EPA-440/4-b b-02 0
June 1981
(Revised Occober
1982)
AN EXPOSURE AND RISK ASSESSMENT FOR BENZO[ajPYRENE AND
OTHER POLYCYCLIC AROMATIC HYDROCARBONS:
VOLUME II. NAPHTHALENE
By
Susan Coons, Melanie Byrne, 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 ana 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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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
¦ iX/
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30373 -101
REPORT DOCUMENTATION
PAGE
1. REPORT NO.
EPA-440/4-85-020 - j/X
3. Recipient's Accession No.
5 222560/i!S
4. Title and Subtitle
An Exposure and Risk Assessment for Benzo [a]pyrene and Other
Polycyclic Aromatic Hydrocarbons: Volume II. Naphthalene
a. Report o«t« Final Revision
October 1982
7. Authorti) Coons, S.; Byrne, M. ; Goyer, M. ; Harris, J.; Perwak, J.
(ADL) Cruse, P.; DeRosier, R.; Moss, K.; Wendt, S. (Acurex)
8. Performing Orga
Rapt. No.
9. Performing Organization Name and Address
Arthur D. Little, Inc.
20 Acorn Park
Cambridge, MA 02140
10. Project/Task/Work Unit No.
Acurex Corporation
485 Clyde Avenue
Mt. View, CA 94042
11. ContractfC) or GranMQ) No.
(a C-68-01-6160
C-68-01-6017
(G)
12. Sponsoring Organization Name and Address
Monitoring and Data Support Division
Office of Water Regulations and Standards
U.S. Environmental Protection Agency
Washington, D.C. 20460
IX Type of Report & Period Covered
Final
14.
IS. Supplementary Note*
Extensive Bibliographies
16. Abstract (limit 200 word*)
This report assesses the risk of exposure to polycyclic aromatic hydrocarbons (PAHs).
This is Volume II of a four-volume report, analyzing 16 PAHs; this volume concerns
naphthalene. 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 substance. In addition, the fate of naphthalene
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 naphthalene
for various subpopulations.
17. Document Analysis a. Descriptors
Exposure
Risk
Water Pollution
Air Pollution
b. I dent! fieri/Open-Ended Terms
Pollutant Pathways
Risk Assessment
e. COSAT1 Field/Group Qgjr 06T
Effluents
Waste Disposal
Food Contamination
Toxic Diseases
Polycyclic Aromatic Hydrocarbons
Naphthalene
PAHs.
JU
IS. Availability Statement
Release to Public
19. Security Class (This Report)
Unclassified
20. Security Class (This Page)
Unclassified
21. No. of Pages
115.
22. Price
(See ANSI—Z39.18)
See instructions on Reverse
OPTIONAL FORM 272 (4-77)
(Formerly NT1S-3S)
Deportment of Commerce
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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 includes
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. It has been
extensively reviewed by the individual contractors ?nd 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 FPA 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. Slimak, Chief
Exposure Assessment Section
Monitoring & Data Support Division (WH-553)
Office of Water Regulations and Standards
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Intentionally Blank Page
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AN EXPOSURE AND RISK ASSESSMENT FOR BENZO[a]PYRENE AND
OTHER POLYCYCLIC AROMATIC HYDROCARBONS
VOLUME I
SUMMARY
1.0 Introduction
2.0 Technical Summary
VOLUME II Naphthalene
3.0
VOLUME III
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
4.0
VOLUME IV
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,
3enzo[b]fluoranthene, Benzo[kjfluoranthene, 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 3iota
5.5 Risk Considerations
v
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Intentionally Blank Page
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TABLE OF CONTENTS
VOLUME II
LIST OF FIGURES ix
LIST OF TABLES x
ACKNOWLEDGMENTS xii
1.0 INTRODUCTION 1-1
3.0 NAPHTHALENE 3-1
3.1 MATERIALS BALANCE 3-1
3.1.1 Introduction 3-1
3.1.2 Production 3-2
3.1.2.1 Overview 3-2
3.1.2.2 Environmental Releases from Production 3-3
3.1.2.3 Inadvertent Sources of Naphthalene 3-3
3.1.3 Uses 3-5
3.1.3.1 Phthalic Anhydride 3-5
3.1.3.2 Carbaryl Insecticide 3-8
3.1.3.3 Synthetic Tanning Agents 3-9
3.1.3.4 Moth Repellent 3-9
3.1.3.5 6-Naphthol 3-11
3.1.3.6 Surface Active Agents 3-12
3.1.3.7 Miscellaneous Organic Chemicals 3-12
3.1.4 Flow Through POTWs 3-13
3.1.5 Summary 3-13
3.2 FATE AND DISTRIBUTION IN THE ENVIRONMENT 3-16
3.2.1 Introduction 3-16
3.2.2 Input to Aquatic Media 3-16
3.2.3 Environmental Fate 3-19
3.2.3.1 Basic Physical/Chemical Properties 3-19
3.2.3.2 Pathways in the Aquatic Environment 3-19
3.2.3.3 Modeling of Environmental Distribution 3-34
3.2.4 Monitoring Data 3-45
3.2.4.1 STORET Data 3-45
3.2.4.2 Other Data Sources 3-50
3.2.5 Summary - Ultimate Fate and Distribution 3-50
3.3 EFFECTS AND EXPOSURE—HUMANS 3-54
3.3.1 Human Effects 3-54
3.3.1.1 Introduction 3-54
3.3.1.2 Pharmacokinetics 3-54
3.3.1.3 Human and Animal Studies 3-54
vii
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TABLE OF CONTENTS (Continued)
Page
3.3.2 Human Exposure 3-61
3.3.2.1 Introduction 3-61
3.3.2.2 Ingestion 3-61
3.3.2.3 Inhalation 3-62
3.3.2.4 Dermal Contact 3-63
3.3.2.5 Overview 3-63
3.4 EFFECTS AND EXPOSURE—AQUATIC BIOTA 3-66
3.4.1 Effects on Aquatic Organisms 3-66
3.4.1.1 Introduction 3-66
3.4.1.2 Freshwater Organisms 3-66
3.4.1.3 Marine Organisms 3-66
3.4.1.4 Factors Affecting Toxicity 3-68
3.4.1.5 Ambient Water Quality Criterion 3-70
3.4.2 Exposure of Aquatic Biota 3-70
3.4.2.1 Monitoring Data 3-70
3.4.2.2 EXAMS 3-71
3.4.2.3 Factors Affecting Bioavailability 3-71
of Sediment Concentrations
3.4.3 Summary - Aquatic Effects and Exposure 3-72
3.5 RISK CONSIDERATIONS 3-73
3.5.1 Introduction 3-73
3.5.2 Humans 3-73
3.5.2.1 Statement of Risk 3-73
3.5.2.2 Discussion 3-73
3.5.3 Aquatic Biota 3-74
REFERENCES FOR 3.1 3-75
REFERENCES FOR 3.2 3-79
REFERENCES FOR 3.3 3-83
REFERENCES FOR 3.4 3-86
APPENDIX A 3-89
APPENDIX B " 3-90
viii
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LIST OF FIGURES
Figure
No.
3-1 Computed Relationship Between Depth & Average Half-
Life for Photolysis of Naphthalene in Top 35 m. of
Seawater
3-2 Pathways Utilized By Mammals and Bacteria for the
Oxidation of Aromatic Hydrocarbons
3-3 Mackay Environmental Model Systems and Predicted
Distribution of Naphthalene
3-4 Sources and Fate of Naphthalene in Aquatic Environ-
ment
3-5 Metabolism of Naphthalene
3-6 Mean Naphthalene Concentrations In Sediments
and Mean Numbers of Benthic Organisms As
Functions of Distance From An Oil Separator Rig
In Trinity Bay, Texas
ix
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LIST OF TABLES
Table
No.
Page
3-1 U.S. Naphthalene Producers and Capacities,
1980 (104 kkg) 3-2
3-2 Estimated Environmental Releases of Naphthalene
from Production and Inadvertent Sources, 1978 (kkg) 3-4
3-3 Estimated Environmental Releases of Naphthalene
from Use, 1978 (kkg) 3-6
3-4 U.S. Phthalic Anhydride Producers and Locations,
and Capacities of Naphthalene Usage 3-7
3-5 Producers of Synthetic Tanning Agents and
Their Locations, 1978 3-10
3-6 Materials Balance: Naphthalene, 1978 (kkg) 3-14
3-7 Naphthalene Releases to Surface Waters (1978) 3-17
3-3 Air-to-Surface Pathway Evaluation For Naphthalene 3-18
3-9 Estimated Naphthalene Releases to the Atmosphere (1978) 3-20
3-10 Basic Physical/chemical Properties of Naphthalene 3-21
3-11 Bioaccumultation of Naphthalene In Two Fish Species 3-27
3-12 Bacterial Biodegradation Products Reported
For Naphthalene 3-31
3-13 Biodegradation Rates of Naphthalene 3-32
3-14 Kinetic Parameters of Naphthalene Transformation
In Oil-Contaminated Stream and Uncontaminated
Stream Sediment Samples 3-33
3-15 Values of Parameters Used For Calculating
the Equilibrium Distribution of Naphthalene
Predicted By the Mackay Fugacity Model 3-37
3-16 Equilibrium Partitioning of Naphthalene
Calculated Using the Mackay Fugacity Model 3-38
3-17 Input Parameters For EXAMS Modeling of the
Fate of Naphthalene In Generalized Aquatic Systems 3-4C
x
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LIST OF TABLES (Continued)
Table
No.
3-18 Steady-State Concentrations of Naphthalene
In Various Generalized Aquatic Systems
Resulting From Continuous Discharge At a Rate
of 0.2 kg/hour
3-19 The Fate of Naphthalene In Various Generalized
Aquatic Systems
3-20 The Persistence of Naphthalene In Various
Generalized Aquatic Systems After Cessation
of Loading at 0.2 kg/hour
3-21 Comparison of Results From Mackay's Equilibrium Model
and EXAMS For Naphthalene In a Pond System
3-22 Distribution of Ambient and Effluent Concentrations
('rig/1) For Naphthalene - STORET 1980
3-23 Distribution of Naphthalene Concentrations In Sediment
and Fish Tissue In Ambient Waters—STORET 1980
3-24 Reported Levels of Naphthalene In Air
3-25 Data on Carcinogenicity of Naphthalene in Animals
3-26 Mutagenicity of Naphthalene In Various Iii Vitro
Microsomal/Mammalian Assay Systems
3-27 Activity of Naphthalene With In Vitro Neoplastic
Transformation Test Systems
3-28 Estimated Air Concentrations Resulting
From Naphthalene Use As a Moth Repellent
3-29 Estimated Upper Limit Human Exposures to Naphthalene
3-30 Acute Toxicity of Naphthalene For Aquatic Species
xi
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ACKNOWLEDGMENTS
The Arthur D. Little, Inc., task manager for the Naphthalene Expo-
sure and Risk Assessment was Susan Coons. The major contributors 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 Naphthalene (Section 3.1) 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.
xii
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1.0 INTRODUCTION
The Office of Water Regulations and Standards (CWRS), Monitoring
and Data Support Division, of Che 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.
• 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
i j
Amliraccne
Aconaplithene
Fluorenc
1*1 umian I In one
Pyrent-
Fluoraniliene
Buiuo|a) pyrenc Acenuplithylune Benz(a) anthracene
Cluysene
Benzo(b) fluoranthene
Dibenz(a,h | anthracene
Benzolk| fluoranthene
Benzo|
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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 3aP group had been identified as carcinogens. Much of
the information regarding this group of compounds is for 3aP.
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 subpopulatior.s
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 PAKs that are produced primarily as byproducts of combustion
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processes. Since most PAH production is inadvertenc rather than
deliberate commercial production, the conventional approach of trying to
balance production versus use ana 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 wi-th 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 1-1 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
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TABLE 1-1. SUMMARY OF EVIDENCE FOR CARCINOGEN'I CITY OF
PRIORITY POLLUTANT PAHs
PAH
Benzo[a]pyrene
Dibenz[a,h]anchracene
Betiz [a ] anthracene
3enzo[g,h,ijperylene
Benzo[b]fluoranthene
Chryser.e
Indeno[1,2,3-c,d]pyrene
Pvrene
Fluoranthene
Benzo[k]fluoranthene
Pher.anthrene
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 net.
tested orally.
1-5
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TABLE l-i.
SUMMARY OF EVIDENCE FOR CARCINOGENICITY 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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3.0 NAPHTHALENE
3.1 MATERIALS BALANCE
3.1.1 Introduction
One perspective from which exposure to a chemical may be evaluated
is that of a materials balance. Since the total mass of all materials
entering a system equals the total mass of all materials leaving that
system, excluding those materials the system accumulates or retains, a
materials balance may be performed around any individual operation that
may ultimately place a specific population at risk (e.g., process water
discharges creating groundwater contamination). Each overall materials
balance, therefore, consists of a collection of smaller ones, each
of which is directed to specific releases to the environment. It is
beyond the scope of this section to predict the fate of the chemical
following release.
This section reviews data concerning the production, use, and re-
lease of naphthalene within the United States. Information from the
available literature has been compiled to present an overview of major
sources of the environmental release of naphthalene. Annotated tables
have been included to aid data evaluation.
A major source of naphthalene released to the environment is combustion.
There are very few monitoring data, and the extent to which the reported
emission factors are representative of the wide range of combustion con-
ditions is unknown. The conventional approach of balancing production
versus use and environmental release is not strictly applicable to naptha-
lene since a major portion of the environmental load is inadvertently
released from combustion sources. Therefore, the estimates reported
within this Section should be regarded as indications of the relative
magnitude of naphthalene releases to the environment and used to identify
the most important sources.
Section 3.1.2 discusses the production of naphthalene and the
releases due to production and inadvertant sources. The major uses of
naphthalene, and the attendant environmental releases, are reviewed in
section 3.1.3. Section 3.1.4 presents a discussion of the disposition
of naphthalene discharged to municipal waste facilities, i.e.,
publicly owned treatment works (POTWs). A materials balance table for
naphthalene and a summary of the major findings are presented in
section 3.1.5.
3-1
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3.1.2. Production
3.1.2.1 Overview
Naphthalene is produced by distillation of coal tar recovered
from byproduct coking of coal and, to a lesser extent, is obtained
from dealkylation of methyl naphthalene found in petroleum. In 1978,
165,000 kkg of naphthalene were recovered from coal tar; 70,290 kkg
were obtained from petroleum (Abshire et al. 1980). Additionally
3,260 kkg of naphthalene were imported and 3,960 kkg were exported,
resulting in an available U.S. supply of 234,590 kkg. Table 3-1 lists
naphthalene producers, along with their locations and capacities.
TABLE 3-1. U.S. NAPHTHALENE PRODUCERS AND CAPACITIES, 1980 (104 kkg)a
Producer
Location
Capacity
Raw Material Used
Allied Chemical
Detroit, MI
I ronton, OH
3.4b
Coal Tar
Ashland Oil
Ashland, KY
4. lb
Petroleum
Getty Oi1
Delaware City, DE
4.5b
Petroleum
Koppers Co.
Cicero, IL
Follansbee, WV
8.6b>c
Coal Tar
Monsanto
Chocolate Bayou, TX
4.1c
Petroleum (Ethylene
By-product)
U.S. Steel
Clairton, PA
Gary, IN
Total
CO
• •
o
o
Coal Tar
a) SRI 1980.
b) Product is sold.
c) Product is captively consumed.
3-2
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In order to recover naphthalene from coal tar, the crude tar is
distilled and fractionated. The middle oil fraction containing most
of the naphthalene and tar acids, is pumped into shallow pans and allowed
to cool, crystallizing the naphthalene. The crystalline material is
centrifuged and recovered as crude naphthalene. For a refined product,
the crude naphthalene is distilled, washed, and sublimed.
Naphthalene is recovered from petroleum fractions containing
large amounts of methyl naphthalenes by dealkylation in the presence
of hydrogen at elevated pressure and temperature. Typical feedstocks
include distilled bottoms from catalytic reformate or refraction cycle
oils (Lowenheim and Moran 1975). Feeds are pumped to the dealkylation
reactor. As the product exits the reactor, it is quenched and sent to
a separator; effluents from the separator are distilled in order to
recover naphthalene, gasoline and fuel oil. Petroleum-derived naph-
thalene is usually >99% pure and low in sulfur content.
3.1.2.2 Environmental Releases from Production
No specific data concerning environmental releases of naphthalene
from production were found; however, an SRI study (Brown 1975) estimated
that 0.0004% - 0.07% of the total naphthalene production is lost to the
environment. Of that portion lost, 48% is estimated to be emitted to
the atmosphere, 6% discharged to water, and 46% land disposed. 3ased upon an
average production loss of 0.035%, a total of 83 kkg of naphthalene was esti-
mated to be released to the environment from production by both coal tar and
petroleum processes; of that amount, 40 kkg were emitted to the atmosphere,
5 kkg discharged to water and 38 kkg disposed of on land (see Table 3-2).
A comparison of coal tar and petroleum-based naphthalene recovery
processes indicates that most of the 5 kkg of naphthalene discharged to
water probably comes from coal tar facilities (Brown 1975). Major waste-
water sources are extraction and wash tank effluents; specific flow rates
and naphthalene concentrations were not found in the literature surveyed.
Land-disposed solid wastes consist of process sludge, discarded
clay (from petroleum purification processes), spent catalysts, and
on-site wastewater treatment sludge. Again, no specific data concerning
quantities of these solids or their naphthalene concentrations were found.
3.1.2.3 Inadvertent Sources of Naphthalene
Although naphthalene itself is not used as a raw material in the
wood preserving, paint, ink, or textile industries, it has been detected
in wastewater streams from these industries (EPA 1980c). Since these
industries utilize many naphthalene-containing products such as creosote,
dyes, and surface-active agents, naphthalene present in such waste streams
is probably due to degradation of these compounds.
