EPA910-R-01-003
United States
Environmental Protection
Agency
Region 10
1200 Sixth Avenue
Seattle WA 98101
Alaska
Idaho
Oregon
Washington
Office of Environmental Assessment
December 2003
Survey of Chemical
Contaminants in Fish,
Invertebrates and Plants
Collected in the Vicinity of
Tyonek, Seldovia, Port Graham
and Nanwalek - Cook Inlet, AK
N
0 10 20
miles
Alaska
Peninsula
Gulf of Alaska
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Survey of Chemical Contaminants in Seafoods
Collected in the Vicinity of Tyonek, Seldovia,
Port Graham and Nanwalek in Cook Inlet, Alaska
EPA910-R-01-003
Prepared by
US Environmental Protection Agency
Region 10
Office of Environmental Assessment
1200 Sixth Avenue
Seattle, WA 98101
December 2003
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ACKNOWLEDGMENTS
This study was conducted by the U.S. Environmental Protection Agency (USEPA), Office
of Water's Office of Science and Technology (OW-OST), through an InterAgency Agreement with
the Department of Interior, Minerals Management Service (TAG No. DW14937850-01-0, May 1,
1997). The USEPA Work Assignment Manger for this study was Mr. Jeffrey Bigler. Sample
collection for the study was conducted by Arthur D. Little, Inc. Representatives from the villages
of Nanwalek, Port Graham, Seldovia, and Tyonek assisted in the study design and field collection
activities. Laboratory oversight was provided by Ecology & Environment, Inc. Data QA review was
provided by DynCorp. A draft risk assessment was prepared by EVS Environment Consultants
(EVS) under contract to Tetra Tech, Inc. The EVS Project Manager for that project was Dr. Steve
Ellis.
This study was designed and conducted because local Tribal residents in Kachemak Bay and
Cook Inlet contested renewal of the oil and gas industry's NPDES discharge permit. The NPDES
discharge permit allows the oil and gas industry in Cook Inlet a waiver to the national zero discharge
law on the assumption that discharges have no adverse effect on traditionally harvested foods. The
Kachmemak Bay and Cook Inlet Tribes worked very hard to get the attention of OW-OST, to make
the study happen and to ensure that it was as meaningful as possible.
The current report which presents a summary of the data was prepared by Dr. Roseanne
Lorenzana, D.V.M., Ph.D., EPA Region 10, Office of Environmental Assessment. Dr. Patricia
Cirone provided editorial review.
11
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TABLE OF CONTENTS
ACKNOWLEDGMENTS ii
LIST OF ACRONYMS iv
LIST OF APPENDICES v
LIST OF FIGURES AND TABLES vi
EXECUTIVE SUMMARY ix
1.0 INTRODUCTION 1
2.0 METHODS 5
3.0 RESULTS
3.1 OVERVIEW 17
3.2 TRACE METALS 19
3.3 POLYCYCLIC AROMATIC HYDROCARBONS 24
3.4 PESTICIDES 26
3.5 POLYCHLORINATEDBlPHENYLS 28
3.6 DlOXINS AND FURANS 29
4.0 UNCERTAINTIES
4.1 Target Species 31
4.2 Age and Size of Specimens 31
4.3 Timing of Sample Collections 31
4.4 Harvest Location 31
4.5 Sample Type 32
4.6 Target Analytes 32
4.7 Chemical Speciation of Inorganic Chemicals 32
4.8 Concentrations Reported as Not Detected 32
4.9 Effects of Cooking 33
5.0 DISCUSSION
5.1 Comparisons of Cook Inlet Fish, Invertebrates and Plants 35
5.2 Comparison with Regional and National Studies 37
5.3 Nutritional Comparisons 42
5.4 Conclusions 43
6.0 REFERENCES 45
in
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LIST OF ACRONYMS
ADFG Alaska Department of Fish and Game
ADL Arthur D. Little, Inc., Cambridge, Massachusetts
Axys Axys Analytical Services, Inc.
DMA dimethlyarsinic acid
EPA US Environmental Protection Agency
OST US Environmental Protection Agency, Office of Water, Office of Science and
Technology
PAH polycyclic aromatic hydrocarbon
PCBs poly chlorinated biphenyl
QA/QC quality assurance and quality control
QAPP quality assurance project plan
QL quantification limit
USEPA US Environmental Protection Agency
IV
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LIST OF APPENDICES
Appendix A: Tribal needs letter
Appendix B: Data Compilation - Detected Concentrations (average, maximum, minimum,
number of detections)
Appendix C: Compact Disk - Electronic Spreadsheet Containing Data for Each Sample
Appendix D: Development document for final effluent limitations guidelines and standards
for the coastal subcategory of the oil and gas extraction point source category
(selected report sections)
Appendix E: Nobmann (1997). Nutritional benefits of subsistence foods
Appendix F: Study plan for conducting field sampling and chemical analysis for the Cook
Inlet contaminant study
Appendix G: Quality assurance project plan for the Cook Inlet contaminant study sampling,
and Quality assurance project plan for sample homogenization, compositing,
and analysis in the Cook Inlet contaminant study
Appendix H: Cook Inlet study samples collected
Appendix I: Sampling station locations
Appendix J: Photographs of target species
Appendix K: Audit report: Sample preparation of Cook Inlet samples by Axys Analytical
Services, Sidney, B.C., Canada
Appendix L:
DynCorp data review narratives for target analytes
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List of Tables
Table 1. Study Design 7
Table 2. Characteristics of Species Sampled in the Study 8
Table 3. Chemical Analytes 9
Table 4. Fish Composite Samples Collected 11
Table 5. Invertebrate Composite Samples Collected 12
Table 6. Chemical analysis methods used for the Cook Inlet Contaminant Study 14
Table 7. List of chemicals not detected in any tissue sample 17
Table 8. Numbers of detected chemicals in the Cook Inlet Contaminant Study 18
Table 9. Number of samples in which chemical was detected 18
Table 10. Total metal concentrations in invertebrate and plant tissue samples (average
milligrams per kilogram, mg/kg, ppm) 22
Table 11. Polycyclic aromatic hydrocarbon compounds detected only in chinook salmon tissue
samples 28
Table 12. Change in concentration of chemicals due to various cooking methods 33
Table 13. Nutrient Composition of Foods (per 100 grams) 42
VI
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List of Figures
Figure 1. Four Native Alaskan villages and oil platforms in Cook Inlet 2
Figure 2. Areas of investigation 6
Figure 3. Cod Tissue Samples - Total Metal Concentrations (5.8 ppm) 19
Figure 4. Chinook Tissue Samples - Total Metal Concentrations (1.4 ppm) 19
Figure 5. Chum Salmon Tissue Samples - Total Metal Concentrations (2 ppm) 19
Figure 6. Sockeye Salmon Tissue Samples - Total Metal Concentrations (3.2 ppm) 20
Figure 7. Flounder Tissue Samples - Total Metal Concentrations (4.8 ppm) 20
Figure 8. Halibut Tissue Samples - Total Metal Concentrations (2.3 ppm) 20
Figure 9. Sea Bass Tissue Samples - Total Metal Concentrations (2.6 ppm) 21
Figure 10. Cadmium Concentration in Cook Inlet Fish Tissue Samples (average micrograms per
kilogram, ug/kg, ppb) 21
Figure 11. Methylmercury Concentration in Cook Inlet Fish Tissue Samples (average
micrograms per kilogram, ug/kg, ppb) 21
Figure 12. Cadmium Concentration in Cook Inlet Invertebrate Tissue Samples (average
micrograms per kilogram, ug/kg, ppb) 22
Figure 13. Blue Mussel Samples - Total Metal Concentrations (2.5 ppm) 23
Figure 14. Methylmercury Concentration in Cook Inlet Invertebrate Tissue Samples (average
micrograms per kilogram, ug/kg, ppb) 23
Figure 15. Total Poly cyclic Aromatic Hydrocarbon Concentrations in Cook Inlet Tissue Samples
(micrograms per kilogram, ug/kg, ppb) 24
Figure 16. Total Organochlorine Pesticides Concentrations in Fish Tissues (nanograms per
kilogram, in Fish Tissues (nanograms per kilogram, ng/kg, ppt) 26
Figure 17. Organochlorine pesticide compounds in chinook tissue samples (total average 11,324
ppt) 26
Figure 18. Total Chlordanes and Hexachlorobenzene Concentrations in Cook Inlet Fish Tissues
(average nanograms per kilogram, ng/kg) 27
vn
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Figure 19. Average Concentrations of total DDTs in Cook Inlet Fish Tissue Samples
(ng/kg, ppt) 27
Figure 20. PCB-Congener Concentrations in Cook Inlet Fish Tissue Samples (average
nanograms per kilogram, ng/kg, ppt) 28
Figure 21. PCB-Congener Concentrations in Cook Inlet Invertebrate Tissue Samples (average
nanograms per kilogram, ng/kg) 29
Figure 22. Cadmium Concentrations in Cook Inlet Fish, Invertebrate and Plant Tissue Samples
(average and maximum micrograms per kilogram, ug/kg, ppb) 35
Figure 23. Methylmercury Concentrations in Cook Inlet Fish and Invertebrate Tissue Samples
(average and maximum micrograms per kilogram, ug/kg, ppb) 36
Figure 24. Organochlorine Pesticide Concentrations in Cook Inlet Fish Tissue Samples and
Columbia River Chinook Tissue Samples (average micrograms per kilogram, ug/kg,
ppb) 38
Figure 25. Dieldrin Concentrations in Cook Inlet Fish Tissue Samples and FDA Market Basket
Samples (average, maximum and minimum nanograms per kilogram, ng/kg, ppt) . 38
Figure 26. DDT-total Concentrations in Cook Inlet Fish Tissue, Columbia River Chinook Tissue
and FDA Market Basket Samples (average nanograms per kilogram, ng/kg, ppt) . . 38
Figure 27. Chlordanes (total) and Hexachlorobenzene Concentrations in Cook Inlet Fish Tissue
Samples and Columbia River Chinook Tissue Samples (average and maximum
nanograms per kilogram, ng/kg, ppt) 39
Figure 28. Poly cyclic Aromatic Hydrocarbon Compound Concentrations in Cook Inlet Chinook
Tissue Samples and Columbia River Spring Chinook Tissue Samples (micrograms
per kilogram, ug/kg, ppb) 40
Figure 29. OCDD Concentrations in Cook Inlet Chinook and Columbia River Chinook Tissue
Samples (average nanograms per kilogram, ng/kg, ppt) 40
Figure 30. Mercury Concentrations in Cook Inlet Tissue Samples, Columbia River Chinook
Tissue Samples and FDA Market Basket Samples (average and maximum
micrograms per kilogram, ug/kg, ppb) 41
Figure 31. Cadmium Concentrations in Cook Inlet Tissue Samples, Columbia River Chinook
Tissue Samples and FDA Market Basket Samples (average and maximum
micrograms per kilogram, ug/kg, ppb) 41
Vlll
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EXECUTIVE SUMMARY
These data were collected by EPA Office of Water (OW), Office of Science and Technology
with assistance from Port Graham and Nanwalek Tribal residents and professional staff. Field
sampling was conducted between June 5 and July 24, 1997. This report is a summary of the data,
only. For chemical concentrations which were detected, the average, maximum and minimum
values are presented. The individual data on an accompanying compact disk (Appendix C).
