United States
Department of
Commerce
National Oceanic and Atmospheric Administration
Environmental Research Laboratories
Seattle WA98115
United States
Environmental Protection
Agency
Research and Development
Office of Energy, Minerals, and
Industry
Washington DC 20460
EPA-600/7-79-164
July 1979
Investigation of
Petroleum in the
Marine Environs of the
Strait of Juan de
Fuca and Northern
Puget Sound
Interagency
Energy/Environment
R&D Program
Report
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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INVESTIGATION OF PETROLEUM IN THE MARINE ENVIRONS OF
THE STRAIT OF JUAN DE FUCA AND NORTHERN PUGET SOUND
Donald W. Brown, Andrew J. Friedman, Douglas G. Burrows,
George R. Snyder, Benjamin G. Patten, Warren E. Ames,
L. Scott Ramos, Patty G. Prohaska, Donald D. Gennero,
D. Douglas Dungan, Marianne Y. Uyeda, and William D. MacLeod, Jr.
NOAA National Analytical Facility
Environmental Conservation Division
Northwest and Alaska Fisheries Center
National Marine Fisheries Service
2725 Montlake Boulevard East
Seattle, Washington 98112
Prepared for the Marine Ecosystem Analysis (MESA) Puget Sound
Project, Seattle, Washington in partial fulfillment of the
Environmental Interagency Agreement #D6-E693-EN
Program Element EHE625-A
EPA Project Officer: Clinton W. Hall (EPA/Washington, D.C.)
NOAA Project Officer: Howard S. Harris (NOAA/Seattle, WA)
This study was conducted
as part of the Federal
Interagency Energy/Environment
Research and Development Program
Prepared for
OFFICE OF ENERGY, MINERALS, AND INDUSTRY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
March 1979
-------
Completion Report Submitted to
PUGET SOUND ENERGY-RELATED RESEARCH PROJECT
MARINE ECOSYSTEMS ANALYSIS PROGRAM
ENVIRONMENTAL RESEARCH LABORATORIES
by
NORTHWEST AND ALASKA FISHERIES CENTER
NATIONAL MARINE FISHERIES SERVICE
NATIONAL OCEANIC AND ATMOSPHERIC ADMINISTRATION
2725 MONTLAKE BOULEVARD EAST
SEATTLE, WASHINGTON 98112
This work presents results of research sponsored by the Environmental
Protection Agency and administered by the National Oceanic and Atmospheric
Administration (NOAA).
NOAA does not approve, recommend, or endorse any proprietary product or
proprietary material mentioned in this publication. No reference shall be
made to NOAA in any advertising or sales promotion which would indicate or
imply that NOAA approves, recommends, or endorses any proprietary product or
proprietary material mentioned herein, or which has as its purpose an intent
to cause directly or indirectly the advertised product to be used or purchased
because of this publication.
11
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FOREWORD
Substantially increased petroleum transfer and refining activities are
anticipated in the Northern Puget Sound and Strait of Juan de Fuca areas.
These activities will increase the chances of chronic and/or acute oil inputs
into the marine environment. To provide a basis for measuring future changes
in environmental levels of petroleum, a regional study was undertaken. This
study was conducted in a region in which only limited amounts of petroleum
constituents have been spilled or leaked; however, this region may experience
increased petroleum inputs in the future due to the increasing volume of
petroleum to be shipped, handled and/or refined. The research was conducted
by the Northwest and Alaska Fisheries Center in Seattle. It was a major part
of an environmental assessment of the region, supported by the U.S.
Environmental Protection Agency and administered by the NOAA Marine Ecosystem
Analysis Puget Sound Project.
ill
-------
ABSTRACT
The Northern Puget Sound and Strait of Juan de Fuca regions have
accommodated the transportation and refining of petroleum without serious
problems from spilled oil. However, proposed activities related to the
transport and use of petroleum in these regions increase the chances of
significant additions of petroleum to this marine environment. This project
was designed to provide an accurate and reliable set of data against which
future levels of petroleum compounds can be compared.
This investigation was initiated in February, 1977, to measure existing
levels of petroleum in Northern Puget Sound and the Strait of Juan de Fuca,
and to investigate spatial and temporal trends in occurrence, concentration,
and composition of petroleum-related hydrocarbons. Sediment and/or mussel
samples from 23 beaches located strategically along shipping lanes in the
Strait of Juan de Fuca, San Juan Islands, and Northern Puget Sound were
analyzed for n-alkanes and aromatic hydrocarbons.
All 23 sites were relatively free from petroleum contamination.
However, hydrocarbons indicative of petroleum were found at Ediz Hook, March
Point, Kydaka Point, Dungeness/Three Crabs, Baadah Point, Sandy Point, Cherry
Point, and False Bay. Hydrocarbon concentrations were generally consistent
for the quarterly samples from individual sites and also from samples taken at
one site every two weeks for three months.
IV
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TABLE OF CONTENTS
Page
Foreword. . ill
Abstract Iv
Figures vii
Tables viii
Acknowledgements ix
Introduction. 1
Overview 3
Conclusions 7
Recommendations 9
Sampling Design Study ......... 10
Methods and Materials 10
Results and Discussion 10
Hydrocarbon Baseline Study 12
Methods and Materials 12
Site Selection 12
Sample Collection 13
Field Observation 14
Laboratory Studies 14
Statistical Treatment of Data 17
Results 18
Field Observations 18
Microgravimetric Determination
of total saturated and total
unsaturated hydrocarbons 18
Gas Chromatographic Analysis 18
Mussel Lipid and Dry Weight Data 21
Sediment Analysis 21
Discussion 26
Evaluation of Hydrocarbon Sites 26
Ediz Hook 26
March Point 27
Baadah Point 27
Kydaka Point 27
Cherry Point 27
False Bay 27
Andrews Bay 28
Dungeness/Three Crabs 28
Sandy Point 28
Shannon Point 28
V
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Page
Individual Hydrocarbons 28
Naphthalene 28
Phenanthrene 29
Benzanthracene 29
Petroleum Contamination , 29
Temporal Variability Study 31
Methods and Materials 31
Results and Discussion 31
Beach Variability Study 35
Methods and Materials 35
Results and Discussion 35
References 37
Appendix I. Data Processing Information 40
Data Location 41
Sample Collection Report 42
Field Data Codes 43
Data Format 45
Appendix II. Field Information 46
List of Sites 47
Description of Sample Sites 48
Beach Characteristics 51
Maps and Photographs of Sites 54
Appendix III. Analytical Procedures , . 77
Materials 78
Tissue Extraction 79
Sediment Extraction 80
Silica-gel Chromatography 81
Gas Chromatography 82
Gas Chromatography/Mass Spectrometry 85
Dry Weight Determination 86
Microgravimetric Determination 86
Appendix IV. Individual Hydrocarbon Data Tabulated per
Site per Quarter 87
VI
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FIGURES
Number Page
1. Sampling sites in the Strait of Juan
de Fuca and Northern Puget Sound 2
2. Gas chromatogram of the saturated
hydrocarbons from Prudhoe Bay crude oil 5
3. Gas chromatogram of the saturated
hydrocarbons from Dungeness intertidal
sediment 5
4. Gas chromatogram of aromatic hydrocarbons
from Prudhoe Bay crude oil 6
5. Gas chromatogram of aromatic hydrocarbons
from an extract of Duwamish River sediment ... 6
6. Sediment sampling implements 14
7. Sediment analysis scheme 15
8. Mussel analysis scheme 16
9. Pristane/phytane ratios for quarterly sediment
and mussel samples 23
10. Phenanthrene in quarterly sediment and mussel
samples 24
11. Benz[a]anthracene in quarterly sediment and
mussel samples 25
Vll
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TABLES
Number Page
1. Hydrocarbon classes, types, and structures
found in refined petroleum products ....... 4
2. Heptadecane in individual sediment samples
at three tidal heights at March Point ...... 11
3. Analyses performed on sediment and mussel
samples .......... .......... 17
4. Total saturated and unsaturated hydrocarbons
in quarterly samples of sediment and mussel
tissue ..................... 19
5. Sum of the concentrations of selected alkanes
and aromatic hydrocarbons in seasonal samples
from each site ................. 20
6. Total lipid and total solids in mussel tissues . 22
7. Organic carbon and sand-to-mud ratio for
sediments .................... 22
8. Hypothetical values of petroleum in dry
sediment assuming all UrCooH. o came
from crude oil containing 0.2% S.~C0H
2042 .....
9. Summary of analytical results from Temporal
Variability Study at March Point ........ 32
10. Concentrations of alkanes and aromatic
hydrocarbons in March Point sediments at
2 week intervals from 9-21 to 11-31 (1977) ... 33
11. Alkanes and aromatic hydrocarbons in March
Point mussels collected at 2 week intervals
from 9-21 to 11-30 (1977) ............ 34
12. Selected data from Beach Variability Study ... 36
viii
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ACKNOWLEDGEMENTS
The work described in this report was performed for the Marine
Ecosystems Analysis (MESA) project. The research was sponsored by the
Environmental Research Laboratories (ERL) MESA Puget Sound Project and was
conducted from February, 1977, to April, 1978.
We would like to express our appreciation to Neva L. Karrick,
coordinator of MESA programs for Northwest and Alaska Fisheries Center
(NWAFC); to Robert C. Clark, Jr. for advice on the initiation of the program;
to Murray Amos for assistance in statistical treatment of data; to
Stephen Parkhill, Gordon Bagley, Paul Darant, and David C. Slade for their
assistance in sample collections; and to National Analytical Facility
personnel, Debra L. Safranek, Russell L. Dills, Victor D. Henry,
Rand G. Jenkins, Joseph L. Schwahn, Teresa I. Scherman, Orlando Maynes, and
Margaret M. Krahn. Raymond W. Riley, MESA and Dean H. Dale and Sidney D.
Stillwaugh, Environmental Data and Information Services, provided technical
assistance with data documentation for this project.
We would also like to express our appreciation to Colleen M. Annis,
Darlene J. Hoover, Christine C. Schneider, Lorna M. Koop, and
Marguerite C. Morey for manuscript typing; to Colleen L. Browne for assembling
and editing various drafts of this report; and to James H. Peacock and
Carol E. Hastings for graphics support.
We acknowledge the following for allowing site access: U.S. Coast Guard,
Crown Zellerbach Co., Merrill-Ring Co., Clallam Co. Parks, Cape George Colony,
U.S. Navy, Seattle Pacific University, Western Washington State University,
MarVista Resort, Puget Sound Power and Light Co. and Birch Bay Village,
Washington State Parks Dept., Webb Camp, Del Mar Estate, Mrs. R. Simmons, and
E. Marshall.
The report was prepared for the MESA Puget Sound Project,
Dr. Howard S. Harris, Manager; the contract was supervised by Edward R. Long
of Dr. Harris' staff.
ix
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INTRODUCTION
This investigation was part of a major interdisciplinary study to
determine the potential effects of increased petroleum transport and refining
activities in the Strait of Juan de Fuca and Northern Puget Sound. The
overall study, funded by the Environmental Protection Agency (EPA) and
administered by the Marine Ecosystem Analysis (MESA) project, was established
to focus the capabilities of NOAA and of Federal, state, and local agencies
upon specific environmental problems through intensive research projects.
Thus far, MESA has funded more than 20 research investigations designed to
help provide a large environmental data base for the region upon which future
regulatory, socioeconomic, and resource management decisions may be based (1).
Studies are being conducted to help define the physical and chemical
oceanography of the Greater Puget Sound area, the abundance and distribution
of the aquatic biota in the area, and the present levels of petroleum
hydrocarbons in sediments and aquatic organisms. The establishment of models
derived from these studies should help in predicting oil spill trajectories
and potential trophic pathways, and in the assessment of environmental impacts
of an oil spill if one occurs in these waters.
The Northern Puget Sound and Strait of Juan de Fuca regions have
accommodated the transportation and refining of petroleum for years without
serious problems from oil spills. However, with the recent increase in tanker
transport of crude oil in this region, the risk of a major spill increases.
Knowledge of the presence and the distribution of current levels of petroleum
is necessary to establish a base to assess future changes and to determine
whether petroleum compounds are increasing in this environment.
In 1975, the MESA Puget Sound Project Office held workshops to help
identify productive areas of research which could achieve MESA goals, and it
invited the Northwest and Alaska Fisheries Center (NWAFC) of the National
Marine Fisheries Service (NMFS) to participate. Since the NWAFC had the
chemical and biological expertise and the needed facilities, MESA authorized a
pilot study during 1976 to study techniques for sample collection and analysis
of petroleum hydrocarbons (2). This pilot study established field sampling
and laboratory analysis methodologies suitable for investigating baseline
levels of hydrocarbons in the intertidal zone.
This investigation is an extension of that pilot study^ It was
initiated during February, 1977, to measure existing levels of petroleum in
Northern Puget Sound and the Strait of Juan de Fuca, and to investigate
spatial and temporal trends in occurrence, concentration, and composition of
petroleum-related hydrocarbons. The principal objective was to provide an
accurate and reliable set of data against which future levels of petroleum
compounds can be compared. To this end, sediment and/or mussel samples were
collected and analyzed from 23 beaches located strategically along shipping
lanes in the Strait of Juan de Fuca, San Juan Islands, and Northern Puget
Sound (Fig. 1).
An initial experiment was conducted to establish the variability of
hydrocarbon levels among individual sediment samples along a 30-m stretch of
1
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1. Birctl Pomi
13. Ltgoe Bay. Lutnm
5. Shannon Point
6. Alexander Beach
, 9. Naval Air Station
7. Fort Casey
8. Keystone
16. Dungeness Spit
17. Ediz Hook
1 5. Dungeness Town
14. Cape George
£>
19. Deep Creek Beach
20. Deep Creek
21. Pillar Point
Figure 1. Sampling sites in the Strait of Juan de Fuca and Northern Puget
Sound. Dotted lines denote shipping lanes
-------
beach and the variability of hydrocarbon levels in sediment samples relative
to tidal height. This initial study, described in the Sampling Design Study,
was conducted during March, 1977. The data resulting from this investigation
were used to design the quarterly sampling protocol. Quarterly sampling,
described in the Hydrocarbon Baseline Study, began in April, 1977, and
continued through February, 1978. Other experiments included (a) studies of
variability of hydrocarbon levels at a single beach over short periods of
time, and (b) comparisons of variabilities in hydrocarbon levels at six
beaches. These experiments are described in the Temporal Variability and
Beach Variability sections of this report. Preliminary findings have been
previously documented in monthly reports to MESA and in oral reports at two
meetings of the MESA Puget Sound project. For clarity, the results are
described in four separate sections.
Overview
Petroleum and its products enter Northern Puget Sound and the Strait of
Juan de Fuca primarily from petroleum transport, petroleum refining
operations, shipping, boating, municipal and industrial effluent, and possibly
natural seepage. Accidental spillage of crude oil from tanker operations is a
potential source of petroleum contamination in these regions (3). If petroleum
spillage occurred, the intertidal zone would probably be seriously
contaminated because of its constant exposure to surface water. Hydrocarbons
are known to accumulate in sediments and may be retained there for periods
ranging from months to years (4,5). Mussels are sedentary organisms that may
concentrate hydrocarbons from the water column and can also depurate them (6).
Therefore, appropriate sampling and analysis of these two substrates should
provide information on exposures of the intertidal zone to hydrocarbons.
Detecting and monitoring environmental intrusion by petroleum are
complicated by the complex composition of petroleum and by the numerous
sources of many hydrocarbons. Petroleum is a complex mixture of thousands of
compounds that vary considerably in relative abundances (7,8). The compounds
are mainly hydrocarbons that range in size from 1 to more than 70 carbon atoms
and may be arranged in classes having similar chemical characteristics. Clark
and Brown (7) classified petroleum hydrocarbons according to Table 1.
Aliphatic hydrocarbons may be saturated or unsaturated, straight chain,
branched chain or cyclic. Aromatic hydrocarbons are highly unsaturated cyclic
hydrocarbons that may be of particular significance because of their potential
biological effects. In addition, petroleum contains many heteroatomic
compounds and metallic constituents.
Many of the hydrocarbons present in the environment also arise from non-
petroleum sources, such as biological materials (5,8,9) and products of
combustion (10,11,12). However, certain distinguishing characteristics permit
partial differentiation between petroleum and non-petroleum hydrocarbons.
These consist mainly of differences in the occurrence and relative abundance
of specific hydrocarbons and classes of hydrocarbons from a given source. The
n-alkanes are quite often the predominant compounds in petroleum. These
alkanes usually have a regular odd-even carbon number distribution throughout
the molecular weight range (Fig. 2) (i.e., the concentration of adjacent
n-alkanes is almost equal). Such a pattern of the n-alkanes indicates a fossil
-------
origin of the hydrocarbons (13). The ri-alkanes produced by recent biological
processes are predominantly odd-carbon numbered (Figure 3) (13,14), as opposed
to the regular odd-even distribution of n-alkanes in petroleum (Fig. 2).
Additionally, the branched-chain alkanes, pristane and phytane, are both
present in petroleum at about the same concentration. Both are also produced
by biogenic processes, but some researchers have found that phytane generally
is not as abundant as pristane (14); thus high ratios of pristane to phytane
abundance may indicate biogenic input.
Table 1. Hydrocarbon classes, types, and structures found in refined
petroleum products.
Molecular Structure
Class
Type
Arrangement of
carbon atoms
Characteristic
bonding
Aliphatic
Alicyclic
Aromatic
Paraffin (alkanes)
Olefins (alkanes)
Cycloparaffins
Cyclo-olef ins
(various types)
Open chain,
straight or branched
Open chain
straight or branched
Closed chain,
(cyclic or ring)
Closed chain,
(cyclic or ring)
Closed chain
(benzenoid ring)
Saturated
Unsaturated
Saturated
Unsaturated
Unsaturated
Due to the chemical complexity of petroleum, often a limited number of
individual compounds common to petroleum are chosen to obtain an indication of
the amount of petroleum present. The abundance of pristane, phytane, and the
C.Q-C,, n_-alkanes are commonly used to indicate the occurrence of
petroleum (13). More recently, data on individual aromatic hydrocarbons are
also being reported for this purpose (7).
The aromatic hydrocarbons in petroleum are characterized by a high
proportion of alkyl substituted homologs compared to their unsubstituted
counterpart, e.g., the ratio of the methylphenanthrene peaks to the
phenanthrene peak in Figure 4. In non-petroleum sources, such as products of
combustion processes, the unsubstituted polynuclear aromatic hydrocarbons of 3
or more rings predominate over their substituted homologs, as in
Figure 5 (11,12).
-------
JJ
.'.. ,'...' ..
Figure 2. Gas chromatogram of the saturated hydrocarbons from Prudhoe
Bay crude oil. C denotes n-alkane of given chain length
n. Conditions were: 30 m x 0.25 mm WCOT glass column
coated with SE-30. 2 yL splitless injection, vaporization
at 280°C, split 10:1 after 18 sec with 22 psig helium
carrier gas. Column temperature 40° for 5 min, then
programmed to 270°C at 4° per min.
u
Pr i stone Phytane
15 C|6 C|7/ C,Q/ C,
Figure 3. Gas chromatogram of the saturated hydrocarbons from
Dungeness/Three Crabs intertidal sediment. Cn denotes
n-alkane of chain length n. Conditions same as for
figure 2, except column coated with SE 54.
-------
Figure 4. Gas chromatogram of aromatic hydrocarbons from Prudhoe
Bay crude oil. Conditions same as for figure 2, except
column coated with SE 54.
:-
Gas chromatogram of aromatic hydrocarbons from an extract
of Duwamish River sediment, Elliott Bay, Seattle, Washington.
Conditions same as for figure 2, except column coated with
SE 54.
-------
CONCLUSIONS
The Northern Puget Sound Study was conducted to establish the existing
degree of petroleum pollution, and to develop data concerning spatial and
temporal trends in occurrence, concentration, and composition of
petroleum-related hydrocarbons. Petroleum can accumulate in sediments, and
components of petroleum in both sediments and the water column can be absorbed
and depurated by organisms. The substrates chosen to indicate the present
concentration of petroleum hydrocarbons were sediments and mussels. Mussels
are sedentary organisms and filter feeders that presumably would reflect the
current petroleum hydrocarbon concentrations in their environment.
A Sampling Design Study was conducted to establish the optimum composite
sample size, the variability of hydrocarbon levels between samples at a given
tidal height, and the variability of hydrocarbon levels in sediment at
different tidal heights. To this end ten sediment samples were collected at
random points along a 30-m line at tidal heights of 0.6, 0.9, and 1.2 m.
Results from this inital study showed that hydrocarbon levels were higher at
the 0.6-m height than at either the 0.9- or 1.2-m heights. We also decided
that ten 50-g sediment samples collected at random positions along a 30-m
length of beach at the 0.6-m tidal elevation could be composited for a sample
representative of the beach. We decided that thirty mussels would be
collected as close to the sediment sampling area as possible, and a sample of
the homogenized composite used for analysis.
The major objective of the Hydrocarbon Baseline Study was to measure
concentrations of hydrocarbons present in intertidal sediments and mussels
along the Strait of Juan de Fuca and Northern Puget Sound. Samples were
collected from 23 beaches adjacent to shipping lanes in the Strait of Juan de
Fuca, San Juan Islands, and Northern Puget Sound on a quarterly basis
beginning April, 1977, and ending February, 1978.
Results from the analyses showed that the sum of C,2 to CjQ
concentrations were generally much higher for the mussels than the
corresponding values for the sediments. The average value for mussels was
900 ng/g dry weight compared to 50 ng/g dry weight for sediment. This
difference is probably due to biological factors.
The results of the quarterly sampling study showed that all sites were
relatively free from petroleum contamination. The average of the sums of the
concentrations of C1 2 to C?Q n-alkanes in sediment samples collected
quarterly, in order of decreasing values, were: Ediz Hook (150 ng/g); March
Point and Kydaka Point (100 ng/g); Dungeness /Three Crabs (86 ng/g); Baadah
Point (55 ng/g); Sandy Point (47 ng/g); Cherry Point (33 ng/g); and False Bay
(8 ng/g) as compared to the average result of 32 ng/g from the other
11 beaches sampled for sediments. Some of the other 11 beaches showed
hydrocarbons that were probably from biological sources which caused their
sums to be high. The quarterly averages of the sum of ten selected aromatic
hydrocarbons, in decreasing order, were: False Bay (42 ng/g); March Point
(39 ng/g); Kydaka Point (29 ng/g) Baadah Point and Sandy Point (19 ng/g);
Dungeness /Three Crabs (13 ng/g); Cherry Point (9 ng/g); and Ediz Hook (8 ng/g)
as compared to the average result of 3 ng/g for the mussels from the other ten
-------
beaches. The hydrocarbons at Ediz Hook, Baadah Point and March Point probably
resulted from local industries," municipal input, and/or boating activities.
The Dungeness/Three Crabs beach, a site generally considered to be pristine,
contained higher concentrations of petroleum-related hydrocarbons than the
14 sites not discussed above. The lowest concentrations were measured at the
Naval Air Station site on Whidbey Island.
We conducted a study to determine if there were major short-term changes
in hydrocarbon concentrations (Temporal Variability Study). We collected
sediment and mussel samples at March Point six times, at approximately two
week intervals, beginning September 21, 1977. The results showed the alkane
concentrations in sediment were generally consistent over short time periods,
e.g., the C,2 to C2Q n-alkane sums ranged from 82 to 113 ng/g dry weight
(average value 94 ng/g). The values from four quarterly sampling events
ranged from 87 to 124 ng/g (average value 100 ng/g). The results for the
aromatic compounds were more variable than for the alkanes. The values for a
compound generally were consistent for these sampling events, which implies
that major changes in concentrations did not occur over short time periods.
The results indicate that seasonal mussel variability and short-term
variability apparently were not greatly different.
Since the protocol of the baseline study called for an analysis of
composited samples from each beach, it was important to determine if the
differences in reported hydrocarbon concentrations were due to differences in
hydrocarbon levels between sites. To this end we conducted a Beach
Variability Study, in which duplicate sediment composites were analyzed from
Cherry Point, March Point, Andrews Bay, Dungeness/Three Crabs, Tongue Point,
and Baadah Point from the spring and summer quarters. The results for
duplicate samples from these six beaches were rather consistent and were
similar to those for replicate analyses of single samples. For example, the
sum of the concentrations of selected alkanes at March Point averaged 119 ng/g
(range 82 to 158). These values were lowest at Tongue Point, having an
average value of 19 ng/g (range 14 to 22). Excepting the Andrews Bay spring
sample, the average of the sum of the concentrations of selected aromatic
hydrocarbons was highest at March Point (63 ng/g, range 26 to 97) and lowest
at Tongue Point (2 ng/g,, range 0 to 3), indicating that the differences noted
between beaches are real.
8
-------
RECOMMENDATIONS
Quarterly monitoring should continue a second year but at a reduced
level; i.e., only sediment samples should be analyzed from the following sites
in Northern Puget Sound and the Strait of Juan de Fuca:
1. Baadah Point
2. Kydaka Point
3. Crescent Bay
4. Ediz Hook
5. Dungeness spit
6. NAS Whidbey Island
7. March Point
8. Andrews Bay
9. Cherry Point
10. Birch Point
Benzo(a)pyrene (BAP), a carcinogen, was found in sediments at March
Point (as high as 16 ppb). It should be determined whether the BAP is
available to the marine organisms that contact these sediments or whether the
BAP is biologically inert because of physical or chemical factors such as
binding of the BAP to the sediments.
-------
SAMPLING DESIGN STUDY
The Initial study in this project was undertaken in February, 1977, to
establish the optimum number of samples needed to prepare a composite sample
for sediment analysis, and to determine the variability of hydrocarbon levels
in sediments at different tidal heights. March Point was the site chosen for
this study because we anticipated that petroleum hydrocarbons would be present
due to its proximity to refinery operations. Results from this study were
used to design sediment sampling procedures for the remainder of the
investigation.
Methods and Materials
Sediment samples were collected at March Point in February, 1977. Three
30-m lines, premarked at 1-m intervals, were placed along the 0.6-, 0.9-, and
1.2-m beach contours. Elevations were gauged from mean lower low water; tidal
elevations were calculated from U.S. Department of Commerce tide tables (15).
