 kkg/yr of anthracene
fallout. It is estimated that about 2% will fall directly on inland surface
waters, representing 1.5-8.0 kkg/yr anthracene. The upper limit on this range
corresponds to deposition in areas near combustion sources, where the anthra-
cene will be primarily adsorbed onto particulates. The percentage of these
PAHs that remains in the atmosphere will be degraded by photolysis to oxy-
genated compounds, including quinones.
4-63
-------
TABLE 4-31. CONCENTRATIONS OF PYRENE IN TISSUES OF EDIBLE
MARINE SPECIES
Concentrations
Marine of Pyrene
Location of Sample Tissue (yg/kg wet wt.)
Long Island Sound Oyster 58
Chincoteague, VA
Black Point Oyster 0.5
Little Toms Cove Clam 1.0
Darien, CN, Scotts Cove Clam 12
Fish Market, Linden, NJ Clam <1
Chesapeake Bay Crab <0.2
Raritan Bay Crab <0.2
Menhaden <0.6
Atlantic Ocean
Long Branch, NJ Flounder <0.6
South of Long Island Flounder 0.5
Falmouth, MA
Little Sippewissett Mussel 2
Wild Harbor Mussel 4
Palacios, TX Shrimp <0.3
Atlantic Ocean
25 mi. off Toms River, NJ Codfish <0.5
SOURCE: Pancirov and Brown (1977),
4-64
-------
TABLE 4-32. AUTOMOTIVE AND COKING SOURCE CONCENTRATIONS OF
FLUORANTHENE IN AIR
Concentration (ng/m3)
Location/Source Site 1 Site 2 Site 3 Site 4 Average
Los Angeles (automotive) 1.9 0.8 3.4 0.12 1.6
Birmingham AL. (coking 4 ? u 2 1Q j ^ ? 4
sources)
SOURCE: U.S. EPA (1980d),
4-65
-------
TABLE 4-33 . CONCENTRATIONS OF ANTHRACENE GROUP PAHs DETECTED
IN THE URBAN ATMOSPHERE
Compound
Fluoranthene
Phenanthrene
Pyrene
Sampling Location
Various U.S. cities
Providence, RI
Urban air
Concentration
0.10 ng/m3 - 4.1 ng/m3
(0.01 - 0.45 ppt)
0.011 ng/m3 - 0.34 ng/m3
(0.001 - 0.04 ppt)
0.18 ng/m3 - 5.2 ng/m3
(0.02 - 0.57 ppt)
Reference
Fox and Staley (1976)
Hoffman and Wynder (1977)
Krstulovic et al. (1977)
Fox and Staley (1976)
Gordon and Bryan (1973)
Comment
average
range
urban
range
urban
range
¦o
i
ON
-------
TABLE 4-34. AVERAGE CONCENTRATIONS 0^ PYRENE AND ANTHRACENE i:i
THE AIR OF SELECTED U.S. CITIES
Concentration (ng/m3)
City
Pyrene
Anthracene
Atlanta
3.4
0.4
Birmingham
9.6
1.3
Detroit
19.4
1.2
Los Angeles
3.2
0.1
Nashville
15.3
1.0
New Orleans
1.3
0.1
San Francisco
1.0
)0.1
a) The report values (U.S. EPA 1980c) were average of
summer and winter concentrations.
4-67
-------
Since the water solubilities of the anthracene group PAHs are
relatively low and the octanol:water partition coefficients are fairly
high, adsorption onto both organic and inorganic matter is a primary
removal pathway for these compounds in the water column. The particu-
late matter will ultimately be transported to the sediment where these
PAHs will accumulate; biodegradation and photo-oxidation in sediments
are expected to be quite slow. The fraction of these PAHs that remain
in the water column is expected to be degraded photolytically; how-
ever, the extent of this removal pathway will be affected by the turbidity
and light penetration in the actual system. Volatilization from water is
not expected to be a major fate process, but the relative importance of
this pathway differs among aquatic systems. Bioconcentration factors
for anthracene are on the order of several hundred; half-lives for
biodegradation have been determined to be 1-2 weeks in acclimated
cultures.
EXAMS calculations for anthracene indicate that in all model
systems, except the oligotrophic lake where sedimentation rates are
low, more than 75% of the anthracene resides in the sediment compart-
ment when the system is at steady state. Rapid photolysis is predicted
by EXAMS for the anthracene remaining in the water column of clear,
quiescent systems; volatilization is important only in the pond and
eutrophic lake systems where light penetration is reduced by suspended
matter. Biological degradation is important only in the highly produc-
tive eutrophic lake. In the more dynamic river systems, physical
transport (downstream) accounts for most of the anthracene removal.
Anthracene and the related PAHs have been detected in all environ-
mental media. Monitoring data support the predictions that significant
amounts of anthracene and related PAHs will reside in the sediments.
The majority of the STORET surface water concentrations of these PAHs
are less than 100 ug/1; STORET effluent data include concentrations
ranging from <1 ug/1 to >1,000 ug/1 for these PAHs. Various other
sources report effluent and sewage concentrations of fluoranthene from
2 ug/1 to 20 ug/1. Levels of pyrene and fluoranthene in soil were high,
up to 120,000 ug/kg. Concentrations of pyrene in several edible marine
species were reported to range from less than 0.6 ug/kg to 58 ug/kg
(wet weight). PAH levels in air from a variety of urban locations were
generally less than 20 ng/m3.
A schematic drawing of the major inputs of anthracene to the aquatic
environment, as well as the major fate and transformation processes, is
given in Figure 4-3. Since the half-lives shown were determined by
various methods, care should be taken in drawing conclusions based on
the absolute rather than the relative rates.
4-68
-------
-p-
I
o
SO
98 % env. releases, 1560 kkg/yr
(rapid photolysis, tl/4 5-10 hrs.)
Atmospheric Deposition
5—26% airborne load
75-400 kka/yr-
X to U.S.
\ inland waters ^
•^—11.5—B-0 kkg/yr; j*
to U.S. land mass
74-390 kkg/yr
Biotransformation
LAND
Sedimentation
V t% = 96-480 hrs
ca I culatedl____
t1/a = 11 hrs.
up to 2 weeks
SEDIMENT
Oxidation
Sorption log K
ow
4.45
De sorption
Physical
^ Transport
2 % env. releases
^ 24 kkg/yr.
tya ^ 300 hrs.
(laboratory conditions)
Photolysis
t,^ 0.75 hrs. (calculated)
Biotranslo cation
Runoff
Direct Discharge
WATER
FIGURE 4-3 SOURCES AND FATE OF ANTHRACENE IN THE AQUATIC ENVIRONMENT
-------
4.3 HUMAN EFFECTS AND EXPOSURE
4.3.1 Human Toxicity
4.3.1.1 Introduction
There is a scarcity of data concerning human health effects af
the six PAHs designated as the anthracene group. The discussion of
these compounds as a group should not be construed to mean necessarily
that they have similar toxic effects either qualitatively or quanti-
tatively. Available data for each compound have been discussed under
the various subsections below.
4.3.1.2 Pharmacokinetics
All of the compounds in the group are lipid soluble, which would per-
mit absorption and distribution throughout the body. Demonstrated toxic-
ity orally and by dermal application supports the notion of ready absorp-
tion. For the most part, detailed studies of the pharmacokinetics and
metabolism of most of the compounds in this group have not been conducted.
However, it is presumed that these compounds are metabolized via the
mixed-function oxidase system, as are naphthalene and other PAHs . Sub-
sequently, possibly toxic metabolites, as well as presumably non-toxic
water-soluble conjugates are formed.
Studies in rats and rabbits suggest that phenanthrene is converted
to phenols, possible 1- and 9-phenanthroLs and to a mercapturic acid.
Anthracene appears to be converted to 1,2-dihydroanthracene-l,2-diols
and their glucuronides. A hydroxydihydroanthracene, 1-anthrylmercapturic
acid, and possibly anthraquinone have also been found in the urine of
these animals. The main urinary metabolite of fluorene in rabbits is
the glucuronide of 2-hydroxyfluorene; small amounts of the free phenol
have also been found (Williams 1959).
Mitchell and Tu (1979) recently reported that pyrene was rapidly
cleared from the respiratory tract of rats exposed to a pyrene aerosol
(500 mg/l; 0.3-0.5 utn particles) for 60 minutes and eliminated primarily
via the liver and bile to the feces. Significant amounts of pyrene
(measured as pyrene fluorescence) were detected in trachea, nasal tur-
binates, and lungs 30 minutes post-exposure; these levels dropped to between
5 and 20% of post-exposure values by 48 hours. The highest tissue concentra-
tions were noted in the GI tract at 24 hours (4-fold increase above 30
min. value), which returned to pre-exposuxe levels within 4 days.
In a separate experiment, Mitchell and Tu (1979) administered 50 pg
pyrene in a gelatin-saline suspension to two rats by stomach tube. At 24
hours, approximately half of the administered pyrene was present in the
GI tract; the remainder was apparently absorbed and was either below de-
tection limits in the various tissues and/or was excreted.
4-70
-------
4.3.1.3 Human and Animal Studies
Carcinogenic!ty
None of the compounds in this group is considered carcinogenic by
the oral route. Anthracene has been considered as a cause of skin cancer
in anthracene-exposed workers (Hueper 1972); however, it would appear
that these workers had been exposed to undefined mixtures (e.g., anthra-
cene oil) in the manufacture and use of anthracene rather than to the
pure substance. Virtually, no data appear to exist on the human carcino-
genicity of the other compounds in this group.
Carcinogenicity results in experimental animal studies are summarized
in Tables 4-35, -36, -37, and -38. Anthracene (Table 4-35) was not carcino-
genic in rats by the oral route (Schmahl 1955). An increased incidence
of injection-site tumors was reported by SchmMhl (1955); however, the
relevance of injection site tumors is disputed, because the response is
generally too non-specific. A study by Innes et^ al^. (1969) indicated
that a possible metabolite of anthracene, anthraquinone, was not carcino-
genic by the oral route.
Fluoranthene was inactive as a complete carcinogen or tumor initiator
in several skin-painting experiments with mice (Table 4-36). However, both
fluoranthene and pyrene are reported to be co-carcinogens; repeated appli-
cation to mouse skin, along with low doses of a complete carcinogen such
as benzo[a]pyrene, produced a considerable enhancement of carcinogenic
effect (Van Duuren £t al.1973, 1976; U.S. EPA 1980b,c). The mechanism of
co-carcinogenesis is not clear, and can only be surmised at this time.:
In addition, specific chemical entities involved, such as the duration of expo-
sure, as well as the dose and dose rate, may influence the final outcome.
Until these divergent points are worked out in sufficient detail, esti-
mations of human risk based on co-carcinogenic results would appear to
be premature.
Buening and co-workers (1979) reported significant tumorigenic
activity with a phenanthrene derivative, phenanthrene Hi+-3,4-epoxide,
but not phenanthrene itself in newborn Swiss mice injected intraperi-
toneal^ with 0.8 pmol of either substance on days 1, 8 and 15 of life.