3-3
-------
Table 3-2. Estimated Environmental Releases of Naphthalene from Production and
Inadvertent Sources, 1973 (kkg)
Environmental Releases
Production
Quantity
Water
Surface
Land
Ai r
POTW
Total
Coal Tar 165,000
Petroleum 70,290
Inadvertent Sources
Wood Preserving13
Textile Industry^
Paint Formulation
Ink Formulatione
Residential Coal
Combustion f
Primary Residential
Wood Heating 9
Auxiliary Residential
Wood Heating9
Cigarette Smoke,
Utility Industrial
Internal Combustion Engines1
Gas-and Oil-Fired •
Residential Sources
Coal Production and
Distillation*
Oil Spills 1
5
38
40
83 a
<1
29
29
neg
<1
neg
NA
<1
neg
<1
neg
NA
<1
neg
<1
neg
NA
<1
neg
neg
1,000
1,000
neg
neg
2,000
2,000
neg
neg
2,000
2,000
neg
neg
2
2
neg
neg
4
4
neg
neg
70
70
300
200
200
300
1,000
30
neg
NA
30
a) Based on Srown 1975 release estimates; see text.
b) See Appendix A, Note 2.
c) Based on total industry flow rate of 1.89 x 10° i/day, 300 d/^r operation, and a median of
22 ugu in secondary effluent (epa 1980c, epa i980d). Ne_ql lqible is defined as <1 kkq.
NA = not available.
d) 3ased on EPA, 1979g. 300 d/yr, 2.4 kg naphthalene discharged/day (total industry).
e) Based on EPA, 1979h. Mass loading of 0.001 kg/day Industry wide, 300 d/yr operation;
>90% of discnarge is sent to POTWs.
f) Based on 0.15g naphthalene emitted/kg coal combusted (EPA 1977a) x 8,688 x 10^
kkg coal consumed for residential combustion {DOS. 1980).
g) Based on 0.25g naphthalene emitted/kg wood consumed (average for baffled and
nonbaffled stoves EPA 1980a) and wood consumption of 6.9 x 106 kkg for primary
heating and 9.2 x 10® kkg for auxiliary heating (EPA 1980a; Census 1979).
h) Based on 616 x 10' cigarettes produced (USOA 1979) x 3 ug naphthalene emitted/
cigarette (Schneltz et a1. 1978J•
i) EPA 1979a.
j) EPA 1979b.
k) Includes emissions from coke oven doors (air release) and 43 kkg (POTW release)
from decanter tank tar sluage from spray cooling of coke oven gases (EPA 1980b).
Based on 90,000 mg naphthalene/kg coal tar (Rhodes 1954; Lowry 1945) and discharge
factors (kg/kkg coke of 0.00395 (ainnonia liquor), 0.0115 (cooler blowdown), and
0.00341 (benzol plant) and coke production of 44.5 x 10° kkg (EPA 1977:1 ; DOE
1979). Distribution^ ^33% direct, 25% POTW, 2% deep well injection, t+o% quenching (20% land,
1) 3ased on 3^.6 x 10' i of various oils - crude (365) diesel (18%) fuel (42%).,
waste (2%) lube (0.3%) and other (1.7%) spilled in navigable waters in 1978 (U.S.
Coast Guard 1980) oil density of 0.85 and naphthalene content of 1 ,000 mg/kg -j p crude oil
(Guenn 1978; Guerin et al 1978. EPA 1979i).
3-4
-------
On the basis of U.S. EPA Effluent Guidelines data concerning wood
preserving plants, approximately 29 kkg of naphthalene are estimated
to be discharged to POTWs per year; less than 1 kkg is discharged
directly to water (EPA 1979d; see Appendix A, Note 1). Approximately
0.7 kkg and 0.003 kkg of naphthalene are discharged annually in raw
wastewater from the paint and ink formulating industries, respectively
(EPA 1979f,g; see Table 3-2). Discharges of naphthalene in textile
mill effluents amount to 0.01 kkg per year (Table 3-2).
As is the case for all PAHs, naphthalene is released to the
environment during combustion of fossil fuel, oil spills, and byproduct
coking operations. Estimates of these releases are summarized in Table 3-2.
3.1.3 Uses
Table 3-3 summarizes the environmental releases estimated to
occur as a result of the commercial use of naphthalene. Use
in moth repellents accounts for the largest single release; this
entire release is to the atmosphere. Phthalic anhydride production
is the second largest source of naphthalene released to the environ-
ment during use.
3.1.3.1 Phthalic Anhydride
The manufacture of phthalic anhydride consumed 140,750 kkg of
naphthalene in 1978 (Harris 1980, EPA 1973). Table 3-4 gives locations
and naphthalene use capacities of the three domestic phthalic anhydride
producers. Phthalic anhydride is obtained by oxidizing naphthalene in the
vapor phase in the presence of a vanadium oxide catalyst (EPA 1977b).
Naphthalene conversion in the reactor is 100% (EPA 1976, Graham e_t al.
1962); therefore, the only atmospheric emission of naphthalene from the
manufacture of phthalic anhydride stems from naphthalene storage facil-
ities (EPA 1976). On the basis of an EPA emission factor of uncontrolled
storage tank losses for naphthalene at phthalic anhydride plants (0.6 kg
naphthalene/kkg phthalic anhydride produced) and assuming 4.5 x 105 kkg/yr
phthalic anhydride produced, approximately 270 kkg of naphthalene were
emitted to the atmosphere in 1978 (EPA 1976, USITC 1979). Emissions can
be reduced 99% by using conservation vents on naphthalene storage tanks;
for the most part, this technique is not employed (EPA 1976, EPA 1977b).
2
(air)
3-5
-------
Table 3-3- Estimated Environmental Releases of Naphthalene from Use, 1978 (kkg)
Estimated Environmental Releases
Use
Quantity
Air
Land
Water
Surface POTW
Total
Phthalic Anhydride3
140,750
270
neg
neg
270
Carbaryl Insecticide1*
46,920
" neg
neg
neg
neg
c
lieta-Naphthol
18,770
neg
neg
neg
Synthetic Tanning Agents^
16,420
neg
neg
neg 2
2
Moth Repellentse
4,690
4,690
neg
neg
4,690
Surface Active Agents^
2,350
neg
neg
g
Miscellaneous Organic Chemicals
4,690
47
47
Exports
3,960
Total
238,550
4,980
16
neg 18
5,010
a) Negligible Is defined as <1 kkg. Atmospheric emissions based on EPA emission factor of 0.60 ( + 10%) kg
naphthalene per kkg phthalic anhydride produced (EPA, 1976a) x 443,540 kkg PA produced in 1978 (USI
1979).
b) Based on EPA (1972a/b) descriptions of waste treatment practices, see text.
c) Negligible release from production.
d) based on Effluent Guidelines Division (EPA 1979h) wastewater data for leather tanning facilities ,* see
Appendix A, Note 2.
e) Naphthalene volatilizes significantly at room temperature (Merck Index, 1976); all naphthalene used as a
moth repellent is emitted to the atmosphere.
f) See Inadvertent Sources, Section 3.1.2.3.
g) See text.
-------
TABLE 3-4. U.S. PHTIIALIC PNHYDRIDE PRODUCERS AND LOCATIONS, AND CAPACITIES OF NAPHTHALENE USAGE
Company
Location
Nominal capacity,
103 kky/yr
Raw Material
Process
Koppers Co.
Bridgeville, PA
40.8
Desulfuri zed
Naphthalene
0WN(fluid bed)
Monsanto Co.
Bridgeport, NJ
40.8
Petroleum
Naphthalene
Badyer-Sherwi n-
Williams
US Steel
Neville Island, PA
Total
68.0
149.6
Desulfuri zed
Naphthalene
Badger-Sherwin-
Wi 11 iains
Source: EPA 1977b.
-------
If 100% of the naphthalene used in phthalic anhydride manufacture
is converted to the desired product in the reactor and all water used
is noncontact cooling water, very little, if any, naphthalene would be
discharged in wastewater (EPA 1973, EPA 1976). Land-destined wastes,
such as those arising from catalyst storage and disposal, contain no
naphthalene (EPA 1976).
3.1.3.2 Carbaryl Insecticide
In 1978, approximately 46,920 kkg of naphthalene were consumed
in carbaryl (Sevin®) insecticide manufacture. The reaction proceeds
as follows:
Union Carbide, the only domestic producer, manufactures carbaryl at its
facility in Institute, WV (EPA 1972a, Sittig 1977). Carbaryl is regis-
tered for use on about 70 crops and is used chiefly in the South and West.
The process wastes are primarily contained in liquid streams,
vents, and a small amount of heavy residue. No specific naph-
thalene content of any waste stream was reported; waste treatment prac-
tices indicate, however, that the naphthalene loss from production of
carbaryl insecticide is probably negligible. All aqueous wastes are
sent to the plant's secondary waste treatment plant'prior to direct
discharge to a nearby river (EPA 1972a). Carbaryl levels in treated
wastewater are relatively low, ranging from 0.01 mg/1 to 1 mg/1 (EPA
1972a); naphthalene concentrations should be even lower because the
compound is converted to tetrahydronaphthalene (a manufacturing inter-
mediate) with high yields. Atmospheric emissions of naphthalene are
judged to be negligible since all toxic vents are flared at about 99%
efficiency. The small quantities of solid residue generated are incin-
erated, also at about 99% efficiency; discarded containers are reportedly
also burned.
The final product carbaryl, applied as a dust or liquid spray,
contains no naphthalene (Kail 1980); therefore, no release to the
environment occurs from its application. Apparently, naphthalene is
not a degradation product or metabolite of carbaryl. Merck Index (1976)
states that carbaryl is resistant to heat, light and acids, but hydrolyzes
in the presence of alkalis. EPA (1972b) data show that carbaryl is not
persistent in the environment; and in waters of pH 7.3 to 8.5, degradation
was 95 to 100% complete in 3 to 7 days (EPA 1972b). The most likely
degradation product (or metabolite) is 1-nap'nthol (EPA 1972c, Kail 1980);
naphthalene is not found among identified mammalian urinary metabolites
(EPA 1972c). 3ased on these data, use of carbaryl insecticide apparently
is not a pathway for environmental release of naphthalene.
nwa
0C0C1
OCONHCH3
3-3
-------
3.1.3.3 Synthetic Tanning Agents
Manufacture of synthetic tanning agents consumed 16,420 kkg of
naphthalene in 1978; producers and their locations are listed in
Table 3-5. Synthetic tanning agents, comprised mainly of 2-naphthalene-
sulfonic acid, its condensates, and salts, as well as small quantities
of 1-naphthalenesulfonic acid, are utilized in both chrome and vegetable
tanning. Naphthalene is released to the environment principally from
wastewater streams; approximately 2 kkg per year are found in raw
wastewater (EPA 1979h, see Appendix A, Note 2). Of the total
188 tanneries currently in operation in the U.S., 177 plants (90%)
discharge to POTWs; 18 plants (10%) are direct dischargers (EPA 1979h).
Approximately 88% of the indirect dischargers perform only coarse
screening wastewater treatment, which is not efficient for naphthalene
removal (EPA 1979h). The direct dischargers treat wastewater streams,
for the most part, by activated sludge or aerated lagoons; naphthalene
removal via these treatment methods is 69-100% efficient. On the basis
of these treatment methods and efficiencies, approximately 1.8 kkg of
naphthalene are believed to be discharged to POTWs from leather tanning;
less than 0.1 kkg is discharged directly to surface water (EPA 1979h).
Atmospheric emissions of naphthalene from use of synthetic tanning
agents are assumed to be negligible, as naphthalene itself is not intro-
duced into the leather tanning facility. Naphthalene is found as a
degradation product of 2-naphthalenesulfonic acid in wastewater streams
and is possibly volatilized in aerated lagoons. On the basis of the
total 2 kkg of naphthalene found in raw wastewater, the amount volatilized
is assumed to be negligible.
Amounts of naphthalene in wastewater treatment sludge disposed of
on land are also judged to be negligible. Although relatively large
amounts of sludge are deposited on land annually from the leather tan-
ning industry (203,000 kkg in 1974, EPA 1979h), no data concerning
naphthalene content were found. These sludges are normally dewatered
by evaporative lagoons and any naphthalene present would probably
be volatilized.
3.1.3.4 Moth Repellent
Approximately 4,690 kkg of naphthalene (2% of the available U.S.
supply) were utilized in moth repellents in 1978. Such use is decreasing
due to the availability of para-dichlorobenzene (10,000 kkg of para-dichloro-
bensene were utilized as moth repellent in .1978' [SRI 1979]) and the
increased use of synthetic fibers. As noted later in Table 3-6,
all of the naphthalene contained in moth repellent is emitted to the atmo-
sphere. This estimate seems reasonable in that naphthalene volatilizes
appreciably at room temperature (Merck Index 1976). Environmental re-
leases from production of moth repellents are included in those for pro-
duction of naphthalene because the compound is produced as a solid flake,
powder or ball and simply repackaged as a consumer product; releases from
handling processes are also included in the previously mentioned emission
estimate for production.
3-9
-------
TABLE 3-5. PRODUCERS OF SYNTHETIC TANNING AGENTS AND THEIR LOCATIONS, 1978
Producer
Location
Ciba Geigy Dyestuff Division
Greensboro, NC
Diamond Shamrock
Carlstadt, NJ
Cedartown, GA
Georgia Pacific Corp.
Bellingham, WA
Rohm and Haas
Philadelphia, PA
Source: Amos 1979.
-------
3.1.3.5 3-Naphthol
Manufacture of B-naphthol consumed approximately 18,770 kkg of
naphthalene in 1978, or about 8% of the available U.S. supply. Only
one company, American Cyanamid, produces g-naphthol at its Willow
Island, WV facility; plant capacity ranges from 15,800 to 18,100 kkg. ^
Production requires reacting naphthalene with sulfuric acid and treating
the sodium salt of the resultant 2-naphthalenesulfonic acid with sodium
hydroxide (EPA 1977c) as shown below. The product is then distilled and
sublimed.
No specific data were found concerning the environmental release
of naphthalene from S-naphthol production. EPA (1977c) states that
wastewater streams probably contain naphthols and naphthalenesulfonic
acids; naphthalene itself was not listed. Washing and distilling the
final product probably release small quantities (<1 kkg) of naphthalene
to wastewater streams. Quantities of naphthalene released to the atmo-
sphere and disposed of on land are unknown; however, process descrip-
tions indicate that these releases are probably small (EPA 1977c).
8-naphthol is used in the manufacture of dyes and antioxidants
for rubber. Releases of naphthalene from the use of these products
could occur as the product decomposes. Such degradation is more likely
to occur via oxidation than reduction; however, no specific data were
found. Naphthalene is possibly formed when dye vats are cleaned by
steam injection of solvents since steam hydrolysis forms naphthalene
from (3-naphthol-. Environmental release from the use of S-naphthol-
containing dyes from the paint and ink industries is considered under
inadvertent sources, Section 3.1.2.3. Release of naphthalene from the
use of antioxidants in rubber is assumed to be negligible, as the com-
pound is tightly bound in the product.
•ONa
OH
3-11
-------
3.1.3.6 Surface Active Agents
In 1978, production of surface active agents consumed 2,350 kkg
of naphthalene, or about 17, of the available U.S. naphthalene supply.
These compounds, used as dispersants and wetting agents in paint, dye,
and paper-coating formulations, consist of 2-naphthalenesulfonic acid,
its alkyl derivatives, and their salts. The compound 2-naphthalene-
sulfonic acid is manufactured by American Cyanamid in Marietta, OH
(SRI 1980).
No specific data concerning environmental releases of naphthalene
from 2-naphthalenesulfonic acid degradation were found. An EPA (1977c)
study states that aqueous wastes streams contain sodium chloride and
sulfate; however, naphthalene is not listed as present in this stream.
Negligible (<1 kkg) discharge of naphthalene is probably a reasonable
estimate in that byproduct 1-naphthalenesulfonic acid is hydrolyzed
back to naphthalene, which is recovered by distillation (EPA 1977c).
Quantities of naphthalene emitted to the atmosphere and disposed of on
land are unknown, but are probably small.
i
Release of naphthalene from the use of surface active agents occurs
indirectly, possibly from their degradation. Since 2-naphthalenesulfonic
acid hydrolyzes to naphthalene in the presence of steam, the naphthalene
detected in various studies of paint, textile, and ink discharge streams
conducted by the U.S. EPA Effluent Guidelines Division is most likely a
degradation product formed when vats and tanks are cleaned by steam in-
jection (EPA 1979e,f). These industries use both surface-active agents
and naphthalene-containing dyes; it is difficult to determine from which
product the naphthalene arises. Therefore, these discharges are considered
together under inadvertent sources, Section 3.1.2.3.
3.1.3.7 Miscellaneous Organic Chemicals
In 1978, approximately 4,690 kkg of naphthalene (about 2% of the
available U.S. supply) were consumed in the manufacture of various
organic chemicals, including a-naphthol, naphthaleneacetic acid, and
decahydronaphthalene. As these compounds are each manufactured by three
or fewer producers, the specific quantities produced are considered pro-
prietary information. Uses of these chemicals are as dye intermediates,
plant growth regulators, and solvents.
No specific data were found concerning quantities of naphthalene
released to the environment from production or use of these compounds.
Assuming a probable worst case scenario of a 1% loss during production,
about 47 kkg of naphthalene would be released to the environment from
manufacture of these compounds. Since naphthalene is converted into
these products, naphthalene release from their use would occur only
from degradation or impurities in the final product. Such releases are
assumed to total less than 1 kkg.
-------
3.1.4 Flow Through POTWs
Naphthalene loading to publicly owned treatment works (POTWs) is
largely dependent upon the industries in the specific area. A framework
for calculating a total naphthalene flow through the nation's POTWs is
provided by data from a recent EPA study (EPA 1980e). A materials balance
of naphthalene can be constructed by using a total nationwide POTW flow
of 10^1 1/day (EPA 1978) and median values of 6.5 *g/l (influent) and
0.2 ug/1 (effluent). It is assumed for 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. On the
basis of these data, 237 kkg of naphthalene entered POTWs and effluents
contained 7 kkg.
Quantities of naphthalene in sludge can-be estimated from the
amount of dry sludge generated annually, 6 x 10° kkg, and a naphthalene
concentration of wet sludge equal to 242 yg/1 (EPA 1980e). As wet sludge
is 95% water by weight, approximately 29 kkg of naphthalene are dis-
charged in sludge, which is assumed to be disposed of on land. Assuming
that degradation of naphthalene within the POTW is negligible, the quan-
tity of naphthalene volatilized, probably from aeration, is obtained by
the difference between influent and effluent plus sludge values. Thus,
a maximum of 200 kkg of naphthalene were emitted to the atmosphere
from POTWs.