A total of 81 tissue samples comprised of seven fish species, eight invertebrates and three
plant species were sampled and analyzed for concentrations of 161 chemicals These results provide
a good survey data set for environmental chemicals present in uncooked, whole body tissues samples
of these Cook Inlet biota. There were detections of global contaminants: mercury, organochlorine
pesticides, and PCB congeners. On the other hand, there was minimal detection of another
ubiquitous contaminant group, dioxins and furans. In the 81 tissue samples analyzed for dioxin
and furan congeners, only one type of dioxin, OCDD, was detected in one duplicate chinook salmon
sample (13 ppt). Detectable concentrations of dioxins and furans were not found in other Cook Inlet
tissue samples. The detection of many individual PAH compounds in the Cook Inlet tissue samples
may have resulted from the use of very sensitive methods. Approximately one-half of the 104
individual PAHs were detected in fish, invertebrate and plant samples. Chinook tissue samples had
the highest total average PAH concentration (253 ppb).
The biota species which were sampled, the size of the biota and the harvest locations were
intended to represent those traditionally used by members of the four Alaskan tribal villages of
Tyonek, Seldovia, Port Graham and Nanwalek. However, all possible harvest sites were not
evaluated. And, not all fish, invertebrate and plant species consumed in a traditional diet were
included in this survey. It is unlikely that this one-time sampling is representative of contaminant
concentrations in these species over the entire lifetime of a human who consumes these species.
Whole-body samples such as these are representative of exposures to the biota, itself, or
predators that consume the whole body. Combining several individuals into a single sample
(composite sample) precluded the availability of chemical concentration data for individual fish,
invertebrate or plant samples. These data contain no definitive information to distinguish wild
versus hatchery or pen-raised fish.
The sensitivity of the analytical methods used in this study should be carefully considered
when using these data. In some cases, the methods were more sensitive than data sets for other
comparable fish samples (e.g. polycyclic aromatic hydrocarbons). But, there were also cases in
which the methods were less sensitive than other data sets (e.g. dioxins and furans). Information
on the sensitivity of method is provided in Appendix C.
Comparisons were made with market basket food contaminant data published elsewhere and
with Columbia River (Washington, Oregon USA) fish contaminant data. With few exceptions,
contaminant concentrations in Cook Inlet area species were similar or lower.
IX
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1.0 INTRODUCTION
In 1997, the US Environmental Protection Agency (USEPA) collected chemical
contaminants in subsistence seafoods collected in the vicinity of four Alaskan tribal villages located
along Cook Inlet, Alaska (Figure 1). There were tribal concerns regarding NPDES waste water
discharge permit renewals for oil and gas industrial activities in Cook Inlet. Tribes in the four
Alaskan tribal villages of Tyonek, Seldovia, Port Graham and Nanwalek were concerned about
potential contaminants in their traditional foods. A copy of the tribal letter is provided in Appendix
A.
Cook Inlet is a large tidal estuary in southeast Alaska that connects to the Gulf of Alaska.
The inlet is approximately 280 km (174 mi) long and 20 to 90 km (12 to 56 mi) wide. Cook Inlet
can be divided into three regions with distinct hydrodynamic characteristics: the head, consisting
of the Knik and Turnagain Arms; upper Cook Inlet, extending from the West Forelands to Point
Woronzof; and lower Cook Inlet, extending from West Forelands to the Gulf of Alaska (ADL 1998).
The village of Tyonek is located along the northwest shore of upper Cook Inlet. The other three
villages, Seldovia, Port Graham, and Nanwalek, are located along the southwest portion of the Kenai
Peninsula in lower Cook Inlet (Figure 1). Coastal oil and gas activities within Cook Inlet are
confined to the upper portions of the inlet, where a total of 15 multiwell platforms are located
(Figure 1).
Thirteen of these platforms were productive as of March 1996. Together they produced
37,400 barrels of oil per day and 385,000,000 cubic feet of gas per day (USEPA 1996). Of the 13
active platforms, 5 separate and treat production fluids (oil, gas, and water) at the platform and
discharge produced water directly to receiving waters within Cook Inlet. The remaining 8 platforms
pipe the production fluids to three shore-based facilities— Granite Point, Trading Bay, and East
Foreland—for separation and treatment. Produced water from the three shore-based facilities is
discharged to Cook Inlet following treatment. Two of the facilities, Trading Bay and East Foreland,
discharge the treated produced water directly from the facility, while the third facility, Granite Point,
sends its treated produced water back to a platform for discharge (USEPA 1996). These three
facilities treat and discharge 96 percent of the produced water generated from all platforms in Cook
Inlet (USEPA 1996).
Approximate distances from the village to the shore-based facilities or production platforms
range from 8 to 44 km (5 to 27 mi). The village of Tyonek is located closest to the oil and gas
operations in Cook Inlet. Seldovia is 188 km (117 mi) from the closest platform. Nanwalek and
Port Graham are the farthest from oil and gas operations at approximately 206 km (128 mi) from the
nearest platform (Figure 1).
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-------
The aim of this study was to collect samples of fish, invertebrates, and marine plants
commonly harvested by members of four Alaskan tribal villages and analyze for a large suite of
chemicals to provide a recent data set. These data were collected by contractors for the EPA Office
of Water (OW), Office of Science and Technology with assistance provided by the participating
Tribes. Included in Appendices F through L are the Quality Assurance Project Plans, audit reports,
data review narratives, sample identification information, sampling station locations and
photographs of sampled species.
This report is a summary of the data, only. For chemical concentrations which were
detected, the average, maximum and minimum values are presented with the expectation that these
data may be used in future evaluations or other activities related to contaminants in Alaskan tribal
traditional foods.
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2.0 MATERIALS and METHODS
The species analyzed include some of the resident and anadromous fish, marine
invertebrates, and marine plants that are harvested by residents of the villages of Tyonek, Seldovia,
Port Graham, andNanwalek. Village representatives were consulted during the development of the
study plan for advice regarding choice of species. Sampling sites were selected based on interviews
with villagers. An area of collection was established for each village (Figure 2). The study plans
developed by EPA are provided in Appendix F (ADL 1997). Listed in Table 1 are the number of
samples and species that were collected within the study areas defined for each village. The study
design shown in Table 1 differs slightly from the original study plan (Appendix F) and quality
assurance project plan (QAPP; Appendix G). Modifications to the study design were primarily due
to the inability to collect sufficient numbers of selected target species during field sampling. To
characterize marine mammals, Beluga whales and harbor seals were supposed to be sampled.
However, these samples were not collected because arrangements could not be made between the
National Marine Fisheries Service and the village of Tyonek. Seals could not be sampled due to the
lack of supervisory staff to oversee the sampling event (ADL 1998). By the time both issues had
been resolved, the sampling period had passed (ADL 1998). A complete description of the field
sampling efforts and the rationale for deviations from the original study plan are provided in Field
Sampling Report for the Cook Inlet Contaminant Study (ADL 1998).
Field sampling was conducted between June 5 and July 24, 1997 (ADL 1998). Consistent
with EPA guidance (USEPA 1995), samples were collected, prepared for shipment, and shipped to
the designated laboratory. A detailed description of the actual field sampling activities is provided
in the report titled Field Sampling Report for the Cook Inlet Contaminant Study (ADL 1998).
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Area Of Investigation
A
N
10 20
=^H
miles
Alaska
Peninsula
/ Anchorage
yoi
ek
Tyonek Sampling
Locations
Kenai
• Soldotna
Kenai
Peninsula
Seward <
Ninilchik
Port Graham
Sampling Locations
Nanwalek
Sampling Locations
Seldovia
Sampling Locations
Nanwaleji
Gulf of Alaska
Figure 2. Areas of investigation
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Table 1. Study Design
VILLAGE CATEGORY SPECIES
Tyonek Fish Chinook salmon
Sockeye salmon
Seldovia Fish Chinook salmon
Sockeye salmon
Halibut
Invertebrates Blue mussel
Butter clam
Chiton
Snail
Port
Graham Fish Chinook salmon
Chum salmon
Sea bass
Flounder
Invertebrates Large clam
Steamer clam
Chiton
Octopus
Snail
Plants Goose tongue
Kelp
Nanwalek Fish Sockeye salmon
Cod
Halibut
Invertebrates Mussel
Chiton
Snail
Plants Goose tongue
Seaweed
SAMPLE TYPE
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Edible portion
Edible portion
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Edible portion
Edible portion
NUMBER OF
COMPOSITE
SAMPLES
3
3
2
3
3
3
3
3
3
1
2
5
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
NUMBER OF
INDIVIDUALS PER
COMPOSITE
3,4,5
5
5
5
5
32, 35, 37
5
>25
>50
5
2,6
1,2,2, 5, 5
2, 3, 10
5
13, 15, 32
30, 38, 45
1
>50
-200-250
>50a
5
5
5
-50
21,21,25
>50
-250
-20
Source: ADL1998
a Also qualified as "a large section."
Characteristics of the species collected during field sampling are listed in Table 2.
Photographs were taken (see Appendix J) but samples were not identified by genus/species at the
time of collection. Photographs were inadequate to later determine the genus/species of some of the
categories named "mussel" and "large clam" at the time of collection. Therefore, the genus/species
for "mussel" and "large clam" are shown on Table 2 as "not determined". The collection locations
for all samples are provided in Appendices H and I.
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The species collected at each location was based on consultations with the four villages. In
Seldovia, the species collected were chinook salmon, sockeye salmon, halibut, butter clams,
mussels, chitons, and snails. At Nanwalek, sockeye salmon, halibut, cod, mussel, snail, chiton,
goose tongue, and seaweed were collected for analyses. At Port Graham, Chinook salmon, chum
salmon, sea bass, flounder, chiton, octopus, snail, large clam, steamer clam, goose tongue, and kelp
were collected. At Tyonek, chinook salmon and sockeye salmon were collected. No invertebrate
or plant samples were collected in the vicinity of Tyonek (i.e., salmon were the primary traditional
food in Tyonek) (ADL 1998).
Table 2. Characteristics of Species Sampled in the Study
SPECIES TAXON
Fish
Chinook salmon Oncorhynchus tshawytscha
Chum salmon Oncorhynchus keta
Sockeye salmon Oncorhynchus nerka
Sea bass Sebastes melanops
Cod Gadus macrocephalus
Flounder Lepidopsetta bilineata
Halibut Hippoglossus stenolepis
Invertebrates
Blue mussel Mytilus cf. trossulus sp.c
Mussel Not determined0
Butter clam Saxidomus giganteuse
Large clam Not determined3
Steamer clam Protothaca stamineae
Chiton Polypi acophora sp.c
Octopus Octopodidae0
Snail Littorina sp.
Plants
Goose tongue Plantago maritima
Kelp/bull kelp Nereocystis luetkeanaa
Seaweed Porphyra sp.9
a Brown pers. comm. 2000a.
b Brown pers. comm. 2000b.
c Brown pers. comm. 2000c.
