-53-

7. Literature Cited

Amico, V., G. Impellizzeri, G. Oriente, M. Piattelli, S. Sciuto, and
C. Tringali. 1979. Levels of chlorinated hydrocarbons in marine
animals from the central Mediterranean. Marine Pollution Bulletin
10:282-284.

Basturk, 0., M. Dogan., I. Salihoglu, and T.I. Balkas. 1980. DOT, DDE and
PCB residues in fish crustaceans and sediments from the Eastern Medi-
terranean coast of Turkey. Marine Pollution Bulletin 11:191-195.

Boehm, P.D. 1980. Evidence for the decoupling of dissolved, particulate and
surface microlayer hydrocarbons in Northwestern Atlantic continental
shelf waters. Marine Chemistry 9:255-281.

Boehm, P.D., and J. Barak. 1978. Chemical analysis of fish samples for
gasoline from the Ocean 250 gasoline spill. Final Report; NOAA Contract
No. 03-78°D01-30. NOAA/NMFS, Narragansett, Rhode Island.

Boehm, P.D., and J. Barak. 1979. Petroleum hydrocarbon analysis of fish
collected in the vicinity of the Argo Merchant oi] spill - April to
October 1977. Final Report, NOAA CoRtreee No. NA-79-FAC-00015.
NOAA/NMFS, Sandy Hook, New Jersey.

Boehm, P.D., and J.G. Quinn. 1977. Benthic hydrocarbons of Rhode Island
Sound. Estuarine and Coastal Marine Science 6:471-494,

Farrington, J.W., and P.A. Meyer. 1975. Hydrocarbons in the marine environ-
ment. In G. Eglinton (ed.), Environmental chemistry, Vol. 1. The
ChemicaT Society Special Report No. 35, United Kingdom.

Farrington, J.W., J.M. Teal, and P.L. Parker. 1976. Petroleum hydrocarbons.
Pp. 3-34 in E. Goldberg (ed.), Strategies for marine pollution monitor-
ing. John Wiley and Sons, Inc., New York.

Graham, J.M. 1976. Levels of PCB's in Canadian commercial fish species
Pp. 155-175 in Proceedings, National Conference on Polychlorinated
Biphenyls. EPA Office of Toxic Substances.

Mackie, P.R., Ked. Whittle, and R. Hardy. 1974. Hydrocarbons in the marine
environment. I. n-alkanes in the Firth of Clyde. Estuarine & Coastal
Marine Science 2:359-374,

McDermott, D.J., D.R. Young, and T.C. Heesen. 1976. PCB contamination of
Southern California marine organisms. Pp. 209-217 in Proceedings,
National Conference on Polychlorinated Biphenyls. EPA Office of Toxic
Substances.


-19-
750 740 qe: - 710 709 63°

87°

base

haze

P4z0

paio

400

MARYLAND

NEW HAMPSHIRE

CHESAPEAKE oh

VIRGINIA

—

@ None detected

@ = .00!—.01 ppm
® 01-1 ppm
A+.5 ppm

a cee ee)
) 50 200

100
KILOMETERS

= 360 }
NORTH {
CAROLINA ‘
care}
HATTERAS _/
76° 750 740 730 720 710 79@ ago 620
fi at i fa : 1 hi iL i

Figure 11. Red Hake—PCB,




-62-

An aliquot of the hexane eluate from all negatively. screened PHC samples
from Phase 1 was analyzed by GC/ECD. Otherwise, an aliquot was taken for
PCB/DDE analysis from the fo eluate of fractionated samples (Phase 3).

2.1.3 Phase 3: Saturated and Aromatic Hydrocarbons

Fifty-three extracts of tissue samples chosen from Phase 1 as probably
containing PHCs were charged to a 11.0 gm silica gel column topped with
1 gm 5% deactivated alumina. Two fractions containing saturated f} compounds,
eluted with 17 ml hexane, and unsaturated (aromatic and olefinic) f2 com-
pounds, eluted with 21 m1 50:50 hexane/MeClo, were collected. Fractions
were concentrated, an aliquot weighed on a Cahn electrobalance, and approxi-
mately 10 ug of sample were applied to either an SE-30 (fj) or SE-52 (f2)
30-m fused silica capillary column run as for Phase 1. Oata collected
from the GC/FID was quantified by computer using the internal standards
androstane (f]) and deuterated phenanthrene (f2) which were spiked to the
initial tissue digestate.

The interpretation of the data on PHC concentrations was based on the
following criteria. Those samples whose initial capcmmbxs GC chromatogram
qualitatively suggested the presence of petroleum were further fractionated
(approximately 40%). All tissues initially screened negative received no
further quantitation of PHC or PAH. Those samples which were fractionated,
and in which there was no unresolved complex mixture (UCM), a common indica-
tion of petrogenic contamination (Farrington et al., 1976) or in which the
UCM was <30% of total (f] + f2) hydrocarbons were also considered negative
with respect to PHC. A positively screened tissue was one in which: 1) saturated
f} fractions demonstrated (a) the presence of an UCM eluting between n-C}3 to
n-Caq and/or n-Cyg to n-C3q (livers), usually >30% of total hydrocarbon for
the % fraction, and (b) an easily discernible n-alkane distribution between
n-C}3 and n-Coq suggestive of paraffinic tars; 2) unsaturated (f2)
fractions disotayed some chromatographic fine detail suggestive of aromatic
assemblages.

As a rule, aromatic resolved and unresolved concentrations were cal-
culated for all samples after subtracting obvious biogenic inputs such as
squalene from the computer-determined resolved peak areas. Alkanes were
identified by their Kovat's indices. Al] UCMs were measured with a planimeter,
and resolved and unresolved areas were converted to micrograms by comparing
to the area of the internal standard. In the ensuing discussions, unless
otherwise indicated, PHC concentrations are the sums of both f; and “fo
fractions.


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-26-
770 76° 75° 749 73° 730 710 70° 30 68° 87° 66°
pad
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é : so. J
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if © 01-.10 ppm
hago ) 4
f :
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CAROLINA : KILOMETERS.
CAPE}
HATTERAS /
76° 1759 740 73° 720 710 79° 69° 68° 67
hi fe 1 fa : fi L i . ri

Figure 17. Winter Flounder—PCB.


-97-

distillate contamination (Fig. 9). The second, late UCM may be biogenic,
with only the earlier UCM representative of a recent petrogenic input.
Therefore, liver samples with early eluting UCMs and a smooth distribu-
tion of n-alkane peaks between n-C}3 and n-C29 should be considered to

be PHC-positive. Some chromatograms support this theory (Figure 15), in
that a pronounced late UCM is present, but only small n-alkane peaks are
visible when compared to the respective muscle tissue. This analysis,
though, may be overly simplistic. Consider that the liver operates as the
primary detoxification organ in the fish, and so contains specific metabolic
pathways not found in other tissues. High boiling n-alkanes, and compounds
comprising the late UCM could be preferentially collected in liver tissues.
PAH analysis of specific aromatics in liver tissue supports this observation
by showing a 10-fold increase in naphthalenes and phenanthrenes in this
organ over muscle tissue. Note that the liver samples investigated do not
necessarily contain high levels of dibenzothiophenes, fluorenes, or mass
202 compounds as compared to muscle, also suggesting a preferential accumu-
lation of certain petrogenic contaminants in this tissue or selective
metabolism of certain PAH compound types. The liver consistently contains
an average 10-fold increase in concentrations of PHC, PCB, and PAH and
demonstrated much greater variability in concentration as compared to
muscle.

It is encouraging to see that muscle concentrations of PCB and petrogenic-
related compounds fall within ranges established by other studies. This
reproducibility of measurement over the last 10 years (covered in Tables 4-1
and 4-2) supports the validity and continuance of the PHC monitoring of
coastal fish and waters. Consistency of PHC and PCB concentrations found
in the broad range of species now monitored encourages the use of fish in
general as good candidates for pollutant chemical monitoring.

This study has been unable to clearly define any regional forcing of PHC
or PCB concentrations in any of the eight species of fish. The hydrocarbon
data do not provide a complete enough survey of each region to identify pet-
rogenic concentration gradients. PCB data, although more complete, also do
not demonstrate any clear regional variation, although for both PHC and PCB
compounds, individual samples at particular stations clearly show evidence
of elevated PHC and PCB levels in the respective GC‘/FID and GC/ECD traces.
The fact that high PHC or PCB concentrations are not found in the same sample
or at the same station well illustrates the general decoupling of PHCs and
PCBs in this survey.

It has been suggested (Nisbet and Sarofinn, 1972) that the ratio of
TODT to PCB may provide an interpretable measurement of organic contamination
in various organisms, independent of that organism's position in the food
chain, and hence the known bioaccumulation of chlorinated hydrocarbons. PCBs
determined for this study fall within range of PCBs determined both in the
northern half of this study and in earlier studies (Table 4-2). PCB/=DOT
ratios range from 4 to +10 with no apparent species preference, a similar
result aS was obtained in the northern half of this study (Boehm, 1980).


“(ODL UONeIS) sapuNno|s yods snoy ul SUOqBDOIPAY, WNajotadg paresnles "Ez aanbi4

-33-

a yryyit yrty ee
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PHASE 1

I

PHASE 2

ma)

PHASE 3

VT

PHASE 4

-58-

Sample

¥.

“1—Dissect
2—Saponify in 6.6 N Aqueous KOH/MEOH;

90°C; 8 Hrs.

3—Extract 3 Times with 50mi Hexane

Extract

1=Concentrate

2—Resaponify and Extract w/Hexane
3—Charge to Alumina/Sodium Sulfate Column
4—Elute w/Hexane

5—Concentrate

> Petroleum
No

_

Y.
Eluate
Petroleum ¢ FID
Yes Gc
1—Alumina/Silica Gel Chromatography L
2—Elute fy w/Hexane ec
3~Elute Fz w/50:50 Hexane/ Gc
Methyiene Chloride =
4—Weigh Fractions
Fy Fo
Saturated Aromatic
PHC’s PHC’s
SE30 SE52
Capillary Capillary -——P
GC-FID GC-FID
Capillary
GC/MS

Figure 1. Multi-Phase Analytical Program.


-29-
— " r 7 — 7
Tr 760 75° 740 770 70 700 9° go 67° 66°
p4ao
430
NEW HAMPSHIRE
420
410
je dQo be |
MARYLAND
“~
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s
ws
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2
=<
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2
é 4
virginia \ i @ None Detected
/ @ 001.01 ppm
( © .01-.10 ppm
b26° : 4
f
NORTH H 100150200
CAROLINA H KILOMETERS
CAPE /
HATTERAS /
76° 1780 749 730 770 70 70° 69° 68° 67°
m fo 1 4. L " 1 L n 1

Figure 20. Windowpane Flounder—PCB.


~61-

Figure 3. Aroclor 1254 Standard Mix, ( * = Quantification Peaks).


-98-

TABLE 4-2

PCB COMPOUNDS IN FISH

PCB

SPECIES LOCATION (ng/g ORY WT.)4 REFERENCE
Hake GAS I (Southeast/Gulf)

Muscle 16-90 This study

Liver 40-410 This study
Flounder GAS I (Southeast/Gulf)

Muscle 10-70 This study

Liver 40-980 This study
Hake GAS I (Northeast) 2-457 Boehm (1980)
Flounder GAS I (Northeast) 2-86 Boehm (1980)
American Dab GAS I (Northeast) 1-24 Boehm (1980)
Haddock ~ GAS I (Northeast) 1-26 Boehm (1980)
Cod GAS I (Northeast) 2-18 Boehm (1980)
Hake East Coast, United States 70-400 Unpublished data
Flounder East Coast, United States 70-350 Unpublished data
Mullet Mediterranean Sea 2,000-3,500 Amico et al. (1979)
Mullet Mediterranean Sea Trace-400 Basturk et al. (1980)
Tuna Mediterranean Sea 90-400 Amico et al. (1979)
Sole West Coast, Southern California 50-2,000 McDermott et al. (1974)



INCIDENCE OF THE PRESENCE OF PHC COMPOUNOS

-39-

TABLE 4-2

CONCEN- CONCEN-
PERCENT TRATION TRATION*
NO. OF OCCUR- (ug/g (ug/g
SPECIES SAMPLES RENCE dry wt.) wet wt.)
Silver Hake 14 86 6-90 1.2-18
Red Hake 14 29 1-5 0.2-1
Yellowtail Flounder 16 45 , 2-7 0.4-1
Winter Flounder 13 15 6-9 1.2-1.8-
Windowpane Flounder 8 38 1-5 0.2-1
Four Spot Flounder 4 50 2-6 0.4=1.2
Summer Flounder 1 25 1 0.2
American Dab 4 25 1-2 0.2-0.4
Haddock 7 0 -- -
Cod 5 0 -- --
Skate 2 0 -- --
Scallop 1 0 -- --
Rock Crab 1 100 327 66
Lobster 2 0 - --

*Ory weight basis + 5.