3.1.5 Summary
Table 3-6 summarizes the major environmental releases of naphthalene
identified in this materials balance. The annual environmental release of
naphthalene was estimated at approximately 11,500 kkg; over 90% was esti-
mated to be due to atmospheric releases. Total releases to the different
environmental compartments were estimated to be as follows: 10,600 kkg
to air, 300 kkg to land, 340 kkg to surface waters, and 240 kkg to POTWs.
Production of naphthalene in 1978 totaled 235,290 kkg, 70% (165,000 kkg)
of which was derived from coal tar and 30% (70,290 kkg) of which came from
petroleum. Approximately 83 kkg of naphthalene were released to the en-
vironment from its production (by both processes). Of that total, 48%
(40 kkg) was emitted to the atmosphere, 46% (38 kkg) was disposed of on
land, and 6% (5 kkg) was discharged to water (Table 3-6)•
Manufacture of phthalic anhydride, the largest single use of naph-
thalene, consumed 60% (140,750 kkg) of the available U.S. supply of the
compound. Environmental releases of naphthalene from production of
phthalic anhydride were approximately 270 kkg, all of which was emitted
to the atmosphere. The remaining 40% (93,840 kkg) was utilized in the
production of carbaryl insecticide, 3-naphthol, synthetic tanning agents,
surface active agents, and miscellaneous chemicals, and directly as a
moth repellent. As shown in Table 3-6, the only appreciable environmental
releases from the use of naphthalene are from its use as a moth repellent
3-13
-------
TABLE 3-6. MATERIALS BALANCE: NAPHTHALENE, 1970 (kkg)
Source
Production
Quantity
Ai r
Estimated Environmental Releases
Land Water
Surface POTW
Total
Coal Tar
Petroleum
Imports
Exports
Use
Plitlialic Anhydride
Carbaryl Insecticide
Beta-Naphthol
Synthetic Tanning Agents
Moth Repellents
Surface Active Agents
Miscellaneous Organic Chemicals
Inadvertent Sources
165,000
70,290
3,260
3,960
140,750
46,920
18,770
16,420
4,690
2,350
4,690
40
38
83
270 neg neg
neg neg neg
neg neg neg
neg neg neg 2
4,690 neg neg
neg —
- —47---
270
neg
neg
2
4,690
neg
47
Wood Preserving
<1
29
29
Textile Industry
<1
<1
Pairit Formulation
,
<1
<1
Ink Formulation
<1
<1
Combustion
5100
5,100
Coal Tar Production/Distillation
300
200
300
200
1,000
Oil Spills
30
30
POTWs
200
29
7
240
a) See Tables 3-2 and 3-3 for specific sources.
-------
(4,690 kkg) and in the production of phthalic anhydride (270 kkg),
miscellaneous organic chemicals (47 kkg), and synthetic tanning
agents (2 kkg); other uses are estimated to release negligible
quantities (<1 kkg).
The wood preserving, paint, textile, and ink industries inadver-
tently release naphthalene to the environment, primarily to water. By
far the largest discharge from these industries is 29 kkg (to POTWs)
from the wood preserving industry; paint, ink, and textile industries
each discharge less than 1 kkg to water. Approximately 5,100 kkg/yr
of naphthalene are released to the atmospheric environment during
combustion. The next largest inadvertent source of naphthalene
releases is coal tar production and distillation, from which 1,000 kkg
of naphthalene are released to the environment per year.
3-15
-------
3.2 FATE AND DISTRIBUTION IN THE ENVIRONMENT
3.2.1 Introduction
This section characterizes the fate processes that determine the
ultimate distribution of naphthalene in the aquatic environment and,
therefore, the opportunities for waterborne exposure of humans and other
biota. Section 3.2.2 presents an overview of the environmental loading
of aquatic media with naphthalene, including releases directly to water and
those resulting from physical transport (deposition from the atmosphere).
In Section 3.2.3, physical/chemical properties of naphthalene are summa-
rized in order to identify the processes that transform and transport
the chemical upon its release to the environment (Section 3.2.3.1).
Section 3.2.3.2 discusses the interplay of fate processes as it outlines
the major pathways of naphthalene in aquatic environmental media. Model-
ling efforts were undertaken based upon environmental loadings estimated
in Section 3.1 in order to characterize the fate and distribution of
naphthalene in specific environmental scenarios; these are described in
Section 3.2.3.3. Monitoring data from STORET and a limited number of
other surveys are summarized in Section 3.2.4 to provide indications of
the concentrations of naphthalene actually detected in aquatic environ-
mental media. Finally, Section 3.2.5 summarizes those aspects of the
fate and ultimate environmental distribution of naphthalene having the
greatest significance for the waterborne exposure of humans and other biota.
3.2.2 Input to Aquatic Media
Data presented previously in Section 3.1 indicate that direct re-
leases of naphthalene to surface water total an estimated 354 kkg each
year. As shown in Table 3-7, about 85 percent of the total is asso-
ciated with coal tar operations.
In addition to direct releases to surface water, naphthalene may
be transported to the aquatic environment indirectly via wet and/or dry
deposition of atmospheric releases. The air-to-surface pathway has been
evaluated for naphthalene, and is detailed in Appendix B of this report.
The results of that analysis are summarized in Table 3-8. Under ambient
conditions in either rural or urban areas, atmospheric naphthalene will
be almost entirely in the vapor phase with very little adsorbed to aerosols;
even near combustion sources, only 2% of the naphthalene will be adsorbed.
Since most naphthalene will be in the vapor phase, dry deposition is ex-
pected to be very slow (0.04-0.06 cm/sec). The vapor/aerosol partitioning
also affects the precipitation scavenging ratio controlling wet deposi-
tion. The scavenging ratios estimated for naphthalene range from 53
under rural conditions to 2,500 for rainfall passing through the plume
of a large combustion source.
Taking into account the observed concentrations of naphthalene,
as well as the chemical degradation rates, it is estimated that only 2-3%
of the emitted naphthalene will be deposited in either rural or urban areas;
most of chat deposition will be due to dry deposition processes.
3-16
-------
TABLE 3-7. NAPHTHALENE RELEASES TO SURFACE WATERS (1978)3
Source
Release to Surface Water
Direct Releases (kkg/yr)
Coal Tar Production and Distillation 300
Other Naphthalene Uses ^12c
Oil Spills 30
POTWs 7
Naphthalene Production 5
Indirect Sources
Atmospheric Deposition to Surface Waters*5 i 3
Total ^359
£
Data from Section 3.1 Materials Balance,
^See following discussion of Atmospheric Deposition.
Q
4 7 kkg release assumed to be divided equally among environmental
compartments.
3-17
-------
TABLE 3-8. AIR-TO-SURFACE PATHWAY EVALUATION FOR NAPHTHALENE3
Rural
Urban
Near
Combustion
Source
Adsorbed Fraction
Of Airborne Mass
7 x 10
-6
3 x 10
-A
2 x 10
-2
Dry Deposition
Velocity (cm/Sec)
0. OA
0. OA
0.06
Precipitation
Scavenging Ratio
ng/1 (water)
Ug/m (air)
53
71
2500
Percent of Atmospheric
Emissions Deposited
-dry deposition
-wet deposition
-total
2
<1
2
2-3
<1
2-3
a
These data are Arthur D. Little, Inc. estimates based on
information in Appendix B and this chapter.
3-13
-------
As shown in Table 3-9 the total amount of naphthalene emitted
to the atmosphere of the United States in 1978 was approximately 10^ kkg
(Section 3.1). The data on deposition rates in Table 3-6 suggest that annual
atmospheric deposition would be about 200 - 300 kkg. Some of the rallout
will be directly deposited onto surface waters. If approximately
2% of the total area of the continental United States is surface
water (U.S. Bureau of the Census 1980), direct deposition to aquatic
systems would amount to approximately 5 kkg. Only a fraction of the
remaining fallout, i.e., that deposited on land, would be transported
to aquatic systems via surface runoff. There are insufficient data
to permit an accurate estimation of the total input due to
land-to-water pathways.
3.2.3 Environmental Fate
3.2.3.1 Basic Physical/Chemical Properties
Table 3-10 summarizes the physical and chemical properties of
naphthalene that are relevant to its environmental fate and transport.
The properties that have particular significance with respect to the
partitioning of naphthalene among the environmental compartments are
vapor pressure, water solubility, and octanoi: water partition coefficient
(K ). The K provides a useful indication of the tendency for
water-lipid ancf water-sediment partitioning, thereby enabling initial
assessments of bioaegradation, bioaccumulation, and sedimentation as
fate processes. The Henry's law constant is simply the ratio of the
vapor pressure at 25° C to the water solubility at the same temperature
(without corrections for activity coefficients). This parameter is a
good measure of the tendency for a solute to escape to the atmosphere
from solution. The saturated concentration of naphthalene vapor in air
was calculated from the Ideal Gas Law, and has been included in Table 3-10.
3.2.3.2 Pathways in the Aquatic Environment
Volatilization and Atmospheric Fate
_2
Naphthalene has the highest vapor pressure (4.9 x 10 torr)
of the PAHs, a fact suggesting that volatilization may be more important
for this compound than for the other PAHs. The actual rate of volatil-
ization in a given setting is dependent upon temperature, wind velocity,
and mixing rates of both air and water columns. In a stream 1.0 m in
depth, naphthalene has been shown experimentally to have a half-life
of 75 hours under conditions of a 0.1-m/sec current velocity and a
0.4-m/sec wind velocity. The rate of volatilization increased by a
factor of 7.5 with a 10-fold increase in current velocity; the rate
increased five times with a 10-fold increase in wind velocity. These
variations are much more dramatic than the changes reported for the
larger PAHs (Southworth 1979). These data are difficult to extrapolate
to environmental systems since the temperature and rates of mixing will
vary considerably with local water and weather conditions.
3-19
-------
TABLE 3-9. ESTIMATED NAPHTHALENE RELEASES TO THE ATMOSPHERE (1978)
Release to Atmosphere
Source (kkg/yr)
Combustion (Primarily Residential 5075
Sources)
Moth Repellant 4690
Coal Tar Production 300
Phthalic Anhydride Manufacture 270
POTWs 200
Naphthalene Production 40
Miscellaneous Organic ^12
Chemicals
TOTAL >10600
Source: Section 3.1
3-20
-------
TABLE 3-10 3ASIC PHYSICAL/CHEMICAL PROPERTIES OF NAPHTHALENE
Property
Structure:
oTo
Reference
Formula: C1rtHa
10 8
MW:
128.19 g/mole
Melting Point (°C): 80.55
Boiling Point (°C): 217.9
Hodgman (1961)
Hodgman (1961)
Hodgman (1961)
Vapor
Pressure
(torr):
0.09 at 25°C
0.22 at 25°C
0.049 at 20°C
SRI (1980)
calculated from data in
Hodgman (1961)
Callahan etal. (1979)
Water
Solubility
(mg/ 1) :
31.7 at 25°C
34.4 at 25°C
SRI (1980)
Callahan et al. (1979)
Log K : 3.37
ow
3.29
Log K : 3.03
oc
Callahan et al. (1979)
SRI (1980)
SRI (1980)
Henry's Law: 4.8 x 10~^ at 25"C
(atm - m3\
mol J ''
Saturated Vapor 0.62 at 25°C
Concentration
(gAn3):
calculated:
vapor pressure
water solubility
calculated: PV=nRT
3-21
-------
There is substantial evidence that, once released to the atmosphere,
PAHs are readily degraded by photo-oxidation to produce oxygenated com-
pounds, including quinone (Radding et al. 1976). No specific data on the
rate of atmospheric photo-oxidation of naphthalene were encountered in
the literature. However, the rate for oxidation of naphthalene by
hydroxyl radicals in the atmosphere can be assumed to be intermediate
between the 10 hours reported for larger PAHs (Radding et al. 1976; see
also Volumes III and IV of this report) and the average of 45 hours
estimated for benzene (Davis et al. 1977). To the extent that atmospheric
naphthalene is adsorbed onto particulate materials, the rate of
photo-oxidation may be lower than the half-life range of 10-45 hours
would imply (Radding et_ al. 1976).
Adsorption and Sedimentation
Depending on the particulate content of the aquatic system, a
significant fraction of- the PAHs in the water column may be adsorbed
onto suspended particulate material. Data on adsorption and concentra-
tion of three- and four-ring PAHs in the presence of various substrates
such as activiated carbon, calcareous material, silica, glass, soil
particles, and organic particles have been cited by numerous authors,
and are summarized in Neff (1979) and in Volumes III and IV of this report.
However, data referring specifically to naphthalene have not been en-
countered. The fact that the log octanol:water partition coefficient
for naphthalene is 3.37 suggests that the extent of adsorption onto
particulate may be lower than the 15-65^ reported (Neff 1979)
for anthracene (log K = 4.45). The adsorption behavior of naphthalene
probably depends upon the type of particulate material present, with
stronger adsorption to organic than to mineral materials [by analogy
to the behavior of anthracene (Volume III)] .
Several authors (Smith et al.1978, Lewis 1975) have demonstrated
that sorption of PAHs and other chemicals onto natural sediments and
biogenous materials is a reversible equilibrium process. Again, the
demonstrations relate specifically to higher molecular weight PAHs and
not to naphthalene per se. However, because of naphthalene's relatively
high water solubility and modest octanol:water partition coefficient the
reversible adsorption/release process would be expected to be more
important in maintaining a significant concentration of dissolved naph-
thalene in the water column. Zepp and Schlotzhauer (19 79) have reported
that naphthalene may exist primarily in the dissolved state in many inland
water bodies and ocean waters.
Transport of the adsorbed naphthalene through the aquatic environ-
ment will be governed largely by the physical laws of sedimentation
applicable to actual environmental conditions. The particulates grad-
ually settle out of the water column; flocculaticn of suspended clay-sized
particles (such as that which occurs in the increasing salinity gradient
of an estuary) will increase the rate of deposition (Neff 1979).
-------
In a study of a dispersion of Prudhoe 3ay crude oil (Lee al.
1978), naphthalenes were rapidly deposited in bottom sediments, while
higher molecular weight PAHs accumulated more slowly. The authors sug-
gested that accumulation by phytoplankton, which subsequently sink to
the bottom, may be a significant means by which these relatively low
molecular weight compounds are deposited in sediments.
Once deposited in sediment, PAHs in general, and presumably naph-
thalene in particular, are much less liable to be degraded photochem-
ically and biologically. The concentration of naphthalene in sediment
can be expected to be about two orders of magnitude higher than the
concentration in solution (Lee and Anderson 1977), while higher mole-
cular weight PAHs would show concentration ratios that were considerably
higher. Sediment transport of naphthalene is probably qualitatively similar
to pathways for other PAHs (see Volumes III and IV), with deltas and estuaries
serving as a trap for riverborne particulate PAHs (White and Vanderslice 198U).
Chemical Degradation
The PAHs generally have high absorptivities for ultraviolet/visible
light at wavelengths above the solar cut-off (300 nm). Direct photochem-
ical degradation (initiated by absorption of light by the PAH compound,
rather than by an intermediate photosensitizer) is expected to be a
significant fate process for PAHs in water, in spite of the inefficient .
nature of photochemical reactions (quantum yields in the range of 0.001
to 0.01) (Andelman and Suess 1971; Smith e_t al. 1978; NAS 1972, Stevens and
Algar 1968; Zepp and Scnlotzhauer 1979). In contrast to the large PAHs,
naphthalene has one of the highest photolysis quantum efficiencies (0.015),
but about the lowest direct photolysis rate (half life = 71 hours) due to
the lower sunlight absorption rates (the naphthalene absorption maxima
coincide with the less intense solar radiation in the 280-320 nm range)
rZepp and Schlotzhauer 1979).
The role of photo-oxidation will vary with actual environmental
conditions and the location of the compound in the water column. In
turbid rivers, photolysis will be slowed by light attenuation and
partitioning of the PAHs to sediments where no light is present.
Figure 3-1 shows the relationship between depth and rate of direct
photolysis for naphthalene during summer in aqueous (marine) environments.
The data show photolysis half-lives for naphthalene of 53 days in mid-
Gulf water and 2,000 days in the coastal environment. The mid-Gulf data
refer to ocean water of low microbial and phytoplankton activity, while
the coastal water data reflect the lower light penetration in the more
biologically active environment. In each case, the rate for naphthalene
photo-oxidation is two to three orders of magnitude lower than that for
the higher molecular weight species, anthracene. The difference in the
slope of the plot for naphthalene vs. that for anthracene results from
the different absorption spectra of the two compounds and from the fact that
the penetration of sunlight also varies with wavelength.
3-23
-------
UJ
H
<
cr
UJ
>
K
<
-I
UJ
a:
N1
I
0.01
20
30
0
10
30
10
20
0
DEPTH, meters
FIGURE 3-1 COMPUTED RELATIONSHIP BETWEEN DEPTH AND AVERAGE
HALF-LIFE FOR PHOTOLYSIS OF NAPHTHALENE IN THE TOP
35 M OF SEAWATER.
Note: Data for anthracene (dashed line) included for comparison. (A) mid-Gulf
and (B) coastal water.
Source: Adapted from Zepp and Schlotzhauer (1979).
3-24
-------
Zepp and Schlotzhauer (1979) calculated the half-lives for photo-
oxidation of naphthalene in near surface waters (at 40°N latitude, mid-
day, mid-summer) to be 71 hours for the direct process, and 10^ hours
for the photosensitized process. Thus, the quantum yield (efficiency)
of the direct reaction (Qr=0.015) is 2 x lO1^ times larger than that for
sensitized photo-oxidation. Specific information on photo-degradation
products of naphthalene was not encountered; napthoquinones such as those
shown below are likely oxidation products.
0
1,2-naphthoquinone
2,6-naphthoquinone
In contrast to the above cited work are the results of Lee and
Anderson (1977), which indicate that photolysis of naphthalene did not
occur when the compound was added to a controlled ecosystem. These
results are not necessarily directly applicable to the natural aquatic
environment since other fate processes were affecting levels of naph-
thalene in the laboratory ecosystem.
The less important, slower oxidative reactions should also be
mentioned in a discussion of the aquatic fate of PAHs. Radding et_ al.
