Maryland Department of Natural Resources draft final report on polynuclear aromatic hydrocarbons and the Chesapeake Bay

[From the U.S. Government Printing Office, www.gpo.gov]

MD. DEPARTMENT OF NATURAL RESOURCES
DRAFT FINAL REPORT ON
POLYNUCLEAR AROMATIC HYDROCARDONS
AND THE
CHESAPEAKE BAY

October 1986

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URAL RESOURCES
MARYLAND DEPARTMENT OF NAT

DRAFT FINAL REPORT ON
POLYNUCLEAR AROMATIC HYDROCARBONS

AND THE
CHESAPEAKE B@/

October 1986

FOREWORD

The Chesapeake Bay is a source of pride and abundant resources for the

State of Maryland and its citizens. Responsible management and protection of

those resources requires consistent, well-planned monitoring of water quality

to identify and assess the effects of pollutants on aquatic plant and animal

life.

The Maryland Department of Natural Resources is committed to the

establishment of concrete knowledge about the types and sources of pollutants

that are entering the Bay. The efforts of DNRIin this regard are essential to

an effective response to a pollution related emergency or imminent danger to

any element,of the Chesapeake Bay environment.

Torrey C. Brown, M. D.

Secretary

..Department of Natural Resources

ABSTRACT

There are several research efforts underway to identify and assess the

sources and effects of organic toxins in the Chesapeake Bay. As part of this

effort, the Maryland Department of Natural Resources is committed to the

detection and analysis of pollutant polynuclear aromatic hydrocarbons (PAH's)

in the upper Bay area within the scope of its striped bass monitoring

project.

Although research into the sources and effects of pollutant PAH's is in a

preliminary phase, existing information about these compounds has provided a

framework from which to develop study guidelines and goals that will lead to a

better understanding with regard to the infusion of PAH's into the Chesapeake

and their modes of action within the estuarine ecosystem. We know that PAH
concentrations are abnormally high in some of the more developed areas of the

Bay and that PAH exposure poses a potential danger to the Chesapeake's living

resources and, ultimately, the human recipients of those resources. It is the

extent of this threat and the mechanisms through which the potential harm is

manifested that is not yet clear.

We are confident that the striped bass monitoring effort will produce

information to help close the gap between general knowledge about PAH's and

.specific knowledge about PAH interactions in the Chesapeake Bay.

DNR is still awaiting 1986 field data on PAH concentrations in striped bass

spawning reaches and in striped bass ad ult tissue and eggs. This data along

with interpretation will be included in the final PAH report.

TABLE OF CONTENTS

Page

Foreword ............................................................ i

Abstract ............................................................ ii

Legend of Tables ..........I .......................................... iii

Legend of Figures ................................................... v

Acknowledgements .................................................... vi

Summary .............................................................. vii

I. BACKGROUND .................................................. 1

PAH Formation ......................................... 1

Structure vs. Origin .................................. 2

Structure vs. Activity ................................ 5

II. PAHIS IN THE AQUATIC ENVIRONMENT ............................ 9

Routes of Entry and Distribution ...................... 9

PAH's in Sediments .................................... 13

PAH's in the Water Column ............................. 14

Transformations & Degradation ......................... 15

Treatment of PAH Contamination ........................ 20

III. INTERACTIONS BETWEEN PAH AND AQUATIC BIOTA .................. 21

PAH's in Aquatic Biota ................................ 21

PAH Toxicity to Marine Organisms ...................... 25

IV. PAHIS AND THE CHESAPEAKE BAY ................................ 29

Bay Geographics ....................................... 29

PAH Studies in the Chesapeake ......................... 32

PAH's and Chesapeake Biota ............................ 50

Approaches to PAH Studies ............................. 51

Chesapeake Bay Monitoring ............................. 51

DNR Striped Bass Sampling (1983-85) ................... 53

1986 Study Design and Methods for DNR Striped Bass

Monitoring ....................................... 53

Future Needs .......................................... 58

Bibliography ........................................... 60

LEGEND OF TABLES

Page

Table 1 PAH pyrolysis products at various temperatures ........ 3

2 Solubility and LC50 for several PAH's ................. 7

3 Carcinogenic potency for various PAH's ................ 8

Table 4 Estimated inputs of PAH to the aquatic environment

from various sources ................................. 10

5 Input rate of various PAH sources to the aquatic

environment ......................................... 11

6 Chemical distribution of PAH's in urban runoff from

four different land uses ............................ 12

7 Relationship between salt concentration and molar

solubility .......................................... 16

8 Octanol/water partition coefficients and molecular

weights for several PAH's ........................... 17

Table 9 Concentrations of selected PAH in the tissues of

oysters Crassostrea virginica ....................... 22

10 Summary of PAH hydrocarbons in marine tissues ......... 23

11 Effect of aromatic hydrocarbons on bacteria ........... 26

12 Effect of long-term, low-level exposure to naphthalene

on feeding and egg production of adult female

Eurytemora .......................................... 27

13 Toxicity of selected PAH's for Neanthes arenaceodentata 28

IV. Table 14 PAH concentrations in water and sediment samples

around Hart-Miller Island (August 1981) ............. 40

15 PAH concentrations in crab and fish tissues from

Hart-Miller Islands area (August 1981) .............. 41

16 PAH concentrations in Elk and Choptank Rivers and

Baltimore Harbor .................................... 42

17 PAH concentrations in rivers neighboring the

Chesapeake region ................................... 48

18 Most common PAH and PASH found in striped bass adults,

eggs and young of the year (1981) ................... 49

19 Detection limits for selected organic contaminants to

be analyzed by EPA, CRL .... o .......................... 55

20 List of methods for organics .......................... 56

LEGEND OF FIGURES

Figure I Proposed reaction scheme for PAH formation ............ 4

IV.

Figure 2 Physiographic map of Chesapeake Bay region ............ 30

3 Striped bass habitats and spawning reaches in the

Chesapeake .......................................... 31

4 oyster bars on the Chesapeake ......................... 33

5 Map of power plant sites around the Maryland portion

of the Chesapeake Bay ............................... 34

6 Distribution of Benzo(a) pyrene in surface sediments

from Chesapeake Bay ................................. 36

7 Distribution of Benzo(a) anthracene in surface

sediments from Chesapeake Bay ....................... 37

8 Sum of pyrogenic PAH's in Chesapeake Bay (Spring 1979). 38

9 Sum of pyrogenic PAH's in Chesapeake Bay (Fall 1979) .. 39

10 PAH's in Elk River seston (1983-1984 Spring) .......... 44

11 PAH's in Choptank river seston 0983-1984 Spring) 45

12 PAH's in Elk River sediments (1983-1984 Spring) ....... 46

13 PAH's in Elk River seston (1983-1984 Spring) .......... 47

14 Sampling procedure for metals and organics ............ 54

15 Sediment analyses procedures .......................... 57

ACKNOWLEDGEMENTS

Within the Maryland Department of Natural Resources, the Monitoring and Data

Management Section of Tidewater Administration has prepared this draft report

for submission to the National Oceanic and Atmospheric Administration under the

terms of Grant No. NA-83-AA-H-CZ026. This grant provides substantial funding

for the monitoring of PAH's in the Chesapeake Bay as part of NOAX's Coastal

Energy Impact Program under its Office of Coastal Resource Management.

The text of this report was prepared by Julie Sobelman with technical input

from Stephen Jordan, Chief of DNR's Monitoring and Data Management. We thank

Candace Marsden for her textual and editorial assistance, and Linda Wall and

Lorane Bruce for their typing assistance.

SUMMARY

The Chesapeake Bay has served man in a variety of ways for hundreds of

years. It has and continues to provide recreational grounds for boating,

fishing and hunting; water for industrial and agricultural uses; and a waterway

for product transport. Anthropogenic activities, particularly those related to

industry, have resulted in a significant chemical pollution problem caused, in

part, by the release of polynuclear aromatic hydrocarbons into the Bay waters.

A large portion of the PAH's that enter the Chesapeake are carried in sediments

of the tributaries which feed into the Bay. Although the Bay can assimilate

some of this material, most remains within the estuary. There is no doubt that

the introduction of polynuclear aromatic hydrocarbons into the Chesapeake Bay

poses a potential threat to the entire Bay ecosystem.

Initial steps in understanding the sources and mechanisms through which

PAH's originate have been accomplished. PAH's have both natural and

anthropogenic sources. Those that occur naturally in the aquatic environment

are produced through the process of sedimentary diagenesis (the chemical and

physical changes that take place in sediments during their conversion to rock),

and biosynthesis (direct or indirect formation by aquatic microbes and plants).

Man-made PAH's are produced through pyrolysis at various temperatures in

industrial heating processes. I t is these pyrolytically produced PAH's, such

as those generated during the combustion of fossil fuels, that have been found

to account for the greatest contribution of PPJi's to the aquatic environment.