-81-

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Hyerocarbon

(400 Samoles)

PCB Anaiysis
4100 Sampies}

2) Homogenize in Ti

1) Oisseet

sue Homagent
=100 ¢ Tissue, 100 3 Sodium: Suiohate
-10C mi Distiliea Hexene

Repeat 3 Times

3) Decant Extract

Extract
|

1) Concentrate to 1 mi

2) Seoonify 4 Hours with
4N Aqueous KOH

3) Add Seturated NaC!

4) Extract with Hexane

fiable Lipids
tract)

1) Charge to Aiuming Cleanvo Column
2} Elure with Methyiene Chioride

Fluate

Petroeum YES

Hyerocarbon

=
€C-GC
Silicie Acid
Column Chromatographic
Fractionation
-—_————
~ ~
F Fo
Saturated Aromatic
Hydrocarbons Hydrocarbons

T

Determination
(~40 Samples)

PAH Snaivsis

» v
Caciliary Capillary
Ge ici

|
~
Capiliary
GC/MS

Figure 1. Proposed Multiohase Analytical Scheme.

+ FIO-GC i Petroleum NO


CONTENTS.

FOREWARD © 2 we ee ee v

1. OBJECTIVES 2 1. Le ee ee ee 1
2. SUMMARY OF ACTIVITIES AND RATIONALE . . 2... eee ee eee 1
2.1 Analytical Strategy 2... 1. ee ee ee ee 1
2.2 Methods and Materials . 2... ee eee eee eee 3
3. SUMMARY OF FINDINGS . 1. 1 2 ee ee ee ee ee ee ee ee 8
3.1 Silver Hake 2 1 We ee ee 8
3.2 Red Hake 2 ww ee ll
3.3 Yellowtail Flounder 2... 1 ee ee ee ee ee ee 16
3.4 Winter Flounder «1. ee ee ee ee ee ee ee 23
3.5 Windowpane Flounder . 2... ee ee ee ee ee ee 23
3.6 Haddock’... ee ee ee 23
3.7) Cod ww ee ee 30
3.8 Four Spot Flounder 2... 1. ee ee ee ee 30
3.9 Summer Flounder 2... 1. ee ee ee ee ee 30
3.10 Rock Crab, Cancer Crab, Scallops, Lobsters ....... 30
3.11 Little Skate... ee ee 35
3.12 American Dab... ee ee ee ee ee 35
4. INTERPRETATION OF FINDINGS .. 2... 1 ee we ee ee eee 35
5. SUMMARY OF DATA ACQUIRED. ©... 2... ee ee ee ee eee 43
6. DATA APPENDICES .. 1. 1 eee ee ee ee 43
7. LITERATURE CITED 2. ee ee 53


~36-

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Lao
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CHESAPE AK BAY

RC=Rock Crab
CC=Cancer Crab
S=Scallops
L=Lobster

@ None Detected
@ .001-.01 ppm
© 01~.1 ppm

© 1-5 ppm

VIRGINIA
el
pase
NORTH so 100 150 200
CAROLINA KILOMETERS
CAPE
HATTERAS
76° 79 740 73° 720 719 70° 69° 68° 670
4. fo L abn 1 1 nm 4. nm

Figure 25 . Benthic Epifauna—PCB.


TOTAL PCB py/gm

-67-

>3,0005 e
2,000 4 e
e
1,0004 ° e °
900 + e
2004
700 5
e
6004
; e
500 4 ° °
°
400 4 e 3 bd °
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% \ /
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104 eccoo coco fo) fool °
54
0 a T T T T 7 T 1
Butterfish Flounder Lizardfish Porgy Scad Snapper Spot Hake
O Muscle
—— ——— Median Vaiues
© Liver

Figure 5. PCB Concentrations Graphed by Species.


-76-

Reproduced from
best available copy.

Figure 12. Representative GC/ECD Trace (Packed Column) of PCBs in a
Lizardfish Muscle Tissue from Region 2, Station 33. Starred Peaks Co-elute with
Aroclor 1254 Standard. Eartier Peaks do not Co-elute with any PCB Mixtures
{e.g. Aroclor 1016 or 1242).


Tilia —

NOAA Technical Memorandum NMFS-F /NEC- 13

This TM series is used for documentation and timely communication of
preliminary results, interim reports, or special purpose information, and
OAM OSI» has not received complete formal review. editorial control, or detailed
YC. editing.

Gulf and Atlantic Survey
for Selected Organic Pollutants
in Finfish

Paul D. Boehm and Pam Hirtzer

Energy Resources Co., Inc., 185 Alewife Brook Parkway, Cambridge, MA 02138

U.S. DEPARTMENT OF COMMERCE

Malcolm Baldridge, Secretary

National Oceanic and Atmospheric Administration
John V. Byrne, Administrator

National Marine Fisheries Service
William G. Gordon, Assistant Administrator for Fisheries

Northeast Fisheries Center

Woods Hole, Massachusetts

April 1982 _



-102-

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~6-

A deactivated alumina column cleanup was employed to obtain an eluate
suitable for GC¢ analysis. The 0.5-ml hexane extract containing the
nonsaponifiable lipids was charged to a column of 6.5 g deactivated (7.5%
water) alumina overlying | g of sodium sulphate in a l-cm (i.d.) glass
column. Twenty-five (25) ml of hexane are used to eluate a single fraction
containing saturated and aromatic hydrocarbons and PCB compounds.

The single fraction was then analyzed by GC2. An automatic sampler
was used to inject ] wl in the splitless mode into an HP 5840A reporting GC
equipped with a 30 m SE-30 (0.25 mm i.d.) fused silica glass capillary
column. Screening was achieved by temperature programming the column from
40° C to 275° C at 5°/min.

2.2.2 Chlorinated Hydrocarbons (PCB, DDE)

Chlorinated hydrocarbons were analyzed by electron capture gas chroma-
tography using a 63Ni EC detector (GC/ECD). An aliquot of the single
hexane eluate was chromatographed using a 3% SP 2250 packed glass (1/4-in
o.d.) column, temperature programmed from 130° C to 230° C at 8°/min and held
at the upper temperature for 20 minutes. PCB and DDE were quantified using
an external standard calibration curve. PCB compounds, measured as Aroclor
1254 (Figure 3) were quantified by measuring and averaging the areas of the
four component peaks indicated and comparing to the standard curve.

As the saponification reaction will convert DDD and DDT to DDE, the "DDT
family" or DDT was measured as a single component, DDE.

2.2.3 Saturated and Aromatic Hydrocarbons

Those extracts of samples screened positively (i.e., containing indica-
tions of PHC content; Reed et al., 1977; Farrington and Meyers, 1975;
Farrington et al., 1976; NAS, 1975) were fractionated by silica gel column
chromatography (Boehm, 1980) and two fractions containing saturated (fj) and
aromatic (fz) hydrocarbons were analyzed by GC2 and quantified using the
internal standard technique by which the areas of resolved and unresolved
(UCM) components of the samples are compared to that of a known quantity of
standard(s) spiked to the initial sample homogenate. Thirty-meter (30-m)
fused silica SE-30 (J&W Scientific) capillary columns were used in the
analysis.

2.2.4 PAH Analysis

Selected silica gel aromatic fractions (fz) were analyzed by computer-
ized GC2/MS to determine the identity and quantities of PAH compounds in
the tissues. The presence of aromatic hydrocarbons from 2 to 5 rings were
examined -by quantitative mass fragmentography.


-48-

TABLE 6-5
ANALYTICAL SUMMARY - WINDOWPANE FLOUNDER

PETROLEUM :
HYDROCARBON PETROLEUM CHLORINATED
SCREEN HYDORCARBONS HYDROCARBONS
NO. OF = ———_—— (ug/g) (ug/g)

STA- INDI- POSI- NEGA-
TION VIDUALS TIVE TIVE RESOLVED TOTAL PCB ZDDT — PCB/EDOT

33 9 x 0.015 0.007 2.1
39 8 x 0.023 0.006 3.8
40 9 Xx 0.018 0.004 4.5
77 6 Xx 0.014 0.002 7.0
79 8 x 1.0 1.7 0.004 ND -
95 8 Xx "6.2 6.5 0.086 0.011 7.8
101 6 x 0.018 0.033 6.0
116 2 x 1.8 4.8 0.004 0.001 4.0
t= Xs ke X=

4.2 0.02 0.004 5.0

+2.3 +0.02 +0.003 + 2.0



-90-

3.2.1 Petroleum Hydrocarbons

Of the six regions analyzed, Region 1, Chesapeake Bay, and Region 6,
Corpus Christi/Port Isabel, had the highest percentage of muscle and liver
tissues screened positive (approximately 66%). No samples of either muscle
or liver tissues in Region 4 were screened positive; one out of six samples
(17%) in the Georgia Bight, Region 2, was screened positive (spot tissue),
and approximately 12% of samples off the Florida West Coast were screened
positive. Fifty percent of the samples analyzed from Region 5, the Flower
Gardens, showed evidence of petroleum assimilation. Figures 16 and 17
display this information geographically.

Table 3-3 presents the above data. It can be seen that muscle PHC
concentrations vary from 5.5 ppm to 20 ppm from region to region, and that
liver values range from 58-551 ppm (Figure 18). No simple corrélation is
apparent between measured PHC liver concentrations, muscle concentrations,
and the percentage of fish screened positive in each region. Flounder is the
only species found in all six regions. Spot consistently contains the
highest or second highest muscle or liver concentrations of PHC wherever the
fish is found (Figure 4).

3.2.2 Chlorinated Hydrocarbons, PCB and DDT

We have not found any consistent regional variation in PCB concen-
trations of muscle tissues, either as the median value of PCB in each region,
or in any significant inter-regional variation in the range of PCB concen-
trations (Table 3-4), except in Region 4. Liver tissue, although varying
between a median value of 155 ppb from. Region 3 to 300 ppb in Region 5, also
does not support any apparent PCB concentration gradients. Ranges are
similar from one area to the next, with Figures 19, 20 and 21 geographically
displaying this information. Easily noted between these two figures is the
order of magnitude increase in concentrations found in liver tissues versus
muscle tissues.

3.3 Polynuclear Aromatic Hydrocarbon (PAH) Results

Sixteen samples of muscle or liver tissues were selected for detailed
analysis by capillary GC/MS. Concentrations of compounds in the naphthal-
ene (2 ring), phenanthrene (3 ring), dibenzothiophene (2 aromatic rings,

1 heterocyclic saturated ring), and fluorene (2 aromatic rings, 1 saturated
ring) families, and the compounds fluoranthene and pyrene (m/e = 202), are
presented for each tissue in Table 3-5. "Families" include zero- (the
parent compound), one-, two-, three-, and four-methy] substituted components.


-69-

3.1.2 Flounder

Thirteen samples of flounder (summer, broad, shoal, gulf, blackbelly,
three-eye, or windowpane) were analyzed from the six different regions
(Table A-2). Overall, flounder tissues contained the lowest amounts of PHC
compounds in muscle or liver, of any of the species analyzed, ranging from
3.2 ppm to 6.9 ppm, with a median value of 5.0 ppm. Two separate samples
were analyzed from Region 5 and demonstrate reasonable reproducibility:
muscle PHCs were 1.2 and 1.0 ppm and liver PHCs were 61 and 119 ppm, respec-
tively. The data from this species also demonstrate the importance of the
resolved vs. unresolved composition of the chromatogram in determining
petroleum contamination: the sample from Station 15 has a large 2UCM but
lower total hydrocarbon concentration than that from Station 53; hence fish
at Station 15 are screened positive while hydrocarbons measured in fish
from Station 53 (also 88 and 143) are assumed to be of biogenic origin.

The same is also found in the liver samples.

Muscle and liver tissue f) fractions (Figure 7) display PHC-related
UCMs, with the “typical” liver GC2 trace easily distinguished by the
second late-eluting UCM between n-C2g and n-C3q and prominent n-C26 to n-C33
alkanes. Both tissues contain a prominent n-alkane series representing
petroleum-related contamination. Also labeled in Figure 7 are the branched
alkanes, pristane and phytane. The f2 fractions (Figure 8) also contain
UCM material which, in some individuals of this species, can account for
70-75% of the total PHC for both the muscle and liver. Late-eluting peaks
in the liver fg chromatogram (Figure 8) are large biogenic olefins which
we found typical of this tissue. These were not included in quantifications.

PCB concentrations found in flounder muscle tissue (Table 3-2, Figure 5)
range from 10 to 70 ppb, with a median value of 30 ppb and, in liver tissue,
are approximately 10 times higher (370 ppb). This species does not demon-
strate a marked regional variation in PCB values of muscle tissue or livers.
The two positively screened PHC tissues from Station 15 and 285 have high PCB
values. Note that in this species, PHC-negative tissues also can contain
significant concentrations of PCBs, and that there is no apparent relation
between PHC and PCB concentrations in liver tissues in general.