Ten sampling points along each line (total of 30 points) were chosen from
tables of random numbers. Duplicate sediment cores (1 for analysis and 1 for
reserve) were collected at the selected points (total of 60 samples).
Individual prewashed, solvent-rinsed cans served as combination corer-storage
containers. Prewashed, solvent-rinsed stainless-steel spatulas were used to
keep the sediment core intact and the can full upon withdrawing the sample.
Each can of sediment was covered with solvent-rinsed aluminum foil and stored
on ice until received in the laboratory, then stored frozen at -20°C until
analysis.
The entire sample in each can, about 200 g, was weighed into an
extraction bottle to avoid variability due to sub-sampling. The samples were
extracted and analyzed using the methods and materials described in Appendix
III. The fractions containing the saturated hydrocarbons were analyzed by gas
chroma tography, and heptadecane was quantitated in each extract. These values
were used to estimate the variability of sampling and analysis*
Results and Discussion
The concentration of heptadecane (^~C,jR^) appeared to correlate with
the concentrations of the other ii-alkanes in tnese samples; i.e., if the
was high, the other n-alkanes appeared to be high. Therefore, the
concentration was chosen for quantitation and interpretation. The
ng data are listed in Table 2.
_
nj-C.yH^
resulti
10
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Table 2. Heptadecane n-C.. yH^g in individual sediment samples
at three tidal heights at March Point.
Tidal Height
0.6-m
0.9-m
1.2-m
26,
32,
21,
15,
40,
15,
Heptadecane
ng/g wet weight
24, 38, 39, 35,
12, 22, 16,
11. 17, 11, 10,
17
9,
7t
, 16,
6, 4,
8, 9,
11, 17
10
35
Ave rage
24
17
16
The highest average concentration of n-C^H^ was found at the 0.6-m
tidal elevation. Fine grain sediments which were selected for analysis were
most consistently found at the 0.6-m level or lower at the proposed sampling
sites.
The results were used to establish the following protocol to obtain
sediment samples for the major study:
a. Samples of about 50 g each would be collected along a 30 m length
of beach at the 0.6-m tidal elevation.
b. Each sample would be taken with an aluminum or stainless steel
corer device 5.5-cm dia. x 2-cm h (47 cm ).
c. The core would be cut "cookie-cutter" fashion with a steel spatula
slipped underneath to lift the core intact. The spatula would be
used to scrape excess sediment from the core and the sample would
then be placed into a 16-oz sample jar.
d. Ten samples so collected would be combined to form a single
composite sediment sample of about 500 g, from which 100 g would
be used for hydrocarbon analysis, 20 g for dry weight
determination, and 100 g for total organic carbon (TOG) and grain
size determination.
11
-------
HYDROCARBON BASELINE STUDY
The major objective of this investigation was to determine the amounts
of hydrocarbons along the Strait of Juan de Fuca and Northern Puget Sound.
Twenty-three sites were chosen for sediment and/or mussel collection (Fig. 1).
Sediment and mussel samples were collected quarterly in the intertidal zone of
beaches adjacent to shipping lanes beginning April, 1977, and ending February,
1978.
Methods and Materials
MacLeod et al. (2) reported the methods used during the 1976 pilot study
to extract and analyze hydrocarbons from sediments and mussels. We later
found that the sediment procedure adopted in that study was less efficient
than the exhaustive Soxhlet method (16). We modified the tumbling method to
obtain extraction efficiencies comparable to Soxhlet extraction (17). The
mussel procedure used was basically the same as described in the pilot study.
Both procedures are given in detail in Appendix III.
Many of the sampling sites in the Northern Puget Sound and Strait of
Juan de Fuca region were considered to be relatively pristine areas;
therefore, the hydrocarbon levels were expected to be low. Consequently, the
most sensitive analytical techniques available were needed to measure trace
hydrocarbon levels in complex mixtures. Gas chromatography using
high-resolution, glass capillary columns provided the desired sensitivity and
resolution (2,18). The data from hydrocarbon analyses were reported to
Environmental Data and Information Services/National Oceanographic Data Center
(EDIS/NODC) on computer paper punch cards (Appendix I).
Site Selection. Criteria for selection of sample sites along the Strait of
Juan de Fuca and Northern Puget Sound included: (a) exposure to the oil tanker
lanes extending from the entrance of the Strait of Juan de Fuca through the
San Juan Islands and north along Northern Puget Sound to the Canadian border;
(b) availability of relatively fine grained sediment at the 0.6-m tidal
elevation (Sampling Design Study) along a minimum distance of 30 m on a beach;
(c) availability of a population of mussels of a length of 3 to 5 cm within
the 0.6- to 0.9-m tidal elevation in sufficient quantities for quarterly
sampling; and (d) availability of both sediment and mussels within 1 km of
each other at each site.
Under these conditions, 23 sampling sites were established (Fig. 1).
Mussel and sediment sites were generally less than 0.5 km apart; however, they
were separated by 1 km at Deep Creek, by 3 km between Fort Casey (sediment)
and Keystone (mussels), by 7 km between Andrews Bay (sediment) and Wescott Bay
(mussels), and by 8 km between Cherry Point (sediment) and Lummi Island
(mussels).
Letters of intent were sent to owners of industrial and institutional
properties in order to gain authorization for access. Private owners were
contacted in person and readily agreed to the study.
12
-------
Sample Collection. The protocol for sediment sampling was developed from the
Sampling Design Study. It consisted of placing a 30-m line along the 0.6-m
beach contour. The elevation was gauged from mean lower low water and
measured using a transit and stadia rod. Tidal elevation was calculated from
U.S. Dept. of Commerce Tide Tables (15). Since sediment and mussels were to
be collected at specific intertidal elevations at the sites four times during
a one-year period, a bench mark was established at each site to locate the
0.6-m tidal height (0.6-m to 0.9-m for mussels) for resampling throughout the
study. The bench mark consisted of a 2-inch steel pipe driven into the ground
or the use of prominent features of natural bedrock. The height of each bench
mark above the 0.0-m tidal elevation was measured with a transit and stadia
rod. Compass bearings were taken on reference points from the bench mark to
help relocate the bench mark should it be destroyed. Detailed maps of a
sampling area were also made so that the specific sampling sites could be
readily relocated. Location maps with a site photograph, directions to the
sampling sites, general description of their topography, and predominant water
forces appear in Appendix II.
Two samples of sediment were taken at opposite corners of a 54 x 54 cm
quadrat at each of 10 random points along the 30-m line. One sample from
each point was then used to make a single composite sample. The samples
were taken with a 5.5-cm dia. x 2-cm height aluminum coring device (47 cm3)
and a stainless-steel spatula (Fig. 6). Both had been rinsed previously with
dichloromethane to prevent hydrocarbon contamination. These implements were
rinsed with distilled water between each subsample collection. The 0.47-L
glass storage jars and the aluminum foil used as a lid seal had been previously
rinsed with dichloromethane. Each jar, containing approximately 0.47-L of
composite sample, was stored on ice in the field and at -20°C in the laboratory
prior to analysis. During the spring and summer, triplicate samples were
collected at six sites to be used in the Beach Variability Study.
A Mussell sample consisting of 30 mussels 3-cm to 5-cm long was collected
randomly within the 0.6-m to 0.9-m tidal height along the 30-m line placed on
the beach (where possible). Two composite samples were collected and placed
in solvent-rinsed, 0.94-L glass storage jars which had lid seals of aluminum
foil previously rinsed with dichloromethane. Samples were collected four
times at three-month intervals from February, 1977, to February, 1978. Two
seven-day periods coinciding with low-tides were required to obtain samples
from all of the sites. Since there was an approximate ten-day separation
between suitable low-tide periods, a set of samples was usually completed
within 25 days.
13
-------
.
- -
. . *
Figure 6. Sediment sampling implements framed with 54 x 54 cm sample
quadrat. Foreground, aluminum coring device; center,
stainless-steel spatula; background, teflon wash bottle
with distilled water.
Field Observations. Physical hydrographic and atmospheric information
collected during each sampling period included air, sediment, and water
temperature; salinity; stage and range of tide; surf conditions; wind vector-
and atmospheric conditions. Physical characteristics of each beach were
recorded (Appendix I), and observations for any visible evidence of oil
contamination (oil slicks) were made. Aerial and ground photographs
(Appendix II), as well as movies, were taken at each site during daytime low
tides«
Laboratory Studies. The sediment and mussel samples were analyzed for
hydrocarbons according to the schemes in Figures 7 and 8. All laboratory
procedures are included in Appendix III. Samples of the sediment composites
were sent to the Department of Oceanography, University of Washington
Seattle, Washington (Dr. Richard W. Roberts, analyst), for total organic
carbon and grain-size distribution analyses (19,20). Portions of homogenized
mussel samples were sent to Bio-Med Research Laboratories, Seattle
Washington, for percent lipid analysis (21).
For hydrocarbon analysis in our laboratory, the samples were solvei
extracted, the extracts filtered through a silica-gel column and then
chromatographed on silica gel to obtain two hydrocarbon fractions. The first
fraction contained the saturated hydrocarbons; the second contained the
14
-------
Mlcrogravimetric.
Analysis
MET IFDTMrNT . -
I
Wash with CH.OH
EXTRACT p SEOIMENT
.Sediment Size
Analysis
_^ Hry Uolfj^f
Determination
\0rganic Carbon
Analysis
)
Extract on tumbler with
2:1 CH2C12/CH3OH
CH2C12/
EXTRA
WASHED C
EXTRA
CT SEDIMENT
TOTAL EXTRACT
Wash with H20
Hn * > ii n/ni on
CT -N
Filter through silica gel
p re column
PARTIALLY PURIFIED
CH2C12 EXTRACT
Concentrate and displace
CH2C12 with «-C6HM
I
CONCENTRATED EXTRACT
IN «-C6HH
Chroma tographic separation with Silica
SATURATED 4
HYDROCARBONS
1 , ARnMSTt
HYDROCARB
Gel
C _fc.M1crogravimetr1
ONS Analysis
Glass Capillary Gas Chromatography
! I
GC/MS Confirmations
Figure 7. Sediment analysis scheme
15
-------
HOMOGENIZED
MUSSEL TISSUE
Dry Weight
Determination
% Lipid Analysis
Saponify with NaOH
Extract with ethyl ether
Filter through silica gel
precolumn
PARTIALLY PURIFIED
ETHER EXTRACT
Concentrate and displace
ether with C2-CfiH..,
CONCENTRATED EXTRACT
IN «-CH
Chromatographic Separation with Silica Gel
Microgravimetric
analysis
SATURATED
HYDROCARBONS
AROMATIC
HYDROCARBONS
Glass Capillary Gas Chromatography
GC/MS Confirmations
Microgravimetric
analysis
Figure 8. Mussel analysis scheme-
16
-------
unsaturated hydrocarbons Including the aromatic hydrocarbons. After
concentration, these extract fractions were analyzed by glass capillary gas
chromatography (GC) for pristane, phytane, C^Q-C-^ n-alkanes, and the aromatic
compounds listed in Table 3. Glass capillary GC combined with computerized
mass spectrometry (MS) was used to confirm the identity of reported aromatic
hydrocarbons. Each fraction was also analyzed microgravimetrically to measure
total saturated hydrocarbons and total unsaturated hydrocarbons.
Table 3- Analyses performed on sediment and mussel samples.
Analysis
Dry weight
% lipid
Total organic carbon
Texture and color
Total aliphatic hydrocarbons
Total aromatic hydrocarbons
Individual aliphatic hydrocarbons
Individual aromatic hydrocarbons
1 nj-Alkanes from C,2 to C3i» pristane
2 n-propylbenzene dibenzothiop
Sediments
X
X
X
X
X
X
X
, phytane.
hene
Samples
Mussels
X
X
X
X
X
X
chrysene
i.-propylbenzene phenanthrene benz(a)anthracene
naphthalene anthracene benzo(e)pyrene
1-methylnaphthalene fluoranthene benzo(a)pyrene
2-methylnaphthalene pyrene perylene
biphenyl methylphenanthrene
Statistical Treatment and Data Management. For each quarter, the average and
standard deviation was determined for the concentration of selected
hydrocarbons in sediment and mussel samples from each site. The averages were
assumed to be distributed normally. The standard deviation times 1.96
(1.96 x S.D.) was arbitrarily used to define the bounds about the mean within
which 95% of the values should fall. By chance alone, one observation in
twenty should fall outside these bounds.
The laboratory and field data were tabulated on sheets developed from
format file type 044, NODC, for transfer to punch cards. After editing and
correction, one complete set of data cards was transferred to NOAA's Seattle
EDIS representative, and another set was stored at NAF. The hydrocarbon data
are included in Appendix IV. All data are available from NODC (Appendix I).
17
-------
Results
Site locations, field conditions at the time of sampling, and all data
resulting from chemical analyses are recorded on computer punch cards and
archived by NODC of NOAA's EDIS (Appendix 1-2). A summary of the analytical
results follows.
Field Observations. Oil slicks or other overt evidence of oil contamination
were not observed at any of the sites during the one-year study. Physical
changes in the beaches were unnoticeable except at Cherry Point, March Point
and Kydaka Point. At Cherry Point, the surf washed away the sand at the 0.6-m
tidal height after spring sampling. This resulted in a cobble beach with sand
interspersed among the cobble. Fall storms probably removed some of the finer
sediment at March Point, resulting in larger patches of coarse sediment. The
Hoko River changed course during a fall flood, rendering the mussel sampling
rocks at Kydaka Point inaccessible for the fall collection.
Mussels in bedrock areas were usually clustered, whereas in cobble areas
they were more evenly distributed along a contour. Bedrock areas existed at
Baadah Point, Kydaka Point, Pillar Point, Tongue Point, Alexander Beach, and
Legoe Bay. Heavy riprap existed at Keystone and March Point. Mussels were
absent or present in quantities too small to sustain sampling throughout the
study at Dungeness Spit, False Bay, Shannon Point, and Cherry Point.
Total Saturated and Total Unsaturated Hydrocarbons. The measurement of total
saturated hydrocarbons is the weight of extractable material present in the
fraction that is eluted from the silica column with petroleum ether. The
fraction eluted from the column with 40% dichloromethane in petroleum ether
was analyzed to determine the total unsaturated hydrocarbons. In both cases
the results included contributions from all material present in that
silica-gel eluate, not just from the individual hydrocarbons selected for GC
quantitation. The data in Table 4 show that the amounts of both saturated and
unsaturated hydrocarbons were generally many times higher in mussels than
sediments; e.g., the average values for unsaturated hydrocarbons are about
100 times higher in mussels than in sediments.
Gas chromatographic analysis. The gas chromatographic conditions are listed
in Appendix III. The detection limit for most hydrocarbons was about 0.1 ng/g
dry weight of sediment and about 5 ng/g dry weight of mussel tissue. The
differences in these detection limits are due to differences in dry weight of
samples analyzed (ca. 80 g dry weight of sediment compared to ca. 1.5 g mussel
tissue)
The concentrations of pristane, phytane, the C,Q through C~, n_-alkanes,
and selected aromatic hydrocarbons in sediments and mussels are reported in
Appendix IV. The data were summarized by (1) adding the concentrations of the
C*2 to ^20 H~alkanes (^Selected Alkanes), and by (2) adding the concentrations
of the following aromatic hydrocarbons: naphthalene, 2-methylnaphthalene,
1-methylnaphthalene, 2,6-dimethylnaphthalene, 2,3,5-trimethylnaphthalene,
phenanthrene, anthracene, 1-methylphenanthrene, benzo(e)pyrene, and
benzo(a)pyrene (^Selected Aromatic Hydrocarbons). The results of these sums
are reported in Table 5. The average value for the ^Selected Alkanes in
sediment was highest at Ediz Hook (150 ng/g dry weight) and second highest at
18
-------
Table 4. Total saturated and total unsaturated hydrocarbons in quarterly
samples of sediment and mussel tissue.
SEDIMENT
SITE
1. Birch Pt.
2. Cherry Pt.
3. Sandy Pt.
4. March Pt.
' 5. Shannon Pt.
! 6. Alexander Beach
7. Fort Casey
8. Keystone
9. Naval Air Station
10. False Bay
11 . Andrews Bay
12. Westcott Bay
13. Legoe Bay/Lummi Is.
14. Cape George
15. Dungeness/3 Crabs
16. Dungeness Spit
17. Ediz Hook
18. Tongue Pt. /Crescent Bay
19. Deep Creek Beach
20. Deep Creek
21. Pillar Point
22. Kydaka Pt.
23. Baadah Pt.
TOTAL SATURATED HYDROCARBONS
SP SU FA WI
3.4 1.1 (36) 2.2
2.8 4.4 2.9 3.1
3.1 1.1 1.8 5.5
7.2 8.1 10 8.6
6.9 3.1 0 1.7
2.9 3.2 3.1 1.6
1.0 1.9 0.8 0.8
Mil ^ 9
1.2 2.5 0.4 2.0
1.9 2.3 2.4 2.5
7.6 3.0 2.7 2.6
Mil C C
Mil 9 ^
1.2 0.7 1.1 2.6
3.8 5.8 1.8 3.3
1.9 1.5 0.01 1.4
19 23 18 13
2.3 3.3 1.6 2.0
6.3 3.0 0.8 3.6
Mil c 5
2.5 3.4 (39) 3.0
4.8 2.2 2.3 3.2
3.4 5.8 3.5 3.8
x1
2.2
3.3
2.9
8.5
2.9
2.7
1.1
E L S
1.5 1
2.3
4.0 1
ELS
ELS
1.4
3.7
1.2
18
2.3
3.4
ELS
3.0
3.1
4.1
TOTAL UNSATURATED HYDROCARBONS
ug/g dry weight
SP SU FA WI X
4.9 5.5 6.2 2.2 4.7
1.4 3.3 2.5 1.4 2.2
3.3 2.0 1.0 3.1 2.4
5.7 11 6.4 8.3 7.9
7.4 3.4 3.1 2.1 4.0
3.2 2.4 (13) 2.2 2.6
2.2 0.5 0.8 0.04 0.9
ONLY- ----------
10.4 2.2 0.2 0.3 0.8
2.8 3.0 5.5 1.5 3.2
(14) 3.7 1.6 0.4 1.9
ONLY-----------
2.1 2.2 0.7 1.5 1.6
9.9 6.2 4.4 7.5 7.0
0.8 0.1 0.3 4.7 1.5
7.1 6.3 5.1 1.2 5.0
5.7 6.9 2.0 2.4 4.3
7.1 1.2 0.4 1.7 2.6
ONLY- ----------
5.2 7.5 6.7 4.3 5.9
4.3 1.6 1.6 0.4 2.0
5.7 3.4 1.5 1.2 3.0
MUSSELS
SITE
1. Birch Pt.
2. Cherry Pt.
3. Sandy Pt.
4. March Pt.
5. Shannon Pt.
6. Alexander Beach
7. Fort Casey
8. Keystone
9. Naval Air Station
10. False Bay
1 1 . Andrews Bay
12. Westcott Bay
13. Legoe Bay/Lummi Is.
14. Cape George
15. Dungeness/3 Crabs
16. Dungeness Spit
17. Ediz Hook
18. Tongue Pt. /Crescent Bay
19. Deep Creek Beach
20. Deep Creek
21. Pillar Point
22. Kydaka Pt.
23. Baadah Pt.
TOTAL SATURATED HYDROCARBONS
ug7g dry welgTit
SP SU FA WI
95 15 7 39
150
2 16 26 110
CO 25 30 320
61 58
280 43 47 96
S E D I
99 26 19 200
77 29 90 340
58 41
? F n T
14 3 22 19
49 34 42 110
13 2 15 19
20 12 22 10
e c n T
250 78 160 330
52 35 15 47
S E n I
59 0 6 6
24 35 4 43
25 41 -- 36
250 250 130 200
X
39
39
no
60
120
MEN.
86
130
50 1
MEN
15
59
12
16
MEN
200 1
37 1
MEN
18
27
34
210
TOTAL UNSATURATED HYDROCARBONS
ug/g dry weight
SP SU FA WI
210 340 390 160
540
260 180 230 140
320 370 320 210
350 130
370 200 470 250
T ONLY------ - -
1470 110 190 250
370 500 2CO 380
150 130
T ONLY- --------
110 690 130 250
230 260 280 260
79 130 80 340
450 110 230 320
T ONLY- --------
( 760 400 180 660
. 130 130 180 220
T ONLY- --------
i 96 500 240 310
260 200 150 280
290 180 180
J 220 200 150 310
X
280
200
310'
240!
320
260 '
380
140
300
260
160
280
500
165
290
220
220
220
1
man o , , (WI) quarters
is denoted by X. Numbers in parentheses are not included in the calculation
of x due to suspected contamination.
19
-------
Table 5. Summary of hydrocarbon levels (ng/g dry weight of sample) in quar-
terly samples of sediment and mussel tissue analyzed by GC.
SEDIMENT
SITE
1. Birch Pt.
2. Cherry Pt.
3. Sandy Pt.
4. March Pt.
5. Shannon Pt.
6. Alexander Beach
7. Fort Casey
8. Keystone
9. Naval Air Station
0. False Bay
1 , Andrews Bay
12. Westcott Bay
3. Legoe Bay/Lummi Is.
4. Cape George
5. Dungeness/3 Crabs
6. Dungeness Spit
7. Ediz Hook
8. Tongue Pt. /Crescent Bay
9. Deep Creek Beach
20. Deep Creek
21. Pillar Point
22. Kydaka Pt.
23. Baadah Pt.
SSELECTED ALKANES (nCi2-C?n)
SP SU FA WI
24 30 67 38
34 54 16 27
49 40 46 51
124 110 88 87
34 60 32 26
20 15 34 16
7 41 26 27
-____.__ MUS'
2 21 1 9
13 32 38 17
87 64 62 75
------- -MUS?
------- _M MCt
4 3 53 27
93 73 56 120
10 21 1 23
190 140 120 130
18 22 25 25
74 48 21 58
MUS*;
28 29 57 30
125 49 110 130
67 62 39 50
x2
40
33
47
100
38
21
25
5 E L S
8
25
72
E L S
E L S
22
86
14
150
23
50
E L S
36
100
55
^SELECTED AROMATIC HYDROrARRnN<;l
SP SU FA WI
7 ND ND 1
7 15 11 3
23 10 6 36
49 61 26 19
12 6 1 3
4 3 Nb 2
1 NJJ Hi) 2
ON 1 V
3 ND 1
14 16 13Q3 7
12 4 ND 5
ON 1 V
ON 1 V
1 5 ND ND
15 18 ND 18
2 3 ND ND
18 9 ND 5
1 4 ND 2
18 9 8 3
ON 1 V
2 3 ND 3
61 8 27 19
31 30 6 7
?
2
g
19
39
6
2
1
1,
423
5
2
13
1
8
2
10
2
29
19
MUSSELS
SITE
1. Girch Pt.
2. Cherry ?t.
2. Sandy Pt.
r. '''r:rc!i ?*.
'.i. Shannon Pt.
0. Alexander Beach
'! . For!; Casey
3. KeystO'io
9. Nuva1 Air Station
10. False Cay
1 ' . Andrews 'Jay
2. V.'es-xo';*. Bay
13. Leroe "ay/lummi Is.
1". Caoe George
" 5. Oungeress/3 Crabs
'."-. S'jtr-.vioss Spit
"7. Ediz 'iook
13. Tongue Pt. /Crescent Bay
19. Deep Creek Beach
20. ?eeo Creek
2\ P'llar Point
!.l. Kydakd Pt.
23. Baadoh °t.
ZSFLECTEO ALKANES (KCi2-nC?o)
SP SU FA WI
560 1100 350 370
760 - -
500 580 780 701
450 520 880 820
210 580
1800 780 1300 1200
960 630 980 890
880 520 1100 770
100 1300 -
79 400 500 480
92 880 . 1400 780
46 1200 250 700
580 570 750 620
L300 1100 2300 17000
ND 410 320 320
310 820 1000 600
480 320 280 120
29 850 - 1100
340 1200 530 750.
X2
600
640
670
400
1300
I M E N
870
820
700 |
I M E N
360
790
550
630
I M E t
5400
260
I M E ti
680
300
660
710
^SELECTED AROMATIC HYDROCARBONS1
S" S'J CA W! x2
140 ND ND 36 44
300 -
100 ND 570 23 170
130 110 440 200 220
120 110 - - 115
180 ND 33 63 69
1 550 16 ND ND 140
51 ND ND ND 13
530 760 - - 650
ND ND ND ND ND
230 18 110 320 170
88 100 160 24 93
90 270 ND ND 90
3100 92 4600 2100 2500
ND ND 13 ND 3.3
ND ND ND ND ND
ND ND ND 49 12
ND 28 - ND 9.3
85 270 330 98 200
Aromatics selected for summation are listed on page 1 8 of the text.
2
The mean of spring (SP), summer (SU), fall (FA), and winter (WI) quarters is denoted by x.
Omitting the value of 130 for the aromatics in the faJl sediment from False Bay gives x = 12.
20
-------
March Point and Kydaka Point (100 ng/g); the highest average value for mussels
was 5400 ng/g at Ediz Hook, about 8 times higher than the average of the other
average values. The highest average values for the Selected Aromatic
Hydrocarbons in sediments were found at March Point, Kydaka Point, False Bay,
Sandy Point and Baadah Point, e.g., 39, 29, 42, 19, 19 ng/g (dry weight)
respectively. The highest average value for mussels was at Ediz Hook
(2500 ng/g dry weight). The data in Appendix IV should be used to evaluate
the summarized data. For example, Table 5 shows 4600 ng/g for the ^Selected
Aromatic Hydrocarbons for the Fall quarter at Ediz Hook, whereas the data in
Appendix IV shows that one compound, 1-methylnaphthalene, accounted for 93% of
the amount.
An interesting observation was that, when benzpyrenes were detected,
both benzo(e)pyrene and benzo(a)pyrene were found, and at similar
concentrations.