SIZE RANGE
TOTAL LENGTH (cm)
59.7-96.5
57.2-73.7
40.6-76.2
30.5-58.4
58.4-81.3
27.9-41.9
67.3-101.6
Not reported"
Not reportedd
Not reportedd
Not reported"
Not reportedd
Not reported"
Not reported"
Not reported"
Not reported"
Not reported"
Not reported"
SAMPLE TYPE
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body
Whole body without shell
Whole body without shell
Whole body without shell
Whole body without shell
Whole body without shell
Whole body without
shell'
Whole body'
Whole body without
shell'
Edible "tongue" portion
Edible bulb portion
Blades
d The field sampling records denote that individuals should be of similar size and of a size traditionally
collected for subsistence (ADL 1998).
e Clam identifications were estimated (Brown pers. comm. 2000a).
f Chiton/snail radula and octopus beak were not removed.
g Taxa were identified at Port Graham, other locations were
not determined (Brown pers.
comm. 2000d).
Composite samples were analyzed. The number of individuals in a composite are shown in
Table 1. With the exception of the marine plants, all analyses were performed on whole-body
samples.
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Table 3 lists all the analytes which were measured in this study. A subset of these analytes
are associated with oil and gas operations, and these are shaded (USEPA 1996; see Appendix D).
The main categories of chemicals were trace metals, polycyclic aromatic hydrocarbons (PAHs),
organochlorine pesticides, polychlorinated biphenyls (PCBs), and dioxins/furans. Before
undertaking the study, quality assurance project plans were developed for this project (Appendices
F, G and H).
Table 3. Chemical Analytes
TRACE METALS
Arsenic
Total Inorganic Arsenic
Arsenic III
Arsenic V
Dimethylarsinic Acid
Monomethylarsenic Acid
Barium
Cadmium
Chromium
Lead
Total Mercury
Methylmercury
Selenium
POLYCYCLIC AROMATIC HYDROCARBONS
C1 -Dibenzothiophenes
C2-Dibenzothiophenes
C1- Fluoranthene/pyrenes
C2- Fluoranthene/pyrenes
C3- Fluoranthene/pyrenes
C4- Fluoranthene/pyrenes
C1 -Naphthalenes
1-Methylnaphthalene
2-Methylnaphthalene
C2-Naphthalenes
1,2-Dimethylnaphthalene
1,3-Dimethylnaphthalene
1,5-Dimethylnaphthalene
1,7/1,6-Dimethylnaphthalene
1-Ethylnaphthalene
2,3/1,4-Dimethylnaphthalene
2,6/2,7-Dimethylnaphthalene
2-Ethylnaphthalene
C3-Naphthalenes
1,3,6-Trimethylnaphthalene
1,3,7-Trimethylnaphthalene
1,4,5/1,2,3-
Trimethylnaphthalene
1,4,6/1,3,5/2,3,6-
Trimethylnaphthalene
2,3,5/1,2,7/1,6,7/1,2,6-
Trimethylnaphthalene
C4-Naphthalenes
C1 -Phenanthrene/anthracene
1 -Methylphenanthrene
2-Methylphenanthrene
3-Methylphenanthrene
2-Methylanthracene
9/4-Methylphenanthrene
1 -Methylanthracene
C2-Phenanthrene/anthracene
C3-Phenanthrene/anthracene
C4-Phenanthrene/anthracene
1-Methylchrysene
1,2,9-Tetrahydropicene
2,2,9-Tetrahydropicene
2,9-Dimethylpicene
3,3,7,12a-Tetramethylocta
Hydrochrysene
3,4,7,12a-Tetramethylocta
Hydrochrysene
3-Methylcholanthrene
4,5-Methylenephenanthrene
5,9-Dimethylchrysene
7-Methylbenzo(a)pyrene
9-Methylbenzofluoranthene
Abietadienol
Acenaphthene
Acenaphthylene
CO
Acephenanthrylene
Anthanthrene
Anthracene
Benz(a)anthracene
Benzo(a)fluoranthene
Benzo(a)fluorene/
3-Methylfluoranthene
Benzo(a)pyrene
Benzo(b,j,k)fluoranthenes
Benzo(b)chrysene
Benzo(b)fluorene
Benzo(b)naphtho(1,2-d)
thiophene
Benzo(b)naphtho(2,3-d)
thiophene
Benzo(b)naphtho(u,n,k)thiophen
e
Benzo(c)phenanthrene
Benzo(e)pyrene
Benzo(g,h,i)fluoranthene
Benzo(g,h,i)perylene
Bisnorsimonellite
Cadalene
Carbazole
Cholanthrene
Chrysene/Triphenylene
Coronene
Cyclopenta(c,d)pyrene
Dehydroabietane
Dehydroabietanol-1
Dehydroabietanol-2
Dehydroabietin
Dibenz(a,j)anthracene
Dibenz(a,h)anthracene/
Dibenz(a,c)anthracene
Dibenzo(2,3-a)pyrene
Dibenzo(a,e)pyrene
Dibenzo(b,k)fluoranthene/
Dibenzo(a,l)pyrene
Dibenzo(e,l)pyrene
Dibenzofuran
Dibenzothiophene
Fluoranthene
ldeno(7,1,2,3-c,d,e,f)
chrysene
lndeno(1,2,3-c,d)pyrene
Naphthalene
Naphtho(1,2-k)fluoranthene
Naphtho(2,1 -e)pyrene/
Benzo(b)perylene
Naphtho(2,3-e)pyrene
Norabietatetraene
Pentaphene
Perylene
Phenanthrene
Picene
Pimanthrene
Pyrene
Retene
Simonellite
Tetrahydroretene
Tetramethyloctahydro-
chrysene-
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Table 3. Chemical Analytes
ORGANOCHLORINE PESTICIDES
ODD
2,4'-DDD
4,4'-DDD
DDE
2,4'-DDE
4,4'-DDE
DDT
2,4'-DDT
4,4'-DDT
DDT/DDD/DDE (Total)
Chlordane (Sum)
Alpha-chlordane
Gamma-chlordane
Oxychlordane
Cis-nonachlor
Trans-nonachlor
Dieldrin
Endosulfan (Total)
Endosulfan I
Endosulfan II
Endrin
Gamma-BHC
Heptachlor Epoxide
Hexachlorobenzene
Mirex
Pentachloroanisol
Toxaphene
POLYCYHLORINATED BlPHENYLS
Aroclors
PCB1016
PCB 1221
PCB 1232
PCB 1242
PCB 1248
PCB 1254
PCB 1260
Congeners
3,3',4,4'-TCB (77)
2,3,3',4,4'-PeCB (105)
2,3,4,4',5-PeCB(114)
2,3',4,4',5-PeCB(118)
2',3,4,4',5-PeCB(123)
3,3',4,4',5-PeCB(126)
2,3,3',4,4',5-HxCB (156)
2,3,3',4,4',5'-HxCB (157)
2,3',4,4',5,5'-HxCB(167)
3,3',4,4',5,5'-HxCB(169)
2,2',3,3',4,4',5-HpCB(170)
2,2',3,4,4',5,5'-HpCB(180)
2,3,3',4,4',5,5'-HpCB (189)
DlOXINS/FURANS
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
NOTE: Shading
- Analytes previously associated with oil and gas exploration operations (USEPA
1996, Appendix D).
Samples offish, invertebrate, and plant species were collected by staff from Arthur D. Little
(ADL), Inc., the Alaska Department of Fish and Game (ADFG), and village residents, in general
accordance with the QAPP (Appendices F and G) and EPA (1995). The following is a brief
summary of procedures used for the collection of all samples. The collection area, sampling station,
and sample replicate were identified with a unique sample identification number. Samples were
collected by hand, wearing gloves. The use of tools for collection was minimized to avoid potential
sample contamination. Samples were rinsed with sea water after collection. Samples were placed
in appropriate labeled containers. Invertebrates (except octopus) and plants were placed in glass
containers; chinook salmon, halibut, and octopus were placed in polyethylene bags; all other fish
were wrapped in precleaned aluminum foil and placed in polyethylene bags (ADL 1998). The
samples were packed into coolers for shipment to the processing laboratory. All coolers were
packed with dry ice to maintain a temperature below -4°C until receipt at the laboratory. Field
record forms were completed for each location where individual and composite samples were
collected. Chain-of-custody forms were used to document the transfer of all samples from field
10
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collection to receipt at the processing laboratory. Photographs were taken to document sample
collection procedures at each village. Field record forms, chain-of-custody forms, photographs,
sample collection locations, sample identification numbers, and compositing information are
provided in ADL (1998). Appendix H summarizes sample ID, location, type, and descriptions.
Maps of sampling locations near each village are included in Appendix I.
Although the fish samples were intended to represent the size range and species regularly
consumed, this goal was not achieved. The composite samples included some individual fish that
were smaller than intended. This deviation was due to the unavailability offish in the size range
specified in the study design (ADL 1998).
Fish were collected by hook and line (sea bass, cod, halibut, sockeye salmon, and flounder)
and gill nets (chinook, sockeye, and chum salmon). Where possible, three stations within each
collection area were sampled (Appendices I and J). This objective was not achieved for chinook
salmon from Seldovia and Port Graham, where difficulties in collecting sufficient numbers offish
resulted in only two and one composite sample(s) being collected, respectively (see Table 1). For
similar reasons, only two composite samples of chum salmon were collected at Port Graham. For
sea bass collected from Port Graham, one fish was analyzed as an individual in addition to the three
composite samples. Photographs of samples collected for analysis are presented in Appendix J. The
size range of individual fish within each composite is shown in Table 4. The Composite ID letter-
plus-number codes shown in Table 4 can be used to identify data in Appendix C (compact disk
containing electronic spreadsheet of data for each sample).
Table 4. Fish Composite Samples Collected
SPECIES
Chinook salmon
Chinook salmon
Sockeye salmon
Sockeye salmon
Sockeye salmon
Chinook salmon
Chinook salmon
Sockeye salmon
Sockeye salmon
Sockeye salmon
Halibut
Halibut
Halibut
Chinook salmon
Chum salmon
Chum salmon
Sea bass
Sea bass
No. OF FISH
PER
COMPOSITE ID COMPOSITE VILLAGE
TY-KS-01
TY-KS-02
TY-RS-01
TY-RS-02
TY-RS-03
SE-KS-04
SE-KS-05
SE-RS-05
SE-RS-06
SE-RS-07
SE-HA-01
SE-HA-02
SE-HA-03
PG-KS-01
PG-DS-02
PG-DS-01,02
PG-SB-01
PG-SB-02
5
3
5
5
5
5
5
5
5
5
5
5
5
5
6
2
5
5
Tyonek
Tyonek
Tyonek
Tyonek
Tyonek
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
SIZE RANGE
(cm) COMMENTS
59.7-96.5a
63.5-68.6
43.2-53. 3a
40.6-53.3
43.2-50.8
68.6-91.4
74.9-94.0
57.2-76.2
55.9-61.0
54.6-68.6
69.9-83.8
67.3-96.5a
72.4-86.4
71.1-91.4
68.6-73.7
57.2-71 . 1 Samples collected from
one site, PG-DS-02
35.6-50.2a
35.6-52. la
11
-------
SPECIES
Sea bass
Flounder
Flounder
Sockeye salmon
Sockeye salmon
Sockeye salmon
Cod
Cod
Cod
Halibut
Halibut
Halibut
COMPOSITE ID
PG-SB-03, 02B,04
PG-FL-01
PG-FL-02,03
NA-RS-01
NA-RS-02
NA-RS-03
NA-CD-01
NA-CD-02
NA-CD-03
NA-HB-01
NA-HB-02
NA-HB-03
No. OF FISH
PER
COMPOSITE
1 or 2
5
5
5
5
5
5
5
5
5
5
5
VILLAGE
Port Graham
Port Graham
Port Graham
Nanwalek
Nanwalek
Nanwalek
Nanwalek
Nanwalek
Nanwalek
Nanwalek
Nanwalek
SIZE RANGE
(cm)
30.5-58.4"
27.9^1.9"
30.5-34.3
67.3-72.4
63.5-73.7
61.0-76.2
58.4-71.1
58.4-78.7a
73.7-81.3
69.9-102.0*
76.2-89.0
71.1-83.8
COMMENTS
Samples collected from
three locations
Samples collected from
two locations
a Minimum individual size is less than 75 percent maximum individual size.