3.1.3 Silver Hake

Two out of four hake samples (Table A-3), including both muscle and
liver tissue, were screened positive for PHC compounds, containing a median
value of 5.6 ppm. Liver tissue contained 158 ppm (190 and 127 ppm). The
two samples are within reasonable agreement for both muscle and liver.

Gas chromatograms are very similar to silver hake analyzed further north in
the first GAS I study (Figures 9 and 10), although concentrations are lower
in the southeast region (see Part I of this program). In the northeast
region silver hake were singled out as the most pollution-impacted species.
Such a designation seems unwarranted in the southeast-Gulf region. The


-30-

any after fractionated and analyzed by GC2. However, GC/MS analysis of
the aromatic fraction from Station 123 reveals PAH compounds: naphthalenes
12 ppb, phenanthrenes 15 ppb, dibenzothiophenes 3 ppb. This illustrates
that GC2 alone is not sufficient to yield detailed information on small
quantities of PAH compounds.

PCB concentrations are also very low (<0.005 ppm) except for one
sample (Station 132) where levels reached 0.026 ppm. Notably, PHC and PCB
compound occurrences are totally unrelated. As the areal coverage only
includes the Georges Bank region (Figures 21 and 22) observed distributions
cannot be related to any source.

3.7 Cod

None of the five cod samples analyzed exhibited’ any PHC compounds, but
PCB were detected in four of the five. The highest concentration (0.018 ppm)
of PCB was detected at Station 113 (see Section 6, Table 6-7).

3.8 Four Spot Flounder

Fifty percent (50%) of the four samples screened contained PHC com-
pounds. The two samples after fractionation were determined to contain PHC
levels from 2 to 6 ppm (see Section 6, Table 6-7), the higher of the two
values occurring at Station 100 on the southern edge of Georges Bank.
Pelagic, paraffinic tar appears to be the main contaminant source
(Figure 23). :

PCB ranged from 0.004 to 0.008 ppm and the DDE component was either
not detected or was extremely low (approximately 0.002 ppm) in these
fish.

3.9 Summer Flounder

The single summer flounder sample (two individuals) analyzed was from
Station 81. It contained no PHC compounds but did contain PCB (0.014 ppm)
and DDE (0.003 ppm) compounds (see Station 6, Table 6-8).

3.10 Rock Crab, Cancer Crab, Scallops, Lobsters

As a group these benthic epifauna contained no detectable hydrocarbons
in the gross screening phase, except for the single rock crab sample from
Station 35 at the mouth of Delaware Bay. This sample contained very large
(327 ppm) levels of petroleum-derived hydrocarbons (Figure 24) and exhibited
6ce profiles indicative of a mid-boiling, degraded distillate oil. Levels
of GC/MS-determined PAH compounds (Table 3-1) were quite high: phenanthrenes
59 ppb; fluorenes 58 ppb.


-42-

TABLE 4-4
INCIDENCE OF THE PRESENCE OF PCB COMPOUNDS

PERCENT CONCENTRATION

NO. OF OCCUR- (ug/g dry MEAN
SPECIES SAMPLES RENCE we ight) PCB/£D0T
Silver Hake 14 100 0.025-0.457 5.
Red Hake 14 . 93 0.002-0.042 3.3
Yellowtail Flounder 16 94 0.002-0.052 4.8
Winter Flounder 13 85 0.002-0.031 5.6
Windowpane Flounder 8 100 0.004-0.086 5.0
Four Spot Flounder 4 100 0.004-0.008 4.5
Summer Flounder 1 100 0.014 4.7
American Dab 4 100 0.001-0.024 5.5
Haddock 7 100 0.001-0.026 -
Cod 5 80 0.002-0.018 2.8
Skate : 2 100 0.002-0.012 6
Scallop 1 100 0.001 -
Rock Crab 1 , 100 0.043 17
Lobster 2 100 0.1-0.15 3.5

*Dry weight basis.


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-47-

TABLE 6-4
ANALYTICAL SUMMARY - WINTER FLOUNDER

PETROLEUM
HYDROCARBON PETROLEUM CHLORINATED
SCREEN _ HYDORCARBONS HYDROCARBONS
NO. OF = ————— (ug/g) (ug/g)

STA- INDI- POSI- NEGA-
TION VIDUALS TIVE TIVE RESOLVED TOTAL PCB cODT  PCB/xDDT

52 8 x 1.0 6.2 0.025 0.004 6.3
55 x 0.031. 0.003 ‘10.0
58 X 0.024 0.003 8.0
95 x 0.021 0.002 10.5
1 8 x 0.006 0.002 3.0
101 6 x 0.005 0,007 «0.7
105 2 x 0.006 ND -
113 4 x. 0.004 0.005 0.8
123 5 x ND ND -
134 1 x 0.004 ND -
139 4 x 1.4 8.7 0.005 ND -
142 1 X ND ND -
157 1 X 0.002 ND -
X= ke X= X=

5.5 0.01 0.002 5.6

+0.01 +0.002 +4.2



-43-

Trace organic pollutants measured here in muscle tissue are more likely
to accumulate in organs such as the liver and kidney to much higher levels
than observed here. While it may be more appropriate in terms of considera-
tions of human consumption to monitor muscle tissue, if chemical measurements
are to be linked to biochemical or physiological change, analysis of the
accumulator organs is required. It is for this reason that in the GAS Ib
study liver tissue, as well as muscle tissue, was analyzed for PHC, PCB, and
EDDE contamination.

Furthermore, while the concept of PHC monitoring seems rational, only
certain components of the broad PHC class of compounds are considered "toxic"
or "mutagenic," i.e., the PAH compounds. Significantly more effort and
emphasis should in the future be placed on GC/MS analysis of PAH compounds,
perhaps using sample extracts obtained here and also in future studies.

The final "problem" or recommendation pertain to evaluating sources of
observed pollutants. In order to fully. evaluate how fish acquire pollutants
and what are the likely future paths of uptake of PHC, PCB, and PAH (com-
pounds), the chemical composition and an evaluation of the key chemical
ratios (e.g., PCB/ZDDT) in suspected sources (water column particulates,
surface sediment, prey, etc.) should supplement fish. monitoring studies.
This combined evaluation of observed pollutant levels and sources of pollu-
tants are the roots of a true monitoring program addressing contaminant
levels in commercially important fish.

5. Summary of Data Acquired

The above-mentioned analytical scheme was applied to those samples
previously inventoried in Section 2, Table 2-1. PAH determinations were made
in those samples presented in Section 3, Table 3-1.

6. Data Appendices
Detailed analytical results are presented in Tables 6-1 through 6-9.


=72-

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MOAA FIRM 25~13 U. S, DEPARTMENT OF COMMERCE

(1-78) * BIBLIOGRAPHIC DATA SHEET NATIONAL OCEANIC AND ATMOSPHERIC ADMINISTRATION
1, NOAA ACCESSION NUMBER 2. 3. RECIPIENT'S A ESSION. NUMBER
NOAA-82070201 PRES “Sib d
4 TITLE AND SUBTITLE 5. REPORT DATE
Gulf and Atlantic Survey for Selected Organic Pollutants April 1982
in Finfish 6.

7. autnoris) Paul D. Boehm and Pam Hirtzer (both Energy Resources]e. REPoRT NO.

Co., Inc., Cambridge, MA 02138) NOAA-TM-NMFS-F/NEC-13
9. PERFORMING ORGANIZATION NAME AND AODRESS 10. PROJECT/TASK NO.

NOAA, National Marine Fisheries Service,

Woods Hole, MA, O2s¢3 11. CONTRACT/GRANT NO.

Northeast Fisheries Center

12, SPONSORING ORGANIZATION NAME AND ADDRESS 13, TYPE OF REPORT AND PERIOD
Same COVERED
Tech. Memo.

14,

18. PUBLICATION REFERENCE

NOAA Technical Memorandum NMFS- F/NEC-13, April 1982. 116 p, 43 fig, 10 tab, 30 ref.

v6. ABSTRACT This issue combines two reports prepared by the Energy Resources Co., Inc.
The first report, "Gulf and Atlantic Survey for Selected Organic Pllutants in Finfish.
1: Gulf of Maine to Cape Hatteras," presents information on both finfish and benthic
invertebrates. The secon report, ''2: Chesapeake Bay to Port Isabel, Texas,'' presents
information on finfish only. Selected finfish and benthic ecpfaunal samples were ana~
lyzed for levels of petroleum hydrocarbons, chlorinated hydrocarbons, and polynuclear
aromatic hydrocarbons contained in edible flesh. The project's goals were to scrutin-
ize a 100-sample subset for the above organic pollutants to (1) establish baseline
levels of these compounds in the species examined, (2) identify potential pollutant
"not sports, (3) identify any pollution gradients that may exist from a potential
source region: through the study area, (4) utilize and evaluate a cost-effective multi-
phase analytical chemical approach to sample analysis and data acquisition, (5) eval-
uate possible sources of observed pollutant distributions within the specimens exam-
ined, and (6) make recommendations for future organic.chemical monitoring strategies

based on the observed results. (Author extracted)
17. KEY WORDS AND DOCUMENT ANALYSIS.

17a. DESCRIPTORS
*Fish, *Fisheries, *Surveys, Pollutants, Hydrocarbons, Benthos
YS, ly

178. IDENTIFIERS/OPEN-ENDED TERMS

Oil pollution, U.S. East Coast, U.S. Gulf Coast

S7¢. cOSATI FIELD/GROUP

8A

Te. AVAILABILITY STATEMENT 19. SECURITY CLASS [21. NO. OF PAGES

(This report)
Released for distributioniy? , UNCLASSIFIED

20, SECURITY CLASS 22. PRICE
L; “ (This report)
C ES (ul Oat UNCLASSIFIED

NOAA FORM 25-12 (1-78) SUPERSEDES ALL PREVIOUS EDITIONS.



-100-

7. Literature Cited

Amico, V., G. Impellizzeri, G. Oriente, M. Piattelli, S. Sciuto, and C.
Tringali. 1979. Levels of chlorinated hydrocarbons in marine animals
from the central Mediterranean. Marine Pollution Bulletin 10:282-284.

Basturk, 0., M. Dogan., I. Salihoglu, and T.I. Balkas. 1980. ODT, DDE and
PCB residues in fish crustaceans and sediments from the Eastern Mediter-
ranean coast of Turkey. Marine Pollution Bulletin 11:191-195.

Boehm, P.D. 1980. Gulf and Atlantic survey - Cape Hatteras to Gulf of Maine
survey for selected organic pollutants in finfish and benthic animals.
Final Report, NOAA Contract No. NA-80-FA-C-00046. NOAA/NMFS Northeast
Fisheries Center, Sandy Hook, N.J.

Boehm, P.D., and J. Barak. 1978. Chemical analysis of fish samples for
gasoline from the Ocean 250 gasoline spill. Final Report, NOAA Contract
No. 03-78<D01-30. NOAA/NMFS, Narragansett, Rhode Island.

Boehm, P.D., and J. Barak. 1979. Petroleum hydrocarbon analysis of fish
collected in the vicinity of the Argo Merchant oil] spill - April to
October 1977. Final Report, NOAA COntract No. NA-79-FAC-00015. NOAA/NMFS,
Sandy Hook, New Jersey.

Boehm, P.D0., J.E. Barak, D.L. Fiest, and A.A. Eskus. 1981. A chemical
investigation of the transport and fate of petroleum hydrocarbons in
littoral and benthic environments: the Tsesis oi] spill. Mar. Environ.
Res. (in press).

Farrington, J.W., J.M. Teal, and P.L. Parker. 1976. Petroleum hydrocarbons.
Pp. 3-34 in E. Goldberg (ed.), Strategies for marine pollution monitoring.
John Wiley & Sons, Inc., New York.

Mackie, P.R., K.d. Whittle, and R. Hardy. 1974. Hydrocarbons in the marine
environment. I. n-alkanes in the Firth of Clyde. Estuarine & Coasta
Marine Science 2:359-374.

McDermott, D.J., D.R. Young, and T.C. Heesen. 1976. PCB contamination of
Southern California marine organisms. Pp. 209-217 in Proceedings,
National Conference on Polychlorinated Biphenyls. EPA Office of Toxic
Substances.

Nisbet, I.C.T., and A.F. Sarofim. 1972. Rates and routes of transport of
PCBs in the environment. Environmental Health Perspectives 1:21-37.


-60-

were routinely checked for purity by GC prior to use. Ninety ml of 6.6N
aqueous KOH in MeOH! and 5 ug of each internal quantification standard
(deuterated naphthalene, androstane, deuterated phenanthrene and deuterated
perylene) were added to all samples and blanks. Tissue was digested overnight
(16 hr) at room temperature (25°C) in Teflon jars, sealed, and then heated

in a water bath to 90°C, with frequent shaking, for approximately 8 hours.