Graphs of the ratio of the concentrations of pristane to phytane for all
sediment and mussel samples are shown in Figure 9. The ratios that are
considerably greater than one indicate the presence of biological material,
but petroleum hydrocarbons could also be present. Figure 10 shows the
phenanthrene concentrations for the sediment and mussel samples. Phenanthrene
was found consistently at March Point, False Bay, Ediz Hook, Kydaka Point, and
Baadah Point. Figure 11 shows the benz(a)anthracene data for sediments and
mussels. The compound was consistently found in March Point and False Bay
sediments but only once in March Point mussels, and in two quarters in False
Bay mussels and Ediz Hook mussels (i.e., 1600 ppb Ediz Hook winter mussels).
Total lipids and total solids in mussels. The amounts of total lipids and
total solids in mussel tissues are reported in Table 6. The total lipids are
reported on a dry weight basis because the hydrocarbons are reported on a dry
weight basis and comparisons are facilitated. However, the values for total
lipids (dry weight) is dependent to some degree on the amount of extractable
water in the tissue; consequently the following comments on lipids are made on
the original results of analyses on the wet tissue. Mussels contain a
relatively small amount of lipid, since the complete range was between 0.7 and
3.1%, with only 3 composite samples having values over 2%. The uniformity of
results precludes attributing differences to factors such as season or site.
The amount of solids ranged from 8.8% to 19.5%; conversely, the range of
extractable water was 91.2% to 80.5%. The seasonal differences were not
pronounced, but at 2/3 of the sites the samples taken in the fall had the
lowest moisture contents.
Sediment Analysis. Total organic carbon (TOG) and sand-to-mud ratios from
sediment grain-size analyses were used to characterize the sediment and are
reported in Table 7. These values are about ten times lower than we have
found for sub-tidal samples in some depositional areas of Central Puget Sound.
21
-------
Figure 9. Pristane/phytane ratios for quarterly sediment and mussel samples.1
Sediments
10 64
J
2.5
0
5
2.5
0
5
2.5
0
!'
.
i
i
''
i
Summer
1
5
2.5
0
i
i
i
i
i
.
n
I
>
i
1
,1
!
,U
!
,
iij
1
I
1
>!
1 . || !
6.2
., 1.
1 I'. 1
.5
Fall
'
J
1
-i . . , i' in' ' ' M ' r. 1 1 i
2
Winter
I
. i
:
J
.1
-I.
bprmg
5
0
1
- u
'l i ' - 1 ' . ' 'i ;.i : i 1 , 1 ii 1
"
i
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25.
"2 10
ii
5
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10
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i 0
11
Summer
.. i i. i M :
Fall
. I. ..
18
16' 19'. 1 ' . : '. , ' in' 1 1 M ' 1 . 1 . "1
B.
3 6.7
10
5
0
Winter
P
! It
-. 1. . -,
i [1
!
In i. i 14 15 II 'i 1
.'..I i. ,,
Station
1. Birch Pt.
2. Cherry Pt.
3. Sandy Pt.
4. March Pt.
§. Shannon Pt.
. Alexander Pt.
7. Fort Casey
8. Keyitone
9. Naval Air Station
10. False Bay
11. Andrews B»y
12, Weitcott Bay
13. Legoe Bay/Lumml I.
14. Cape George
15. Dungerieu/3 Crabi
16. Oungeness Spit
17. Edlz Hook
18. Tongue Pt./Crment Bay
19. Deep Creak Beach
20. Deep Creek
21. Pillar Pt.
22. Kyaka Pt.
23. Baadah Pt.
Stations at which pristane and/or phytane were not found are left blank, I.e. are
given a value of 0.
22
-------
Figure 10. Phenanthrene in quarterly sediment and mussel samples.
Mussels
250 ng/g , spring
520 2600
25 ng/g
Sediments
28
Spring
250
Summer
620
37
25 ng/g Summer;
250 ng/g FaM
25 ng/g Fan
I'
250 ng/g
Winter
14
25 ng/g winter
161 I I ' :
Station
1. Birch Pt.
2. Cherry Pt.
3. Sandy Pt.
4. March Pt.
5. Shannon Pt.
6. Alexander Pt.
7. Fort Casey
§. Keystone
. Naval Air Station
10. Falie Bay
11. Andrews Bay
12. Weitcott Bay
13. Legoe Bay/Lumml I.
14. Cepe George
15. Dungeness/3 Crabs
16. Dungeness Spit
17. EdlZ Hook
18. Tongue Pt./Cresent Bay
19. Deep Creek Beach
20. Deep Creek
21. Pillar Pt.
22. Kyaka Pt.
23. Bondah Pt.
23
-------
Figure 11. Benz[a]anthracene in quarterly sediment and mussel samples.
Mussels Sediments
1000 ng/g
Spring
25 ng/g spring
' ' >']" i "'i ' i.4 r'' i'' i u -;l '-.''.'
I, II,--,-, -, n, -. . U o-
in I ; ' i I :- I. IT I 1 . I .I.' 2-
1000
Summer
25 nq/g Summer
in , ' I I L' I1.' 1. ' |: '. ii' I
5 ng/g Fan
25 ng/g Faii
in i ! ' M i'. \r \,' i- I . ;
58
, '', -' I I ! 1 l, I , 1 .'I
1000 ng/g : Winter
1600
25 ng/g
' M"' , III It.' 17"!
Winter
Station
1. Birch Pt.
2. Cherry Pt.
3. Sandy Pt.
4. March Pt.
5. Shannon Pt.
6. Alexander Pt.
7. Fort Casey
8. Keyitons
9. Naval Air Station
10. False Bay
11. Andrews Bay
12. Westcott Bay
13. Legoe Bay/Lummi I.
14. Cape George
15. Dungenets/3 Crabs
16. Dungeneii Spit
17. Edlz Hook
18. Tongue Pt./Cre»ent Bay
19. Deep Creek Beach
20. Deep Creek
21. Pillar Pt.
22. KyakaPt.
23. Beadah Pt.
24
-------
Table 6. Total liplds and total solids in mussel tissue.
QTTF
1. Birch Pt.
2. Cherry Pt.
3. Sandy Pt.
4. -March Pt.
5. Shannon Pt.
6. Alexander Beach
7. Fort Casey
8, Keystone
9. Naval Air Station
10. False Bay
1 1 . Andrews Bay
12. Westcott Bay
3. Legoe Bay/Lumri Is.
4. Cape George
5. Dungeness/3 Crabs
16. Dungeness Spit
7. Ediz Hook
18. Tongue Pt. /Crescent Bay
19. Deep Creek Beach
20, Deep Creek
21. Pillar Point
22. Kydaka Point
23. Baadah Pt.
percent ary weight
SP SI) FA HI
7.4 13.8 11.5 9.2
7.5
8.7 16.3 9.4 9.8
13.2 12.7 15.9 12.1
10.4 12.5
11.9 10.7 14.1 12.4
12.7 11.0 12.5 8.8
11.9 12.7 10.2 8.0
12.3 12.1
13.3 12.5 9.5 11.7
12.2 10.0 10.8 11.6
11.2 11.0 11.0 10-5
10.6 9.0 9.4 6.5
18.2 9.8 12.1 12.9
8.6 11.7 10.6 10.6
9.7 8.1 9.9 8.8
9.8 10.3 11.3 12.7
10.4 9.7 -- 10.0
11.2 lfl.8 10.4 12.5
x1
10.5
n.o
13.5
11.5
12.3
11.3
10.7
12.2
11.8
11.2
11.0
8.9
13.3
10.4
9.1
11.0
10.0
13.2
TOTAL SOLIDS
percent
SP SU FA VII
12.3 10.7 15.5 12.3
8.8
10.4 11.7 13.0 11.4
12.2 12.0 19.5 11.5
12.3 13.6
13.5 15.4 18.1 15.7
11.0 13.5 12.6 12.5
13.1 14.7 14.2 14.0
13.2 13.3
11.7 10.3 12.7 11.3
14.6 14.0 16.8 11.9
15.2 14.9 14.9 13.8
11.6 12.8 14.1 10.9
10.0 10.9 15.4 13.7
12.4 16.7 16.3 16.0
9.5 12.1 12.6 12.0
14.5 16.2 15.4 16.2
9.9 10.3 - 10.7
16.3 15.5 17.5 14.7
X
12.7
11.6
16.7
13.0
16.0
12.4
14.0
13.3
11.5
14.3
14.7
12.4
12.5
15.4
11.6
18.5
10.3
16.0
average value of spring (SP), summer (SU), fall (FA), and winter (WI) quarters is denoted by x.
Table 7. Total organic carbon and sand-to-mud ratio for sediments.
SITE
1. Birch Pt.
2. Cherry Pt.
3. Sandy Pt.
4. March Pt.
5. Shannon Pt.
6. Alexander Beach
7. Fort Casey
8. Keystone
9. Naval Air Station
10. False Bay
11. Andrews Bay
12. Westcott Bay
13. Legoe Bay/Lummi Is.
14. Cape George
15. Dungeness/3 Crabs
16. Dungeness Spit
17. Ediz Hook
18. Tongue Pt. /Crescent Bay
19. Deep Creek Beach
20. Deep Creek
21. Pillar Point
22. Kydaka Pt.
23. Baadah Pt.
TOC (r.)
SP SU FA WI
0.22 0.16 0.37 0.14
0.11 0.18 0.13 0.10
0 17 0.18 0.25 0.19
0 19 0.14 0.27 0.15
0.18 0.12 0.13 0.11
0.15 0.06 0.27 0.12
0.11 0.07 0.11 0.12
0 12 0.07 0.09 0.05
OJ4 0.14 0.36 0.13
0.10 0.14 0.14 0.11
0.11 0.07 0.10 0.10
0 3S 0.31 0.27 0.12
0.08 0.07 0.05 0.05
0 11 0.10 0.10 0.12
0.16 0.16 0.12 0.14
0.21 0.07 0.10 0.13
0.21 0.20 0.19 0.19
0.12 0.08 0.09 0.24
0.12 0.10 0.12 0.16
x1
0.22
0.13
0.20
0.19
0.14
0.15
0.10
0.08
0.19
0.12
0.10
0.35
0.06
0.11
0.15
0.13
0.20
0.13
0.13
SAND/MUD RATIO
SP SU FA WI
50 84 18 59
250 130 100 110
69 99 100 47
50 33 25 06
96 100 45 100
130 95 41 130
240 180 160 240
170 210 210 110
140 52 64 43
98 130 88 130
42 51 34 28
8 11 10 3
180 165 210 120
139 118 150 110
99 110 85 77
64 190 170 56
70 49 58 52
80 170 91 140
150 180 150 150
x
53
150
79
49
85
99
210
180
75
110
39
a
170
130
93
12fl
57
120
160
'The average value of spring (SP) , summer (SU), fall (FA), and winter (WI) quarters is denoted by x.
25
-------
Discussion
We assessed the data obtained in this study for petroleum contamination
at the 23 sites. The sites used in this study were relatively free from
petroleum contamination. For the most part, the highest concentrations of
individual hydrocarbons indicative of petroleum were present in sediments at
low ppb. We found values about 100 to 1000 times higher in sub-tidal
sediments from some urban depositional areas in Puget Sound.
Evaluation of ^tydrocarbons at Sampling Sites. The hydrocarbon data from the
samples indicate the presence of low levels of petroleum at Ediz Hook, March
Point, Baadah Point, Kydaka Point, Cherry Point, Sandy Point, and False Bay.
Individual hydrocarbons from petroleum and/or biological sources were evident
at Birch Point, Pillar Point, Dungeness/Three Crabs, Shannon Point and Cape
George (Tables 5, 8 and Appendix IV). The sites not mentioned above appeared
to be more pristine than Dungeness/Three Crabs, a site considered to be
relatively pristine. The lowest individual hydrocarbon levels were measured
at the Naval Air Station on Whidbey Island. Fort Casey, Crescent Bay,
Alexander Beach, Cape George and Dungeness Spit had similarly low levels.
Shannon Point, Birch Bay, Pillar Point, Andrews Bay, Deep Creek Beach and
False Bay had slightly higher levels than the Naval Air Station.
The sites that had elevated levels of hydrocarbons which might indicate
the presence of petroleum are discussed below.
Ediz Hook. This site is on the harbor side of a spit facing the city of
Port Angeles (population: ca. 16,000). There are lumber and paper industries
nearby and considerable boating activity in Port Angeles harbor. Several
small creeks empty into the harbor. The sampling site is protected from
direct waves from the Strait of Juan de Fuca, but is subjected to surge waves
from shipping activity.
The amounts of total saturated and total unsaturated hydrocarbons from
Ediz Hook sediments were among the highest found at any of the sites
(Table 4). Measurable levels of both individual alkanes and aromatic
hydrocarbons, as determined by gas chromatography, were present in all mussel
samples collected at Ediz Hook. Statistical treatment of the hydrocarbon data
showed levels of individual hydrocarbons to be consistently higher at Ediz
Hook than the all-site average plus 1.96 x S.D. for that compound. The
average of the quarterly iSelected Alkanes for sediments and mussels (Table 5)
was highest each quarter at Ediz Hook. The average of the quarterly ^Selected
Aromatic Hydrocarbons was the highest for Ediz Hook mussels, but the sediment
value was close to the average for all sites.
In all the quarterly samples, the presence of alkyl-substituted aromatic
hydrocarbons and the nearly even distribution of n_-alkanes strongly suggest
petroleum input. The slight predominance of odd carbon-number r^-alkanes
suggest only minor biogenetic input. It is interesting that 4300 ng/g of
1-methylnaphthalene found in the fall mussel sample. We have no clear
explanation for the presence of this much 1-methylnaphthalene when
2-methylnaphthalene was not detected. These two compounds are usually found
in comparable concentrations.
26
-------
March Point. This sampling site is located on the northeast side of
March Point, Fidalgo Island, adjacent to a boat launch area. Two major oil
refineries, a large wood pulp mill, and the city of Anacortes (population
about 8,000) are nearby. Marine flora and fauna were abundant at this site.
March Point sediment contained elevated levels of hydrocarbons relative
to the other sites in this study. The microgravimetric results for sediments
and mussels (Table 4) were high, the average value of the ^Selected Alkanes in
sediments was second highest, and the average value of the ^Selected Aromatic
Hydrocarbons was highest in sediments and second highest in mussels.
Statistical treatment of the hydrocarbon data showed persistent levels of
individual hydrocarbons outside the average values for all of the sites plus
1.96 x S.D. The n-alkanes did not show odd-carbon predominance and the
pristane/phytane ratios were close to one. These results indicate the
presence of petroleum contamination at March Point. Interestingly, March
Point sediment samples generally had higher levels of the polynuclear aromatic
hydrocarbons phenanthrene, pyrene, benzo(e)pyrene, and benzo(a)pyrene than any
of the other sites. Alkanes and arenes were found in all quarterly mussel
samples from March Point.
Baadah Point. This sampling site is at the edge of Neah Bay, an active
fishing port. Waadah Island and a breakwater protect the area from direct
waves from the Strait and could serve to hold spilled oil in the area. Both
aliphatic and aromatic hydrocarbons were found in all quarterly mussel samples
and sediment samples* The GC patterns and the hydrocarbon data indicate the
presence of petroleum hydrocarbons. Statistical treatment of the sediment
hydrocarbon data showed concentrations of certain compounds above the average
plus 1.96 x S.D., but not for more than two quarters.
Kydaka Point. This site is along the Strait of Juan de Fuca near the
mouth of the Hoko River. The entire area is subjected to heavy wash from the
Strait of Juan de Fuca. The data indicate the presence of petroleum
(Table 5).
Cherry Point. This site is exposed to the Strait of Georgia near
Ferndale, Washington, between two oil refineries and an aluminum plant.
Hydrocarbon levels in sediments were very low, mostly less than 10 ppb. High
winds, wave action, and currents probably account for the comparatively low
hydrocarbon levels at this site, despite its proximity to industrial activity
known to put hydrocarbons into the environment. Mussels were available at
Cherry Point only for the spring sampling. They contained measurable levels
of both individual aliphatic and aromatic hydrocarbons. The consistently low
level of hydrocarbons suggest that petroleum hydrocarbons are not accumulating
in this high-energy beach area.
False Bay. The n-alkanes from the sediment samples were present at very
low concentrations and exhibited significant odd-carbon-nuraber predominance,
implying the presence of biological hydrocarbons. Low levels of aromatic
Hydrocarbons were measured in these sediments. The spring, summer, and winter
levels were less than 10 ppb for aromatic compound except fluoranthene (20 ppb
in the spring sediment). The fall sediment contained higher levels, e.g.,
170 ppb fluoranthene. Mussel samples were available at False Bay during
spring and summer quarters only. These samples contained low levels of
aromatic hyrocarbons; however, phenanthrene and fluoranthene were about
27
-------
500 ppb in both spring and summer samples. Apparently, then, the hydrocarbons
in False Bay samples are from Both biological and fossil sources.
Andrews_Ba^. The spring sediment sample contained high concentrations
of pristane (and/or some compound that interfered with the analysis of
pristane) and phytane. This ratio was closer to 1 for the other samplings.
The n-alkanes and aromatic hydrocarbons in the spring sediment sample indicate
the presence of petroleum. Based on the n-alkane distribution, it was
probably a distilled fuel oil, as opposed to a crude oil or a residual oil.
Samples from the other seasons showed much lower hydrocarbon levels. Mussel
samples were not collected at Andrews Bay. Other than the one spring sediment
sample, the Andrews Bay samples contained levels of hydrocarbons similar to
those at Whidbey Island NAS (which contained the lowest levels of hydrocarbons
measured in this study).
Dungeness/Three Crabs_. Individual aliphatic and aromatic hydrocarbons
were present in all samples from Dungeness/Three Crabs. Sediment samples all
contained n-alkanes; however, the odd carbon numbered n-alkanes predominated.
Aromatic hydrocarbons were found in Dungeness/Three Crabs sediment samples,
but at concentrations less than 10 ppb (except for chrysene in the spring
sample at 30 ppb). The data from these samples indicate this area to be
relatively free of petroleum.
Sandy Point. This site has extensive mud flats and is exposed to high
wind and wave action from the Strait of Georgia. Commercial fishing for
Dungeness crab occurs in this area. Regularly distributed n-alkanes were
found in all sediment samples, suggesting petroleum input. Alkanes were
measured in extracts from all sediment and mussel samples. Aromatic
hydrocarbons were measured in extracts from all sediment samples, but at the
ppb level. Of the 24 aromatic compounds quantitated, none were found in the
extract from summer mussels, and only three or four aromatic compounds were
detected in the other extracts from mussel samples. The statistical treatment
of the sediment data showed that certain hydrocarbon levels were elevated, but
not for more than two quarters. Petroleum appears to be present at Sandy
Point at levels similar to those at Dungeness/Three Crabs, which is a
relatively pristine area.
Shannon Point. Mussels were collected only in the spring and summer.
Alkanes were present in sediment and mussel extracts, at low ppb
concentrations (Appendix 4). Aromatic compounds were measured in sediment and
mussel extracts, but only 2 of the 24 compounds quantitated were found in the
fall sediment, spring mussel, and summer mussel extracts. Shannon Point
contains generally lower concentrations of petroleum hydrocarbons than
Dungeness/Three Crabs.
Individual hydrocarbons
Naphthalene. Naphthalene is considered relatively labile and is subject
to both chemical and biological oxidations. It is found in the water soluble
fraction from petroleum. It is also considered a toxic component when present
in water. Sediments from 18 of the sites contained naphthalene during the
spring and/or summer. The highest concentration was 4 ng/g, dry weight, which
is about 2 orders of magnitude lower than the concentration we found in a
28
-------
subtidal sediment sample from a moderately polluted urban area of Puget Sound.
Naphthalene was not detected in the fall and winter sediment samples. Mussels
from 8 sites contained naphthalene, although at 5 of these sites it was
present at only one sampling. Mussels at Kydaka Point and Legoe Bay contained
naphthalene only in the summer samples, while mussels at Alexander Beach,
March Point and Tongue Point contained naphthalene only in the fall.
Naphthalene was found in mussels at: Ediz Hook in both summer and fall
samples; Cape George in both summer and winter samples; and Baadah Point in
the summer, fall and winter samples. Spring samples did not contain
detectable levels of naphthalene at any of the sites. The three samples from
Baadah Point and one from Ediz Hook had the highest concentration
(approximately 40 ng/g dry weight). The low concentrations of naphthalene,
and the few times it was found in mussels at more than one sampling, suggests
that the naphthalene found in the mussels reflects recent exposures to low
concentrations.
Phenanthrene. Phenanthrene is found in many petroleum products and is
not considered to be a natural biological compound. The phenanthrene data
generally support the conclusion, noted above, that there was evidence of
fossil fuels in samples from Ediz Hook, March Point, Kydaka Point, Sandy
Point, Shannon Point, False Bay, Baadah Point, and Cherry Point. Phenanthrene
was found in sediment samples each quarter from Cherry Point, Sandy Point,
March Point, Shannon Point, False Bay, Deep Creek Beach, Kydaka Point, and
Baadah Point, and in three quarters from Alexander Beach, Andrews Bay,
Dungeness/Three Crabs, and Ediz Hook (Figure 10). Phenanthrene was detected
in all four quarterly mussel samples from March Point, Ediz Hook, and Baadah
Point. March Point and False Bay generally had the highest concentrations of
phenanthrene in sediment samples, whereas the Ediz Hook winter samples had the
highest concentration in mussels. The concentrations generally were lowest in
the fall samples. A greater number of the spring mussel and sediment samples
contained phenanthrene, and generally the levels in spring samples were higher
than in samples from the other samplings.
Benz(a)anthracene. Benz(a)anthracene, though present less often than
phenanthrene, was found in sediment from March Point, Sandy Point, Cherry
Point, and False Bay, and in two samplings in False Bay and Ediz Hook mussels
(False Bay mussels were only collected twice).
Petroleum Contamination. The microgravimetric results for hydrocarbons in
sTdiments imply that the sites studied are relatively free of petroleum.
Clark & MacLeod's review of published studies (21) showed that "petroleum
polluted beaches generally contained 100 yg or more of total hydrocarbons per
gram of dry sediment. Generally values were over 1000 yg/g. In the present
study, all results for total'hydrocarbons were less than 25 yg/g, and most
were less than 10 pg/g (Table 4).
One of the questions generally asked "What amount of petroleum is
present?" Since only a fraction of any oil is included in analyses of
individual compounds, we attempted to relate the concentration of one compound
to a quantity of reference oil in order to hypothesize about the amount of
petroleum at the different beaches. The following argument can thus be
developed for the purpose of discussion: If one assumes the even numbered
n-alkanes (such as n-C,0) all came from petroleum, one may correlate the
concentration of that compound to a concentration of a reference sample of
29
-------
petroleum. If crude oil containing 0.2% H~C
20
is use<^ as a reference
petroleum, then 1 ppb of n-C?/s in a sample would correspond to 1/2
microgram/gram (yg/g) of crude oil in that sample. Following this reasoning,
none of the sediment samples contained more than 10 yg/g (ppm) of oil
(Table 8).
Table 8. Hypothetical values of petroleum present in dry sediment
assuming all H-Con^/.? came from crude oil containing 0.2%
-~C20H42*
Spring Summer
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
Birc,h Pt.
Cherry Pt.
Sandy Pt.
March Pt.
Shannon Pt.
Alexander Beach
Fort Casey
Keystone
Naval Air Station
False Bay
Andrews Bay
Westcott Bay
Legoe Bay/Lummi Is.
Cape George
Dungeness/3 Crabs
Dungeness Spit
Ediz Hook
Tongue Pt. /Crescent Bay
Deep Creek Beach
Deep Creek
Pillar Point
Kydaka Pt.
Baadah Pt.
ug/8
1
2
2
10
1
3
0.7
-
0.2
1
3
-
-
0.2
5
1
10
2
6
-
2
6
4
U&/K
2
2
3
8
2
1
3
n u s s
2
3
3
MUSS
MUSS
0.3
4
1
10
2
4
MUSS
3
4
5
Fall
"g/R
1
1
3
4
4
2
2
E L S 0 N
0.3
4
5
E L S 0 N
ELS ON
2
4
0.3
7
2
3
E L S 0 N
4
7
3
Winter
ug/g
O.'j
2
3
5
2
2
1
L Y
0.6
1
5
L Y- - - -
L Y
1
6
1
8
2
4
L Y
3
8
3
30
-------
TEMPORAL VARIABILITY STUDY
Sediment and mussel samples were collected at March Point six times at
approximately 2 week intervals beginning September 21, 1977, to determine
whether hydrocarbon concentrations would indicate major short-term changes
that might not be observed by quarterly monitoring. For example, would
individual hydrocarbons that are found in petroleum be present at high
concentrations at one sampling and decrease significantly by the next
sampling, or would these values be rather consistent? Consistent values might
imply that the compounds are removed by the various processes at about the
same rate at which they are added.
Methods and Materials
The same sampling and analysis protocols were followed as in the
Hydrocarbon Baseline Study.
Results and Discussion
Results from the sediment and mussel analyses are summarized in Table 9
and the data for the individual compounds are reported in Tables 10 and 11.
Since this study was done to evaluate possible short term changes, it is
probably best to evaluate the data for individual compounds. The values in
Tables 10 and 11 are very low. These results are reported as parts per
billion (ppb) and as such they might appear to be more variable than they
actually are. For example, the data for n.-C]_4H30 in Table 10 ranges from
4.3- to 7.8 ppb which is 0.043 to 0.078 ppm. In other words, there is little
difference between 4.3 ppb and 7.8 ppb. The data for the alkanes are
surprisingly consistent. The data for the aromatic compounds appear to be
more variable than data for the alkanes. For example, the results for some
compounds in the sample collected September 21 are different from those from
some other samples by about 30 times; the value for benzo(e)pyrene in
sediments is 34 for the September 21 sample vs. 1.2 for the November 1 sample.
The values for some of the alkanes in mussel samples in Table 11 are much
higher than those for sediments. For example, the average value for _n-C,5H»,,
in sediments is 12 ppb, and in mussels is 293 ppb. The detectable
concentration for hydrocarbon compounds in the mussel samples is about 10 ppb
and values of 20, 40, even 60 are low concentrations.
These data generally show that the individual compounds were not
introduced as a slug of petroleum that disappeared with subsequent samples.
The data for the quarterly samplings (Appendix IV) are similar to the data in
Tables 10 and 11, and imply that hydrocarbons are present at a rather constant
level.