The size range of collected invertebrates was consistent with the design. Sampling sites were
selected based on interviews with villagers. Three composite samples were collected for each
species (see Table 1). The number of individuals in composite samples and weight information is
provided in Table 5. The Composite ID alphanumeric codes shown in Table 5 can be used to
identify data in Appendix C (compact disk containing electronic spreadsheet of data for each
sample). Mussels, snails, and octopi were collected by hand. Butter clams and large clams were
hand-collected from holes dug with a shovel. Steamer clams were collected by digging with a
shovel and rake. Chiton were hand-collected using a stainless steel blade to pry the organisms off
the rocks.
Table 5. Invertebrate Composite Samples Collected
SPECIES
Butter clam
Butter clam
Butter clam
Blue mussel
Blue mussel
Blue mussel
Snail
Snail
Snail
Chiton
Chiton
Chiton
Large clam
NO. OF INDIVIDUALS
COMPOSITE ID PER COMPOSITE VILLAGE
SE-BC-01-01
SE-BC-01-02
SE-BC-01-03
SE-MU-01-01
SE-MU-01-02
SE-MU-01-03
SE-SN-01-01
SE-SN-01-02
SE-SN-01-03
SE-CH-01-01
SE-CH-01-02
SE-CH-01-03
PG-LC-01-01
5
5
5
35
37
32
>50
>50
>50
>25
>25
>25
5
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Seldovia
Port Graham
WET WEiGHT(g)
a
a
a
a
a
a
a
a
a
350b
345b
362b
a
12
-------
NO. OF INDIVIDUALS
SPECIES
Large clam
Large clam
Steamer clam
Steamer clam
Steamer clam
Octopus
Octopus
Octopus
Snail
Snail
Snail
Chiton
Chiton
Chiton
Mussel
Mussel
Mussel
Snail
Snail
Snail
Chiton
Chiton
Chiton
COMPOSITE ID
PG-LC-01-02
PG-LC-01-03
PG-CL-01-01
PG-CL-02-01
PG-CL-03-01
PG-OT-01-01
PG-OT-01-02
PG-OT-02-01
PG-SN-01-01
PG-SN-02-01
PG-SN-02-02
PG-CH-01-01
PG-CH-01-02
PG-CH-02-03
NA-MS-01-01
NA-MS-02-01
NA-MS-03-01
NA-SN-01-01
NA-SN-02-01
NA-SN-03-01
NA-CH-01-01
NA-CH-02-01
NA-CH-03-01
PER COMPOSITE VILLAGE
5
5
32
15
13
1
1
1
>50
>50
>50
38
45
30
-50
-50
-50
>50
>50
>50
25
21
21
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Port Graham
Nanwalek
Nanwalek
Nanwalek
Nanwalek
Nanwalek
Nanwalek
Nanwalek
Nanwalek
Nanwalek
a Not reported. Field sampling records denote that individuals should be of similar size and of a
for subsistence (ADL 1998).
b Weight of sample after shucking. Individual chiton lengths ranged from 4 to 8 cm.
WET WEiGHT(g)
a
a
a
a
a
4,700
6,000
1,200
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
size traditionally collected
All plants were collected by hand and three composite samples were collected for each
species. Composite goose tongue samples were composed of the edible tongue portion of the plant
from approximately 200 to 250 individuals. Kelp samples were only collected in the vicinity of Port
Graham; the three composite samples consisted of the edible bulb portion from approximately 50
plants (ADL 1998). Seaweed samples were only collected in the vicinity of the village of Nanwalek;
the three composite samples each consisted of the blades from approximately 20 plants.
The following provides a brief discussion of the laboratory procedures for sample receipt,
processing, distribution, chemical analysis, and QA/QC processes. Sample processing and
distribution was conducted by Axys Analytical Services, Inc. in Sydney, British Columbia, Canada.
Coolers containing samples were received at Axys from June 27 through September 4, 1997. All
samples were received frozen and in good condition (Ecology and Environment, Inc., 1998).
Samples were stored in freezers at -20°C until all details on sample preparation and subsequent
analysis were approved by the Office of Water, Office of Science and Technology and the sample
13
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control center, operated by DynCorp in Alexandria, Virginia (Ecology and Environment, Inc., 1998).
Sample homogenization and compositing was initiated on February 25, 1998. Composite
samples of whole fish, invertebrates, and marine plants were homogenized. Before homogenization,
shells were removed from invertebrates by hand; gloves were worn and solvent-rinsed shucking
tools were used. Composite samples of octopi were not analyzed; each whole-body octopus was
homogenized individually. Three types of blenders were available for use in homogenization—a
Virtis mixer, Oster blender, and commercial meat grinder. The type of blender used depended on
the amount and type of tissue in the sample. Samples were hand mixed between each pass through
the blender. Homogenization equipment was cleaned thoroughly after each composite sample was
prepared. Equipment was cleaned with soap and water, then rinsed with acetone, hexane, and
dichloromethane, then with a 5 percent nitric acid solution, and lastly with deionized water.
Composite samples were assigned EPA sample numbers. Aliquots of material were placed
into appropriate containers for future analysis and frozen at -20°C. Sample aliquots and blanks were
shipped frozen to Pacific Analytical, Inc., in Carlsbad, California, and Battelle Marine Sciences in
Sequim, Washington; or were retained at Axys for subsequent chemical analysis.
On March 2, 1998, Ecology and Environment, Inc., staff from Lancaster, New York,
conducted an audit of the sample preparation and compositing samples by Axys. The results of this
audit are provided (see Appendix K). It was concluded from the audit that the processing and
homogenization of samples were being conducted in accordance with the standard operating
procedures designated in the QAPP (see Appendix G).
The analytical methods used for the analysis of samples are listed in Table 6. All analytical
methods are established EPA methods. Some methods were modified for the analyses of tissues
(rather than water) or to include analytes not listed for that method. An example of the latter is the
use of Method 1638 for the analyses of chromium and barium.
To provide data regarding the toxic chemical species of mercury and arsenic, methylmercury,
trivalent arsenic, pentavalent arsenic, dimethylarsinic acid and monomethylarsenic acid were
included in the analytes.
Table 6. Chemical analysis methods used
for the Cook Inlet Contaminant Study
ANALYTE
METHOD
Dioxins/furans
Polychlorinated biphenyls
Polycyclic aromatic hydrocarbons
Organochlorine pesticides
Trace Metals:
USEPA Method 1613, Revision B
USEPA Method 1656 (Aroclors)
USEPA Method 1668 (congeners)
USEPA Method SW846, modified methods
8270C-SIM and 3630
USEPA Method 1656
14
-------
ANALYTE METHOD
Total mercury USEPA Method 1631
Methylmercury USEPA Method 1630
Selenium USEPA Method 1638
Cadmium USEPA Method 1638
Chromium USEPA Method 1638
Barium USEPA Method 1638
Lead USEPA Method 1638
Total Arsenic USEPA Method 1638
Arsenic III USEPA Method 1632, revision A
Arsenic V USEPA Method 1632, revision A
Monomethylarsenic acid USEPA Method 1632, revision A
Dimethylarsinic acid USEPA Method 1632, revision A
The performance of all analyses were consistent with quality control elements described in
the versions of EPA 600 and 1600 series methods current in 1998. The QA/QC review of the data
was performed by DynCorp of Alexandria, Virginia. All data were acceptable according to the data
review guidelines for the various methods (specified in Appendix L).
Summary statistics for the analytical results are compiled in Appendix B. For each analyte
in each species, the summary statistics include the maximum and minimum detected concentrations,
the arithmetic average of the detected concentrations, and the number of detections.
15
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[This page intentionally blank]
-------
3.0 RESULTS
3.1 Overview
A total of 81 samples consisting of fish, invertebrates and plants were collected. Samples
were analyzed for 161 chemicals in five chemical groups (metals, PAHs, pesticides, PCBs, and
dioxins/furans). Approximately one-half (85) of these analytes were not detected in any sample
(Table 7). And, approximately one-half (76) of these chemical were detected (Table 8). The
numbers of detected chemicals by sample type and chemical group are shown (Table 9).
Mean contaminant concentrations are provided in Appendix B. The entire data set is
provided on a compact disk which accompanies this report (Appendix C). The results of the quality
assurance review are provided in Appendix L.
Table 7. List of chemicals not detected in any tissue sample
PAHs 1,2,9-Tetrahydropicene
1,2-Dimethylnaphthalene
1,3,7-Trimethylnaphthalene
1,4,5/1,2,3-Trimethylnaphthalene
1,5-Dimethyl naphthalene
1-Ethylnaphthalene
1-Methylchrysene
2,2,9-Tetrahydropicene
2,3,5/1,2,7/1,6,7/1,2,6-Trimethylnaphthalene
2,9-Dimethylpicene
2-Ethylnaphthalene
2-Methylanthracene
3-Methylcholanthrene
3,3,7,12A-Tetramethyloctahydrochrysene
4,5-Methylenephenanthrene
5,9-Dimethylchrysene
7-Methylbenzo(a)pyrene
9-Methyl benzofluoranthene
Acephenanthrylene
Anthanthrene
Anthracene
Benzo(a)fluoranthene
Benzo(a)fluorene/3-Methylfluoranthene
Benzo(a)pyrene
Benzo(b,j,k)fluoranthenes
Benzo(b)chrysene
Benzo(b)naphtho(1,2-d)thiophene
Benzo(b)naphtho(2,3-d)thiophene
Benzo(b)naphtho(u,n,k)thiophene
Benzo(c)phenanthrene
Benzo(e)pyrene
Benzo(g,h,i)fluoranthene
Benzo(g,h,i)perylene
Bisnorsimonellite
C3-Fluoranthene/pyrenes
Cholanthrene
ChryseneAriphenylene
Coronene
Dehydroabietanol-1
Dehydroabietanol-2
Dibenz(a,j)anthracene
Dibenz(a,h)anthracene/Dibenz(a,c)anthracene
Dibenzo(2,3-a)pyrene
Dibenzo(a,e)pyrene
Dibenzo(b,k)fluoranthene/Dibenzo(a,l)pyrene
PAHs, cont.