Tables 4-37 and 4-38 present the results of two studies on the ability
of anthracene, pyrene, and phenanthrene to act as initiators in the mouse
skin carcinogenesis model. In both studies, phenanthrene was apparently
a more potent initiator than pyrene, while anthracene was apparently
without activity. Results of Scribner (1973) show that phenanthrene is
far less active than benz[a]anthracene in terms of potency, latency and
incidence. At this time, it is difficult to assess the importance to
human health of the classification of a compound as an initiator in the
mouse skin carcinogenicity model, without evidence of its direct carcino-
genicity .
4-71
-------
TABLE 4-35. RESULTS OF CARCINOGENICITY STUDIES WITH ANTHRACENE
Species Route: Dosage Findings Reference
Rat (BD I &III)
Oral: 5-15 mg/day, 6d/wk,
550 days (total
dose 4.5 g/rat)
Intraperitoneal: 20 mg/wk
x 33 wks
Subcutaneous: 20 mg/wk
x 33 wks
Tumors in 2/28; one associated with a liver
parasite cyst, the other an adenocarcinoma
of the uterus.
Control incidence, 0.5%. Both above tumors
were not attributed to anthracene.
0/10 tumors
5/9 injection site sarcomas
0/10 injection site sarcomas in naphthalene
treated group with oil vehicle.
Schmahl (1955)
Mice (cc 57)
Subcutaneous: 2.5 mg in
0.5 ml peach oil
0/25 tumors up to 260 days
Bergol'ts and
Il'yina (1951)
Mice (C 57BL/6 x
C3H/Anf)
Oral(Anthraquinone): 464
mg/kg in gelatin gavage,
7-28 days of age; then,
1206 ppm diet
No significant elevation in tumor indicence
in 72 mice (male and female) after 18 months
Innes et al. (1969)
-------
TABLE 4-36. RESULTS OF CARCINOGENICITY STUDIES WITH FLUORANTHENE
Species
(No.)
Maior Effects
Dose
Exposure
(ff administrations)
Routt
Incidence
Comments
Mice
Papillomas and
Carcinomas
AO pg in acetone
40 ug + 5 t'g BaP
in acetone
5 gg BaP in acetone
vehicle comrol
3 X weekly for 440 Skin
days painting
0/50 papillomas, 0/50 squamous v.ai ci nomas
39/50 " ; 37/50
16/50 papillomas; 12/50 squamous caic inomas
0/50 " ; 0/50
coc.ii cmogenic acLiviLy
Mice
Tumors
0.1 mg in acetone every 2nd day for 10
applications + 3.8 mg croton oil/dose
for 20 weeks
Skin painting
1/29 Ho significant
tumor initiating at.
tivity
1
lo
Mice
(20)
Mice
(25-50)
No tumors
No tumors
by 13 months
0.32 in benzene
2 X/wk
Skin painLing
0 60-70% mortality af-
ter 6 months
10% in acetone
3 X/wk
Skin painting
Mice
(20)
No tumors by
15 months
50 pi of 1.0% in
acetone
3 X/wk for 12
mon ths
Skin painting
"o mortality enioun-
tt l cd
Mice
(15)
No tumors by
12 months
50 mg in decalin 2 X/wk for 82 wks Skin painting
0 13/15 alLve at 12
mouths
Mice
(15)
Mice
(14)
No tumors by
12 months
No tumors by
19 months
50 mg in 50 50
decalin:dodecnne
2 X/wk for 82 wks Skin painting
10 mg in glycerol 4 injections
Subcutaneous
0 1J/15 alive at 12
months
0 6/18 survived for
18 months
Source: U.S. EPA (1980b)
-------
TABLE 4-37. RESULTS OF THE SCREENING OF ANTHRACENE, PHENANTHRENE,
AND PYRENE FOR TUMOR-INITIATING ACTIVITY
I
¦c-
Total Dose No. of Test Substance Croton Oil
Compound (rag) Mice Application3 Application*1
Tumor Incidence at End
of Croton Oil Treatment0
Tumor-Bearing
Mice
Total
Tumors
Anthracene
30
20
5%; 2 applica- 18 weekly appli-
tions with inter- cations of 0.3 ml
val of 30 minutes, sol'n in acetone
repeated 3x/wk for (0.17% wk 1;
20 applications 0.085% wk 2,3;
Phenanthrene
Pyrene
Controls
540
250
20
20
20
18%, 3x/wk for
10 applications
8.3%, 3x/wk for
10 applications
0.17% wk 4-18)
as above
as above
as above
12d
Survivors
17
20
20
19
Each application was 0.3 ml of solution in acetone at concentration shown (w/v for solids, v/v for liquids).
^Croton oil treatment began 25 days after last test substance application.
c
All tumors recorded were benign papillomata.
^p < 0.05; chi-square test, one-tailed.
Source: Salaman and Roe (1956).
-------
TABLE 4-38. TUMOR INITIATION BY APPARENTLY NONCARCINOGENIC
POLYCYCLIC AROMATIC HYDROCARBONS
Compound
Dose
(yj mole)
Dose of
TPA (n mole)a
Animals
per Group
No. of papilloTnas/mouse
(% tumor-bearing mice)
10 wk.
15 wk.
20 wk.
25 wk.
30 wk.
35 wk.
35 i
0
0
0.07
0.10
0.14
0.14
28
(0)
(0)
(7)
(10)
(14)
(14)
0
0
0.07
0.07
0.17
0.21
29
(0)
(0)
(7)
(7)
(17)
(17)
0
0.10
0.27
0.37
0.50
0.60
30
(0)
(10)
(20)
(23)
(30)
(40)
0.4
1.83
1.50
1.60
1.86
2.00
29
(30)
(57)
(50)
(53)
(69)
(62)
0
0
0
0.03
0
0
30
(0)
(0)
(0)
(3)
(0)
(0)
Anthracene 10
Pyrere 10
Phenanthrene 10
Benz [a ]anthracene 2.2
None
10
10
30
30
30
30
30
12-0-tetradecanoylphorbol-13-acetate - applied 2x/wk one week after initiation with hydrocarbon
X <: 17. p < .05:
test, one-tailed.
Source: Scribner (1973).
-------
Pfeiffer (1973, 1977) tested ten non-carcinogens and two carcinogens
in combination by subcutaneous injection in NMRI mice. The ten "non-
carcinogens" were benzo [ejpyrene (2-70 ug); benz[a]anthracene (3-100 ug) ;
phenanthrene (125-4000 ug) ; anthracene (31-1000 pg); pyrene (62-2100 ug);
chrysene (3-100 ug); perylene (0.2-7.0 ug); benz [g,h,i]perylene (12.8-400
yg); coronene (3-100 yg) and fluoranthene (28-900 ug). Benzo[a]pyrene
(3-100 pg) and dibenz [a,hjanthracene (2-70 ug) were the two carcinogens
in the mixture. The carcinogenic effect of the mixture was attributed
to the presence of the two carcinogens; neither an inhibitory or stimu-
lating effect was attributed to the ten non-carcinogens of the mixture.
In summation, none of the compounds in this group of PAHs has been
shown to be carcinogenic by the oral route. Phenanthrene, and possibly
pyrene, have been shown to possess weak tumor-initiation activity in the
mouse skin carcinogenesis model; anthracene and fluoranthene appear in-
active. Augmentation of carcinogenic action has been demonstrated with
both fluoranthene and pyrene, but an assessment of human risk based on
co-carcinogenic results would appear to be premature at this time. No
studies were found for acenaphthene or fluorene alone; tests with complex
mixtures of PAHs suggest no carcinogenic activity, but do not allow firm
conclusions to be drawn.
Teratogenicity
No data have been found.
Mutageniclty
Various mutagenicity studies conducted with anthracene, phenanthrene,
fluorene, and pyrene have produced essentially negative responses (see
Table 4-39). A single experiment with acenaphthene produced positive
findings in one strain of Salmonella typhimurium in the presence of rat
liver activation, but only at concentrations that were toxic to the bac-
teria. No other data were available for this compound. Data for fluoran-
thene are mixed. Kaden et al. (1979) reported that fluoranthene induced
a significantly greater number of mutations in Salmonella typhimurium TM 677
than an equimolar concentration of benzo[a]pyrene, the positive control.
However, negative results have been reported for four other strains of
Salmonella (Salamone et al. 1979), as well as in a mouse embryo cell assay
(Kamei 1980).
Other Toxic Effects
Little is known concerning other toxic effects associated with expo-
sure to compounds designated as the anthracene group.
Relatively low acute toxicity has been reported for fluoranthene;
i.e., an oral LD50 of 2g/kg in the rat and a dermal LD50 of 3.18g/kg in
the rabbit (USEPA 1980b).
4-76
-------
tabls *-39 siffetmr or mnconc activity roa cam cckpoumos *m typhlaurlua^
In vitro TA 96 TAiOO TA »» TA ISM TM 677
Unachadulad
ONA OKA
Bcpatr Svnthaala
Aflthracaoa - - - ------ - Baslar and ftobrboro
Cibaoa jt at
U97$ Had as ft, ^
$97$ liii fl U
Harcto
Mll° 1£ (^7$ '
Hlahr* u <197(%
Polrlar and da 8ar-
raa(197%#$ Boaalnakr-
Cftchtr «t al. (197<$)
Salaaoo* fl «l
097$ Strlanol and
Uuan* (197$
wra at al (197<)
AcnupbtbfBi + Kadaa a£ a±. (1979)
riuoriatbfna _ ~ Kadan at al.097Sfc
uui Ti9sqt-
(14 «o*a K a^.
<197* Salaaeoa jt
al 0979)
ft.ananthrane
Cibaoa «t a^ (197$
La Vol* «i aj.
(197$} Suataura §t_
«1 <1970
Bayar and BtalMcbc
(197ft Bucbar al.
>1974; ttubaruQ
Q97>; ttubatMO aod
Sacha (197$ Udao
21 At 097ft Lafca
at al U97&
La Vol* al_.
097^; Harquardt
-------
Limited data on acenaphthene indicate loss of body weight, changes
in peripheral blood, increased aminotransferase levels in blood and mild
morphological damage to both liver and kidney in rats administered 2g/kg/
day orally for 32 days (Knobloch jet al. 1969). Another study noted
toxic effects on blood, lungs and glandular constituents in rats inhaling
12 mg/m3 4 hours/day, 6 days/week for 5 months. The bronchial
epithelium showed hyperplasia and metaplasia, but this appears to be
related to pneumonia which killed a large portion of the study population.
There were no controls (Reshetyuk ejt 1970).
4.3.1.4 Overview
Ambient Water Quality Criteria - Human Health
The U.S. EPA (1980a) determined that sufficient data were not avail-
able to derive an ambient water quality criterion that would protect
against potential toxicity of acenaphthene. The mammalian and human
health effects of acenaphthene are virtually unknown. The level for
controlling undesirable taste and odor quality of ambient water was
estimated at 0.02 mg/1.
A criterion has been established for fluoranthene (USEPA 1980b).