31
-------
Table 9. Summary of analytical results from Temporal Variability
Study samples at March Point.
1977
9/21 10/6 10/14 11/1 11/17 11/30
MICROGRAVIMETRIC
DETERMINATION (yg/g dry)
Sediment
Total sat'd hydrocarbons
Total unsat'd hydrocarbons
Mussels
Total sat'd hydrocarbons
Total unsat'd hydrocarbons
GC ANALYSIS (ng/g dry)
Sediment
ZSelected Alkanes
(n-Cl2-C20)
^Selected Aromatic
Hydrocarbons
Mussels
ZSelected Alkanes
(n-Cl2-C20)
ISelected Aromatic
Hydrocarbons
MUSSEL ANALYSES
% Lipid
%Dry weight
SEDIMENT ANALYSES
% Organic Carbon
Sand/Mud Ratio
6.4
9.4
55
190
9.0
6.9
60
360
10
6.4
30
320
4.7
4.5
38
140
7.0
5.6
54
140
5.3
4.2
17
110
113
27
82
13
84
26
90 98
26 40
890 1500
ND 140
19.0 15.9
17 18
0.18 0.27
25 25
98
37
880 700 790 680
412 120 550 190
15.9 12.0 14.7 9.4
19 16 17 16
0.27 0.21 0.25 0.16
25 24 31 41
Selected aromatics are listed in text on page 18.
32
-------
Table 10. Concentration of alkanes and aromatic hydrocarbons (ng/g dry) in March Point sediments at two-
week intervals, from 9/21 to 11/30.
n-alkane
cio
Cll
C12
C13
C14
C15
C16
C17
Pristane ^
C18
Phytane
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
C31
9/21
ND
ND
4.5
5.2
7.8
16
13
22
20
14
8.6
18
12
12
10
19
11
17
9.1
26
7.7
23
13
13
10/6
ND
ND
3.9
4.0
5. fl-
lC
7.2
18
15
10
6.0
15
8.6
9.5
7.1
14
8.2
19
6.7
35
8.8
29
2.3
19
DATE OP
10/14
ND
ND
3.8
7.7
4.3
11-
5.9
18
23
8.6
4.2
16
8.3
10
7.7
16
8.7
21
8.3
41
9.7
3.3
19
24
SAMPLE
11/1
ND
ND
2.5
3.3
4.4
15
9.3
15
11
11
4.4
19
10
13
8.0
16
7.0
IS
5.5
27
5,, 4
21
11
14
11/17
ND
ND
3.4
3.7
5.1
11
9.1
21
15
13
7.4
21
11
12
11
18
13
?R
13
44
11
31
S.fl
19
11/30
ND
ND
4.8
5.6
6.8
11
9.0
21
10
11
4.4
19
q.q
11
12
15
10_ ...
79
9.8
82
Tl
26
49
14
Aromatic Hydrocarbon
o-Xylene
Isopropylbenzene
n-Propylbenzene
Indan
1,2,3 , 4-Tet ramethy Ibenzene
Naphthalene
BenzothiopheiN?
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
2,6-Dimethylnaphthalene
2,3, 5-Tr imethy Inaphthalene
Fluorene
Oibenzothiophene ^
Phenanthrene
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Benz [a] anthracene
Chrysene
JJenzo [e] pyrene
Benzo [a] pyrene
Perylene
9/21
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.4
3.0
1.5
3.7
1.7
48
7.8
-------
Table 11.
Concentration of alkanes and aromatic hydrocarbons (ng/g dry) in
week intervals, from 9/21 to 11/30.
March Point mussels at two-
n-alkane
cio
Cll
C12
C13
C14
C15
C16
C17
Pristane
C18
Phytane *
C19
C20
C21
C22
C23
C24
C25
C26
C27
SB
C29
C30
C31
9/21
220
210
150
84
84
350
130
93
260
ND
ND
ND
ND
ND
ND
57
ND
41
55
130
55
100
ND
ND.
10/6
420
360
240
120
140
460
380
130
650
5.7
120
ND
26
86
38
99
26
50
24
110
19
75
ND
ND
DATE OF
10/14
410
360
250
110
81
190
52
87
620
19
100
63
29
31
32
85
18
38
10
19
ND
26
ND
ND
SAMPLE
11/1
330
270
150
80
78
290
ND
42
240
ND
53
41
22
20
16
72
ND
48
22
110
20
130
ND
ND
11/17
140
140
81
84
160
270
33
88
280
24
52
20
33
34
36
84
34
56
23
69
27
81
ND
ND
11/30
68
79
51
59
35
200
250
34
340
ND
58
35
20
31
27
71
29
52
29
130
26
63
ND
ND
Aromatic Hydrocarbon
o-Xylene
Isopropylbenzene
n-Propylbenzene
Indan
1,2,3, 4-Tet ramethylbenzene
Naphthalene
o
Bcnzothiophene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
2,6-Dimethylnaphthalene
2,3, 5-Tr imethylnaphthalene
Fluorene
o
Dibenzothiophene
I'hcnanthrenc
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Benz[ a] anthracene
Chrysene
Benzo[e]pyrene
Benzo[a]pyrene
Perylene
9/21
ND
ND
" ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
I
10/6
ND
ND
ND
ND
ND
ND
ND
28
30
ND
ND
ND
ND
ND
80
ND
ND
110
87
ND
57
ND
ND
ND
>ATE OF
10/14
ND
ND
ND
ND
ND
3.3
ND
20
190
ND
ND
ND
ND
ND
160
ND
39
100
45
ND
ND
ND
ND
ND
SAMPLE
11/1
ND
ND
39
ND
ND
13
ND
ND
17
ND
ND
ND
ND
ND
88
ND
ND
94
78
ND
ND
ND
ND
ND
11/17
ND
ND
ND
ND
ND
ND
ND
72
250
ND
ND
ND
ND
ND
210
ND
ND
190
17
ND
ND
ND
17
ND
11/30
ND
ND
ND
ND
ND
11
ND
20
ND
14
ND
ND
ND
ND
160
ND
ND
140
100
ND
ND
ND
ND
ND
a branched alkane
a sulfur-substituted aromatic hydrocarbon
ND=not detected
-------
BEACH VARIABILITY STUDY
The objective of this study was to determine if differences in the data
from different sites were greater than the differences for replicate samples
from a single site; i.e., do the different sites contain measurably different
levels of hydrocarbons? Duplicate samples of sediments were collected and
analyzed during the spring and summer quarters from Cherry Point, March Point,
Andrews Bay, Dungeness/Three Crabs, Tongue Point, and Baadah Point. Duplicate
analyses of six spring samples were performed to determine differences in
results from single composite samples.
Methods and Materials
The same methods and materials were used in this study as in the
Hydrocarbon Baseline Study section.
Results and Discussion
The results of these analyses are summarized in Table 12 and the data
for the individual hydrocarbons are reported in Appendix IV. The summarized
data provide a mechanism to evaluate differences in replicates and differences
between sites. The differences between duplicate analyses of a sample and
between analyses of duplicate samples from a site were within expected results
in most cases. The greatest differences between duplicates are in the data on
sums of selected alkanes and sums of selected aromatic hydrocarbons. The
duplicate analyses of the spring sample number 1 at Andrews Bay show the
greatest difference, almost tenfold. We occasionally obtain such unexpected
results from samples. Every step in the procedure is thoroughly checked and
usually, as in this instance, no explanation is found for the discrepancy.
We used the ESelected Alkanes and ZSelected Aromatic Hydrocarbons to
rank the beaches according to hydrocarbon concentrations. The order is the
same for both classes of compounds. The decreasing order with the respective
values for alkanes and aromatics is as follows: 1. March Point (119,63);
2. Baadah Point (114,30); 3. Dungeness/Three Crabs (85,16); 4. Andrews Bay
(78,11); 5. Cherry Point (42,10); and 6. Tongue Point (19,2).
This limited data set suggests that hydrocarbon concentrations can be
used to indicate differences in petroleum compounds present at different
sites, even in areas such as Northern Puget Sound where all sites have
relatively small amounts of contamination.
35
-------
TABLE 12. Data from Beach Variability Study.
Sample Number
Mlcrogravimetric
Analysis (pg/g dry)
Total sat'd he's
Total unsat'd he's
GC Analysis (ng/g dry)
^Selected Alkanes
(«C12-C2o)
^Selected Aromatic
hydrocarbons^
Sediment Analysis
Total Organic
Carbon (%)
Sand/Mud Ratio
Sample Number
Microgravimetric
Analysis (vg/g dry)
Total sat'd he's
Total unsat'd he's
GC Analysis (ng/g dry)
^Selected Alkanes
(«ci?-r20)
^Selected Aromatic
hydrocarbons
Sediment Analysis
Total Organic
Carbon (%)
Sand/Mud Ratio
CHERRY PT.
sP
1A IB 2A
2.6 2.8 3.1
1.0 1.3 1.9
32 43 27
6 10 6
0.11 0.12
247 252
DUNGENE5S/3
SP
1A 2A 2B
4.8 3.8 2.8
18 8.9 2.8
110 80 90
17 11 16
0.35 0.40
6.58 8.46
SU
1A 2A
4.6 4.1
2.9 3.6
50 58
13 17
0.36 0.12
123 137
CRABS
su
1A 2A
3.9 7.6
3.4 9.0
73 73
18 18
0.26 0.31
13.4 10.8
MARCH PT.
SP
1A IB 2A 2B
7.6 8.8 7.1 5.4
4.7 5.8 7.4 4.7
82 124 132 158
39 33 97 26
0.19 0.18
39,2 61.2
SU
1A 2A
6.2 10
8.4 10
130 89
47 75
0.13 0.15
27.4 39.0
TONGUE PT.
5F1
1A 2A 2B
5.5 2.0 1.5
11 3.6 2.5
22 18 14
200
0.14 0.16
99.2 125
SU
1A 2A
3.3 6.0
5.3 8.4
21 22
3 3
0.16 0.16
73.3 112
ANDREWS BAY
SP
1A IB 2A 2B
11 5.0 8.2 6.2
12 3.4 31 7.7
600 75 98 90
530 17 13 14
0.10 0.18
108 87.3
BAADAH PT.
SP
1A 2A
3.4 3.3
8.9 2.5
67 67
41 20
0.11 0.13
127 168
SU
1A 2A
5.0 6.5
4.3 2.4
62 263
27 32
0.09 0.11
154 201
SU
1A 2A
2.7 3.3
4.0 3.3
52 76
4 7
0.15 0.12
123 128
Selected aromatlcs are listed in text on page 18
Analyses of duplicate samples taken at one place are indicated
by 1 and 2, e.g., 1A and 2A in the summer at Cherry Pt. Duplicate
analyses of a single sample are indicated by A and B, e.g., 1A
and IB in the spring at Cherry Pt.
36
-------
REFERENCES
1. MESA (Marine Ecosystem Analysis Program). 1978. Description
of research activities. The Puget Sound Project. National
Oceanic and Atmospheric Administration, Environmental Research
Laboratories, Boulder, Colorado. .
2. MacLeod, W. D., Jr., D. W. Brown, R. G. Jenkins, L. S. Ramos,
and V. D. Henry. 1976. A Pilot Study on the Design of a
Petroleum Hydrocarbon Baseline Investigation for Northern Puget
Sound and the Strait of Juan de Fuca. National Oceanic and
Atmospheric Administration. Technical Memorandum ERL MESA-8,
Boulder, Colorado.
3. Clark, R. C., Jr. 1976. Impact of the transportation of petro-
leum of the waters of the northeastern Pacific ocean. Marine
Fisheries Review. 38 (11): 20-26.
4. Farrington, J. W. and B. W. Tripp. 1975. A comparison of analysis
methods for hydrocarbons. In T. M Church (ed.) Surface Sediments,
Marine Chemistry in the Coastal Environment pp. 267-284. American
Chemical symposium series #18. American Chemical Society,
Washington, D.C.
5. Farrington, J. W. and P. A. Meyer. 1975. Hydrocarbons in the
marine environment. In: G. Elington (ed.) Environmental Chemistry.
Volume I, pp. 109-136. The Chemical Society, London.
6. Clark, R. C., Jr., and J. S. Finley. 1975. Uptake and loss of
petroleum hydrocarbons by the mussel, Mytilus edulis, in laboratory
experiments. Fishery bulletin. 73: 503-515.
7. Clark, R. C., Jr., and D. W. Brown. 1977. Petroleum: Properties
and Analyses in Biotic and Abiotic Systems. In D. C. Malins (ed.)
Effects of Petroleum on Arctic and Subarctic Marine Environments
and Organisms, Vol. I, pp. 1-89. Academic Press, New York.
8. Farrington, J. W., J. M. Teal, and P. L. Parker. 1976. Petroleum
hydrocarbons. In E. D. Goldberg (ed.) Strategies For Marine
Pollution Monitoring, pp. 3-33. John Wiley & Sons, Inc., New York
9. Clark, R. C., Jr. and W. D. MacLeod, Jr. 1977. Inputs, Transport
Mechanisms, and Observed Concentrations of Petroleum in the Marine
Environment. In D. C. Malins (ed.) Effects of Petroleum on Arctic
and Subarctic Marine Environments and Organisms, Vol. I,
pp. 91-223. Academic Press, New York.
37
-------
10. Blumer, M. and W. W. Youngblood. 1975. Polycyclic aromatic
hydrocarbons In soils and recent sediments. Science. 188: 53-55.
11. Youngblood, W. W. and Blumer, M. 1975. Polycyclic aromatic
hydrocarbons in the environment: homologous series in soils and
recent marine sediments. Geochimica et Cosmochimica Acta. 39:
1303-1314.
12. LaFlamme, R. E. and R. A. Kites. 1978. The global distribution
of polycyclic aromatic hydrocarbons in recent sediments. Geochim.
Cosmochim. Acta. 42: 289.
13. Clark, R. C., Jr., and J. S. Finley. 1973. Techniques for
analysis'of paraffin hydrocarbons and for interpretation of data to
assess oil spill effects in aquatic organisms. Proceedings of
the 1973 Joint Conference on Prevention and Control of Oil Spills
pp. 161-172. American Petroleum Institute/Environmental
Protection Agency/United States Coast Guard, Washington, B.C.
14. Farrington, J. W. 1973. Analytical techniques for the
determination of petroleum contamination in marine organisms.
Technical Report WHOI-73-57. Woods Hole Oceanographic Institution.
Woods Hole, Massachusetts.
15. U.S. Dept- of Commerce. 1977. Tide tables, high and low water
predictions, west coast of North and South America, including
Hawaiian Islands. U.S. Department of Commerce, National Oceanic
arid Atmospheric Administration, National Ocean Survey,
Washington, D.C.
16. Carpenter, R. and T. Bates. Private communication. Department
of Oceanography, University of Washington. Seattle, Washington.
17. Brown. D. W., L. S. Ramos, A. J. Friedman, and W. D. MacLeod, Jr.
(in press). Analysis of trace levels of petroleum hydrocarbons
in marine sediments using a solvent/slurry extraction procedure.
Proceedings of the 9th. Materials Research Symposium on Trace
Organic Analysis: A New Frontier in Analytical Chemistry.
National Bureau of Standards, Washington, D.C. (in press).
18. Ramos, L. S., D. W. Brown, R. G. Jenkins, and W. D. MacLeod, Jr.
(in press). Modification of conventional gas chromatographic
inlets for use of glass capillary columns. Proceedings of the
9th Materials Research Symposium on Trace Organic Analysis: A
New Frontier in Analytical Chemistry. National Bureau of
Standards, Washington, D.C. (in press).
19. Jackson, M. L. 1958. Soil Chemical Analysis. Prentice-Hall,
Inc. Englewood Cliffs, New Jersey.
38
-------
20. Krumbeln, W. C. and F. J. Pettijohn. 1938. Manual of Sedimentary
Petrography. Appleton-Century-Crofts, Inc. New York, New York.
21. Hanson, S. W. F. and J. Olley. 1963. Application of the Bligh
and Dyer method of lipid extraction to tissue homogenates.
Biochem. J. 89: 101.
39
-------
APPENDIX I
Data archival information, the field data record sheet (figure 1-1) and
the key to codes (Table 1-1) are included in the following pages.
Also included is the formatting sheet used in preparing data for
transfer onto punch cards (figure 1-2).
40
-------
DATA LOCATION
All data from the quarterly studies and the Temporal Variability Study
are available from NODC at:
U.S. Department of Commerce
National Oceanic and Atmospheric Administration
National Oceanographic Data Center
Records Section
Washington, D.C. 20235
under the following titles:
Study Title Accession // Track
Spring 77 HBSP77 77-0777 TR1893
Summer 77 HBSU77 78-0025 TR2716
Fall 77 HBFA77 78-0393 TR3070
Winter 77 HBWI77 78-0393 TR3071
Temporal Variability 77 78-0393 TR3072
41
-------
NORTHERN PUGET SOUND HYDROCARBON BASELINE STUDY
SAMPLE COLLECTION REPORT
STATION I.D.
(11-15)
DATE/TIME
YR. MO. PAY HR. MIN.
LATITUDE
PEG. MIN. SEC. HEM.
(16-25)
TIDES
STAGE HT. (m)
(4
44]
WAVES
ENERGY HT.(m)
(45-47)
N
LONGITUDE
PEG. MIN. SEC. HEM.
(26-32)
WEATHER
(33 -40)
WIND
DIR. SPEED (m/i)
i o "^
(49-54)
w
TEMPERATURE (eC)
AIR WATER SEDIMENT
(55-66)
SALINITY
(ppt)
PHOTO
(67-71)
UJ
Q
UJ
V)
SAMPLE I.D.
(16-16)
GEAR SUBSAMPLE
TYPE SUR. AREA(m2) OEPTH(mm) NO.
2 2
(19-28)
(29-31)
SAMPLE ELEVATION EXTENT
LO (m) HI (m) (m)
BEACH OIL
ORGANICS POLLUTION COLOR
(32-37)
(38-40)
(41-43)
(44-46)
(47)
CO
_l
UJ
CO
CO
SAMPLE I.D.
GEAR TYPE
SUBSAMPLE
NO.
(16.18)
(19-20)
SAMPLE ELEVATION EXTENT
LO(rr) Hl(m) (m)
SUBSTRATE
(32-37)
(38-40)
(29-31)
ORGANISM SIZE (mm)
MEAN MIN. MAX.
(48-50)
(51-59)
UJ
o
CO
SIGNATURE .
Figure 1-1. Record sheet for collecting field data.
42
-------
Table 1-1. Key to codes used to record data on the field data
record sheet.
ID Number Station
1008 Birch Point
1012 Cherry Point
2014 Ediz Hook
2021 Dungeness Spit
2046 Cape George
2054 Pillar Point
2056 Baadah Point
2058 Deep Creek
2059 Crescent Bay/Tongue Point
2066 Keystone
2067 Deep Creek Beach
2068 Dungeness/Three Crabs
ID Number
2069
2070
2071
3067
3074
3107
4001
4047
4053
4092
4096
Station
Fort Casey
N.A.S./Whidbey is.
Kydaka Point
False Bay
Andrews Bay
Westcott Bay
Sandy Point
March Point
Shannon Point
Legoe Bay/Lummi Is.
Alexander Beach
B: Tidal Stage Code
Blank = no information
1 = ebb
2 = ebb slack
3 = flood
4 = flood slack
Weather Code
Blank = no information
0 = clear (cloudless)
1 = partly cloudy
(scattered or broken)
2 = completely overcast
3 = sandstorm, duststorm or
blowing snow
4 = fog, thick dust, or
haze
5 = drizzle
6 = rain
7 = snow, or rain and snow
mixed
8 = shower
9 = thunderstorm
C: Wave Energy/Beach Gradient Code
Blank = no information
1 = low wave energy; low beach gradient
(slope< 15%)
2 = low wave energy; moderate beach gradient
(slope, 15-30%)
3 = low wave energy; high beach gradient
(slope>30%)
4 = moderate wave energy; low beach gradient
5 = moderate wave energy; moderate beach gradient
6 = moderate wave energy; high beach gradient
7 = high wave energy; low beach gradient
8 = high wave energy; moderate beach gradient
9 = high wave energy; high beach gradient
Gear Code
12 = hand collections
22 = surface coring device
cylinder 2 cm deep x 5 cm across
E. Photo Code
Blank = no information
0 = no photos taken
1 = ground: black and white only
2 = ground: color only
3 = ground: black and-white and color
4 = aerial: black and white only
5 = aerial: color only
6 = aerial: black and white and color
7 = aerial and ground: black and
white only
8 - aerial and ground: color only
9 = aerial and ground: black and
white and color
43
-------
Table 1-1. cont'd.
H: Beach Organics Code
Blank = no information
1 = chiefly shell fragments
2 = detritus, accumulated wood, sticks, and undecayed organtcs
3 = fibrous peat
4 = pulpy peat
5 = muck, completely decomposed organic materials
6 = eel grass
7 = kelp ,
8 = periphyton
9 = no organic materials evident
I: Oil Pollution Code
Blank = no information
0 = slick, indeterminable type
1 = slick, fish oils ("bait slick")
2 = slick, petroleum, thin
3 = slick, petroleum, thick
4 = frothy, petroleum, thin
5 = frothy, petroleum, thick
6 = tar, petroleum, thin
7 = tar, petroleum, thick
8 = other
9 = clean beach (no oil or carcasses observed]
A F some tarballs found
B = many tarballs found
C - light sheen on water
D = physical evidence of possible petroleum contamination
(such as oil cans, gas tanks, oiled cardboard, etc.)
E = abnormal number of marine carcasses
F = abnormal number of bird carcasses
6 = motorized boat within 50' of sampling site
H = other petrochemical contaminants (plastic, etc,)
J: Sediment Color Code
Blank = no information
1 = black
2 = black-gray
3 white
4 tan
5 chocolate brown
6 light brown
7 yellow
8 green
9 red
A = gray
B = gray-brown
K: Substrate Composition
Blank = no information
0 = indeterminable
1 = mud
2 = sand
3 = shell
4 = small rocks
5 = medium rocks
6 = large rocks
7 = bed rock
8 = wood
9 = tide pool
A = dirt
B = scree
L: Method Code
1 = mussel analysis code (original)
2 » sediment analysis code (original)
C = vegetation
D = clay
E = peat
F = gravel
G = boulders
H = combinations
J = talus
K = volcanic ash
1 = concrete
m = wooden pilings
n = pebble
p = cobble
-------
D«. _
p
FOR ALL CARDS ON THIS PAGE
r»
SUMITTCD IV
T
NUMBER OF SHEET
^
or..
SMninnin!aniESfsn^^^Fn23EQiraEflnHEanEnfflQiraHe:ai]njn:n3LTJii];2Ensm^
Card
1
A
ft
D
y
G-
H
;
J
Z
DATE and
YR M
SAMPLE
ID
IAMPLE
ID
SAMPLE
ID
SAMPLE
ID
SAMPLE
ID
SAMPLE
ID
SAMPLE
ID
SAMPLf
ID
SAMPLE
ID
0 DY
TIME
HR MIN
LATITUDE LONGITUDE TIDES
DEC MIN SE
GEAR
TYPE SURF. AREA
DEPTH
SAMPLE WEIGHT
I DRY
DEPTH OF
iAMPLE IN
COLUMN
ALIQUOT
WATER
VOLUME (L)
TOTAL
ALIPHATICS
1
M
I C
1- I-PROPYL
! BENZENE
1 DIMETHYL
i NAPHTHALENE
«1
CHRYSENE
SUB-
SAMPL
NO.
DEG MIN
ELEVATION
LOU HIGH
SEC B HT
EXTENT H
WAVES
C
I
HT
SEDIMENT GRAIN SIZE AS FRACTION
<-2 -2 TO 0
0 TO 2 2 TO 1
^
TOTAL
AROMATICS
C,a
_'»_
N-PROPYL
BENZENE
TRIMETHYL
NAPHTHALENE
PERYLENE
10
Cl,
,...c:°...
INDAN
FLUOR ENE
DIBENZO
THIOPHENE
Cn
So
_>_
TETRAMETHYL
BENZENE
PHENANTHRENE
BENZOlA)
PYRENE
J
WIND
0
:IR
K
SPEED
TEMPERATURE
AIR
WATER
ORGANISM SIZE
MEAN
PERCENT
TO 8
12
C-
C30
NAPHTHALENE
ANTHRACENE
BENZOlEl
PYRENE
> 8
HIN. MAX.
MEAN S/
GRAIN ,
SIZE "
C,3
C"
BENZO-
THIOPHENE
1-METHYL
KCNANTHRENE
SED
SALINITY E
TAXONOMIC CODE
ND:HUD
ATIO
C><
C«
3
PRISTANE
NAPHTHALENE
FLUORANTHENE
ZTOTAL
ORGANIC
CARBON
15
C«
PHYTANE
NAPHTHALENE
PYRENE
ITOTAL
LIPID
Cis
C25
0-XYLENE
BIPHENYL
BENZU1
ANTHRACENF
i
LAB
NO.
LAB
NO.
LAB
NO.
LAB
NO.
LAB
NO.
LAB
NO,
LAB
NO.
LAB
NO.
LAB
NO.
LAB
1
;
TTT!
\
1
Figure 1-2. Model of formatting sheet used to prepare data for
transfer onto punch cards.
45
-------
APPENDIX II
FIELD INFORMATION
List of Sites 48
Description of Sample Sites 49
Beach Characteristics 52
Maps and Photographs of Sites 55
46
-------
List of Sites
1. Birch Point
2. Cherry Point
3. Sandy Point
4. March Point
5. Shannon Point
6. Alexander Beach
7. Fort Casey
8. Keystone Jetty
9. NAS Whidbey
10. False Bay
11. Andrews Bay
12. Westcott Bay
13. Legoe Bay
14. Cape George
15. Dungeness/Three Crabs
16. Dungeness Spit
17. Ediz Hook
18. Crescent Bay/Tongue Point
19. Deep Creek Beach
20. Deep Creek
21. Pillar Point
22. Kydaka Point
23. Baadah Point
47
-------
DESCRIPTION OF SAMPLE SITES
Birch Point. Located in Birch Bay Village, Recreation Area Number Three,
approximately five miles south of the Canadian Border. Forms upper boundary
of Birch Bay proper. Cobble beach with intermittent patches of medium to fine
sediment. Few large boulders. Tide pools with abundance of organisms. Low
beach gradient. Abundance of Mytilis edulis. Private access.