Although the sources and structures of PAH's have been established,

critical areas of concern remain unresolved. These areas have to do with the

Vii

extent and treatment of PAH contamination in the Bay and the impact of these

contaminants on aquatic life and man.

Varying traces of PAH's have been detected in a broad range of aquatic

organisms, and it has been determined that there is significant potential of

@bioaccumulation and magnification through food chains. Rates of uptake in

aquatic materials and organisms are directly related to levels of

concentration which have been found to be consistently higher in the urban

and industrial areas of the Bay. Concentration levels are determined by the

molecular and carbon makeup of naturally existing and pollutant PAH's in the

water column. These structural makeups determine solubility and stability

which, in turn, affect degree of concentration.

Just as there are considerable variations in both the sources and

structures of PAH's, so too there are numerous routes by which these

substances make their way into the aquatic environment. These include

wastewater discharge and surface runoff, which account for proportionately

large amounts-of pollutant PAH's in the Bay,.as well as casual spillage and

atmospheric deposition.

Further experimental exploration is needed to determine, among other

things, the mechanisms of PAH toxicity in the Chesapeake Bay through

observation of PAH/PAH interaction and PAH reactions with other chemicals

present in the water column. Testing of proposed treatment methods will aid in

the discovery of legitimate anti-pollution procedures. Research of-the early

life stages of fish beginning with egg, larval and juvenile phases on through

the entire life cycle will produce valuable information regarding the modes of

PAH action and the effects of specific toxins on the reproduction of various

Viii

aquatic species. Finally, continued water and sediment monitoring is necessary

to establish seasonal trends in PAH concentrations in the Bay. Current data is

inadequate to draw any conclusions-in this area.

Continued and extensive efforts in the areas noted are essential in light

of the reciprocal relationship that exists between the Chesapeake Bay and the

populace.

I. -.BACKGROUND

PAH @ormation

Polynuclear Aromatic Hydrocarbons (PAH's) originate by one of three

mechanisms: pyrolysis, sedimentary diagenesis or direct biosynthesis by

microbes and plants. For each method of formation, there are different

sources, reactions, and product PAH's.

Pyrolytic formation occurs when organic matter is expoosed to a broad range

of high temperatures. Anthropogenic activities, such as the coking of coal and
coal tar production, yield PAH's at temperatures from 1400-20000C. The scope

of pyrolytic activity is so large, especially in urban and industrialized

areas, that this mechanism appears to be the greatest contributor of pollutant

PAH's to the aquatic environment.

Sedimentary diagenesis produces PAH's in fossil fuel sources such as

petroleum, natural gas, minerals including idrialite and curtisite, and coal.

Temperatures associated with these formation processes are low, probably less
than 1500C, with reactions occurring over long periods of time.

Biosynthesis of PAH's by microbes and plants is a controversial issue.

Pigments in sea lilies and sea urchins contain PAH's which apparently are

synthesized by the organisms (Blumer, 1976). There are data indicating

that benzopyrene accumulates through bacterial synthesis in amounts of 2-6

ug/kg of dried material. Aliphatic and aromatic hydrocarbons produced by

phytoplankton in the ocean may be as high as 3 tons/year (Andelman, 1970).

Nonacosane, a PAH compound present in crude oil, is derived from terrigenous

plant material (Boehm, 1984). Neff (1979) reported data indicating that

bacterial biosynthesis of benzo (a) pyrene and perylene may depend on growth

medium. Specific substrates such as fatty acids may be necessary for bacteria

to carry out PAH synthesis. Hase and Hites (1976) suggest that bacteria do not

produce PAH's but bioaccumulate them from their environment. The possibility

exists that blanks used in other experiments caused a lack of sensitivity and,

therefore, apparent biosynthesis was actually an artifact.

All organic compounds containing carbon and hydrogen may serve as

precursors of PAH. PAH such as benzo(a)pyrene could be formed from a simple

C2 unit being gradually built up by a series of free radical combinations.

Most proposed mechanisms involve chain lengthening reactions followed by

cyclization, possibly followed by degradation. For examples of pathways of PAH

formation refer to Table 1 and Figure 1. Table 1 shows a variety of PAH's

formed at various temperatures.

Structure Vs. Origin

Several relationships seem to exist between PAH origin and structure. By

definition, PAH's consist of two or more fused benzene rings which may be

arranged in linear, angular or cluster forms (Blumer, 1976). Of the three

arrangements, those of the linear type, as found in naphthalene or anthracene,

are the least stable. Greater stability is found in the cluster arrangement of

compounds such as pyrene and benzopyrene. Phenanthrene is an example of an

angular arrangement which, of the three, has the most stable ring

organization. Overall stability in arrangement is relative to the amount of

strain placed on the bond angles between carbon and hydrogen molecules found in

TABLE 1. Products from pyrolysis of malic acid, observed at various
temperatures

5000 6000 7000 8000 9000

Benzene + + + + +
Toluene + + + + +
Indene + + + + +
Biphenyl + + +
Naphthalene + + +

Ethylbenzene
M..@, p-Xylene + + +

Styrene + +
a-Styrene

Dimethylnaphthalene +
Acenaphthylene + +
Anthracene (Phenanthrene) + +
Fluorene + +
Pyrene +
Chrysene +

Phenol + + +
m-Cresol + + +
p-Cresol + + + +
o-Cresol + + + +
2,5-Xylenol + + +

Fumaric acid + + +
Succinic acid- + + +

(from Schmeltz, I. and Hoffmann, D. 1976. Copyright permission pending)

C
C C C C
I C C
C

C
I.v C

OC)

TETRALIN
BENZO(A)PYRENE
Vil VI v

Figure 1. Proposed reaction scheme for PAH formation.

(from Crittenden, B. D. and Long, R. 1976. Copyright
permission pending).
OR

the benzene ring. If rings bind to each other in such a manner that is

energetically difficult to maintain, the molecules will be more prone to find

an arrangement of lesser stress.

in petroleum, PAH's consist of a homologous series of compounds in which

the methyl and higher alkyl-substituted isomers significantly outnumber the

parent hydrocarbons. Aromatic hydrocarbons from the combustion of fossil fuel

or wood, however, contain certain predominant amounts of the parent hydrocarbon

(Boehm, 1984). This relationship is probably related to differences in the

formation temperatures for the two processes. Blumer (1976) noted that the

abundance of side chains increases with decreasing temperatures of production

and that the average number of five-member rings around an aromatic nucleus is

greater in petroleum than in PAH's formed at higher temperatures. This

observation was also noted in diesel engines where the total number of

alkylated PAH's increases as the cylinder temperature decreases (Jensen,

1983).

Regardless of origin, lower molecular weight three- aM four-ring

structures are produced in greater quantities than five- and seven-ring PAH
(Mix, 1984). Rings"with no side chains (alkyl groups) are most common.

Structure Vs. Activity

The chemical structure of PAH's lend to the many ways they interact both

alone and with other substances in the environment. PAH's tend to be both

hydrophobic and lipophylic in nature. In the aquatic environment, PAH's are

relatively low in water solubility and readily available for uptake into fatty

tissues of organisms, or binding to humic substrates.

Compounds of higher molecular weight persist longer than those of lower

molecular weight (Hinga, 1980). The number of chemical bonds and the strength

of those bonds which need to be broken in order to separate or degrade the

substance provides a possible explanation for this phenomenon. Phenanthrene

and higher molecular weight alkylated naphthalenes are removed from sediments

at a slower rate than lower molecular weight naphthalene and 2-3 carbon alkyl

naphthalenes. Higher molecular weight compounds have a longer residence time

than lower molecular weight compounds once incorporated into animal tissues

(Farrington, 1980). In general, two- and three-ring PAH have been shown in

laboratory studies to be acutely toxic to aquatic organisms (Mix, 1984).

Many authors allude to a correlative relationship between higher solubility

of low molecular Weight PAH and greater acute toxicity. So little is actually

known, however, about the mechanisms of PAH toxicity that relationships of this

type are more on the order of theoretical ideas than concrete facts. Table 2

list s some PAH's along with their relative solubilities and LC50 values.

According to Mix (1984), all of the proven PAH carcinogens contain 4-6 rings.

Table 3 includes a number of PAH's along with their carcinogenic potency.

Although some PAH's are carcinogenic by nature, others may be activated to a

highly carcinogenic form in the presence of specific conditions. This may take

place through a two-step oxidation process with the eventual formation of a

dihydrodiol epoxide (Cassarett, 1980). Higher molecular weight polycyclic and

heteroaromatic compounds possess the greatest potential for bioaccumulation, as

well as carcinogenic and mutagenic effects in aquatic animals and man, and

acute toxicity to aquatic organisms (Giesy, undated). One mechanism through

which carcinogenicity or mutagenicity may be achieved is by direct binding of

PAH to DNA. This could cause a crosslinkage of bases which may produce cancer

or mutation (Josephson, 1984).