Based on a no-effect level for mortality (6.1 mg/kg/day) ..n a chronic
mouse skin-painting study (Hoffmann et al. 1972), an assumption of 100%
absorption of the applied dose, and an uncertainty factor of 1000, an
acceptable human daily intake of 0.4 mg is calculated, which corresponds
to an ambient water quality criterion of 42 yg/L.
No specific criteria have been established for the remaining com-
pounds in this group, none of which is a carcinogen by ingestion.
Other Considerations
None of the compounds in this group (anthracene, acenaphthene,
fluoranthene, fluorene, phenanthrene, pyrene) is carcinogenic by
the oral route; however, most of these compounds have not been extensive-
ly studied. An increased incidence of injection site tumors was noted
with anthracene, but this type of oncogenic effect is generally regarded
as irrelevant to human exposure. Phenanthrene, and possibly pyrene, are
weak initiators in the mouse skin carcinogenesis model, although con-
siderably less active than benzo [a]anthracene. It is difficult to assess
the relevance of these findings to human health in the absence of direct
carcinogenic effects. Fluoranthene and pyrene have been shown to be
co-carcinogens with benzo [ajpyrene. Current understanding of the co-
carcinogenesis process, however, is not sufficiently adequate to allow
estimation of human risk.
4-78
-------
Mutagenicity studies for most of these compounds are essentially
negative; mixed data were obtained for fluoranthene. Additional
data are needed to resolve this issue. No reproductive data were found
for these compounds, and virtually no toxicological data are available.
4.3.2 HUMAN EXPOSURE
4.3.2.1 Introduction
This section examines human exposure to the anthracene group PAHs
via ingestion (food and drinking water), inhalation, and dermal contact.
As is apparent from Section 4.2.4, monitoring data for these compounds
are very limited.
4.3.2.2 Ingestion
Drinking Water
Basu and Saxena (1977, 1978) sampled 16 water samples in New York,
Pennsylvania, and West Virginia. Fluoranthene was detected in four
samples at levels of 2.4-94.5 ng/1. Removal efficiencies ranged from
98.9-100%; treatment plants at which removal efficiencies were measured
utilized activated carbon treatment. Harrison et^ al. (1976) showed a
70% reduction with settling, filtration and chlorination. These
concentrations are considered to be low, and thus in areas where these
treatment methods are used, drinking water levels of PAHs will be low.
Fluoranthene was also detected in the National Organic Monitoring
Survey (NOMS) in 20 of 110 samples at a detection limit of 10 ng/1. The
mean of the positive samples was 20 ng/1 and the range was 10-80 ng/1
(U.S. EPA 1978). The U.S. EPA (1980b) estimated an average concentration
of 8.6 ng/1 in drinking water, utilizing the data of Basu and Saxena
(1977, 1978) and by assigning the detection limit to those samples in
which none was detected. These assumptions appear to be reasonable in
view of the limited data available.
Anthracene/phenanthrene was detected in 7 of 39 public water system
wells; the maximum concentration was reported to be 21 ug/1 (Kim and
Stone 1979). No data on drinking water levels were found for the other
chemicals in this group (acenaphthene, fluorene, and pyrene). Furthermore,
they are rarely detected in ambient water (see Section 4.2.4). Anthracene
was reported only twice in ST0RET as levels above the detection limit:
1 yg/1, 27 yg/1.
Table 4-40 contains estimated daily exposures via drinking water.
Typical estimates are only shown for fluoranthene because sufficient
data on drinking water levels are lacking for the other PAHs in this
group.
4-79
-------
Food
Levels of PAHs in raw foods appear to be generally low. However,
vegetables or fruits grown in the vicinity of releases to air may
contain higher levels (U.S. EPA 1980c). The highest levels of PAHs in
food appear to result from the cooking process, especially charcoal
broiling and smoking.
Table 4-41 estimates the exposure to PAHs via ingestion of such
foods, as well as the various assumptions made. The data on contamination
levels were taken from U.S. EPA (1980 a,b,c) and White and Vanderslice
(1980); data are very limited for many of these chemicals. Columns in
the table were not always totaled since the exposure shown represents
an unknown portion of the actual exposure.
Considering all of the uncertainties, typical daily intakes for
fluoranthene have been estimated to be 0.3 ug/day; pyrene, 0.1 ug/day,
and anthracene, 0.02 ug/day. Data were too fragmentary for the other
compounds for making an estimate of total daily exposure. The maximum
intakes shown represent a maximum level of contamination in the food
and maximum daily consumption. The total is meant to represent a worst
case. It is apparent that charcoal broiling represents the major source
of exposure. However, consumption of fruits and vegetables from contam-
inated locations may also contribute significantly to exposure in some
cases.
4.3.2.3 Inhalation
The U.S. EPA (1980 c,d) has summarized the available monitoring
data for PAHs in air, mostly for urban areas. These limited data, in-
cluding data from Section 4.2.4, were utiliEed to develop exposure estimates
for an assumed respiratory flow of 20 nP/day (ICRP 1975) . The results are
shown in Table 4-42. As is the case for exposure due to food and drinking
water, fluoranthene appears to represent the largest exposure of chemicals
in this group.
In addition to ambient air, smoking can contribute to inhalation of
PAHs. For comparison, Hoffman et^ a!L. (1972) have estimated that smoking
one cigarette may contribute up to 0.26 yg fluoranthene to the lungs;
thus a person smoking one pack per day could receive 5.2 ug/day via
mainstream smoke from this source. Similarly, mainstream smoke from one
cigarette was found to contain 0.42 yg of fluorene, resulting in an
exposure of 8.4 yg/day from smoking one pack per day.
4.3.2.4 Dermal Contact
No direct information is available regarding the dermal exposure of
humans to PAHs in water. However, due to the low levels found in wate^
any dermal exposure is expected to be low.
4-80
-------
TABLE 4-40. ESTIMATED HUMAN EXPOSURE TO THE ANTHRACENE GROUP
PAHs VIA DRINKING WATER
Compound
Anthracene
Acenaphthene
Fluoranthene
Fluorene
Phenanthrene
Pyrene
Concentration (ng/1)
Typical Maximum
NA
NA
8. 6C
NA
NA
NA
21,000
NA
94.5d
NA
21,000£
NA
Estimated Daily
Exposure (pg/day)^
Typical Maximum
NA
NA
0.02
NA
NA
NA
40
NA
0.2
NA
40E
NA
Not available,
Based on a 2-liter per day consumption of drinking water
(ICRP 1975).
:U.S. EPA (1980b) .
^Basu and Saxena (1977, 1978).
Reported as undifferentiated data for anthracene/phenanthrene
(Kim and Stone 1979).
"Calculated from maximum reported for unresolved anthracene/phenanthrene.
4-31
-------
TABLE 4-41. LEVELS OF ANTHRACENE GROUP PAHs IN FOOD AND ESTIMATED EXPOSURE VIA INGESTION OF FOOD
ANTHRACENE
FLUORANTHENE
FOOD
CATEGORY
CONSUMPTION CONTAMINATION
(a/day) (fg/kg)
Typicale Max. Typlcale Max.
INTAKE ()'g/day)
Typlcale Max.
CONTAMINATION
(Mfi/kfi)
Typicale Max.
INTAKE (MR/day)
Typicale Max.
Charcoal-
broiled beef8
Hamburger
Steak
10
3
86
NA
4.5
NA
NA
NA
0 .01
NA
NA
5
30
15
50
0.05
0.09
4.3
Charcoal ^
broiled pork
1
27
7.1
NA
0.007
NA
10
49
0.02
1.3
Smoked pork'3
1
27
NA
NA
NA
NA
3
NA
0.003
NA
£
Smoked sausage
1.5
30
NA
NA
NA
NA
15
40
0.02
1.2
Smoked fish''
0.1
14
2
26
0.0002
0.4
3
12
0.0003
0.2
Oil
18
NA
NA
36
NA
0.6
5
450
0.09
8.1
Leafy
40
NA
NA
12
NA
0.5
NA
180
NA
7.2
Vegetables
Total ...
0.02
0.27
Consumption of beef - 86 g/day, 15% charcoal broiled - 80% hamburger, 20% steak. Worst case maximum: 86 g consumption
of charcoal-broiled steak.
^Consumption of pork - 27 g/day, 5% smoked, 5% charcoal-broiled. Worst case maximum: 27 g/day charcoal-broiled.
Consumption of sausage - 30 g/day, 5% smoked. Worst case maximum: 30 g/day smoked.
^Consumption of fish - 14 g/day, 1% smoked. Worst case maximum: 14 g/day smoked.
p I
"Typical" may be defined here as a qualitative estimate based on average consumption of the range of concentrations.
The available contamination data did not lend themselves to statistical treatment.
Source: USDA (1978, 1980), U.S. EPA (1980 a.b.c), White and Vanderslice (1980).
-------
TABLE 4-41. LEVELS OF ANTHRACENE GROUP PAHs IK FOOD AND ESTIMATED EXPOSURE VIA INGESTION OF FOOD
(Continued)
FLUORENE
PYRENE
PHENANTHRENE
FOOD
CATEGORY
CONSUMPTION
(K/day)
CONTAMINATION
(Ps/kg)
INTAKE
(^k/day)
CONTAMINATION
(Mg/kg)
INTAKE
(pfi/day)
CONTAMINATION
(WR/ks)
INTAKE
(^ft/day)
Typicale Max. Typical0 Max. Typlcale Max. Typicale Max. Typicale Hax. Typicale Max. Typlcale Max.
Charcoal-
broiled
beefa
Hamburger
Steak
10
3
86
NA
NA
NA
NA
NA
NA
NA
NA
NA
20
NA
35
NA
0.06
NA
3
NA
NA
NA
21
NA
NA
NA
1.8
Charcoal
broiled
porkb
1
27
NA
NA
NA
NA
NA
42
NA
1.1
NA
58
NA
1.6
Smoked
porkb
1
27
NA
NA
NA
NA
5
161
0.005
4.3
NA
NA
NA
NA
Smoked
sausagec
1.5
30
NA
NA
NA
NA
1.5
NA
0.002
NA
NA
NA
NA
NA
Smoked
f ishd
0.1
14
5
67
0.0005
0.9
3
6
0.0003
0.08
10
52
0.001
0.7
,0il
18
HA
NA
NA
NA
NA
2
15
0.04
0.03
NA
51
NA
0.9
Leafy
vegetables
40
NA
NA
NA
NA
NA
NA
109
NA
4.4
NA
88
NA
3.5
Total ...
l
0.11
Consumption of beef - 86 g/day, 15% charcoal broiled - 80% hamburger, 20% steak. Morse case maximum: 86 g consumption
of charcoal-broiled steak.
^Consumption of pork - 27 g/day, 5% smoked, 5% charcoal-broiled. Worse case maximum: 27 g/day charcoal-broiled.
Consumption of sausage - 30 g/day, 5% smoked. Worst case maximum: 30 g/day smoked.
^Consumption of fish - 14 g/day, 1% smoked. Worst case maximum: 14 g/day smoked.
"Typical" may be defined here as a qualitative estimate based on average consumption of the range of concentrations.
The available contamination did not lend themselves to statistical treatment.