(1976) have summarized data on relative half-lives for oxidation of
PAHs in aquatic environments by various agents: peroxide radicals (RO^),
singlet oxygen (0*)> ozone (0^), chlorine (C^) and hydroxyl radical
(OU*). Although naphthalene was not included in the study, the half-lives
for other PAHs were generally >1,000 days for reaction with RO^, 5 hours
for reaction with 0*, <0.5 hours for reaction with C^, and about
10 hours for reaction with HO*. Reaction rates for naphthalene will
probably be comparable to, or slower than, those for the higher mole-
cular weight PAHs.
Possible reaction of naphthalene and other PAHs with chlorine (or
ozone) in water or wastewater treatment plants is of interest as a
possibly significant pathway within the cultural aquatic environment.
During chlorination of biphenyl and naphthalene, Smith et_ al^. (1978)
identified several polychlorinated aromatics in addition to the quinones.
Since many of these polychlorinated aromatics may be highly toxic and
persistent, this pathway may be important as a potential source of new
hazardous pollutants.
3-25
-------
Biological Fate
Introduction
3iological processes such as uptake, depuration, and biodegradation
are considered as pathways for naphthalene in aquatic systems. Overall,
bioaccumulation of naphthalene is not significant in terms of reducing
environmental concentrations of naphthalene, whereas neither microbial
biotransformation nor biodegradation is considered the predominant fate
mechanism for naphthalene in water.
Bioaccumulation
Bioaccumulation studies have been performed on both vertebrate and
invertebrate species from freshwater and marine systems. In general, the
results show rapid bioaccumulation but also a potential for depuration
after exposure ceases.
Rainbow trout fingerlings (3-6 g) were exposed to naphthalene at
concentrations of 0.023 or 0.005 mg/1 for 8 hours, followed by a 24-hour
elimination period. Naphthalene was readily accumulated in the 8 hours,
but was also rapidly depurated with 4% of the tissue content remaining
after 24 hours. Following a 6-week exposure to 0.017 mg/1, depuration
took several hundred hours. Examination of the fish muscle tissue
indicated that naphthalene itself broke down but its metabolites accumu-
lated over the long term. The authors concluded that measurement of only
the parent compound may give a false impression of rapid depuration of naptha-
lene while its metabolites may be quite persistent (Melancon and Lech 1979).
Coho salmon and starry flounder were exposed to naphthalene at a
concentration of 0.003 ± 0.002 mg/1. At five weeks, the point of maximum
accumulation, the bioconcentration factor (BCF) was 80 for the salmon;
the highest BCF measured in the flounder was 700 after one week of
exposure (Table 3-11) (Roubal et^ al. 1978).
The benthic amp'nipod Anonyx laticoxae was exposed to naphthalene
for periods from 4 to 2 7 days. Compared with levels in the surrounding
environment (sediment or water), tissue bioconcentration factors were
the least during sediment exposure (2-4), intermediate during static
water exposure (10-50), and greatest in a flowing water system (1,000).
The results of sediment exposure demonstrated relatively low bioavailability
of naphthalene; the more significant routes of entry appeared to be via
interstitial and water column exposure. During a constant exposure to
22 yg/1 total naphthalenes, the amphipods reached a threshold of
accumulation after 7 days; most of the uptake was of the alkylated forms
of naphthalene (Anderson et: al. 1979).
3-2b
-------
TABLE 3-11 -
UIOACCUMUIATION OK NAPHTHALENE IN TWO FISH SPECIES'1
NAPHTHALENE ACCUMULATION
U)
I
M
--]
Species
Colio Salmon
(Oncorhynchus klsutcli)
Starry Flounder
(P. stel latus)
nig/kg dry
BCF 11 ssue _
20 0.07 10.03
Weeks Of Exposure _
nig/kg dry
BCF tissue
50 0.14*0.07
mg/kg dry
BCF tissue
80 0.24 i 0.06
mg/kg dry
BCF t Issue
40 f.. 12.t0.06
Weeks Of Exposure
V 2
mg/kg dry mg/kg dry
BCF tissue BCF tissue
Weeks Of Depuration
1 2
mg/kg dry
BCF tissue
700 2.1 1 1.5
240 0.72 1 0.30 100 0.30*0.02
mg/kg dry
BCF _ tissue
270 0.80 > 0.04
a) Flow-through exposure to 0.003 l 0.002 nig/1.
b) Note thaL after 6 weeks of exposure and I week of depuration, no naphthalene was detected.
Source: Kouhal et al. (1978)
-------
. Harris £t^ al. (1977) reported a whole-body BCF of 5,000 (wet weight
basis from dry weight data) in the saltwater species copepod (Eurytemora
affinis) after 9 days of exposure. Lee et al. (1972) determined BCFs
for three benthic marine fish in short-term studies (1-3 hours): sand
goby (Gillichtus mirabilis) 63; sculpin (Oligocottus maculosus) 32;
and sand dais (Citharichtys stigmaeus) 77.
Microbial Biotransformation
Naphthalene is one of the most commonly studied PAHs in regard to
oiodegradation. It is readily susceptible to microbial degradation;
however, the rate and extent of degradation vary considerably depending
upon environmental conditions. Influences on the rate include temperature,
availability of other nutrients, and the microbial population, among
others. Most studies have been conducted in simplified systems with the
goal of eliciting biodegradation; actual environmental persistence may be
longer than persistence measured in laboratory studies due to external
factors that are controlled in the laboratory. This section describes the
biodegradability of naphthalene based upon laboratory and field studies,
including data on rate and metabolic pathways, with a discussion of the
effect of important variables on the rate of reaction.
It is commonly thought, for several reasons, that microbial communi-
ties have had time to evolve the requisite enzyme systems for degradation
of this class of organics, in contrast to some of the highly persistent
synthetic organic compounds. Naphthalene, as well as other PAHs, is
present naturally in many soils (Alexander 1977). It has been suggested
that natural plant organics, such as diterpenes and sterols, may undergo
reduction and aromatization to PAHs (McKenna and Heath 1976). Natural
combustion sources (wildfire) may also introduce PAHs into the environment.
Since PAHs are commonly found in association, naphthalene is
rarely found alone in the environment. There is evidence that co-metabolism
of PAHs may occur in the presence of monocyclic aromatics; for example,
naphthalene was more completely degraded in the presence of dodecane or .
benzene than it was alone (Walker and Colwell 1975). Most of the studies
discussed in this section, however, concern direct biodegradation of
naphthalene itself.
The metabolic pathway followed in the biodegradation of naphthalene
is both compound- and species-dependent. In general, however, the two
processes shown in Figure 3-2 are typical. Microbial (more specifically,
bacterial) degradation is reported to occur through cis-dihydrodiol
(Gibson 1976, 1977). Further oxidation leads to formation of catechols,
which are subsequently subject to further ring fission. There is evidence
that yeasts, molds, and fungi (Cunninghamella bainierri) may oxidize
naphthalene by the mono-oxygenase-induced mechanism reported for mammmals
(Gibson 1977). This process forms reactive arene oxides, which isomer-
ize to phenols or undergo enzymatic hydration to yield trans-di'nydrodiols.
-------
NADP
NADPH
**
Arene Oxide
rra/u-Diol
Catechol
2H > 2e
( NADH
OH NAD
Dioxetane
c/'s-Diol
FIGURE 3-2 PATHWAYS UTILIZED BY MAMMALS AND BACTERIA FOR THE
OXIDATION OF AROMATIC HYDROCARBONS
Source: Gibson (1976).
-------
Table 3-12 presents a number of reaction products reported to
result from the biodegradation of naphthalene. For the most part, they
are intermediates in the multistep pathway of reactions leading ultimately
to complete mineralization of naphthalene into its inorganic constituents.
The rate of biodegradation of naphthalene is quite variable.
Table 3-13 presents quantified rates of biodegradation reported for
naphthalene in soil and freshwater systems. Due to the variation in
test methods, analytical techniques, microbial species, and data analyses
used in biodegradation testing (i.e., a lack of a standard procedure),
the results from the different tests reported in Table 3-13 cannot be
compared directly.
The turnover time and transformation rates in Table 3-14 in
both acclimated and unacclimated stream populations (Schwall and Herbes
1978) provide an estimate of naphthalene's environmental persistence and
illustrate the effect of microbial adaptation on the overall rate. The
turnover time was 7.1 hours in acclimated populations and 125 days in
nonacclimated populations. Based upon other laboratory studies, the
7.1-hour acclimated turnover time seems quite slow. Other processes,
such as adsorption and deposition into inaccessible bottom sediments,
may have affected the removal of naphthalene from solution before
significant biodegradation could take place. The extent to which these
rates are applicable to other aquatic systems is unknown because of the
scarcity of field data.
Because biodegradation may be a significant fate pathway for
naphthalene, it is worthwhile to briefly review the environmental factors
influencing biodegradation. The fission of aromatic rings usually requires
the addition of oxygen, most often from O2 (Alexander 1977), a fact
implying that PAH biodegradation can "take place only under aerobic con-
ditions. In the absence of O2» it has been hypothesized that the presence
of nitrate, which is rapidly reduced, may supply oxygen that can be used
in degradation (Alexander 1977) . The assimilation of hydrocarbons by
sulfate-reducing bacteria is thought to occur primarily with aliphatics
and not aromatics, although several bacterial strains have been isolated
in the laboratory that can utilize aromatic hydrocarbons (Haas and
Applegate 1975).
The pH of the soil solution also influences degradation rates.
A pH increase from 4.5 to 7.4 approximately doubled the rate of break-
down of PAHs (Verstraete ej: al_. 1976). Whether this increase was due to
population changes or to direct impact on the chemical reaction was not
explored.
Natural humic polymers may act as stabilizing agents on aromatics
and reduce their biodegradability (Pitter 1976). In addition, adsorption,
which is an important process for insoluble compounds like PAHs, may
reduce microbial access to these substances. However, since the organic
fraction of the sediment would eventually be subject to microbial break-
down in the course of the system's carbon cycling, any adsorbed naphthalene
3-30
-------
TABLE 3-12. 3ACTERIAL BIODEGRADATION PRODUCTS REPORTED FOR NAPHTHALENE
Degradation Product Reference
1-naphthol; 4-hydroxyl-l-tetralone; Cerniglia et_ al.
trans-1,2-dihydroxyl-l,2-dihydro- (1979)
naphthalene; 2-naphthol; 1,2- and
1,4-naphthoquinone
cis-dihydrodiols
Cerniglia et_ al.
(1979)
1,2-dihydroxynaphthalene, salicyl-
aldehyde, salicylate, catechol
Colwell and Sayler
(1978)
3-31
-------
TABLE 3-13. B101) KG RABAT I ON RATES OF NAPHTHALENE
Test Type/Population
Ori ^In
COj evolution from stream
sediment populations from
petroleum contaminated area
Compound Tested
14
C-naphthalene
Results
90% of total PAH transformed at
AO hours; rate = 0.14 hr
Source
Schwall and llerbes
(1978)
Warburg O2 consumption,
non-accllmated sludge
populat ion
Naphtha] cue
33-64% of TOI) transformed
Malaney e£ al.
(1967)
u>
1
u>
fO
Sliake flask
freshwater sediment
po|m 1 at ion
Hydrocarbon mixture
(parraffines, mono-
and dlcycllc
hydrocarbons)
Naphthalene; 3-12% decrease Walker and ColweLl
together with dodecane: 25-35% (1975)
decrease (1% sterile hydrocarbon;
28 days)
14
CO2 evolution with
seawater population
from treated area
Naphtha 1ene
0.4 [ig/l/day (by day 3)
Lee £t al,
(1978)
aTheoretical Oxygen Demand
-------
TAIILK 3-]'*. KINETIC PARAMETERS OF NAPHTHALENE TRANSFORMATION IN OIL-CONTAMINATED STREAM AND UNCONTAMTNATED
STREAM SEDIMENT SAMPLES
u>
I
Co
CO
o I)
Rate Constant k (l/li) Turnover Time Trans format Ion Rate (pk/r I'1-'1" h)
Conipoimd Contaminated llncontanilnated Contain Ina ted llncon t.mil natcd Contaminated Uncontamlnated
Naphthalene 1 .4 x 10 '
-------
would in time be subject to biodegradation. Adsorption onto organic
matter may also increase biodegradation by retaining the substrate in
areas with dense and active microbial populations, which tend to be
concentrated on organic particulates. The fate of naphthalene adsorbed
onto inorganic sediment is unknown; however, it would probably be more
persistent than that on organic sediment.
Thus, naphthalene is one of the most readily biodegradable
PAHs. However, an initial period of acclimation by the degrading popu-
lation is usually required. Reported half-lives for microbial degrada-
tion are on the order of 1 to 2 days in laboratory studies with
acclimated populations.
3.2.3.3 Modeling of Environmental Distribution
Introduction
Very limited monitoring data are available to describe the extent
of naphthalene contamination in the environment. Of the 16 PAHs, naph-
thalene has the highest water solubility, and is released to the environ-
ment at a higher rate than the others, suggesting that waterborne expo-
sure to naphthalene would be higher than to other PAHs. Several model-
ing efforts were undertaken in order to estimate the distribution of
naphthalene among the environmental compartments, and to describe the
important aspects of the behavior of naphthalene in selected environ-
mental settings. The Mackay equilibrium model was used to predict the
partitioning of naphthalene among environmental compartments in equili-
brium. The Exposure Analysis Modeling System (EXAMS), developed by the
U.S. EPA, was used to study the fate of naphthalene in generalized
aquatic environments.
Mackay Equilibrium Partitioning Model
As an initial step in hazard or risk assessments for toxic chemicals
and as an aid in the interpretation of monitoring data, a preliminary
estimate of a pollutant's environmental distribution can often be made
by inspection of the chemical's properties. A simple approach to approx-
imating the environmental partitioning has recently been proposed by
Mackay (1979) based upon the fact that in a system at equilibrium, the
fugacity of the pollutant must be the same in all phases.
In Mackay's Level I Model, all environmental compartments (phases)
are assumed to be directly or indirectly connected and at equilibrium.
The compartments considered are air, water, suspended solids in water,
sediment, and aquatic biota. The Level I calculations require that these
compartments be described roughly (volumes, temperature, biota "concen-
tration", etc.), and the model output will clearly depend upon the nature
3-34
-------
of the "environment" selected. The selected compartments are shown
schematically in Figure 3-3. The figure is not drawn to scale, although
compartment size and density, where appropriate, have been indicated.
The temperature was assumed to be 25"C.
A relatively small number of chemical-specific parameters is
required to calculate equilibrium partitioning; these are presented
in Table 3-15. For an absolute estimate of the equilibrium concentra-
tions in each phase, it is necessary to estimate the total amount of
the chemical that is likely to be in the selected environment. (Note
that the predicted concentration ratios between the phases will not be
affected by the value selected.) For these calculations, the total
amount of naphthalene in the system was 22.5 kg. Details of the
model calculation methods are provided elsewhere (Mackay 1979)
and are not repeated here.
The results obtained for naphthalene are presented in Table 3-16.
Naphthalene undergoes considerable volatilization upon standing, as one
might expect from its relatively high vapor pressure. The Mackay model
predicts that at equilibrium 77.8% of the environmental naphthalene
will reside in the air compartment. The different fractions of material
in the suspended solids and sediments are a result of the different sizes
of the compartments in the model; concentrations in each of these com-
partments are essentially the same. Within the water column, most of the
naphthalene is estimated to be in solution; suspended solids and biota
contain only a small percentage of the total water column quantity. The
water concentrations are lower than concentrations in the solid phases
by a factor of 20.
EXAMS Model
The U.S. EPA Athens Environmental Research Laboratory has developed
an interactive system designated as EXAMS (Exposure Analysis Modeling
System) to carry out exposure analyses for organic chemicals in six fresh-
water environments (Smith et al. 1978, U.S. EPA 1980c). In performing these
analyses, the model assumes "steady-state" behavior and considers the fate
and transport of the organic chemical as it passes through a system composed
of one or more water and sediment compartments. Within the aqueous compart-
ments, biota (fish, algae) may be assumed to exist and the extent of bio-
concentration of the organic chemical in the species may be calculated.
Using the precompiled environments, plus chemical-specific input
parameters, EXAMS models the bulk transport of a chemical within aqueous
compartments (mixing, dilution, transport downstream), as well as the
processes of volatilization (loss to the atmosphere), adsorption onto
sediments and suspended solids (by physical forces or ion exchange),
hydrolysis (assumed first-order reaction), photolysis (assumed first-order
reaction), biodegradation, and dissociation (for organic acids, bases,
complexes).
3-35
-------
Air Volume
3x107 m3
Water:
Volume 2x104 m3
Biomass 12.9 mg/l
Suspended Solids 30 mg/l
Sediment:
Volume 5x103 m3
Biomass 50.01 g/m3
77.8%
FIGURE 3-3 MACKAY ENVIRONMENTAL MODEL SYSTEMS
AND PREDICTED DISTRIBUTION OF NAPHTHALENE
3-36
-------
TABLE 3-15. VALUES OF PARAMETERS USED FOR CALCULATING THE EQUILIBRIUM
DISTRIBUTION OF NAPHTHALENE PREDICTED 3Y THE MACKAY FUGACITY
MODEL
Chemical - Specific Parameters (25°C)
3 A
Henry's Law Constant (m -atm/mole) 4.8 x 10
Adsorption Coefficients:
Suspended Solids (0.01 x K ) 21.43
Sediment (0.01 x K ) °C 21.43
oc
Biota (0.2 x K ) 468.9
ow
Total Amount in System (kg) 22.5(175 moles)
Compartment - Specific Parameters (25°C)
Air: ^ 2
area 1 x 10-m
depth 3 x lOy^o
volume 3 x 10 m
Water: ^2
area 1 x 10 m
depth 2m , _
volume 2 x 10 m
biomass content 12.9 ng/1
suspended sediment 30 mg/1
Sediment: , „
•i ->^4 2
area 1 x 10 m
depth 5 x 10~^m
volume 5 x lO^m^
biomass content 50.01 g/m^
wet sediment density 1.85 g/cm
sediment dry weight « (100 x wet weight)/137
-------
TABLE 3-16. EQUILIBRIUM PARTITIONING OF NAPHTHALENE CALCULATED USING
THE MACKAY FUGACITY MODEL
Particioning At Equilibirum
Compartment Moles Concentration Percent
Air 136.7 0.583 mg/m3 77.8
Water 4.7 0.33 mg/1 2.7
Suspended Solids 0.003 0.65 mg/kg 0.0017
Sediment 34.3 0.65 mg/kg 19.53
Aquatic Biota 0.03 14.24 mg/kg 0.0163
Sediment Biota 0.003 14.24 mg/kg 0.0016
TOTAL IN SYSTEM
175
-------
EXAMS was run for naphthalene. 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 3-17. 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 impor-
tant for naphthalene or were calculated by the model using the basic
input data.
