Exwon Vuldez Oil Spill
StateFederal Natural Resource Damage Assessment
Final Report
Petroleum Hydrocarbon-InducedInjury to Subtidal Marine Sediment Resources
Subtidal Study Number 1A
Final Report
Charles E. OClair
Jeffrey W. Short
Stanley D. Rice
National Oceanic and Atmospheric Administration
NationalMarine Fisheries Service
Auke Bay Laboratory
11305 Glacier Highway
Juneau, Alaska 99801-8626
April 1996
Petroleum Hydrocarbon-Induced Injury to Subtidal Marine Sediment Resources
Subtidal Study Number 1A
Final Report
Studv Historv: This study began asNRDA AirlWater Study Number2 "Petroleum
Hydrocarbon-Induced Injury to Subtidal Marine Sediment Resources" in 1989. Status reports
under this study numberwere submitted in 1989 and 1990. In 1991 the number of the study was
changed to Subtidal Study Number 1 . The title remained the same. A status report under the
new number was submitted in November 1991. The final report for Subtidal Study Number 1
was submitted in September 1994. Reviewers' comments were received by the authors in March
1995. A paper titled "Contamination of Subtidal Sedimentsby Oil from the Exxon Vu€dezin
Prince William Sound, Alaska" has been accepted for publication in the Emon Vuldez Oil Spill
Symposium Proceedings.
Abstract: To determine the distribution of oil in subtidal sediments after theExxon Vuldez oil
spill we sampled sediments at six depths (0,3,6,20,40 and 100 m) at 53 locations in Prince
William Sound and the northern Gulf of Alaska from 1989 to 1991, Results are based on 1278
sediment samples analyzed by gas chromatography/mass spectrometry. In 1989, the oil
concentration was greatest in the Sound at0 m. The greatest subtidal concentration ofExxon
Valdez oil occurred at shallow depths
(3-20 m), Little Emon VuIdez oil reached deep sediments
(r40 m). Outside the Sound,Exzon Vuldez oil occurred at ChugachBay, Hal10 Bay, Katmai Bay,
and Windy Bay in 1989. The totalpolynuclear aromatic hydrocarbon concentration outside the
Sound was highest in intertidal sediments. The oil reached subtidal depths at ChugachBay and at
Windy Bay. Hydrocarbons oftenmatched Emon Vuldez oil less closely, oil was more patchily
distributed, and the oil concentration decreased in sediments after 1989. By 1990, the total
polynuclear aromatic hydrocarbon concentrationin sediments from 0 m atmany oiled sites had
declined to pre-spill levels (100-200 ng/g). Subtidally, Exxon Vuldez oil was consistently present
only at Northwest Bay in 1991.
Kev Words: Emon Vuldez,hydrocarbon concentrations, northernGulf of Alaska, Prince
William Sound, subtidal sediments
Citation: O'Clair, C.E., J.W. Short and S.D. Rice. 1996. Petroleum hydrocarbon-induced
injury to subtidal marine sediment resources. Exxon Vuldez Oil Spill StatelFederal Natural
Resource DamageAssessment Final Report (Subtidal Study Number IA), National Oceanicand
Atmospheric Administration, National Marine Fisheries Service, Auke Bay Laboratory,Juneau,
Alaska.
ii
TABLE OF CONTENTS
EXECUTIVESUMMARY
5
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INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8
METHODS
RESULTS
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DlSCUSSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
57
CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
71
LITERATURECITED
APPENDIX1
APPENDIX11
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APPENDIX111
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84
APPENDIXIV
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93
1
LIST OF TABLES
Table 1.--Location of sitesin PWS and number of stationssampled at each site where intertidal
and subtidal sediment were collected in 1989. A dash indicates that no sampling was
,
conducted during the time period shown. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11
Table 2.--Location of sites in PWS where intertidal and subtidal sediment samples were collected
i n 1990. A dash indicates that no sampling was conducted during thetime period shown.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Table 3.--Location of sites in PWS where intertidaland subtidal sediment samples were collected
in 1991. A dash indicates that no sampling was conducted during thetime period shown.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
14
Table 4.--Location of sites outside PWS
and number ofstations sampled at sites where intertidal
and subtidal sediment samples were collected in July/August 1989. . . . . . . . . . . . . . . . 15
Table 5.--Concentration (nglg)of TPAH in sediments from all stations at assessment locations
where shores weremoderately to heavily oiled in PWS, Alaska by the EVOS. Numbers in
the body of the table are mean,TPAH,
number of replicatesanalyzed (superscripts), and
coefficient of variation(in parentheses). Numbers arein bold where the PAH composition.
pattern matched weathered EVO. S denotes surrogate recoveries for one
or more PAH
analytes outsideacceptablerange.
.......................................
20
Table 6.--Concentrationof in sediments fromall stations atassessment locations where shores
were moderately to heavily oiled in PWS, Alaska by the EVOS. Numbers in the body of
the table aremean TNA (nglg), number of replicatesanalyzed (superscripts,) and
coefficient of variation(in parentheses). S denotes surrogate recoveriesof one or more
alkanes outside acceptable range.
..................................................................
24
Table 7.--Mean CPI for sediments fromall stations atassessment locations where shores were
moderately to heavily oiled in PWS, Alaska by the EVOS. S denotes surrogate
recoveries of one or more alkanesused in the CPI outside acceptable range.NA indicates
that CPI could not be calculated. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 7
8.--Concentration (ng/g) of TPAHin sediments from all stations at reference locations
(italics) and assessment locations where shoreswere lightly oiled inPWS, Alaska by the
EVOS. Numbers in the body of thetable are mean TPAH, number of replicatesanalyzed
(superscripts) and coefficient of variation(in parentheses). Numbers are in bold when
PAH composition patterns match weathered EVO. S denotes surrogate recoveriesfor
one or more PAH analytes outside acceptable range. ND indicates that TPAH analytes
were below detectionlimits.
..................................................................
29
Table 9.--Concentration of TNA in sediments from all stations at reference locations (italics)
and
assessment locations where shores werelightly oiled inPWS, Alaska by the EVOS.
Numbers in the body of the table are
mean TNA (nglg), number of replicates analyzed
(superscripts), and coefficient of variation (in parentheses). S denotes surrogate
recoveries of.one or more alkanes outside acceptable range. ND indicates that n-alkane
2
1
Table 10.--Mean CPI for sediments from all stations at reference locations (italics) and assessment
locations where shores were lightly oiled in PWS, Alaska by the EVOS. S denotes
surrogate recoveries of one or more alkanes used in the CPI outside acceptable range.
NA indicates that CPI could not be calculated.
..................................................................
below
~9
Table 1 1.--Concentration (ng/g) of perylene in sediments from all stations at assessment locations
where shores were moderately to heavily oiled in PWS, Alaska by the EVOS. Numbers in
the body of the table are mean perylene concentration, number ofreplicates analyzed
(superscripts), and coefficient of variation (in parentheses). S denotes surrogate
recoveries outside acceptable range. ND indicates that perylene concentrations were
below detection limits.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
48
Table 12.--Concentration of perylene in sediments from all stations at reference locations (italics)
and assessment locations where shores werelightly oiled in PWS, Alaska by the EVOS.
Numbers in the body of the table are mean perylene concentration (ng/g), number of
replicates analyzed (superscripts), and coefficient of variation (in parentheses). S denotes
surrogate recoveries outside acceptable range. ND indicates that perylene concentrations .