TABLE 2. Solubility and LC50 for several PAH's

Compound Solubility LC50(ppm)
observations 96hr
mg/L

Naphthalene 20 + 2 3.8

2-6-Dimethylnapthalene 2.4+ .5 2.6

Fluorene .8+ .2 -1.0

Phenanthrene .6+ .1 .6

Fluoranthene .1+ .06 .5

LC50 values represented are for the marine polychaete (Neanthes araceodentata).

(Adapted from Neff, J. M., 1979.)

TABLE 3. Polynuclear aromat ic hydrocarbons in the water environment

List of PAH compounds

Carcinogenica Empirical
Compound potency formula

anthracene ? C14H10
alky1fluoranthene ?
acenaphthylene C12H8
alkylpyrene ?
anthanthrene C22H12
1,2-benzanthracene + C18H12
3,4-benzfluoranthene ++ C20 12
10,11-benzfluoranthene ++ C20 12
11,12-benzfluoranthene C20H012
3,4-benzpyrene C20H12
1,2-benzpyrene + C20H12
1,12-benzperylene 2H12
chrysene + C18H12
coronene C24HI2
1,2,5,6-dibenzanthracene + 2H14
9,10-dimethyl-1,2-benzanthracene (active) C20H16
fluorenthene C16H10
fluorene -b C13H10
indeno (1,2,3-cd)pyrene + C22H12
3-methylcholanthrene (active) C21H16
phenanthrene ? C14H10
perylene C20H12
pyrene C16H10
triphenylene C18H12
18 12

apotency notation: +++ active; ++, moderate;+,weak;-,inactive;?,
unknown. (Compounds labelled "active" are so listed by several authors). The
notation is taken from Hoffman & Vynder (1962).
bReference from Graf & Nowak (1966).

(from Andelman, J. B. et al. 1970, with permission of the publisher, World
Health Organization)

II.- PAH'S IN THE AQUATIC ENVIRONMENT

Routes of Entryand Distribution

The modes of PAH transport into the aquatic environment are as diverse as

their sources and structure. The various routes of entry include wastewater

discharge, surface runoff, casual spillage and atmospheric deposition.

Different circumstances affect PAH entry into the water via various routes.

Interms of relative quantity and distribution, spillage may release large

amounts of PAH's into the water causing a local increase in PAH concentration

in and around the area where the substance, usually oil or gas, has been

spilled or has seeped out. Spillage may occur anywhere in the aquatic

environment, from a boat docked near shore, to a drilling station in the middle

of the ocean.

Both wastewater discharge and surface runoff make significant contributions

to local PAH-levels in rivers, estuaries, and coastal marine waters.

Sources which contribute to these routes of entry are almost all anthropogenic,

and are found largely in.urban industrialized areas. Tables 4, 5 and 6 provide

examples of PAH distribution from various routes of entry and land use areas.

Higher PAH concentrations from discharge and runoff are due to an increase in

sources which feed these routes of entry (Hamilton, 1984; Farrington, 1980).

Weather conditions such as heavy rainfall may cause an increase in PAH's

entering the aquatic environment via wastewater discharge, surface runoff and

atmospheric deposition. Most of the aquatic PAH burden remains relatively

close to the source of PAH deposition and concentrations can be expected to

decrease approximately logarithmically with distance from the source (Neff,

TABLE 4. Estimated inputs of benzo[alpyrene and total PAH to
the aquatic environment from various sources

.Sources Input in metric tons/year
BaP total PAH

Biosynthesis 25 2700
Petroleum spillage 20-30 170000
Domestic and industrial wastes 29 4400
Surface runoff from land 118 2940
Fallout and rainout from air 500 50000

Total input 697 230040

(from Neff, J. M. 1979, with permission of the publisher, Applied Science
Publishers Ltd.)

TABLE 5. Input rate, million metric tons/year (mta)

Source Probable Range Best Estimate*

Natural Sources

Marine Seeps 0.02 - 2.0 0.2
Sediment Erosion 0.005 - 0.5 0.05
Total Natural Sources 0.025 - 2.5 0.25

Offshore Production 0.04 - 0.06 0.05

Transportation

Tanker Operations 0.4 - 1.5 0.7
Drydocking 0.02 - 0.05 0.03
Marine Terminals 0.01 - 0.03 0.02
Bilge and Fuel oils 0.2 - o.6 0.3
Tanker Accidents 0.3 - 0.4 0.4
Non-Tanker Accidents 0.02 - 0.04 0.02
Total Transportation 0.95 - 2.62 1.47

Atmosphere 0.05 - 0.5 0.3

Municipal and Industrial
Wastes and Runoff

Municipal Wastes 0.4 - 1.5 0.7
Refineries 0.06 - 0.6 0.1
Non-Refining Industrial
Wastes 0.1 - 0.3 0.2
Urban Runoff 0.01 - 0.2 0.12
River Runoff 0.01 - 0.5 0.04
Ocean Dumping 0.005 - 0.02 0.02
Total Wastes & Runoff 0.585 - 3.12 1.18

TOTAL .1.7 - 8.8 3.2

(from Farrington, J. W.. 1985)

TABLE 6. Chemical distribution of PAHs in urban runoff from four
different land uses (mean percentage of sum of 14 quantified
PAHs)

Residential Commercial Industrial Highway

naphthalene 0.2 + 0.2 5.6 + 9.9 1.8 + 2.3 0.7 + 0.7
2-methylnaphthalene 3.3 + 5.4 3.0 + 3.7 1.3 + 1.2 1.2 + 1.2
1-methylnaphthalene 2.1 + 3.5 3.4 + 4.7 1.1 + 1.5 0.6 + 0.8
biphenyl 0.4 + 0.4 1.7 + 2.9 0.2 + 0.3 0.5 + 0.8
2-ethylnaphthalene 0-0@-+ 0.03 1.4 2.4 1.3 -+ 1.6 0.8 + 1.1
fluorene 0.2 +70.3 1.3 1.7 7.8 7 11.5 2.9 + 4.2
dibenzothiophene 0.2 0.2 3.0 5.2 3.3 2.1 1.5 -+ 2.3
phenanthrene 3.7 3.0 12.4 7 7.0 lo.6 6.3 15.8 + 15.6
fluoranthene 33.6 + 4.0 20.4 + 7.9 21.5 + 6.3 33.6 + 2.2
pyrene 19.8 + 5.6 16.5 + 10.3 19.2 + 12.3 19.3 + 15.5
benz[alanthracene 4.9 + 1.9 4.8 + 3.6 22.9 + 22.2 8.7 + 10.3
+ 2.9 - 6.0
chrysene 7.7 + 8.1 11.2 + 14.9 1.6 3.5 +
benzo[elpyrene 13.3 + 12.8 5.8 + 4.6 3.2 + 4.6 3.8 + 2.4
benzo[alpyrene 10.9 + 11.2 8.9 + 11.4 5.6 + 5.0 3.0 + 2.9

(from Hoffman, E. J. et al. 1984. Copyright permission pending.)

1979). Weather conditions such as heavy rainfall may cause an increase in

PAH's entering the aquatic environment via wastewater discharge, surface runoff

and atmospheric deposition.
@tmospheric deposition is the primary means of PPji distribution and

dispersion. Winds can carry PAH particulates for miles, depositing them in all

reaches of the aquatic environment. PAH's from natural sources such as forest

and prairie fires, along with those from industrial and exhaust emissions may

be transported via this route.

Estimates of total PAH's entering the aquatic environment are variable,

ranging from 230,000 metric tons/year (Neff, 1979), 3.2 million metric
tons/year (NAS, 1985-from Farrington, 1985), to 1-10X106 tons/year (Calder,

1976) (Tables 4 & 5).

What happens to these compounds once they reach the water? Where do they

go? PAH's are partitioned into different compartments in the aquatic

enviro nment. Relative concentrations are highest in sediments, intermediate in

aquatic biota, and lowest in the water column (Neff, 1979).

PAH's In Sediments

Sediments seem to be the ultimate "sink" for PAH's. These settled

materials contain insoluble particulates which enter the water column and are

unavailable for uptake by biota. For example, PAH of pyrogenic origin pass

through other components of the ecosystem and accumulate in sediments

(Farrington, 1985). Sediments also contain particulates from the water column,

including phytoplankton, detritus and zooplankton (Lee, 1978). Concentration

of PAH is greater by a factor of 1,000 or more in sediments than in overlying

water (Neff, 1979). PAH concentration in urban industrialized associated

sediments are generally higher than those in sediments more remote from urban

'13

areas. This divergence in PAH concentration levels for industrialized and non-

industrialized regions is largely attributable to combustion processes.