The loading rate used for the EXAMS calculations was estimated
from data presented in the materials balance section of this chapter
(3.1). The largest continuous discharge of naphthalene to surface
waters arises from coal tar production activities; a much smaller discharge
is estimated to occur when the coal tar is used to produce naphthalene.
'Appendix A of Volume IV of this report lists coke-oven tar production sites
in 19 states, with production by state ranging from 26% to 0.5% of the total
production. Assuming that there is one site per state, and that the
release of naphthalene is proportional to the production level at each
site, the annual release at each site can be expected to range from
78 kkg/yr to 1.5 kkg/yr (i.e., 26% to 0.5% of the 300 kkg/yr
discharged from coal tar production and distillation reported in Table 3-7) .
Assuming plant operation of 300 day/yr, the daily load by state would
range from 260 kg/day to 5 kg/day. Since it is possible that there nay be
more than one site per state, the lower loading rate was considered a
more appropriate approximation of the actual discharges to environmental
waters. Therefore, a discharge rate of 0.2 kg/hr (4.8 kg/day) was used
in the model.
One scenario that could result in short-term discharges at con-
siderably higher levels than the level chosen for use in the EXAMS cal-
culation is spillage or leakage of petroleum [crude oil has a naphthalene
content of 1,000 mg/kg (see Section 3.1)]. There are insufficient data
to estimate either the amount of naphthalene released to the aquatic
environment in such an incident, or the behavior of the naphthalene
released in crude oil. Partitioning among the compartments and removal
processes could be different from those characteristic of low-level,
continuous discharges used in the model since equilibrium may not be
achieved.
When the calculated concentration of naphthalene is below the
maximum solubility level, maximum concentrations and accumulations will
be proportional to the loading and can be adjusted accordingly, without
affecting the self-purification times and percentage distribution of
naphthalene. Table 3-18 summarizes the naphthalene concentrations
predicted by EXAMS for the simulated environments under steady-state con-
ditions. Water concentrations in the relatively static pond and lake systems
were approximately 0.005 rag/1 to 0.48 rng/1; concentrations in the river
systems were considerably lower, 1.9 x 10 ¦ rag/1 to 1.7 x 10~3 -g/1, due to
dilution and physical transport mechanisms. These aqueous concentrations are
3-39
-------
TABLE 3-17. INPUT PARAMETERS FOR EXAMS MODELING OF THE FATE OF
NAPTHALENE IN GENERALIZED AQUATIC SYSTEMS
Input
Explanation Value
Molecular wt. (g/mole) 128.1
Ratio of volatilization 0.460
to reaeration rate
Aqueous solubility (mg/1) 31.7
Partition coefficient 322.0
biomass:water
-4
Henry's Law Constant 4.8 x 10
(atm mole~l)
Partition coefficient 2344
octanolrwater
Second-order bacterial 1 x 10 ^
degradation rate constant
(in water and in sediment)
(ml/cell/hr)
Increase in bacterial de-
gradation rate per 10°C 2
in temperature
_3
Photolysis rate constant 9.76 x 10
Reference latitude for 35.00
photolysis rate constant
References
Weast (1970)
SRI (1980)
May et_ _al_. (1978)
SRI (1980)
Table 3-10
Callahan et al. (1979)
SRI (1980)
SRI (1980)
Calculated from data
in Zepp and Schlotzhauer
(1979)
Zepp and Schlotzhauer
(1979)
Loading rate (kg/hr)
0.2
Data in Section 3.1
-------
TABLE 3-18. STEADY-STATE CONCENTRATIONS OF NAPHTHALENE IN VARIOUS GENERALIZED AQUATIC SYSTEMS RESULTINC
FROM CONTINUOUS DISCHARGE AT A RATE OF 0.2 kg/hour0
Maximum Concentrations
System
Loading
Rate
(kg/hr)
Dissolved
Water
(ing/L)
Total
Water
(mg/I.)
Pore
Water
(mg/L)
Sediment
Deposits
(nig/kg)
Plankton
(I'g/g)
Benthos
-------
well below the 31.7 mg/1 solubility of naphthalene; therefore, these
results may be extrapolated for larger discharges, providing steady-state
conditions are reached.
Sediment concentrations ranged, from 0.002 mg/kg in the turbid river
system to 58 mg/kg in the pond. The high levels in the pond sediment
result from the fact that removal processes, such as volatilization and
physical transport, were too slow to compete with adsorption and sedimentation.
The pond also contains a large amount of biota that are subject to sedi-
mentation; the concentrations in biota are generally two to three orders
of magnitude above levels in water.
Table 3-19 presents the EXAMS results concerning the fate of naph-
thalene in the aquatic systems. The distribution shown indicates the
importance of the environmental conditions in the partitioning of naph-
thalene between water and sediments. The pond has significant
sediment/water mixing and a large amount of suspended sediment and
biota; adsorption and sedimentation is facilitated in this system,
accounting for the observation that 80.54% of the naphthalene
will be residing in the sediment. In contrast, the oligotrophic lake
has more transport across system boundaries than the pond, and has very
little suspended matter; consequently only 1.8% of the naphthalene
will be in the sediment of this system. Furthermore, the lake contains
more biota of the type that are not available for sedimentation, and fewer
plankton than the pond, causing transport of naphthalene to lake sediment
to be a slower process.
In the more dynamic systems, such as the rivers, transport beyond
the model boundaries of the system accounts for most of the removal
of naphthalene. Biological transformation is also important in the
coastal plain river, which contains a significant amount of biota.
Volatilization is particularly important as a removal process in the
oligotrophic lake and the pond; chemical transformation (photolysis)
is also significant in the clear oligotrophic lake, where light penetra-
tion is high; and biological transformation competes with volatilization
in the pond. The fate of naphthalene in eutrophic lakes is governed
primarily by biological transformation.
Based upon the distribution and fate data, and the input parameters
for the various removal and degradation processes, the persistance of
naphthalene can be estimated for each of the aquatic systems. These data
are presented in Table 3-2 0. More than one-half of the accumulated load
is removed from the river systems (physical transport) and the eutrophic
lake system (biodegradation) within half a day. In contrast, EXAMS
predicts that within 12 days of the cessation of discharge, only 28%
of the naphthalene will be removed from the pond system (volatilization,
chemical and biological degradation) and 56% will be removed from the
oligotrophic lake system.
3-42
-------
TABI.K 3-19.
TI1K FATE OF NAPIITIIAI.ENE IN VARIOUS CICNKRALIZED
AQUATTC SYSTEMS3
System
Residing In
Water at
Steady-Sta te
Residing In
SedimenL at
Steady-State
Transformed
by Chemical
Processes
Transformed
by
Blologica1
Processes
Volatllized
Lost
by Other
Processes
Time
System Self-
Purl f icul ion'
Pond
19.46
80.54
7.02
35.61
50.99
6.38
233.5 days
Eu trophic lake
86.41
13.59
0.45
95.87
3.65
0.03
15.2 days
01igotrophlc lake
98.20
1 .80
39.12
0.33
56.77
3.78
58.56 days
River
78.06
21.94
0.06
3.08
1.11
95.75
15.1 days
Turbid River
86.26
13.74
0.05
3.05
1.10
95.81
6.5 days
Coastal Plain River 54.55
45.45
0.41
23.88
8.60
67.11
58.8 days
''All data simulated by the EXAMS (U.S. EPA-SERI,, Athena Ga.) model, (See text for further information about input
parameters and Smith e£ aK (1978) for a description of the model.)
Including loss through physical transport beyond system boundaries.
CKstimate for removal of ca. 97% of the toxicant accumulated in system (5 apparent system half-lives). Estimated
from the results of the half-lives for the toxicant in bottom sediment and water columns, with overall cleansing
I'line weighted according to the pollutant's initial distribution.
-------
TABLE 3-2O. THE PERSISTENCE OF NAPHTHALENE IN VARIOUS GENERALIZED
AQUATIC SYSTEMS AFTER CESSATION OF LOADING AT 0.2 kg/hour3
%
Lost
from
Time Total
Period % Lost % Lost System
System
(days)
from Water
from Sediment
Pond
12
90.85
13.55
28.59
Eutrophic Lake
0.5
62.53
0.70
54.13
Oligotrophic Lake
12
56.94
7.17
56.04
River
0.5
99. 98
2.51
78.59
Turbid River
0.5
99.98
3.71
86.76
Coastal Plain River
0.5
92.93
1.34
51.30
SA11 data simulated by the EXAMS (U.S. EPA-SERL, Athens, Ga.) model.
[See text for further information about input parameters and Smith et_ al.
(1978) for a description of the model.]
3-44
-------
Comparison of Mackay and EXAMS Predictions
The pond environment was chosen as the most appropriate EXAMS system
to compare with the Mackay model since a pond has the least amount of
transport across system boundaries. In spite of the fact that the
Mackay water system was sized to correspond to the EXAMS pond, the two
models are not directly comparable since other assumptions of each
model are often quite different. The Mackay model includes the air
compartment, whereas EXAMS models only the aquatic system. Further-
more, the Mackay model is simply a partitioning model; EXAMS utilizes
kinetic data and includes processes that may occur after the chemical
has been partitioned into one of the aquatic compartments. The concen-
tration data predicted by the Mackay model are calculated from the
amount of the chemcial partitioned to each compartment and' the size
of the compartments. Since these parameters are arbitrarily set, the
raw concentration data cannot necessarily be taken as indicative of
actual environmental concentrations, and the relative partitioning
among the compartments is the most valuable result.
I
Table 3-21 summarizes some of the relevant data from the two models.
The total load for the Mackay model was chosen so that the amount parti-
tioned to water and sediment would be equal to the EXAMS pond accumulation.
The .actual concentrations predicted by the Mackay model are lower than
the EXAMS data. However, the ratios of the concentrations predicted for
the various compartments by the two models are fairly consistent. The
ratios of the percentages of naphthalene expected to be dissolved or
adsorbed are also in agreement. Note that 77.8% of the initial
load to the Mackay system was partitioned to the atmosphere due to the
large Henry's Law Constant for naphthalene.
3.2.4 Monitoring Data
3.2.4.1 STORET -Data
Introduction
Monitoring data from the STORET Water Quality Information System
(U.S. EPA 1980a and 1981) indicate limited sampling of naphthalene in
ambient and effluent waters since 1978. Sampling activities have not
been uniformly distributed across the country, representing only the
geographic areas of the East (excluding New England), the South, and the
West. Naphthalene concentrations for ambient and effluent waters, sediment,
and fish tissue were recorded in the STORET system.
STORET monitoring data for naphthalene include observations for
26 states and the U.S. territory of Puerto Rico. Roughly 490 monitoring
stations have recorded information; the following discussion is cf
ambient data registered as of November 20, 1980.
3-45
-------
TABLE 3-21. COMPARISON OF RESULTS FROM MACKAY'S EQUILIBRIUM MODEL AND
EXAMS FOR NAPHTHALENE IN A POND SYSTEM
EXAMS Results
(Pond, 4.8 kg/day loading
5.0 steady-state accumulation)
Maximum Concentrations
Mackay's Results
(22.5 kg in system)
Concentrations
Water
0.48
mg/1
Water
0.03 mg/1
Aquatic Biota
154
mg/kg
Water Biota
0.65 mg/kg
Sediment Biota
128
mg/kg
Sediment Biota
0.65 mg/kg
Sediment
58
mg/kg
Sediment
0.65 mg/kg
Accumulation
% in Water 19.46
% in Sediment 80.54
Percent of Chemical per Compartment'
% in Water 2.7%
% in Sediment 19.5%
77.8% of the initial load was partitioned to the atmosphere.
3-46
-------
Ambient and Effluent Waters
Roughly 302 ambient observations of naphthalene are stored in the
STORET system; 96% of these observations are remarked. The remarked
observations are reported as the detection limits, used in sampling, and range ud
to 20 ug/l for naphthalene. A limit of 10 ug/l is recorded most fre-
quently, i.e., for 52% of all samples analyzed. Table 3-2 2
presents the percentage distribution of ambient concentrations for naph-
thalene. Of the 294 remarked concentrations, 17% are no higher than 1 ug/l,
70% are between 1.1 and 10 ug/l, and 13 % are between 10.1 and 100 ug/l.
The eight unremarked concentrations range from 0.005 ug/l to 17 ug/l-
The state locations of these observations are also shown in Table 3-22.
Eighty-seven percent of the 534 effluent concentrations recorded
as of April 9, 1981 (from 271 monitoring stations) are remarked. Table
3-22 shows the percentage distribution of effluent concentrations, re-
marked and unremarked, for naphthalene. Thirty-six percent of the 466
remarked concentrations are less than or equal to 1 ug/l, 60% between
1.1 and 10 ug/l, and 2% between 10.1 and 100 ug/l. Of 68 unremarked
effluent concentrations, 12% are no higher than 1 ug/l, 22% between 1.1
and 10 ug/l; 50% are between 10.1 and 100 ug/l; 9% are between 100.1 and
1000 ug/l; and 7% are over 1000 ug/l. Three of the five observations
over 1000 ug/l were recorded from sampling at a disposal site in Wash-
ington State; the fourth was from a textile plant effluent in South Bronx,
New York; and the fifth from a chemical plant effluent in Kentucky.
Sediment
Eighty-four percent of the 130 observations for naphthalene in
sediment (ambient waters) are remarked. The detection limits range
up to 10,000 ug/kg, with 2,000 and 2,500 ug/kg accounting for 38% of the
remarked observations.
Twenty-one unremarked observations indicate naphthalene concentra-
tions in sediment ranging from 0.02 ug/kg to 496 ug/kg. The percentage
distribution of observed concentrations of naphthalene in sediment is
shown in Table 3-23.
Fish Tissue
All observations of naphthalene in fish tissue are remarked. Of
the 73 remarked observations in STORET, 14% of the detection limits are
no higher than 1 mg/kg; 86% are between 1.1 and 10 mg/kg (Table 3-23).
3-47
-------
TABLE 3-22. DISTRIBUTION OK AMBIENT AND EFFLUENT CONCENTRATIONS (pg/1) FOR NAPHTHALENE - STORET 1980
AMBIENT DATA
TOTAL!
NUMBER
IN REMARKED CONCENTRATION RANCES
TOTAL
NUMBER IN UNREMARKED CONCENTRATION
RANCES
SI
1.1-10
10.1-100 100.1-1000 >1000
<1 1.1-10 10.1-100 100.1-1000
>1000
294
50
206
38
8
6 1 1
—
Location of Unremarked Concentrations
Washington State: 0.06, 0.11, and 0.2 pg/1
Oregon: 0.005 pg/l
Pennsylvania: 0.24 and 1.4 |ig/l
New York: 0.6 pg/1
North Carolina: 17 |ig/l
EFFLUENT DATA
.totaiJ
NUMBER
IN REMARKED CONCENTRATION RANCES
TOTAL
NUMBER TN UNREMARKED CONCENTRATION
1 w
I
z,
1000
±1
1.1-10 10.1-100
100.1-1000
>1000
466
177
280
9
68
8
15 34
6
5
Location of Unremarked Concentrations >1000 pr/1:
Washington State: 6300, 9800, and 36000 pg/l (Queen City Disposal SlLe)
New York: 1030 pg/1 (Plant Effluent - Textile)
Kentucky: 1300 pg/l (Treatment Plant Effluent - Clieoiical)
Source: STORET data as of April 9, 1981.
-------
TABLE 3-23. DISTRIBUTION OF NAPHTHALENE CONCENTRATIONS IN SEDIMENT AND
FISH TISSUE IN AMBIENT WATERS—STORET 1980
Sediment (;jg/kg):
Remarked
Unremarked
Fish Tissue (mg/kg):
Remarked
Unremarked
TOTAL
NO.
108
21
73
NUMBER OF OBSERVATIONS IN CONCENTRATION RANGES
<1 1.1-10 10.1-100 100.1-1000 >1000
25
4
1
'3
2
11
12
3
68
10 63
Source: STORET data as of November 20, 1980.
3-49
-------
3.2.4.2 Other Data Sources
Drinking Water
According to the U.S. EPA criteria document for naphthalene (U.S.
EPA 1980b), naphthalene has been detected in drinking water supplies
at concentrations up to 1.4 ug/1, in ambient water at up to 2.0 ug/1,
and in sewage plant effluents at up to 22 pg/1. Levins et al, (1980)
found no detectable levels of naphthalene in tap water samples from
drainage basins in Cincinnati, St. Louis, Atlanta, and Hartford. Av-
erage concentrations found in raw wastewaters from the four municipal
areas were:
2.1 ug/1 from residential areas
2.6 ug/1 from commercial areas
50.7 ug/1 from light industrial areas
11.6 ug/1 at POTW influent.
Effluents
Rawlings and DeAngelis (1976) have shown the range of naphthalene
in textile effluents to be 0.003-300 ug/1. Other levels of naphthalene
in industrial effluents have been reported by the U.S. EPA (1980b); the
maximum industrial effluent concentration was 32,000 ug/1. Naphthalene
concentrations in final effluents from industrial sewage were measured at
a maximum level of 22 ug/1. Neither the location nor the type of industry
was reported for these data.
Air
Various investigators have measured both the vapor and particulate
levels of naphthalene in air. Krstulovic et_ aL (1977) reported particu-
late levels of naphthalene for three Rhode Island cities corresponding
to urban, suburban, and rural areas. These levels were 0.25 ng/m^,
0.03 ng/m^, and 0.003 ng/m^, as presented in Table 3-24. Table 3-24
also includes data for air levels of naphthalene in samples taken at
industrial sources. Bjorseth et_ al. (1978a,b) reported naphthalene vapor
levels ranging from 11-1,100 for vapor, and 0.09-4.0 ug/rn^ for
particulate matter. The U.S. EPA has reported a measurement of 0.50 ng/ra^
of naphthalene in urban air; this concentration is an average of reported
levels (U.S. EPA 1980b).