were
detection limits. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Table 13.--Concentrations (ng/g) of TPAHs in sediments from all stations in the NGOA. One
replicate was analyzed at each station. Numbers are in bold when PAH composition
patterns matched weathered EVOS. S denotes surrogate recoveries for one or more PAH
analytes outside acceptable range.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
55
Table 14.--Concentration (ng/g) of T N A in sediments from all stations in the NGOA. One
replicate was analyzed at each station. S denotes surrogate recoveries outside acceptable
range. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Table 15.--CPI for sediments from all stations in the northern Gulf of Alaska. One replicate was
analyzed at each station. S denotes surrogate recoveries of one or more alkanes used in
the CPI outside acceptable range. NA indicates that CPI could not be calculated. . . . 59
Table 16.--Concentration (ng/g) of perylene in sediments from all stations in the NGOA. One
replicate was analyzed at each station. ND indicates that perylene concentrations were
below detection limits. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Table 17.--Comparison of PAHs in intertidal sediments at Olsen Bay and Rocky Bay during 1977
to 1980 and 1989 to 1990. Numbers in the body ofthe table are means and 95%
confidence intervals. Significance levels are: *, P < 0.05; **, P < 0.01.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3
LIST OF FIGURES
Figure 1 .--Distribution of study sites in PWS. See Tables 1-3 for the geographical coordinates of
each location sampled in 1989, 1990, and 1991. Numbered locations are: 1) Applegate
Island; 2) Bay of Isles 86; 3) Bay of Isles 90;' 4) Bay of Isles Bioremediation; 5) Bay of
Isles; 6 ) Block Island; 7) Block Island 47; 8) Chenega Island; 9) Disk Island; IO) Drier
Bay; 11) Eshamy Bay; 12) Ewan Bay; 13) Foxfarm; 14) Green Island 22; 15) Green
Island; 16) Heather Bay; 17) Herring Bay 53; 18) Herring Bay 110; 19) Herring Bay
125; 20) Herring Bay; 21) Iktua Bay 2; 22) Iktua Bay; 23) Ingot Island; 24) NE Knight
Island Bioremediation; 25) Knight Island; 26) Lower Herring Bay 5; 27) MacLeod
Harbor; 28) Moose Lips Bay; 29) Northwest Bay 4; 30) Northwest Bay 5; 3 1)
Northwest Bay; 32) Oisen Bay; 33) Paddy Bay; 34) Point Helen; 35) Port Fidalgo; 36)
Rocky Bay; 37) Rua Cove; 38) Sleepy Bay; 39) Smith Island; 40) Snug Harbor 25; 41)
Snug Harbor; 42) Snug Harbor Meiofauna; 43) Two Moon Bay; 44) West Bay; 45)
ZaikofBay. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Figure 2.--Distribution of study sites outsidePWS sampled in 1989. See Table 4 for the
geographical coordinates of each site. Numbered locations are: 46) Agnes Cove; 47)
Black Bay; 48) Chignik Bay; 49) Chugach Bay; 50) Hallo Bay; 5 1) Ivanof Bay; 52)
Katmai Bay; 53) Windy Bay. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I O
Figure 3.--Mean relative abundances of PAHs in intertidal sediments at Disk Island, Herring Bay,
and Northwest Bay combined and in Exxon Vnldez mousse collected 11 days after the
Spill. Error bars are 95% confidence intervals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Figure 4.--Mean relative abundances of TPAHs in sediments from t 100 m, all sites inside PWS
combined and in &on Vnldez mousse collected 11 days after the Spill. Error bars are
95% confidence intervals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1
Figure 5.--Percentage of sediment samples in five concentration ranges of TPAHsin sediments
from the intertidal region (0 m) and the subtidal region at bathymetric depths of 3 m to 20
m, 40 m and 100 m at reference stations and heavily oiled stations from 1989 to 1991.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Figure 6.--Mean relative abundances of PAH compoundsin intertidal sediments at Rocky Bayand
in LXXO~I
Valdez mousse collected 1 1 days after the Spill. Error bars are 95% confidence
intervals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Figure 7.--Depth distribution of mean concentrations of TPAHsat Disk Island, Olsen Bay and
Rocky Bay in July 1989. Error bars arei one standard error of the mean. . . . . . . . . . . 42
Figure S.--Stacked bar graph of the coeficient of
variation proportion classes in two ranges of
mean concentration of TPAHs forsediments in the depth range0 to 20 m at (A) reference
locations and (B) assessment locations where the EVO-PAH composition pattern wasnot
consistently present in replicate samples and (C) at depths 240m at all locations in PWS
and (D) at depths of 0-20m where the EVO-PAH composition patter was
consistently
present among replicate samples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Figure 9.--Correlation of concentrations of TNAs and perylene in subtidal sediments at all stations
in PWS where the weathered EVO-PAH composition pattern was generally absent. . . . 54
4
EXECUTIVE SUMMARY
In the three yearsfollowing the Exxon Vulde: oil spill, we sampled subtidal sediments at
45 locations in Prince William Sound and eight locations in the northern Gulf of Alaska to
determine the geographical,bathymetric, and temporal distribution of oil from the Spill in the
sediments. We sampled sediments near mean lower low water and at five subtidal depths in the 3100 m range. Sediments were sampled in spring, summer, and fall each year. Oil from the Spill
was found to have contaminated shallow (3-20 m) subtidal sediments near heavily oiled shorelines
in Prince William Sound.
Subtidal sediments showed polynuclear aromatic hydrocarbon composition patterns
similar to Exxon Valde: oil at 80% ofthe locations whereoil had come ashore(oiled locations) in
1989, 78% of oiled locations in 1990, and 57% of oiled locations in 1991. Contamination of
subtidal sediments by Exxon Valdez oil at oiled locations reached a depth of at least 20 m at five
sites in 1989 and seven sites in 1990. Two sites showed contamination of sediments by Exxon
Vulde: oil at 20 m in 1991
Sediments at mean lower low water(0 m) at locations where oil had come ashore had the
greatest concentrations of total polynuclear aromatic hydrocarbonsfound in benthic sediments in
1989. An average concentration (n = 3) as high as 12,729 ng/g was found at 0 m at Disk Island in
July 1989. The 0 m station was several meters below the zone where theoil initially was
stranded.
In subtidal sediments the greatest concentrations of E m m Valdez oil were at theshallow
depths. The highest mean total polynuclear aromatic hydrocarbon concentration where the
weathered Euon Vuldez oil composition pattern was evident was 1,486 ng/g in sediment
collected at 3 m at Northwest Bay in July 1989.
Concentrations of petroleum hydrocarbons derived from Exxon Vuldez oil decreased, and
Exxon Valdez oil hydrocarbons became morepatchily distributed in intertidal and subtidal
sediments after 1989. Hydrocarbons measured in benthic sediments after 1989 were more
difficult to match with Exxon Vulde: oil. By 1990, the mean total polynuclear aromatic
hydrocarbon concentration in lower intertidal sediments at many oiled sites had declined to
between 100 and 200 ng/g. These numers are comparable to total polynuclear aromatic
hydrocarbon concentrations of the petrogenic background. In shallow subtidal sediments, a
polynuclear aromatic hydrocarbon composition pattern characteristic of weatheredEmon Zhldez
oil was consistently present only at Block Island and Northwest Bay in 1990. Additional
decreases in total polynuclear aromatic hydrocarbon concentrations were observedat oiled sites in
1991. The weathered Exxon Vuldez oil pattern was consistently present only at Northwest Bay in
1991. We anticipate that in succeeding years these polynuclear aromatic hydrocarbons will
continue to decline and probably become more patchily distributed.
5
In deep sediments (240 m) we found little evidence ofkkcon Vuldez oil. The total
polynuclear aromatic hydrocarbon concentrations in sediments at these depths weresimilar at
oiled and reference locations. The polynuclear aromatic hydrocarbon composition pattern
characteristic of weathered Exxon Cirldrz oil was rarely consistently present among replicate
samples at these depths regardless ofsampling location. The total polynuclear aromatic
hydrocarbon concentration in the deepest sediments ( z 100 m) usually exceeded that at 40 m.
Petroleum hydrocarbons at depths 240 rn were probably from sources otherthan the Spill.
Outside PrinceWilliam Sound, evidence o f E n o n Vuldez oil may have been more difficult
to find because of the patchy distribution of theoil stranded on the shore. This was causedby the
breaking up of the oil slick as thedistance between it and the site of the Spill increased. Outside
the Sound, patches of theslick came ashore over an extensivelength of coastline. In the northern
Gulf of Alaska, a polynuclear aromatic hydrocarbon composition pattern consistentwith
weathered fixon Valdez oil was found at Chugach Bay, Hallo Bay, Katmai Bay, and Windy Bay
in summer 1989. The total polynuclear aromatic hydrocarbon concentration was highest in
intertidal sediments collected from Hallo Bay (348 ng/g) and Katmai Bay (339 ng/g). The
weathered Exxon Vuldez oil pattern also appeared in subtidal samples at 6 m and 20 m at Chugach
Bay (total polynuclear aromatic hydrocarbon = 80.6 ng/g and 362 ng/g) and at 3 m at Windy Bay
(total polynuclear aromatic hydrocarbon = 224 ng/g).
In contrast to the intertidal region where Enon Vuldez oil caused major biological
impacts, oil concentrations in subtidal sediments probably did not reach levels that were acutely
toxic to benthic or demersal macrobiota. The Exxon Vuldez oil in shallow subtidal sediments may
have induced subtle changes in the biotic communities in heavily oiled bays. At greater depths
(240 m), contamination by Emon b’ulde: oil was negligible; therefore, what changes, if any, that
occurred in deep benthic communities as a result of the Spill were probably obscured by natural
variability.
6
INTRODUCTION
A substantial proportion of the approximately 11 million gallons of Prudhoe Bay crude oil
released into the marine environment of Prince William Sound (PWS) after the grounding of the
tanker E x x o ~Vu'nldezbecame stranded on the shoreline of PWS and the northeastern Gulf of
Alaska (NGOA). Wolfe et al. (1994) estimate that by mid-April 1989 about 25% of the oil had
evaporated, 25% had floated out of PWS, and most of the remainder (about 4045%) had been
beached within PWS. Some of the beached oil and oil-contaminated fine sediments were
transported to subtidal sediments after reintroduction into nearshore watersby processes such as
wave-induced redistribution, leaching by groundwater flowing through the intertidal region from
the backshore, and by shoreline cleanup activities. Owens et al. (1987, see also Boehm et al.