Estimates have revealed higher concentrations of 1 or more orders of magnitude

in industrial areas (Farrington, 1985). Both Mix (1984) and Boehm (1984) have

noted that combustion processes are the source of most, but not all, of the PAH

incorporated into sediments.

Fine grained sediments such as silts and clays tend to contain higher
concentrations of organic compounds than coarse sediments. Boehm (1984) noted

higher concentrations of PAH in sediments with high silt/clay ratios. The

organic carbon content of substrates such as sediments and soils seems to cause

increased sorption of PAH. PAH's found in sediments with high silt/clay

ratios, and high levels of organic carbon, are dominated by compounds from

combustion (pyrogenic) sources.

Surfacesediments seem to be more highly enriched in PAH than deeper

sediments. Wakeham (1980) estimates that PAH concentration levels range by a

factor 5-50 times higher in surface sediments than deeper layers. Recent

increases in anthropogenic sources of input associated with human activities,

and more widespread industrialization are the most probable explanations for

this phenomenon. PAH in deeper layers is apparently derived from early

diagenetic processes (Wakeham, 1980).

PAH's In The Water Column

The most important physical properties influencing PAH concentrations in

the water column are their solubility and stability. In general, PAH

solubilities can be related to their non-polar structure. An inverse

relationship seems to exist between solubility and molecular weight; decreased

solubility occurs as molecular weight increases (Rossi, 1978) (Neff, 1979).

PAH's appear to have even lower solubilities in seawater due to "salting out."

Table 7 illustrates the relationship between salt concentration and solubility

(Eganhouse, 1976). PAH-PAH interactions as well as PAH reactions with other

chemicals in water affect overall solubility. Both naphthalene and

phenanthrene work to enhance the solubility of acenapthylene, while biphenyl

and phenanthrene together exhibit mutual solubility reduction (Neff, 1979).

Micelles formed in the water by synthetic detergents increase PAH solubility
(Andelman, 1970). The presence of surfactants in the range of 10-50 mg/1

increase PAH solubility from 2-10 times as shown in laboratory studies;
however, these'surfactant concentrations are rare in natural waters (Andelman,

1974).

Another physical property of significance in the understanding of Ppdi/water

interactions is the partition coefficient, which expresses the equilibrium

c
oncentration ratio of an organic liquid (e.g. octanol) and water. The

partition coefficient may also be useful as a means to predict soil adsorption,

lipophilic storage, biological uptake, and biomagnification (Chiou, 1977). A

trend seems to exist between increasing molecular weight and higher partition

coefficients, as seen in Table 8, which shows the octanol/water partition

coefficients for several PAH's. This is in agreement with the relationship

between increasing molecular weight and decreasing water solubility noted

previously.

Transformation and Degradation

PAH's in the aquatic environment may be transformed or degraded through a

variety of mechanisms. In the water column, photooxidation plays a major role

in PAH transformation. Photooxidation is most effective for removal of high

molecular weight PAH (Lee, 1978) for which transformation-requires short

TABLE 7. Relationship between salt concentration (Ppt)
and solubility (mg/L)

0 ppt 35 ppt
naphthalene 31.3 + .4 22.0 + .293

biphenyl 1.45 + .1 4.76 + .060

phenanthrene 1.07 + .01 .71 + .025

(from Eganhouse, R. P. and Calder, J. A. 1976. Copyright permission pending)

TABLE S. Physical property data for 16 EPA priority PAII

Molecular Solubility in Water Log Octanol/Water
Compound Structure Weight (250C) mg/L Partition Coefficient Biodegradability

Benzo-a-anthracene 228.3 .014 5.61 not significantly
degraded

Benzo-b-fluoranthene 0 252.3 .0012 6.57 not available
0

Benzo-k-fluoranthene 252.3 .00055 6.84 not available

Benzo-a-pyrene 0 0 252.3 .0038 6.04 not available
000

Ideno-1,2,3-c,d-pyrene 276.3 .62 7.66 not available

(continued)
0
0

TABLE 8 (continued)

Molecular Solubility in Water Log Octanol/Water
Compound Structure Weight (2500 mg/L Partition Coefficient Biodegradability

Benzo-ghi-perylene 276 .00026 7.23 not available

D 0

Acenaphthene H HH 154.2 3.42 4.33 significant degradation
rapid adaptation

H
Acenaphthylene 152.2 3.93 4.07 significant degradation
rapid adaptation

C21 Anthracene 178.2 .073 4.45 significant degradation
gradual adaptation

Chrysene 228.3 .002 5.61 not significantly
degraded

(continued)

TABLE 8 (continued)

Molecular Solubility in Water Log Octanol/Water
Compound Structure Weight (25cC) m[Y/L Partition Coefficient Biodegradability

Fluoranthene 202.3 .26 5.33 significant degradation
gradual adaptation

Fluorene 166.2 1.98 4.18 significant degradation
gradual adaptation

Naphthalene 128.2 34.4 3.37 significant degradation
rapid adaptation

Phenanthrene 178.2 1.29 4.46 significant degradation
gradual adaptation

Pyrene 202 .14 5.32 significant degradation
rapid adaptation

(Ad'apted from U. S. EPA Treatability Manual, EPA-60012-82-001a, February 1933)

wavelengths of light capable of penetrating only a few meters. The

photoreactivity of PAH adsorbed to the surface of particulates in the water

column appears greater than those found in solution (Neff, 1979). Low

molecular weight PAH's may be removed from the aquatic environment by

evaporation from surface waters. Evaporation is considered to be one of the

main routes of transformation for low molecular weight PAH (Lee, 1978).

Giesy (undated) found photolytic degradation to be the most important

pathway of flux within channels studied both experimentally and in

simulations. There appear to be discrepencies, however, between field and lab

studies. Ultraviolet light from the sun, which was shown to degrade PAH in lab

experiments, proved to be of minor importance to PAH degradation in field

experiments.

Treatment of PAH Contamination

Ozonation,, chlorine disinfection and filtration are among the methods

under consideration for treating PAH contamination. Ozonation has been found

to be an effective treatment for the removal of PAH in water (Andelman, 1974).
At 250C and pH 7, half lives for pyrene, phenanthrene, and benzo(a)pyrene
are .18, .44, and 1.00 seconds, respectively, at normal 03 concentrations
(10-4M; Butkovic, 1983).

Chlorine disinfection is another method under consideration for PAH

removal. However, there is evidence that some component(s) in waste water

effluent may react with chlorine to yield more toxic compounds than were

present in the original effluent (Pickering, 1983).
Filtration through activated carbon, followed by ozonation, is currently

thought to be the most effective PAH removal method. Although these methods

may be impractical for widespread application, they may be useful in wastewater

treatment, thereby alleviating one source of PAH to the natural environment.

III. INTERACTIONS BETWEEN PAH AND AQUATIC BIOTA

PAH's in Asuatic Biota

PAH's affect aquatic biota in a variety of ways. Their non-polar

hydrophobic structure makes PAH's relatively high in lipid solubility which may

allow for easier entry through cell membranes and collection in fatty tissues.

As a method of measurement, concentrati ons of various organic compounds

accumulated in fish are determined largely by fish lipid content (Chiou,

1985). PAH's have been found in a broad range of aquatic biota including

bacteria, algae, phytoplankton, zooplankton, shellfish, and finfish. Thus,

significant potential for bioaccumulation and magnification through food chains

exists. Concentrations in organi sms from polluted sites tend to be greater

than those found in non-polluted sites. Mussels from environments containing

higher PAH concentrations themselves showed higher PAH concentrations. Initial

rates of hydrocarbon uptake in oysters is directly related to hydrocarbon

concentrations up to at least 450 ug/l (Stegeman, 1973). Tables 9 and 10 give

PAH concentration data for various marine organisms.

Aquatic animals contribute to PAH transformations in a variety of ways.

One means of helping to eliminate PAH's from their environment is through

physical mixing of buried oiled sediments which brings them to the sediment

surface where there is greater chance of resuspension, solubilization, and more

oxic conditions favorable to microbial attack. By pumping water through

sediments, organisms may accelerate solubilization., allowing forremoval of

more soluble components, and may introduce oxygen into deeper sediments

(Wakeham, 1980). Some marine fish have a detoxification system (mono-furrction

TABLE 9. Concentrations of selected PAH in the tissues of oysters,
Crassostrea virginica, from the harbor of Norfolk, Virginia, USA

Compound Approximate concentration
(ug/kg wet weight)

Fluoranthene 600-1000
Pyrene 100-160
Chrysene 20-40
Benz[ a] anthracene <10
Benzo[klfluoranthene 8-12
Benzo[alpyrene 2-6
Benzo[elpyrene <20
BenzoEghilperylene 1-5

(from Neff, J. M. 1979, with permission of the publisher, Applied Science
Publishers Ltd.)