Cherry Point. Variability site. Located near Ferndale, Washington, between
Arco and Mobile refineries and adjacent to Intalco Aluminum Co. Access owned
by Puget Sound Power and Light Co. Medium cobble beach with small
intermittent patches of fine sediment. Non-sustaining colony of Mytilis
edulis. Beach area exposed to Strait of Georgia. Large colonies of herring
inhabit area during early summer. Public access.
Sandy Point. Confines upper end of Lummi Bay. Located approximately five
miles from Interstate 5 between Bellingham and Ferndale. Extensive tide flats,
bordered above the 0.6-m tidal level by medium sized cobble. Cobble contains
relatively large colony of Mytilis edulis. Commercial Dungeness crab area.
Expos.ed to surf action from Strait of Georgia. Private access.
March Point. Fidalgo Island. Located northeast side of March Point adjacent
to boat launch area. Mussels attached to south side of boat launch jetty.
Extensive tide flat area. Extensive population of water fowl. Variety and
abundance of marine flora and fauna, particularly interstitial worms. Bounded
by Padilla Bay on the east, Guemes Channel on the North and Fidalgo Bay on the
West- Site of Shell and Texaco Oil Refineries. Public access.
Shannon Point. Fidalgo Island, west end of city of Anacortes. Located on
Western Washington State University property adjacent to Washington State
Ferry terminal property. Most of beach area covered with rocks, cobble to
boulder size. Sediment sample area at west end of Univesity property, faces
Guemes Channel, near County park. Not enough mussels to sustain a continuing
sample. Private access.
Alexander Beach. Del Mar Development. Located just south of Skyline Marina
(Anacortes) on Burrows Bay. Faces Rosario Strait. Vast area of fine sediment
interspersed with bedrock. Adequate colony of mussels on rocks. Private
access.
Fort Casey. Seattle Pacific University. Located on Whidbey Island adjacent
to Keystone Ferry and Washington State Parks Dept. Property. Sample area in
line with abandoned lighthouse. Coarse sediment in gravel area with few large
rocks. Faces Admiralty Inlet. Private access.
Keystone Ferry Landing. Whidbey Island. Mussel site on South side of ferry
landing jetty. Faces Admiralty Inlet. Ecology reserve, must have permission
from Washington State Parks to sample. Public access.
U.S. Naval Air Station. Whidbey Island. Sizeable beaches of fine sediment.
Good colonies of blue mussels. Exposed to turbulence from Rosario Strait.
Sediment/mussel area located directly in front of Norwester Club. Private
access. Permission from Base Commander through security officer.
48
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False Bay. San Juan Island. Located west side, lower half of Island facing
Haro Strait. Limited sediment at 0.0-m tidal level. Large areas of bedrock.
Many tide pools, abundance of a variety of marine life. Mussel colonies very
sparse. Private access. Permission from owners of Marvista Resort.
Andrews Bay. San Juan Island. Located upper half, west side of Island.
Limited sediment coarse to fine at 0.0-m tidal level. No mussel crop.
Greater than moderate beach gradient. Faces Haro strait. Private access.
Permission from individual land owners on bay.
Westcott Bay. San Juan Island. Mussel site only. Located west side, upper
half of island. Sheltered from Haro Strait by Henry Island. Mud flat area,
produces variety of shellfish. Site of numerous University of Washington
shellfish studies and aquaculture programs. Private access. Permission by
Webb Camp caretaker.
Legoe Bay. Lummi Island. Alternate choice for Cherry Point mussel site.
Located west side of island below Village Point, faces Strait of Georgia.
Gravel beach. Good mussel colonies found on southern point of bay on bedrock
and concrete blocks. Private access. Permission through Lummi Aquaculture
School (formerly Hawleys resort).
Cape George. Access through the Cape George Colonies development; sampling
site is 200 m north of the marina-picnic beach parking lot. Location is on the
east entrance of Discovery Bay. Beach is of small to large cobble with some
sand between rocks and limited sandy stretches at the 0.3-m level and above.
Mussels were abundant within a 150-m length of beach. Private access.
Dungeness Town. Access by parking at 3 Crabs Restaurant and hiking to bench
mark that was 300 m to the west. Sampling zone was 120-m due north of the
bench mark. Beach was of 2 to 6-cm gravel interspersed with a sand-to-mud
sediment. Sediment appeared to be highly organic. Mussels were wide-spread
throughout the sampling area and were attached to the rocks or clusters of
gravel. This area was protected from direct wave action from the Straits, but
choppy conditions created heavy water-born sedimentation. Private access.
Dungeness Spit. Reached by parking at the Clallam County Dungeness Spit Park
and hiking 0.9 km to the beach. USCGS bench mark was available at the end of
the trail. The sampling area was 50 m northwest of the bench mark. The beach
was always subject to a heavy wash from the Strait. Mussels were not
available anywhere on the outer spit. Access subject to permission from the
Clallam County Parks authorities.
Ediz Hook. Sampling area was reached by passing onto U.S. Coast Guard Station
on Ediz Hook, proceeding past last hangar to a point 200 m east of the wooden
seaplane ramp. Bench mark was the 1-m square concrete drain pipe extending
onto the beach* Beach was of 5 to 20-cm cobble above the 0.0-m tidal level,
except for a limited sand area to the east of the bench mark that served as
the sediment collection area. Mussels were abundant through the cobble near
the 0.6-m tidal level. Although the area was protected from direct waves from
the Straits, the area was subject to surge waves and waves from the heavy
shipping activity in the area. Access subject to permission from the Coast
Guard.
49
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Tongue Point. Access by parking in the Clallam County Park parking lot at the
mouth of the Lyre River and hiking 400 m to the sampling area. Beach is of
sand except for bedrock areas at shore edge and the prominent 25-m high
pinnacle and bedrock projection adjacent to the pinnacle. Sediment was
collected due south of the pinnacle and mussels were taken at the base of the
pinnacle- The sampling area is semi-protected from the direct waves of the
Strait. Sampling of sediment and mussels subject to permission from the
Clallam County Parks authorities.
Deep Creek Beach. Access from pull-off zone of Highway 101 that is one
kilometer east of Deep Creek. Beach of gravel above the +0.6-m level and of
continuous sand beyond with boulders interspersed. Sediment only. Public
access.
Deep Creek. Access through unregulated public camping area along the east
bank of Deep Creek. Beach of large cobble through entire area* Mussels
available in restricted area near the +0.6-m tidal level adjacent the Deep
Creek bed. Mussels are subject to fresh water wash from Deep Creek. Public
access.
Pillar Point. Sampling site was reached by proceeding over Merrill- Ring Tree
Farm road that follows the Pysht River and ends at the inner (southeast) beach
of Pillar Point. The beach is entirely of sand while the point is of bedrock.
Sediment reference mark was the southmost, low (0.4 m high) large rock at the
+0.6-m level. Mussel samples were taken from the isolated boulders due south
of Pillar Point. Access subject to permission from Merrill-Ring.
Kydaka Point. Access through the Crown-ZeHerbach public camping area at the
mouth of the Hoko River. Sediment bench mark is at the tip of the vegetated
area that separates the Hoko River from the sea. Beach is entirely of sand
except for the bedrock formation at the mouth of the Hoko River. Sediment was
sampled north of the bench mark and 200 m west of the bedrock area; mussels
were sampled at the +0.3 to 0.9-m tidal level of the bedrock. The entire area
was subject to heavy wash from the Strait during storms. The mussel area was
subjected to brackish water from the Hoko River. Access subject to permission
from Crown-Zellerbach.
Baadah Point. Access to sampling site (while heading westbound on State
Highway 9A) by taking the first right turn past the Bureau of Indian Affairs
office and proceeding to Baadah Point and parking at the small creek.
Sediment was taken between the creek and the bedrock area of Baadah Point (an
area which was entirely sand). Mussels were abundant between the +0.6 to
1.0-m levels of the bedrock area of Baadah Point. The sampling area was
sheltered from direct waves from the Straits by Waadah Island. Public access.
50
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Table II-l. Location and characteristics of the 23 sampling sites ranging from Baadah Point at west
end of the Strait of Juan de Fuca to Birch Bay at the south end of the Strait of Georgia
Site Beach ~~
Latitude "N"
Longitude "W" Gradient Substrate
Exposure to waves
Substrate
M=mussels
S=sediment
Baadah Point Moderate,
48°22'25" 5-15°
124°35'23"
Kydaka Point
48°17I45"
124°21'40"
Pillar Point
48°12'48"
124°06f10"
Deep Creek
48010'35"
124°01I20"
Moderate,
10-15°
Low, <5C
Low, <5'
Deep Creek Beach Moderate
48010'20" 5-15°,
124°01fOO" Initial
50 m; then
low-5°
Tongue Point
48°09'54"
123°42T18"
Ediz Hook
48008'22"
123°24I18"
Low, <5(
Moderate,
5-15°
Grey well washed sand with solid
bedrock on the point.
Grey well washed sand with solid
bedrock on the point.
Grey washed sand interspersed
with bedrock outcroppings.
Continuous cobble of a 10-30 cm
greatest dimension.
Gravel beach graduates to grey
washed sand at the +0.6»m level,
Patches of cobble and large
rocks at lower, elevations.
Grey washed sand with bedrock
outcroppings and continuous
bedrock on point.
Cobble to gravel with a few
patches of sand.
Protected from direct ocean M-S
waves but subject to heavy
surge.
Directly exposed to frequent M-S
winter storms causing heavy
wave action. Hoko River washes
over mussel area on point.
Protected from direct waves M-S
from the Strait for all wind
directions except north and
east.
Directly exposed to surf from M
the Strait. Deep Creek washes
over mussel collection area.
Negligible protection from S
waves from Strait.
Receives surge of waves from M-S
Strait with modest protection.
Lyre Creek empties 100 m from
sample sites.
Protected from direct waves of M-S
Strait and is subject to waves
from shipping activity.
-------
Table II- 1 , (cont'd)
Dungeness Spit
48°08'45"
Dungeness/
Three Crabs
480o9'io"
123007'15"
Cape George
48°06'15"
122°53'04"
Whidby Island,
Keystone
48°09'21"
122°40'15"
Whidby Island,
Fort Casey
48009'45"
122°47'55"
Steep, 15'
Low, <5'
Moderate,
10-15°
Steep, 20c
Moderate,
10-15°
Whidby Island, Moderate,
Naval Air Station 10-15°
48°20!32"
122°41'07"
Alexander Beach Low, <5°
48°28'36"
122°39f38"
Shannon Point
48°30'17"
122°41'17"
Moderate,
10-15°
Course sand subject to heavy
wash almost constantly.
Fine sand to occasional pebbles.
Considerable infauna and
organic material incorporated
in sediment.
Large cobble, 10 to 40 cm in
greatest dimension, some loca-
tions interspersed with sand
patches.
Beach is of heavy gravel;
mussel collection area is
heavy rock riprap for jetty.
Upper elevation is of gravel to
cobble; at +0.6 m substrate is
of sand with boulders.
Upper elevation is of gravel to
cobble; at +0.6 m substrate is
of sand with 2-m boulders.
Fine, grey sand from 1 m to
lower low water. Above 1 m
bedrock and large boulders.
Fine, grey sand at 0.6-ro level.
Sediment area surrounded by
medium to large rocks.
Subject to constant heavy wash
from Strait and tidal action.
Subject to wind generated M-S
waves of general modest height.
No heavy surge wave action.
Occasionally subject to moder-
ate wave actdon; heavy surge
never observed.
M-S
Wave action sometimes heavy. M
Tidal currents are consistently
extremely swift.
Wave action often heavy. Tidal S
currents are usually swift but
less swift than at Keystone.
Wave action often heavy. M-S
Moderate wave action, sheltered M-S
from Rosario Strait by Burrows
Is. and Allen Is.
Faces Guemes Channel, subject to M-S
moderate to high wind and wave
action.
-------
Table II-l (cont'd)
LO
March Point
48°29'54"
122033I41"
Sandy Point
48°47'10"
122°42I20"
Cherry Point
48°51'20"
122043'45"
Birch Point
48°55f55"
122047'24"
Westcott Bay
48°35'50"
123°08T27"
Andrews Bay
48°32'50"
123°09I23"
False Bay
48°28f53"
123°03'54"
Legoe Bay
48°42I52"
122°41'54"
Moderate,
10°
Low, <5'
Moderate,
5-10°
Low, 5'
Low, 5'
Moderate,
10-15°
Moderate,
10-15°
Moderate,
5-10°
Fine to coarse sand to gravel.
Noticeable seasonal change in
structure and algal composition.
Small boulders, concrete blocks.
Extensive mud flats. Upper
beach small cobble, with
extensive mussel colony.
Patches of fin sand inter-
spersed with extensive cobble
on lower beach. Upper beach
sand and gravel.
Fine to coarse sand inter-
spersed with medium cobble.
Large mussel colony, variety
of fauna.
Mud flat area, variety of
shellfish and other fauna.
Small patches of fine sand
interspersed with coarse
sand and gravel at 0.0m..
Beach area confined by
bedrock.
Fine sand at O.O.-m tidal
level. Large areas of bedrock.
Wide variety of fauna.
Gravel beach, areas of bedrock
and concrete block. Good
mussel colonies.
Moderate to low wind and wave M-S
action from Padilla Bay and
Guemes Channel.
Moderate to heavy wave and M-S
wind action from Strait of
Georgia.
Faces Strait of Georgia. S
Moderate to heavy wind and
wave action.
Forms upper boundary of M-S
Birch Bay, faces turbulence
from Strait of Georgia.
Confluent with Garrison Bay. M
Low wave action. Sheltered
from Haro Strait by Henry Is.
NW corner of San Juan Is.
Subject to direct wind and S
wave action from Haro Strait.
Upper Middle San Juan Is.
Moderate wave action, sheltered
from Haro Strait.
Moderate wind and wave action, M
faces Strait of Georgia.
-------
Birch Point: Strait of Georgia,
54
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2. Cherry Point: Strait of
Georgia.
- ;. > .-
-------
3. Sandy Point: Strait
of Georgia.
56
-------
PA DILL
4. March Point: Guemes Channel,
Padilla Bay.
57
-------
FLOUNDER BAY
Numerous pnvtteiy mainjiined m«rkers
ind pilfng rrijrk the «ntf»ice channel.
5. Shannon Point; Rosario Strait,
Guemes Channel.
58
-------
R R O W S* BnA\ M
6e Alexander Beach: Roaario Strait,
59
-------
,7
7, Fort Casey: Rosarlo Strait,
Admiralty Inlet.
I
60
-------
Hedd \ : ' /:- ' \
^-i %? -\
. t XT-' . I
8. Keystone Ferry: Rosario Strait,
Admiralty Inlet,
61
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9. Naval Air Station, Whidbey Island:
Rosario Strait.
62
-------
FALSE :8AY
., 33;'::.;."' ::" '...,
10 . False Bay: Haro Strait.
-------
11, Andrews Bay: Haro Strait.
64
-------
!2. Westcott Bay: Haro Strait.
65
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13. Legoe Bay, Lummi Island:
Strait of Georgia.
66
-------
111. Cape George: Strait of
Juan de Fuca.
-------
15. Dungeness/Three Crabs:
Strait of Juan de Fuca.
3MB!
-------
... , .. . »-
.,
16, Dungeness Spit: Strait of
Juan de Fuca.
.3*. '-**-.
vl
v
-------
-'v -;''\ < '
^^^"s^<..^\ V
PORT ANGELES HARBOR
t
S
17. Sdiz Hook: Strait of JUEJI cie Fuca.
70
-------
Crescent Bay/Tongue Point:
Strait of Juan de Fuca.
71
-------
19. Deep Creek Beach (sediment):
Strait of Juan de Fuca.
72
-------
20. Deep Creek (mussels) :
Strait of Juan de Fuca.
73
-------
' "-ptXI*- _^.»T«TI «KMj»T10»«L UCA
7 X^/SX ... * » ..
21c Pillar Point: Strait of
Juan, ole Fucae
74
-------
4n?000m.r» iHTCwioR-oeoLOttFCAL i
*" * WASHINGTON O C 1««
Kydaka Point: Strait of
Juan de Fuca.
75
-------
23. Baadah Point: Strait of
Juan de Fucac
76
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APPENDIX III
ANALYTICAL PROCEDURES
Materials 78
Tissue Extraction 79
Sediment Extraction 80
Silica-Gel Chromatography 81
Gas Chromatography 82
Gas Chromatography/Mass Spectrometry 85
Dry Weight Determination 86
Microgravimetric Determination 86
77
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Materials
Materials contacting the sample were confined to glass, Teflon, metal or
residue-free solvents and reagents. This includes caps and lids. All
glassware was washed with hot water and laboratory detergent, dried, and
rinsed with reagent grade methylene chloride dispensed from a previously
cleaned Teflon wash bottle. Teflon and metal foil sheeting and metal
implements were also rinsed with methylene chloride before use. Reagents used
in this study were of the highest purity obtainable. Solvent ratios are given
on a vol./vol. basis.
List of Items:
Laboratory scalpels
Homogenizer: Tekmar tissumizer, //SDT-182EN
Centrifuge tubes: 50 mL: Corning #8422
Test tube racks: A. H. Thomas Co., //9266-N32
Centrifuge: Dupont Instruments/Sorvall, #GLC-2B
Glass (Pyrex) wool: Corning #3950
Dish, aluminum, utility, 57-mm diameter
Teflon caps for centrifuge tubes: Saxillex Corp.,
Minnetonka, Minn., #0624 teflon closures
Ether peroxides test paper: EM Laboratories, Inc., #10061-9G
Pipets, transfer (Pasteur type): Curtin Matheson Scientific,
Inc., #355-123
1-L bottles: Wheaton #219180
Teflon bottle caps: custom-machined from 38 mm o«d. Teflon
rod
250 and 600-mL beakers
500-mL Teflon wash bottle: Nalge #2403-0500
150-mL coarse, fritted-glass filter: Corning #36060
1-L separatory funnel with Teflon stopcock: Corning #6402
500-mL Erlenmeyer flask
Chromatography column, 19 mm i.d.: Kontes #K-420280, size 232
Chromatography column, 10.5 mm i.d.: Kontes #K-420280,
size 213
500-mL Erlenmeyer flask, 24/40 STJ
Snyder distilling column: Kontes #K-503000, size 121
25-mL concentrator tube: Kontes #K-570050, size 2525
Teflon boiling chips: Bel-Art Products #41001, Pequannock,
N.J.
Reflux column: Kontes #K-569251, size 3-19
Vials: Wheaton #223682
Vial caps: Hewlett Packard #5080-8766
Vial capper: Hewlett Packard #871-0979
Capillary GLC columns: Supelco Inc. and Quadrex Corp.
Ball-mill tumbler: model 8-RA, Scott-Murray Manufacturing,
8511 Roosevelt Way, N.E., Seattle, WA (frame, roller
bars, motor only)
78
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Constant temperature water bath
Tube heater block: Kontes #K-720003
Tube heater control unit: Kontes #K-720001
Gas chromatograph: Hewlett-Packard #5840A, with flame
ionization detector and automatic liquid sampler (#7661A)
Mass spectrometer: Finnigan #3200
Oven with temperature range up to 125°C
Electrobalance, automatic: Cahn Model #4700, Ventron
Instruments Corp., Cerritas, Calif.
Balance, top loading: Mettler #P1210
Balance, analytical: Mettler #H33AR
Dessicator: Boekel #1340
Reagents
Methanol: MCB Spectroquality MX0475, Lot 7G13
Petroleum ether: Mallinckrodt Nanograde, #4977
Dichloromethane: Mallinckrodt Nanograde, #3023
Hexane: Burdick and Jackson U-V grade, distilled in glass
Distilled water: carbon-filtered 0.2 mm filtered, and
distilled in glass
Ethyl Ether: Burdick and,Jackson, Distilled in glass,
unpreserved
Silica-gel, 100-200 mesh: MCB #5X144-06
Sodium sulfate, anhydrous: Mallinckrodt, #8064
Sand: MCB #SK78, CB1045
Sodium hydroxide: Mallinckrodt #7708
Copper granules: Mallinckrodt #4649
Hexamethylbenzene (GC internal standard), nj-declycyclohexane
(alkane recovery standard) and 1,3,5,-triisopropylbenzene
(aromatic recovery standard): Chemical Samples Co.
Aliphatic and aromatic reference compounds were purchased
from: Aldrich, Analabs, Applied Science Labs., and
Chemical Samples Co.
Tissue Extraction Procedure For Mussels
Pry open the shells with a clean spatula and separate the two halves by
severing the adductor muscle. Scrape the tissue from the shell into a 250-mL
beaker for compositing with other individuals.
Blend the tissue with the homogenizer at medium speed for at least
30 sec. Weigh 10 g of sample into a tared 50-mL screwcapped centrifuge tube.
Add 6 mL of 4N sodium hydroxide to each sample. Cap each tube tightly with a
Teflon screwcap, set tube on vortex stirrer for 1 min and place each sample
tube in an oven at 30°C for 18 hr (overnight). Cool the samples to room
temperature and shake to check completeness of digestion. If well digested,
add 15 mL of peroxide-free diethyl ether, recap tubes tightly, and place on
vortex stirrer for 3 min. If not well digested, see Note 1 below. Check the
caps for tightness, then centrifuge the tubes at 3,000 RPM for 20 min. If the
79
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upper, ether phase is clear, transfer it with a Pasteur pipet to a clean,
rinsed concentrator tube and stopper it. Avoid any carryover of the lower
aqueous phases. If the supernatant ether phase is not transparent, see Note 2
below before proceeding. Repeat the extraction with 10 mL of ether and
combine the extracts. A persistent turbidity indicates the presence of
residual water which must be removed by anhydrous sodium sulfate before
proceeding.
Attach a reflux column, and add a Teflon boiling chip. Place the
apparatus in the tube heater at 80°-85°C.
Shroud the apparatus with aluminum foil to enhance distillation and
concentrate the solution to 3-5 mL. Place sample on 10.5-mm diameter
chromatography column containing 1 tsp (5 mL) silica gel under ether. Rinse
concentrator tube 2x with ether and add to column. Drain extract through
silica gel into a clean concentrator tube and rinse down column once with no
more than 1 bed volume (ca. 5 mL) of ether. Concentrate to ca. 1 mL, add 2 mL
of hexane and a second Teflon boiling chip and concentrate to 1 mL to remove
ether completely. The sample is now ready for silica-gel chromatography.
Note 1; Shake sample and return to oven. Check hourly to see if digestion
is complete, and, if not, shake again and return to oven, repeating
until digestion is complete.
Note 2; If the emulsion layer is small, remove clear ether layer and proceed
to the second extraction. If the emulsion layer is extensive,
remove the clear ether layer and re-centrifuge the mixture for an
additional 20 min. If the emulsion is still extensive, add 1 g of
anhydrous sodium sulfate to the mixture, swirl gently, and
centrifuge for 20 min. Transfer ether phase to the concentrator
tube and proceed with the second extraction.
Sediment Extraction Procedure
To a 100 g sample of sediment in a 1-L bottle, add 50 mL of CH3OH.
Gently agitate the bottles by hand to dewater the sediment. Decant the
methanol into a 600-mL beaker and repeat the dewatering step. Add 100 mL of
CH2C12/CH~OH (2/1), seal bottles with Teflon screw caps and roll on a ball-
mill tumbler for 16 hr (overnight) at ca. 75 rpm. Decant the extract into a
600-mL beaker containing the methanolic extracts. Rinse the sample with 5 mL
of Cl^Cl- and decant again into the 600-mL beaker. Repeat the extraction step
for 6 hr, then again for 16 hr (overnight); combine all extracts.
Filter extracts through a fritted-glass filter into a 1-L separatory
funnel, and rinse the beaker and filter twice with small amounts of CHnCln'
Gently swirl the filtrate for 2 min with 500 mL of distilled water to
partition the CHoOH between the aqueous and Ct^Cl^ phases. After the phases
separate, drain the lower, CH2C12, phase into a 500-mL Erlenmeyer flask.
Back-extract the aqueous phase with 20 mL of CH2C12, and add to the previous
CH~C1_ phase. After discarding the aqueous phase, repeat the aqueous
extraction and CH2C12 back-extraction steps.
80
-------
Filter the total CH^Cl- extract through a 19-mm i.d. chromatography
column containing 20 mL of silica gel in CH-Cl- covered with a 1-cm layer of
sand. Elute the column with 2 bed volumes of CH^C^ and collect eluate in
500-mL Erlenmeyer flask equipped with a 24/40 joint.
Place the flask, equipped with a Snyder distillation column, in a 60°C
water bath and concentrate eluate to ca. 15 mL. Transfer the concentrate to a
25-mL concentrator tube and rinse flask 2x with small amounts of CH-Cl ,
adding rinses to the tube. Add a boiling chip, attach a reflux column, and
concentrate on a tube heater to ca. 1 mL. Add 2 mL of hexane and
reconcentrate the extract to ca. 1 mL.
Silica-gel Chromatography
Column Preparation. Prepare columns immediately prior to use. Fill a 10.5-mm
i.d. chromatography column with methylene chloride (bulb 1/4 full). Push a
0.5-cm glass-wool plug to the bottom of the column with a glass rod. Measure
15 mL (7 g) of 100-200 mesh silica gel (activated at 125°c for 24 hr, then
cooled in a dessicator) into a 250 mL beaker. Add 25 mL of methylene chloride
and swirl vigorously to make a slurry. Place a curved-stem funnel into the
column such that the tip rests off-center on the bottom of the reservoir just
below the surface of the methylene chloride.