1987) discuss thefirst two processes in conjunction with the Baffin Island experimental oil spill.
Oil can be transported to the subtidal region when sorbed by settling particulate matter or
encapsulated into thesettling feces of zooplankton that have ingested small particles of oil
(Conover 1971, Clark and MacLeod 1977, Bassin and Ichiye 1977). Short et al. (In press (a))
show that settlement of hydrocarbon-contaminated particulates played a role in the contamination
of PWS subtidal sediments as deep as 20 m after the Exxon Vuldez oil spill (EVOS).
.
Wolfe et al. (1994) estimatethat between 8 and 16% of the spilled oil was transported to
the subtidal region by October 1992. Estimates of the percentage of spilled oil that reached
subtidal sediments after othermajor spills ranges from 0.5 to8% (Johansson et al. 1980, Boehm
et al. 1982, Gundlachet al. 1983). The estimate of Wolfe et al. (1994) of theproportion of
spilled Erwon Vuldez oil (EVO) transported to subtidal sediments was similar to that of Gearing et
al. (1979) for water-accommodated No. 2 fuel oil transported to sediment (7-16%) in
experimental releases of the fuel oil into marine microcosms.
Before the EVOS, backgroundpetroleum hydrocarbon concentrations in intertidal
sediments at most locations in PWS were very low, generally near detection limits (Karinen et al.
1993). Prior to the Spill, there were no published measurements of oil concentrations in subtidal
sediments in PWS or the NGOA, but concentrations in those sediments were probably low also.
Measurements since the Spill have identified several possible sources of petroleum hydrocarbons
probably present at low levels in subtidal sediments prior to the Spill. These sources included the
Katalla oil seep, vessel traffic, pyrogenic sources frommajor forest fires, and oil perhaps from
ruptured storage tanks following the 1964 earthquake (Kvenvolden et al. 1993, Page et al. 1995).
The purpose ofthis report is to describe the chemical composition, distribution and
persistence of petroleum hydrocarbons from theEVOS in subtidal sediments in PWS and in the
NGOA. Measurements of thechemical composition of the hydrocarbons wereneeded to
distinguish EVO from other sources ofpetroleum hydrocarbons. The study reported here tracked
the spatial and temporal distribution of that proportion of thebeach-stranded oil that was
transported to subtidal sediments. This study provides long-term sediment hydrocarbon data
usehl to a number of biological studies encompassing a range of taxa from microbes to
vertebrates that requireinformation on environmental hydrocarbon levels to interpret their
7
findings. This study also provides the basis for evaluating natural recovery of the subtidal
sediments from EVO contamination.
OBJECTIVES
A. Determine the composition and concentration of petroleum hydrocarbons from the EVOS in
intertidal and subtidal sediments (0-100 m) in PWS and the NGOA by gas chromatographyimass
spectrometry.
1. Determine the concentrations of totalpolynuclear aromatic hydrocarbons (TPAHs) and
n-alkanes in subtidal sediments and compare with intertidal sediments.
2. Determine the hydrocarbon analyte distributions in subtidal sediments and compare
those distributions with the analyte distribution in EVO.
B. Determine the distribution of EVO with bathymetric depth in PWS and the NGOA
C. Determine the persistence of EVO in subtidal sediments over time in PWS
D. Compare theconcentrations of EVOin subtidal sediments to those ofhydrocarbons from
other sourcesand to those found in subtidal sediments after other large oil spills.
METHODS
Study Sites
Throughout this report, geographical position is described by three terms: location, site,
and station. Location refers to a general area where one or more sampling sites were established
(e.g., Northwest Bay). Site refers to a relatively small geographical area containing the
bathymetric transect used to sample various bottom depths forsediments (e.g., M a y 4 = Site
#4 in Northwest Bay). The origin of the bathymetric transect (where it intersected the shore) is
shown as the geographical position of each site in Tables 1 to 4 and Figures 1 and 2. Station
refers a specific spot along a bathymetric transect where sediment samples were collected (e.g.,
the 20-m-depth station). Assessment locations are those where EVO was reported to have come
ashore. Reference locations are those where no oil came ashore.
Sediments were sampled at 29 locations (45 sites) in PWS (4 reference locations and 25
contaminated locations; Table 1, Fig. 1) in 1989. Eighteen locations were studied intensively,
8
Figure 1.--Distribution of study sites
in PWS. See Tables 1-3 for the geographical coordinatesof
each location sampled in 1989, 1990, and 1991. Numbered locations are: 1) Applegate Island; 2)
Bay of Isles 86; 3) Bay of Isles 90; 4) Bay of Isles Bioremediation; 5) Bay of Isles; 6) Block
Island; 7) Block Island 47; 8.) Chenega Island; 9) Disk Island; 10) Drier Bay; 11) Eshamy Bay;
12) Ewan Bay; 13) F o x f m ; 14) Green Island 22; 15) Green Island; 16) Heather Bay; 17)
Herring Bay 53; 18) Herring Bay 110; 19) Herring Bay 125; 20) Herring Bay; 21) Iktua Bay 2;
22) Iktua Bay; 23) Ingot Island; 24) NE Knight Island Bioremediation; 25) Knight Island; 26)
Lower Herring Bay 5; 27) MacLeod Harbor; 28) Moose Lips Bay; 29) Northwest Bay 4; 30)
Northwest Bay 5; 3 1) NorthwestBay; 32) Olsen Bay; 33) Paddy Bay; 34) Point Helen; 35)
Port Fidalgo; 36) Rocky Bay; 37) Rua Cove; 38) Sleepy Bay; 39) Smith Island; 40) Snug
Harbor 25; 41) Snug Harbor; 42) Snug Harbor Meiofauna; 43) Two Moon Bay; 44) West.Bay;
45) Zaikof Bay.
9
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PP Lf LPI
EO Ef09
Zt *f LPI
LE
60 9 f LPI
LO f f 09
9c PC LPI
XP 60 09
I Z SP L t l
Zf 09
IS
90 LP LPI
00 90 09
ZP 65 LPI
SZ 09
OE 85 LPI
2
9
f
9Z 85 65
Of 01 8PI
z
,S
E
LS L I 09
90 SZ LPI
81 91 09
81 9z LPI
9
E
PC 92 65
91 OS L b l
Pf 92 09
Z I LP 8bl
02 6Z 09
LO f b LPI
9
f
.
OP 6 f LPI
9
PS 9Z 09
55 62 09
00 E2 09
PS PP L b l
6P I f 09
01 9f LPI
b
6P I t 09
92 9 f LPI
t
6P 61 09
62 00 861
b
E
9
OP Lf 09
61 8 0 X t l
P
LE ZZ 09
LZ ZP L P I
P
fS ZZ 09
st Lt LPI
P
37
Rua Cove
"
"
60 20 38
55
147
27
147
11
38 Bay Sleepy
60 04 01
39
Smith Island
60 31 47
40
Snug Harbor 25
60 14 13
41
Snug Harbor
60 14 23
50
45
4
2
6
3
147 20 45
6
3
I4743 58
..
147
07
6
4
4
3
42
Snug Harbor M
60 I5 46
147 46 02
3
4
a. Al sites occupied illNovember or h e m b w 1989 were estahlisl~edand sampled by lite Alaska Department ofEnvironmental C o ~ j s e ~ a t i o a
except Sleepy Bay which WRS established by N O M .
b. Depths sampled were 0 and 6 nt.
E. Depth sampled were 0,3,6,
20.40, and 100 m.
d. Depths sampled were 0.3. atd 6 m. The 20-3" depth was rarnpled at site "06 20.3 I , and 42.
e. Depths sampled were 3.6, IO. and 20 m.
t Depths sampled were 0, 3, 6, 20,and 40 811.
12
10
60 19 12
1474403
12
602200
148 08 00
26
M
24 12
111.1148
21
59 53 43
1414548
28
60 12 30
147 1x06
32
60 45 05
1 4 6 II 13
33
602500
l48MOO
2
35
€450 12
146
1235
36
60 20 19
44
6
i
6
i
6
.1
24
4
i.
6
4
4
6
4
147 0759
4
6
60 51 53
1464631
4
6
45
60 16 53
14102 19
4
6
3
60 ?? 53
1474245
3'
4
60 22 54
1 1 1 42 45
5
60 23 00
14144 Y
4
1
6 0 3 1 496
I4125 36
4
8
60 19.19
1480024
4
6
4
Y
6 0 2 9 55
14139 M
4
6
4
I1
60 26 54
14158 30
2
13
59 58
26
148 1030
4
14
601157
1.11 25 oh
4
1
I5
60 16 18
14126 18
4
4
19
60 29 20
14143 01
4
20
60 25 51
I114106
4
22
6006w
1.17 59 M
2
4
2
4
2
6
4
4
2
6
6
1
4
2
24
60 26 21
1413 1 39
. 25
602621
117 3 1 39
4
6
4
31
60 33 07
14134 36
4
6
4
38
60MOI
117 50 II
4
6
4
39
60 31 41
147 20 45
4
6
4
M
60 I 4 I3
I4143 58
4
4
4
41
601546
117 45 si
2
13
Table 3.-kocation ofsites i n PWS where intertidal and suhtidal sediment samples were collected in 199 1. A dash indicates that
sampling was conducted during (lie time periodS ~ O W I I .