21-

TABLE 10. Summary of PAH hydrocarbons in marine tissues (ppb, wet weight)

Depth, Benz(a) Benzo(a) Methyl- Other Dry Wt./
Location, lat., long. m anthracene pyrene Pyrene pyrene PAH's* Wet Wt.

Sunner flounder
(Paralichthys dentatus) 37053-51N, 74010.61W 102 <1 <1 2 1 1.1-1.5 0.21

Scup
(Stenotomus chrysops) 38011.41N, 74009.11W 66 <1 <1 2 <1 <1-<3 0.26

Black sea bass
(Centropritus stricta) 38033.21N, 7400.5.0'W 57 <1 <1 <1 <1 <0.1-<1 0.23

Butterfish
(Paprilus triacanthus) 38037-71N, 74018-51W 39 <20 <5 <1 <2 <2-<13 0.29

Sea scallops
(Placopeskin magellianicus) 38047-O'N, 73022.8'W 78 1.1 <1 4.1 2.7 <5-8.7

Red hake
(Arophysate chuss) 38047.01N, 73022.8'W 78 0.3 <11 <5 <6 <2-9

Includes fluoranthene, chrysene, triphenylene, benzo(e)pyrene, and Perylene

(from Brown, R. A. et al. 1979. Copyright permission pending).

oxidase) which renders PAH water-soluble. These soluble PAH are returned to

the water via urine (Lee, 1972a). Crustaceans also seem to have the ability to

metabolize and discharge petroleum hydrocarbons in a less dangerous form (Lee,

1976).

Microbial degradation also plays a major role in PAH transformation.

Degradation of PAH's by microbial action seems to be more rapid near the

surface than in deeper layers (Hinga, 1980; Floodgate, 1972). This mechanism

works on both low and high molecular weight compounds but is a more predominant

source of degradation in high molecular weight hydrocarbons after sedimentation

(Lee, 1978). Degradation usually occurs during the stationary phase of

bacterial growth.

Among the first scientists to study microbial degradation of PAH's was

Zobell in 1946. His studies showed that microbes could degrade PAH's under

both aerobic and anaerobic conditions, and that degradation by aerobes appears

equally good at any oxygen concentration in the range of .1-20 or 30 mg/l. The

temperature range for bacterial oxidation tends to vary. Zobell's experiments
showed bacteria to be more active at 30-370C than at 200C, whereas Mitchell
(1974) stated that decomposition occurs between a 50C low and 250C

optimum.

.Generally, the following rules seem to apply to PAH degradation regardless

of mechanism: 1) PAH degrade faster in aqueous solutions than in pure organic

solvents or crystalline form; and 2) higher temperatures, oxygen

concentrations, and light intensities yield faster rates of degradation for

certain PAH as do increased flow velocity and greater particle surface area

(Andelman, 1970).

PA[i Toxicity to Marine Organisms

Bacteria and PAH's interact on a variety of levels. Some may be involved

with PAH synthesis or degradation, while others are themselves adversely

affected by PAH's. In some bacterial strains PAH's decrease growth rate and

maximum cell density. Inherent toxicity increases inversely with PAH

solubility (Calder, 1976; Table 11).

Bacteria are only the beginning of a long list of organisms which exhibit

toxic and other detrimental effects from exposure to PAH. PAH's may inhibit

filtering ability in mussels (Lee, 1972b). DiSalvo (1975) discussed the fact

that a potential mechanism of PAH release was in mussel eggs, which were found

to be particularly enriched compared to total body burden. Studies have yet to

be done to determine the effects of PAH on gestation.

In copepod populations, exposure to PAH's reduced the lifespan and egg

production by 25% (Corner, 1975). Copepods, along with most other organisms,

accumulate PAH's in "fatty tissues". Corner suggests that since lipid levels

in copepods vary with season, so too may rates of hydrocarbon release. \Here

again exists a potential problem for offspring. Female copepods carrying eggs

usually have higher lipid levels (possibly related to season of mating),

thereby creating an environment for higher PAH levels which, in turn, could be

transmitted to eggs. Again, it is not certain what effect this has upon

gestation. Females initially exposed to PAH levels in excess of 1 mg/l become

narcotized. Narcotization is reversible upon transfer to fresh seawater;

however, mortality increases with increased length of exposure. Exposure to

TABLE 11. Effect of aromatic hydrocarbons on bacteria
(Properties of hydrocarbons studied)

W& (C) Toxicityp
Hydroc*arbons Mol wt (A) Solubilitya(M) umoleb index

Naphthalene 128.16 2.43 x 10 -4 o.4 97
2-Methylnaphthalene 142.19 1.73 x 10 _4 2.1 363
2,6-Dimethylnaphthalene 156.22 o.83 x 10-5 12.8 106
Phenanthrene 178.22 0.66 x 10-5 4.0 26
Pyrene 202.24 0.73 x 10_ 6 170 124
Benzopyrene 252.3 0.30 x 10 7 881 >26
2,3-Dihydroxynaphthalene 160.16 >16.5x 10-4 68 >1,120

aIn distilled water at 250C, 1 atm.
bAverage&%'(decrease in bacterial d ensities relative to controls) per umole
of PAH.

C 6
C = AxB x 10

(from Calder, J. A. et al. 1976, with permission of Americ*an Society for
Microbiology. Author permission pending.)

TABLE 12. Effect of long-term, low-level exposure to 14c-l-naphthalene
on feeding and egg production of adult female Eurytemora sp.

Naphthalene concentrati?n
Control 10 ugl.-1 50 ugl.-

Mortality during 18 27 31
10 days
Ingestion rate 4 x 3.39 3.4o 4.33
(Isochrysis cellT x 1@ S 1.72 1.90 1.83
ingested female- 24h- n 10 10 10

Egg productiop x 2.83 3.07 3.39
(eggs female-124h- s 3.71 3.63 4.79
n 10 10 10

Radioactivity in animal. x - 2.47 6.22
at end of 10 days s 0.33 1.69
exposure as naphthalene n 5 5
equivalents (ng female-1)

(x = mean, s = standard deviation, n number of determinations).

,(from Berdugo, V. 1977, with permission from Pergamon Journals, Inc. Author
permission pending.)

VIN _r

TABLE 13. Toxicity of selected polynuclear aromatic hydrocarbons (PAH's)
for Neanthes arenaceodentata. 96h T@M values, 95% confidence
limi , and corresponding slope functions were calculated
by the method of Litchfield & Wilcoxon (1949). TLm values
are expressed as concentration (ppm) PAH initially present in
test solution as determined by UV analysis. Values for
chrysene, benzo(a)pyrene, and dibenzanthracene are not
presented since these hydrocarbons were not lethal at the
highest concentration tested Oppm).

PAH .96 h TLm Confidence interval Slope (TLM/ppm)

Naphthalene 3.8 4.1-3.5 1.5
2,6-dimethylnaphthalene 2.6 2.9-2.3 1.4
2,3,6-trimethylnaphthalene 2.0 2.4-1.6 1.2
Fluorene 1.0 1.3-0.7 1.4
Phenanthrene o.6 0.8-0.4 1.7
1-methylphenanthrene 0.3 0.4-0.2 1.1
Fluoranthene 0.5 0.7-0.3 1.2
Chrysene - -
Benzo(a) pyrene
Dibenzanthracene

*TLm = median tolerance limi ts.

(from Rossi, S. S. 1978, with permission from Pergamon Journals, Inc. Author
permission pending.)

concentrations of 1 mg/1 naphthalene for 24 hours resulted in lower rates of

egg production, fecundity and overall length of life (Berdugo, 1977; Table

12). Benzopyrene was found to be lethal to marine copepods (Calanus

helgolandicus) at concentrations of 4 ppm (Lee, 1972).

Initial rates of hydrocarbon uptake in oysters are directly related to the

hydrocarbon concentration of surrounding.waters up to at least 450 ug/l.

Oysters remained closed during exposure to concentrations of 900 ug/l. Some of

the accumulated hydrocarbons in contaminated oysters were rapidly depleted upon

transfer to clean seawater. The portion remaining was apparently retained in

some stable compartment within the organism (Stegeman, 1973).

In the polychaete Neanthes arenaceodentata, toxicity appears to be related

to both solubility and residence time in test solutions. A trend toward

increasing toxicity with increasing molecular weight can be seen in the series

naphthalene through fluoranthene (Rossi, 1978; Table 13).*

The main routes of entry to fish are through the gills and gut. Anthracene

in concentrations of approximately 12 ug/l was acutely toxic to bluegill

sunfish, due to a phototoxic mechanism (Giesy, undated). Fin erosion and liver

neoplasms have been reported in fish from highly contaminated sediment areas

(Malins, 1984).