The digestate containing saponified and nonsaponifiable lipids was
then extracted three times with hexane, concentrated to 0.5 ml by rotary
evaporation, and resaponified in 20 ml 1N aqueous KOH in MeOH for 2-4 hr at
90°C to complete the conversion of polar lipids to alcohols and fatty acid
salts. The sample was next extracted three times with 15 ml hexane, and
concentrated to 0.5 ml.

An alumina column cleanup was employed to obtain an eluate suitable
for GC2 analysis. The 0.5-m1 hexane extract was charged to a column of
6.5 gm 7.5% deactivated alumina topped with sodium sulfate. Hexane (25 ml)
was used to elute a single fraction (f} and f2) containing saturated
and aromatic hydrocarbons and PCB and DDT compounds.

The single fraction was then analyzed by GC2 using a HP 5840 reporting
gas chromatograph equipped with a glass lined splitless injection port, a
flame ionization detector, and an HP 7671 automatic liquid sampler. Approx-
imately 1 u1 of sample was injected onto a 0.25 mm i.d. x 30 meter SE-30
fused silica capillary column (J&W Scientific), and the column oven was
temperature-programmed from 40°C to 290°C at 3°/min. Chromatograms thus
obtained were screened either positive or negative for petroleum-type
hydrocarbons based on the following PHC-positive criteria: (1) presence
of an unresolved complex mixture (UCM) eluting between n-C}3 to n-C2Q,
(2) suggestion of aromatic assemblages in the fine detail of the chromato-
gram, and (3) suggestion of a paraffinic tar by the presence of a smooth
distribution of high molecular weight n-alkane peaks. Positively screened
tissues were further fractionated in Phase 3.

2.1.2 Phase 2: Chlorinated Hydrocarbons (PCB, DDT)

Chlorinated hydrocarbons were analyzed by electron capture gas chroma-
tography using a ®3Ni EC detector (GC/ECD). A 1.5% SP 2250/1.95% SP 2401
packed glass (0.25-in o.d.) column was temperature programmed from 130°C to
230°C at 8°/min and held at the upper temperature for 10 minutes. PCB and
DDE were quantified using external standards of Aroclor mixtures and DOE.
PCB compounds, measured against the best matching Aroclor, were quantified
by adding the areas of the five component peaks indicated (e.g., Figure 3)
and comparing this value to the same peak areas in the Aroclor standard.

As the saponification reaction will convert DDD and DDT to DDE, the "DDT
family" or tO0DT was measured as a single component, DDE.

Liver tissues: 45 ml KOH in MeOH.


~46-

TABLE 6-3
ANALYTICAL SUMMARY ~ YELLOWTAIL FLOUNDER

PETROLEUM
HYDROCARBON PETROLEUM CHLORINATED
SCREEN HYOORCARBONS . HYDROCARBONS
NO. OF =———_—— (.g/g) (u9/9)

STA- INDI- POSI- NEGA- -
TION VIDUALS TIVE TIVE RESOLVED TOTAL PCB EDDT PCB/EDOT

40 7 x 0.037.011 3.4
49 6 x 0.028 0.039 0.8
55 7 x 4.5 6.5 0.007 0.001 7.0
58 8 x 0.039 0.006 ~=«6.5
60 6 x 1.3. 4.0 0.033 0.007 4.7
68 2 x 2.1 2.1 0.008 0.002 4.0
77 5 x 0.011 0.002 «5.5
79 8 x 0.008 0.002 4.0
95 8 x 0.003 = ND 5.5
101 3 x 2.4 3.7 0.025 0.005 4.0
106 8 x 0.003 ND -
123 4 x 0.002 ND 5.0
132 5 x 0.002 ND -
139 5 x 2.0 3.7 0.015 0.002 --
144 3 x NO ND 7.5
146 x 0.082/ NDS =-/
0.002 ND -
Ks Xs X= Xe
4.0 0.018 0.005 4.8
#1.7 £0,017 +0.009 + 7.0



-95-

Individual concentrations of the naphthalene and phenanthrene alkylated
families are tabulated to illustrate the degree of alkylation. The amount
of alkylation indicates the relative abundance of petroleum versus combustion
sources for the PAH. Petroleum contains substantial alkylated PAH while
combustion sources are more abundant in the parent compound. Therefore, a
higher abundance of alkylated compounds is indicative of petroleum assimila-
tion in fish tissues.

As compared to the northern half of this study (Boehm, 1980-Part I of
this program), naphthalenes, dibenzothiophenes, and 202 family compounds
are of similar concentrations. Phenanthrenes and fluorenes, though, are
lower than previously determined. As can be seen, the values of PAH
compounds in liver tissues are an order of magnitude greater than in
corresponding muscle tissues, following the observed pattern for PHC
concentrations in general. Note that the three samples (flounders, Stations 53
and 143, and porgy, Station 54), which were screened negative for PHC
(criteria listed in Section 2), still contain similar low concentrations of
PAH compounds. Hence, PAH distributions are somewhat independent of gross
PHC diagnostics (GC‘/FID) with low-level tissue burdens probably being
ubiquitous in coastal fish populations.

4. Interpretation of Findings

Inputs of PHC, PAH, PCB, and DOT to marine fish populations in the U.S.
southeastern and Gulf coasts have been successfully monitored in this study.
Utilizing a sequential, progressively more complex analytical scheme, we have
screened a large number of fish muscle and liver tissues, in an effort
to establish ambient levels of organic pollutants on the Atlantic coast and
in the Gulf of Mexico. These data have also been assessed regionally so as
to define, if possible, any geographic point source contaminants or concen-
tration gradients.

Two of the fish species studied here, silver hake and flounder, were
monitored in the earlier GAS I study, covering the North Atlantic from Maine
to Cape Hatteras. Table 4-1 provides a summary of PHC compounds in these
fish, as well as data from other studies. Values for both species are within
the lower range of those fish analyzed in the northern half of this study
(Boehm, 1980), and off of Georges Bank (Boehm and Barak, 1979).

Most of the concentration data presented in Table 4-1 are for muscle
tissue. In this study, we have also investigated the PHC burden in fish
livers. Capillary GC chromatograms presented earlier (Figures 13 and 15),
demonstrate a characteristic GC pattern of n-alkanes (large n-C2¢ to
n-C3q4 peaks) and a late-boiling UCM. The source of this distibution is
not apparent from this study but is probably related to biochemical synthe-
sis and/or modification of assimilated PHC residues. Sample GC traces
occasionally demonstrate a bimodal UCM, the earlier unresolved compounds
eluting between n-C13 and n-Cag, a typical range indicative of petroleum


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-16-

5 ug/g. One sample (Station 126) contains a GC2 distribution attributable
to petroleum (Figure 9), although there appears to be very little if any
indication of the presence of aromatic hydrocarbons from the f2 trace (not
shown). GC/MS was not performed on any red hake samples.

PCB and DDE concentrations (see Section 6, Table 6-2) are quite low
(PCB = mean 0.015 + 0.015 g/g; median value = 0.01 ug/g; DDE = 0.004 +
0.006 ug/g). Several samples containing the highest red hake PCB values
(Station 66 = 0.032 ppm; Station 116 = 0.025 ppm) contain no detectable PHC
compounds, thus indicating differential sources for these two classes of
compounds for this species.

GC/ECD chromatograms for red hake consistently illustrate an Aroclor
1254 type distribution with a prominent DDE component peak.

The geographic distributions of PHC and PCB compounds indicate no
regional "point source" pollutant forcing of contaminant concentrations
in this species (Figures 10 and 11). Significant levels of PCB were not
coincident with detectable PHC compounds, indicating, unlike the case for
silver hake, that PCB and PHC sources are decoupled with respect to this
species.

3.3 Yellowtail Flounder

One-third (31%) of the samples of this species contained evidence of
PHC contamination but at very low levels (2 to 7 ppm) (see Section 6,
Table 6-3). A typical GC2/FID distribution of the saturated hydrocarbon
fraction (Figure 12) indicates that small amounts of pelagic tar-like
material contribute to the observed PHC distributions. Associated with this
PHC distribution are PAH compounds (naphthalenes 2 ppb; phenanthrenes 54 ppb,
dibenzothiophenes 14 ppb, fluorenes 7 ppb) as determined via a single
GC/MS analysis (Table 3-1).

Nearly all (94%) of the samples contained detectable levels of PCB
compounds (Aroclor 1254) (X = 0.018 + 0.016 ppm) and lower levels of DDE
(0.005 + 0.009 ppm).

There appears to be little correspondence between PCB and PHC levels.
Indeed for this species some of the highest PCB levels are found in those
fish exhibiting no PHC compounds. The highest PHC value found at Station
58 Corresponds with a low PCB value.

The PCB distribution appears similar to an Aroclor 1254 distribution,
much like the situation for the other species examined.

Geographic distributions of PHC and PCB compcunds for this species are
indicated in Figures 13 and 14.


-99-

Monitoring this ratio, then, may refiect the introduction of new chlorinated
hdyrocarbons, either PCB or ZDDT, into the environment or the migration of
fish populations into high PCB or £DDT areas.

In conclusion, the baseline data accumulated in this study, together
with earlier results from Maine to Cape Hatteras, will be indispensible for
accurate, consistent monitoring of the Atlantic coastal waters and the Gulf
of Mexico. The analytical method presented here has proven capable of
providing rapid yet detailed information on pollutants measured in biological
species. A larger, more complete sampling of the coastline, with perhaps .an
added Sephadex cleanup of fz fractions, will greatly aid the investigator's
abilities to clearly define organic pollutants and regional concentration
gradients.

This study has further expanded the information gathered in last year's
GAS Ia study (see part I of this volume). The inclusion of liver tissues in
the monitoring program has provided both new information and. new questions as
to the extent of petroleum and PCB contamination in coastal fish. Further
investigation is needed to define metabolic mechanisms and. possible prefer-
ential accumulation and distribution of petrogenic compound or metabolites in
the liver vs. the muscle. The possible correlation between tissue lipid
content, species variation in lipid content and the accumulated PHCs and PCBs
can be explored. The ratio of liver to muscle contamination may provide
information on exposure patterns, should compound distribution in the tissue
be time dependent. Also, the inclusion of an alternate clean-up step
involving Sephadex LH-20 (Ramos and Prohaska; 1981) will remove biogenic
olefins which interfere with accurate quantification of the aromatic fraction
or unfractionated tissues originally screened. The above information will
greatly aid the interpretation of data as accumulated in this study.

To better identify any regional or species variance in PHC or PCB
concentrations, a more complete sampling of each species in each region
is greatly needed. This study did not provide sufficient samples to
statistically demonstrate regional or species trends. Continued monitoring
of both muscle and liver tissue is strongly recommended so as to increase
the data base for the Atlantic and Gulf Coasts and to identify regional
trends.

5. Summary of Data Acquired
The above mentioned analytical scheme was applied to those samples

previously inventoried in Section 2, Table 2-1. — PAH determinations were made
in those samples presented in Section 3, Table 3-5.

6. Data Appendices
Detailed analytical results are presented in Tables A-1 through A-8.


-28-
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TABLE 6-9
ANALYTICAL SUMMARY - AMERICAN DAB

PETROLEUM :
HYDROCARBON PETROLEUM CHLORINATED
SCREEN HYDORCARBONS HYDROCARBONS

NO. OF = ——___- (ug/g) (ug/g)

STA- INDI- POSI- NEGA-
TION VIDUALS TIVE TIVE RESOLVED TOTAL PCB IDDT PCB/ SDDT

105 2 x 0.005 0.001 5
106 5 x 1.0 1.5 0.024 0.003 8
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125 9 x 0.001 ND
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Meyers, 1975) were subjected to adsorption chromatographic fractionation
(silica gel column chromatography) to yield two hydrocarbon fractions.

Both of these fractions were analyzed by GC2. Of those samples fractionated
and analyzed, a selected number of samples appearing to contain petroleum-
type aromatic hydrocarbons and representative of the various species were
further analyzed by glass capillary gas chromatographic mass spectrometry
(GC2/MS) to determine the identity and levels of the PAH compounds.

2.2 Methods and Materials

The detailed sample processing and analytical methods utilized in this
study are presented in this section. Samples were obtained on the R.V.
Albatross cruise no. AL-80-02, 27 February-5 April 1980, and a 100-sample
subset chosen by NMFS scientists from those stations indicated in Figure 2
and Table 2-1.

2.2.1 Hydrocarbon Screening

This analytical task involved the processing (dissection, digestion,
extraction, cleanup, analysis) of a large number (100) of fish samples as
the first level analytical task. While the residue cleanup and analytical
parts of this task were geared towards the rapid generation of- information,
the extraction techniques used were rigorous so as to allow for the use of
the same extracts for quantitative analysis in later tasks. Extraction
techniques are based on those of Warner (1976).