-------
TABLE 4-42. ESTIMATED EXPOSURE TO ANTHRACENE GROUP PAHs
DUE TO INHALATION OF AMBIENT AIR
Ambient _
j 3 b
Concentration (ng/m ) Intake (yg/day)
Chemical Urban Rural Max. Urban Rural Max.
Anthracene 0.1-1.3 NA NA 0.003-0.03 NA NA
Acenaphthene 0.7 NA NA 0.014 NA NA
Fluoranthene 4 NA 40 0.08 NA 0.8
Fluorene NAC NA NA NA NA NA
Phenanthrene 0.011-0.34 NA NA 0.0002-0.007 NA NA
Pyrene 1.0-19.4 NA NA 0.02-0.4 NA NA
^J.S. EPA (1980 a,b,c).
^Based on respiratory flow of 20 m^/day (ICRP 1975).
c
NA = Not available,
4-84
-------
4.3.2.5 Overview
Very little information is available regarding the exposure of humans
to anthracene and the other chemicals in this group. These compounds
have rarely been detected in drinking water, surface water, or air.
Monitoring and detection in food appears to be more frequent, especially
for charcoal-broiled and smoked foods.
Table 4-43 summarizes the exposure estimates previously discussed.
Food appears to be the major exposure medium, although exposure due to
inhalation may be comparable in some urban areas. Smoking could dominate
all ot these routes, however, since intakes from this source of
5.2 pg/day and a.4 ug/day have been estimated for fluoranthene and
fluorene, respectively I Of the chemicals in this group, fluoranthene
appears to represent the greatest exposure of humans. The presence of
anthracene contamination in drinking water supplies could possibly
result in a high exposure level. The exposure calculated for ingestion
of drinking water containing the maximum reported concentration of
anthracene/phenanthrene was 40 ug/day.
4-85
-------
TABLE 4-43. ESTIMATED HUMAN EXPOSURE TO ANTHRACENE GROUP PAHs
"Typical"5 Exposure (yg/day)
Inhalation in
Compound Drinking Water Food Urban Areas Smoking
Anthracene
b
NA
0.02
0.003-0.03
NA
Acenaphthene
NA
NA
0.01
NA
Fluoranthene
0.02
0.3
0.08
5.2
Fluorene
NA
>0.0005°
NA
8.4
Phenanthrene
NA
>o.ooic
0.0002-0.007
NA
Pyrene
NA
0.1
0.02-0.4
NA
"Typical" may be defined here as a qualitative estimate based on
average consumption of the range of concentrations. The available
contamination data did not lend themselves to statistical treatment.
b
NA = Not available,
c
Insufficient data available.
Source: Estimates derived in Section 4.3.2.
4-86
-------
4.4 EFFECTS AND EXPOSURE—AQUATIC BIOTA
4.4.1 Effects on Aquatic Organisms
4.4.1.1 Introduction
The acute toxicity data for this group of manufactured PAHs
were not extensive and were available for only four of the six
compounds under consideration. Some limited information on the
toxicity of anthracene was available from general studies and through
personal communication with investigators presently conducting
toxicity studies.
4.4.1.2 Acute Toxicity
Limited data for freshwater fish and invertebrates are presented in
Table 4-44. The acute toxicity of acenaphthene and fluoranthene was
measured for the bluegill sunfish and cladoceran; LC data ranged from
1700 ng/1 to 325,000 yg/1.
The acute toxicity data for marine fish and invertebrates
(Table 4-45) are more extensive. The range in values is quite
broad, from 40 yg/1 (fluoranthene, juvenile mysid shrimp) to
2230 yg/1 (acenaphthene, sheepshead minnow). For all of the
four compounds tested, invertebrates are generally more sensitive
(range 40-1090 yg/1) than fish (range 150-2230 yg/1), but the data
for fish are somewhat limited. The most sensitive fish species was
the mosquito fish (Gambusia affinis) with an LC5Q of 150 yg/1 phenanthrene.
Among the invertebrates, there are some data indicating differences
in the toxicity of different PAHs to the same species. Acenaphthene
was 24 times more toxic to mysid shrimp (Mysidopsis bahia) than was
fluoranthene to juveniles of the same species. Data from one study on
the marine polychaete worm (Neanthes arenaceodentata) indicate that
for three PAHs tested, toxicity increased with increasing molecular
weight. The order of toxicity was fluoranthrene > phenanthrene > fluorene
(Table 4-45). The opposite trend was seen with both freshwater and
marine algae species tested (Table 4-46), as acenaphthene was
significantly more toxic than fluoranthene.
4.4.1.3 Chronic Toxicity
This group of PAHs has been tested for chronic effects to marine
species only. Chronic effects levels (Table 4-47) ranged from
12 yg/1 (fluoranthene in mysid shrimp) to > 500 (acenaphthene in
sheepshead minnow). This limited data set suggests that chronic
toxicity may increase with greater molecular weight.
4-87
-------
TABLE 4-44. ACUTE TOXICITY OF ANTHRACENE GROUP
PAHs FOR FRESHWATER SPECIES
Species Compound
Cladoceran
Daphnia magna
Blueglll Acenaphthene
Lepomis marcrochirus
Cladoceran Fluoranthene
Daphnia magna
Bluegill Fluoranthene
Lepomis marcrochirus
LC 5 0
(yg/1) Reference
1,700 U.S. EPA (1978)
325,000 U.S. EPA (1978)
3,980 U.S. EPA (1978)
Acenaphthene 41,200 U.S. EPA (1978)
4-88
-------
TABLE 4-45. ACUTE TOXICITY OF ANTHRACENE GROUP
PAHs FOR MARINE INVERTEBRATES AND FISH
Species
Compound
Invertebrates
Mysid shrimp
Mysidopsis bahia
Mysid shrimp
(juvenile)
Grass Shrimp
Palaemonetes pugio
Grass shrimp
Acenaphthene
Fluoranthene
Phenanthrene
Fluorene
Polychaete Fluorene
Neanthis arenaceodenta
Polychaete
Phenanthrene
Polychaete
Fluoranthene
Fish
Sheepshead minnow Fluorene
Cyprinodon variegatus
Sheepshead minnow Acenaphthene
Cyprinodon variegatus
Mosquito fish
Gambusia affinis
Phenanthrene
lc5 0
(yg/D
Reference
970
U.S. EPA (1978)
40
U.S. EPA (1978)
370
(24 hr.)
320
1,090
600
500
Young (1977)
Wofford and Neff
(1978)
Rossi and Neff
(1978)
Rossi and Neff
(1978)
Rossi and Neff
(1978)
1,680
2,230
150
Wofford and Neff
(1978)
U.S. EPA (1978)
U.S. EPA (1978)
4-89
-------
TABLE 4-46.
TOXICITY OF
ANTHRACENE GROUP
PAHs FOR
FRESHWATER AND
MARINE PLANTS
96-Hour
Species
Compound
ECsn (hk/1)3
Reference
Freshwater Species
Alga
Acenaphthene
530 Chlorophyll a
U.S.
EPA
(1978)
Selenastrum capricornutum
Alga
Acenaphthene
520 Cell numbers
U.S.
EPA
(1978)
Alga
Fluoranthene
54,400 Cell numbers
U.S.
EPA
(1978)
Alga
Fluoranthene
54,600 Chlorophyll a
U.S.
EPA
(1978)
Saltwater Species
Alga
Acenaphthene
500 Chlorophyll a
U.S.
EPA
(1978)
Skeletonema costatum
Alga
Acenaphthene
500 Chlorophyll a
U.S.
EPA
(1978)
Alga
Fluoranthene
45,000 Chlorophyll a
U.S.
EPA
(1978)
Alga
Fluoranthene
45,600 Cell numbers
U.S.
EPA
(1978)
EC50 = concentration causing effect on 50% of test organisms.
4-90
-------
TABLE 4-47. CHRONIC TOXICITY OF ANTHRACENE
GROUP PAHs FOR MARINE SPECIES
Species
Compound
Effects Level
(ug/l)
Reference
Sheepshead minnow
Cyprinodon variegatus
Acenaphthene
520-970
embryo-larval
test
U.S. EPA (1978)
Mysid shrimp
Mysidopsis bahia
Fluoranthene
12-22
life-cycle
U.S. EPA (1978)
Mud Crab
Rithropanopeus harrisii
Phenanthrene
200
decreased
growth
Neff (1979)
Grass shrimp
Palaemonetus pugio
Phenanthrene
100 @ 30 days
decreased
growth
Young (1977)
4-91
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4.4.1.4 Other Toxicity Studies
No bioassay toxicity data were available for anthracene, but the
compound is believed to be acutely toxic to freshwater organisms in
the low pg/1 range. In microcosm stream model studies at the
Savannah River Ecology Laboratory, anthracene in concentrations of
1-10 yg/1 killed all fish (bluegill sunfish) and insects (chironomids)
in the system in 8 hours. Photolysis is an important degradation
process for anthracene (and other PAHs). The toxicity of anthracene
appeared to be increased by sunlight since the results were not
reproduced in the laboratory or outside at night (personal communication,
P. Landrum et al., Savannah River Ecology Laboratory, 1980).
4.4.1.5 Factors Affecting Toxicity
In order to study the effect of salinity on the toxicity of
various concentrations of phenanthrene to larvae of the mud crab
Rithropanopeus harrisii, Laughlin and Neff (1979) tested concentrations
of 0, 100, 150, and 200 yg/1 at salinities of 5, 15, and 25 loo.
Concentrations of 200 yg/1 were acutely toxic to these crabs, and
mean survival was lowest at the low salinity values. The threshold
of acute toxicity was at 150yg/l, and survival was f30% at 5 /oo salinity.
At 15 and 25 °/oo salinity, survival was higher, as was the case at
200 yg/1 phenanthrene. These studies show that variations in
environmental factors such as salinity, even when well within the
normal tolerance range of the species, may create slightly stressful
environmental conditions which in turn may significantly increase
organisms' sensitivity to PAHs (Laughlin and Neff 1979).
4.4.1.6 U.S. EPA Ambient Water Quality Criteria
No ambient water quality criteria for protection of freshwater
or saltwater life from these PAHs have been proposed at this time.
This is due to a lack of sufficient data on the toxicity of this
group of PAHs to aquatic life.
4.4.1.7 Conclusions
From the limited data available for this group of PAHs, some
generalizations can be made about the toxic effects of these compounds.
• Acute effect levels for freshwater invertebrates and fish'
range from 1700 yg/1 (acenaphthene/bluegill) to 325,000 yg/1
(f1uo ran thene/nap hn i* ^.
• Marine fish and invertebrates are somewhat more sensitive than
freshwater species with acute values ranging from 40 pg/1 (fluoranthene/
mysid shrimp) to 2230 yg/1 (acenapthene/sheepshead minnow).
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o Data for marine invertebrates indicate that toxicity
increases with increasing molecular weight, but this trend
is not similarly demonstrated with all other organisms.
Therefore, nothing definitive can be concluded regarding
the relative toxicity of these PAHs.
o Chronic toxicity values range from 12 iag/1 to greater than
500 ug/1- However, data were available for only four
marine species and for no freshwater species.