IV. PAHIS AND THE CHESAPEAKE BAY

Bay Geogra_phics

The Chesapeake Bay holds the distinction of being the largest estuary on

the Atlantic Coast of the United States. It lies in the coastal plain region

along the Atlantic seaboard between the states of Maryland and Virginia and is

2-0

0(y
76*3V .-75*30'
76'
3
PA@
--Chesan"Veake --I M.
Region
b

N.J.

OD
7-@

SCA E

NAUTICAL MILES
0 5

10 15 20 25
STATUTE MILES
77*0(Y ..:7q3O' -rq@00- 75,'30' 7
Figure 2, Physiographic map of Chesapeake Bay region.
C,

30-

Penns I-i.
striped bass

EDAdult Distn6ution
Major Surnmer CaVentrations
Adlu @rxl Ju-voi-
8810- Major Winter Concentrations
MO. -d J-1-

0-. by x-

E2 Sponing Areas
iO

-C

Figure 3. Striped Bass habitat and spawning reaches in the Chesapeake Bay.

(from The Chesapeake Bay in flaryland: An Atlas of Natural Resources, Johns Hopkin's
University Press, 1973. Copyright permission pending).

part of a drainage basin which includes Maryland, Delaware, Pennsylvania and

portions of West Virginia and Virginia. Over 150 rivers, branches and

tributaries flow into its waters. Figure 2 depicts the Chesapeake Bay region.
-The estuary is a plentiful source of plant life, fish, and shellfish.

There are approximately 326,000 acres of oyster bars and 250,000 acres of clam

habitat in the Maryland portion of the Chesapeake. Figure 3 illustrates

striped bass habitat and spawning reaches in the Maryland portion of the

Chesapeake. The general distribution of oyster habitat along the Bay is

shownin Figure 4. Besides the permanent biotic residents of the Chesapeake,

the Bay area is a winter home for Canada geese and a spawning ground for many

different types of marine organisms.

The land region around the northwest portion of the Chesapeake is highly

developed, especially around the Potomac, Patapsco and portions of the

Susquehanna River areas. Development along the eastern and southwestern shores

is relatively sparse down to the southern tip of the Bay around Norfolk where

another highly developed land area is found.

In and around the Chesapeake Bay region are petroleum and chemical

industries,.fossil fueled power plants (Figure 5), paper and paper pulp

industries, fish processing industries, and iron smelting and refining. Much

of the land in the lesser developed regions of the Bay is put to agricultural

use.

PAH Studies in the Chesapeake

The Virginia Institute of Marine Science (VIMS) has, by far, done the most

research on PAH's in the Chesapeake Bay region. Figures 6-9 are from a study

conducted by VIMS showing PAH concentrations along the Chesapeake Bay. As

32!

10HP

7/-
@,N
Xj@
A, J@

Z-A A-
c

t
J,
%
), -- I " <7

..........

Figure 4. American oyster habitat in Chesapeake Bay region.
(from DNR Chesapeake Bay Lcw Freshwater inflow Study Phase II Biota Assess
May 1982)

21,

14 1 a

A19
2
16

(C.P.,ity in NO

C.. Nat of
Plant W- utility St... T-bi.. Sk ... Dolt
20
YETCO 550 Oi! 4 15
"ge 0 C
Pt CO 11116 252 oil 4
4: C.!, i;'.
In.cli SC&Z 1650
ICb I i I WCO 1901 48
C
'. C'. 376
, ACH J4 C. ILD
Di"....:* Perco 543 11 Co.)
C-*,:.It"*t DC&E 103 Oi1 9
to PEPCO 1164 1 Co.)
10. Ztcb C11 3C 1121,
F:"Y-.if ""El 204
to rEPCO 480 Coal
.3 1i "1 172 Oi
14P* 1* itb PE Co.
:"17 It
5 OP&L 141 17 0i
W. So- IG&E 955 14 t/C..1
..."-t SG&S 126 its OiI

Plant Dm*d by 0,t-of-St,te Utilitlof ( A
?ECO 512 "Yd'.
VEPCO "1 16 C*I
10- VJPCO .21 26 C
21, r. PECO 1900

Figure 5. Frontispiece. Location of Power Plants in Maryland.

(Power Plant Cumulative EnviroruTental Impact Report for Maryland,
Maryland DNR Power Plant Research Program, March 1986)

noted, there is a very strong correlation between heavy PAH concentration and

high land development. The same is true for more industrialized regions of the

Bay. Concentrations increase from the Potomac River North to Baltimore Harbor

and again in the South near Norfolk, Virginia.

PAH contributors in the northern portion of the Bay are largely domestic

sewage, as well as chemical and metal processing plant wastes. In the Norfolk

area, especially in the Elizabeth River, the main source of PAH is attributed

to now-abandoned wood treatment plants which used creosote (Bieri, 1983).

As mentioned before, sediments seem to house the majority of PAH's. The

highest concentrations of organic chemicals in sediments found in the

Chesapeake are in the Patapsco and Elizabeth Rivers. PAH concentrations are

1-90 ppm in the Patapsco and 1-over 100 ppm in the Elizabeth River

(EPA, 1983).

Some of the problems caused by PAH contamination in the Patapsco and

Elizabeth Rivers are changes in benthic community abundance, diversity and

community structure. The two subject regions exhibit both low benthic

diversity and abundance, and a dominant population of pollution-tolerant
annelids, in compar ison to non-polluted reference areas.
p

In a paper by Hargis (1984), results of a study were shown in which

spot (Leiostomus xanthurus) were exposed separately to contaminated

Elizabeth River sediments and non-contaminated James River sediments with PAH

concentrations of 2,500 ppm and 1.2 ppm, respectively. Elizabeth River exposed

fish showed: 1) penetrating integumental lesions within 8 days of exposure;

2) severe fin and gill erosion; and 3) severely reduced hematocrits. James

River exposed fish showed none of these symptoms. In another study by Weeks

(1984) Leiostomus xanthurus and Trinectes maculatus (hogchoker) were exposed to

ARM 494.3 BanzoCc>pyrana
Is PP6 lea PP6 1 ppm IS ppo too ppm I ppl;

/Z 24

123
23
X22
22
. ........ .
21

20
x l@

lox
17

16 14

X13 12

to
x1l

tax
9x
No

Figure 6. Benzo(a)pyrene in sediments, Fall 1979.
(from Bieri, R. H. et al. 1983)

'ARI 397.1
to ppki- too PP6 1 ppm Is ppm too pprn I PPk

215

2*3
X22
22

20
x le"

lax
17

13
x A

X13 12

X11

lot
9x

Fiqure 7. Benz (a) anthracene in sediments, Fall 1979.

(from Bieri, R. H. et al. 1983)

SUM OF PYROGENIC PAH'S
IS PPb 188 PPb I PP"% to PPIR lea PPM I PPk

25
V2
24
JOT I---
W
24

123
23
.7
X22
22

2.
21

x 1-f
IQ

f7
lax
f7

Ifix 14

X13 13

X13

xll

lox
9 x
3ta

4'.
Iles

Figure B. SUM of pyrogenic polynuclear aromatic hydrocarbons, Spring 1979.

(from Bieri, R. H. et al. 1983)

SUM OF PYROGENIC PAH"S

18 PV6 lea ppb I ppm 10 ppin lea ppm I ppv

X23
23
X22
22

20
0 Nk
X I'D

lox
17

Is
16xp 14
xis 13

to
X11
a G
lox
9 X

Figure 9. Sum of pyrogenic PAIVS, Fall 1979.

(from Bieri, R. H. et al. 1983)

3-9

TABLE 14. PAH concentrations in sediment and water column samples
around Hart and Miller Islands (August 1981)

Compound Concentrations

Water column (ppb) Sediments (ppm)

Naphthalene <.04 - .05 <.0041 - .0098
Fluorene <.04 - .12 .0061- .207
Phenanthrene X.04 - .07 .0061- .0497
Anthracene X.04 - .09 <.0007 - .0395
Fluoranthene <.04 - .07 .0086- .597
Pyrene <.04 - .07 <.0098 - 1.429
Benzo(a)pyrene <.04 - .07 <.0067 - 1.61
Benzo(a)anthracene <.04 <.0098 - 1.69
Chrysene <.04 <.0067 - .0923
Acenaphthylene <.04 <.0040 - .0098

(Adapted from Chesapeake Research Consortium Data Report on Hart and Miller
Islands, October 1982)

TABLE 1-5. PAH concentrations in crab and fish tissues from
Hart and Miller Islands area (August 1981)

Compound Organism Concentration (ppb)

Naphthalene Callinectes sapidus <1.5 - 3.8
Fluorene 11 Q-0 - 10.6
Phenanthrene if <3.0 - 11.3
Anthracene if <3.0 - 12.1
Fluoranthene it Q-0 - 13.6
Pyrene Q-0 - 15.2
Benzo(a)pyrene 2.3 - 9.8
Benzo(a)anthracene <1.5 - 3.0
Chrysene <1.5 - 15.2
Acenaphthylene Q-0 - 9.8

Naphthalene Morone americana 0.5 - 33.3
Fluorene it 0.5 - 68.2
Phenanthrene It <1.5 - 68.2
Anthracene It <1.5 - 68.2
Fluoranthene it 9.09 - 68.2
Pyrene It 12.1 - 68.2
Benzo(a)pyrene it <1.5 - 68.2
Benzo(a)anthracene 0.5 - 68.2
Chrysene <1.5 - 68.2
Acenaphthylene 0.5 - 68.2

Same As Above Scolecolepides viridis <403 - 4530

Naphthalene Leiostomu.s xanthurus <1.5 - 385
Fluorene <1.5 - 385
Phenanthrene <1.5 - 385
Anthracene 0.5 - 385
Fluoranthene IT 5.3 - 385
Pyrene 5.3 - 385
Benzo(a)pyrene 0.5 - 385
Benzo(a)anthracene 0.5 - 385
Chrysene 0.5 - 385
Acenaphthylene <1.5 - 385

(Adapted from Chesapeake Research Consortium Data Report on Hart and Miller
Islands, October 1982)

41.A.