Samples consisted of from 1 to 10 individual specimens of those fish
species shown in Table 2-1. Muscle tissue from each specimen was obtained,
after removal of the surface skin, by dissection with solvent-rinsed stain-
less steel utensils. A total of approximately 100 g (wet weight) of tissue
were thus obtained. A small aliquot of this tissue was obtained for dry
weight determination. The tissues were introduced to 150 ml, 10 N aqueous
KOH in a 500-m1 Teflon jar. Internal quantification standards of saturate
(androstane) and aromatic (fully deuterated anthracene, hexamethy] benzene,
and 9-phenylanthracene) hydrocarbons were spiked to the aqueous digestion
mixture. The jars were sealed with threaded Teflon lids and the mixture
allowed to digest at room temperature (25° C) for 24 hours.

The digestate containing the saponified lipids and nonsaponifiable
lipids (e.g., hydrocarbons) was transferred to a 1-liter separatory funnel
where 75 ml saturated NaCl were added and the mixture extracted three times
with 75 ml distilled hexane. The hexane extracts were isolated, combined,
and centrifuged to remove any emulsions present. The extracts were concen-
trated to approximately 0.5 ml and were resaponified (1.0 ml aqueous 10 N
KOH; 9.0 ml methanol) in a closed centrifuge tube at 100° C to complete the
conversion of lipids to alcohols and fatty acid salts. The saponification
mixture was then extracted with three 10-ml hexane portions which were dried
over pre-extracted sodium sulphate and concentrated by rotary evaporation to
0.5 ml.


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-77-

PCB concentrations in muscle tissues are among the highest found through-
out the eight species analyzed (Table 3-2, Figure 5). The median muscle
concentration was 78 ppb, with no evidence of regional variation or coupling
to PHC values (Table A-5). The median liver value was 240 ppb, also with no
correlation to PHCs or with regional variation.

3.1.6 Scad

Seven scad samples were analyzed from three different regions (Table
A-6). Scad tissues were among the three species containing the highest
concentrations of PHC compounds in muscle or liver tissue (Table 3-1). The
capillary GC traces illustrated (Figure 13) are of the f}] muscle and liver
samples screened positive from Region 6. Although the total concentration of
PHC is low in the muscle, the petrogenic nature of the fy fraction is
pronounced, with sizeable branched alkane peaks, including phytane, also
evident. The large amount of pristane in both GC traces in Figure 13 is due
to a biogenic origin. The liver chromatogram is very typical of this tissue,
with a late UCM (eluting at n-C2¢ to n-C3q) and high concentrations of
n-alkanes n-C26 to n-C3q. The total (fy + fa) PHC measured in liver
from different regions for this species ranged from 136 ppm to 486 ppm, with
a median value of 311 ppm.

Scad muscle PCB concentrations do not demonstrate a strong regional
variation, with a median of 30 ppb found in the samples from the three
regions analyzed. Liver tissues show a much wider variation in PCB con-
centrations both within and throughout the regions anaiyzed, with a range
from 60 to 11,400 ppb, and thereby also lacking in any regional dependence.
PCB and PHC data trends are not related; the sample with the highest PCB
concentration determined in this study (11,400 ppb, Station 101) was nega-
tively screened for PHC, and contained average amounts (30 ppb) of PCB in the
muscle.

3.1.7 Snapper

PHC content measured in this species was about the median of the eight
species analyzed, both for muscle and liver tissue (Table 3-1). Gas chro-
matograms are similar to those already illustrated. The n-alkanes, branched
alkanes, and unresolved/resolved compositions all suggest a petrogenic input
to those samples screened positive.

PCB concentrations found in snapper tissues for both muscle and liver
are similar to the other species analyzed (Table 3-2): muscle - median
value of 20 ppb, and liver - 235 ppb, demonstrating the commonly found
4-to-10-fold-higher PCB concentrations in the liver. A similar situation
is found with PHC compound concentrations, but quantitation is difficult
due to interference of biogenic compounds. PCB data, on the other hand,


GULF AND ATLANTIC SURVEY
FOR SELECTED ORGANIC POLLUTANTS
IN FINFISH

I. GULF OF MAINE TO CAPE HATTERAS


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-75-

Reproduced from
est available copy.

Figure 11. Representative GC/ECD Trace (Packed Column) of PCB’s in a Hake
Muscle Tissue from Region 1, Station 14. Starred Peaks Co-Elute with Aroclor 1254
Standard. Sample Contained 90 ng/g PCB.


~101-

Parker, P.L., J.K. Winter, and J. Morgan. 1972. A baseline study of petro-
leum in the Gulf of Mexico. Pp. 555-581 in Baseline studies of pollu-
tants in the marine environment background papers workshop. Brookhaven
National Laboratories, New York.

Ramos, and Prohaska. 1981. Sephadex LH-20 chromatography of extracts of
marine sediment and biological samples for the isolation of polynuclear
aromatic hydrocarbons. J. Chromatog. In press.

Warner, J.S. 1976. Determination of aliphatic and aromatic hydrocarbons in
marine organisms. Anal. Chem. 48:578-583.

Whittle, K.J., P.R. Mackie, R. Hardy, A.D. McIntyre, and R.A.A.. Blackmann.
1977. The alkanes of marine organisms from the United Kingdom and
surrounding waters. Rapp. P.-v. Reun. Cons. Int. Explor. Mer 171:72-78.


~86-

TABLE 3-3 (Continued)

PHC (ug/g DRY WT.)

% SCREENED
POSITIVE MUSCLE LIVER
NO. OF
REGION SAMPLES MUSCLE LIVER MEDIAN RANGE@ MEDIAN RANGE@

4. Apalachicola Area

a. Butterfish 1 0 0 - -

b. Flounder 2 0 0 - -

c. Lizardfish 2 0 0 - -

d. Porgy 1 0 0 - -

e. Hake 1 0 0 - -

All species 7 ~?O ~O t ~T
5. Flower Gardens

a. Butterfish 1 0 0 - -

b. Flounder 5 0 20 - 61

c. Lizardfish 2 100 100 VV 9.4-12 811 480-1, 143

d. Porgy ] 100 100 5.8 146

e. Scad 2 100 50 20 12-29 486

f. Snapper 2 50° 50 7.0 182

g. Spot 1 100 100 22 59

All species 14 “50 50 12 5.829 182  59-1,143
6. Corpus Christi/

Port Isabel

a. Flounder 1 100 100 6.9 235

b. Lizardfish 3 33 33 5.9 170

c. Porgy 2 100 50 5.0 4,3-5.8 103

d. Scad 2 50 50 4.1 136

e. Snapper 1 100 100 5.7 122

All species 9 “67 $6 5.8 4.1-6.9 134 103-235

af available.


-54-

National Academy of Science. 1975. Petroleum in the marine environment.
NAS, Washington, 0.C.

Pancirov, R.J., and R.A. Brown. 1977. Polynuclear aromatic hydrocarbons in
marine tissues. Environmental Science and Technology 11:989-992.

Parker, P.L., J.K. Winter, and J. Morgan. 1972. A baseline study of
petroleum in the Gulf of Mexico. Pp. 555-581 in Baseline studies of
pollutants in the marine environment background papers workshop.
Brookhaven National Laboratories, New York.

Reed, W.R., I.R. Kaplan, M. Sandstrom, and P. Mankiewicz. 1977. Petroleum
and anthropogenic influence on the composition of sediments from the
Southern California Bight. Pp. 183-188 in 1977 Oil Spill Conference,
American Petroleum Institute, Washington, D.C.

Warner, J.S. 1976. Determination of aliphatic and aromatic hydrocarbons in
marine organisms. Anal. Chem. 48:578-583.


-50-

TABLE 6-7
ANALYTICAL SUMMARY - COD AND FOUR SPOT FLOUNDER

PETROLEUM
HYDROCARBON PETROLEUM CHLORINATED
SCREEN HYDORCARBONS HYDROCARBONS
NO. OF =—————— (ug/g) (ug/g)
STA-  INDI-  —POSI- NEGA- .
TION VIDUALS TIVE TIVE RESOLVED TOTAL PCB ZDDT  PCB/EDOT
cop

101 3 x ND ND --
105 6 x 0.003 0.004 ~=—0.75
113 3 x 0.018 0.005 3.6
123 3 x 0.003/ 0.001 4.0

0.005
142 3 x 0.002 ND -

X=

0.005

+ 0.002
FOUR SPOT FLOUNDER

60 9 x 0.004 ND --
116 10 x 0.005 0.001 5
118 10 x 1.7 1.8 0.008 0.002 4
100 1 x 3.3 5.7 0.004 ND -

our
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POLYNUCLEAR AROMATIC HYDROCARBONS - CONTENT OF SELECTED SAMPLES

-12-

TABLE 3-

1

TOTAL TOTAL TOTAL TOTAL TOTAL TOTAL
STA- PHC N P OBT F 202
TION = (ug/g) (ng/g) (ng/g) (ng/g) (ng/g) (ng/g)
Silver Hake 40 37.5 -- 4.0 -- -- <0.1
Silver Hake 66 15.2 1.4 20.3 -- 0.3 1.0
Silver Hake 100 17.5 10.4 14.5 10.9 1.0 1.5
Silver Hake 55 93.1 0.8 63.5 ‘15.0 1.2 1.1
Silver Hake 60 75.0 3.4 2.8 -- -- 1.3
Silver Hake 39 32.3 84.6 54.2 4.1 18.5 15.0
Yellowtail 55 6.5 2.0 53.8 14.4 7.4 1.8
Flounder
Winter Flounder 55 ND -- 3.0 -- 0.2 1.
Haddock 123 2.0 12.1 14.5 3.4 -- ed
Rock Crab 35 327 0.3 59.0 -- 58.0 --
N = ‘naphthalenes
P = phenanthrenes
OBT = dibenzothiophenes
F = fluorenes
202 = fluoranthene + pyrene


-41-

TABLE 4-3

PCB COMPOUNDS IN FISH

RANGE OF
PCB LEVELS
ORGANISM (ug/g dry wt.) REFERENCE LOCATION
Red Hake 0.07-0.40 Unpublished data East Coast,
United States
Flounder 0.07-0.35 Unpublished data East Coast,
United States
Mullet 2-3.7 Amico et al. Mediterranean Sea
(1979)
Mullet Trace-0.4 Basturk et al. Mediterranean Sea
(1980)
Tuna 0.09-0.4 Amico et al. Mediterranean Sea
(1979)

Groundfish 0.35 (mean Graham (1974) East and West
(Cod, Catfish, of 147 Coasts, Canada
Flounder, Halibut, samples)

Haddock, Cod,
Pollack, Redfish,
Snapper, Rockfish,
Skate, Sole,
Plaice)

Pelagic - Estuarine 2.0 (mean Graham (1974) East and West
(Alewife, Capelin, of 73 Coasts, Canada
Dogfish, Herring, samples)

Salmon, Smelt,
Swordfish, Tuna)
Sole 0.05-2.0 McDermott et al. west Coast-
(1974) Southern

California



-45-

TABLE 6-2
ANALYTICAL SUMMARY - RED HAKE

PETROLEUM ;
HYDROCARBON PETROLEUM CHLORINATED
SCREEN HYDORCARBONS HYDROCARBONS
NO. OF = ———____ (ug/g) (ug/g)
STA- INDI- — POSI- ‘NEGA-
TION VIDUALS TIVE TIVE RESOLVED TOTAL . PCB =DDT — PCB/EDDT
21 6 X 1.6 1.6 0.042 0.023 1.8
33 15 X 0.006 0.006 1.0
35 12 X 1.6 2.0 0.013 0.004 3.3
47 10 x 0.007 ND -
60 10 x 0.010 0.004 2.5
66 6 x 0.032 ND --
m 3 x 0.002 NO --
116 10 Xx 0.019/ 0.000/ 3.2/
0.0385 -0.011 3.2
118 8 x 1.0 1.0 0.007 0.001 7
125 8 x 0.004 0.001 «4
126 7 x 2.9 5.4 0.035 0.008 4.4
135 9 x 0.016 0.007 2.3
137 6 X 0.003 ND -
157 X NO ND -
X= X= X= X=
7.5 0.015 0.005 3.3
+1.7 +0,013 +0.006 + 1.8



-74-

petrogenic nature of the f] fractions of both muscle and liver tissue is
readily discernible. The large UCM and bimodal PHC distribution of the fy
liver fraction is indicative of mixed sources of petrogenic and bi genic
compounds, and is characteristic of many of the liver samples. GC¢ traces
of the fg fractions of muscle and liver tissues show little indication of
petroleum, perhaps due to biochemical metabolism of aromatic compounds as
well as to the low absolute concentrations encountered.