Site
No.
NumberofStafions
West
Name
Lalitude*
0 ' "
Imigitude
0 ' "
60 19 I 44
2
147
60
148 08 00
Aprmg
Jun
Sep
Reference Sitcs
IO
Drier Bay
12
EwanBay
26 Bay
Herring
Lower 48
27
22
47
147
00
Olsen Bay
33
k'dddy
45
Bay
36Bay Rocky
44
Bay
West
45
ZaikofBay
60
- .
I806
2
Sd
6
05
146 I I 13
2
6 0 25 00
1480 6 110
2
5960 20 19
07
02
2
7
147
60 12 30
Bay28 Lips Moose
7E
12 60 24
59 534843 45 I47
M x L e o d Harbor
32
00
6
?
2
I47
6
60 52 21
146 47 54
?'
I47 60 16 53
19
6
Assessment Sites
23 60
00 54 44147
5
Bay of Isles
47
Block Island
6031 49
147 36 24
6
8
Chenega
Island
60 1949
148 00 24
7
9
Disk
Island
60 29 55
147 3940
6
1I
Eshamy
Bay
60 2654
147 58 30
2
-
13
Foxfarm
59 58 26
I48 IO 30
7
2
20
Herring Bay
60 2551
147 47 06
2
2
22
Iktua
Bay
6 0 06 00
147 59 42
2
31
Northwest
Bay
60 33 07
147 34 36
38
Sleepy
Bay
60 04 0I
I47 50 I 1
40
Snug
Harbor
60 I4 13
I47 43 58
4
4I
Snug
Harbor
60 I 5 46
117 J5 55
IC
42
Snug Harbor
60 I5 46
147 16 02
25
M
7
7
2
6
2
2
a. Latitudebngitude refers to Ihe " 0m station at each site where"0" is mean lower low water.
b. Depths sampled in MayiJun and Sep were0 and 6 m.
c. Depths snmpled = 0,3.6,20.40. 100. 140 m where n = 7.
d. Depths sampled = 0,3,6,20,40. and 100 m where n = 6.
e. Depths ssmpled were 40 and 100 m.
14
7
7
7
2
110
Table 4.--Location of sites outsde PWS and number of stations sampled at sites where inteltidal and subtidal sediment
samples were collected in JulyiAuguust 1989.
Site
No.
Agnes46
Bay Black
North
Wes1
Latitude
Longitude
Number
0 , "
0 '
.
Name
59Cove
47
of
Stations
'I
46 00
I49 34 24
6a
593207
150 12 17
6
48
Chignik Bay
56 1936
1582506
5b
49
Chugach Bay
59 I I I2
151 3748
6
50
Hallo Bay
58 27 29
15400 14
6
5I
lvanof Bay
55 50 16
159 23 17
6
52
Katmai
Bay
57 5 5 00
05
155
00
6
59 I 3 50
151 31 00
6
20, 40, and 100 m where no. of stations was 6.
b. Depths sampled were 0, 3,6, 20, and 30 m
53
Bay
Windy
a. Depths sampled were 0, 3.6,
typically involving sampling at six stations that extended from the intertidal region to 100 m in
July 1989. Three additional locations were sampled at three depths (intertidal, 3 m, and 6 m).
Usually one site was established at each location, but up to three sites were sampled at some
locations (Table I ) . In 1990, sediments were sampled at 25 locations (1 1 reference locations and.
14 contaminated locations; Table2). The total number of locations sampled in 1991 was 21(10
reference locations and 11 contaminated locations; Table 3).
Outside PWS, eight locations were studied in 1989. The locations were distributed such
that four locations wereon the Kenai Peninsula and four locations wereon the Alaska Peninsula
(Table 4, Fig. 2).
In 1989, sampling in PWS was conducted during three periodsby NOAA (3-13,May, 1-18
July, and 5-1 1 September) and during one period (7 November to 8 December) by the Alaska
Department of Environmental Conservation (Lindstrom and Weiner 1990; Table I). In 1990,
sampling was conducted during threeperiods (3 1 May to 9 June, 27 June to 23 July, and 4-16
September; Table 2). Dates of sampling.in 1991 were 27 April to 2 May, 15-25 June, and 5-9
September (Table 3). Outside PWS sampling was conducted from 25 July to 22 August 1989 .
(Table 4).
Sediment Collection
Standard operating procedures were adopted for the
collection of all sediments (Appendix
I). Intertidal collections weremade at about MLLW (0 m); actual sampling elevation was within
the range of + O S to -1 m depending on the distribution of fine sediments. Intertidal sediment
collections were made by beach teams, or divers, depending on tide stage. Subtidal collections
were made at depths of 3, 6, 20, 40, and 100 m below MLLW. Additional depths were sampled
at some sites in 1989. Collections at 3, 6, and 20 m were made by divers on transects laid along
the appropriate isobaths. (In July 1989, the 20-m station was usually sampled with a Van Veen
grab, except where remote sampling could not be effectively conducted, such as in boulder fields
or dense algal beds.) Three samples, each a composite of eight subsamples collected randomly
along a 30-m transect laid along the appropriateisobath, were taken ateach of the shallow
stations (0-20 m).
A Van Veen grab (1989) or a stainless-steel Smith-McIntyre grab (1990-91) were used to
collect samples at 40 and 100 m depths. Remote sampling with a grab included three grabs taken
at each depth. Four cores were removed from randomly selected points on the surface of the
sediment contained in each grab. The depth of each core was 2 cm. The subsamples were
combined to form one sample per grab.
All samples collected by hand (including those removed by hand from the grab) were
taken from the surface(top 0-2 cm) of the sediment column. Samples taken by hand in the
intertidal region, or by divers, were collected with a stainless-steel core tube or spoon. Each.
subsample was transferred to a sample jar by a spatula. The core tube and the spatula were
16
washed, dried, and rinsed with methylene chloride between sampling periods. Sample jars,
certified hydrocarbon-clean according to EPA standards, were used to store sediments. If these
jars were unavailable, glass jars baked at 440°C or rinsed with methylene chloride were
substituted. The jars werefitted with teflon-lined caps rinsed with methylene chloride before use.
Samples were kept cool after collection and frozen within a few hours. Appropriate blanks were
collected at each site.
Chain-of-custody procedures were followed after sample collection. The samples were
packed in boxes and sealed with custody tape. Boxesof samples were placed in coolers with
enough blue ice to keep the samples frozen while in transit from thefield to the laboratory. All
samples were accompanied by chain-of-custody forms from thefield to the Auke Bay Laboratory
for temporary storage in a locked freezer before shipment to the analytical facility. At least one
field worker traveled with the samples from the field to the Laboratory. At the Auke Bay
Laboratory, custody of thesamples was signed over to a representative ofTechnical Services
Study # I . Hydrocarbon Analytical Support Services and Analysis of Distribution and Weathering
of Spilled Oil.
. .
Hydrocarbon Analvsis
Sediment samples wereanalyzed for petroleum hydrocarbonsby means of gas
chromatography/mass spectrometryby the Geochemical and Environmental Research Group
(GERG) at Texas A&M University using methods summarized by Short et al. (In press (b)). A
program of quality assurancekpality control ofanalytical procedures and protocols was
established under Technical Services Study # l . Implementation of the program was overseen by
the Analytical Chemistry Group ofTechnical Services Study # I
Results of thechemical analysis were screened on thebasis of surrogate recoveriesand
minimum detection limits (MDLs). Individual analytes and the summary statistics affected by
them (e.g., totalpolynuclear aromatic hydrocarbonsincluding perylene (CPAH), TPAH, total
normal alkanes (TNA) and total hydrocarbons) wereexcluded from the analysis if the recoveries
of corresponding analyte surrogates fell outside the range30-1 SO%. For example, if the surrogate
of onePAH analyte fell outside the acceptablerange, the CPAH and TPAH concentrations for
that sample were excluded from the analysis. Concentrations of individual analytes reported by
GERG below MDL were replaced by "0's" for our analyses. The MDL for aromatic
hydrocarbons was 1 ng/g and for aliphatic hydrocarbons was I O ngg. TNA is the sum of those
alkanes from CIO to C30 excluding pristane and phytane. Results of the analysis of field blanks is
shown in Appendix 11. A group of 165 samples was excluded from the study becauseof
extraneous contamination (Appendix 111).
Criteria were established for comparing hydrocarbon concentrations in sediments with
those in EVO. The pattern of PAH concentrations
in the sediment samples was judged similar to
EVO if it met three criteria: (1) the ratio of alkyl dibenzothiophenes to alkyl phenanthrenes
17
exceeded 0.30, (2) the ratio of alkyl chrysenes to alkyl phenanthrenes exceeded 0.10, and (3) the
concentration of alkyl phenanthrenes exceeded 5.0 ng/g.