Quickly pour the slurry into the funnel and wash the residual slurry
into the funnel with methylene chloride from a Teflon wash bottle. The
adsorbent particles should quickly settle to the bottom of the column with
little turbulence at the settling front. Swirl the column reservoir gently to
wash the particles into the column. When the settling front reaches the top
of the suspended particles, open the stopcock all the way to complete the
settling. After 1 min, carefully add ca. a 1-cm layer of clean sand through a
funnel to the top of the gel, followed by 2 cm of anhydrous sodium sulfate for
mussel samples (see note 1) or 2 cm of activated copper for sediment samples
(see section on copper activation). When the methylene chloride surface is
just above the top of the column, add 40 mL of petroleum ether and continue to
elute. Close the stopcock when the solvent meniscus almost reaches the top of
the column. Discard the rinse eluates.
Sample Chromatography. The sample extract should be in 1 mL of hexane in the
concentrator tube. Carefully transfer the extract solution with a Pasteur
pipet to the top of the column and elute into a clean 25-mL concentrator tube.
Never allow the liquid meniscus to go below the upper surface since air will
be entrapped which will disrupt the column. Rinse the concentrator tube 2x
with 0-5 mL of petroleum ether each time, add to the column, and elute (see
note 2). When the meniscus just reaches the column top, carefully add 15 mL
of petroleum ether. Care must be exercised not to disturb the upper surface
of the column during each addition. When the meniscus again just reaches the
top of the column, add 5 mL of 20% methylene chloride in petroleum ether.
When 18 mL has eluted into the concentrator tube receiver, replace it with a
second tube. The 18-mL eluate, referred to as fraction 1, contains the
saturated hydrocarbons.
81
-------
Continue eluting into the second tube. As the meniscus just reaches the
top of the column, add 25 mL of 40% (v/v) methylene chloride in petroleum
ether. Collect 25 mL in second tube. This eluate, fraction 2, contains the
unsaturated and aromatic hydrocarbons. Discard any remaining solvent in the
column.
Copper Activation. Prior to silica-gel chromatography sediment extracts are
passed through activated fine granular copper to remove elemental sulfur.
Activated copper should be prepared just prior to use by washing it with
concentrated hydrochloric acid (HC1). Rinse the activated copper five times
with acetone to remove the HC1 and then five times with methylene chloride to
remove the acetone.
Note 1: Both sand and sodium sulfate are dried in an oven at 125°c
overnight and cooled in a dessicator for 30 min prior to use.
Note 2: Let the sample and rinses each remain in the copper layer
and the sodium sulfate layer for ca. 2 min to remove sulfur and
water respectively.
Gas Chromatography (GC)
GC Sample Preparation. Attach a reflux column to the concentrator tube
containing the eluate from silica-gel chromatography. Evaporate the solvent
in the heater block as previously described. After concentrating to
0.7-1.0 mL, transfer the samples to the GC vials, add 50 yL of internal
standard solution (80 ng/yL hexamethylbenzene) and crimp on the Teflon-lined
septum caps. Replace the cap each time it is pierced by a syringe to avoid
evaporative losses.
GC Apparatus and Modifications. GC analysis is performed on a microprocessor-
controlled gas chromatograph (Hewlett-Packard model 58AOA) equipped with: an
automatic sample injector (model 7671A); a wall-coated, open tubular (WCOT)
glass capillary column (20-30 ra length, 0.25 mm i.d»); and a hydrogen flame-
ionization detector (FID).
The GC sample injection port is modified as described by Ramos, et^ al-
(5).
GC Sample Analysis. Analysis is carried out according to conditions listed in
Table III-l. GC Samples in crimp-sealed, septum-capped vials are loaded into
the automatic sampler. Then the desired operating conditions are programmed
into the microprocessor. A sample volume of 2 uL is injected per analysis.
After 5 min, the column temperature is programmed at 4°C/min to 280°C and held
for 30 min. Separated compounds are detected by the FID as they emerge from
the GC column. The gas chromatogram is constructed by the microprocessor,
which prints compound retention times alongside each peak on a strip chart.
Peak areas are automatically computed using "valley to valley" mode
baseline correction. Areas are printed in tabular form at the end of the GC
run according to retention times* The quantities of compounds represented by
the peak areas are also computed automatically by ratio of the individual peak
82
-------
areas to the area of the known amount of internal standard peak. If reference
samples are available for compounds of interest, relative response factors for
these compounds with respect to the internal standard should be determined
experimentally under identical conditions.
83
-------
Table III-l
Gas Chromatography Conditions
Column
type
Column:
Liquid phase:
Film thickness:
30 m x 0.25 mm i.d. wall-
coated glass capillary
SE-30 GC (dimethyl siloxane
polymer) or SE 54
4-5xlO~4mm
Inlet
Gases
Detector
Carrier gas:
Split ratio:
Column flow:
Bypass flow:
Makeup I
Air
Hydrogen
He
10:1
2 mL/min
20 mL/min
(bypass:column)
30 mL/min
240 mL/min
24 mL/min
Temperatures
Initial Temp:
Program rate:
Final temp:
Injector:
Detector:
50°C (for 5
4°c/min
min)
280°C
280°C
300°C
84
-------
Gas Chromatography/Mass Spectrometry (GC/MS).
The identity of compounds detected and measured by GC are confirmed by
GC/MS analysis as necessary. A capillary column similar to that used in GC
analysis is employed. Effluent from the GC column is fed directly into the
ion source. Table III-2 lists analysis conditions. A 1 to 2 -uL sample is
injected into the GC/MS while the ion source filament and electron multiplier
voltage are turned off. Passage of the solvent peak from GC to MS is noted on
the instrument high vacuum gage as a transient rise and fall in pressure.
After this, the source filament and multiplier voltage are restored to normal
settings and data acquisition by the computer is initiated for mass scans
every 2 sec. The GC column is subjected to virtually the same analytical
parameters for the GC/MS confirmation run as in the GC detection and
measurement run. At the end of the run, the chromatogram is reconstructed
(RGC) from the total ion current of each individual scan. Specific ion
chromatograms featuring abundancies of ions characteristic of a particular
molecular configuration may also be produced. Primarily, compounds shown to
be present in the GC/MS chromatogram are identified by comparing their mass
spectrum (background subtracted) with standard reference tables of mass
spectra or laboratory spectra of reference compounds.
Table III-2
GC/MS Analysis Parameters
GC: Same as Table III-l, except no make-up gas
GC/MS interface temp.: 250°
MS:
Filament emission: 500 A
Electron multiplier voltage: 1800 V
Electron energy: 70 eV
Data acquisition:
Mass range: 80-280 (aromatic samples)
50-300 (alkane samples)
Integration time: 6 msec/scan
Scan time: 2 sec
85
-------
Dry Weight Determination
Sediment. Thaw sediment and remove pebbles using a spatula or a sieve.
Thoroughly mix with a spatula. Add 10-20 g of the sediment to a tared
aluminum dish. Weigh and record the weight of the dish and sample. Cover the
dish and sample loosely with aluminum foil. Dry the sample in an oven at
120°C for 24 hr, then remove and cool for 30 min in a dessicator. Reweigh and
record the dried weight. Calculate percent dry weight as:
weight (dry) - weight (tare)
weight (wet) - weight (tare)
Tissue. Place ca. 3 g clean coarse sand and a small glass spatula in an
aluminum dish and dry overnight in a 120°c oven. Cool the dish in dessicator
for 30 min- Weigh and record as tare weight.
Weigh 0.5 g of sample (to the nearest 0.1 mg) into the dish. Thoroughly
mix the sample with the sand, using the spatula taking care to avoid loss of
sand granules. Dry the sample in a 120°c oven for 24 hr, then remove and cool
in a dessicator for 30 min. Reweigh and record the dried weight. Calculate
percent dry weight as:
weight (dry) - weight (tare)
weight (wet) - weight (tare)
100
Microgravimetric Determinations
Recored the volume of the eluate or extract. Then transfer 25 yL onto the
balance pan of a microbalance and allow the solvent to evaporate until weight
stabilizes. Record Cahn weight and calculate Total Hydrocarbons (yg/g dry
weight) as:
Volume of eluate or extract (yL) x Cahn weight
25 x percent dry weight x sample weight (g)
100
86
-------
APPENDIX IV
Individual hydrocarbon data tabulated per site per quarter. All data
are reported as ng/g dry weight of sample. ND = not detected.
87
-------
BIRCH POINT
SEDIMENTS
H-Alkanes Spring
if carbons 1A IB
10
11
12
13
14
15
16
17
ND
ND
ND
0.30
0.21
7.5
2.2
8.5
Pristane 5.9
18
3.1
Phytane 3.1
19
20
21
22
23
24
25
26
27
28
29
30
31
6.3
2.0
4.4
3.3
8.1
4.2
16
3.6
12
5.7
12
ND
7.3
n.-Alkanes
it earbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
ND
ND
ND
ND
0.49
3.9
1.7
6.7
6.3
2.4
2.4
0.08
1.8
2.8
2.1
4.2
2.3
8.7
1.9
8.2
4.5
8.4
NO
4.8
Spring
19
17
19
31
77
280
75
62
890
8
14
ND
n
21
16
37
25
59
27
94
ND
ND
ND
ND
Summer
ND
ND
0.57
ND
0.83
8.3
2.1
, 7.4
3.2
3.9
1.6
2.9
4.2
6.1
12
21
23
33
19
20
13
11
3.8
ND
Summer
ND
68
86
48
52
280
58
570
29
ND
ND
ND
ND
ND
ND
21
ND
30
ND
ND
ND
ND
ND
ND
Fall
ND
ND
1.3
1.6
2.4
43
3.5
54
27
3.8
2.4
4.2
2.1
2.6
3.6
6.5
2.5
8.5
1.5
10
ND
ND
ND
ND
Fall
ND
18
ND
ND
ND
350
ND
ND
180
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter Aromatic hydrocarbons
ND
ND
0.82
0.96
1.2
12
0.97
16
11
2.5
6.1
2.2
0.92
2.3
2.9
7.3
6.9
9.6
7.3
9.9
8.6
8.8
7.1
8.5
Winter
ND
ND
ND
ND
ND
260
78
27
170
ND
ND
ND
ND
ND
ND
ND
ND
38
ND
95
ND
ND
ND
ND
p_-Xylene
I sopropyl benzene
n-Propyl benzene
Tndan.
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methyl naphthalene
1 -Methyl naphthalene
Biphenyl
2, 6-Dimethyl naphthalene
2 ,3, 5-Trimethyl naphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Peryl ene
MUSSELS
Aromatic hydrocarbons
p_-Xyl ene
Isopropyl benzene
£-Propyl benzene
Indan
1,2, 3 ,4-Tetramethy 1 benzene
Naphthalene
Benzothiophene
2-Methyl naphthalene
1 -Methyl naphtha! ene
Biphenyl
2, 6-Dimethyl naphthalene
2,3, 5-Trimethyl naph thai ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Peryl ene
Spring
1A IB
ND
0.16
0.14
0.13
0.27
1.0
ND
0.98
1.0
ND
0.5
1.1
0.22
0.58
2.3
0.22
0.65
ND
ND
0.62
11.0
ND
ND
ND
Spring
ND
17
34
43
ND
ND
NO
ND
ND
no
86
ND
ND
ND
29
ND
26
37
60
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.45
ND
0.46
ND
ND
ND
1.9
ND
2.0
1.9
0.1
1.1
ND
ND
ND
ND
ND
ND
ND
Summer
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Summer Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.47
ND
ND
ND
ND
ND
ND
ND
1.0
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
36
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
7.0
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.77
2.7
18
2.4
ND
ND
ND
-------
CHERRY POINT
SEDIMENTS
n-Alkanes
Taarecne
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
1A
ND
ND
ND
0.52
1.4
4.6
3.0
6.3
3.2
4.6
2.2
6.9
4.5
8.6
12
26
29
56
39
47
35
33
20
24
Spring
IB
ND
ND
0.16
0.46
1.4
4.1
2.6
17
2,6
4.7
2.2
7.6
4.9
9,4
13
25
27
51
34
41
30
28
17
20
n-Al kanes
J" carbons
\ n
1 U
11
12
1 T
1 J
1 4
1 5
1 £
1 O
17
Pristane
18
Phytane
19
2i
22
24
25
26
27
nft
CO
nn
a
31
Summer
2 1 2
ND 2.2
ND 1.0
1,5 0.30
1.1 0.70
2.0 2.8
2,9 16.0
2.7 2,4
6.7 9.9
2.8 5.6
3.5 5,1
1,7 2.4
6.5 7.5
ND 4.8
5.3 5.1
1.5 3.4
6.8 6.1
ND 3.8
12 5.4
0.40 3.5
9.0 8.9
2.5 4.4
5.7 6.9
1.9 3.7
4.9 ND
ND
1.3
1.1
2.0
4.4
19.0
4.0
11.0
4.9
5.1
2.2
6.8
4.4
4.4
3.1
5.5
3.8
4.3
2.3
6.7
2.7
5.0
ND
ND
Spring Summer
78
71
41
30
JO
100
350
Qfi
yo
98
57
20
31
ND
01
L I
43
69
67
250
59
200
wn
NU
ND
ND
I1U
ND
..
__
..
»
__
--
Fall Winter Aromatic hydrocarbons
ND
ND
ND
ND
ND
2.8
ND
4.6
1.3
2.6
1.4
2.8
2.9
2.7
3.1
5.2
2.7
6.3
2.4
8.0
1.4
5.3
0.90
3.5
ND
ND
1.7
1.7
2.2
3.0
2.4
4.8
5.3
3.4
7.0
4.6
3.5
4.1
4.0
7.9
5.9
9.5
5.1
10
4.4
7.5
2.8
5.4
M
Fall Winter
._
_.
__
..
__
..
..
..
.-
--
.-
_-
--
_-
__
--.
o-Xylene
Tsopropyl benzene
n-Propyl benzene
Indan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methylnaphthalene
1 -Methyl naphthal ene
Biphenyl
2, 6-Dimethyl naphthal ene
2 ,3 ,5-Trimethy 1 naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
U S S E L S
Aromatic hydrocarbons
o-Xylene
Tsopropylbenzene
n-Propylbenzene
Tndan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methylnaphthalene
1 -Methyl naphthal ene
Biphenyl
2,6-Dimethylnaphthalene
2,3, 5-Trimethylnaphthalene
Fluorene
Dibenzothlophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Peryl ene
1A
ND
0.05
ND
0.84
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
5.7
ND
ND
11
7.0
3.5
9.0
ND
ND
no
Spring
ND
ND
ND
26
ND
ND
ND
ND
ND
un
nu -
120
ND
ND
NO
180
ND
ND
520
390
580
680
ND
ND
ND
spring
IB
ND
0.26
ND
0.70
ND
1.3
ND
ND
ND
ND
ND
ND
0.40
ND
8.3
0.56
ND
12
9.4
3.0
8.4
ND
ND
ND
Summer
~
--
-
--
*-
--
--
--
-
-
-
~~
--
""
2
ND
5.5
ND
ND
ND
2.4
ND
ND
ND
ND
ND
ND
ND
ND
4.0
ND
ND
5.9
5.3
ND
ND
ND
ND
ND
Fall
..
*-
~~
"
--
-
--
~-
--
--
--
*-
"""
"
""
"
bumm
1
ND
ND
ND
ND
ND
1.9
ND
ND
ND
ND
ND
ND
1.0
ND
6.8
0.54
ND'
15
5.9
2.3
8.1
3.6
1.2
ND
Winter
--
~
~
--
"
--
--
-
--
"
--
-
-
~~
__
"
2
ND
ND
2.5
0.92
ND
1.2
ND
0.75
0.86
0.43
ND
ND
1.3
3.1
12
2.0
ND
15
13
2.6
16
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
0.98
0.47
0.60
ND
ND
0.73
ND
6.7
0.2
0.18
11
5.7
5.3
3.9
2.0
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.3
3.3
ND
ND
6.1
8.0
ND
2.5
ND
ND
ND
89
-------
SANDY POINT
rv-Alkanes
# carbons
10
11
12
13
14
15
15
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Spring
1A IB
2.4
3.1
1,9
3.2
4.1
6.0
5.5
6.7
1.1
6.9
3.9
11
3.1
11
7.5
9.8
9.2
20
11
17
12
12
5.1
8.0
a-Al kanes
# cartons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
2.7
3.2
1.7
3.2
4.2
6.1 ,
5.9
7.5
0.95
7.5
4.0
10
4.1
10
6.0
7.1
5.0
9.6
4.3
8.7
4.9
5.9
ND
2.8
Spring
16
23
21
13
81
250
70
61
43
NO
24
ND
ND
18
24
45
42
77
45
no
ND
ND
ND
ND
SEDIMENTS
Summer
HO
0.60
3.4
3.5
4.1
5.7
3.8
4.6
5.5
3.6
3.9
6.4
5.3
5.8
4.7
5.7
3.3
6.6
2.7
4.5
2.3
3.6
1.7
6.0
Summer
ND
ND
47
ND
64
200
45
220
8.5
ND
ND
ND
ND
ND
ND
ND
ND
19
14
ND
ND
ND
ND
ND
Fall
ND
ND
4.6
4.3
4.5
6.2
5.0
2.4
30
5.7
2.9
7.0
6.1
4.8
4.5
6.3
4.8
5.2
3.5
6.7
5.0
8,8
3.3
4.5
Fall
29
38
32
40
80
360
100
78
36
29
ND
26
30
29
35
53
19
34
18
32
ND
ND
ND
ND
Winter
ND
ND
3.4
3.9
3.9
5.4
4.4
11
4.8
5.9
3.5
7.4
5.4
7.1
6.0
8.8
6.4
10
6.9
19
7.2
8.7
3.1
n
Winter
ND
ND
ND
ND
75
280
110
120
100
47
29
69
ND
60
55
98
81
110
67
140
64
ND
ND
ND
Aromatic hydrocarbons
o-Xylene
I sopropyl benzene
n-Propyl benzene
Indan-
1,2,3, 4-Tetramethy 1 benzene
Naphthalene
Benzothiophene
2-Met hy 1 naphtha 1 ene
1 -Methyl naphthalene
Biphenyl
2, 6-Dimethyl naphthalene
2, 3, 5-Trimethyl naphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methy 1 phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
MUSSELS
Aromatic hydrocarbons
o_-Xylene
Isopropylbenzene
n-Propyl benzene
Indan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methyl naphthalene
1 -Methy 1 naphtha 1 ene
Biphenyl
2, 6-Dimethyl naphthalene
2, 3, 5-Trimethyl naphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A IB
ND
0.94
ND
ND
0.07
2.7
ND
2.5
1.1
0.89
1.7
ND
1.4
ND
14
1.3
0.33
1.3
13
3.4
n
ND
ND
ND
Spring
ND
ND
39
ND
ND
ND
ND
ND
ND
ND
86
ND
ND
ND
18
ND
ND
71
81
ND
ND
ND
ND
ND
ND
0.06
0.14
0.02
0.12
2.3
ND
2.6
1.0
0.94
1.6
ND
1.3
0.25
n
2.0
0.22
1.2
10
3.0
n
ND
ND
ND
Summer
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Summer
ND
ND
ND
1.1
ND
2.3
ND
0.98
0.44
ND
0.99
ND
0.64
ND
5.4
ND
ND
5.2
0.75
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
470
ND
ND
ND
ND
ND
96
ND
1.0
39
34
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.2
1.6
ND
0.97
0.20
3.8
ND
0.51
6.4
5.1
2.7
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
23
ND
ND
ND
ND
360
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.61
1.8
1.2
2.1
1.6
9.6
5.3
3.7
33
47
24
14
6.2
8.1
2.2
90
-------
MARCH POINT
n^Alkanes
* carbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
ZO
21
22
23
24
25
26
27
28
29
30
31
1A
ND
0.27
0.52
2.1
4.0
8.9
8.9
14
6.9
12
7.4
21
11
16
17
27
29
54
27
39
26
29
9.6
16
Spring
IB ZA
ND NO
ND ND
1.4 0.64
2.5 2.4
4.4 5.2
11 14
12 16
19 27
30 23
22 30
18 12
32 38
20 25
21 26
21 24
28 30
25 27
43 41
21 23
28 29
17 18
20 23
5.4 9.0
12 16
f -Alkalies
carbone
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Summer
ZB
ND
NO
6.0
7.0
10
20
18
23
66
21
45
6.8
20
22
3.3
45
54
72
43
45
30
30
13
17
Spring
69
76
53
39
80
170
34
58
100
9.0
27
NO
9.4
11
12
28
22
60
25
63
ND
ND
NO
ND
1
2.1
3.2
1.4
4.2
7.7
16
12
21
24
21
13
28
19
24
14
17
9.4
16
7.1
17
19
18
4.0
12
Summer
150
180
110
45
55
200
40
68
82
ND
ND
ND
ND
22
ND
33
ND
21
ND
ND
ND
ND
ND
ND
2
1.2
2.3
1.3
3.5
5.8
12
8.7
15
19
13
8.7
18
12
12
7.6
11
5.9
7.8
4.5
13
17
9.2
7.9
9.8
Fall
410
360
250
110
81
190
52
87
620
19
100
63
29
31
32
85
18
38
10
19
ND
26
NO
ND
Fall
ND
ND
3.8
7.7
4.3
15
5.9
18
23
8.6
4.2
16
8.3
10
7.7
16
8.7
21
8.3
41
9.7
3.2
19
24
Winter
ND
180
65
69
61
290
140
190
360
ND
110
ND
ND
ND
ND
78
44
70
52
120
49
110
ND
ND
SEDIMENTS
ND o-Xylene ND
ND Tsopropylbenzene 0.15
2.7 n-Propylbenzene 0.37
4.1 Tndan 0.17
6.0 1,2,3,4-Tetramethylbenzene 0.18
9.7 Naphthalene 3.9
10 Benzothiophene ND
18 2-Methyl naphthalene 4.0
12 1-Methylnaphthalene 1.6
13 Blphenyl 1.4
7.1 2,6-Dimethylnaphthalene 1.6
14 2,3,5-Trimethylnaphthalene 2.1
9.9 Fluorene 1.9
11 Dlbenzothiophene 0.26
7.6 Phenanthrene 18
9.3 Anthracene 6.1
5.5 1 -Methyl phenanthrene 1.3
9.0 Fluoranthene 13
4 . 5 Pyrene 22
7.3 Benz(a)anthracene 7.9
10 Chrysene 19
13 Benzojejpyrene ND
16 Benzo(a)pyrene ND
10 Perylene ND
MUSSELS
Spring
IB
3.6
0.47
0.81
0.68
0.26
5.2
ND
4.4
1.7
1.3
1.6
1.7
1.6
0.30
14
3.1
0.90
7.1
16
7.6
20
ND
NO
ND
Aromatic hydrocarbons Spring Summer
o-Xylene NO
Tsopropylbenzene ND
n-Propyl benzene 63
Tndan 17
1,2,3,4-Tetramethylbenzene 76
Naphthalene ND
Benzothiophene ND
2-Methyl naphthalene ND
1-Methylnaphthalene ND
Blphenyl ND
2,6-Dimethylnaphthalene 60
2,3,5-Trlmethylnaphthalene ND
Fluorene ND
D1benzoth1ophene ND
Phenanthrene 68
Anthracene ND
1 -Methyl phenanthrene ND
Fluoranthene ' 140
Pyrene 50
Benz(a)anthracene ND
Chrysene ND
Benrotelpyrene ND
Benzo(a)pyrene ND
Perylene ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
49
61
ND
93
ND
ND
ND
ND
ND
ND
2A
ND
0.29
ND
1.6
ND
2.5
ND
ND
0.52
ND
ND
ND
1.0
ND
19
3.5
0.2
46
52
13
34
ND
ND
ND
2B
ND
0.21
ND
0.40
ND
5.7
ND
4.8
1.9
0.25
3.8
5.8
4.4
1.50
62
10
2.5
73
77
21
48
ND
ND
ND
summer
1
ND
ND
1.2
ND
ND
4.3
ND
2.8
ND
0.36
1.5
0.38
2.8
0.79
24
4.2
1.3
33
30
5.3
12
5.0
3.8
2.0
2
ND
ND
3.4
ND
ND
6.0
ND
4.3
1.6
0.92
2.6
0.53
4.6
1.2
50
7.9
1.7
62
94
16
48
ND
ND
NO
Fall
ND
ND
ND
ND
ND
ND
ND
2.9
1.6
0.03
0.64
0.63
0.29
ND
9.6
1.5
0.48
11
8.3
8.5
6.5
4.2
4.2
0.73
Winter
ND
ND
ND
ND
ND
ND
ND
NO
ND
0.93
2.2
ND
3.0
0.89
12
1.6
1.0
16
2<
14
5.4
2.3
0.35
ND
Fall Winter
ND
ND
ND
ND
ND
33
ND
20
190
ND
ND
ND
ND
ND
160
ND
39
100
45
ND
ND
ND
ND
ND
ND
ND
no
ND
ND
ND
ND
NO
ND
ND
IID
ND
IID
CD
200
ND
KD
1200
910
280
160
ND
ND
ND
91
-------
SHANNON POINT
n-Alkanes Spring
f oarbone 1A IB
10
11
12
13
14
15
!6
17
1.1
0.39
ND
ND
0.90
3.4
3.7
13
Pristane 5.7
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
10
5.2
9.1
17
46
140
280
380
510
340
280
200
130
5.3
73
n-ATkanes
T aarbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
0.97
0.31
ND
ND
ND
0,71
0.49
2.0
0.98
2.4
ND
3.1
2.3
3.0
2.2
3.9
1.5
11
1.3
6.2
2.2
4.8
0.23
6.2
Spring
21
24
ND
ND
ND
no
20
45
360
12
100
ND
26
26
38
47
40
61
31
44
ND
ND
ND
ND
Summer
1.1
1.4
4.8
5.8
2.1
6.5
8.2
14
8.4
6.9
2.7
6.9
4.8
11
6.8
9.6
10
15
8.1
12
5.9
7.1
5.8
10
Summer
ND
30
52
18
120
160
65
160
200
ND
ND
ND
ND
59
ND
17
ND
6.3
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
3.0
2.8
3.7
3.4
4.2
2.9
9.6
8.4
9.4
6.0
8.4
4.7
84
4.5
11
1.1
ND
ND
ND
Fall
__
._
--
--
..
S
Winter
ND
ND
1.5
1.3
1.5
2.7
2.6
4.4
2.8
3.3
0.14
5.7
3.4
3.8
3.2
4.1
2.6
4.4
2.4
5.9
2.7
6.0
ND
ND
Winter
..