Aquatic organisms appear to be fairly resistant to anthracene
group PAHs in laboratory experiments, and overall these PAHs are
similar in their toxicity to biota. However, the results of microcosm
studies, which simulate natural environmental conditions, indicate
that anthracene is acutely toxic to stream biota at relatively low
levels (1-10 yg/1) and warrant further in situ studies of the toxicity
of anthracene, particularly since photodegradation is a significant
environmental fate process for anthracene.
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4.4.2 Exposure of Aquatic Biota
4.4.2.1 Introduction
PAHs are universal components of the aquatic and terrestrial
environment, and, as discussed in Section 4.1, originate from
direct input of petroleum-related processes, urban runoff, industrial
effluents, and air to water deposition.
The anthracene group PAHs are all commercially produced. This
is reflected in the monitoring data and numerous studies which reveal
higher concentrations of anthracene group PAHs near industrialized
areas, major ports, and areas of petroleum-related activity. Higher
levels of these PAHs are also found in sediment, as opposed to water
at the same location.
4.4.2.2 Monitoring Data
Summary descriptions and percentage distributions of STORET
observations for the PAHs in the anthracene group were given previously
in Section 4.2.4. Nearly all (>75%) of the STORET observations for
ambient and effluent water, and sediment were remarked, i.e., they
represent detection limits of the analytic procedure and not concentra-
tions actually detected. Of the few unremarked values reported (64 for
ambient water, 88 for effluent water, and 128 for sediment), a majority
(1000 yg/1; this would support
the modeling predictions discussed in Section 4.2 that anthracene will
accumulate in the sediments. The highest levels observed (eight values)
were in the range of 1-10 mg/kg, and occurred consistently in several
places, including Puget Sound and the Washington State coast, the
Oregon coast, San Francisco Bay and North Coastal California, a hazardous
waste site in North Carolina, and the Houston ship channel. It is
apparent that PAHs tend to accumulate in the sediments near industrialized
or major port areas. Levels in soil have also been found to be as high
as 5,000-120,000 ug/kg.
Other monitoring data (Section 4.2.2.5) indicate that PAH levels
in (industrial and domestic) wastewater are in the low yg/1 range,
indicating that overall the levels in surface waters are not high, even
those in the vicinity of effluent discharges.
4.4.2.3 Aquatic Fate
Environmental conditions have a significant influence on the
disposition of the anthracene group PAHs In aquatic systems. The results
of the EXAMS modeling indicate that in five of the six generalized
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aquatic environments examined, greater than 70% of the anthracene
accumulated in the sediments, as opposed to that remaining in the water
column (see Section 4.2.3.3). Anthracene is persistent in sediment,
and for all six environments the amount of anthracene lost from the
sediments is at least five times less than that lost from the water in
the same time period. Photolysis is a significant and rapid fate process
for anthracene in the water column. Anthracene (and/or its metabolites)
from the sediments is available to deposit-feeding organisms, and may
also be reintroduced, but apparently in small amounts, into the water
column. Regarding exposure of biota to anthracene from sediments as
compared with the water column, one study has shown that uptake from
water is greater than from sediment (Giddings £t al. 1978).
4.4.2.4 Biosynthesis
Biosynthesis of PAHs in the environment from naturally occurring
quinones is believed to take place, particularly under conditions of
high sediment organic content. It has been postulated, however, that
direct biosynthesis probably contributes little to the global PAH burden,
but may represent a significant localized source of PAHs (Neff 1979).
Evidence against biosynthesis as a source of substantial amounts of PAH
in sediments has been suggested in that the PAHs formed by biosynthesis
would be expected to be much simpler in composition than the complex
PAH assemblages found in environmental samples (Youngblood and Blumer
1975). Thus biosynthesis would not be assumed to contribute to the
exposure of biota to the anthracene-group PAHs.
4.4.2.5 Conclusions
For all of the anthracene group PAHs, most of the levels detected
in water were remarked values in the 10-500 ug/1 range. Although no
water quality criteria for these PAHs have been established due to
insufficient data, the concentrations reported are below the range of
toxic effects seen in the laboratory for those compounds for which
effects data are available.
It should be noted, that in experiments at the Savannah
River Ecology Laboratory, concentrations of 10 ug/1 anthracene killed
all organisms present in a pond microcosm experiment exposed to sun-
light, whereas in the laboratory outside at night, acute effects did
not occur at this low concentration (personal communication, P. Landrum
1980). This suggests that laboratory data may not reflect toxicity
of the compounds under actual environmental conditions.
Although some sediment levels have been found in the range of levels caus-
ing acute toxic effects in aquatic organisms, the complex processes affecting
the bioavailability of anthracene would probably result in biota being
exposed to lower concentrations than those sampled, however, the direct
4-95
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toxicity of sediments has not yet been tested. A greater concern than
toxicity is that high levels of these compounds may be available
chronically for bioaccumulation by organisms and biomagnification in
the food chain.
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4.5 RISK CONSIDERATIONS
4.5.1 Introduction
The purpose of this section is to evaluate potential risks to humans
and aquatic biota resulting from exposure to the commercially produced
PAHs in this group (anthracene, acenaphthene, fluoranthene, fluorene,
phenanthrene, ana pyrene). This risk analysis is hampered greatly by the
lack of quantitative data on the levels that may produce health effects,
and by the very limited amount of monitoring data available to indicate
the extent of environmental exposure.
4.5.2 Humans
4.5.2.1 Statement of Risk
The human effects data for this group of compounds are inadequate
to allow a quantitative extrapolation of the human risk associated with
environmental exposure to these compounds. The few studies of long-term
exposure that were found did not indicate carcinogenic or mutagenic
activity. Pyrene and fluoranthene act as co-carcinogens when applied to
mouse skin in combination with other, carcinogenic compounds, but the
significance of this finding to human health is unknown at this time.
The dose levels of concern for acute or sublethal toxic effects have not
been evaluated. The levels of environmental exposure estimated for these
PAHs are low. Fluoranthene and pyrene are the two PAHs in this group with
the highest potential exposure levels, reaching maximum daily intake levels
on the order of 10-20 ug/day for the general population. Smokers could
receive additional exposures on the order of 5.2 ug/day fluoranthene and
8.4 ug/day fluorene.
4.5.2.2 Discussion
All of the compounds in the anthracene group are lipid soluble, a
characteristic that would suggest that they may be absorbed and distri-
buted throughout the body following ingestion or inhalation.
None of the six compounds in this group is considered carcinogenic
by the oral route. An increased incidence of injection-site tumors was
noted with anthracene, but this type of oncogenic effect is generally not
regarded as relevant to human exposure. Phenanthrene, and possibly pyrene,
show weak tumor-initiation activity in the mouse skin carcinogenicity model.
However, it is difficult to assess the significance to human health of
classifying these compounds as tumor-initiators in the absence of their
direct carcinogenicity. Fluoranthene and pyrene were both shown to be
co-carcinogens in the mouse skin carcinogenesis model; however, the mech-
anism of co-carcinogenesis is not clear and can only be surmised at this
time. An assessment of human risk based on co-carcinogenic results would
thus appear to be premature.
Mutagenicity studies with this group of PAHs have produced essentially
negative results, and no data on adverse reproductive effects were found.
Since virtually no toxicological data are available for these compounds,
4-97
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considerable uncertainty exists with respect to the relative risk asso-
ciated with human exposure to these materials.
There is also very little information quantifying the human environ-
mental exposure to the PAHs in the anthracene group. These compounds are
rarely detected in drinking water, and the levels reported in ambient air
are very low. The available monitoring data indicate that fluoranthene
exposure from ingestion of drinking water could reach a maximum of 0.2 yg/day.
On the basis of urban air concentrations, inhalation exposure to each of the
compounds in this group, except pyrene, is estimated to be considerably less
than 0.1 yg/day; daily intake levels of pyrene in urban air could reach
0.4 ug/day.
For the general population, the primary route of environmental expo-
sure to these compounds is oral intake of contaminated foodstuffs, espe-
cially cooking oil, smoked or charcoal-broiled meats, and fruits or veg-
etables from contaminated areas. The exposure estimates in Section 4.3.2
indicate that fluoranthene and pyrene are the most prevalent of these PAHs
in food. Estimated daily intake levels range from typical levels of
0.3 ug/day and 0.1 ug/day to maximum levels of about 20 ug/day and
10 ug/day for fluoranthane and pyrene, respectively; a typical daily
anthracene exposure from food was estimated to be 0.02 ug/day. Data for
the other compounds were insufficient to permit estimates of daily exposure
via this route.
Cigarette smokers may be exposed to 5.2 ug/day of fluoranthene and
8.4 ug/day of fluorene in the mainstream smoke of one pack of cigarettes
(20 cigarettes). One-third of all U.S. adults smoke cigarettes and 25-30%
of the smokers smoke more than 25 cigarettes per day. The risk to this
subpopulation due to smoking may be significantly higher than the total
risk to the general population from all of the typical exposures estimated
for the six PAHs in this group.
4.5.3 Aquatic Biota
Risk to aquatic biota exposed to ambient concentrations of these
PAHs is expected to be low. The U.S. EPA has not established ambient
water quality criteria for these compounds for the protection of aquatic
life. However, all ambient concentrations in the ST0RET data base were
below the levels that were reported to be acutely toxic to freshwater
organisms. The STORET concentration data for surface water do overlap
the range of chronic and acute toxic effects levels for marine organisms,
which appear to be more sensitive to these PAHs; however, there are
no monitoring data specifically for marine systems. Since the potential
does exist for bioaccusiulation of these PAHs in zooplankton and subsequent
biomagnification by fish, direct comparison of ambient concentrations with
effects levels may not adequately describe the risk to aquatic organisms.
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4-111
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Schmahl, D. Priifung von Naphthalin und Anthracen auf carcenogene Wirkung
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teria for fluoranthene. Washington, D.C.: Office of Water Regulations
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4-112
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4-113
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REFERENCES FOR 4.4
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TN: Environmental Sciences Division, Oak Ridge National Laboratory;
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and polycyclic aromatic hydrocarbons on the survival and development
rate of larvae of the mud crab Rhthropanopeus harrisil. Marine
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London: Applied Science Publishers, 1979.
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to the polychaete neanthes arenaceodentata. Mar. Pollut. Bull. 9:
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pollutants: comparative toxicity of fluorene, dibenzofuran, dibenzo-
thiophene and carbazole to estuarine crustaceans and fish (unpublished
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U.S. Environmental Protection Agency (U.S. EPA). Ambient water quality
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EPA; 1980b.
4-114
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APPENDIX A
NOTE 1: Acenaphthene, fl uoranthene, fluorene, phenanthrene, and
pyrene are not listed in the 1979 edition of the U.S. International
Trade Commissions' Synthetic Organic Chemicals Production and Sales
Publication (USITC, 1979). Consequently, according to a spokesperson
for that Commission (Edmund Cappuccil1i), these chemicals most likely
were not produced domestically; and any plants producing them would
have made <1 kkg (i.e., <2,200 pounds).