Data Analvsis
The carbon preference index (CPI; Farrington and Tripp 1977) was used t O distinguish
oiled from non-oiled sediments. The index has the form:
CPI =
2(n-C2,+n-C,,)
n-C26+2n-C*,+n-C,,
where n-C, is the concentration (ng/g) of the n-alkane of carbon number I. The CPI is near 1 for
oiled sediments. Values from 5 to 7 indicate unoiled sediment.
*
Concentrations shown in the text are given as mean concentration the standard error of
the mean (SE). Unless otherwise noted means are the averageof three replicates. Differences in
within-station TPAH concentrations in samples processed in contaminated catalogs compared
with those processed in uncontaminated catalogs were tested with a paired (-test of logtransformed data (Appendix 111). The Kruskal-Wallis test was used to test the difference in the
magnitude of the increasein the TPAH concentrationin contaminated replicates over that in
uncontaminated replicates at oiled versus reference locations.
RESULTS
This study analyzed 1337 sediment samples, for hydrocarbons, from a total of 53 locations
over a three year period. The hydrocarbon data from theanalyses were extensive (Appendix 111).
We have organized the results by general geographic location (PWSand the NGOA), benthic
region, year, and level of oiling.
pws
Oil became stranded extensively on shorelines in PWS, particularly in bays facing
northeast, in the first weeks after the EVOS. Intensive cleaning activity took place at many of the
most heavily oiled shorelines in summer 1989 and to a lesser extent in summer 1990. Some of the
stranded oil was resuspended and deposited in the subtidal region over time by natural processes
and by the shoreline cleaning activity. The intensive cleaning activity probably substantially
increased the variability of hydrocarbon concentrations in intertidal sediments between sampling
periods at some locationsin 1989.
18
Heavilv Oiled Locations. 1989
Ten assessment locations were sampled in 1989, and five (Disk Island, Herring Bay,
Northwest Bay, Sleepy Bay, and Snug Harbor) were heavily oiled in the upper intertidal zone by
EVO. Of the remaining five locations, one was a protectedbay that was sporadically oiled (Bay
of Isles), two were in the southwestern passages of PWS along the exit path of the floating oil
(Iktua Bay and Foxfarm), and two were near the periphery of the Spill path (Green Island and
Eshamy Bay).
Intertidal Stations
We found high aromatic hydrocarbon concentrations in intertidal sediments (0 m station)
at three of theheavily-oiled locations: Disk Island, Herring Bay, and Northwest Bay (Table 5).
Because we sampled at about MLLW, the concentrations ofEVO hydrocarbons in our intertidal
sediments were probably lower than at upper shore levels where the oil had become stranded.
The highest mean TPAH concentrations found during this study was 12,700 f 2,760 ng TPAWg
dry sediment weight (n = 3 ; mean i standard error) in intertidal samples collected at Disk Island
(Table 5). No intertidal sediment samples were collected subsequently from Disk Island in 1989.
but samples collected from Northwest Bay in July 1989 contained 11,700 f 3,280 ng/g (n = 2)
and in September contained 2,862 f 306 ng/g (n = 3 ) . The TPAH concentration ranged from
1,300 ng/g to 6,000ng/g in sediments collected at 2-m intervals along a 20-m transect laid
perpendicular to the shoreline at Northwest Bay in September 1989. At Herring Bay, intertidal
sediment samples collected in May, July, and September 1989 contained 1,340f 286; 1,840 f
753; and 769 115 ng TPAWg (n = 3 ) , respectively.
*
The PAH composition pattern in sediments, at three intertidal assessment station locations
where the TPAH concentration was high, was consistent with weathered EVO. (Hereafter, this
PAH composition pattern will be referred to as theEVO-PAH pattern.) The most abundant PAHs
measured in these sediments generally corresponded with the most abundant PAHs reported by
Short et al. (In press(a)) for moussesamples collected 11 days after theinitial Spill; except the
sediment PAHs reflected greater losses of lower-molecular-weight and of less-substituted PAHs
(Fig. 3 ) . The pattern of these losses was consistent among sediment replicates. In addition, it is
noteworthy that ( I ) the high-molecular-weight and unsubstituted PAHs that were less abundant in
the mousse samples were also less abundant in the sediments, and (2) phytane, which was
abundant relative to other aromatic analytes in the weathered mousse, was consistently more
abundant relative to those analytes in the sediments. This wasmainly a consequence of the
differential PAH losses in the sediments. Finally, the normal alkanes, with molecular weights
greater than n-eicosane, were present at concentrations that wereapproximately as high as the
alkyl-substituted PAH homologues in the sediment samples, and the unresolved complex mixture
(UCM) was large (i.e., present at concentrations greater thanIO6 kg/g in some samples).
19
oz
OZ
61
LI
.IOf'Z
81
.(LZ80)rLZ8
El
6
1
9
5
P
E
Z
Northwesl Bay 5
31
37
38
38
-
.
39
40
41
42
Now89
.
DsC.89
Jul-89
11,686*(0397)
Jul-89
sep-89
2,862’(0.185)
Jua-90
166’(0.316)
Jul-90
4,650
360’(0.144)
Sep.90
Jun-91
584’(0.719)
Nuv-89
May89 193’(0.130)
Jal-89
Sep-89
335’(0.099)
Nov-89
Jun-90
176’(0.722)
Jul-90
80.9*(1.014)
Srp-90
253’(0.453)
May-91
18.2’(0.516)
Jun-91
235’(0.269)
Srp-91
29.3’(0.295)
DW.89
Jun-90
386
Nov-89
.
Jus-90
33.5’(0.531)
Jul-90
Z.SSl’(0.833)
Jus-91
128’(0.028)
Jul-89
592’(0.606)
sep-89
Jul-90
Jun-91
3.607
Sep-91
Jul-89
420’(0.654)
Scp-89
1.026’(1.659)
Jun-90
177’(0.480)
Sew90
106’10.203)
Snug Harbor
Meiofauna
614
194
1.486’(0.886)
2,6661
517’(0.431)
193
403’(0.577)
684*(0.261)
1.057’(0.163)
l.Wl’(0.387)
517‘(0.266)
91 l’(0.998)
457*(0.352)
1,061
5(0‘(0.006)
422
1,710
264
157’(0.222)
810’(1.072)
IZY(0.477)
14J
106‘(0.109)
182*(0.112)
51.2’(0.226)
-
1%
-
379
132’(1.058)
143’(0.678)
S
214’(0.910)
468’(0.329)
2,088
261’(0.416)
991’(0.561)
366’(0.440)
559
657’(0.378)
1.849’(0.514)
375’(0.265)
245’(0.134)
940’(0.057)
309’(0.287)
163’(0.028)
254’(0.355)
40.1’(0.227)
193’(0.063)
358’(0.497)
67110.064)
I~S(I.IZ~~
202’(0.924)
940‘(0.531)
70.8’(0.052)
238’(0.478)
55.2
346
133’(0.718)
40.0
377
265’(0391)
.
.
437*(0.631)
506’(0.274)
781
391Y0.263)
l,0712(0.9Z4)
2.816‘
1,226’(0.693)
366’(0.054)’
355
350’(0.872)
S96’(0.335)
125
101’(0.080)
219’(0.807)
2.734*(0.023)
1.547
169‘(0.520)
66.6’(1.326)
8.77971.303)
1.629’(0.305)
I PO
21
907‘(0.189)4
111.
141’(0.318)’
31.3’(1.034)
.
.
94.4
474’(0.578).
2321(0.120,)0
652’(0.206)
891’(0.114)
1,404’(0.600)
95.9
1,097’(0.147)
534’(0.190)
Phytane
Benzo
c4ch??11
Benzokfl
Benepy
Benapy
lndeno
Dibenz
Benzop
C 3 E
Benanth
Ch sene
C%hrys
C2chrys
C3chrys
Acenttiy
Acenthe
Fluorene
Clfluor
C2fluor
C3fluor
Dithio
Cldithio
C2dithio
C3dithio
Phenanth
Clphenan
C2phenan
C3phenan
C4phenan
Anthra
Fluorant
rL
0
VI
Relative Percent
2
0
cn
A
I
<
The TNA concentrationwas highest when the TPAH concentration was highest and the
EVO-PAH pattern was present (Table 6). The highest TNA concentration of this study was
3 1,100 ng/g in intertidal sediments from Northwest Bay in July 1989; the samesamples contained
nearly the highest TPAH concentration of thestudy ( 1 1,700 ng/g; a TNA concentration was not
available for the stationat Disk Island where the TPAH concentrationwas 12,700 n d g because of
inadequate surrogate standard recoveries for those alkanes). The ratio of TNA to TPAH in these
samples was 2.66, as comparedto weathered EVO (3.62-4.68 for EVOmousse samples). The
highest TNA concentration (31,100 ngg) at an EVO contaminated assessment site was more than
twice as high as the highest TNA concentration at any reference station or any assessment station
where the EVO-PAH pattern wasgenerally absent.