.-
-.
--
E D I M E N T S
Aromatic hydrocarbons
o-Xylene
I sopropyl benzene
n_-Propylbenzene
Indan-
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methyl naphthalene
1-Methylnaphthalene
Biphenyl
2, 6-Dimethyl naphtha! ene
2, 3, 5-Trimethyl naphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo{a)pyrene
Perylene
MUSSELS
Aromatic hydrocarbons
o-Xylene
Isopropylbenzene
n-Propyl benzene
Indart-
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methyl naphtha! ene
1 -Methyl naphtha! ene
Biphenyl
2,6-Dimethylnaphthalene
2,3, 5-Trimethy 1 naphtha! ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spri
2.9
ND
ND
ND
ND
1.9
ND
1.7
0.9
1.4
1.0
3.0
5.4
0.17
4.4
ND
9.5
160
1.9
3.6
19
ND
ND
11
Spring
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
15
ND
100
ND
24
ND
ND
ND
ND
ND
ng
1.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.70
ND
0.20
150
ND
3.5
ND
ND
ND
ND
Summer
6.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.7
ND
ND
ND
ND
ND
ND
ND
Summer
ND
ND
ND
ND
ND
2.0
ND
ND
ND
0.16
ND
ND
ND
ND
1.7
ND
2.6
1.2
ND
ND
ND
ND
ND
ND
Fall
__
--
--
--
--
--
-.
--
--
--
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.36
0.51
ND
ND
ND
ND
ND
ND
ND
ND
Winter
_
--
--
--
--
--
--
--
--
--
--
~
--
--
Wi nter
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.58
ND
2.4
0.14
0.34
3.5
3.9
0.55
0.36
0.36
ND
ND
92
-------
ALEXANDER BEACH
n-Alkanes Spring
W carbons 1A IB
10
11
12
13
14
15
16
17
1.4
1.3
NO
ND
0.39
2.1
2.2
4.1
Prlstane 110
18
3.7
Phytane 2.3
19
20
21
22
23
24
25
26
27
28
29
30
31
7.1
5.1
7.8
7.9
12
9.4
15
11
12
7.8
8.7
4.1
10
jl-A 1 kanes
t carbons
10
11
12
13
14
15
16
17
Prlstane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
0.35
0.27
ND .
ND
0.25
0.18
0.18
3.2
98
2.8
ND
4.9
3.5
5.4
5.6
9.5
7.7
16
6.5
9.5
6.2
7.0
3.2
7.7
Spring
18
59
150
5.9
81
220
590
77
5000
54
1600
500
130
29
77
49
25
89
64
260
370
610
830
1300
Summer
NO
0.20
0.49
0.65
0.73
1.7
1,5
2.8
150
1.3
0.97
3.1
2.3
2.8
0.13
ND
ND
4.1
ND
0.15
ND
4.3
ND
ND
Summer
ND
ND
25
ND
57
300
92
190
1200
55
no
23
38
64
ND
44
35
51
83
49
84
ND
52
ND
Fall
ND
ND
1.5
1.4
1.7
7.4
2.1
6.1
ND
3.0
1.4
5.8
4.9
4.9
4.7
9.4
5.3
12
4.5
12
4.6
>3
5.6
11
Fall
11
28
50
36
200
830
98
11
3400
12
47
37
22
ND
22
55
23
750
27
120
19
40
ND
ND
S
Winter
ND
ND
0.70
0.79
1.2
1.9
2.0
ND
ND
2.8
1.6
3.8
3.3
3.9
2.9
4.9
2.3
6.8
2.5
6.0
2.7
5.4
ND
ND
Winter
ND
ND
ND
75
270
450
100
170
3700
85
540
ND
71
66
50
84
56
190
48
140
ND
90
ND
ND
E D I M E N T S
Aromatic hydrocarbons
£-Xy1ene
Isopropyl benzene
n-Propyl benzene
Tndan -
1,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2 -Methyl naphthalene
1 -Methyl naphtha 1 ene
Blphenyl
2, 6-Dimethyl naphthalene
2,3, 5-Tr1 methyl naphthal ene
Fluorene
D1benzoth1ophene
Phenanthrene
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
MUSSELS
Aromatic hydrocarbons
o-Xylene
Tsopropyl benzene
n-Propyl benzene
Tndan
1,2,3, 4-Tetramethy 1 benzene
Naphthalene
Benzothiophene
2-Methyl naphthalene
1 -Methyl naphthal ene
Blphenyl
2, 6-D1methyl naphthal ene
2, 3, 5-Tr1methyl naphthalene
Fluorene
Dibenzothlophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A IB
2.5
1.9
1.4
ND
ND
1.7
ND
0.40
ND
ND
ND
ND
ND
ND
0.80
ND
ND
6.9
0.70
0.60
ND
ND
ND
ND
Spring
ND
ND
48
27
ND
ND
ND
23
13
ND
ND
31
150
ND
31
ND
83
14
49
ND
ND
ND
ND
NO
0.80
0.70
0.50
ND
0.10
1.0
ND
0.40
ND
ND
ND
ND
0.20
ND
2.7
ND
0.60
9.2
2.7
1.7
ND
ND
ND
ND
Summer
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Summer
ND
2.0
1.1.
ND
ND
0.86
ND
0.40
0.10
ND
ND
ND
0.084
ND
1.3
ND
0.19
2.5
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
15
ND
ND
ND
ND
ND
ND
ND
ND
18
ND
ND
ND
7.4
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
5.9
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
63
ND
ND
350
ND
11
5.3
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.88
ND
1.9
ND
0.20
3.8
3.1
ND
0.45
ND
ND
ND
93
-------
FORT CASEY
SEDIMENTS
n-ATkanes
IT oarbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Spring
1A
ND
ND
0.50
0.50
1.3
2.1
2.1
1.3
ND
2.3
ND
2.2
1.4
2.6
2.6
IB
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
3.7 0.15
3.4 0
5.6 0
2.6
3.8
3.3
3.7
ND
ND
.43
.31
ND
ND
ND
ND
ND
ND
Summer
ND
ND
3.5
3.2
5.8
3.6
4.2
7.1
1.5
4.0
1.2
4.6
5.2
5.5
3.7
3.3
2.5
4.8
2.3
3.6
3.6
3.8
ND
ND
Fall
ND
ND
1.6
1.8
2,5
3.0
3.2
3.9
3.1
3.6
0.90
3.2
3.2
2.5
2.2
3.0
1.8
2.4
1.6
2.9
0.92
2.2
ND
ND
Winter
ND
ND
3.6
3.5
3.8
3.1
2.7
2.6
2.2
2.5
1.1
3.1
2.2
2.2
2.2
3.5
2.7
2.9
2.2
2.7
2,3
3.4
1.4
1.9
Aromatic hydrocarbons
o-Xylene
I sopropyl benzene
rj-Propyl benzene
Indan.
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2- Methy 1 naphthal ene
1-Methylnaphthalene
Biphenyl
2 , 6-Dimethyl naphthal ene
2, 3, 5-Tri methyl naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methy 1 phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A IB
ND
ND
0.43
0.32
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.66
ND
ND
1.9
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.42
ND
ND
ND
ND
ND
ND
Summer
ND
ND
ND
1.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.7
0.63
0.04
ND
1.4
ND
ND
ND
ND
ND
KEYSTONE
n-Al kanes
? carbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
Ort
20
21
22
23
24
25
26
27
28
29
30
31
Spring
34
45
47
37
150
300
52
290
37
14
30
54
20
75
34
44
37
170
41
ND
NO
ND
ND
ND
Summer
ND
ND
39
27
120
270
87
90
830
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
79
180
520
110
78
460
11
74
ND
ND
ND
ND
51
54
72
39
68
42
88
ND
ND
Winter
ND
ND
28
56
140
270
110
140
270
57
93
29
56
61
62
52
75
47
71
37
61
130
ND
ND
MUSSELS
Aromatic hydrocarbons
o^Xylene
Isopropyl benzene
n-Propyl benzene
Tndan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methyl naphthal ene
1 -Methyl naphthal ene
Biphenyl
2, 6-Dimethyl naphthal ene
2,3, 5-Trimethyl naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
ND
19
23
30
ND
ND
ND
ND
ND
ND
220
ND
ND
ND
170
ND
160
410
280
280
300
ND
ND
ND
Summer
ND
ND
95
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
16
26
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
270
150
38
ND
ND
ND
94
-------
NAVAL AIR STATION/WHIDBEY ISLAND
SEDIMENTS
n-Alkanes Spring
T carbons 1A IB
10
11
12
13
14
15
16
17
0.28
ND
ND
ND
ND
ND
ND
0.37
Prlstane 0.68
18
0.38
Phytane ND
19
20
21
22
23
24
25
26
27
28
29
30
31
0.17
0.40
NO
0.44
0.22
ND
4.7
ND
1.3
ND
ND
ND
NO
UrAlkanes
# oafbona
10
11
12
13
14
15
16
17
Prlstane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
0.28
ND
ND
ND
ND
ND
ND
0.23
0.34
0.39
ND
0.51
0.39
0.44
ND
ND
ND
4.0
ND
ND
ND
ND
ND
ND
Spring
150
470
410
180
170
9.0
33
57
77
24
25
ND
ND
18
14
49
21
51
24
100
ND
ND
ND
ND
Summer
ND
ND
1.0
1.2
1.5
1.5
1.9
4.1
2.7
2.6
1.1
3.6
4.0
6.6
9.5
14.0
15.0
19.0
11.0
12.0
7.8
7.7
ND
ND
Sunmer
ND
64
100
54
62
230
47
11
11
ND
ND
ND
12
14
16
27
28
32
49
92
72
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.33
0.57
1.1
1.1
2.5
1.4
3.1
1.5
4.3
1.1
3.6
ND
2.3
Fall
23
72
130
75
200
450
100
ND
ND
ND
ND
ND
120
ND
ND
53
14
410
11
50
33
44
ND
ND
Winter Aromatic hydrocarbons
ND
ND
0.20
1.0
1.4
1.3
1.3
0.070
2.5
1.1
1.8
1,1
1.2
1.4
1.2
2.4
1.2
2.1
1.2
2.4
ND
1.8
ND
ND
Winter
ND
74
68
58
74
260
61
63
550
27
250
no
47
23
59
73
59
76
55
100
47
54
ND
ND
£-Xylene
Isopropyl benzene
n-Propyl benzene
Indaa
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothlophene
2-Methyl naphthalene
1 -Methyl naphthal ene
Biphenyl
2 , 6-Dimethyl naphthal ene
2,3, 5-Tr1methy 1 naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzofejpyrene
Benzo(a)pyrene
Perylene
MUSSELS
Aromatic hydrocarbons
o-Xylene
Tsopropyl benzene
n-Propyl benzene
Tndar*
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothlophene
2-Methyl naphthal ene
1 -Methyl naphthal ene
Biphenyl
2 ,6-D1methyl naphthal ene
2,3,5-Trimethylnaphthalene
Fl uorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A IB
0.54
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.5
ND
ND
ND
ND
ND
ND
Spring
ND
ND
no
. 21
77
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
51
33
58
ND
ND
ND
ND
ND
1.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
3.1
ND
ND
ND
ND
ND
ND
Summer
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Summer Fall
ND
ND
ND
ND
0.69
2.4
NO
ND
ND
0.079
ND
ND
ND
ND
1.0
ND
ND
2.0
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.5
0.46
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
HD
HD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.3
1.1
ND
ND
2.5
1.1
ND
ND
ND
ND
ND
95
-------
FALSE BAY
rWUkanes
# carbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Spring
1A IB
0.25
0.24
ND
ND
ND
1.6
1.0
2.1
5.7
1.8
0.92
2.7
2.0
4.1
8.3
16
20
36
20
21
13
9.5
5.2
7.2
n-Alkanes
F carbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
1.1
0.4
ND
ND
0.38
2.0
1.5
2.6
7.9
0.70
ND
3.9
3.1
5.1
8.3
15
17
33
16
19
12
9.5
4.5
7.9
Spring
ND
ND
ND
ND
ND
100
ND
ND
330
ND
ND
HO
ND
7.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Summer
ND
ND
1.4
1.6
1.6
3.6
2.6
8.7
'13
3.3
1.3
4.2
5.1
10
18
34
42
62
39
40
29
21
8.7
10
Summer
180
140
75
130
180
580
140
120
91
27
61
4.6
ND
19
17
51
86
280
47
52
ND
ND
ND
ND
Fall
ND
ND
ND
ND
0.18
5.1
2.4
14
8.3
4.5
2.3
3.2
8.2
8.7
8.2
12
6.3
14
5.6
34
3.7
11
3.0
6.7
Fall
..
--
--
--
__
--
-_
--
--
S
Winter
ND
ND
1.2
1.5
1.7
3.1
1.9
2.3
2.9
1.5
1.5
2.2
2.0
2.7
2.3
4.1
2.7
4.5
2.3
6.7
3.2
7.9
ND
ND
Winter
..
--
--
--
..
..
--
E D I M E N T S
Aromatic hydrocarbons
<3-Xylene
Isopropyl benzene
n-Propylbenzene
Tndarr
1,2, 3 ,4-Tetramethy 1 benzene
Naphthalene
Benzothiophene
2-Methyl naphthalene
1-Methylnaphthalene
Biphenyl
2, 6-Dimethyl naphthalene
2, 3, 5-Tri methyl naphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
MUSSELS
Aromatic hydrocarbons
o-Xylene
Isopropyl benzene
n-Propyl benzene
Tndan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Hethy 1 naphthal ene
1 -Methyl naphthal ene
Biphenyl
2,6-Dimethyl naphthal ene
2, 3, 5-Trimethyl naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A IB
1.2
0.50
0.30
ND
ND
2.6
ND
2.1
0.80
ND
ND
ND
2.0
ND
7.2
ND
1.5
22
3.8
5.1
ND
ND
ND
ND
Spring
ND
ND
20
ND
ND
ND
ND
ND
5.3
ND
ND
ND
22
86
520
ND
ND
610
190
270
42
ND
ND
ND
2.2
0.50
0.50
ND
ND
2.7
ND
2.0
0.60
ND
ND
ND
2.0
ND
7.0
ND
0.60
19
4.8
4.5
ND
ND
ND
ND
Summer
ND
ND
13
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
620
80
64
760
610
710
540
ND
ND
ND
Summer
ND
ND
ND
ND
ND
3.0
ND
ND
ND
ND
ND
ND
2.2
0.40
9.9
1.9
ND
17
0.83
8.2
5.3
1.7
0.34
ND
Fall
..
_
__
..
__
__
__
__
_.
-_
..
Fall
ND
ND
ND
ND
ND
ND
ND
1.2
0.88
ND
ND
ND
5.2
ND
44
79
1.0
170
76
58
85
22
19
3.0
Winter
..
..
...
..
__
__
__
__
__
__
._
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.22
ND
ND
2.1
3.1
5.3
1.5
ND
7.3
8.4
ND
2.0
ND
ND
ND
96
-------
ANDREWS BAY
n-Alkanes
~F carbons
10
11
12
13
14
15
16
17
Prlstane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
1A
4.5
6.3
15
33
49
69
7.3
94
260
95
29
100
72
54
45
52
56
83
51
50
34
30
15
20
Spring
IB
4.8
4.0
5.3
5.7
6.5
9.4
7.6
12
190
9.0
5.8
13
6.9
13
16
23
25
42
25
28
20
19
9.5
15
2A
ND
10
7.5
7.9
9.8
10
9.8
16
320
7.9
4.5
15
6.0
16
31
45
57
66
43
39
24
21
11
24
2B
ND
8.6
7.0
7.3
8.9
9.3
8.8
16
280
8.3
6.0
17
15
31
74
140
190
250
180
170
130
97
66
74
Summer
1
NO
3.5
3.3
4.4
5.8
7.8
4.3
7.8
5.4
5.5
2.2
7.3
5.9
4,9
4.8
5.9
3.5
7.1
2.3
5.1
2.3
5.9
1.3
NO
2
4.2
8.5
5.9
6.0
8.9
11
8.0
11
14
7.9
2.7
9.5
7.7
8.3
6.3
7.8
4.9
9.2
3.0
6.6
3.3
6.6
NO
ND
Fall
ND
ND
2.3
2.8
3.7
8.3
6.2
10
8.5
8.8
3.7
8.8
11
11
8.7
10
6.4
7.9
4.9
9.2
2.4
7.1
1.3
3.2
S E
D I M E N T S
Winter Aromatic hydrocarbons
ND
ND
6.2
6.6
6.6
7.9
8.2
10
7.4
9.2
3.4
11
9.4
9.3
8.2
9.1
6.5
9.7
5.3
8.9
4.6
8.1
ND
ND
o-Xylene
Tsopropyl benzene
n-Propyl benzene
Tndan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methyl naphthal ene
1 -Methyl naphthal ene
Biphenyl
2 ,6-D1methyl naphthalene
2, 3, 5-Trimethyl naphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A
ND
ND
0.57
0.45
2.2
11
0.70
220
120
1.4
97
7.5
20
1.2
65
3.1
6.7
1.9
3.0
1.9
15
NO
ND
ND
IB
3.2
0.12
0.73
NO
0.15
Z.O
ND
3.0
1.4
0.72
2.0
0.34
2.0
ND
6.4
2.2
0.15
3.9
1.0
1.2
47
ND
ND
ND
2A
ND
3.6
ND
3.5
ND
0.95
ND
0.56
1.2
ND
1,6
ND
1.0
0.69
8.4
ND
0.92
3.4
25
2.4
ND
ND
ND
ND
2B
ND
ND
ND
1.4
ND
2.4
ND
ND
ND
ND
ND
ND
ND
0.62
7.9
1.6
0.81
4.8
ND
NO
t'.Q
ND
ND
ND
Summer
1
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.7
ND
ND
4.6
3.0
ND
ND
ND
ND
ND
2
ND
ND
1.2
0.46
ND
1.3
ND
0.71
0.87
0.84
NO
ND
1.1
ND
3.4
0.74
ND
ND
0.87
ND
ND
ND
ND
ND
Fall
ND
ND
ND
NO
ND
NO
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.56
ND
1.0
ND
3.4
0.21
ND
7.1
6.9
ND
1.0
0.36
0.40
ND
WESTCOTT BAY
MUSSELS
n-Alkanes
F carbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Spring
ND
ND
ND
ND
ND
43
36
ND
ND
ND
ND
ND
ND
150
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Summer
ND
ND
26
ND
54
200
64
55
ND
ND
ND
ND
ND
ND
ND
ND
ND
11
ND
42
ND
ND
ND
ND
Fall
ND
ND
ND
20
95
230
no
44
ND
ND
ND
ND
ND
240
ND
ND
ND
ND
14
ND
ND
49
ND
ND
Winter
ND
ND
ND
ND
62
260
47
no
68
ND
ND
ND
ND
ND
ND
ND
ND
63
ND
ND
ND
ND
ND
ND
Aromatic hydrocarbons
o-Xyl ene
Tsopropyl benzene
rv-Propyl benzene
Indan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methyl naphthal ene
1 -Methyl naphthal ene
Biphenyl
2 ,6-Dimethyl naphthal ene
2, 3, 5-Trimethyl naphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Genz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
24
ND
ND
ND
ND
ND
Summer
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
97
-------
LEGOE BAY/LUMMI ISLAND
n-Al kanes
i carbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Spring
ND
ND
ND
ND
ND
92
ND
ND
230
ND
ND
ND
ND
ND
ND
ND
38
ND
ND
ND
ND
ND
ND
ND
Summer
260
250
220
67
52
150
73
320
250
ND
ND
ND
ND
170
ND
ND
ND
ND
ND
13
ND
ND
ND
ND
-
Fall
940
850
520
no
130
430
65
130
840
9.9
46
ND
28
28
30
53
26
170
24
160
22
860
ND
ND
Winter
ND
ND
ND
46
150
350
100
130
230
ND
ND
ND
ND
ND
ND
ND
no
ND
no
ND
ND
230
ND
ND
MUSSELS
Aromatic hydrocarbons
p_-Xylene
Isopropyl benzene
n-Propyl benzene
IndaR
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methy 1 naphthal ene
1 -Methyl naphthalene
Biphenyl
2, 6-Dimethyl naphthalene
2, 3 , 5-Trimethyl naphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
15
ND
180
ND
54
200
95
42
ND
ND
ND
ND
Summer
34
ND
ND
ND
ND
18
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
110
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
50
ND
ND
240
30
ND
92
ND
230
130
ND
ND
ND
98
-------
CAPE GEORGE
n-Alkanes 5pr
f oarbone 1A
10
11
12
13
14
15
16
17
ND
ND
ND
ND
ND
0.6
0.2
1.5
Prlstane ND
18
0.70
Phytane ND
19
20
21
22
23
24
25
26
27
28
29
30
31
1.5
0.50
0.90
0.72
1.1
0.31
4.3
ND
2.6
1.1
3.0
ND
ND
.rv-Alkanes
# aarbone
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Trig
IB
ND
ND
ND
ND
ND
ND
ND
0.70
ND
ND
ND
0.80
0.60
0.70
0.92
1.7
1.5
3.7
1.4
3.5
2.1
2.7
ND
ND
Spring
ND
ND
ND
ND
ND
46
ND
ND
140
ND
ND
ND
ND
52
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SEDIMENTS
Summer
0.4
ND
ND
ND
ND
2.0
ND
0.57
4.0
ND
ND
ND
0.55
2.4
3.3
7.5
7.4
8.4
6.6
8.3
3.5
5.6
ND
ND
Summer
150
70
no
74
120
370
100
370
no
28
23
54
ND
17
15
23
72
99
44
56
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
19
ND
ND
ND
29
4.9
8.5
2.2
5.7
3.0
8.1
2.7
13
2.1
8.7
ND
6.7
Fall
ND
ND
ND
ND
7.3
240
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
1.4
1.6
2.1
8.5
1.6
7.9
3.1
0.010
1.4
2.6
1.7
2.8
2.3
4.2
2.5
5.6
3.2
13
4.3
6.4
0.52
9.3
M
Winter
ND
ND
ND
57
150
290
83
no
86
ND
ND
ND
ND
ND
MD
ND
ND
ND
ND
98
ND
ND
ND
ND
Aromatic hydrocarbons
£-Xylene
Isopropyl benzene
n-Propyl benzene
Tndan-
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothlophene
2-Hethyl naphthalene
1 -Methyl naphthalene
Blphenyl
2, 6-D1methyl naphthalene
2,3, 5-Trimethyl naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
U S S E L S
Aromatic hydrocarbons
o-Xylene
Tsopropyl benzene
n-Propylbenzene
Tndan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothlophene
2-Hethyl naphthal ene
1 -Methyl naphtha! ene
Biphenyl
2, 6-D1methyl naphthalene
2,3,5-Trlmethylnaphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benzfajanthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A IB
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.37
ND
ND
ND
0.39
ND
1.2
ND
ND
ND
Spring
ND
ND
ND
96
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
88
ND
ND
ND
no
ND
ND
ND
ND
ND
ND
ND
0.14
0.66
ND
HD
ND
0.11
ND
ND
ND
ND
ND
0.18
0.54
ND
ND
ND
0.51
ND
1.4
ND
ND
ND
Summer
22
ND
63
4.0
ND
18
ND
ND
ND
ND
ND
ND
ND
51
ND
ND
86
ND
ND
ND
ND
ND
ND
ND
Summer Fall
ND
ND
ND
ND
ND
1.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.3
ND
ND
ND
ND
ND
ND
ND
Fall
ND
ND
28
ND
ND
ND
ND
ND
ND
ND
ND
ND
MD
ND
160
ND
ND
150
62
ND
ND
ND
ND
ND
MD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
24
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
110
ND
ND
ND
ND
.ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
llw
ND
1.8
1 n
J * U
12
3.0
ND
ND
ND
99
-------
DUNGENESS/THREE CRABS
SEDIMENTS
.n_-A1kanes
ft cafbons
10
11
12
13
14
15
16
17
Pristine
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Spring
1 2A
NO ND
3.4 2.0
6.3 5.3
8.5 8.5
11 4.3
19 27
9.8 8.9
17 13
29 11
8.6 9.2
4.2 3.9
17 16
13 9.3
17 17
21 20
41 38
30 28
100 100
19 27
140 120
17 27
130 100
7.0 16
88 80
n-Alkanes
F aarbona
10
11
12
13
14
15
16
17
Prlstane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
2B
ND
ND
3.0
4.7
7.1
12
7.6
11
13
8.8
4.3
15
11
23
45
85
92
180
89
170
70
120
35
90
Spring
13
14
23
42
5.4
310
94
71
71
19
.NO
3.0
14
36
22
54
62
240
74
240
76
260
NO
240
Summer
1 2
1.7 0.5
5.9 4.7
4.4 3.7
7.1 7.0
8.0 8.1
13 14
6.9 6.1
8.9 9.0
20 22
6.8 6.6
3.2 3.3
11 ' 11
7.2 7.1
9.9 11
7.7 7.1
15 16
7.6 7.7
33 36
6.9 7.3
58 65
7.8 8.4
46 49
6.0 5.3
35 37
Summer Fall
ND 31
5.3 34
43 32
31 24
120 160
250 260
61 100
67 130
ND 11
ND 19
ND ND
ND 20
ND ND
ND ND
ND ND
ND 25
ND ND
23 53
ND ND
63 120
ND ND
ND ND
ND ND
ND ND
Fall
ND
ND
6.9
7.0
7.5
1.3
5.9
6.1
12
5.7
2.7
8.1
7.2
10
11
24
16
67
20
150
15
120
18
99
Winter Aromatic hydrocarbons i
ND o-Xylene ND
ND Tsopropyl benzene 3.4
7.7 n-Propyl benzene ND
9.5 Tndan 1.6
10 1,2,3,4-Tetramethylbenzene ND
21 Naphthalene 4.6
13 Benzothiophene ND
18 2-Methyl naphthalene 1.0
32 1 -Methyl naphthalene 1.3
13 Biphenyl ND
9.8 2,6-Dimethylnaphthalene ND
15 2,3,5-Trimethylnaphthalene ND
13 Fluorene ND
17 Dibenzothiophene 0.71
13 Phenanthrene 7.8
32 Anthracene ND
14 1 -Methyl phenanthrene 1.8
81 Fluoranthene 1.5
1 5 Pyrene 1 3
160 Benz(a)anthracene ND
18 Chrysene 33
130 Benzo(e)pyrene ND
15 Benzo(a)pyrene ND
130 Perylene ND
MUSSELS
Winter Aromatic hydrocarbons Spring
ND
ND
ND
no
55
300
100
160
54
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
89
ND
ND
ND
ND
o-Xylene ND
Isopropylbenzene ND
n-Propyl benzene ND
Tndan ND
1,2.3,4-Tetramethylbenzene ND
Naphthalene ND
Benzothiophene ND
2-He thy! naphthalene ND
1-Methylnaphthalene ND
Biphenyl ND
2,6-Dimethylnaphthalene 86
2,3,5-Trimethylnaphthalene ND
Fluorene ND
Dibenzothiophene ND
Phenanthrene ND
Anthracene ND
1 -Methyl Phenanthrene ND
Fluoranthene ND
Pyrene ND
Benz(a)anthracene ND
Chrysene ND
Benzo(e)pyrene ND
Benzo(a)pyrene ND
Perylene ND
Spring
2A
ND
0.02
ND
3.8
ND
2.4
ND
NO
1.8
ND
ND
ND
ND
ND
6.7
ND
5.7
4.8
11
ND
27
ND
ND
ND
Summer
ND
ND
39
ND
ND
ND
ND
ND
ND
ND
34
ND
ND
48
ND
ND
80
ND
ND
ND
ND
ND
ND
ND
2B
ND
ND
ND
1.2
ND
1.8
ND
0.62
1.2
ND
ND
ND
ND
ND
6.2
ND
1.3
2.9
9.2
ND
26
ND
ND
ND
Fall
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Summer
1 2
ND
1.9
1.2
0.63
0.35
1.5
ND
4.5
3.3
0.073
2.2
o.:o
0.18
ND
5.8
ND
0.43
4.7
0.47
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
110
ND
ND
290
690
CD
NO
NO
MO
ND
ND
ND
0.92
4.2
ND
2.1
ND
2.5
2.3
ND
1.8
0.40
0.72
ND
7.1
1.1
0.24
ND
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
KD
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.1
2.2
2.3
ND
ND
9.1
0.74
1.1
4.8
7.3
ND
ND
2.2
ND
1.1
100
-------
DUNGENESS SPIT
n-Alkanes
F carbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
bO
29
30
31
Spring
1A IB
ND
ND
0.50
0.40
1.1
~\'.5
1.6
2.0
0^90
2.0
ND
2.1
2.7
2.2
1.8
1 .6
1.4
1 .8
0.71
1.3
2.0
o!so
ND
ND
ND
ND
ND
ND
ND
0.30
0.40
0.90
ND
1.4
ND
1.4
0.80
1.5
1.2
1.5
1.4
2.0
1 .1
1.8
1.9
ND
ND
ND
Summer
ND
2.0
2.4
2.2
2.0
2.3
2.3
2.9
1.5
2.3
0.84
2.1
2.3
2.7
2.6
5.3
5.3
4.9
7.8
8.5
5.4
4.8
5.9
4.6
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.33
0.57
1.0
1.4
1.9
1.7
2.2
1.5
3.1
0.93
1.9
ND
ND
S
Winter
ND
ND
3.0
2.6
2.8
2.7
2.5
2.3
1.9
2.4
1.2
2.9
2.1
2.2
2.2
3.5
2.8
2.9
2.0
3.5
1.9
3.3
1.4
4.2
E D I M E N T S
Aromatic hydrocarbons
o-Xylene
Tsopropyl benzene
n-Propyl benzene
Tndan.