Pesticides
PCS Aroclors
PCB Congeners
Dioxins
Furans
Dibenzo(el)pyrene
lndeno(7,1,2,3-c,d,e,f)chrysene
lndeno(1,2,3-c,d)pyrene
Naphtho(1,2-k)fluoranthene
Naphtho(2,1 -e)pyrene/Benzo(b)perylene
Naphtho(2,3-e)pyrene
Norabietatetraene
Pentaphene
Perylene
Picene
Retene
Tetramethyloctahydrochrysene
Toxaphene
PCB 1016
PCB 1221
PCB 1232
PCB 1242
PCB 1248
PCB 1254
2,3,4,4',5-PeCB(114)
3,3',4,4',5-PeCB(126)
2,3,3',4,4',5'-HxCB(157)
3,3',4,4',5,5'-HxCB(169)
2,3,3',4,4',5,5l-HpCB(189)
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
Note: PAH - polycyclic aromatic hydrocarbon
PCB - polychlorinated biphenyl
Shading - Analytes previously associated with oil and gas exploration operations (USEPA 1996, Appendix D).
17
-------
Table 8. Numbers of detected chemicals in the
Cook Inlet Contaminant Study
CHEMICAL GROUP
Trace metals
Polycyclic aromatic hydrocarbons
Pesticides
Polychlorinated biphenyls:
Aroclors
Congeners
Dioxins/furans
Total
TOTAL NUMBER
OF CHEMICALS
MEASURED
7
104
13
7
13
17
161
NUMBER
DETECTED
7
47
12
1
8
1
76
Table 9. Number of samples in which chemical was detected
Fish3
Shellfish"
Other
Invertebrates0
Plants"
TOTAL
NUMBER
OF
SAMPLES
33
15
21
12
NUMBER OF SAMPLES IN WHICH CHEMICAL WAS DETECTED
METALS
33
15
21
12
PAHs
33
10
19
9
PESTICIDES
33
1
8
1
PCB
AROCLORS
5
0
0
0
PCB
CONGENERS
33
1
8
0
DlOXINS/
FURANS
1
0
0
0
Chinook salmon, chum salmon, sockeye salmon, sea bass, cod, flounder, halibut.
Blue mussel, mussel, butter clam, large clam, steamer clam.
Chiton, octopus, snail.
Goose tongue, kelp, seaweed.
18
-------
3.2 Trace Metals
3.2.1 Fish
Arsenic (total), barium, cadmium, chromium, lead,
methymercury and selenium were analyzed. In addition,
analyses of arsenical species included trivalent arsenic
(As3+), dimethylarsinic acid and monomethylarsenic. The
total average concentration of metals ranged from 1.4 ppm
to 5.8 ppm. The highest total concentrations were in cod
tissue samples (average 5.8 ppm, Figure 3)
Arsenic (total) is shown because concentrations were
detected in all fish species. In contrast, inorganic arsenic
concentrations did not have a consistent pattern.
Arsenic
(total)
72%
Figure 3.
Barium
8%
Chromium
r 9%
Methyl-
^ Mercury
1%
elenium
10%
Cod Samples - Percent Metal
Concentrations (total 5.8
ppm)
Barium
10%
The lowest total concentrations were in chinook
tissue samples (average 1.4 ppm, Figure 4).
Selenium/
26%
Cadmium
8%
I
Chromium
13%
Lead
3%
Methyl-
mercury
3%
Figure 4. Chinook Samples - Percent Metal
Concentrations (total 1.4 ppm)
Arsenic (total), barium, chromium,
methylmercury and selenium were detected in all
seven species of fish. Lead was only detected in
chinook and flounder (average 4.2 ppm in both).
In chum salmon, barium accounted for the greatest
percentage (Figure 5).
Selenium
26%
Barium
38%
Cadmium
3%
Chromium
Methyl- 20%
mercury
1%
Figure 5. Chum Salmon Samples - Percent Metal
Concentrations (total 2 ppm)
19
-------
In sockeye salmon, chromium
accounted for the greatest percentage (Figure
6). The highest concentrations of chromium
were found in sockeye salmon tissue samples
(maximum =11.7 ppb, average =1.9 ppm).
Barium Cadmium
1%
Selenium^
19% """
Methyl-
mercury
0.4%
Chromium
62%
Figure 6. Sockeye Salmon Samples - Percent Metal
Concentration (total 3.2 ppm)
Arsenic (total) average concentrations ranged from 0.24 to 4.2 ppm. The highest average
arsenic (total) concentrations were detected in cod tissue samples. The lowest average arsenic (total)
concentrations were detected in chum salmon. Except in chum and sockeye salmon, arsenic (total)
accounted for the greatest percentage of the metals concentrations (Figures 3 through 9). Inorganic
arsenical species were detected in four fish species. Trivalent arsenic and monomethylarsenic
cocentrations were detected only in flounder tissue samples (average 0.012 and 0.013 ppm,
respectively). Dimethylarsinic acid concentrations were detected in tissue samples of cod, halibut
and sea bass (range of averages 0.024 to 0.055 ppm).
Arsenic,
total -i
61% \
Barium
19%
Cadmium
Selenium
11%
Chromium
7%
Lead
/ Methyl- ~~ 1%
mercury
0.4%
Barium
6%
Cadmium
2%
Chromium
15%
Selenium
21%
Methyl-
L mercury
1%
Figure 7. Flounder Samples - Percent Metal
Concentrations (4.8 ppm)
Figure 8. Halibut Samples - Percent Metal
Concentrations (2.3 ppm)
20
-------
Selenium
23%
Barium
26%
Cadmium
2%
Methyl-
mercury
3%
Chromium
15%
Figure 9. Sea Bass Samples - Percent Metal
Concentrations (2.6 ppm)
Cadmium was detected in all fish tissue
samples, except cod tissue samples (range of
averages 37 to 109 ppb) (Figure 10).
Figure 10. Cadmium Concentration in Cook Inlet
Fish Tissue Samples (mean micrograms
per kilogram, ug/kg, ppb).
Average concentrations of
methylmercury ranged from 15 to 75 ppb (note
ppb, not ppm, Figure 11). The highest average
methylmercury concentrations were in sea
bass. The lowest average methylmercury
concentrations were in sockeye salmon.
o
1
1
o
o
£4
H
micrograms per kilogram (ug/kc
ou
7fl
DU
50
Af\
on
on
•in
•
• Mean (ug/kg, ppb)
• _
•
' |
XX "VX / /
Figure 11. Methylmercury Concentration in Cook Inlet
Fish Tissue Samples (mean micrograms per
kilogram, ug/kg, ppb).
21
-------
Selenium was detected in all fish tissue samples. The highest mean tissue concentration was
measured in sockeye salmon tissue samples (621 ppb). However, the highest maximum
concentration was measured in flounder tissue samples (1580 ppb).
3.2.2 Invertebrates
Arsenic (total), barium, cadmium, chromium and selenium were detected in all 8 invertebrate
tissue samples. Lead was detected in all tissue samples, except steamer clams. The average
concentrations of total metals in invertebrates ranged from 0.3 to 8.4 ppm (Table 10). The highest
total average concentrations were found in snail tissue samples. The lowest total average
concentrations were found in mussel tissue samples. In most cases, total arsenic contributed the
greatest percentage (range of averages 40% to 81%). However, in snail tissue samples cadmium
contributed the greatest percentage (54%, Table lOandFigure 12). Individual metal concentrations
detected in each species are provided in Appendix B.
Table 10.
Total metal concentrations in invertebrate and plant tissue samples
(average milligrams per kilogram, mg/kg, ppm).
Sample
Blue mussel
Butter clam
Large clam
Mussel
Steamer clam
Goose Tongue
Kelp
Seaweed
Chiton
Octopus
Snail
Total Metal
(mg/kg)
2.5
7.5
5.5
2.0
3.3
0.3
3.6
3.6
4.2
5.0
8.4
Highest
Concentration
Arsenic, total
Arsenic, total
Arsenic, total
Arsenic, total
Arsenic, total
Chromium
Arsenic, total
Arsenic, total
Arsenic, total
Arsenic, total
Cadmium
Percent of
Total
49%
53%
58%
48%
73%
46%
71%
81%
40%
59%
54%
Arsenic (total) concentrations are comprised of many different arsenical species. In this
study, four arsenical species were analyzed (dimethylarsinic acid, monomethylarsenic, trivalent
inorganic arsenic and pentavalent inorganic arsenic). In the invertebrate tissue samples, these four
arsenical species accounted for a small portion of the total arsenic concentration. This is illustrated
by blue mussel sample results which were typical of the invertebrate results (Figure 13).
Figure 12.
Cadmium Concentrations in Cook Inlet
Invertebrate Tissue Samples (mean
micrograms per kilogram, ug/kg, ppb).
Not shown: Snail, mean concentration 4493 ppb.
22
-------
Arsenic (total) average
concentrations ranged from 0.013 to 3.9
ppm. The highest arsenic (total) average
concentrations were detected in butter clam
tissue samples. The lowest arsenic (total)
average concentrations were detected in
mussel tissue samples. Trivalent arsenic
was detected in tissue samples from blue
mussels, butter clam, large clam, steamer
clam and snail (range of averages 0.005 to
0.053 ppb). Snail tissue samples had the
highest trivalent arsenic concentrations.
Dimethylarsinic acid concentrations were
detected in all invertebrate tissue samples
(range of averages 0.031 to 0.208 ppm).
Monomethylarsenic concentrations were
not detected in any tissue samples.
Methyl-
mercury
0.1%
Selenium
12%
Chromium
8%
Cadmium
19%
\lnorganic As3+
0.2%
Unknown
Arsenic Species
47%
Barium
10%
Arsenic,
total 49%
Figure 13.
Blue Mussel Samples - Percent
Metal Concentrations (2.5 ppm)
Chromium was detected in all invertebrate tissue samples. The highest mean tissue
concentrations were measured in butter clams (2.0 ppm) and large clam (1.0 ppm). Mean tissue
concentrations in these two species were approximately 10 times higher than other invertebrate
tissue samples, which ranged from approximately 0.128 to 0.612 ppm.
Methylmercury average concentrations were detected in all invertebrate tissue samples
(Figure 14). Average methylmercury concentrations ranged from 1.8 to 7.9 ppb (note ppb, not ppm).
The highest average methylmercury concentrations were detected in octopus tissue samples. The
lowest average methylmercury concentrations were detected in chiton tissue samples.
Figure 14.
Methylmercury
Concentration in
Cook Inlet
Invertebrate Tissue
Samples (mean
micrograms per
kilogram, ug/kg,
ppb).
00
g1 4
1ll\*an(ug'kg, ppb)
3.2.3 Plants
Metals were detected in the three plant species analyzed. Barium was detected in goose
tongue and kelp tissue samples (averages 112 and 363 ppb, respectively). Cadmium concentrations
were detected in kelp and seaweed (averages 301 and 510 ppb, respectively). Mean chromium
concentrations detected in the three plant species ranged from 128 to 232 ppb. Lead concentrations
were detected in goose tongue and kelp (averages 26 and 25 ppb, respectively). Mean selenium
concentrations detected in kelp were 135 ppb.
Total arsenic was present in the greatest percentage of the total metals in kelp and seaweed
(Table 10). Chromium was the greatest percentage of total metals in goose tongue (Table 10).
23
-------
3.3 Polycyclic Aromatic Hydrocarbons (PAHs)
3.3.1 Fish
The 81 tissue samples consisting offish, invertebrates and plants were analyzed for 104
PAHs (Table 3). Approximately one-half of these PAHs were detected in the Cook Inlet tissue
samples. PAHs were detected in all fish tissue samples (Figure 15 ).
Figure 15.