The median PCB concentration in hake muscle was 70 ppb (Table 3-2) and
in hake liver, 165 ppb. Both concentrations are mid-range of the eight
species analyzed. No evidence of PCB/PHC coupling was found in the hake.
Figure 11 illustrates a typical GC/ECD chromatogram of PCBs. Starred peaks
were used for quantification. DDE is also labeled.

3.1.4 Lizardfish

Four of the 12 lizardfish samples were screened positive for both muscle
and liver tissues (Table A-4). Muscle tissue PHC values were average,
ranging from 5.9 ppm to 12 ppm (median = 7.7) throughout the four regions
sampled. Liver tissues from each of the four fish samples show a wide
concentration range of PHC (34-1140 ppm) with the highest median value,

325 ppm, determined for all species. As in earlier examples, GC2 traces
of f] muscle and liver samples (not shown) demonstrate the presence of
PHC, with the n-alkanes and isoprenoids easily found in the fy fractions
of muscle and liver. The fg fractions also contained large UCMs, indi-
cative of exposure to anthropogenic hydrocarbon source(s).

Illustrated in Figure 12 is a packed column GC/ECD trace of a lizardfish
muscle tissue; the starred PCB peaks correspond to those in the standard
Aroclor 1254 formulation. The median PCB concentration for this species was
20 ppb in the muscle (range from 10 to 80 ppm) (Table A-4, Figure 5). In the
liver, the median was 310 ppb with a range of 100-2,130 ppb. Although
PHC-positive muscle and liver tissues also contain higher concentrations of
PCB, the statistical sample size (n=4) is not large enough to conclusively
establish this.

3.1.5. Porgy

Of the four porgy samples examined (Table A-5), three muscle tissues
were screened positive, with a median value of 5.8 ppm. The two liver
samples containing PHC averaged 124 ppm. Gas chromatograms generally support
a petroleum-like contamination. A smooth n-alkane distribution (n-Cjg to
n-C34) is visible in f] fractions of positively-screened tissues.

Porgies contained the third lowest concentrations of PHCs of the eight
species analyzed, for both muscle and liver tissue.


a

Quantification Peaks

— od
Reproduced from
best available copy.

Figure 3. PCB Standard—Aroclor 1254.


-49-

TABLE

6-6

ANALYTICAL SUMMARY ~ HADDOCK

PETROLEUM CHLORINATED
PETROLEUM HYDROCARBONS HYDROCARBONS
NO. OF HYDROCARBON SCREEN (ug/g) (ug/g)
INDI-

STATION VIDUALS POSITIVE NEGATIVE RESOLVED TOTAL PCB DDT
105 a X 1.0 1.0 0.004 ND
1 5 X 0.004 0.002
113 5 X 0.002 ND
123 4 x 2.0 2.0 0.004 0.001
132 1 x 0.026 0.002
139 4 x 0.001 ND
147 6 x 0.003 ND

X= X=
1.5 0.006
+ 0.008



II. CHESAPEAKE BAY TO PORT ISABEL, TEXAS

OBJECTIVES © 1 ww ee 56
SUMMARY OF ACTIVITIES AND RATIONALE... . 2.2.2. + eee 56
2.1 Sampling Locations and Sample Distributions ...... 56
SUMMARIZATION OF FINDINGS .. 2... 2. eee ee ee ee ee 63
3.1. Interspecies Variation .........2.2..0004 63
3.2 Regional Variations... 2... ... . eee ee eee 79
3.3 Polynuclear Aromatic Hydrocarbon (PAH) Results .... 90
INTERPRETATION OF FINDINGS . 2... . ee ee ee eee 95
SUMMARY OF DATA ACQUIRED .. 2... . eee ee ee eee 99
DATA APPENDICES . 2... ee ee ee "99
LITERATURE CITED . . 1... ee eee ee ee ee 100

-iv-


-66-

TABLE 3-2

SUMMARY OF CHLORINATED HYDROCARBONS (PCB

SP. S VARIATION

=D0T)

PCB (ng/g dry wt.)@

ZDDT (ng/g dry wt.)@

SPECIES MUSCLE LIVER MUSCLE LIVER
Butterfish 80 100 3 16
: (ND-120) (ND-1,020) (1-62) (3-143)
Flounder 30. 370 5 49
(10-70) (40-980) (1-52) (1-294)
Lizardfish 20 310 6 180
(10-80) (100-2,130)  (ND-46) (51-1170)
Porgy 78 240 12 27
(20-180) (30-420) (2-25) (10-53)
Scad 30 205 6 23
(20-60) (60-11,400) (1-32) (9-1000)
Snapper 20 235 W 35
(10-40) (70-1, 420) (2-135) (18-288)
Spot 30 280 5 37
(10-170) (50-1,230) (2-92) (2-267)
Hake 70 165 16 16
(10-90) (40-410) (2-25) (9-128)

a@Median values, followed by range.


-21-
77° 76° 750 740 Te 730 Tre 708 g9° eo «670 66°
aso
1
hago . H
NEW HAMPSHIRE
420
baro

ro

MARYLAND:

y
( new sersey

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© Negatively Screened
e@ 1-5 ppm
© 5-10 ppm

VIRGINIA
— Fi
36° }
NORTH H 50 100150200
CAROLINA H KILOMETERS
cape /
HATTERAS /
76° (750 740 730 ne 710 70° 90 680 670
4 Jo 4. 4 1 7 n n be

Figure 13. Yellowtail Flounder—Petroleum Hydrocarbons.


~64-

TABLE 3-1

INCIDENCE OF PETROLEUM HYDROCARBONS (SPECIES VARIATION)

% SCREENED CONCENTRATION OF PHC
POSITIVE (ug/g DRY WT.)
#
SPECIES SAMPLES MUSCLE LIVER MUSCLE LIVER
Butterfish 7 29 0 23 --
(20-27)
Flounder 13 15 23 5.0 61
(3.2-6.9) (47-235)
Lizardfish n 36 36 7.7 325
(5.9-12)  (34-1,140)
Porgy 4 75 50 5.8 124
(4.3-5.8) (103-146)
Scad 8 38 25 12 311
(4.1-29) (136-486)
Snapper 7 29 29 6.3 152
(5.7-7.6) (122-182)
Spot 7 29 57 30 316
(22-38) (59-885)
Hake 4 50 50 5.6 158
(5.0-6.1) (127-190)

aMedian values, followed by range.


-57-

TABLE 2-1
SUMMARY OF FISH SPECIES ANALYZED

SPECIES # SAMPLES STATIONS
Butterfish
unspeciated 4 14, 13, 30, 31
deepwater 1 41
gulf 2 53,107
Flounder
summer 1 14
broad 2 31, 88
shoal 4 45, 140, 143 ,285
gulf 1 49,
blackbelly 1 53
3-eye 3 140, 53, 88
windowpane 1 15
Lizardfish
unspeciated 5 48, 49, 46, 33, 54
offshore 0
short jaw 1 53
inshore 4 256, 101, 130, 143
largescale 1 101
Porgy 4 54, 101, 256, 72
Scad
unspeciated 3 48, 49, 42
round 1 43
rough 4 107, 101, 140, 117
Snapper
vermillion 4 48, 42, 46, 43
wenchman 3 140, 88, 117
Spot 7 49, 107, 15, 43, 41, 30, 31
Hake 4 14, 41, 13, 53
6 samples



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VIRGINIA : e@ =.00!-.01 ppm
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CAROLINA : KILOMETERS
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Figure 7, Silver Hake—PCB.


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cape}
HATTERAS /
760 79 740 re 728 710 709 39° a0 87°
n ae re Je n L n mn rn o

Figure 21. Haddock—Petroleum Hydrocarbons.


-51-

TABLE 6-8

ANALYTICAL SUMMARY - OTHER SPECIES

PETROLEUM :
HYDROCARBON PETROLEUM CHLORINATED
SCREEN HYDORCARBONS HYDROCARBONS
NO. OF = =———__ (9/9) (19/9)
STA- _INDI- — POSI-._ NEGA-
TION VIDUALS TIVE TIVE RESOLVED TOTAL PCB EDDT — PCB/ ZDOT
SUMMER FLOUNDER
81 2 X 0.014 «0.003 4.7
LITTLE SKATE
95 0.012 0.002 6
116 0.002 ND -
ROCK CRAB
35 12 x 77 327 0.043 0.025 1.7
CANCER CRAB
125 4 x 0.002 NO --
SCALLOPS
47 5 X 0.001 ND -
LOBSTER
47 6 X 0.095 0.024 4
49 3 x - 0.150 0.050 3



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>3,000 4
2,000 =

1,000 4
900 4
800 4
700 4

36004

4007
300

200 +4

904

4

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T T T T T 1
Region 1 Region 2 Region 3 Region4* Region 5 Region 6

© Muscle
-———— — — — Median Values

@ Liver * Median Estimated from
PHC Negative GC Results

Figure 18. PHC Concentrations Graphed by Regions.


-38-

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can be more rigorously evaluated, as biogenic inputs are not a major

factor in quantitation. One liver sample from Station 88, Region 5,

has a high PCB value of 1,420 ppb, but a muscle value of 20 ppb (Table A-7),
suggesting non-equilibrium distributions of PCB within the fish.

Also, this sample was screened negative in both muscle and liver tissues
for PHC. This species shows no evidence of coupling of PHC and PCB

values.

3.1.8 Spot

This species contained the highest PHC concentrations determined for
muscle and the second highest concentrations in liver tissue of the eight
species analyzed and, with the exception of one liver, was consistently the
highest tissue in each of the four regions in which spot were found. Muscle
tissue contained 30 ppm (range 22 ppm to 38 ppm; Table 3-1 and Figure 4).
Liver tissue averaged 316 ppm (range of 59-885 ppm). Gas chromatograms of
spot muscle and liver tissue from Region 5 (Figures 14 and 15) again illustrate
prominent UCMs for fy and f2 fractions and the n-alkane and branched
alkanes of petroleum in liver and muscle fj fractions. Again, the liver
has a late-boiling UCM, but little early-boiling UCM, as was seen for some
other species (e.g., see Figure 9). The higher boiling n-alkanes were more
pronounced in the liver than in muscle. Total PHC for this example was
22 ppm (muscle) and 59 ppm (liver).

This species, as with porgy, has moderate levels of PCB in muscle tissue
(Table A-8).. The median concentration is 30 ppb, with a range of 10 to
170 ppb. The median concentration of PCB in liver tissue was 280 ppb with
a range from 14 to 1,230 ppb, with no apparent regional input. PCB values
are decoupled from PHC concentrations, again suggesting a differential
source input of organic contamination.

3.2 Regional Variations

The eight different species of fish have also been grouped into six
different regions to assess. regional variation of PHC (Figures 16, 17 and 18)
and PCB (Figures 19, 20 and 21) values. The six regions investigated were
Chesapeake Bay (1), Georgia Bight (2), Florida West Coast (3), Apalachicola
area (4), Flower Gardens (5), and Corpus Christi/Port Isabel (6).

Regional trends of PHC have been evaluated in terms of median total PHC
concentrations in the muscle or liver, and/or by the percentage of samples
screened positive, Table 3-3. Regional gradients of PCBs have been viewed in
terms of a median value, and a range of concentrations, Table 3-4.


-56-

1. Objectives

Information on the levels of organic pollutants in species of fish
either presently or potentially of commercial importance is generally lack-
ing. An informational gap relates to the influence that regional sources of
pollution (e.g., drainage basins containing major population centers) have
in affecting contaminant levels in both migratory and non-migratory fish
populations.

In order to address these important questions, a specialized analytical
Program was used to quantify PHC, PAH, PCB, and DDT family concentrations
in the muscle and livers of several species of fish collected by the National
Marine Fisheries Service from the U.S. southeastern coastal and Gulf of
Mexico regions. A hierarchical analytical approach in which progressively
more sophisticated analytical techniques were used has allowed an initial
rapid and informative screening of tissue samples and yet, at the most
complex level, provides detailed information as to the composition and
concentrations of organic contaminants in the coastal fish analyzed.

2. Summary of Activities and Rationale

2.1 Sampling Locations and Sample Distributions

The analytical chemical goals of this investigation were considered
sequentially in the following four phases (Figure 1). Overall recoveries
for PHC, PCB and DOT compounds averaged 80 percent. Samples were obtained on
the R/V Albatross, cruise no. 80-01, February 1980, and the Oregon II, cruise
no. 105, March 1980, by NMFS scientists, as shown in Table 2-1 and Figure 2.

2.1.1 Phase 1: Hydrocarbon Screening

This analytical task involved the processing (dissection, digestion,
extraction, cleanup, analysis) of 61 fish samples as the first level analyt-
ical task. A muscle and liver subsample was obtained from each sample
(122 samples for analysis). While the residue cleanup and analytical parts
of this task were geared towards the rapid generation of the qualitative
PHC composition, the extraction techniques used were rigorous so as to allow
for the use of the same extracts for quantitative analysis in later tasks.
Extraction techniques are based on those of Warner (1976), Boehm et al.
(1981), and Boehm (1980).