TABLE 16. PAH concentrations in Elk and Choptank Rivers
and Baltimore Harbor (Maryland DNR Upper Bay survey)

Compound Elk River Choptank River

Seston Sediment Seston Sediment

Acenaphthylene .01 - .05 .008 - .01 .01 .02
Anthracene 1.02- .05 .001 - .03 .22 .02
Benzo(a)anthracene .03 - .14 .004 - .04 .01 - .16 .10
Chrysene .03 - .17 .01 - .04 .02 - .21 .12
Fluoranthene .09 - .34 .05 - .19 .01 - .22 .31
Fluorene .01 - .05 .01 - -
Naphthalene .07 - .15 .02 - .08 - -
Phenanthrene .09 - .19 .05 - .11 .02 .10
Pyrene .10 - .33 .06 - .20 .02 - .29 .31

Baltimore Harbor Sediments
October 1983

Compound Concentration (mg/kg)

Anthracene .015 - .028
Benzo(a)anthracene .027 - .087
Fluoranthene .003 - .190
Phenanthrene .016 - .053
Pyrene .001 - .173

44-

Elizabeth River conditions and Ware River controls. Elizabeth River exposed

fish showed a marked reduction in macrophage phagocytosis compared to the

control group; however, this activity returned to normal after fish were held

in clean water for several weeks.

PAH concentration data is also available from a study conducted by the

Chesapeake Research Consortium on Hart & Miller Island sediment, crab, fish and

water column samples. This data is presented in Tables 14 and 15. This study

confirmed findings from other studies in that PAH concentrations proved to be

lower in the water column and higher in both biota and sediments. The highest

overall concentrations from this data were found in Scolecolepides sp. This

might have been due to higher lipid concentration, greater bioaccumulation, or

the polychaete's inability to synthesize or degrade PAH's.

Table 16 contains data on PAH concentrations in the Elk and Choptank

Rivers, and Baltimore Harbor sediments. These measurements were made by the

Maryland Department of Natural Resources. Although PAH's were found in all of

these areas, none were in concentrations as high as those in the the Elizabeth

River region.

Water and sediment sampling data as presented do not cover an adequate span

of time to draw any conclusions in terms of seasonal or long-term trends in PAH

concentrations. Computer analyses of Maryland's DNR Elk and Choptank River

sediment and seston studies show that concentrations were the same in both 1983

and 1984 in some cases, but in other instances, measurements fluctuated

(Figures 10-13). It is important that this type of monitoring continue so that

water quality trends concerning PAH's can be established.

Aside from the reported high PAH concentrations in the Patapsco and

Elizabeth Rivers, data developed from studies in other regions of the Bay show

4 3)

Figure 10. PAH's in Elk River Seston

1.7 -

1.6-

1.5

1.4

1.3

1.2

Aw 0.9-

0.8-

0.7-

0.6-

0.5-

0.4-

0.3-
0.2- Zoo

0.7-

0-
04129183 05116163 05131 /83 Od/@7/83 04130184 05121184 06171184
V z I

Date (month1da 1year)

Figurell-.PAH's in Choptank River Seston, 1983-84
ND no data; BDL below detectlon
2

1.6-

1.7-

1.5

4:U 0.9-
Co
0.8-

0.7-

0.6-

0.5-

0.4-

0.3-

0.2-
0.1- ND BDL BDL BDL BDL BDL
0 z
05109163 05125163 OB117163 04125164 05116164 05130164 OB113164

Date (monthldaylyear)

12. PAH's in Elk River Sediment
1083-7984

CU
2 -

0
05/10/83 05116163 05123183 05131183 05121164 05125164 06104164 06111164

Date (monthldaylyear)

---- PAH's in Choptank River Sediment
Figure 13.
1983-1984i BDL below detectIon

4 -

4h. Q.

co
2 -

BDL BDL
0
05125183 06/03/&13 04119184 05110164 06/07/64

Date (month1da
y1year)

TABLE 17. PAH concentrations in rivers neighboring the Chesapeake region

Benzo(a)pyrene Total PAH
Concentration ng/L

Monongahela River 42-47 600-663
at Pittsburgh, Pa.

Ohio River 5.6 57.9
at Huntington W. Va.

Delaware River 41.1 351.8
at Philadelphia, Pa.

(Adapted from Neff, J. M. 1979)

TABLE 18. Most common PAH and PASH (sulfur-containing PAH's) found in
striped bass adults, eggs, and young-of-year collected in
1981. Residues expressed in ng/g

Sample- Compounda
type Location 1 2 3 4 5 6 7 8

Nanticoke 16.2 12.8 98.7 96.9 16.6 - 20.2 8.5
Choptank 16.0 13.3 106 111 37.7 - 5.1
Hudson 18.9 19.7 72.5 54.5 21.1 7.6 2.4 12.5
ADULT Savannah 17.2 13.5 36.2 43.8 10.6 - 6.3 -
FEMALES Santee 11.3 7.0 10.8 6.9 1.8 - "12.9 --
St. John 13.4 - -- 13.3 - - 8.4
Brookneal 15.3 2.8 12.3 13.5 - - 3.2 --
Hatchery

Nanticoke 12.0 - 89.4 - 19.3 -
Choptank 11.6 3.9 83.8 - 44.7 - 1.5
Hudson 10.4 5.3 6o.3 6.7 122 -
EGGS Savannah 26.6 6.2 18.2 - 22.4
Santee 22.8 2.8 154 14.4 303
St* John 10.8 - 12.2
Brookneal 4.7 - 1.8 4.6 4.7
Hatchery

Nanticoke 15.4 6.5
YOUNG Choptank 28.5
OF Hudson 38.0 4.6 11.3 1.2 4.9 - 8.0
YEAR Santee 19.3 2.7 2.3 1.8 -

a - Code for above compounds #Is 1-8:

1. Phenanthrene 5. Benzo[alanthracene
2. Fluoranthene 6. Dibenzothiophene
3. Pyrene 7. Phenanthro[4,5-bcdlthiophene
4. Benzo[alfluorene 8. Benzo[blnaphtho[2,1- d1thiophene

(from U. S. Dept. of Interior, Columbia National Fisheries Research Laboratory,
Impacts of Contaminants on Early Life Stages of Striped Bass, Progress Report
1980-1983)

concentrations to be lower than those found to cause any of the toxic reactions

discussed earlier in this paper. However, Table 17 shows both benzo(a)pyrene

and total PAH concentrations from rivers in neighboring areas to be at least

three orders of magnitude lower than in the Chesapeake Bay. Additionally,

oyster tissues sampled from Norfolk, Virginia showed higher PAH concentrations

than those noted for other sample locations.

PAH's and Chesapeake Biota

Information derived from these studies should stimulate marked concern for

the Chesapeake Bay and the biota which inhabits it. Special attention should

be given to the effects of PAH's on recruitment of various biotic species in

the Bay. As a general rule, eggs, larvae and juveniles are the most sensitive

life stages. In the Chesapeake, freshwater spawners including alewife,

catfish, shad, striped bass, and both white and yellow perch release their eggs

in the fluvial or tide-fresh reaches of the bay system. Such reaches tend to

be the first exposed to the toxic chemicals and suspended sediments from the

rivers feeding the Bay (EPA, 1983).

Figure 3 shows approximate boundaries of striped bass spawning reaches

within the Chesapeake. Many of these reaches fall in the northern and western

portions of the Bay where PAH concentrations are highest. Concentrations of

PAH's found in adult female striped bass, eggs and young of the year are

presented in Table 18 (Columbia National Fisheries Research Lab). It is

possible that adult females excrete PAH through their eggs, as noted in other

species, or that the PAH's are taken up by the eggs at a later time.