3.2.5 Summary - Ultimate Fate and Distribution
Most of the environmental releases of naphthalene are to the atmosphere.
Atmospheric deposition (wet and/or dry fallout) is expected to remove only
2-3% (200-300 kkg on the basis of 1978 data) of the total atmospheric load.
It is estimated that the amount deposited directly onto U.S. inland surface
waters will be proportional to their area, i.e., 2% of the total continental
United States. Therefore, ^5 kkg can be expected to fall on inland surface
waters of the U.S. annually; only a fraction of the fallout to land ^rill
3-50
-------
TABLE 3-2 4. REPORTED LEVELS OF NAPHTHALENE IN AIR
Concentration (ng/m )
Area fnvestigated
Atmosphere of coke
plant'
Atmosphere of
aluminum reduction
p i ant*5
Vapor Level
1.1 x 10^ - 1.1 x 106
Particulate Level Total
0 - 4.4 x 10"
7.2 x 102 - 3.1 x 105 90 - 4 x 103
Reference
Bjorseth e^_ al.
(1978a)
Bj orseth e^t al.
(1978b)
U)
i
Ul
Providence, R.I.
Kingston, R.T.
Naragansett Bay, R.I.
0.1
0.03
0.05
0.25
0.03
0.003
0.35
0.06
0.053
Krstulovic ^t al.
(1977)
Krstulovic e^t al.
(1977)
Krstulovic et^ al.
(1977)
Range includes measurements for fall and spring sampling, using mobile, stationary, and personal
sampling techniques.
'Ranges are for measurements using stationary and personal sampling techniques.
"Samples collected in September 1975: 9-hour collection time, northwest wind.
-------
ultimately reach aquatic systems via runoff and leaching. The naphthalene
remaining in the atmosphere is expected to undergo rapid photo-oxidation
to quinones and other oxygenated compounds; however, a thorough review of
the atmospheric fate pathways is beyond the scope of this report.
Since naphthalene has a vapor pressure of 0.09 torr at 25°C, and log
of the octanol:water partition coefficient of 3.37, a large amount of the
naphthalene in surface waters can be expected to be removed to the atmos-
phere via volatilization; removal to the sediment via adsorption and sedi-
mentation may be important if there is a significant amount of suspended
material in the aquatic system. Biodegradation may also be a significant
fate process for naphthalene in aquatic systems. The application of the
Mackay equilibrium partitioning model (Mackay 1979) confirms the prediction
that large amounts of the environmental naphthalene will be in the atmos-
phere (78%) and sediment (20%) . Calculations based on the Exposure Analysis
Modeling System [EXAMS] also predict that biotransformation, volatilization,
photolysis, and physical transport could all be important fate processes,
depending upon the actual conditions in the environment. In comparison
with the other PAHs, photolysis, oxidation, and sedimentation of naptha-
lene are less important pathways; volatilization is the most important
fate process in static aquatic systems. The extent of volatilization
depends upon temperature, wind velocity, and current velocity. In rivers,
the major fate pathway is transport of adsorbed naphthalene to the oceans.
EXAMS results for six generalized aquatic systems suggest that the
naphthalene in sediment will tend to remain there unless there is con-
siderable mixing between the sediment and the water column, since neither
photolysis nor anaerobic degradation are important fate pathways. In
summary, although the sediments and the water columns of aquatic systems
may contain naphthalene, accumulation will occur in the sediment.
Monitoring data confirm that concentrations in sediment are higher
than those in water. The STORET data base reports actual measurements of
naphthalene in ambient waters ranging from 0.005 ug/1-17 ug/1; effluent concen-
trations up to 36,000 yg/1 are reported. Actual sediment concentrations
reported in STORET range from 0.02 pg/kg to 496 ug/kg. Drinking water
concentrations up to 1.4 yg/1 were reported in the literature. Ambient
air concentrations of naphthalene were reported to be 0.35 ng/m3 in an
urban area, and 0.05 ng/m3 in a rural area. Concentrations to which
industrial workers may be exposed range from 102 ng/m3 to 10° ng/m3 in
the vapor phase, and up to 4 x i03 ng/m3 adsorbed onto particulate matter.
Some of the major sources of aquatic naphthalene, the predicted
distribution, and the major fate processes are shown in Figure 3-4.
There are very few experiments examining rates of degradation and re-
moval specifically for naphthalene; most of the half-lives are estimated
from measurements for the larger PAKs.
3-52
-------
OJ
I
Ul
LO
93%env. releases, 10 kkg/yr.
(rapid photolysis, t(/j 5-10 hrs.)
Atmospheric Deposition
2—3% airborne load,
200-300 kkg/yr.
to U.S.
inland waters
to U.S. land mass
^ 250 kkg/yr
5 kkg/yr
Volatilization
Biotranslocation
ty 3.2—75 hrs
Photolysis
t,/ 'V 71 hrs
Runoff
Oxidation
an
t 10—45 nrs.
(limited by concentration of oxidants)
)n lo9Kow
-v.*:-
WATER
'
Sorption log KQW = 3.37 (Slower than other PAH)
Physical
Transport
Desorption
Biotransformation
Od tv 24-48 hrs.
LAND
Sedimentation
~
SEDIMENT
Direct Discharge
3 % cnv. releases
354 kkg/yr.
"v.
FIGURE 3 4
SOURCES AND FATE OF NAPHTHALENE IN THE AQUATIC ENVIRONMENT
-------
3.3 EFFECTS AND EXPOSURE—HUMANS
3.3.1 Human Effects
3.3.1.1 Introduction
This section of the report summarizes the pertinent health effects
associated with naphthalene exposure. The U.S. EPA (1980a) concluded
that there were few or no quantitative data concerning the chronic tox-
icity or carcinogenicity of naphthalene from which to derive a water
quality criterion for drinking water. Based on the apparent low levels
of naphthalene in natural waters, they concluded that it did not appear
that significant adverse effects would result from ingestion of water
containing these low levels of naphthalene.
3.3.1.2 Pharmacokinetics
Naphthalene appears to be absorbed via all routes of exposure—
ingestion, inhalation, and skin contact. The rate and extent of absorp-
tion by any route have not been studied in detail; however, numerous case
reports of toxicity following ingestion or inhalation indicate appreciable
absorption by these routes. One report by Dawson et_ al. (1958) suggests
that skin absorption of naphthalene vapors occurred in infants when the
skin was covered with baby oil. As is discussed below, newborn infants
may be highly sensitive to naphthalene exposure.
The tissue distribution of naphthalene following absorption has
apparently not been studied in detail; one study in ducks (Lawler et al.
1978), along with consideration of the high lipid solubility of naphthalene,
suggests that naphthalene has a wide tissue distribution.
The metabolism of naphthalene has been extensively studied. The
major pathways that have been elucidated are given in Figure 3-5. Pre-
sumably, these pathways are similar among human and other mammalian
species. Of importance is the metabolism of naphthalene to toxic meta-
bolites including 1- and 2-naphthol, 1,2-dihydroxynaphthalene and
1,2-naphthoquinone. Though the importance of the liver in the metabolism
of naphthalene is clearly established, the involvement of other tissues
has apparently not been studied with the exception of the metabolism
in the eye.
3.3.1.3 Human and Animal Studies
Carcinogenicity
Results of the few studies on naphthalene carcinogenicity via oral
or subcutaneous routes do not indicate a carcinogenic response (Table 3-25).
Two experiments by Knake (1956) indicated a nonstatistically significant
increase in lymphosarcomas in rats (subcutaneous injection) and of lympho-
cytic leukemia in mice (skin painting). These experiments, however,
3-54
-------
/'CO
oso3h
2
NHCOCH
SCHjCHCOOH
H
Glucuronide
0
OSO3H
OGIucu ronide
FIGURE 3-5 METABOLISM OF NAPHTHALENE
Note: (1) Naphthalene; (2) naphthalene epoxide; (3) 1,2-dihydro-1,2-dihydroxynaphthalene
(naphthalene diol); (4) 1-naphthol; (5) N-acetyl-S-( 1,2-dihydro-2-hydroxynaphthyl)
cysteine; (6) 1,2-dihydroxynaphthalene; (7) 1,2-naphthoquinone (^-naphthoquinone);
(8) 1-naphthyl sulfate; (9) 1-naphthyl glucuronide; (10) 2-hydroxy-1-naphthyl sulfate;
(11) 1-glucosiduronide of (3); (12) 2-naphthol.
Source: Van Heyningen (1979).
3-55
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TABLE 3-25. DATA ON CARCINOGENICITY OF NAPHTHALENE IN ANIMALS
Spec i es
Route/Dosage
Findings
Reference
Test Control
ral
mouse
a'^Subcu taneous/
500 mg/kg,
every other week
for total of 7
treatments,
observed for 18
months
a,cSkin painting/
0.5% naphthalene
in benzene, 5 days/
week for lifetime
rat
(HI) I and BD II)
Oral/10 g/rat
"over a period
of time"
Subcutaneous/
820 mg/rat
Lymphosarcoma
Other Malignant Tumors
5/34
0/34
Lymphocytic Leukemia
Lung Adenoma
4/25
3/25
1/32
0/32
0/21
1/21
None of 28 rats developed tumors
Rats followed for up to 1000 days
None of 10 rats developed tumors.
717
Knake (1956)
Knalce (1956)
Druckrey and
Schinahl (1955)
Coal tar naphthalene contained 10% unknown impurities.
^ Carbolfuchsin, a known carcinogen, was applied to the site prior to each injection.
c Benzene has shown to be an animal carcinogen (Maltoni and Scarnato 1979) and may have contributed
to Lhese findings.
-------
are equivocal with respect to the role of naphthalene because: an esti-
mated 10% of the coal tar naphthalene used in the study consisted of an
unknown impurity; carbolfuchsin, a known carcinogen, was applied to the
site prior to each subcutaneous injection; and the skin-painting experi-
ment utilized benzene, a known animal carcinogen (Maltoni and Scarnato
1979), as the solvent. Several other skin-painting studies were negative
for naphthalene (Kennaway 1930, Kennaway and Hieger 1930, Bogdat'eva and
Bid 1955).
Mutagenicity
Consistent with its apparent non-carcinogenicity, naphthalene was
not mutagenic in bacterial mutagenicity assays (Table 3-26). In vitro
cell transformation assays were also negative (Table 3-2 7).
Teratogenicity
Retarded cranial ossification and heart development were observed
in twice as many rats from Sprague-Dawley dams injected intraperitoneally
with 395 mg naphthalene/kg bodyweight on days 1-15 of gestation compared
to controls (p<0.Q01). No additional information was presented in the
meeting abstract (Harris et al. 1979).
A metabolite of naphthalene, 2-naphthol, when given to pregnant
rabbits (dose, route and time of administration not indicated) caused
cataracts and evidence of retinal damage in the newborn (Van der Hoeve
1913). The capability of naphthalene to induce cataracts is discussed below.
Reports of toxicity to newborn infants subsequent to maternal exposure
to naphthalene were cited in the criteria document on naphthalene (U.S. EPA
1980a);however, details on dose and effects were not discussed.
Acute and Subchronic Toxicity
The oral LDLo (lowest dose reported to cause lethal effects) for
naphthalene in children was reported to be ^100 mg/kg (Sax 1979). In
rodents, the oral LD-n (dose reported to be lethal to 50% of the subjects)
is in the vicinity or 2000 mg/kg (U.S. EPA 1980a). Long-term sequelae to
acute, sublethal exposures to naphthalene in humans include cataracts,
sometimes accompanied by retinopathy, and hemolysis, which can lead to
jaundice and renal disease from precipitated hemoglobin. These effects
have been reported in both infants and adults (U.S. EPA 1980a).
Near blindness developed within 8 to 9 hours in a 36-year-old
pharmacist who ingested 5 g (^80 mg/kg) naphthalene; bilateral cataracts
was also reported by Ghetti and Mariani (1956) who examined 21 workers
exposed to naphthalene. Details on severity, control incidence, and
exposure levels were not indicated in the criteria document (U.S. EPA 1980a).
3-57
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TABLE 3-2 6. MUTAGENICITY OF NAPHTHALENE IN VARIOUS TN VITRO MICROSOMAL/MAMMALIAN ASSAY SYSTEMS
System
Strain
Result
Reference
Rat microsome/
Salmonella typhlmurium
Mouse microsome/
Sri ImonelJa typhlmurium
Mouse microsome/
Escherichia coli
TA100
TA1535
TA 1537
TA 98
TM 677
C46
K] 2
I)
ested at 10, 100, 500, and 1000 pg/plate
rested at 2 niM concentration .
Negative
Negative'
Negative*"
Negative'
Negative^
Negative
Negative
McCann et^ a^. (1975)
McCann et^ al_. (1975)
McCann et aj^. (1975)
McCann a_L. (1975)
Kaden et^ al_. (1980)
Kraemer ^t £l. (1974)
Kraemer et al, (1974)
"Naphtha!ene-1,2-oxide used in the test system
-------
TAHLK 3-2 7. ACTIVITY OF NAPHTHALENF. WITH IN VITRO NEOPLASTIC TRANSFORMATION TEST SYSTEMS
Test System
Rat embryo eells/pretreated with
Rauscher leukemia virus3**5
Mouse embryo eells/pretreated with
AKR leukemia virus9
Mouse mammary gland
whole organ culture
Dose (pg/L)
50
1,000
5,000
10,000
50,000
100,000
100
500
1,000
5,000
1
10
100
1,000
Result
Negative
Negative
Negative
Negative
Negative
Negative
Negative
Negative
Negative
Negative
Negative
Negative
Negative
Negative
Reference
Freeman t?t_ ad. (1973)
Freeman et_ aj_. (1973)
Freeman ej^ a_l. (1973)
Freeman et_ a_K (1973)
Freeman et_ jrl. (1973)
Freeman et (1973)
Rhim et al. (1974)
Rhim _et al_. (1974)
Rhim ejt nj_. (1974)
Rhim et_ £l1. (1974)
Tone 11 1. et^ al. (1979)
Tonelli et al. (1979)
Tonelli et_ aJL (1979)
Tonelli et al. (1979)
Jn addition to transforming ability, treated cells were injected into newborn rats or mice,
respectively, without any evidence of Lumorigenicity .
^Dissolved in acetone .
Dissolved in dimethylsuJfoxide .
-------
Cataracts and retinopathy have been produced in experimental
animals at dose levels of ^1000 mg/kg/day, although the onset of lens
and retinal changes was noted to occur as early as 1 and 2 days. We
were unable to determine the steepness of the dose-effect relationship
and the level of a threshold dose from the available data.
The biomolecular mechanisms by which naphthalene induces cataracts
in rabbits have been studied by Van Heyningen and coworkers (1967, 1970,
1976, 1979). Reactive metabolites, 1,2-dihydroxynaphthalene and
1,2-naphthoquinone, are formed in the eye, then combine irreversibly
with thiol groups of lens protein to form a brown precipitate, resulting
in degenerative changes in lens epithelium. Hydrogen peroxide and oxalic
acid are formed, and NADPH levels are depleted as the 1,2-dihydrodiol and
the quinone are interconverted. Hydrogen peroxide and oxalic acid deplete
reduced glutathione (GSH), which normally acts as a metabolic "scavenger"
of toxic metabolites that react with thiol groups.
Hemolytic anemia caused by naphthalene exposure seems to be asso-
ciated with a relative deficiency of enzymes responsible for maintaining
GSH, lowering its availability. In the absence of GSH, oxidative denatur-
ization of hemoglobin occurs, leading to stiffening and consequent fra-
gility of red blood cell membranes. Relative deficiencies in the
glucose-6-phosphate dehydrogenase (G6PD), which is necessary for main-
tenance of GSH levels in red blood cells, are known to occur in certain
population groups, e.g., blacks who trace their ancestry to malaria
hyperendemic areas (Goldstein 1974). Approximately 100 million people
worldwide have G6PD deficiency (Wintrobe et al. 1974).
A total of 24 cases of naphthalene-related hemolytic anemia were
reported in the world literature between 1920 and 1958; 80% of these
cases occurred in blacks or Orientals; three cases involved newborn
infants (Dawson et_ al. 1958). Anecdotal reports suggest an increased
susceptibility of newborn infants (1-2 weeks) to the hemolytic effects
of naphthalene (Schafer 1951, Cock 1957, Zinkham and Childs 1957). In
a review of two cases, in which infants were wrapped in clothing heavily
impregnated with either naphthalene or naphthol, Dawson £t al. (1958)
noted that the affected newborns, as well as one to several other members
of the immediate family, showed signs of G6PD deficiency. Along with the
genetic susceptibility of these infants, several other factors may have
contributed to the production of hemolytic anemia. These include:
(1) the application of baby oil to the skin of both infants prior to
dressing , thus increasing the absorption of these highly lipid-soluble
materials; (2) the reduced thickness of skin in newborns; (3) the
diminished glutathione reductase levels normally found in all newborn
infants; and (4) a decreased capacity of conjugation with glucuronide
in the newborn, thus allowing an accumulation of toxic metabolites
(1,2-dihydroxynaphthalene and 1,2-naphoquinone) (Dawson et_ al. 1958) .
3-60
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The dose-effect relationship between naphthalene and hemolytic
anemia is not clear. It would appear that in a healthy but G6PD defi-
cient adult low level exposure to naphthalene would lead to shortened
life for red blood cells, but this effect could be readily compensated
by increased production of red blood cells. Dose-effect relationshiDs
cannot be estimated from the anecdotal reports of young infants having
toxic reactions to naphthalene vapors from clothing which had been
stored in naphthalene moth flakes.
Ambient Water Quality Criterion - Human Healt-h
There are no adequate chronic toxicity or epidemiological studies
available for use as a basis for a naphthalene water criterion. The
U.S. EPA (1980a)has, therefore, established that a satisfactory criterion
for naphthalene cannot be derived at this time.