Samples consisted of 1 to 32 individuals of the fish species shown in
Table 2-1. Livers were excised from specimens with solvent-rinsed stainless
steel utensils. A composite sample of up to 100 g of muscle tissue was then
dissected by skinning and dissecting all or part of each fish comprising the
sample. An aliquot of both liver and muscle tissue from each species of fish
was reserved for a wet/dry weight determination. All solvents and KOH used


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-25-
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CAROLINA i KILOMETERS
care}
HATTERAS /
76° 1758 740 730 720 718 7090 90 68° 670
fi aa L i fi fi fa L i “

Figure 16. Winter Flounder—Petroleum Hydrocarbons.


-1-

1. Objectives

Selected finfish and benthic epifaunal samples were analyzed for
levels of petroleum hydrocarbons (PHC), chlorinated hydrocarbons (poly-
chlorinated biphenyls [PCB], DDT compounds), and polynuclear aromatic
hydrocarbons (PAH) contained in edible flesh (i.e., muscle). Samples were
collected as part of the Gulf and Atlantic Survey (GAS I) sampling effort
undertaken by National Marine Fisheries Service (NMFS) personnel.

The project's goals were to scrutinize a 100-sample subset for the
above organic pollutants to (1) establish baseline levels of these compounds
in the species examined, (2) identify potential pollutant “hot spots" in
the Cape Hatteras to Gulf of Maine region, (3) identify any pollution
gradients that may exist from a potential source region through the study
area, (4) utilize and evaluate a cost-effective multiphase analytical
chemical approach to sample analysis and data acquisition, (5) evaluate
possible sources of observed pollutant distributions within the specimens
examined, and (6) make recommendations for future organic chemical monitoring
strategies based on the observed results.

2. Summary of Activities and Rationale

2.1 Analytical Strategy

The analytical chemical goals of this investigation focused on four
major questions which were linked together into an hierarchical analytical
scheme in which the analytical complexity increased as the four successive
levels were reached. The analytical questions (levels) were as follows:

1. Which samples contained the detectable levels of petroleum
hydrocarbons (PHC)?

2. What are the levels of PCB and DOT compounds?

3. What are the concentations and sources of saturated (f}) and.
aromatic (fz) hydrocarbons in the samples?

4. What are the absolute concentrations of polynuclear aromatic
hydrocarbons (PAH) in the tissues?

This sequential scheme (Figure 1) essentially screened a large number
of fish samples by solvent extraction followed by rapid sample cleanup and
rapid analysis. The initial cleanup was sufficient to yield the gross
character of the hydrocarbon composition by glass capillary gas chromatography-
flame ionization detector (GC2/FID) and gross concentration levels of PCB
compounds. Those samples containing hydrocarbon compositions resemb1 ing
those of a possible petroleum origin (Reed et al., 1977; Farrington and


-40-

PAH levels (see Section 3, Table 3-1) are also similar to those pre-
viously reported and indicate a combined source of PAH compounds; petroleum
where naphthalene and fluorene compounds dominate and pyrogenic (combustion
sources), where m/e = 202 compounds are significant and where parent aroma-
tics (e.g., phenanthrene) are more abundant than the alkylated members of an
homologous series (e.g., methyl phenanthrenes) as is the case with most of
those samples (see Section 3, Table 3-1) subjected to GC/MS.

Therefore, it is encouraging to observe that when viewed against pre-
vious data sets, PHC levels fall into previously established ranges. This
bodes well for future monitoring efforts. Of the finfish examined for PHC
levels, silver hake, yellowtail flounder, and possibly winter and/or window-
pane flounder appear to be good candidates for pollutant chemical monitoring
as these species all exhibit tendencies to acquire low levels of PHC compounds,
with the PHC sources being distinguishable and therefore monitorable.

PCB and DDE compounds are more widespread than the PHC compounds
and, although present in very low levels, behave independently of PHC dis-
tributions. Recent literature values for PCB levels in fish are presented in
Table 4-3. A summary of this study's findings is presented in Table 4-4.
Values are well within the range of other reported values, tending towards
the low end of the range. The ratio of PCB to ZDDT compounds was computed
for each species (Table 4-4). The species means of this ratio for the finfish
fall in a narrow range - 3-6, perhaps indicative of a singular source material
having a chlorinated pollutant composition reflecting this ratio. Monitoring
this ratio might then indicate if a new chlorinated hydrocarbon source
affects subsequent tissue measurements.

The baseline data amassed here will be most useful for monitoring future
changes in pollutant loadings in these important fish species. Not enough
information has been gathered as part of this study to monitor important
benthic species in the same fashion. Indeed, benthic species will accumulate
these pollutants to a greater degree than the finfish due to the former's
conduct with the pollutant sink, i.e., the benthos.

Although silver hake appears to be forced by a New York Bight PHC and
PCB source, the situation is less clear for the other species. It is probably
more appropriate to designate regional means for petroleum and chlorinated
hydrocarbon levels around which valia expected statistical variations can be
bracketed, as was done in Section 6, Tables 6-1 to 6-9. The migratory
behavior of fish require this treatment of the data. It would be much more
appropriate to evaluate environmental change with regards to organic pollutant
monitoring in terms of these regional means. Perhaps subregional (e.g., New
York Bight, Chesapeake, Georges Bank) means could be established if a more
intensive sampling and/or analytical program were pursued.

Finally, the analytical protocol used here proved to be useful for
rapid, cost-effective screening and easily converted to the more sophisti-
cated and revealing technique of capillary GC/MS.




-34-

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Figure 24. Petroleum Hydrocarbons in Rock Crab {Station 35).


-13-

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CAROLINA ! XILOMETEAS
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Figure 6. Silver Hake~Petroleum Hydrocarbons,


-8-

3. Summary of Findings

Tabulations of the analytical results of this study are presented in
Section 6, Tables 6-1 to 6-13, for each species. All quantitative results
are reported on a dry weight basis. One can convert these data to a "fresh
weight" (i.e., wet weight) basis by dividing by approximately a factor of
five (dry weight/wet weight -0.2).

The results of the petroleum hydrocarbon (PHC) screening are presented
in these tables. Where screening results indicated a probable or possible
presence of PHE compounds, the sample, was fractionated and analyzed quanti-
tatively by GC“/FID. The combined GC2/FID results (i.e., f) + f2) are
presented in the tables along with GC/ECD results for PCB and EDDT levels.
GC@/MS was performed on a set of samples selected for their likelihood of
containing PAH compounds and/or to obtain a representative analytical set
for most species.

The remainder of this section of the report focuses on the analytical
results for each species examined and on the geographical factors involved
with each analytical set.

3.1 Silver Hake

Most samples of this species contained detectable levels of total
petroleum hydrocarbons (i.e., >1.0 ppm). Concentrations (f] + fz) ranged
from 6 to 90 9/9 (Xpyc = 27 + 29) (see Section 6, Table 6-1). The high

incidence (86%) of petroleum hydrocarbon contamination of this species
is unique among the various species analyzed.

Several representative gas chromatograms are shown in Figures 4 and 5.
The qualitative hydrocarbon assemblage is nearly constant for all PHC-positive
samples of this species. The GC? distributions illustrate a distribution
of PHC compounds in the fj (saturate) fraction indicative of either or both
of two sources of PHC material: (1) the residues of a crude oi], and
(2) anthropogenic inputs of a terrigenous origin. Support for this source
evaluation is as follows.

GC2 traces of tissue samples taken from the Amoco Cadiz spill impact
region a year after the spill are comprised of a very similar PHC boiling
range distribution; a. prominent unresolved complex mixture (UCM) in the
n-C13 to n-C2q boiling range and a resolved peak distribution consisting of
several prominent branched alkane and isoprenoid compounds. The organisms
seem to retain a narrow distribution of the overall crude oi] distribution
(or alter the crude oi] to yield the observed distribution). The fz (aroma-
tic) distributions are "typical" of an altered crude oi] distribution with
the presence of prominent naphthalene, phenanthrene, and dibenzothiophene
compound families (see GC/MS discussion below).


FOREWORD

This issue of the NOAA Technical Memorandum NMFS-F/NEC series
combines two reports prepared by the Energy Resources Co., Inc.
(ERCO), under contract to the National Oceanic and Atmospheric Admin-
istration's (NOAA) National Marine Fisheries Service (NMFS). The
contracts for both reports (i.e., NOAA Contract No. NA-80-FA-C-00046
and NOAA Contract No. NA-81-FA-C-00013) were awarded as part of NOAA's
Northeast Monitoring Program, and were monitored by Dr. John B. Pearce,
Chief of the Division of Environmental Assessment for NMFS's Northeast
Fisheries Center.

The first report, "Gulf and Atlantic Survey for Selected Organic
Pollutants in Finfish. I. Gulf of Maine to Cape Hatteras," presents
information on both finfish and benthic invertebrates; it was submitted
as a final report on 10 November 1980. The second report, "Gulf and
Atlantic Survey for Selected Organic Pollutants in Finfish. II. Chesa-
peake Bay to Port Isabel, Texas," presents information on finfish only;
it was submitted as a final report on 5 January 1982.

Both’reports have been reprinted virtually as submitted; no sub-
stantive changes have been made. Some minimal format changes (i.e.,
title wording, section numbering, and text pagination) have been made
to avoid confusion as a result of combining two separate reports.
Both reports refer to specific trade names; such reference does not
imply NOAA/NMFS endorsement.

Jon A. Gibson, Coordinator
NOAA Technical Memorandun
NMFS-F/NEC series

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-63-

2.1.4 Phase 4: PAH Analysis

Selected unsaturate fractions (f2) were analyzed with a HP 5985 GC/MS
computer system using GC conditions previously described (Boehm et al., 1981).
The presence of aromatic hydrocarbons from two to five rings were identified
by quantitative (internal standard = deuterated phenanthrene) single ion
monitoring of major mass fragments. Samples were chosen to provide a range
of species and geographic locations.

3. Summarization of Findings

3.1 Interspecies Variation

The following presentation will outline, by species, the information we
have gathered concerning PHC, PAH, PCB, and DOT concentrations found in fish
dissected for both muscle and liver analysis. Summaries of the incidence and
concentrations of PHC and PCB/DDT compounds in ug/gm (ppm) and ng/gm (ppb)
dry weight tissue are presented in Tables 3-1 and 3-2. Dry weight concentra-
tions can be converted to fresh weight concentrations by dividing by 5. The
information is also displayed graphically in Figures 4 and 5. Detailed
analytical data are presented in Section 6, Tables A-1 to A-8.

3.1.1 Butterfish

Seven samples of butterfish were analyzed from five different regions
(Table A-1). Fractionated muscle tissues ranged from 20 ppm to 27 ppm
(median = 23 ppm). These fish contained the next to highest concentrations
of PHC found in muscle tissue, and the lowest concentration of PHC in the
liver (Table 3-1, Figure 4). The saturated (f]) fraction of a muscle
sample from Region 3 (Figure 6) illustrates a large UCM between n-Cj3 and
n-C29 and prominent n-alkanes distinctive of petroleum contamination. The
unsaturated f2 fraction contains a UCM also indicative of oil contamination.
The large peak in the fz fraction at approximately 78 min is squalene, a |
large biogenic olefin. PAH determinations were obtainable only by GC/MS
analysis (see Section 3.3).

The median PCB concentration found in butterfish muscle tissue was
80 ppb through the five different regions where butterfish were found
(Table 3-2, Figure 5). Values ranged from none detectable (ND) to 120 ppb
(Table A-1). The median concentration of PCBs in livers of this species
was 100 ppb, with a range from ND to 1,020 ppb. No correlation of PCB and
PHC data is found in either the muscle or liver tissues, probably owing to
different sources for these compound classes. PCB values in the butterfish
Muscle suggest some regional dependence, with higher concentrations found
in fish from Region 1. However, fluctuations in liver PCB and £DDT concen-
trations within regions do not support this observation.


778 75° “749 73° 779 he 70° 38° a0 679 36°
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MARYLANO

CHESAPEAKE wht

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VIRGINIA

NORTH
CAROLINA

RAS
CF 740
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710

Figure 10. Red Hake—Petroleum Hydrocarbons.


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778 76° 75° 74° 7° Ere) me 70° 90 6e° 87° 66°
L sao
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NEW HAMPSHIRE

Lazo
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VIRGINIA
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CAROLINA ! KILOMETERS
care;
HATTERAS |’
769 759 740 73° 729 710 79° 690 a0 670
eS Lt i 4 nm 1 ” nm n n

Figure 2. Map of Sampling Locations for Petroleum Hydrocarbon and PCB Analysis.