Shallow Subtidal Stations
We found substantially lower concentrationsof EVO hydrocarbons in shallow subtidal
sediments than in intertidal sediments. In 1989, shallow subtidal (3-20 m) sediment samples were
collected at a l l locations where intertidal samples had been collected, and at an additional six
locations where intertidal samples had not been collected. At the three locations where wefound
the highest mean TPAH concentration, similar in composition to weathered EVO in intertidal
sediments, we found a substantially lower mean TPAH concentration (also indicating weathered
EVO) in subtidal sediments. This occurred most often at Northwest Bay, less often at Herring
Bay, but not at Disk Island. We also found the EVO-PAH pattern at relatively low TPAH
concentrations in subtidal sediments at three locations where intertidal sediments were not
sampled: Block Island, Rua Cove, and Smith Island.
At Northwest Bay, the EVO-PAH pattern wasconsistently evident in subtidal sediments
from 3 m to 10 m. This pattern was less consistently observed ,in 20-m sediments. At the
Northwest Bay 4site, the EVO-PAH pattern appeared in all samples (unreplicated) collected
from 3 m to 20 m in November 1989; the TPAH concentrationranged from 588 ng/g to 2,660
ng/g (Table 5). At the NOAA Northwest Bay site in July 1989 mean TPAH concentrations
ranged from 474 158 ng/g to 1,490 i 762 ng/g (n = 3) in subtidal sediments from depthsof 3 m
to 10 m. Concentrations of unsubstituted PAHs were relatively high in many of these samples,
indicating additional PAH sources. especially in two of thethree replicate samples from the 3-m
depth in July 1989 (Table 5). In the 20-m sediments from this site, mean TPAH concentration
ranged from 366 i 93.0 to403 134 ng/g (n = 3). The PAH composition differed from
weathered EVO and was more variable among the replicates. At the Northwest Bay 5 site, one
sample replicate each was analyzed from the 3m and 20 m depths sampled in December 1989.
The EVO-PAH pattern was present at 3 m (TPAH, 194 ng/g), but not at 20 m (TPAH, 193 nglg).
*
*
23
3
Bay of Isles 90
4
5
Bay of Isles BR
Bay of I d e s
Nov-89
Jun-90
Jd-90
Jul.89
Sw89
Jun-90
Jul-90
Sepw
6
7
9
Block Islad 7
Block Island 47
Disk Island
Jun9 I
Nov-89
Nov-89
J"ll-90
Jul-90
Jul-89
Jun-90
J"l.90
13
Foxfam,
Juw91
May49
Jul-89
Sep89
3""-90
Jul-90
sepw
17
18
19
20
Herring Bay 53
Hnring Bay I IO
Herring Bay I25
Herring Bar
20
29
30
N c 4 w e s l Bay 4
N d M Bay 5
Apr-9 I
Sep91
Nov-89
Nov-89
Nov-89
J""40
May-89
Jul-89
Sep89
1""-90
Jul-90
Sep90
Apr-9 1
Jun-91
sep91
Nov-89
Dec-89
926'(0.025)
891'(0.541)
S
1,416z(0.172)
1,548'(0.214)
2.455
1,994*(0.087)
8,297(0.113)
429'(0.183)
488V0.342)
886'(0.072)
76.3'(0.477)
JSO'(0.659)
S
S
S
3,53l'(0.008)
S
4,169
2,425'(0.469)
1,7@(0.374)
2,026'(0.517)
736
113@(0.469)
S
S
266'(0.646)
S
164'(l.l32)
IO1
S
-
8,291'(0.070)
2,584'(0.314)
4,159'(0.074)
1,576'(0.174)
8,925'(0.052)
996Y0.173)
3,2241(0.150)
8,223'(0.053)
6,725'(0.468)
4,248'(0.(0.119)
S'
S
1,611
1.351'(0.3221
1,762'(0.093)d
1,119
S
589
3,174
372
1,705
S
2,207
4,054'(0.054)
1,768
5
599'(0.240)
203
43 I
144
65.9
37.2
194'(0.560)
323
354
1,032'(0.691)
5
5
l59'(l.ll8)
l42'(0.469)
928'(0.133)
4.08O'(0.477)
3,l89'(0.461)
4,334'(0.648)
883'(0.342)
2,044
678'(0.137)
573*(0.301)
419*(0.179)
296'(0.430)
S
1,737'
1,2l6'(0.518)
7,181'(0.206)
S
62O'(0.355)
377Y0.807)
397
168
5,777
1.425'(0.322)
. .
1.387
1.241'(0.206)
4,320'(1.242)
477'(0.296)
88.2
378
370'(0.490)
4,866'(0.449)
l,69O'(0.394)
l,M6'(0.221)
1,276
l79'(0.466)
lJ042(0.456)
1,701
940
S
705
S
976
398'(0.192)
879'(0.160)
875'(0.502)
69r(om)
531*(0.679)
SSO'(O.I59)
343'(0.219)
1,484'(0.664)
23r(o.z16)
64r(o.363)
S
1,707YO.408)
71r(o.z64)
853
795
SOS'(0.439)
168
S
lPll
24
1,653*(0.478)'
231=(0.197y
871
666'(0.124)
696'(0.312)
..
1,65O'(0.332)
933'(0.074)
918
710'(0.598)
I,O13'(0.185)
1,643'
S'
Table 6.-(Conl.).
Sile
No.
31
39
40
41
42
Name
Nanlwesl
Ba,
Smill>Island
Snug Harbor 25
Snug Harbor
.
Date
31.076
Jul-89
Jul-89
Sep-89
Jun-90
Jul-90
Sep90
Jun-91
Now89
May-89
Jul-89
Sep89
Nov-89
Jun-90
Jul-90
Sep-90
May91
1””-91
sq9.
I
Dec-89
Jun-90
Nov-89
Jun-90
Jul-90
hn-9 I
Jul-89
Sep-89
Jul-90
Jun-91
Sep91
Stwp Harbor
JuI-89
M
Sep89
Jun-90
Sep90
May91
0m
3m
4,128’(1.034)
6 111
1,700’(0.236)
2.543’(0.267)
Depth
20 m
’
40 111
927y0.059)
100 m
Other
236)’
1.717‘(0.184)
1.700’(0
1.17$(0.428)’
10.466‘(0.084)
821’(0.417)
6.537‘(1.014)
1,365V0.327)
1.650’(1.098)
2,542’(0.005)
2.286
1.0832(0.010)
797‘10.079)
719
848
647’(0.224)
S
805
172
~~~
201‘(0.131)
131’(0.177)
758’((1.439)
54.1’(0.507)
963
122’(0.820)
4.644
86.5’(0.077)
1.236’(0.31 I )
574’(0.310)
1.345‘(0.570)
306’10,325)
458
S
369
78.4’(0.151)
466
978
1,206
974’(0.557)
1,664’(0.257)
s
4,414‘(0.440)
735
716’(0.241)
3.238‘(0.079)
1.748’(0.282)
3.087’(0.009)
525’(0.205)
25
s
s‘
1.316’(0.017)
566‘(0.125)’
2.392
1,499
713’(0.083)
282‘
270’(0.615)’
3,574’(0. I5 I )
2.268’(0.192)
S
534’(0.365)
2.088
1,387’(0.l26)
s
S
276’(0.185)
S
2,646‘(0.147)
1.212’(0.165)
1,9441(0.931)
3,057‘(0.149)
1,121‘(0.269)
1,342’(0.614)
1.408’(0.427)
259“(0.155) 490’(0.158)
704’(0.073)
416’(0.059)
778’(0.438)
S
S
2.635
793’(0.482)
1,700
401’(0.10S)
1,532’(0.434)
1.397’(0.243)
137’((1.473) 352’(0.825)
889’(1.033)
I 19’(0.046)
247
208
884
742’(0.184)
1.560
212’(0.512)
2.627’(0.107)
2.465
S
1.000‘(0.126)
744‘(0.584)
3.603’(0.144)
1,836’(0.141)
1.743V.224)
837’(0.434)
781‘(0.478)
As with TPAH, the TNAconcentration decreased rapidly with increasing bathymetric depth
at Northwest Bay in July 1989; whereas, the CPI increased with increasing depth. At the NOAA
Northwest Bay site, 3 m, the mean TNA concentration was 4,130 2,470 ng/g (n = 3),
decreasing to 1,700 * 232 ng/g (n = 3) at 20 m (Table 6). The CPI increased from 1.27 at 3 m to
3.38 at 20 m (Table 7).