Other Risk Considerations
There are few quantitative data on carcinogenic or long-term
effects of naphthalene exposure. The chemical appears to be absorbed
readily by all routes of exposure, but the extent of absorption is not
clearly defined. The two major effects linked to naphthalene exposure
include cataract formation and hemolytic anemia. Information on the
production of cataracts is mainly anecdotal, but a single report noted
an effect following ingestion of ^80 mg/kg. Individuals with relative
deficiencies in the enzymes needed to maintain reduced glutathione
levels, as well as the fetus and young infants (1-2 weeks old), appear
at increased risk to develop hemolytic anemia, which can lead to renal
damage. Dose-response relationships, however, are unclear.
3.3.2 Human Exposure
3.3.2.1 Introduction
Few monitoring data are available for naphthalene. (See Section 3.2.4.)
The major source of human exposure is probably through the use of naphthalene-
containing mothballs, involving both inhalation and dermal routes. This
section examines the various exposure routes (ingestion, inhalation, and
dermal contact) to the extent permitted by the available data.
3.3.2.2 Ingestion
Drinking Water
Naphthalene has only rarely been found in drinking waters. It was
detected, but not quantified in a few samples in the National Organics
Monitoring Survey (U.S. EPA 1978). In addition, it has been reported
that drinking water supplies contain up to 1.4 ug/1 (U.S. EPA Region IV,
3-61
-------
unpublished data). These data are Inadequate to provide a good estimate
of exposure through drinking water. However, assuming a maximum con-
centration of 1.4 ug/1 and a 2-liter daily intake, a maximum exposure of
2.8 yg/day can be estimated, but it is not known how widespread such
exposures might be.
Food
Data for naphthalene in food have not been reported (U.S. EPA 1980a).
However, the bioaccumulation factor (BCF) of 10.5 calculated by the U.S.
EPA (1980a) suggests that accumulation would occur in food items consumed
by humans. There is some controversy, however, regarding the potential
for accumulation since naphthalene may be rapidly metabolized. Assuming
an ambient water concentration of 2 yg/1 (U.S. EPA 1980a), a BCF of 10.5,
and a fish consumption of 21 g/day (U.S. DA 1978), a possible exposure of
0.4 yg/day can be estimated. This represents a worst-case assumption,
since naphthalene has not actually been detected in food items.
3.3.2.3 Inhalation
Krstulovic et al. (1977) reported total naphthalene concentrations
of 0.35 ng/m^ in urban air in Providence, Rhode Island and 0.06 ng/m^ in
suburban and r.ural air in Kingston and Narragansett Bay, Rhode Island.
Assuming these concentrations to be representative, and taking an average
respiratory flow of 20 m^/day (ICRP 1975), estimated exposures are
0.007 yg/day and 0.001 ug/day, respectively.
Inhalation exposure to naphthalene also results from smoking (Akin
et al. 1976). Schmeltz et al. (1976) measured about 3 yg resulting in the
mainstream smoke of a 85-mm commercial U.S. nonfilter cigarette, and 46 yg
resulting in the sidestream smoke. Thus, exposure of smokers to naph-
thalene could range from 3 to 300 yg/day assuming a range of consumption
of 1-100 cigarettes per day (U.S. DHEW 1979). The extent of this exposure
may vary with the type of cigarette smoked and the amount inhaled, as well
as the number of cigarettes smoked. An estimated 33.2% of adults over 17
years old smoke cigarettes or 54.1 million persons in the United States.
Of smokers, 25-30% smoke more than 25 cigarettes per day (U.S. DHEW 1979);
thus a large segment of the population could be exposed to naphthalene in
the 75- to 300-yg/day range.
In addition, nonsmokers may be exposed to naphthalene through in-
halation of sidestream smoke. Although no measurements of naphthalene have
been taken in smoke-filled rooms, concentrations may be estimated from
measurements of CO levels, which have been summarized by Burns (1975) . The
results are not consistent, but apparently depend upon a number of variables.
They show levels of 44 to 92 mg/m^ CO in rooms (38-93 m^) where 30-80 cig-
arettes had been smoked with no ventilation. The Surgeon General's Report
(U.S. DHEW 1979) reported levels up to 50 mg CO produced in sidestream
smoke per cigarette, as compared to the 46 yg naphthalene produced per
cigarette. Thus, by analogy, a room concentration of up to 83 yg/nH can
be calculated. Alternatively, using 46 yg naphthalene/cigarette, and
assuming a room size of 48 m^ with no ventilation in which 40 cigarettes
3-02
-------
were smoked, a concentration of about 38 ug/m^ can be calculated. A non-
smoker exposed to such a situation 2 hours/day would receive about 140 ;:g/day
to 300 yg/day, assuming a respiratory flow of 1.8 m-Vhr. Smokers in the
same situation would receive a combined exposure from sidestream and
mainstream smoke.
There are problems with using CO levels to estimate naphthalene
levels in a smoke-filled room since they would be due to sidestream
smoke and exhaled'mainstream smoke. In addition, the concentration
of CO and naphthalene would be influenced by type and amount of tobacco
smoked, extent of inhalation, size of room, ventilation, and duration
of exposure. The estimates provided above are probably en the high side
since worst-case assumptions were frequently made. It appears, however,
that concentrations of naphthalene in smoke-filled rooms do not exceed
the OSHA standard of 50 mg/m3 as a time-weighted average.
Inhalation exposures may also occur through the use of naphthalene
mothballs. About 26 million households use mothballs; not all contain
naphthalene (U.S. EPA 1908b). According to section 3.1, about one-third
of the moth repellents produced in the U.S. contain naphthalene. There-
fore, this could represent an exposure route to a large sub-population.
Estimated concentrations of naphthalene in air resulting from this
use were derived using monitoring data for 1,4-dichlorobenzene (also used
as a moth repellent) and assuming the concentration of naphthalene to be
comparable when the two saturation vapor concentrations are taken into
account. This estimation also assumes that the application rates are
the same. The results are shown in Table 3-28. Using the estimated
bedroom concentration of 7 yg/m and assuming a respiratory flow of
20 m^/day, an intake of 140 ug/day can be calculated. This estimate
may be high since a continuous 24-hour exposure to these levels is un-
likely. However, effects have been observed resulting from this use,
suggesting that it is a significant route of exposure in some cases.
3.3.2.4 Dermal Contact
The use of naphthalene-containing mothballs represents the primary
route of dermal exposure; handling of wood products treated with preserva-
tives that contain naphthalene may be an additional source of dermal exposure.
The extent of significance of exposures via the dermal route is unknown.
3.3.2.5 Overview
It is apparent that very little information is available regarding
human exposure to naphthalene. Estimated exposures are shown in
Table 3-29. Most of these estimates provide only a rough idea of ex-
posure. Naphthalene is rarely detected in drinking water; intake through
food has been calculated by using a bioconcentration factor. It is diffi-
cult to identify the predominant route of exposure for the general popula-
tion, but inhalation of ambient air appears to be a relatively minor route
of exposure. Smokers clearly receive the largest exposures, although non-
smokers present in a smoke-filled room can receive comparable exposures.
The use of naphthalene moth repellents may also result in relatively
high indoor air concentrations.
3-63
-------
TABLE 3-28. ESTIMATED AIR CONCENTRATIONS RESULTING FROM NAPHTHALENE USE
AS A MOTH REPELLENT
Saturation
Compound Vapor Concentration
Dichlorobenzene
(g/m3)
Naphthalene 0.62
Air Concentration
(ug/m^)
£
wardrobe 1700
£
closet with 315
wardrobe
associated 105a
bedroom
wardrobe 117^
closet with 22^
wardrobe
associated 7^
bedroom
Measured concentration (Morita and Ohi, 1975).
^Estimated concentration.
-------
TABLE 3-29. ESTIMATED UPPER LIMIT HUMAN EXPOSURES TO NAPHTHALENE3
Exposure
Route (yg/day)
Ingestion
Drinking water 2.8 maximum
Food-fish 0.4 maximum
Inhalation
Ambient Air
Urban 0.007
Rural/suburban 0.001
Bedroom-with mothball use 140
Smoker (1-100 cigarettes/day) 3-300
Non-smoker in smoke filled room 140-300 (2-hour exposure)
Occupational (at 0SKA standard) ^500,000 (8-hour exposure)
£
For assumptions see text. Please note that all of these estimates are based
upon very limited data, and are not necessarily representative of typical
exposures.
3-65
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3.4 EFFECTS AND EXPOSURE — AQUATIC BIOTA
3.4.1 Effects on Aquatic Organisms
3.4.1.1 Introduction
Aquatic toxicity data are limited for naphthalene; some of the
available data are the results of static bioassays in which concentrations
are measured only at the initiation, not during the course, of the experi-
ment. Since naphthalene rapidly volatilizes and biodegrades, the results
of these studies may tend to underestimate the toxicity of naphthalene by
not accounting for loss of the compound during a test. Aquatic species
tested include fish, invertebrates, and plants from both marine and
freshwater systems.
3.4.1.2 Freshwater Organisms
Acute toxicity data for naphthalene are presented in Table 3-30;
LCcq's (concentrations lethal to 50% of test organisms) range from 0.92
mg/1 to 150 mg/1. The most sensitive of the five animal species tested
were pink salmon fry (0.92 mg/1) and rainbow trout (2.3 mg/1).
The only freshwater chronic study available was an embryo-larva test for
the fathead minnow. A chronic value of 0.62 mg/1 (limits 0.45-0.85 mg/1)
was measured (U.S. EPA 1980a).
Several studies have demonstrated the sublethal effects of naphthalene to
aquatic organisms. The feeding rate of copepods (Eurytemora affinis) was
reduced by 10% and 16% following 24-hours'exposure to 1 mg/1 and 2 mg/1
naphthalene, respectively. Prolonged exposure at lower concentrations
(10 days at 10 ug/1 and 50 !-:g/l) resulted in an increase in mortality and
decrease in egg production and feeding rate of these copepods (Neff 1979).
Studies of sublethal effects in pink salmon fry (Onchorhynchus gorbauscha)
indicated that at a naphthalene concentration of 0.76 mg/1, oxygen con-
sumption and the breathing rate increased sharply. However, with continued
exposure, both oxygen consumption and breathing rate decreased (Thomas and
Rice 1978).
Freshwater algae are less sensitive than are fish to naphthalene; in
studies on the green algae Chlorella vulgaris, growth and reproduction were
inhibited by concentrations of between 3.3 and 30 mg/1 (Kauss and Hutchin-
son 1975); the fifty percent effects concentration (EC50) was 33 mg/1.
Photosynthetic activity was inhibited at 30 mg/1 in 89% of a test culture
of the algae Clamydomonas angulosa (Kauss £t^ al. 1973).
3.4.1.3 Marine Organisms
Acute toxicity values for saltwater biota are comparable to those
measured for freshwater organisms (Table 3-30). With the exception of the
Pacific oyster (Crassostrea gigas) with an acute effects level of 199 mg/1,
the acute values ranged fron 2.3 mg/1 (grass shrimp) to 3.3 mg/1 (polvchaete
worm).
3-66
-------
TABLE 3-30. ACUTE TOXICITY OF NAPHTHALENE FOR AQUATIC SPECIES
Species
Method
a
Cladoceran
Daohnia magna
Rainbow trout
Salmo gairdneri
Fathead minnow
Plmephales promelas
Mosquitofish
Gambusia affinis
Pink salmon (fry)
Onchorhynchus gorbuschl
Polychaete S,U
Neanthes aranaceodentata
S.U
FT,M
FT,M
FT, M
Pacific oyster
Crassostrea gigas
Grass shrimp
Palaempneces puglo
Crown shrimp
Panaeus aztecus
Sheepshead minnow
Cyprlnodon variegacus
Amphipod
Elasmopus pectenicrus
Dungeness crab (zoeae)
Cancer ^agister
S,U
S.M
Freshwater Species
LCsn(mg/l)
8.5
2.3
4.9
150.0
0.92
Saltwater Species
3.8
199.0
2.3
2.4
2.5
Reference
2.4
2.7
>2.0
U.S. EPA (1978)
Degraeve et al. (1980)
Degraeve et al. (1980)
Wallen et al. (1957)
Thomas and Rice (1978)
Rossi and Neff (1978)
Legor (1974)
Tatem (1975)
Meff et al. (1976)
Anderson et al. (1974)
Anderson et al. (1974)
Lee and .N'icol (1978)
Caldwell et al.(1977)
S"static; F7=flow through; M=raeasured; U=unr:easured
3-67
-------
Certain sublethal effects have been attributed to even lower con-
centrations. The blue crab (Callinectes sapidus) was found to be able
to detect naphthalene, as indicated by certain behavior, at concentra-
tions of 0.12 mg/1 (Pearson and 011a 1979). Naphthalene also induced
sublethal effects in zooeal stages of Dungeness crabs (Cancer magister)
at concentrations of 0.13 mg/1 (Neff 1979). Histopathologic changes,
specifically necrosis of tastebuds, were found in the estuarine fish
mummichog at concentrations from 2 ug/1 to 20 ug/1.
In a field study, Armstrong £t al. (1979) looked at the relationship
between sediment naphthalene concentration and the presence of biota in the
vicinity of an oil separator rig in Trinity Bay, Texas. They found an in-
verse correlation between naphthalene concentrations in sediment and
numbers of benthic organisms. Figure 3-6 shows the relationship between
sediment concentrations and number of organisms collected at corresponding
distances in different directions from the separator platform. The first
station, 15 m. from the rig, had the highest concentration of naphthalene
(approximately 21 mg/1, see Figure 3-6), and the area was almost completely
devoid of organisms. At 75-150 m from the rig the concentrations dropped
significantly while the benthic populations were improved slightly, al-
though still depressed. The populations were at or above control levels
at 685 m to 1675 m from the rig at which point naphthalene concentrations
were <7 mg/1. The authors hypothesized that a low (possibly 2 mg/1)
persistent concentration of naphthalene is capable of restricting many
marine species (Armstrong et_ al. 1979) .
3.4.1.4 Factors Affecting Toxicity
Some studies have been conducted of the relationship between various
environmental factors and the toxicity of PAHs in general, and naphthalene
in particular. The factors most extensively studied have been salinity
and temperature.
Temperature could affect the survival of aquatic organisms exposed
to compounds such as PAHs in at least three ways: (1) by changing the
rate of loss from the waterbody through volatilization and bioaegradation,
thus altering the persistence of these compounds in water; (2) by affecting
the sensitivity of the organism by changing rates of hydrocarbon uptake,
metabolism, and depuration of metabolites and parent compound; and (3)
by placing additional stress on an organism through exposure to temperatures
that deviate from its optimal range. Compounds such as PAHs probably
remain at toxic concentrations for longer periods of time at lower tem-
peratures because of reduced volatility"and biodegradation of aromatic
compounds in water. However, generalizations about the direction
(increasing or decreasing) and magnitude of the effects of temperature
changes on fish exposed to specific PAHs cannot be made. The data of
Korn et al. (1979) indicated that for pink salmon, naphthalene threshold
limit values (TLV) did not vary significantly between 1°C and 12°C. In
shrimp, naphthalene was two times more toxic (as measured by the TLV) at
12°C than at 1°C.
-------
5
a.
a.
I-
<
cc
LU
O
z
o
u
24
22
20
—K
18
H \
16
- Y\
14
w \
-1 \
12
- \\
10
- v-
8
»
"
6
4
—
2
_L
I
I
I
_L
75 150 300 600 1200 2400 4800 9600
DISTANCE (METERS)
Mean concentration of total naphthalenes in sediments for stations in Trinity Bay in relation to
distance from the C-2 Separator Platform for the months of December, 1974-December, 1975.
600
<
Z
3
<
LL
500
Z
0
1
I-
400
CO
u.
300
Control
Stations
200
NE
100
NW
UJ
75
150
300
600
1200 2400 4800 9600
DISTANCE (METERS)
Mean number of individuals (benthic infauna) collected from ail stations from April, 1974—
December, 1975 in relation to distance from the brine discharge.
FIGURE 3-6 MEAN NAPHTHALENE CONCENTRATIONS IN SEDIMENTS
AND MEAN NUMBERS OF BENTHIC ORGANISMS AS
FUNCTIONS OF DISTANCE FROM AN OIL SEPARATOR RIG
IN TRINITY BAY, TX.
Note: (For both graphs, each line represents a separate sampling transect emanating
from the pollutant source in the direction indicated.)
Source: Armstrong et a! (1979)
3-69
-------
The effect of salinity on the toxicity of PAHs has also been
investigated. The toxicity of four concentrations (0, 125, 250 and
500 ug/1) of naphthalene at three salinities (5, 15, and 25 parts per
thousand, /oo was tested on zoeae of the mud crab Rhithropanopeus
harrisii. Survival was high at 125 yg/1 and 250 yg/1 for all salinities
and at 500 yg/1 in 15 and 25 /oo S; but at 5 /oo salinity, fewer organ-
isms survived. Naphthalene also increased the development rate of the
larvae (Laughlin and Neff 1979). Experiments on mummichog (Fundulus
heteroclitus), a euryhaline, estuarine fish, also show the influence
of salinity. Levitan and Taylor (1979) tested five salinities
(2, 8, 15, 23 and 33 /oo) and concentrations of 4 mg/1 and 6 mg/1
naphthalene. At 6 mg/1, survival was greatest at 8 °/o S and 15 /o S,
and it decreased at the salinity extremes. At a concentration of 4 mg/1,
survival was greater at lower salinities than at high. Thus, as with
temperature, salinity-toxicity interactions do not necessarily occur
in a uniform, predictable manner.
3.4.1.5 Ambient Water Quality Criterion
At this time, there is no ambient water quality criterion for
naphthalene for the protection of either freshwater or saltwater aquatic
life. This is due to a lack of sufficient toxicity data on which to base
the criterion. However, the criterion document (U.S. EPA 1980) states
that acute and chronic toxicity to freshwater life may occur at con-
centrations as low as 2.3 mg/1 and 0.62 mg/1, respectively. Acute
toxicity to saltwater life may occur at concentrations as low as 2.4 mg/1;
no chronic data were available. The criterion document also points out
the possibility that there are more sensitive species than those tested.
3.4.2 Exposure of Aquatic Biota
3.4.2.1 Monitoring Data
The STORET water quality data base for naphthalene is very limited.