Total Polycyclic Aromatic Hydrocarbon Concentrations in Cook Inlet Tissue Samples
(micrograms per kilogram, ug/kg, ppb)
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In fish tissue samples, total PAHs average concentrations ranged from 1 to 253 ppb. The
highest average concentrations were detected in chinook tissue samples. The lowest average
concentrations were detected in cod tissue samples.
Acenaphthylene, carbazole, dibenzofuran, fluoranthene, and phenanthrene were only
detected in chinook salmon. The mean chinook tissue concentrations and detection frequencies for
these chemicals are shown in Table 11.
Table 11. Polycyclic aromatic hydrocarbon compounds
detected only in chinook salmon tissue samples
CHEMICAL
Acenaphthylene
Carbazole
Dibenzofuran
Fluoranthene
Phenanthrene
MEAN CHINOOK SALMON
CONCENTRATION
(/jg/kg, ppb)
1.2
1.3
3.8
2.6
7.2
DETECTION
FREQUENCY
2 of 6
2 of 6
2 of 6
1 of 6
2 of 6
2-Methylnaphthalene was only detected in chinook salmon tissue samples. In these samples,
this chemical was detected in two of the six tissue samples analyzed; the mean whole-body tissue
concentration was 4.5 ppb.
24
-------
Acenaphthene was not detected in sockeye salmon, cod, or flounder. Acenaphthene was
detected infrequently in chinook salmon, chum salmon, sea bass, and halibut. The mean tissue
concentrations in these tissue samples ranged from 0.82 ppb in chum salmon tissue samples to 8.95
ppb in chinook salmon tissue samples.
Benz(a)anthracene was only detected in one out of four sea bass tissue samples analyzed;
the mean whole-body tissue concentration for these tissue samples was 1.0 ppb. This chemical was
not detected in any other fish tissue sample.
Fluorene was detected infrequently in chinook salmon, sockeye salmon, and sea bass tissue
samples. The mean tissue concentrations in these tissue samples ranged from 0.78 ppb in sea bass
tissue samples to 3.85 ppb in chinook salmon. This chemical was not detected in chum salmon, cod,
flounder, or halibut tissue samples.
Naphthalene was detected in two chinook salmon tissue samples, one sockeye salmon
sample, and one halibut sample at mean tissue concentrations ranging from 2.3 to 3.45 ppb. This
chemical was not detected in chum salmon, sea bass, cod, or flounder tissue samples.
Pyrene was detected in one sample of flounder (mean =1.3 ppb).
3.3.2 Invertebrates
Except for mussel tissue samples, PAHs were detected in all invertebrate tissue samples
(Figure 15). Total PAHs average concentrations ranged from 3 to 34 ppb. The highest average
concentrations were detected in snail tissue samples. The lowest average concentrations were
detected in large clam tissue samples.
2-Methylnaphthalene was only detected in snail tissue samples. In these samples, 2-
methylnaphthalene was detected in two of the nine tissue samples analyzed; the mean whole-body
tissue concentration was 1.5 ppb. Naphthalene was detected in blue mussel (mean = 2.5 ppb) and
snail tissue samples (mean = 4.55 ppb). Acenaphthene, benz(a)anthracene, fluorene and pyrene were
not detected in any of the invertebrate tissue samples.
3.3.3 Plants
PAHs were detected in all plant tissue samples (Figure 15). Total PAHs average
concentrations ranged from 5 to 133 ppb. The highest average concentrations were detected in
goose tongue tissue samples. Pyrene was detected in one sample of goose tongue (mean = 4.1 ppb).
Acenaphthene, benz(a)anthracene, fluorene and naphthalene were not detected in any of the plant
tissue samples.
25
-------
3.4 Pesticides
The 81 tissue samples consisting offish, invertebrates and plants were analyzed for 13
organochlorine pesticides.
3.4.1
Fish
The occurrence of all pesticides detected in fish tissue samples is illustrated in Figure 16.
Average concentrations were less than 12,000 ppt. The lowest average concentrations were detected
in flounder tissue samples (1,243 ppt) and highest average concentrations were detected in chinook
and sea bass tissue samples (1 1,324 and 1 1,090 ppt, respectively).
Figure 16.
Total Organochlorine Pesticides Concentrations
in Fish Tissues (average nanograms per kilogram, ng/kg, ppt)
O D)
1g -S
^ O
o> ^
.E 2
o "c
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-------
The highest concentrations of several pesticides — hexachlorobenzene, endrin, and dieldrin
— were measured in chinook salmon tissue samples. The highest concentrations of DDT
compounds, chlordanes, heptachlor epoxide and mirex were detected in seabass tissue samples. The
highest concentrations of endosulfans, lindane and pentachloroanisole were detected in sockeye
tissue samples.
The concentration of DDT compounds (DDT-
total) was estimated as the sum of the isomers—
2,4-DDD, 2,4-DDE, 2,4-DDT, 4,4-DDE, 4,4-DDD,
and 4,4-DDT (Figure 18). DDT compounds were
detected in all fish tissue samples, and represented the
greatest organochlorine pesticide concentration (range
of averages 588 to 5894 ppt). Highest average
concentrations were detected in Sea Bass tissue
samples (5894 ppt), and lowest average concentrations
were detected in flounder tissue samples (588 ppt).
DDE isomer concentrations were present in the
greatest amount followed by DDT, then ODD
concentrations.
The concentration of total chlordanes was
estimated as the sum of alpha-chlordane,
cis-nonachlor, gamma-chlordane, oxychlordane and
trans-nonachlor (Figure 19). Chlordane compounds
were detected in all species, except halibut. Highest
average concentrations were detect in sea bass tissue
samples (2732 ppt), and the lowest average
concentrations were detected in flounder tissue
samples (372 ppt). Hexachlorobenzene was detected
in all fish species (Figure 19). Highest average
concentrations were detected in chinook tissue
samples (1787 ppt), and lowest average
concentrations were detected in cod tissue samples
(237 ppt).
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d D Hexachlorobenzene (mean,
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Figure 18. Total Chlordanes and
Hexachlorobenzene Concentrations
in Cook Inlet Fish Tissues (average
nanograms per kilogram, ng/kg)
DDT-Total Concentration
anograms per kilogram (ng/kg
7000 -i
innn
u
• DDT -total (mean) 1
• • 1
•
• H 1
•
• |
// V>VV
Figure 19. Average Concentrations of total
DDTs in Cook Inlet Fish Tissue
Samples (ng/kg, ppt)
Dieldrin was not detected in chum salmon or flounder tissue samples. Highest average
concentrations were detected in chinooktissue samples (769 ppt), and lowest average concentrations
were detected in cod tissue samples (237 ppt).
Endosulfans were detected only in chinook and sockeye salmon tissue samples (averages 544
and 664 ppt, respectively). Endrin was detected only in chinook, halibut and sockeye (range of
averages 407 to 582 ppt). Heptachlor epoxide was detected only in chinook, sea bass and sockeye
tissue samples. Average concentrations in chinook and sea bass tissue samples were 238 ppt and
310 ppt, respectively. While average concentrations in sockeye tissue samples were 174 ppt.
Lindane was detected only in chinook and sockeye tissue samples (averages 185 and 275 ppt,
respectively). Mirex was detected only in sea bass tissue samples (average 379 ppt).
Pentachloroanisole was detected in chinook, halibut, sea bass and sockeye tissue samples. Highest
27
-------
average concentrations were detected in sockeye tissue samples (1919 ppt), and lowest average
concentrations were detected in halibut tissue samples (226 ppt).
3.4.2
Invertebrates
There were very few detections of organochlorine pesticides in invertebrates. The
compounds for which there were no detections in any species included chlordane compounds, DDT
compounds, dieldrin, endosulfans and mirex.
The organochlorine pesticide compounds which were detected included endrin (chiton,
average 266 ppt), lindane (chiton and snail, average 175 and 155 ppt, respectively), heptachlor
epoxide (chiton, average 207 ppt) and hexachlorobenzene (mussel and snail, average 301 and 624
ppt, respectively).
3.4.3
Plants
Of the three plant species tested in this study, only DDD was detected in one of the goose
tongue samples (218 ppt).
3.5 Polychlorinated Biphenyls
The 81 tissue samples consisting of
fish, invertebrates and plants were
analyzed for seven commercial PCB
mixtures (Aroclors) and thirteen individual
coplanar PCB congeners. Aroclor 1260
was the only Aroclor detected and was
found only in chinook salmon, chum
salmon, and sea bass. Aroclor 1260 was
detected in 5 of 81 tissue samples
analyzed. Five of the 13 PCB congeners
(114, 126, 157, 169, and 189) were not
detected in any of the tissue samples
analyzed. Figure 20. PCB-Congener Concentrations in Cook Inlet Fish
Tissue Samples (average nanograms per kilogram,
Fish sample concentrations of the ng/kg»PPt)
eight detected PCB congeners (77, 105,
118, 123, 156, 167, 170 and 180) are shown in Figure 20. The only congeners which were detected
in all seven fish tissue samples included 118, 170 and 180. Except in flounder and sea bass, PCB
congener 118 concentrations were present in the highest amount of all the congeners (range of
averages 39 - 593 ppt). In flounder and sea bass, PCB congener 180 concentrations were present
in the highest amount (range of averages 55 - 807 ppt). PCB congener 77 was present in the lowest
concentrations (range of averages 3-9 ppt).
Chinook tissue samples contained concentrations of all the eight detected PCB congeners.
Sea bass tissue samples contained the highest sum of averages of all PCB congeners (2,030 ppt).
Flounder tissue samples contained the lowest sum of averages of all PCB congeners (135 ppt).
• PCB 180 DPCB 170
DPCB 167 BPCB 156
DPCB 123 DPCB 118
28
-------
Butter clam, octopus and snail were the only invertebrate tissue samples with detected PCB
congeners (Figure 21). PCB congener 77 was detected in one butter clam sample (9 ppt). PCB
congeners 118 and 180 were detected in octopus tissue samples (averages ~ 24 ppt). PCB congeners
170 and 180 were detected in snail tissue samples (average 23 ppt and 57 ppt, respectively).
Only one PCB congener was detected in plant tissue samples. PCB congener 118 was
detected in seaweed (average 45 ppt).
Seaweed Octopus
Snail
Figure 21.
3.6 Dioxins and Furans
PCB-Congener Concentrations in Cook
Inlet Invertebrate Tissue Samples
(average nanograms per kilogram, ng/kg)
The 81 tissue samples consisting offish, invertebrates and plants were analyzed for seven
dioxin and ten furan congeners. Dioxins and furans were rarely detected in tissue samples. In the
81 tissue samples analyzed for dioxin and furan congeners, only one congener, OCDD, was detected
in one duplicate chinook salmon sample (13 ppt). Detectable concentrations of dioxins and furans
were not found in other Cook Inlet tissue samples.
29
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[This page intentionally blank.]
30
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4.0 UNCERTAINTIES
4.1 Sampled Species
The extent to which concentrations in the samples analyzed in this study are representative
of concentrations in other Cook Inlet biota consumed by Alaskan tribal villagers is unknown. Not
all fish, invertebrate and plant species consumed in a traditional diet were included in this study.
The chinook captured in 1997 off the Seldovia breakwater and off the beach at Port Graham
are most likely adult fish that have resulted from stocking of hatchery smolts in this area to enhance
local fisheries (L. Pelts, ADFG, pers. comm., February 21, 2001). Data on fin tags, clips or other
hatchery identification were not collected during sampling. Hence, these data contain no definitive
information to distinguish wild versus hatchery or pen-raised fish.