NOTE 2: According to an Allied Chemical Corporation spokesperson
(Dick Ritchie), Allied sells all of the anthracene they recover from
coal tar to Toms River Chemical Corporation. A spokesperson (William
Hagman) from that corporation confirmed that statement and said they
receive the anthracene from Allied via alcarri; each holds 40 tons.
More than 100 kkg of anthracene were produced and shipped to Toms
River Chemical Corporation in 1979.
NOTE 3: Acenaphthene is used as a starting material in the
production of four pigments:
Acenaphthenf
~naphthalic-
anhydride
~naphthalimide
pigment brown 26 (CI 71129);
Acenaphthene—~ 5,7-diketo-lH-cyclopenta-[cd]-phenalene ~
1,4,5,8-naphthalene-tetracarboxylic acid—~vat red 14 (CI 7110)
potassium hydroxide
ethanol
-pigment vat orange 7 (CI 71105)
~vat red 15 (CI 71100)
Source: EPA, 1977d; USITC, 1979.
NOTE 4: Acenaphthene was found in influent wastewaters from
3 of 26 pharmaceutical plants in the following concentrations: 135,
2, and 92 ug/£. The flow rates of the wastewaters for those plants
were 378,500, 189,250, and 37,850 1/day, respectively. These plants
were assumed to operate 360 days/year. Therefore, with an average
concentration of 76 ug/l and annual flow rate of 72,670,000 a, 5 kg of
acenaphthene were contained in influent wastewaters generated by three
pharmaceutical plants. If the ratio of 3 plants of the 26 plants
sampled represents the entire industry (464 plants), then 54 plants
possibly generated wastewaters (influent) that contained 270 kg or <1
4-115
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kkg of acenaphthene. Furthermore, because these wastewaters were
treated to remove this compound, acenaphthene was
probably not discharqed to water (EPA 1980e).
NOTE 5: Of all the PAHs shown in Table A-2, acenaphthene was
contained in pharmaceutical influent wastewaters at the highest
concentration (i.e., 270 kg, derived in Note 4). If acenaphthene
represents a worst case scenario, then <1 kkg each of anthracene,
fluoranthene, fluorene, phenanthrene, and pyrene was contained in
pharmaceutical industry influent wastewaters. Furthermore, because
these compounds were not found in pharmaceutical effluent wastewaters,
it is assumed that these chemicals are not released to aquatic
environments. Also, because pharmaceutical wastewater treatment
facilities usually remove chemicals and deep well inject or lagoon
them, the <1 kkg of each chemical removed is assumed to be disposed to
1 and.
NOTE 6: Pyranthrone (CI Vat Orange 9), a comnermical 1y important
dye, can be prepared by condensation of pyrene with benzoyl chloride
and aluminum chloride to give dibenzoyl-pyrene, which upon heating
with aluminum chloride provides pyranthrone (Chung and Farris 1979).
Pyranine (CI 59040, Ext. D+C Green 1) is another dye in which pyrene
is used as a starting material:
Pyrene ~ 1,3,6,8-tetrasulfonic acid
pyranine.
Source: EPA 1977d.
NOTE 7:
a. Oil:
Water figure based on 3.6 x 107 i of various oils -
crude (36%), diesel (18%), fuel (42%), waste (2%), lube
(0.3%) other (1.7%)- spilled in navigable waters in 1978
(U.S. Coast Guard, 1980).
Land figure based on 5.1 x 105 i of crude oil spilled in
1978 by common carrrier (23%), private carrier (22%), rail
(6%), and "other" (49%) (U.S. Dept. of Transportation,
1980). Average oil Density = 0.85.
Gasoline:
Water - 1.1 x 107 z spilled: aviation/automobile
gasoline (98%) and natural (Casinghead) Gasoline (2%) (U.S.
Coast Guard, 1980).
4-116
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Land - 3.7 x 106 % spilled: common carrier (53%),
private carrier (47%), rail (0.8%), "other" (<0.01%) U.S.
Dept. of Transportation, 1980). Gasoline density: 0.73.
NOTE 8:
Residential Coal Combustion
Emissions were calculated from the emission factors in Table
A-8 (EPA 1977a) and the value 8,688 x 10^ kkq of coal consumed
for residential combustion (DOE 1980.)
Fireplaces
Emissions were calculated from emission factors (see Table
A-8) that represented the averaqe of three tests (EPA 1980b), The
total mass of wood burned in fireplaces in 1976, 2.7 x 106 kkg
(EPA 1980a) was extrapolated to 1977, based upon the number of housing
units in each region of the country, the percentage of those housing
units with fireplaces (see Table A-10), an average consumption of
98.3 kg/housing unit (EPA 1980a). These assumptions led to the
estimate that 3.0 x 106 kkg of wood were burned in 1977.
Residential Primary and Auxiliary Heat from Wood
Emissions from these sources were calculated using the emission
factors presented in Table A-9 and 1977 wood consumption of 6.9 x
106 kkg and 9.2 x 106 kkg for primary and auxiliary heating,
respectively. The emission factors presented in Table A-8 are
averages of those for baffled and nonbaffled wood stoves (EPA 1980a).
Total 1977 wood consumption for primary heating was obtained from the
number of housing units that used wood for primary heat in 1976 and
1977 (912,000 and 1,239,000) a proportional extrapolation of the
estimated 5.1 x 106 kkg of wood burned in 1976 to 6.9 x 106
kkg for 1977 (EPA 1980a and Census 1979). Total 1977 wood consumption
for auxiliary heating (9.2 x 106 kkg) was extrapolated from the
1976 estimate of 8.5 x 10*> kkg (EPA 1980a) on the basis of the
increase in the number of houses with fireplaces (see Fireplaces).
Cigarettes
The emission factors for cigarette smoking shown in Table
were used along with the number of cigarettes produced (616 x 109)
(USDA 1979). The emission factors are all from Neff (1979), except
that for naphthalene, which is from Schmeltz, et al_. (1978)'.
4-117
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Coal Refuse Piles
Using the composition of the particulate polycyclic organic matter
(POM) shown in Table A-8, emissions were calculated based upon a refuse
pile volume of 190 x 10^ m^ (21% of which is estimated to be burning),
a density of 1.5 kkg/m^, and a POM emission rate of 1.3 x 10*8 kg/kkg-hr
(EPA 1978a). Only particulate emissions were analyzed here, and only
preliminary sampling data are presented.
Carbon Black
An estimated 1.0 x 10^ kkg of carbon black were produced in 1977
(SRI 1979). The emission factors in Table A-8 (Serth and Hughes 1980)
were used to estimate PAH emissions, although the resulting estimates
are limited by the fact that testing was performed upstream of an
emissions control device (burner).
An estimate of PAH production associated with carbon black
manufacture is presented in Table A-10.
NOTE 9:
Prescribed Burning
The emission factors in Table A-8 (EPA 1978a) and an estimated
36 x 10° kkg (dry weight) of fuel burned by prescribed burning
(Pierovich 1978) were used to estimate emissions. Note that this does
not include agricultural burning.
NOTE 10:
Wildfi re
The emission factors in Table A-8 (McMahon and Tsoukalas 1977)
are averages obtained from six tests on pine needles with differing
fuel densities used for heading and backing fires; hence these factors
cannot provide an accurate basis for nationwide emissions estimates.
The total amount of fuel burned was estimated by assuming that 10'" nr
(3 x 106 acres) of land were burned on the average (Dahl 1980), and that
the fuel loading was 2 kg dry weight consumed/m^ (based upon estimates
by EPA 1978b).
4-118
-------
NOTE 11:
Tire Wear
A crude estimate of PAH emission from tire wear associated with
carbon black (see Table A-11) was developed from the following data:
- 365 da/yr.
- 7.4 x 10x6 bbl/da gasoline consumption (Oil and Gas
Journal 1979).
- 14.7 miles/gal average (EPA 1975).
- 42 gal/bbl.
- 0.34 g/vehicle-mile weight loss from tires of which 0.19
g/vehicle-fnile is airborne particulates and 0.15
g/vehicle-mile is deposited on road surface (EPA 1979a).
- Rubber composed of 33% carbon black (SRI 1979).
- Average PAH composition of carbon black in Table A-12
(Locati et a]_. 1979).
NOTE 12:
Agricultural Open Burning
Emissions were calcualted on the basis of the forest fire
emission factors in Table A-3 and an estimated 13 x 106 kkq (dry weight)
material burned. (EPA 1977b).
NOTE 13:
Motor Vehicles
Motor vehicle PAH emissions were calculated by using the emission
factors in Table A-8 (Hangebrauck 1977), an estimated 2.7 x
10*5 meters/yr travelled (see note on tire wear for estimation of
vehicle miles travelled), and an assumed emission reduction of two
thirds. This emission reduction was based upon the following
i nformation:
Fraction of Automobile
Population Control Present Reduction
0.32 catalytic Converter 99
0.58 Engine Modification 65
0.10 None 0
The automobile population is from EPA (1978b), and the percent
reductions are based on ranges given in that document.
4-119
-------
The concentrations of PAHs in used crankcase oil are shown in
Table A-12. Releases to sewers and landfills were assumed to account
totally for 2 x 1(F £ of oil disposed of by the public (Tanacredi 1977);
however, this figure does not take into account used oil that is
recycled.
NOTE 14:
Coal- and Oil-fired Utility Boilers
The estimates of total PAHs released to the environment are based
upon the emission factors averaged from Table A-l4 and a total coal and
oil consumption for electricity generation of 4.8 x 10° and 7.8 x 10' kkg
per year, respectively (Monthly Energy Review 1980).
These emissions are uncontrolled releases calculated from 1967
emissions factors and are probably lower today with the use of baghouses
or electrostatic precipitator units. Further, the emission factors for
oil are for small- or intermediate-sized units, and thus serve as an
upper limit of the PAH releases from higher capacity plants.
NOTE 15:
Municipal Incinerators
Releases were calculated from the release factors in Table A-l 3
(Davies 1976) for 104 plants with an average capacity of 385 kkg/day
operating at full capacity {EPA 1978b).
Commercial Incinerators
Releases were assumed to be similar to those from municipal
incinerators. Even using the higher emission factors in Table A-13,
emission of any given PAH was negligible without controls. The
population was assumed to be 100,000 units, firing 3 hours/day,
260 days/yr at an average capacity of 0.1 kkg/hr (EPA 1978b).
4-120
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Table A-l. Frequency of Select PAHs in the Pharmaceutical
Industry3
Usageb
Pollutant
As raw Material In
Final Product
Acenaphthene
1
Anthracene
1
1
Fluoranthene
1
Fluroene
1
Phenanthrene
1
Pyrene
1
a) Four-hundred and sixty-four U.S. pharmaceutical
plants existed at
the time the data was collected where 212 plants responded to the
questionnaire.
b) Number of positive responses obtained from 212 U.S. pharmaceutical
plants.
Source: EPA 1980e.
4-121
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Table A-2.