*
At Herring Bay, the EVO-PAH pattern was occasionally found at 3-m and 6-m depths in
1989. At the NOAA Herring Bay site (sampled July and September 1989) and Herring Bay site
53 (sampled November 1989), this patternwas present in 3-m sediments where themean TPAH
concentration ranged from 239 f 36.7 ng/g (n = 3) to 921 182 ng/g (n = 2). At Herring Bay
site 125, the EVO-PAH pattern waspresent in 6-m sediments and the mean TPAH concentration
was 220 64.1 ng/g (n = 3), but at 3m the PAH pattern differed from weathered EVO and the
mean TPAH concentration was lower (I64 39.3 ng/g, n = 2). The EVO-PAH pattern was not
evident in sediments from the 3-m depth at Herring Bay site 1 IO, nor in sediments from depths
greater than 6 m at any Herring Bay site. Mean TPAH concentrations were consistently less than
350 ng/g in shallow subtidal sediments from depths greaterthan 3 m except in one sample
(Herring Bay 53, 10 m; TPAH, 2,300 ng/g; Table 5). The relative abundances of PAH in this
sample differed from that of weathered EVO dueto lower proportions ofchrysenes, which
indicates diesel oil as themost likely source. (Referenceto a PAH in the plural (e.g. chrysenes)
denotes theun-substituted PAH togetherwith the alkyl-substituted homologues collectively as a
group).
*
*
At Disk Island, we did not observe the EVO-PAH patternin subtidal sediments despite the
presence of that pattern and high TPAH concentration in intertidal sediments. Mean TPAH
concentrations in the shallow subtidal samples ranged from 160 ng/g to 553 173 ng/g (n = 3;
Table 5) with low concentrations of chrysenes and often low concentrationsof dibenzothiophenes
relative to other PAHs.
*
At Block Island, the composition and concentration of hydrocarbons in subtidal sediments
resembled those from Northwest Bay Site 4. The EVO-PAH pattern was
consistently present in
all subtidal sediment samples from the 3-m to 20-m depths. The mean TPAH concentration
ranged from 539 ng/g (n = I ) to 903 8 1.9 ng/g (n = 3). The EVO-PAH pattern was present in
the single subtidal sediment sample analyzed from Rua Cove(3-m depth) and in the single 3-m
depth sample from Smith Island. The TPAH concentration in the Rua Cove and Smith Island
samples was 264 ng/g and 196 ng/g, respectively.
*
Deeo Subtidal Stations
The TPAHconcentration and the PAH composition patternin sediments at depths 240 m
were similar at reference locationsand locations where moderateto heavy beach oiling occurred
in PWS. The EVO-PAH pattern was rarely present consistently among replicate samples at these
depths regardless of sampling location (Tables 5 and 8). The PAH composition patterndiffered
from weathered EVO in that concentrations ofdibenzothiophenes were relatively low (Fig. 4).
26
3
4
5
6
7
2.40
8.56
Bay oflsles
Biorwwdiation
Bay oflsles
5.78
6.50
33.9
10.9
NA
NA
Disk Island
3.31'
7.17
6.19
6.60
9.24
6.41
NA
.
9.33
5.59
4.99
4.29
4.80
6.59
6.14
6.18
6.76
2.68
1.52'
S
S
S
I .44
9
2.54
3.88
3.19
S
3.67
6.36
I .49
4.54
Blwk Island 7
Block Island 47
0.64
1.41
S
5.27
1.99
5.46
4.91
4.63
2.78
S
1.68
1.50
6.09
4.06
4.04
S'
S
1.18
S
8.76
2.27
3.40
4.08
4.85
1.70
6.89
5
3.17
5
13
S
11.86
S
3.61
0.65
I.43
NA
NA
17
18
19
Hming Bay 53
Herring Bay I10
Hming Bay I25
20
Herring Bay
20
29
30
31
Hming Bay
2.81
2.50
S
NA
S
4.92
0.59
1.48
0.95
1.26
1.26
1.53
1.65
5.34
NA
0.89
NA
1.05
3.10
1.46
1.89
2.40
2.20
4.31
4.85
0.62
1.60
1.49
S
2.54
38.8
1.52
2.11
2.25
NA
NA
1.46
S
0.84
7.76
3.05
3.93
3.31
12.8
5.62
5.05
4.49
NA
NA
S
8.25
3.93
1.11
2.48
5.34
5
S
3.52
1.47
2.91
27
..
12.7
12.8
5.50
10.3
3.36
4.91
4.88
5.30
9.24
3.68
NA
2.01
S
1.12
3.42
1.91
5
1.78'
3.78'
3.10'
S'
2.41
1.75
2.86'
4.441
Table 7.-(Conl.)
Site
Name
Date
0.57
Sew89
No.
Juri-90
37
38
39
40
41
12
Rua Cove
Sleepy Bay
Smith Island
Snug Harbor 25
Snug Harbor
Snug Harbw M
Jul-90
Sep-90
Jun-9 I
Nov-89
May-89
Jul-89
Sep-89
Nov-89
Jun-90
Jul-90
Sep90
May91
Jun-91
Sep-91
Dec-89
Jun-90
Nov-89
Jun-90
Jul-90
Jun-91
Jul-89
S~D-89
J"i.90
Jun-9 I
sep-91
Jul-89
ST-89
Jun-90
Sep-90
Mav-91
0 "1
3.57
0.52
1.64
2.93
3 111
0.82
0.80
I .69
2.33
1.44
3.17
1.00
S
2.57
2.26
33.8
NA
0.88
NA
0.57
NA
0.83
NA
2.48
S
3.74
4.94
2.96
7.56
3.43
Depth
20 "1
1.78
6m
0.83
1.35
I .02
1.78
1.78
S
4.49
I .60
1.08
40 m
100 11,
2.14
1.95
3.15
4.46
NA
1.98
Otller
s'
1.13
2.31
1.32
7.43
2.64
1.38
4.80
2.37
1.16
S
1.53
18.3
14.5
1.06
2.91
NA
5.34
0.49
NA
NA
NA
NA
4.90
0.52
0.52
NA
NA
NA
NA
0.92
0.92
7.92
S
1.81
1.23'
S
S
2.18
3.28
5.31
1.62'
35.8
1.56
10.4
2.23
0.28
11.7
4.05
9.97
18.7
4.62
3.15
6.19'
I 5. I'
7.51
2.88
S
7.19
10.4
2.87
S
S
5.93
7.91
5 00
3.83
NA
S
28
I
X
10
Drrer Boy
II
Erhamy Bay
12
14
I5
16
21
22
21
21
25
Green Island 22
Green Island
Heather Boy
Iktua Bay 2
lktua Bay
Nov-X9
Nov-X9
Jun-90
Jul-90
Jul-90
Ssp90
Juw91
May89
Jul-89
srpx9
Juw90
Sep90
Apr-9I
Scp-91
May-X9
srp-x9
Jun40
Sep-90
Apr-91
sep-9 I
Nov-X9
Jun-90
Jul-X9
Jul-90
Jul-X9
Jul-89
May-X9
Jul-89
srpx9
Jun-90
Sep90
Apr-91
s r p 9I
Nov-X9
Jul-90
Jul90
Nov-X9
Jun90
I80
S
1,164’(1.092)
91.7
95.8’(0.279)
22.5‘(0.051)
21470.309)
46.5’(1.228)
12.2’(0.980)
49.9
13.1’(0.017)
375’(0.435)
306’(0.607)
25.6’(0.467)
l7.0’(1.118)
1.570’(1.350)
17.4
95.8’(0.450)
118
98.5
38.3’(0.682)
86.7’(1.032)
69.9
18.4
253
5.8
1.195’(0.399)
6.12‘(1.411)
12.9’(0.382)
840’(0.860)
I94’(0.I55)
54.0’(0.656)
22.2
271
69.7
55.0’(1.190)
130‘(0.307)
56.2’(1.346)
219’(0.356)
112’(1.652)
5.89’(0.402)
542’(1.416)
20.3
34.6
39.37
45.8‘(0.001)‘
229
41.0’(0.045)
I 93
34.7
18.4
X15’(0.494)
63.5’(0.712)
307’(0.947)
82.6’(0.449)
37.3’(0.234)
191’(0.451)
34.3’(1.231)
28.9’(0.404)
419
132*(0.562)
102’(0.433)
I lO‘(0.845)
13.4’(0.470)
16.5’(0.534)
10.321’(0.626)
20.0
113’(1.064)
116’(0.403)
30.3
18l~(l.191)
162’(0.890)
156’(0.176)
547‘(1.261)
116’(1.581)
22.3’(0.409)
535*(0.951)
123’(0.292)
238
23.8‘(0.709)‘
22.4’(1.665)
29
73.0
300
22.1
360‘(0.228)
72.6
967’(0.614)
227
1.187‘(0.053)
546’(0.966)
484’(0.253)
1.069’(0.244)
577’(0.548)
975
960’(0.054)
S’
25.5’(0.420)’
191’(0.243)
84.1’(0.444)
283
253
955
340
578
S
294
57.7
S
S
209’(0.240)
240
1.1 IX’(0.233)‘
S‘
s’
Table 8.-<cMll.)
Site
No.