4.2 Age and Size of Specimens
The size of the biota species sampled in this study was intended to be representative of the
size of organisms traditionally harvested by Cook Inlet Alaskan tribal villagers for consumption.
However, contaminant concentrations in specimens smaller or larger than the sizes analyzed in this
study may vary. For example, in this study smaller sized halibut were sampled (see Table 2). Even
though smaller size halibut are eaten, very large halibut which are likely older with higher
contaminant burdens are also eaten. The size of an organism may be correlated with its age. Older
specimens which have longer exposure durations may have higher tissue concentrations of
chemicals that bioconcentrate over time (Gutenmann et al. 1992, USEPA 1995). Organic
contaminants in fish have been shown to increase with age (Armstrong and Sloan 1980, Hansen et
al. 1982). Fish length was positively correlated with total PCB concentrations in chinook salmon
(Miller 1994) and with mercury concentrations in freshwater sportfish (Gilmour and Riedel 2000).
4.3 Timing of Sample Collections
The range of chemical concentrations in the sampled species over time periods that they are
susceptible to harvest by Cook Inlet Alaskan tribal villagers has not been documented. The values
presented in this report reflect chemical concentrations measured in whole body samples collected
during the months of June and July 1997. The tissue concentrations measured in samples during this
study may not be representative of tissue concentrations measured during other times of the year.
It is unlikely that this one-time sampling is representative of contaminant concentrations in these
species over the entire lifetime of a human who consumes these species.
4.4 Harvest Location
Harvest locations were intended to be representative of areas used by members of the four
Alaskan tribal villages of Tyonek, Seldovia, Port Graham and Nanwalek. However, all possible
harvest sites were not evaluated.
31
-------
It was not determined whether harvest locations coincided with sediment deposit!onal areas
or locations where contaminant deposition could be linked with oil and gas operations in Cook Inlet.
Additionally, no samples were collected from harvest sites known to be representative of
background conditions; i.e. where Cook Inlet oil and gas operations would have no influence.
Therefore, due to the sampling design confident conclusions linking identified contaminants to oil
and gas operations can not be made.
4.5 Sample Type
The contaminant concentrations presented in this report are based on analyses of uncooked
whole-body, unsealed fish samples. For the purposes of a contaminant survey, whole-body samples
are representative of exposures to the fish or predators that consume the whole fish. However,
chemical concentrations derived from a whole-body measurement may not be representative of
exposures resulting from consumption of individual body parts.
Specimens were collected such that each fish in a composite sample was of similar size with
the smallest length or weight no less than 75% of the largest (ADL 1997). Compositing of
individual fish limits the information available for chemical concentrations in individual fish.
4.6 Chemical Analytes
One hundred sixty-one analytes were measured in fish, invertebrate, and plant tissues
collected from Cook Inlet. While the chemicals analyzed in this study include ones that have often
been detected in regional and national fish and shellfish monitoring programs (USEPA 1992, Tetra
Tech 1996), a complete analysis of all possible chemical contaminants present in Cook Inlet sampled
species was not conducted. Therefore, the potential presence of other contaminants, including those
which could be associated with oil and gas operations in Cook Inlet, was not analyzed in this study
and is unknown. However, many of the detected analytes have been previously reported in
conjunction with oil and gas operations in Cook Inlet as indicated in Table 2-3.
4.7 Chemical Speciation of Inorganic Chemicals
Seven inorganic chemicals were measured (arsenic, barium, cadmium, chromium, lead,
mercury, selenium). All of these have multiple chemical species (chemical forms). The hazard
potential of the various chemical forms vary from practically nontoxic to very toxic. Except for
arsenic, the various chemical forms were not separately measured. In the case of arsenic, several
chemical forms of arsenic were measured. For this study, the potentially toxic forms which were
measured included trivalent arsenic, pentavalent arsenic, dimethylarsinic acid or arsenosugars
which can be metabolized to dimethylarsinic acid (Le et al. 1999). Dimethylarsinic acid has been
classified by the EPA as a B2 carcinogen (USEPA 2001).
4.8 Concentrations Reported as Not Detected
In determining mean contaminant concentrations, only the detected values were used.
However, the concentration in a sample reported as not detected can actually range from zero up to
the reported detection limit.
32
-------
Detection limits associated with the analytical methods used in this study should be carefully
considered when using these data. In some cases, the detection limits were lower than limits in data
sets for other comparable biota (e.g. polycyclic aromatic hydrocarbons). But, there were also cases
in which detection limits were higher than limits in other data sets (e.g. dioxins and furans). The
reported quantitation limits are provided (Appendix C).
4.9 Effects of Cooking and Preparation
Cooking can change chemical concentrations in fish through volatilization, loss of moisture,
and changes in fat content (Skea et al. 1979). The concentrations of chemicals that tend to
accumulate in fat tissue, such as PCBs, dioxins, and organochlorine pesticides tend to be lowered
by cooking methods that reduce the fat content of the fish sample (Table 12). The cooking process
can also increase the chemical concentrations in fish. Methylmercury binds strongly to proteins and
therefore is found primarily in the muscle tissues offish (Gutenmann and Lisk 1991). The weight
reduction of a fish sample due to loss of moisture and fat content during cooking can increase the
concentration of mercury in the fish tissue that is consumed (Table 12). The smoking offish has
also been shown to increase the concentration of PAHs in processed fish (Zabik et al. 1996).
The fish and invertebrate samples analyzed in this study were uncooked whole-body
samples. The values shown in Table 13 illustrate that an analysis of an individual's exposure to
chemicals in fish based on uncooked samples may be substantially different than their actual
exposure to chemicals in cooked fish.
A wide variety of cooking methods were used in the studies which are summarized in Table
12. Cooking methods included smoking, broiling, deep frying, pan frying, baking, canning and
boiling. This information is reviewed in the USEPA 2000 edition of "Guidance for Assessing
Chemical Contaminant Data for Use in Fish Advisories", Volume 2, Appendix C (USEPA 2000).
An important point which can be observed in the results shown in Table 12 is that, in general, for
organic contaminants in fish cooking appears to result in a decrease of concentration. In contrast
for mercury in fish tissue, cooking may result in an increase in concentration as confirmed by one
study (Morgan et al. 1997).
Table 12. Change in the concentration of chemicals due to various cooking methods.
CHEMICAL
PCBs
Dioxins/Furans
DDT, DDE, ODD
Chlordane
Dieldrin
Mercury
1 Armbruster et al. ( 1 987)
2 Moya etal. (1998)
3 Puffer and Gossett (1983)
4 Salama etal. (1998)
5 Skea etal. (1979)
CHANGE IN CONCENTRATION (%)
6
7
8
9
10
-74 to +4
-80 to -33
-75 to -2
-37 to -39
-21 to -53
+10 to +100
Smith etal. (1973)
Wilson etal. (1998)
Zabik etal. (1979)
Zabik etal. (1995)
Zabik and Zabik (1995)
1,2,3,4,
10,11
3, 5, 6, 7,
10,12
8,10,12
13
11
12
13
REFERENCE
5, 6, 7, 8, 9, 12
8,11,12
Schecter et al. (1998)
Zabik etal. (1996)
Morgan etal. (1997)
33
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[This page intentionally blank.]
34
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5.0 DISCUSSION
5.1 Comparisons of Cook Inlet Fish, Invertebrates and Plants
Average concentrations of total metals across all species ranged from 0.279 ppm to 8.4 ppm
in goose tongue and snail tissue samples, respectively. Average concentrations of total arsenic in
cod, flounder and halibut tissue samples were in the same range as the average concentrations in
bivalve shellfish tissue samples. In contrast, total arsenic concentrations - both the average and the
maximum concentrations - in salmon tissue samples (chinook, chum, and sockeye) were lower than
total arsenic concentrations in all other species' tissue samples, except goose tongue.
Concentrations of inorganic trivalent arsenic (As 3+) detected in flounder tissue samples were in the
same range as As 3+ concentrations detected in blue mussel, butter clam, large clam and steamer
clam tissue samples. In contrast, As 3+ concentrations detected in snail tissue samples were 2 to 10
times higher than concentrations detected in other samples. Dimethylarsinic acid (DMA) was
detected more frequently in invertebrate and plant tissue samples than in fish tissue samples.
Average DMA concentrations in fish were lower than all other samples, except blue mussel and
octopus.
Barium was detected in all tissue samples except seaweed. It was detected in 69 of the 81
tissue samples analyzed. The range of mean tissue concentrations in fish (129 to 912 ppb),
invertebrates (129 to 1063 ppb), and plant tissue samples (112 to 363 ppb) were similar.
The range of average cadmium concentrations in fish tissue samples, 37 to 109 ppb, was
lower than the range of average concentrations in invertebrate tissue samples, 100 to 1123 ppb
(Figure 22). Average cadmium concentrations in snail tissue samples, 4493 ppb, were higher than
all other samples (not shown in Figure 22).
Figure 22.
Cadmium Concentrations in Cook Inlet Fish, Invertebrate and Plant Tissue Samples
(mean and maximum micrograms per kilogram, ug/kg, ppb).
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Methylmercury concentrations in invertebrate tissue samples were approximately ten times
lower than methylmercury concentrations detected in fish tissue samples (Figure 23).
Figure 23.
Methylmercury Concentrations in Cook Inlet Fish and Invertebrate Tissues Samples
(mean and maximum micrograms per kilogram, ug/kg, ppb).
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the Columbia River provided the most comprehensive data set for comparisons to the whole-body
samples collected in this study. These comparisons are intended to provide a general idea of how
concentrations in Cook Inlet tissue samples compare with other locations. Statistical comparisons
of the Cook Inlet data set with other data sets were not possible.
It should be noted that differences in analytical methods, analytical detection limits, the size
of organisms analyzed, lipid content, and timing of sampling may all influence the conclusions
discussed in this section. Some of the reasons that quantitative comparisons were not possible
include: inability to determine whether variances in data sets were comparable, inability to
determine if detection limits and analytical methods in data sets were comparable, inability to
determine whether sampling designs were comparable (e.g. compositing, whole body, etc), and
inability to determine whether species were comparable (e.g. could have been same species/genus
but comparability of age, diet, habitat, etc could not be determined). Therefore, only qualitative
comparisons were made.
The rational for comparison of Columbia River chinook and Cook Inlet chinook is discussed
in this paragraph. Chinook salmon (Oncorhynchus tshawytscha) have two fundamental life histories
referred to as "stream-type" and "ocean-type" life cycles. In North America, stream-type fish, which
include the spring and summer races of chinook salmon, typically occur in northern latitudes and
in the headwaters of more southern rivers. These fish usually spend one or more years rearing in
fresh water before migrating to sea. Ocean-type fish, which includes the fall race, are typically
found south of 56°N on the Pacific Coast and usually migrate to the ocean in their first year of life
(Healey 1991). Chinook salmon typically spend 3 to 4 years (range 2 to 8 years) feeding and
growing in the ocean (Wydoski and Whitney 1979). Cook Inlet chinook salmon are 97 to 99 percent
stream-type fish (Healey 1983). Both the Columiba River chinook and the chinook collected for this
study, in Cook Inlet near Seldovia, Port Graham, and Tyonek, Alaska, are believed to be the stream-
type race of chinook salmon.