Quantities of Select PAHs Released from US Pharmaceutical Industries in 1979 (kkg)a
Environmental Releases (kkg)c
Detection
c
Quantity Contained (kkg)
Water Land Air
Pollutant
Frequency'5
Influent
Effluent
Surface POTW
Acenaphthene
3/26
<1
ND
<1
Anthracene
1/26
<1
ND
<1
F1uoranthene
0/26
<1
ND
<1
F1uorene
2/26
<1
ND
<1
Phenanthrene
1/26
<1
ND
<1
Pyrene
0/26
<1
ND
<1
a) Based on screening/verification data of wastewater samples from 26 of the 464 US pharmaceutical
plants. EPA 1980e.
b) Number of times the pollutant was detected in samples from 26 plants.
c) See Notes 4 and 5, Appendix 4 for calculations; ND = not detected with a detection limit of 10 pg/1.
-------
e A-3. Coke-Oven Tar Produced in the United States, Used by Producers, and Sold in 1978, By State
(Thousand Liters)
Produced
Used by Producers
Sold for Refining
Into Tar
Products
Value
L/kkg of
For Refinery
As
Thousand
Average
On-hand
Total
Coal Coked
or Topping
Fuel
Other
quantity
Dollars
Per Liter
Dec. 31
State
Alabama
- 130,000
27
a
.
130,000
5 11,970
$0.09
9,700
Calif., Colo., Utah
- 130,000
35
-
-
-
130,000
11,905
0.09
13,000
111Inols
- 59,000
25
-
-
-
60,000
5,593
0.09
5,700
Indiana
- 350,000
33
a
a
a
120,000
12,840
0.11
21,000
Ken., Mo., Tenn., Tex.—
- 34,000
25
-
a
-
31,000
3,021
0.10
2,700
Maryland, New York
- 170,000
32
-
a
-
120,000
12,911
0.11
25,000
Michigan
a
a
-
-
-
a
a
a
a
Minnesota, Wisconsin
- 20,000
23
-
a
-
19,000
1,938
0.10
a
Ohio
- 330,000
31
-
170,000
a
180,000
17,529
0.10
27,000
Pennsylvania
- 580,000
35
a
a
a
280,000
29,425
0.11
55,000
Virginia, West Virginia-
a
a
a
-
-
a
a
a
5,700
Undistributed
- 240,000
30
500.000
190,000
32,000
150,000
12,904
0.09
14,000
Total (1978) b
2,100,000
44
500,000
360,000
32,000
1,200,000
120,036
0.10
180,000
At Merchant Plants
89,000
34
c
_
89,000
8,986
0.10
4,900
At Furnace Plants
2.000.000
44
500.000
360.000
32.000
1.100.000
111,050
0.10
170.000
Total (1977)b
2,200,000
32
570,000
550,000
38,000
1,100,000
106,728
0.10
160,000
a) Included with "Undistributed" to avoid disclosing Individual company data.
bj Data may not add to totals shown due to Independent rounding.
c) Included with "Furnace Plants" to avoid disclosing Individual company data.
Source: DOE 1979.
-------
Table A-4. Concentrations of Various PAHs in Coal and Coal Tar Derivatives (mg/kg)a
Coal
Coal Tar
Creosote
Coal
Tar
Pitch
Oil
Acenaphthene
io,ooo|>
40,000°
Anthracene
9,000®
20,000c
Phenanthene
30,000"
100,000°
<3 ^
Benzo[a]anthracene
<0.007"
<10^
Benzo[a]pyrene
0.7
30*J
10^
nggd.e
Chrysene
4,000
<10d
Fluoranthene
6,000b
10,000°
40,000°
F1uorene
30,000c
Naphthalene
90,000
200,000°
Pyrene
3,0009
30,000°
a) All numbers rounded to one significant figure; blank spaces = data not available.
b) Sources: Rhodes 1954; Lowry 1945 (averaging of data).
c) Source: Stasse 1954; as cited in Weiler 1963.
d) Source: IARC 1973.
e) Less than 0.01 ppni.
f) Source: Rhodes 1954; and Lowry 1945.
g) Source: Rhodes, 1954.
-------
Table A-5. PAH Wastewater Discharge: By-Product Cokemaking3
Ammonia Liquor
Discharge Factors (kg/kkg coke)
Cooler Blowdown
Benzol Plant
(kkg) Total Discharge
Acenaphthylene
0.00073
0.000097
0.000129
40
Benzo[a]anthracene
0.000006
0.000032
0.000125
7
Benzo[a]pyrene
0.000032
0.000024
ND
3
Chrysene
0.000045
0.000018
0.000155
10
Fluoranthene
0.000196
0.000323
0.000189
30
Fluorene
0.000145
0.000048
0.000049
10
Naphthalene
0.00395
0.0115
0.00341
800
Pyrene
0.000393
0.000026
0.000109
20
a) Based on the total of three factors and a 1978 coke production of 44.5 x 106 kkg (DOE 1979). Distribution:
33%-direct, 25%-POTWs, 2%-deep wel1, 40% quenching (20% land, 20% air) (EPA 1979d).
Source: EPA 1979d.
-------
Table A-6. Concentration of Select PAHs in Petroleum Products, mg/kg
Crude Oil
Gasoline
Kerosene
Petroleum
Asphalt
Diesel
Fuel
Number
Heatinc
Acenaphthene
NDa
Acenaphthylene
400
Anthracene
trace
3
0.4
3
4
Benzo(a)anthracene
trace
3
<0.1
0.04
0.1
0.04
Benzo(b)fluoranthene
<5
Benzo(k)fluoranthene
<5
Benzo(ghi Jperylene
.02
2
<0.1
0.03
0.03
Benzo(a)pyrene
1
2
0.01
0.01
0.07
0.03
Chrysene
<100
2
ND
0.02
0.5
0.6
Di benzo(a,b)anthracene
,F1 uoranthene
100
7
0.09
0.5
2
F1uorene
200
Indeno[l ,2,3-cd]pyrene
Naphthalene
1,000
Phenanthrene
100
ND
ND
ND
Pyrene
100
5
0.2
0.4
1
a) ND means not detected.
Source: Guerin 1978; Guerin et al. 1978; EPA 1979f
-------
Table A-7. Emissions of PAHs from Catalyst Regeneration in Petroleum Cracking, ug/m^ Oil Charges
Type of Unit Benzo(a) Benzo(ghi)- Anthra- Phenan- Fluoran-
pyrene Pyrene perylene cene threne thene
FCC :a
Regenerator outlet 0.7 - 73 6.4 - 24-67 63,560 7.0 - 3,180
4,450
Carbon monoxide boiler
outlet 1.7 - 3.4 3.9 - 26 8.8 330 3.2 - 13
HCC:
b
Regenerator outlet 32,600 - 20,700 - 47,700 - 146 - 3,340 - 1,320 -
36,700 20,800 60,400 318 4,600 1,810
TCC:c
Air lift, regenerator
outlet 8,900 - 21,000 - 7,000 - 1,640 - 52,500 - 1,685 -
19,100 41,300 11,450 1,685 56,000 4,610
TCC:
Brucket lift, regen-
erator outlet 5 46-57 9.17
NOTE: Blanks indicate data not available. Emission factors used are arithmetic averages over the four
types of units listed.
a) Fluid catalytic cracking.
b) Houdriflow catalytic cracking.
c) Thermofor catalytic cracking.
Source: Hangebrauck, et al. 1967.
-------
Table A-8.
Emission Factors
Primary and
Coal
Residential
Auxil iary
Refuse
Forest
Carbon
Coal
Wood
Piles
F i reg)
Black
Gasoline
Combustion
Fireplaces
Heating
Cigarettes
(kg/kg)
(ng/g)
yg/g
(ng/m)
(q/kg)
(gAg)
(g/kg)
(ug/cig)
POM
(dry fuel)
Acenaphthene
0.039
0.0012
0.0076
Acenaphthylene
0.010
0.057
800
Anthracene3
0.008
0.010
0.076
0.17
0.1
2,500
35
4.3
Benzo[a]anthracene
0.002
0.0008
0.0071
0.02
3,100
4.5
Benzo[b]f1uoranthenec
0.002
0.0008
0.0058
0.01
1,300
15
Benzo[k]fluoranthene
0.002
0.0008
0.0058
0.01
1,300
15
Benzo[ghi]perylene
0.0009
0.0053
2,500
12
47
Benzo[a]pyrene^
Chrysene"
0.0015
0.0008
0.0040
0.01
0.005
740
11.5
0.002
0.008
0.0071
0.02
3,100
4.5
Dibenzo[a,h]anthracenee
0.003
0.0001
0.0007
<0.001
F1 uoranthene
0.005
0.0028
0.019
0.01
0.05
5,500
60
75
F1uorene
0.026
0.0047
0.016
Indeno[l,2,3-cd]pyrene
0.002
ND
ND
0.006
<0.001
1,700
<2
Naphthalene
0.15
0.0403
0.25
3
Phenanthrene
0.008
0.010
0.076
0.36
0.1
2,500
35
30
Pyrene
0.005
0.0028
0.016
0.16
0.05
4,600
500
110
a) Reported as anthracene/phenanthrene, assumed equal division between them.
b) Reported as chrysene/benzo[a]anthracene, assumed equal division between them.
c) Reported as benzo fluoranthenes, assumed divided solely between benzo[b]fluoranthene and benzo[k]fluoranthene.
d) Reported as benzopyrene(s) and perylene, assumed to be 50% benzo[a]pyrene.
e) Reported as dibenzanthracene, assumed to be solely dibenzo[a,h]anthracene.
Sources listed in Appendix 4 text.
-------
Table A-9. Fireplace Population
Region
Number of
Housing
Units (1977)
Percentage
w/Fireplace
Fireplaces
Northeast
17,707,000
47
8,300,000
North Central
21,181,000
33
7,000,000
South
26,422,000
29
7,700,000
West
15,406,000
46
7,100,000
Total
30,100,000
Sources: Census 1979 and EPA 1980a
4-129
-------
Table A-10. PAH Associated with Carbon Black (pg/g)a
Carbon
PAH Black
Type
Vulcan J
Regal 300
330 HAF
660 GPF
339
Avg
Contained in
Carbon Black (kkg)
Anthracene^
0.5
ND
0.05
ND
1
0.3
0.5
Benzofluoranthenes
10
ND
<0.9
4
7
4
6
Benzo[ghi]perylene
166
16
25
41
164
82
100
Benzopyrenes
20
1
3
8
32
17
30
F1uoranthene0
68
9
10
13
52
30
50
Indenopyrene
24
1
0.3
7
35
13
20
Phenanthrene
0.5
ND
0.05
ND
1
0.3
0.5
Pyrene
314
58
47
52
207
140
200
a) Based 1.6 x 106 kkg carbon black production (SRI 1979).
b) Reported as anthracene/phenanthrene, assumed equal division among them.
c) Excluding benzo[ghi]fluoranthene, reported separately.
Source: Locati et al. 1979
-------
Table A-ll. PAH Releases From Tire Wear (kkg)a
Sedimentary or
Airborne directly trans-
Initial Reentrained ferred to Roadway Total
Anthracene
Benzofluoranthenes
Benzo[ghi]perylene 1
Benzopyrenes 0.3
Fluoranthene 0.5
Indenopyrene 0.2
Phenanthrene
Pyrene 2
7 7 20
1 1 3
3 2 6
1 1 2
10 10 20
See Appendix text for calculations and sources
a) Blanks indicate <1 kkg/yr. For all entires, totals may not add due
to rounding.