-23-.

3.4 Winter Flounder

Boehm and Barak (1979) reported concentrations of hydrocarbons in this
species ranging from 5 to 240 ppm (dry weight). However, the bulk of the
hydrocarbons were of a biogenic origin. The petroleum hydrocarbon component
of the total hydrocarbon number was about 2 to 20 ppm. Winter flounder
examined in the present study were relatively free of petroleum contamination.
Only 15% of the samples contained PHC compounds (Figure 15) in primarily
degraded petroleum residues exhibiting mainly an unresolved complex mixture
(or hump) of naphthenic hydrocarbons. This.is quite unlike the distribution
reported by Boehm and Barak (1979) which more resembled the tar-like distribu-
tion described in the previous section. PHC concentrations were more or less
invariant (6 to 9 ppm) (see Section 6, Table 6-4) and significantly lower
than previously reported.

PCB and DDE levels were quite low (X = 0.01 + 0.01 ug/g; &% =
0.002 + 0.002 ug/g, respectively). An Aroclor 1254 type distribution is
again typical. Again, the presence of chlorinated hydrocarbons and PHC
appear independent of one another.

The areal distributions of both PHC and PCB compounds are presented in
Figures 16 and 17. While the occurrence of PHC compounds in winter flounder
seems not to be coupled with geographic pollutant point sources, elevated
chlorinated hydrocarbons can be loosely ascribed to New York Bight sources.

3.5 Windowpane Flounder

Where PHC compounds were present (38%; Stations 79, 95, 116), the
absolute concentrations were low (see Section 6, Table 6-5) and the source of
these hydrocarbons again appeared to resemble paraffinic tar (Figure 18).
Concentrations of PHC (1 to 5 ppm) are slightly lower than previously reported
(Boehm and Barak, 1979) values of 2 to 20 ppm for the PHC component of the
samples. However, the previously reported frequency of occurrence of PHC in
this species was much higher, approximately 82%.

Quantities of PCB (Aroclor 1254) ranged from 0.004 to 0.086 ug/g and
were found in all samples examined.

No evident New York Bight or other regional forcing or organic pollu-
tant concentrations are apparent (see Figures 19 and 20).

3.6 Haddock

Similarly to that previously reported (Boehm and Barak, 1979), PHC
concentrations are very low in haddock samples from the Georges Bank region
(1 to 2 ppm) (see Section 6, Table 6-6). Two of the seven samples showed
slight indications of possible PHC compounds when screened, but little if


~92-

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-85-

TABLE 3-3

INCIDENCE OF PETROLEUM HYDROCARBONS (REGIONAL VARIATIONS)

PHC (ug/g ORY WT.)

% SCREENED
POSITIVE MUSCLE LIVER
NO. OF
REGION SAMPLES MUSCLE LIVER MEDIAN RANGE® MEDIAN RANGE@

1. Chesapeake Bay

a. Butterfish 2 0 0 - -

b. Hake 2 100 100 5.5 5.0-6.1 158 127-190

c. Flounder 2 50 50 3.2 47

d. Spot 1 100 100 38 885

All species 7 "6 66 5.5 6.1-39 158 47-885
2. Georgia Bight

a. Butterfish 2 50 0 20 -

b. Flounder 1 0 0 - -

c. Lizardfish 1 0 0 - -

d. Spot 2 0 50 - 551

All species 6 “W7 WT 2 551
3. Florida West Coast

a. Butterfish 1 100 0) 27 -

b. Flounder 2 0 0 - -

c. Lizardfish 3 33 33 6.0 34

d. Hake 1 0 0 - -

e. Scad 4 0 0 - -

f. Snapper 4 0 0 - -

g. Spot 3 0 33 - 82

All species 18 “Tr 13) 166.027 5B 34-82

af available.


-5-

TABLE 2-1
SUMMARY OF FISH SPECIES ANALYZED

NO. OF
SPECIES STATIONS STATION LOCATIONS

Silver Hake 14 33, 39, 40, 47, 55, 60, 66, 68,
100, 118, 125, 126, 137, 157

Red Hake 14 21, 33, 35, 47, 60, 66, 111, 116,
118, 125, 126, 135, 137, 157

Yellowtail Flounder 16 40, 49, 55, 58, 60, 68, 77, 79, 95,
101, 106, 123, 132, 139, 144, 146

Winter Flounder 13 52, 55, 58, 77, 95, 101, 105,
113, 123, 134, 139, 142, 157

Windowpane Flounder 8 33, 39, 40, 77, 79, 95, 101, 116

Four Spot Flounder 4 60, 100, 116, 118

Summer Flounder 1 81

American Dab 4 105, 106, 111, 125

Haddock 7 105, 111, 113, 123, 132, 139,
147

Cod 5 101, 105, 113, 123, 142

Skate 2 95, 116

Scallop 1 47

Rock Crab 1 35

Lobster 2 47, 79



-91-

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-96-

TABLE 4-1

PETROLEUM HYDROCARBONS IN FISH

PHC
TOTAL +

SPECIES LOCATION (ug/g ORY WT.)a REFERENCE
Hake GAS I

Muscle 5.0-6.1 This study

Liver 128-190 This study
Flounder GAS I

Muscle 1,.0-6.9 This study

Liver 47-235 This study
Hake GAS I 1-90 Boehm (1980)
Flounder GAS I 1-9 Boehm (1980)
Anerican GAS I 1-2 Boehm (1980)
Dab
Haddock GAS I ND Boehm (1980)
Cod GAS I ND Boehm (1980)
Hake Georges Bank 5-50 Boehm & Barak (1979)
Flounder Georges Bank 1-50 Boehm & Barak (1979)
Haddock Georges Bank 1-5 Boehm & Barak (1979)
Cod Georges Bank 1-10 Boehm & Barak (1979)
Flounder Rhode Island 25-250 Boehm & Barak (1978)

Coast
Hake Scot and 30b Mackie et al. (1974)
Flounder Gulf of Mexico 430 Parker et al. (1972)
Cod British Isles  0.025-1.5D Whittle et al. (1975)
@ND = none detected.
bRepresents n-paraffins only, values converted to dry

weight for comparison.




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>3,0005
2,000 4
1,000 4 e
900 4 °
800 5
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600 4
500 - ry e
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300 4
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904

TOTAL HYDROCARBONS pg/gm

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605 °
504 °

405
304

204 ONY,
Nee,

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54

T r T T T T T 7
Butterfish* Flounder Lizardfish Porgy Scad Snapper Spot Hake

O Muscle
————— Median Values

@ Liver * Median Estimated from
PHC Negative GC Resuits

Figure 4. Petroleum Hydrocarbon Concentrations Graphed by Species.


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© Muscle
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@ Liver

Figure 21. PCB Concentrations Graphed by Regions.


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Figure 8. PCB and DDE in Silver Hake (Station 33).


-44-

TABLE 6-1
ANALYTICAL SUMMARY - SILVER HAKE

PETROLEUM
HYDROCARBON PETROLEUM CHLORINATED
SCREEN HYDORCARBONS HYDROCARBONS
NO. OF =§ ————_— (ug/g) (ug/g)

STA- INOI- POSI~ NEGA-
TION VIDUALS TIVE TIVE RESOLVED TOTAL PCB =DDT  PCB/E DOT

33 10 x 4.0 9.0 0.149 0.036 4.1
39 6 x 9.0 32.3 0.284 0.075 3.8
40 12 x 10.0 37.5 0.157 0.047 3.3
47 5 X 2.3 6.5 0.076 0.015 5.1
55 u x 19.7 93.1 0.457 0.073 6.3
60 10 x 21.4 75.0 0.215 0.063 3.4
66 8 x 6.2 15.2 0.203 0.030 6.8
68 10 X 2.9 3.0 0.025 0.003 8.0
100 7 x 6.0 17.5 0.319 0.038 8.4
118 8 X 4.3 15.7 0.035 0.010 3.5
125 6 x 2.5 10.4 0.079 0.002 4.0
126 10 X 4.2 6.0 0.100 0.026 4.0
137 3 x 0.031 0.016 += 2.0
187 4 X 0.017 0.002 8.5
k= i= k= X=

26.8 0.15 0.031 5.1

+ 28.9 40.13 40.026 + 2.1



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The higher boiling or secondary source input observed in those samples
containing higher levels of PHC compounds probably originates in material
associated with pelagic tar balls (Boehm, 1980) and/or benthic PHC compounds
(Boehm and Quinn, 1977).

The chromatographic distribution of hydrocarbon compounds (saturated and
aromatic) were nearly identical to that previously reported (Boehm and Barak,
1979) for this species. Hydrocarbon concentrations, reported here in the
range of 6 to 90 ppm (dry weight), were similar to those previously determined
(10 to 40 ppm; Boehm and Barak, 1979).

Those samples scrutinized for their PAH content by GC/MS (Table 3-1)
contain primarily compounds in the naphthalene (2 ring), phenanthrene
(3 ring) and dibenzothiophene (3 ring, organosulfur) families. Compounds
containing zero (parent compound) and one, two, three and four methyl sub-
stances were quantified individually and combined as a total "family" in all
of the tables of results. PAH values obtained were similar to those reported
previously (Boehm and Barak, 1979) for these species.

A geographic dependence of the hydrocarbon concentration and composi-
tional patterns, indicating a potential gradient from pollutant sources,
appears to occur with increasing concentrations of PHC with proximity towards
the inner New York Bight region (Figure 6).

The same is true for PCB levels. Figure 7 illustrates the PCB distribu-
tions in silver hake from the study region. Highest levels (0.1 to 0.5 ppm)
are found in those fish from the New York Bight region. PCB levels in
general are higher in this species than in any of the other finfish examined,
although levels are two orders of magnitude below FDA “action level" of
approximately 25 ppm (dry) (= 5 ppm fresh or wet weight).

DDT values measured as the sum of p,p' DDT and p,p' DDE and determined
as_a single p,p' DDE peak range from 0.002 to 0.073 ppm. The occurrence of
DDE closely follows that of PCB compounds. A representative GC/ECD trace for
this species shows an Aroclor 1254 PCB distribution and a prominent: DDE peak
(Figure 8).

The correspondence of PHC and chlorinated hydrocarbons is quite pro-
nounced in this species, indicating a similar source(s) of these pollutants
to silver hake.

3.2 Red Hake
The incidence of PHC compounds in red hake is far less than that in

silver hake (26 versus 86%), as are the determined concentrations in those
samples screened positively. PHC concentrations are low, ranging from 1 to


GULF AND ATLANTIC SURVEY
FOR SELECTED ORGANIC POLLUTANTS
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PCB distributions were varied for these benthic epifaunal species with
concentrations of PCB ranging from 0.001 ppm for scallops to 0.150 ppm for
lobsters from Station 79 on the outer Rhode Island shelf (See Section 6,
Table 6-8). In general, the lobsters contained high levels of PCB (and
DDE) at both stations scrutinized (Stations 45 and 79). The rock crab
also contained significant PCB and DDE levels.

Areal distributions of PCB are shown in Figure 25, which is incon-
clusive with regard to source(s) of these organic compounds.

3.11 Little Skate

Both little skate samples (Stations 95, 116) contained no PHC com-
pounds and low levels (0.002 to 0.012 ppm) of PCB. The previous study
of Boehm and Barak (1979) indicated that this species contained no or low
(1 to 5 ppm) levels of PHC compounds.

3.12 American Dab
Of the four samples of this species analyzed, one contained small
amounts of petroleum hydrocarbons (Station 106; 1.5 ppm). This sample also

contained the highest quantities of the chlorinated hydrocarbons measured
in this species (0.024 ppm PCB; 0.003 ppm sDDT) (See Section 6, Table 6-9).

4. Interpretation of Findings

Data on the concentrations of PHC compounds in fish are not plentiful.
Recent studies include those of Boehm and Barak (1978, 1979), Pancirov and
Brown (1977), Whittle et al. (1975), Mackie et al. (1974), and Parker et al.
(1972). The lack of consistent analytical techniques and reporting formats
somewhat impair one's ability to compare the various data shown in Table 4-1.
What can be said, though, is that levels reported here (Table 4-2) are well
within the range previously reported for the region of interest (Boehm and
Barak, 1979) and lower than those PHC levels reported in fish samples along
the coast (Boehm and Barak, 1978).

The sources (i.e., GC trace) of hydrocarbons in the PHC-positively
screened samples ranged from pelagic tar (e.g., Figure 23) with a pronounced
paraffinic GC pattern to a degraded petroleum residue in.silver hake (e.g.,
Figure 4) very similar in appearance to residues in animal tisues a year
after exposure to the Amoco Cadiz spill (Boehm and Neff, unpublished data).
The PHC composition and concentrations in silver hake appear remarkably
constant, with GC patterns previously reported (Boehm and Barak, 1979)
identical to those observed here.