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methy 1 naphthal ene
1 -Methyl naphthalene
Biphenyl
2,6-Dimethylnaphthalene
2,3,5-Trimethylnaphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A IB
ND
ND
ND
0.82
ND
ND
ND
0.41
ND
ND
ND
ND
ND
ND
1.5
ND
ND
0.45
0.28
ND
ND
ND
ND
ND
ND
ND
0.10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1,4
ND
ND
0.29
ND
ND
ND
ND
ND
ND
Summer
ND
1.1
0.51
ND
ND
0.57
ND
ND
ND
0.18
ND
ND
ND
ND
1.3
ND
0.87
0.13
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
101
-------
EDIZ HOOK
nWU kanes
# aarbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Spring
1A IB
ND
1.9
5.5
13
21
29
25
27
40
31
27
42
29
24
21
16
11
22
6.0
10
13
17
ND
5.0
f -AT kanes
aarbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
ND
1.4
4,7
11
22
23
16
18
25
19
18
28
20
18
17
13
11
22
6.0
10
17
16
ND
4.4
Spring
55
180
210
63
ND
270
22
580
630
ND
170
72
130
57
180
23
12
ND
ND
ND
ND
ND
ND
ND
Summer
0.9
2.4
3.4
6.8
11
16
16
22
29
20
20
26
21
14
12
12
5.9
4.0
1.3
1.4
5.4
11
18
22
Summer
290
260
200
65
51
190
69
350
240
ND
50
150
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Fall
ND
ND
6.6
9.4
14
17
13
14
20
13
13
17
14
10
9.0
9.3
7.6
6.5
4.8
6.0
8.4
10
1.8
4.1
Fall
370
530
590
180
360
590
68
200
540
77
150
35
180
170
230
280
190
170
130
200
120
47
ND
ND
S
Winter
ND
ND
5.3
9.4
14
17
14
16
27
17
18
22
17
13
11
11
7.9
9.7
4.4
6.0
7.4
8.3
1.6
4.6
Winter
560
5000
7800
5500
1600
770
27
230
2600
ND
1500
510
260
420
450
370
230
150
110
ND
ND
ND
ND
ND
E D I M E N T S
Aromatic hydrocarbons
o-Xyl ene
Isopropyl benzene
n-Propyl benzene
Indan-
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methy 1 naphthal ene
1 -Methyl naphthal ene
Biphenyl
2 ,6-Dimethylnaphthal ene
2 , 3, 5-Trimethy 1 naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
MUSSELS
Aromatic hydrocarbons
p_-Xylene
Isopropyl benzene
n-Propylbenzene
Tndaa
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methy 1 na phthal ene
1 -Methyl naphthal ene
Biphenyl
2 ,6-Di methyl naphthal ene
2, 3, 5-Trimethy 1 naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1-Methyl phenanthrene
Fluoranthene
Pyrene
Benz ( a )anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Peryl ene
Spring
1A IB
3.1
ND
ND
0.34
0.32
3.0
ND
5.0
1.6
0.74
2.4
1.7
1.0
2.5
7.1
0.54
0.56
0.58
4.1
0.61
4.8
ND
ND
ND
Spring
ND
ND
ND
ND
150
ND
ND
ND
ND
ND
ND
ND
180
68
2600
ND
470
4000
300
540
ND
ND
ND
ND
1.4
ND
ND
0.09
0.10
2.7
ND
3.8
1.2
0.5
1.6
ND
0.89
2.1
4.5
0.54
ND
1.5
3.9
0.61
3.4
ND
ND
ND
Summer
41
ND
56
99
ND
42
ND
ND
ND
ND
ND
ND
ND
ND
50
ND
ND
320
610
ND
ND
ND
ND
ND
Summer
ND
1.3
0.67
ND
0.094
1.5
ND
1.8
0.64
ND
0.49
ND
ND
ND
3.6
ND
0.66
3.1
3.5
ND
ND
ND
ND
ND
Fall
ND
ND
HD
ND
ND
7.0
ND
21
4300
ND
ND
ND
ND
ND
65
ND
190
8.8
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
86
ND
42
40
160
no
1400
200
120
ND
4100
1600
730
130
100
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.1
1.5
4.9
ND
ND
5.3
7.8
ND
0.83
ND
ND
ND
102
-------
TONGUE POINT/CRESCENT BAY
n-Alkanes
tTcarbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
1
ND
ND
1.1
0.82
1.5
2.1
2.2
4.1
2.8
2.5
2.8
7.8
ND
9.6
19
35
42
57
32
35
21
23
11
22
Spring
2A
91
24
ND
ND
ND
1.4
1.6
2.5
2.2
1.7
1.8
3.5
2.9
5.4
7.7
14
14
25
13
17
10
n
ND
ND
n-Alkanes
10
12
13
14
15
16
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
31
Summer
2B 1 2
100 0.8
29. 0.9
ND 0.3
ND 0.1
ND 2.1
1.8 3.9
2.1 1.0
3.2 2.5
5.1 7.7
2.2 2.3
2.3 2.1
4.8 5.5
3.9 3.8
8.2 6.4
14 4.4
27 8.1
31 5.2
50 14
31 4.9
34 12
23 4.1
23 11
ND 2.6
ND 7.6
ND
ND
ND
ND
2.4
4.0
1.4
2.4
2.0
2.5
2.2
5.4
4.0
6.2
4.0
8.7
6.0
11
5.6
13
5.0
12
1.4
6.4
Spring Summer
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
180
ND
230
180
ND
ND
ND
ND
ND
ND
70
76
63
83
130
92
67
ND
ND
Fall
ND
ND
2.1
1.8
1.9
2.6
2.4
2.4
3.6
2.7
1.5
4.2
4.6
6.5
6.7
12
11
27
13
28
20
23
8.0
24
S E
Winter
ND
ND
0.81
0.89
1.5
2.5
3.0
4.4
5.6
3.7
2.1
4.4
4.1
5.8
4.7
7.9
5.5
14
6.2
17
8.4
19
13
29
H
Fall Winter
ND
ND
ND
16
26
160
50
64
490
ND
ND
ND
ND
17
24
47
35
93
30
100
17
77
ND
ND
ND
ND
ND
ND
ND
170
ND
150
180
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
D I M E N T S
Aromatic hydrocarbons
o-Xylene
Tsopropyl benzene
n-Propyl benzene
Tndan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
2, 6-Dimethyl naphthalene
2 ,3, 5-Trimethyl naphthalene
Fluorene
DibenzotMophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Peryl ene
U S S E L S
Aromatic hydrocarbons
o-Xylene
Isopropylbenzene
n-Propyl benzene
Tndan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
2, 6-Dimethyl naphthalene
2,3, 5-Trimethyl naphtha 1 ene
Fluorene
Dibenzothlophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrer.e
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzofajpyrene
Peryl ene
1
ND
ND
ND
1.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.0
ND
ND
ND
30
ND
2.3
ND
ND
ND
Spri ng
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Spring
2A
ND
ND
ND
1.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.56
52
ND
ND
ND
ND
ND
Summer
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
2B
ND
ND
ND
2.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.79
77
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
13
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
25
ND
ND
ND
ND
ND
Summer
1 2
ND
2.3
0.97
ND
ND
1.0
ND
0.49
ND
ND
ND
ND
ND
ND
1.7
ND
0.17
4.5
ND
NO
NO
ND
ND
NO
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
'.")
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.5
0.61
ND.
2.8
ND
0.65
ND
ND
ND
ND
ND
ND
ND
ND
ND
13
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.15
ND
ND
0.41
ND
1.7
ND
ND
2.3
2.6
ND
0.57
ND
ND
ND
103
-------
DEEP CREEK BEACH
n-Alkanes
W carbons
10
11
12
13
14
15
16
17
Pristane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Spring
1A IB
ND
ND
0.40
2.5
3.6
6.1
6.2
8.6
39
8.6
6.8
15
11
21
36
62
80
110
75
75
54
48
22
30
ND
ND
1.5
3.6
4.9
8.3
8.1
12
50
12
9.1
20
15
31
59
100
130
180
120
no
81
66
31
39
Summer
ND
2.3
3.0
3.6
4.5
4.7
5.5
7.3
20
5.2
2.2
7.1
7.2
9.6
6.3
6.4
4.1
13
3.3
5.6
4.7
8.2
6.3
8.2
Fall
ND
ND
ND
ND
ND
0.47
0.98
4.1
13
4.8
2.2
5.1
5.8
5.2
6.5 '
9.2
6.9
9.7
6.3
11
4.5
7.4
2.4
4.8
S
Winter
ND
ND
3.1
3.9
4.9
5.9
6.7
8.3
28
7.5
5.3
8.9
8.7
11
11
15
14
19
13
23
12
18
8.9
15
E D I M E N T S
Aromatic hydrocarbons
o-Xylene
I sopropyl benzene
n-Propylbenzene
Tndan-
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methy 1 naph thai ene
1 -Methyl naphthalene
Biphenyl
2 , 6-Dimethyl naphtha! ene
2,3, 5-Trimethyl naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Benz (a ) anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A IB
ND
ND
0.66
0.37
0.18
1.8
ND
3.7
3.1
0.10
1.7
3.0
ND
ND
4.4
0.03
1.7
8.5
15
ND
8.8
ND
ND
ND
ND
ND
0.12
0.08
0.37
0.90
ND
3.4
2.9
0.70
1.5
1.8
0.06
ND
3.7
ND
1.3
6.3
1.6
0.31
8.3
ND
ND
ND
Summer
ND
0.73
1.1
0.25
0.25
1.8
ND
1.6
1.0
ND
ND
ND
ND
ND
2.4
ND
1.7
1.2
0.32
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
2.1
1.3
ND
ND
ND
ND
ND
2.9
ND
1.4
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.79
2.5
ND
ND
1.4
1.4
ND
ND
ND
ND
ND
DEEP CREEK
JT.-A1 kanes
# carbons
10
11
12
13
14
15
16
17
Pn'stane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Spring
7.8
ND
ND
ND
34
ND
ND
140
8.8
45
31
33
55
68
62
74
57
130
53
ND
ND
ND
ND
ND
Summer
ND
ND
38
40
99
310
93
240
31
ND
ND
ND
ND
ND
ND
50
48
37
52
63
23
ND
ND
ND
Fall
ND
ND
43
40
170
420
100
160
200
21
ND
26
23
80
72
130
120
320
84
200
37
97
ND
ND
Winter
ND
ND
ND
ND
120
250
68
160
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
90
ND
ND
ND
ND
MUSSELS
Aromatic hydrocarbons
o-Xylene
Isopropyl benzene
ri-Propyl benzene
Indan-
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Me thy 1 naphthal ene
1 -Methyl naphthal ene
Biphenyl
2, 6-Dimethyl naphthal ene
2,3, 5-Trimethy 1 naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Peryl ene
Spring
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Mfl
ND
ND
MD
ND
ND
ND
ND
ND
MD
ND
ND
Summer
32
ND
no
1C
o
ND
ND
ND
ND
ND
ND
ND
ND
wn
PJU
ND
ND
kin
ND
ND
ND
ND
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
MD
ND
MD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
MD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
120
ND
ND
ND
ND
ND
ND
104
-------
PILLAR POINT
ItAI k'anes Spr
# carious 1A
10
11
12
13
14
15
16
17
0.78
0.30
ND
ND
0.86
2.6
3.0
3.9
Prlstane 74
18
4.0
Phytane NO
19
20
21
22
23
24
25
26
27
28
29
30
31
4.4
4.4
7.6
8.9
17
16
36
16
27
14
20
6.8
22
H.-A1 kanes~
# aafbone
10
11
12
13
14
15
16
17
Pristine
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
1ng
IB
1.1
1.4
0.43
0.77
1.8
3.3
3.3
5.0
69
4.7
ND
7.7
5.7
11
20
38
43
73
41
48
28
29
1.1
26
Spring
11
ND
ND
15
30
210
74
57
520
18
27
1.9
77
30
32
46
36
no
35
99
34
40
ND
ND
Summer
3.4
ND
1.1
1.5
2.6
4.5
3.1
1.0
82
2.5
3.7
6.2
6.2
8.1
9.3
15
15
30
13
22
14
20
15
22
Summer
68
24
ND
ND
23
210
44
43
3500
ND
ND
ND
ND
NO
ND
42
45
47
65
130
ND
ND
ND
ND
Fall
NO
ND
0.77
0.79
5.2
8.7
6.7
5.7
34
7.5
7.6
13
9.0
11
11
18
11
24
13
31
3.4
19
ND
ND
Fall
ND
ND
ND
ND
19
160
51
49
ND
ND
29
ND
ND
ND
26
ND
21
150
14
87
ND
ND
ND
ND
SEDIMENTS
Winter Aromatic hydrocarbons
ND
ND
1.6
1.9
2.6
4.0
3.9
ND
ND
5.1
3.9
5.3
5.4
6.8
6.3
9.9
7.5
15
8.2
21
9.7
20
ND
15
Winter
ND
ND
ND
ND
NO
65
ND
55
62
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2 Xylene
Isopropylbenzene
n-Propylbenzene
Tndan-
1 ,2,3,4-Tetramethylbenzene
Naphthalene
BenzotMophene
2-Methy 1 naph thai ene
1 -Methyl naphthal ene
Blphenyl
2,6-D1methylnaphthalene
2,3, 5-Trlmethyl naphtha 1 ene
Fluorene
Dlbenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
MUSSELS
Aromatic hydrocarbons
o-Xylene
Tsopropyl benzene
n-Propyl benzene
Tndan
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothlophene
2-Methy 1 naphthal ene
1 -Methyl naph thai ene
B1 phenyl
2 , 6-D1 methyl naphthal ene
2,3,5-Trlmethylnaphthalene
Fluorene
Dlbenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spr
1A
0.90
ND
ND
ND
ND
ND
ND
0.90
0.70
ND
0.80
ND
ND
ND
0.30
ND
ND
12
0.50
3.8
ND
ND
ND
ND
Spring
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
35
ND
88
ND
ND
ND
ing
IB
0.20
ND
ND
ND
ND
ND
NC
0.50
0.50
ND
0.80
ND
ND
ND
0.30
ND
ND
12
3.5
3.4
0.2
ND
ND
ND
Summer
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Summer Fall
ND
ND
ND
ND
ND
1.7
ND
0.18
0.63
ND
ND
ND
ND
1.7
ND
ND
ND
2.2
ND
ND
ND
ND
ND
0.94
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NO
ND
ND
49
ND
ND
140
52
66
32
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.49
ND
2.4
ND
0.25
6.6
3.1
ND
ND
ND
ND
ND
105
-------
KYDAKA POINT
jv-Alkanes Spring
H carbons 1A IB
10
11
12
13
14
15
16
17
ND
3,4
12
12
15
16
16
16
Prlstane 13
18
19
Phytane 6.1
19
20
21
22
23
24
25
26
27
28
29
30
31
25
20
27
28
35
34
52
31
40
31
34
16
25
n-Alkanes
T oaf bone
10
11
12
13
14
15
16
17
Prlstane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
NO
ND
7.2
8.0
9.7
11
11
10
9.6
13
3.9
16
12
17
17
20
18
29
18
24
19
22
9.7
16
Spring
20
20
ND
ND
13
ND
ND
ND
ND
ND
ND
ND
16
27
20
50
37
120
ND
170
ND
ND
ND
ND
Summer
0.6
2.3
3.0
4.3
5.4
5.0
5.1
6.2
10
4.6
1.7
7.8
7.1
8.7
7.9
8.7
8.4
12
6.7
9.9
10
8.7
7.5
10
Summer
180
200
170
70
55
410
77
65
420
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
22
ND
ND
ND
ND
Fall
ND
ND
12
12
12
12
9-6 ,
10
13
10
3.3
14
15
18
23
33
36
46
44
64
23
50
29
37
Fall
..
--
--
--
--
--
--
--
--
--
--
--
S
Winter
ND
ND
11
13
3.2
15
16
17
22
16
3.3
17
17
19
19
23
20
23
20
25
12
16
16
22
Winter
ND
ND
ND
130
93
420
no
380
170
ND
ND
ND
ND
ND
ND
71
550
420
370
930
670
660
490
350
E D I M E N T S
Aromatic hydrocarbons
o-Xylene
Isopropylbenzene
Jl-Propylbenzene
Indan-
1 ,2,3,4-Tetranethylbenzene
Naphthalene
Benzothiophene
2-Methy 1 naphthal ene
1 -Methyl naphthal ene
Bi phenyl
2,6-Dimethy'l naphthalene
2, 3, 5-THmethyl naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a}anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
MUSSELS
Aromatic hydrocarbons
o-Xylene
Tsopropyl benzene
n-Propyl benzene
Thdanf
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methy 1 naphthal ene
1 -Methyl naphthal ene
Bi phenyl
2 ,6-D1methyl naphthal ene
2, 3, 5-Trimethyl naphthal ene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1 -Methyl phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spring
1A IB
ND
0.02
1.1
ND
0.14
3.1
ND
12
8.4
4.4
9.2
4.8
1.5
2.7
24
0.38
1.0
1.6
4.3
0.16
20
ND
ND
ND
Spring
ND
ND
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
210
NO
42
ND
ND
ND
ND
ND
0.88
ND
0.13
2.9
ND
11
7.5
2.8
9.0
4.6
1.6
ND
23
0.26
0.90
1.1
4.0
0.06
19
ND
ND
ND
Summer
37
ND
ND
120
ND
28
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Summer
ND
ND
1.1
ND
ND
2.0
ND
1.9
1.5
0.47
1.6
0.37
ND
ND
0.58
ND
0.39
ND
ND
ND
ND
ND
ND
ND
Fall
..
..
-.
--
..
...
--
__
..
__
^f
..
_.
__
__
..
...
__
Fall
ND
ND
ND
ND
ND
ND
ND
3.9
4.0
1.3
4.5
ND
ND
ND
13
ND
1.2
1.7
ND
ND
3.8
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
23
47
ND
. ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.7
6.5
3.0
0.58
ND
13
ND
2.4
1.8
3.0
ND
3.0
ND
ND
ND
106
-------
BAADAH POINT
SEDIMENTS
ji-Alkanes Spring
# carbons 1 2
10
n
12
13
14
15
16
17
Prlstane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
ND ND
6.1 ND
5.7 2.9
7.2 4.9
8.7 5.5
7.0 7.3
7.7 6.9
11 8.5
41 0.29
7.2 8.8
6.6 6.0
12 13
ND 9.3
4.1 15
ND 23
ND 39
ND 46
ND 73
ND 57
ND 65
ND 60
ND 57
ND 39
ND 55
n-Al kanes
f carbons
10
11
12
13
14
15
16
17
Pri stane
18
Phytane
19
20
21
22
23
24
25
26
27
28
29
30
31
Summer
1 2
4.0
4.5
4.6
2.8
6.2
11
8.2
1.2
150
7.2
3.4
11
10
9.7
10
12
12
21
9.9
13
6.8
13
9.9
11
Spring
ND
ND
ND
ND
ND
91
17
39
78
ND
300
120
71
63
17
ND
ND
ND
ND
ND
ND
36
ND
ND
2.8
5.8
4.3
6'.8
11
24
27
50
49
50
31
56
34
25
16
16
9.3
7.3
6.6
11
3.7
6.4
ND
8.6
Sunnier
24
ND
110
32
66
230
70
88
27
56
820
360
140
150
220
170
180
190
no
160
320
430
350
470
Fall
ND
ND
3.0
3.0
3.3
4.3
4.2
4.2
8.4
5.1
3.7
6.4
5.6
4.6
6.0
11
12
14
14
19
13
14
6.8
7.6
Fall
ND
ND
14
6.7
14
170
47
60
1300
12
310
no
97
59
120
81
48
59
23
8.0
6.1
ND
ND
ND
Winter
NO
ND
3.8
4.5
5.2
5.6
5.8
5.8
10
5.9
3.9
7.0
6.7
6.4
6.6
8.2
6.7
9.7
5.8
8.6
5.9
9.3
ND
ND
Winter
ND
ND
ND
NO
30
220
59
180
970
47
400
130
87
100
120
130
78
71
ND
56
ND
210
ND
ND
Aromatic hydrocarbons
o-Xylene
Isopropyl benzene
n-Propylbenzene
Tndan .
1,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methyl naphthalene
1-Methyl naphthalene
Biphenyl
2 ,6-Dimethy 1 naphthal ene
2, 3, 5-TH methyl naphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
MUSSELS
Aromatic hydrocarbons
o-Xylene
Tsopropyl benzene
n-Propyl benzene
Indaa
1 ,2,3,4-Tetramethylbenzene
Naphthalene
Benzothiophene
2-Methyl naphthal ene
1 -Methyl naphthal ene
Biphenyl
2, 6-Dimethyl naphthal ene
2,3,5-Trlraethylnaphthalene
Fluorene
Dibenzothiophene
Phenanthrene
Anthracene
1-Methylphenanthrene
Fluoranthene
Pyrene
Benz (a) anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Spn ng Summer
1212
ND
ND
ND
ND
ND
5.2
ND
10
6.9
0.91
5.2
3.2
1.1
0.78
10
ND
0.89
8.7
4.8
ND
ND
ND
ND
ND
Spring
ND
ND
ND
72
ND
ND
ND
ND
ND
ND
ND
ND
ND
19
85
ND
ND
36
51
ND
ND
ND
ND
ND
ND ND
0.25 ND
ND ND
0.85 ND
ND 0.23
2.5 3.3
ND ND
4.1 5.2
3.2 3.4
0.65 0.78
2.2 3.1
1.6 ND
0.75 1.2
ND 0.45
6.0 5.4
ND ND
ND 0.63
2.9 5.9
6.7 5.3
0.46 0.4
3.1 2.1
ND 5.6
ND ND
ND ND
Summer Fall
29 ND
ND ND
23 ND
ND ND
ND ND
43 39
ND ND
no no
ND 27
ND ND
ND ND
ND ND
ND ND
19 ND
120 130
ND ND
ND 21
230 ND
98 81
49 ND
150 ND
ND ND
ND ND
ND ND
ND
ND
1.9
0.41
ND
3.7
ND
8.0
6.0
3.3
5.6
0.67
1.8
ND
8.4
ND
0.21
ND
7.5
ND
ND
ND
ND
ND
Fall
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.2
2.0
ND
ND
NO
3.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.85
1.6
ND
1.4
ND
4.9
ND
ND
4.5
4.5
ND
ND
ND
ND
ND
Winter
ND
ND
ND
ND
ND
38
ND
23
ND
ND
ND
ND
NO
ND
37
ND
ND
650
700
150
15
ND
ND
ND
107
------- |