4-131
-------
Table A-12. Concentrations of PAHs in Used Crankcase Oils (mg/1)
Anthracene
0.3
Benzo[a]anthracene
0.9
Benzo[k]fluoranthene
1.4
Benzo[ghi]perylene
1.7
Benzo[a]pyrene
0.4
Chrysene
1.2
F1uoranthene
4.4
Fluorene
1.5
Phenanthrene
7.8
Pyrene
6.7
Source: Peake and Parker 1980.
4-132
-------
Table A-13. Municipal Incinerators Release Factors (ng/kg refuse)
Environmental Release Factors (pg/kcr refuse)
Aira Land Waterb
Benzo[a]anthracenec
1.5
18
0.08
Benzo[b]fluoranthened
0.5
21
0.01
Benzo[k]fluoranthened
0.5
21
0.01
Benzo[ghi]perylene
1.8
10
0.007
Benzo[a]pyrenee
0.04
16
0.016
Chrysenec
1.5
18
0.08
F1uoranthene
2.5
12
0.14
Indeno[l,2,3-cd]pyrene
0.77
<2.1
<0.002
a) After scrubber.
b) Taken as one half reported benzo[a]anthracene + chrysene emissions.
c| Taken as one third of benzo[b+k+j]fluoranthene emissions.
d) Taken as one half of benzo[a+e]pyrene emissions.
e) Scrubber water.
Source: Davies 1976.
4-133
-------
Table A-14. Emissions of PAHs from Coal-Fired Plants and Intermediate/Smal1 Oil-Fired Units
(ug/109 J Fuel)
Benzo[a]- Benzo[ghi]- Phenan- Fluoran-
Type of Unit pyrene Pyrene perylene threne thene
Pulverized coal (vertically-fired,
dry-bottom furnace) 18 - 123 70 - 218 79 80 - 389
Pulverized coal (front-wall-fired,
dry-bottom furnace) 16 - 20 152 - 190 13 190 12 - 152
Pulverized coal (tangentially-
fired, dry-bottom furnace) 123 133 142 30 370
Pulverized coal (opposed-, down-
ward inclined burners; wet
bottom furnace) 20 - 133 37 - 114 142 - 1,042 52 - 199
Crushed coal (cyclone-fired,
wet-bottom furnace) 72 - 351 237 - 1,706 34 - 341 42 - 104
Spreader stoker (traveling
grate) <14 - 23 20 - 56 20 - 56
Oil-fired:
Steam atomized
Low pressure air atomized
Pressure atomized
Vapori zed
<19 - 45
853
<38 - <57
<95
46 - 284
5,780 285
14 - 1,700
1,140
1,700
3,320
8,440
53 - 256
1,800
72 - 4,470
14,200
NOTE: Blanks indicate data not available.
Source: Hangebrauck et al. 1967.
-------
APPINDIX B. APPLICATION OF THE AIR-TO-SURFACE PATHWAY EVALUATION
METHOD FOR POLYNUCLEAR AROMATIC HYDROCARBONS
A method has been developed for estimating airborne toxicant
deposition rates (air-to-surface pathway evaluation method, Arthur D.
Little, Inc., 1981). The method accounts for both wet and dry
deposition to land and water surfaces. When deposition to a water-
shed or other land area is estimated, this can be interpreted as an
upper bound on the chemical loading to an associated surface water
body resulting from air deposition, since only a fraction of the
mass deposited on land surfaces will be delivered to the water body.
The air-to-surface pathway evaluation method accounts for the parti-
tioning of an airborne contaminant between adsorbed and vapor phases,
with differing deposition rates inferred for the separate phases. It
relies on fundamental physicochemical properties and is designed to
use available data, while filling in data gaps with estimated values of
various parameters. The evaluation method has been applied to naphtha-
lene, anthracene, and benzo[a]pyrene. Each of the three PAHs modeled has
an atmospheric chemical degradation of roughly 0.1 hr.~l leading to half-
lives of 5-10 hours (Radding et al. 1976). Under typical meteorologic con-
ditions this corresponds roughly to the travel time across major urban areas.
Since urban areas also would be expected to have much greater emission
densities than rural areas, significant urban/rural differences in air
concentrations of PAHs are expected, and indeed observed. These factors
suggest that deposition rates under urban and rural conditions should
be considered separately.
One of the most important chemical properties influencing air-to-
surface transfer is the vapor pressure. The vapor pressure affects the
partitioning of airborne contaminants between vapor and adsorbed phases.
The deposition rate is typically much greater for the adsorbed fraction
of the airborne contaminant. The effect of vapor pressure is expressed
by equation (5) of the Arthur D. Little report (1981):
. .1659
* = P0 + .165
where
is the adsorbed fraction of the total airborne mass,
cm2
0 is the available aerosol surface area —t and
cm-J
p0 is the saturation vapor.pressure of the contaminant at
ambient temperature (torr)
The available aerosol surface area is typically greater in urban
areas where concentrations of total suspended particulates are higher
4-135
-------
than in rural areas. In the plume from a combustion source, the aerosol
surface area is even higher than typically found in urban air. Appli-
cation of the above equation results in aerosol partitioning for the
three FAHs as shown below:
Adsorbed Fraction of Total Airborne Mass
PAH
Rural
Urban
Near Combustion Sources
-6
-4
Naphthalene
7x10 °
3x10
0.02
Anthracene
0.002
0.06
0.97
Benzo[a]pyrene
.99
1.00
1.00
Benzo[a]pyrene is strongly partitioned with the aerosol phase, regard-
less of ambient conditions, while at the other extreme naphthalene
exists primarily as a vapor in the atmosphere. Anthracene exhibits
intermediate properties, and the adsorbed fraction is sensitive to
ambient conditions.
The dry deposition flux is proportional to the dry deposition
velocity, , i.e.,
Dry Flux = V, C .
d air
where
Ca^r is the ground-level air concentration.
The dry deposition velocity with respect to the total airborne con-
taminant is calculated as the (mass) weighted average of the deposition
velocity for the vapor and sorbed fractions, i.e.,:
Vd * Vd,s* + Vd,v (1-«
(Eq. 6 of Arthur D. Little 1981)
According to the air-to-surface pathway method (Arthur D. Little
1981), the respective dry deposition velocities are given below:
Dry Deposition Velocity
PAH
d,v
(cm/sec)
d,s
(cm/sec)
Rural
Urban
Combustion
Source
Naphthalene
0.04
1
0.04
0.04
0.06
Anthracene
0.02
1
0.02
0.08
1.00
Benzo[a]pyrene
0.02
1
1.00
1.00
1.00
4-136
-------
Wet deposition is controlled by the precipitation scavenging
ratio, r, which expresses the ratio of pollutant concentration in
precipitation (ng/1) to pollutant concentration in air (pg/m^). The
scavenging ratio is calculated by contributions from the vapor and
sorbed fractions, i.e. :
r = r () + r (1-$)
s v
where r, rs and ry are scavenging ratios for the total airborne mass,
the sorbed contaminant, and the vapor phase, respectively. Once the
scavenging ratio is known, the wet deposition flux is given by wet
flux = rRCa^r, where R is the rainfall rate. These parameter values
have been estimated, as shown below:
Precipitation Scavenging Ratios
r
r *
Combustion
PAH
s
V
Rural
Urban
Sources
Naphthalene
6x10*
53
53
71
2.5x103
Anthracene
6xl04
14
130
3.6x10"*
1.2xl05
Benzo[a]pyrene
6xl04
5.4xl04
6xl04
6x10 4
1.2xl05
For the purpose of further analysis a generic urban environment
has been modeled on the basis of characteristics of Philadelphia and
Cleveland. The average wind speed is 10.25 kts (5.3 m/s) and the
annual rainfall is 1.0 m/yr. The urban area is 100 nri.2 (2.6 x 10® m^).
The generic rural area is defined as a volume of air within which
an associated urban source would contribute to rural concentrations.
The size of the area is constrained by the half-life in air, such that
the concentration is typical of an area significantly affected by the
urban source. At a half-life of 5 hours, and typical wind speed of 5.3
m/sec., naphthalene contamination from an urban area could be significant
over an area of 10 ^ m^ (roughly 40,000 square miles).
Median observed ambient concentrations for three PAHs in urban and
rural areas are presented below (White and Vanderslice 1980):
'Tabulated rs values apply for rural and urban conditions. Near a com-
bustion source the adsorbed phase is expected to be associated with
larger particles resulting in a scavenging ratio, rs = 1.2x10 .
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Median Observed
Concentration (ug/m3)
PAH
Rural
Urban
Naphthalene
7xl(T5
5xl0-4
Anthracene
lxlO~3
8x10"3
Benzofa]pyrene
lxlCf3
lxlO-2
Using the pathway evaluation method we have estimated the emission
that would result in a specific ambient concentration, given the degra-
dation rate, deposition velocity, rainfall rate, and precipitation
scavenging ratio. Applying the equation for wet flux and dry flux we
also estimated the amount deposited in the generic rural and urban study
areas. Then, by comparison of the deposition rates with emission rates,
we estimated the fraction of total atmospheric emissions of each of the
three PAHs which would be deposited within the urban and rural study
areas. These results are shown below:
Deposition Rate
% of
Emissions
% of
Emissions
Dry Deposited
Wet Deposited
% Deposited
PAH
Rural
Urban*
Rural
Urban
Rural
Urban
Naphthalene
2
2-3
<1
<1
2
2-3
Anthracene
1
4-19
<1
1-7
1
5-26
Benzo[a]pyrene
22
19
4
4-7
26
23-26
From the results above, it is apparent that a very small fraction
of atmospheric emissions of naphthalene are deposited on land or water
surfaces. The fraction of air emitted anthracene that is eventually
deposited is uncertain, but could be fairly large percentage. Approxi-
mately one-fourth of all benzo[a]pyrene emitted into the atmosphere
will eventually be deposited on land and water surfaces, where it would
contribute to the contamination of surface runoff and surface water
bodies.
*The range for urban areas reflects alternative assumptions that the
chemical has equilibrated with ambient aerosol or remains associated
with particulates in the plume from the combustion zone.
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APPENDIX
REFERENCES
Arthur D. Little, Inc. Air-to-surface pathway evaluation methodology.
Draft final reporr. Contract No.68-01-5949. Washington, DC: Monitoring
and Data Support Division, Office of Water Regulations and Standards,
U.S. Environmental Protection Agency; 1981.
Radding, S.B.; Mill, T.; Gould, C.W.; Liu, D.H.; Johnson, H.L.; Bomberger,
D.C.; Fojo, C.V. The environmental fate of selected polynuclear aromatic
hydrocarbons. Washington, D.C.: Office of Toxic Substances, U.S. Environ-
mental Protection Agency; 1976.
White, J.B.; Vanderslice, R.R. POM source and ambient concentration
data review and analysis. Research Triangle Park, NC: U.S. Environ-
mental Protection Agency; 1980.
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