Data were available for ambient and effluent water, sediment, and fish
tissue, but there were very few unremarked observations in each of these
categories. The range of concentrations for the unremarked data were
described in Tables 3-22 and 3-2 3, and are briefly summarized below.
Unremarked Data:
Sample Source
No. Observations
Range of Values
Ambient water
8
<1.0-100 yg/1
Effluent water
68
<1->1000 yg/1
Sediment
21
0.02-496 yg/kg
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Most of the STORET data, particulary for ambient water, were remarked;
i.e., the values were either detection limits or the actual value was less
than that indicated. Fifty-two percent (52%) of the remarked naphthalene
observations ranged from 0.005 to 17 yg/1. The unremarked sediment levels
are generally higher than ambient water level concentration, which
illustrates the tendency of naphthalene to accumulate in the sediments
over time.
3.4.2.2 EXAMS
EXAMS modeling data indicate that of the six aquatic systems ana-
lyzed, the only system in which a majority of the naphthalene went to the
sediments was the pond; naphthalene was almost equally divided between
sediments and water in the coastal plain river, and distributed to a
greater extent in water than in sediments in the other rivers and lakes
(>78% in water column). In all six environments, fate processes such
as volatilization, photolysis, and biotransformation are all significant,
and, thus, in water naphthalene would not persist as the parent compound
for very long. However, once naphthalene is in the sediments, it tends
to persist and is lost at a rate five times less than that of naphthalene
in water.
The EXAMS modelling data indicate that, based on a loading rate
of 0.2 kg/hr, an approximate discharge rate from a coal-tar plant, the
highest naphthalene concentrations in water would be in the pond (0.48 mg/1).
It is not likely that such a discharge would occur directly into a pond
ecosystem.
3.4.2.3 Factors Affecting Bioavailability of Sediment Concentrations
The various factors that affect partitioning of naphthalene between
water and sediments are discussed in Section 3.2.3.4. It is known that
aquatic biota are exposed to naphthalene directly from water, but the
extent to which they may be exposed to sediment concentrations of this
compound is less well understood.
Several laboratory and field studies have been conducted to deter-
mine the extent of uptake of naphthalene from sediments by aquatic organ-
isms. The organisms most often studied include deposit feeders such as
polychaete worms (Neanthes arenaceodentata), (Phascolosoma agassizii),
and clams (Rangia cuneata, Macoma inquinata), and the suspension feeding
clam Protothaca staminea. Accumulation of naphthalene was noted in all
of these organisms, but depuration was rapid and nearly total upon re
moval to clean water (Neff*1979). Accumulation of hydrocarbons, including
naphthalenes from oil-contaminated sediments by the English sole Paraphrvs
vetulus has also been investigated (McCain ejt al. 1978) . Results from
several separate studies (Roesijadi et al. 1978, rucitc et al. 1977,
Anderson et al. 1977) indicate that overall uptake of PAHs is not signiri-
cant, but is greater by suspension feeders tnan deposit feeders, and i_nat
3-71
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accumulation by fish is greater from water than from sediment. The
conclusion has been made that the source of PAH taken up is, to a greater
extent, PAH in interstitial waters (dissolved) and in the water column
(dissolved and/or adsorbed onto suspended solids), rather than PAH
desorbed from the sediment itself (Neff 1979).
These studies also indicated that sediment adsorbed PAHs are not
readily metabolized by benthic invertebrates. However, based on the
few species studied, it is apparent that benthic organisms could take up
naphthalene from sediment and interstitial waters to a moderate degree
since the dynamics of desorption of naphthalene from sediment to water
are not well understood; so, it is impossible to quantify the degree
to which accumulation of PAHs in sediment represents a major source of
exposure to aquatic biota.
3.4.3 Summary - Aquatic Effects and Exposure
Naphthalene concentrations at which acute toxic effects have been
reported for aquatic organisms range from 0.92 mg/1 to 199 mg/1. Certain
sublethal effects (behavioral) on aquatic organisms have been observed
at concentrations as low as 0.12 mg/1; histopathologic changes were noted
in estuarine fish at concentrations from 0.002 mg/1 to 0.02 mg/1. A
chronic effects value of 0.62 mg/1 was obtained in an embryo-larva test
conducted on fathead minnows. Monitoring data for naphthalene indicate
that the levels in ambient waters are generally about 10 ug/1; sediment
levels range from 0.02 yg/kg to less than 500 yg/kg.
3-72
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3.5 RISK CONSIDERATIONS
3.5.1 Introduction
The purpose of this section is to evaluate potential risks to humans
and aquatic biota resulting from exposure to naphthalene in the environ-
ment. This risk analysis is hampered by the scarcity of quantitative data
on health effects levels, and by the very limited amount of monitoring data
and other information available to use as an indication of the extent
of exposure. All data reviewed in this section are presented in more
detail in the preceeding sections of this chapter.
3.5.2 Humans
3.5.2.1 Statement of Risk
There appears to be little risk to the general population as a result
of environmental exposure to naphthalene. Although this compound has been
linked with cataract formation and hemolytic anemia, the levels at which
these effects have been observed are considerably higher than the maximum
estimated human intake levels. There are several orders of magnitude
separating the maximum estimated exposure to certain subpopulations via
smoking or mothball usage, and the lowest level at which acute human
effects have been observed. On the basis of the available monitoring
data, the estimated daily exposure to the general population via ingestion
of water and food and inhalation of ambient air is at least five orders
of magnitude less than the lowest reported toxic dose (the LDL reported
for children was 100 mg/kg, or ^1000 mg).
3.5.2.2 Discussion
Naphthalene appears to be absorbed via all routes of exposure
(ingestion, inhalation, and skin contact), but the extent of that absorp-
tion has not been defined. The two major effects of naphthalene exposure
are hemolytic anemia and cataract formation; individuals with deficiencies
in the enzymes needed to maintain reduced glutathione levels, as well as
the fetus and newborn, are at an increased risk of developing
hemolytic anemia.
Studies on the chronic effects of naphthalene have generally been
negative. This substance has not been shown to be carcinogenic, or
mutagenic; anecdotal reports of teratogenicity were cited (U.S. EPA 1980a).
Accidental ingestion of large amounts of naphthalene was reported to
have caused near blindness, demonstrating the potential for severe
adverse effects.
The sources of naphthalene to which the general population is exposed
represent very small intake levels: up to 2.8 x 10~3 mg/day from ingestion
of drinking water; up to 0.4 x 10-3 mg/day from consumption of contaminated
fish; and up to 7 x 10~D mg/day from inhalation of ambient air. There are,
3-73
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however, a number of subpopulations exposed to much higher levels in air.
Heavy smokers (about 10% of U.S. adults) may be exposed to levels in main-
stream smoke up to 0.3 mg/day; nonsmokers in a smoke-filled room may be
exposed to similar levels. On the basis of assumptions outlined in Sec-
tion 3.3.1, inhalation exposure due to mothball usage may be as high as
0.14 mg/day. (It has been estimated that 26 x 10° households use moth-
balls; only one-third contain naphthalene.) An additional major source
of exposure is the occupational environment, but quantification of that
exposure route is beyond the scope of this report. Since naphthalene is
potentially toxic via inhalation, these scenarios may pose some level of
risk to specific subpopulations.
3.5.3 Aquatic Biota
There is very little information available on the extent of expo-
sure of aquatic biota to naphthalene. However, the available monitoring
data suggest that concentrations reported in ambient water are about two
orders of magnitude lower than the levels associated with acute or
chronic effects to aquatic organisms.
3-74
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Freeman, A.E.; et al. Transformation of cell cultures as an indication
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Ghetti, G.; Mariani, L. Eye changes due to naphthalene. Med. Lav.
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the basis of pharmacology. 2nd edition. New York: John Wiley and Sons;
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Harris, S.J.; Bond, G.P.; Neimeir, R.W. The effects of 2-nitropropane,
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Biochem. Jour. 24:497; 1930. (As cited in U.S. EPA 1980a).
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3-33
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Knake, E. Uber schwache geschwulsterzengende wirkung von naphthalin
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O O /
j-U4
-------
U.S. Department of Agriculture (U.S.DOA). Food consumption, prices, ana
expenditures. Washington, D.C.: U.S. Department of Agriculture; 1978.
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criteria for naphthalene. Washington, D.C.: Criteria and Standards
Division, Office of Water Regulations and Standards; 1980a. Available
from NTIS, Springfield, Virginia. EPA 440/5-80-059.
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pesticide usage study 1976-1977. EPA 54019-80-002. Washington, D.C.:
Office of Pesticide Programs, U.S. Environmental Protection Agency; 1980b.
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Exp. Eye Res. 9:38-48; 1970.
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effect on the eye. Biochem. Jour. 102:842-852; 1967.
Van Heyningen, R.; Pirie, A. Naphthalene cataract in pigmented and
albino rabbits. Exp. Eye Res. 22:393-394; 1976.
Van der Hoeve, J. Wirkung von naphthol auf die augen von menchen,
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and Febiger; 1974. (As cited in U.S. EPA 1980a).
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3-35
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REFERENCES FOR 3.4
Anderson, J.W.; Kiesser, S.L.; Blaylock, J.W. Comparative uptake of
naphthalenes from water and oiled sediment by benthic amphipods. Am.
Petrol. Instit. Pub. 4308:579-584; 1979.
Anderson, J.W.; Neff, J.M.; Cox, B.A.; Tatem, H.E.; Hightower, G.M.
Characteristics of dispersions and water-soluble extracts of crude
and refined oils and their toxicity to estuarine crustaceans and fish.
Marine Biology 27:75-88; 1974.
Armstrong, H.W.; Fucik, K.; Anderson, J.W.; Neff, J.M. Effects of oil
field brine effluent on sediments and benthic organisms in Trinity Bay,
Texas. Marine Environ. Res. 2:55-69; 1979.
Caldwell, R.S.; Caladrone, E.M.; Mallon, M.H. Effects of a seawater-soluble
fraction of Cook Inlet crude oil and its major aromatic components on larval
stages of the Dungeness crab, Cancer magister Dana. Wolfe, D.K., ed. Fate
and effects of petroleum hydrocarbons in marine organisms and ecosystems.
New York, NY: Pergamon Press; 1977. pp210-220.
DeGraeve, G.M. et_ al_. Effects of naphthalene and benzene on fathead
minnows and rainbow trout. Submitted to trans. Amer. Fish. Soc.; 1980.
(As cited in U.S. EPA 1980).
Fucik, K.W.; Armstrong, H.W.; Neff, J.M. The uptake of naphthalenes by
the clam, Rangia cuneata, in the vicinity of an oil-separator platform
in Trinity Bay, Texas. Proc. 1977 oil spill conference (prevention,
behavior, control, cleanup). Washington, D.C.: American Petroleum
Institute; 1977.
Kauss, P.B.; Hutchinson, T.C. The effects of water-soluble petroleum
on the growth chlorella vulgaris Beijerinck. Environ. Pollut. 9:157-194;
1975. (As cited in Neff 1979).
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toxicity of crude oil and its components to fresh water algae. Proc.
1973 conference on prevention and control of oil spills. Washington, D.C.:
American Petroleum Institute; 1973. pp703-714.
Korn, S.; Moles, D.A.; Rice, S.D. Effects of temperature on the median
tolerance limit of pink salmon and shrimp exposed to toluene, naphtha-
lene, and Cook Inlet crude oil. Bull. Environm. Contam. Toxicol. 21:
521-525; 1979.
Laughlin, R.B.; Neff, J.M. Interactive effects of salinity, temperature,
and polycyclic aromatic hydrocarbons on the survival and development rate
of larvae of the mud crab Rhthrooanoaeus harrisil. Marine Biology 53:
281-291; 1979.
3-86
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Lee, W.Y.; Nicole, J. C. Individual and combined toxicity of some
petroleum hydrocarbons to the marine amphipod, Elasmopus pectenicrus.
Mar. Biol. 48:215-222; 1978.
Legore, R.S. The effect of Alaskan crude oil and selected hydrocarbon
compounds on embryonic development of the Pacific oyster, Crassotrea
gigas. Doctoral thesis, Univ. Washington; 1974.
Levitan, W.M.; Taylor, M.H. Physiology of salinity dependent naphthalene
toxicity in Fundulus heteroclitus. J. Fish. Res. Board Can. 36:615-620,
1979.
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Myers, M.S.; Vandermeulen, J. H. Bioavailability of crude oil from
experimentally oiled sediments to English sole (Parophrys vetulus), and
pathological consequences. J. Fish. Res. Board Canada 35(5):657-664;
1978. (As cited in Anderson 1979).
Neff, J.M.; Anderson, J.W.; Cox, B.A.; Laughlin, R.B.; Rossi, S.S.; Tatem,
H.E. Effects of petroleum on survival, respiration and growth of marine
animals- In Sources, effects, and sinks of hydrocarbons in the aquatic
environment. Arlington, VA: American Institute of Biological Sciences; 1976
Neff, J.M. Polycyclic aromatic hydrocarbons in the aquatic environment.
London: Applied Science; .1979.
Pearson, W.H.; 011a, B.L. Detection of naphthalene by the blue crab,
Callinectes sapidus. Estuaries 2(1):64—65; 1979.
Roesijadi, G.; Anderson, J.W.; Blaylock, J.W. Uptake of hydrocarbons
from marine sediments contaiminated with Prudhoe Bay crude oil: Influence
of feeding type of test species and availability of polycyclic aromatic
hydrocarbons. J. Fish. Res. Board. Can. 35:608-614; 1978.
Rossi, S.S.; Neff, J.M. Toxicity of polynuclear aromatic hydrocarbons
to the marine polychaete, Neanthes arenaceodentata. Mar. Pollut. Bull.
9:220-223; 1978. (As cited in Laughlin and Neff 1979).
Tatem, H.E. Toxicity and physiological effects of oil and petroleum
hydrocarbons on estuarine grass shrimp Palaenomontes pugio Holthius
Ph.D. Thesis. Texas A&M Univ.; 1976. (As cited in U.S. EPA 1980).
Thomas, R.E.; Rice, S.D. The effect of exposure temperatures on oxygen
consumption and opercular breathing rates of pink salmon fry exposed to
toluene naphthalene, and water-soluble fractions of Cook Inlet crude
oil and No. 2 fuel oil. Vernberg, F.J.; Vernberg, W.B.; Calabrese, A.,
eds. Marine Pollution: functional processes. New York, NY: Academic
Press; 1978. (As cited in Neff 1979).
-------
U.S. Environmental Protection Agency (U.S. EPA) ambient water quality
criteria for naphthalene. EPA 440/5-80-059. Washington, D.C.: Office
of Water Regulations and Standards, U.S. Environmental Protection
Agency; 1980.
Wallen, I.E.; Greer, W.C.; Lasater, R. Toxicity to Gambusia affinis
of certain pure chemicals in turbid waters. Sewage Ind. Wastes
29:695-711; 1957.
n Q
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APPENDIX A
NOTE 1: EPA, 1979g. Raw waste loading of naphthalene from the
wood preserving industry is based on the following flows and respec-
tive naphthalene concentrations and applying the average to the total
number of facilities. Assume 300 day/yr operation.
Plant
Flow (106 1/day)
Naphthalene (mg/£)
Naphthalene
1,078
0.057
3.14
0.05
1,100
0.236
0.464
0.03
897
0.160
3.47
0.1
591
0.013
34.7
0.1
548
0.122
31.0
1.1
267
0.034
45.0
.0.5
average 0.3
387 plants x 0.3 kkg naphthalene/yr = 116 kkg naphthalene
available for discharge/yr.
Waste load % reduction for naphthalene ranges from 50% (current pretreat-
ment technology) to >99% (current BPT). Therefore, about 87 kkg of
naphthalene are removed prior to discharge. The remaining 29 kkg are
for the most part (95-100%) discharged to POTWs.
NOTE 2: The maximum naphthalene discharge (raw wastewater) of
2 kkg/yr from manufacture of synthetic tanning agents was calculated
based on the geometric mean of average naphthalene concentration
(ug/£) and a total industry wide flow of 200 x 10° Jl/day, assuming
365 day/yr operation (EPA 1979e).
Subcategory Naphthalene (yg/£)
1 46
2 49
3 32
4 "present"
5 27
6 "present"
7 26
geometric mean = 24 yg/£
"Present" was assumed to be at the detection limit, 10 ug/£.
24 yg/i x 200 x 10° l/day x 365 d/yr = 2 kkg naphthalene
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APPENDIX 3. APPLICATION OF THE AIR-TO-SURFACZ 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 phvsicochemical 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 £t^ 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. Tne effect of vapor pressure is expressed
by equation (5) of the Arthur D. Little report (1981):
, _ .1658
p0 + .165
where
$ is the adsorbed fraction of the total airborne mass,
cm^
e is the available aerosol surface area —r 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
3-90
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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 PAHs as shown below:
Adsorbed Fraction of Total Airborne Mass
PAH
Rural
Urban
Near Combustion Sources
-6
-4
0.02
Naphthalene
7x10
3x10
Anthracene
0.002
0.06
0.97
3enzo[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
Dry Flux = Vd Caij.
velocity, V,, i.e.,
a
where
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.»* + 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
Naphthalene
Anthracene
3enzo[a]pyrene
Vd.v
(cm/sec)
0.04
0.02
0.02
V
d,s
1
1
1
Combustion
Rural
Urban
Source
0.04
0.04
0.06
0.02
0.08
1.00
1.00
1.00
1.00
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Wee 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 (yg/m3). The
scavenging ratio is calculated by contributions from the vapor and
sorbed fractions, i.e.:
r = rg ($) + rv (1-)
where r, rs and rv 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 = r^Ca^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
6xl04
53
53
71
2. 5x10-3
Anthracene
6xl04
14
130
3.6xl03
1.2xl05
Benzo[a]pyrene
6xl04
5.4x104
6xl04
6xl04
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 mi^ (2.6 x 10^ ra^).
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 10^0 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 = 1.2X103.
3-92
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Median Observed
Concentration (je/m3)
PAH
Rural
Urban
Naphthalene
7xl0-5
5xl0"4
Anthracene
IxlO"3
8xl0~3
3enzo[a]pyrene
lxlO"3
IxlO"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.
3-93
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APPENDIX
REFERENCES
Arthur D. Little, Inc. Air-to-surface. pathway evaluation methodology.
Draft final report. Contract N. 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.; 3omberger,
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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