5.2.1 Pesticides
Concentrations of organochlorine pesticides in Columbia River Spring and Fall chinook
samples were 3 to 30 times higher as compared to concentrations in Cook Inlet finfish samples even
though dieldrin and endrin were not analyzed in the Columbia River chinook samples (Figure 24).
In Cook Inlet tissue samples, dieldrin and endrin concentrations accounted for ~5 to 15% of the total
mass of organochlorine pesticides (Figure 16). Compared to FDA market basket samples, dieldrin
concentrations in Cook Inlet samples were in the same general range of concentrations - except
"salmon, baked" which was 2 to 20 times higher than any Cook Inlet sample (Figure 25).
37
-------
Figure 24.
Organochlo rine Pesticide
Concentrations in Cook Inlet Fish
Tissue Samples and Columbia River
Chinook Tissue Samples (mean
micrograms per kilogram, ug/kg, ppb)
" ^oc
* C 20
« lis
•1 8*10-
1! «-
u o o
Mean Concentration (ug/kg;
ppb)
i — i
n
II l-l rn „
— i
ll / / ^ / / /
1 1 n
///
Figure 25.
Dieldrin Concentrations in Cook Inlet
Fish Tissue Samples and FDA Market
Basket Samples (average, maximum '-g E 3000
and minimum nanograms per
kilogram, ng/kg, ppt)
0) '*•««'
s^
=;: Annn
•3,4000
C C ocnn
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Average
(max, min)
ng/kg
> i i
t
Comparison Data ^ ^
"
1 0
* T *
T I * ^ *
Q s y x
Average concentrations of
DDT compounds (DDT-total) in
Cook Inlet chinook and sea bass tissue samples were in the range of average concentrations in
Columbia River chinook tissue samples (Figure 26).
O)
Figure 26. o> IOUUU
DDT-total Concentrations in Cook --- 1 4000
— P -lOfififi
Inlet Fish Tissue, Columbia River § « 1200°
Chinook Tissue and FDA Market U §>1UUUU
Basket Samples (average "E 5
nanograms per kilogram, ng/kg, 8 5
Ppt) R to onnn
"J5 m n
i i i i i i
111111
Mean Concentration
(ng/kg, ppt)
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38
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DDT-total concentrations of other Cook Inlet fish samples were less than concentrations in
Columbia River chinook tissue samples (Figure 26). DDT-total accounted for the greatest
percentage of organochlorine pesticides in both Columbia River samples and Cook Inlet Samples.
In Columbia River chinook samples, DDT-total represented 70% of the total organochlorine
pesticides, and in the Cook Inlet samples DDT-total represented 30% to 70% (lowest: sockeye;
highest: cod).
In both Columbia River and Cook Inlet samples, chlordane compounds (sum of alpha-,
gamma-, cis-nonachlor and trans-nonachlor) and hexachlorobenzene were the other major
contributors to the total concentration of organochlorine pesticides (Figure 27). Average
concentrations of chlordane compounds in all Cook Inlet finfish samples were lower compared to
Columbia River chinook results. The approximate average for both Columbia River Spring and Fall
chinook was 5.5 ppb. The highest average concentration of chlordane compounds in Cook Inlet fish
samples was found in sea bass samples (2.5 ppb). Among the Cook Inlet samples, a single
composite sea bass sample had the highest maximum concentration of chlordanes (7.5 ppb). The
maximum concentrations of chlordane compounds in Columbia River Spring and Fall chinook were
approximately 13.3 ppb and 10.8 ppb, respectively. Except for Cook Inlet chinook and sockeye
samples, both the average and maximum hexachlorobenzene concentrations were less than the
average concentrations in Columbia River Spring and Fall chinook (Figure 27). For Cook Inlet
chinook and sockeye samples, the maximum concentrations of hexachlorobenzene exceeded
Columbia R. Spring chinook average concentrations (Figure 27).
Figure 27.
Chlordanes (total) and
Hexachlorobenzene Concentrations
in Cook Inlet Fish Tissue Samples
and Columbia River Chinook Tissue
Samples (average and maximum
nanograms per kilogram, ng/kg, ppt)
c
O
0)
5.2.2
PAHs
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O TO
i!
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annn
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D Chlordanes, total mean & max , ppt
• Hexachlorobenzene, mean &
max, ppt
T_^ 1
1
[% H^ *_ — PL ^
•
H
i Data
i
Comparison of total PAH concentrations between Cook Inlet samples and Columbia River
samples was not possible due to significant differences in the analytical methods used to extract and
detect the individual PAH compounds. An enhanced method was utilized for the the Cook Inlet
samples, hence many individual PAH compounds were detected. The individual PAH compounds,
acenaphthene and 2-methylnaphthalene, were detected in both Cook Inlet chinook samples and
Columbia River Spring chinook samples. Comparisons of concentrations of these two individual
PAH compounds are shown in Figure 28. Average concentrations of both individual PAH
compounds were higher in Columbia River Spring chinook samples as compared to Cook Inlet
chinook samples.
39
-------
Figure 28.
Polycyclic Aromatic Hydrocarbon Compound
Concentrations in Cook Inlet Chinook Tissue Samples
and Columbia River Spring Chinook Tissue Samples
(micrograms per kilogram, ug/kg, ppb)
5.2.3
Dioxins and Furans
.2 '*
C 9" 19
o 3
"*""' £
1 I? 8
o .2
c s
u S
v o. ,
D) M 4
2 E ,
tf ^
^ 0 n -
• ACENAPHTHENE
• 2-METHYLNAPHTHALENE
•
H
•
Comparison
Data
Chinook Columbia R. Spring
Chinook
Figure 29.
OCDD Concentrations in Cook Inlet Chinook and
Columbia River Chinook Tissue Samples
(average nanograms per kilogram, ng/kg, ppt)
In the Columbia River composite
Spring and Fall chinook samples, basin wide
average concentrations of the sum of
chlorinated dioxins and furans were
approximately 2 ng/kg. In Columbia River
Spring chinook samples, 17 different dioxin
or furan congeners were detected. While in
Columbia River Fall chinook samples, 9
different dioxin or furan congeners were
detected. However, the analytical detection
limits in methods used for the Cook Inlet
tissue samples were higher than the analytical
detection limits in methods used for the
Columbia River tissue samples. For example,
for 2,3,7,8-TCDD the Cook Inlet study
detection limits were 70 times higher than
limits in the Columbia River Study.
OCDD concentrations were detected in one of six Cook Inlet chinook composite samples.
In the Columbia River samples, OCDD was detected in 21 of 24 Spring chinook samples and 3 of
15 Fall chinook samples. OCDD average concentrations in the Cook Inlet chinook sample were
approximately 40 times higher than basin wide average concentrations detected in Columbia River
Spring or Fall chinook samples (Figure 29).
14
o ^ 12
15
g E 10
o 8" R
0 | 8
-------
concentration of Cook Inlet chinook samples was slightly higher than the FDA market basket baked
salmon sample; however, both the average and maximum mercury concentrations were lower than
concentrations in Columbia River Spring and Fall chinook and FDA market basket canned tuna
samples. In Cook Inlet sea bass samples, the average mercury concentration was similar to average
concentrations in Columbia River Spring and Fall chinook. In contrast, Cook Inlet sea bass mercury
concentrations were higher than FDA market basket baked salmon samples and less than FDA
market basket canned tuna samples (Figure 30).
325
300
_ 275
u> 250
£ 225
o> 200
175
o —
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ra S
i_ (3
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n
^ (Q
PP )
» Mean (ug/kg, ppb)
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T
T l
T
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Average and maximum cadmium concentrations in Cook Inlet snail tissues samples greatly
exceeded all other samples' tissue concentrations (4,493 and 10,100 ug/kg, respectively). Cook Inlet
octopus tissue samples had the next highest cadmium concentrations. Average cadmium
concentrations in Columbia River Spring chinook samples were slightly higher than Cook Inlet
chinook samples.
Only maximum concentrations were available for FDA market basket samples (Figure 31).
Cadmium concentrations in all the Cook Inlet samples were higher than the maximum
concentrations in FDA market basket samples.
A report by the Agency for Toxic Substances and Disease Registry states, "Cadmium has
been detected in nearly all samples of food analyzed with sufficiently sensitive methods." and
"Shellfish, liver and kidney meats have higher concentrations than other fish or meat (up to 1 ppm).
Particularly high concentrations of cadmium of 2-30 mg/kg (ppm) have been found in edible meat
of marine shellfish" (ATSDR, 1999). In this study, mean cadmium concentrations in tissue samples
were less then 30 ppm, the high end of the ATSDR range.
5.3 Nutritional Comparisons
The nutritional composition of Cook Inlet tissues sample in this study was not measured.
The values shown in Table 13 were obtained from the literature (USDA 2003). In Table 13, the
nutrient composition of the tissue types collected in this study are compared with commercial
protein foods (chicken, hamburger, pork, lamb) or green vegetables (broccoli, celery). Based on the
published values, the fish and invertebrate tissue are assumed to be lower in saturated fat, higher in
Vitamin A and selenium, and provide more energy from protein than from fat as compared to the
chicken, hamburger,
pork and lamb shown in ^
@
the table. Seaweeds are 5 ^
higher in protein, energy, j? 45 _ a ^
calcium and iron than
broccoli or celery.
Table 13.
Nutrient Composition of
Foods (per 100 grams)
Food Item
Chinook Salmon, raw
Chum Salmon, raw
Sockeye Salmon, raw
Sea Bass, raw
Cod, raw
Flounder, raw
Halibut, raw
Mussel, raw
Clam, raw
Chiton, raw
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81.8
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94.6
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5.5 Conclusions
Seven fish species, eight invertebrates and three plant species were sampled and analyzed
for concentrations of 161 chemicals. These results provide a good survey data set for environmental
chemicals present in uncooked, whole body samples of these Cook Inlet biota. There were
detections of global contaminants: mercury, organochlorine pesticides, and PCB congeners. There
was minimal detection of another ubiquitous contaminant group, dioxins and furans. The minimal
detection of dioxins and furans may be an artifact of the analytical detection limits associated with
the methods used in this study. The detection of many individual PAH compounds in the Cook Inlet
tissue samples may have resulted from the use of enhanced analytical methodology. Approximately
one-half of the 104 PAHs were detected in fish, invertebrate and plant samples. Chinook tissue
samples had the highest total average PAH concentration (253 ppb). This gives the appearance of
relatively high total PAH concentrations. However, this is an uncertain finding which would benefit
from additional verification.
Although the EPA has no current plans for additional studies, these results can contribute
important information to the design of future investigations undertaken by others. Since most trace
metals naturally occur in biota and many organic chemicals are worldwide contaminants, it will be
important for future study designs to carefully consider the comparison or control data set that will
be needed.
In addition, this report provides the individual data on an accompanying compact disk
(Appendix C). With these data, other queries can be made. For example, segregating data and
calculating descriptive statistics (e.g. mean concentrations) by location (e.g. beach collection sites)
or by group characteristics (e.g. hatchery salmon and wild salmon) may provide another view of the
results. The evaluation of polycyclic aromatic hydrocarbon patterns may also provide additional
insight. The availability of these data is a significant product of this study (Appendix C).
43
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[This page intentionally blank.]
44
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