Apart from localized effects in severely contaminated coastal and estuarine

zones, it is difficult to determine the overall stresses and impacts a chemical

pollutant may have on a given species or aquatic biota in general. Not only is

5 0

there the problem of deciding whether the chemical in question is acting on its-.-

own or in concert with another chemical or physical property, but organisms may

be lost or damaged indirectly by the toxin acting on another trophic level.

Bearing this in mind, one can easily see how PAH's could pose an enormous

threat to the Chesapeake Bay as well as to other ecosystems.

Approaches to PAH Studies

A variety of approaches have been adopted in the study of PAH's. Initial

work usually consists of water column and sediment analysis of an area in

question to determine the types and quantities of particular PAH compounds. In

areas where there have been found to be high levels of chemical pollutants,

such as the Elizabeth River, sediments can be brought into laboratory tanks and

used to monitor biotic reactions. In many cases "artificially" derived PAH's

are used for experimental studies, so that concentrations can be metered out at

desired time intervals and in desired quantities. Both of these methods are

equally important; the first to determine effects of existing conditions, and

the second to determine various hazard limits and modes of action. In cases of

chemicals such as PAH where such a wide range of interactions come into play,

simulation models are often used to evaluate various components of an ecosystem

and the combined effects of each of these components.

Chesapeake Bay Monitoring

Organic chemical monitoring efforts are currently underway in the

Chesapeake Bay within the scope of EPA's Chesapeake Bay Program. Regular

monitoring of the Bay mainstem is conducted by the Maryland Office of

Environmental Programs and the Virginia State Water Control Board. PAH's are

5.1

among hundreds of organic toxics targeted for sediment content analysis. DNR

has also measured PAH concentrations as part of its striped bass spawning

season monitoring.

Of the twenty-six organic pollutants detected in sediments and biota during

the course of the 1984-85 upper Bay monitoring period, PAH's were the most

prominent. Contamination levels ranged from 10,000 ppb in Baltimore Harbor to

less than 1 ppb at the mouth of the Potomac River. PAH concentrations were

particularly high around urban areas. According to the 1986 State of the Bay

Report (in press), a majority of these PAH's were produced by the combustion

of carbonaceous fuels.

Virginia's analysis of organic chemical content in lower Bay sediment

samples revealed a predominant abundance of PAH compounds. Although PAH

concentrations were not excessively high, only 4-8 percent were naturally

derived. At the entrance to Hampton Roads, however, total PAH's increased in

1985 from 1984 by a factor of 4.

Although there is presently no known direct threat to human health with

regard to the unnaturally high PAH levels that have been found to exist in some

parts of the Bay, the effects of long-term, low dose PAH exposure upon

organisms is not well understood. There is concern that these toxic organic

compounds may cause an imbalance in species due to reduced fish reproduction,

deformities, abnormal behavior or disease. There is also concern that PAH's

can be accumulated by organisms that reach the family dinner table.

It is recognized that a number of ecological processes impact PAH

concentration levels. However, the natural variability of contaminants in the

Bay system, seasonal cycling of pollutants within sediments and the pathways by

which those toxics go from sediment to the Bay's living resources are not fully,..

understood. These ambiguities warrant continued benthic surveillance.

Several general conclusions have come out of the 1984-85 Chesapeake Bay

Program: 1) bioaccumulation seems to depend on both the organic content and

grain size of sediment; 2) occurrences of non-cancerous lesions in croaker from

the Chesapeake could be correlated with sediment concentrations of total

PAH's.

DNR Striped Bass Sampling (1983-85)

Striped bass larvae and water quality samples were collected and analyzed

for metals and organics once a week at one location in the Upper Bay

and one location in the Choptank River. These samples were centrifuged in the

field for recovery of particulates and dissolved fractions. Organic chemical

analysis was performed on recovered particulates and filtered water. Figure 14

shows the collection and analysis scheme for metals and organic chemicals.

Table 19 indicates detection limits for selected organic contaminants analyzed

by EPA, and Table 20 shows the methods used for organics.

Sediments were taken in the vicinity of Elk Neck State Park for the Upper

Bay and Dover Bridge for the Choptank River. Analysis focused on metals and

organics as well as organic matter. Figure 15 shows sediment analyses

procedures.

1986 Study Design and Methods for DNR Striped Bass Monitoring

Composite water samples were collected from surface, mid depth and bottom

at 18 stations using a bilge pump and hose. Subsamples of the composites were

Pump wate
from depth, Water pumped
using submersible into carboy
PUMP

Particulate
matter placed Particulate matter Water from carboy
in teflon removed from <@-to centrifuge
container centrifuge

:150 grams particulate Water from centrifuge to
needed two 50 gal. carboys
@1

Composite water from
centrifuge for dissolved
Place on ice organics and metals analysis
@ 40C Placed- <- into precleaned glass
on ice containers
@ 40C

Analysis in LAB Analysis for
for ORGANICS metals and Measure amount of
METALS organics, TOC water centrifuged
TOM, TOC lipids
B

Figure 14. Sampling procedure for metals and organics.

TABLE 19. Detection limits for selected organic contaminants
to be analyzed by EPA, CRL

Aldrin .33 - 0.2 ppt
a - BHC .23 - 0.14 ppt
b - BHC .33 - .0.26 ppt
d - BHC .43 - 0.26 ppt
g - BHC .23 - 0.14 ppt
Chlordane 4.3 - 2.6 ppt
DDD 1.3 - o.8 ppt
DDE 0.67 - 0.41 ppt
DDT 1.67 - 1.0 ppt
Dieldrin 0.67 - 0.4 ppt
Endrin 1.0 - 0.6 ppt
Heptachlor 0.23 - 0.14 ppt
Heptachlor-Epoxide 0.43 0.26 ppt
PCB 1242 5.5 - 3.32 ppt
1254 9.0 - 5.4 ppt
1260 16.67 - 10.7 ppt
Atrazine 5.67 - 3.4 ppt
Linuron 10.0 - 6.0 ppt
2-4-D 10.0 - 6.0 ppt
2-4-5-T 10.0 - 6.0 ppt

TABLE 20. List of methods for organics

PAH's GUMS Method 625: Rev 3.1 DB-5 capillary column Ext.
Organic Screen Fed. Reg. December 3, 1979.

Pesticides Capillary - ECD

Method 608: Modified with DB-5 cap. column Fed. Reg.
December 3, 1979.

Linuron APLC, JAOC vol. 59, No. 5, 1976, p. 1066.

Triazines GC Triazine Analysis in water and wastes Fed. Reg. 38,
No. 75, 11/28/73-

Phenoxy Acid Fed. Reg. 38, No. 75, 11/28/73-
Herbicides

Surficial Sediment
SAMPLE

place in cleaned glass jar
with teflon lined cap (150 grams)
place on 40C for metals and
organics analysis, TOC

Figure 15. Sediment analyses procedures.

placed in pre-washed and fired glass jugs (with teflon cap liners) and frozen

for PAH analysis. These samples were thawed,.filtered and analyzed, using gas

chromatography, for the sixteen PAH's selected by EPA as priority pollutants.

Eight fixed monitoring stations in the Upper Chesapeake Bay region were

sampled twice a week. Four fixed stations were sampled in the Choptank River

with sampling occurring once a week. There were also 2 movable stations per

system in the Nanticoke, Potomac and Choptank Rivers. These station locations

varied depending on where striped bass larvae were found. Sample collection

occurred once a week.

Daily composite samples were also collected at two bioassay locations;

one in the Upper Bay region at Elk Neck State Park, and the other in the

Choptank River at Ganey's Wharf. Standard EPA analytical methods were used for

identification of PAH's from samples taken from the above-mentioned striped

bass monitoring sites.

DNR is still awaiting the results of these analyses. When available, the

results will be reported in DNR's final report on PAH's in the Chesapeake Bay.

Future Needs

Notwithstanding the recent implementation of intensive research efforts

concerning the effects of PA[ils, there seems to be a large gap in the work

devoted to early life stages among fish, particularly in the Chesapeake Bay

region. This is where efforts should be focused in order to obtain conclusive

evidence regarding biotic reactions to PAH exposure.

It is important to determine the chemical impact of PAH's on.the egg,

larval, and juvenile stages on.through the rest of the life cycle. Abnormal

effects should be noted on both an apparent observational level and a molecular

level to help determine a given PAH's mode of action. Another important and

necessary study involves the observation of,reproductive success of fish who

have been exposed to a given toxin throughout their life cycle in order to

ascertain potential alteration in reproductive ability. If species experience

a significant reduction in population or cease to exist altogether, it is too

-often the case that not only is one group adversely affected; so are all its

preditors, prey or competitors along the food web.

Before we start losing aquatic life to PAH pollutants, every effort should

be made to project their possible impact and implement the appropriate

procedures to relieve the Bay of their burden.

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