Name
25
Kn@
i Island
26
LowerHernng
Depth
Date
Jul-90
Jul-911
3m
Om
1335*(0.%6)
S
9.41‘(0.191)
11.7‘(1.064)
15.1’(0.939)
95.7
163‘(0.073)
398’(0.082)
14.2’(0.614)
I78
246’(0.224)
42330.456)
34.2
59.3’(0.073)
305’(0.785)
268’(0.009)
32.1’(0.346)
308’(0.653)
sen-9n
s
6 nl
4.68
l04‘(l.344)
3.89
74.6*(0.998)
30 I
231’(0.688)
~~
25.7’(0.305)
8.43’(1.218)
6.47’(0.544)
42.7’(0.866)
27.6’(0.022)
36.2
21.8’(1.580)
7.53
52.9(0.913)
83.4V0.2751
270’(0.709)
211
44
ZoikofBav
~,
Dec-X9
Juri-90
la1-9l1
Jun-90
Jul-90
Jun-91
34.9
100 11,
Of1,cr
854’(0.074)
1,702‘(0.U96)
620‘(0.041)
671’(0.015)
5W(0.466)
188’(0.114)
117’(0.225)
884
719
244‘(0.018)
135’(0.542)
148’(0 508)
66.4‘(1.069)
594’(0.878)
210‘(0.066)
46Z2(0.618)
474’(0.104)
574’(U.172)
575’(0.108)
350’(0.462)
26.5;(0.406)
16.6’(0.187)
275’(0.580)
13.6
172
181
155
6.30
3162(0.001)
29 1
2IlY0.1051
5.45
306’(0.283)
8.55
193
800
-
S
1,051
54.9’(0.747)
T w o M w n Boy
WesrBay
358
40 rn
144’(0.698)
68.8’(0.685)
220’(0.1491
s
42
43
20 “1
88.3’(1.018)
S
.
,
I16
10.3Y0.065)
210
8.47‘(0.496)
216’(0.973)
439
126‘(0.010)
Nb’
.
,
213*(0.093)
’
287’(0.166)
Nb’
223’(0.018)
1.201’(0.591)
.
,
673‘(0.1731
290‘(0.0761
’
639
29.6’(0.075)
234‘(0.021)
1521(0.640)
95.1’(0.823)
303
418
543Y0.124)
21.5‘(0.021)
41.4Z(0.128)
72.4;(0.22i)
l62’(0.048)
I,Ol7’(0.154)
240‘((1.71(2)
366y1.067) 466‘(0.100)
T.Biorennedialion tree.ltmcn1d e .
30
22.4‘(0.448)
470‘(0.355)
507‘(0.027)
749*(0.106)
468?(0.023)
782‘
Dibenz t
Benzop
Phytane
I
0
.
I
ul
I
ul
0
I
A
A
.
0
ru
EipheliylpAcenthy
Naph
Menap:
Menap'
Relative Percent
0
ul
0
-L
ul
A
0
N
At.the 40-m depth, the median TPAH concentration was 277 ng/g, and 308 ng/g at locations near
moderate to heavily oiled beaches and reference locations, respectively. The mode fell within the
range 100 ng/g to 300 ng/g (Fig. 5). At the 100-m depth and greater, the median concentration
was 899 ng/g, and 574 ng/g at moderate to heavily oiled locations and at reference locations,
respectively. The mode wasabove 400 ng/g (Fig. 5 ) . 'The TPAH concentrationin sediments at
depths 240 m was often higher than in sediments in the 3-m to 20-m depth range.
Moderately Oiled Locations, 1989
Intertidal Stations
The EVO-PAH pattern was occasionally found at relatively low concentrations at the
intertidal stations at four moderately oiled locations sampled in 1989: Bay of Isles, Foxfarm,
Sleepy Bay, and Snug Harbor. The mean TPAH concentration was highest at Snug Harbor; it
ranged from 420 f 159 to 1,030 f 983 ng/g (n = 3), but the PAH pattern differed from the EVOPAH pattern. The mean TPAH concentration at the other stations generally ranged from 160 to
408 ndg; although, by September 1989 the TPAH concentration at the Foxfarm intertidal station
had declined to 68.5 f 17.4 ng/g (n = 2).
Subtidal Stations
At Bay of Isles, Snug Harbor,and Sleepy Bay, locations where a low TPAH concentration
and EVO-PAH pattern were occasionally found in intertidal sediments, we found similar results
for subtidal sediments. At the NOAA Bay of Isles site, the EVO-PAHpattern was generally not
evident. The EVO-PAH pattern was found in two ofthree replicate samples from 6-m depth in
September 1989 (Table 5). During other sampling periods and at other depths in the range 0-20
m, the PAHcomposition pattern differed from the EVO-PAH pattern owing to low relative
concentrations of chrysenes. At the other two sites in the Bay of Isles where subtidal (but not
intertidal) samples were collected, the EVO-PAH pattern was encountered more frequently.
Results for these sites (Bay of Isles 86 and 90) were similar to those for Block Island and
Northwest Bay 4. A l l subtidal sediment samples from the 3-m to 20-m depths at these Bay of
Isles sites contained the EVO-PAH pattern (Table 5).
.
At Snug Harbor, the EVO-PAH pattern was observed at five stations: the NOAA site, 3-m
and 6-m depths, July 1989; Snug Harbor Site25, 10-m and 20-m depths, November 1989 ;the
Snug Harbor meiofauna site, 6-m depth (Table 5). Other subtidal sediments often contained a
relatively high TPAH concentration, but the composition patterns differed markedly from that of
weathered EVO. The PAH pattern characteristic of combustion products (i.e.. relatively high
concentrations of higher-molecular-weight unsubstituted PAHs) was observed at two of the sites
( N O M site and the meiofauna site). The TPAH concentration exceeded 16.800 nglg in one
sample; a relatively large concentration to have been caused by a combustion source alone.
32
L
.
40
60-
-
20 .
=
Oiledshore, N = 54
I
I
0
I
Oiled shore, N = 183
-
3 100
C
80
Reference, N = 15
Oiled shore, N = 21
$
2
60
40
20
0
100
Reference, N = 18
Oiled shore, N = 23
80
60
40
20
0
0-100
100-200 200-300
300-400
400+
TPAH Concentration Range (nglgdry wt)
Figure 5.--Percentage of sediment samples in five concentration ranges of TPAHs in sediments
from the intertidal region (0 m) and the subtidal region at bathymetric depths of 3 m to 20 m, 40
m and 100 m at reference stations and heavily oiled stations from 1989 to 1991.
97
>>
Subtidal sediments from 3 m and 6 m at Snug Harbor25 contained a low TPAH concentration
composed mainly of naphthalenes (Table 5).
At Sleepy Bay. the results for subtidal sediments were similar to those for intertidal
sediments. The EVO-PAH pattern was found in samples from 3 m to 20 m in September and
November 1989. The mean TPAH concentration ranged from 193 7.0 ng/g to 810 f 501 ng/g
(n = 3), and usually showed a low variability in TPAH concentration among sample replicates
(Table 5). The highest mean TPAH concentration of samples collected earlier (May and July
1989) was 309f 5 1.2 ng/g (n = 3), and the PAHcomposition pattern of these samplesdiffered
from weathered EVO (Table 5).
*
The TNA concentration at moderately oiled stations was relatively small and any EVO alkane
pattern that may have existed at these stations was obscuredby n-alkanes from natural sources.
The median TNA concentration at these stations was 774ng/g; 80.6% ofthe samples contained a
TNA concentration lower than2,000 ng/g (n = 165). The median CPI was 2.71; 80.8% ofthe
samples had a CPI greater than 1.5 (n= 193). The highest TNA concentration observed at these
stations was above 8,000ng/g in subtidal sediments at Bay of Isles in July 1989. The CPI, for
these samples exceeded 4.
Lishtlv Oiled Locations and Reference Locations. 1989
Intertidal Stations
The EVO-PAH pattern was generally not found at intertidal stations at the three lightly oiled
locations sampled in 1989: Eshamy Bay, Green Island, and Iktua Bay. Mean TPAH
concentration at these stations wasusually below 150 ng/g; naphthalenes were the most abundant
PAHs present. However, mean concentrations of 219 f 45 ng/g and 214 f 38.2 ng/g (n = 3)
were observed at Iktua Bay and Eshamy Bay in September 1989.
At intertidal reference stations, PAHs were detected sporadically and at low concentrations,
and did not exhibit the EVO-PAH pattern. The median of the mean TPAH concentrations of all
the reference intertidal stations sampled. during all three years of this study, was 40 ng/g; over
83% of theobservations were below 300 nglg (Fig. 5). By contrast, TPAH concentrations
exceeding 300 ng/g were found in sediments from 43% of the intertidal stations, at moderately to
heavily oiled locations, over the three years of
our study (Fig. 5).
At Rocky Bay, a distinctive PAH composition patternwas observed with a mean TPAH
concentration of 3 16 + 0.2 ng/g (n = 2) in 1989. Distinctive characteristics of the pattern
included: (1) a general absence of dibenzothiophenes; (2) alkyl-phenanthrene and alkyl-chrysene
concentrations that decreased with increasing alkyl substitution; unsubstituted phenanthrene waas
the most abundant PAH and (3) the presence ofunsubstituted 4- and 5-ring PAHs including
fluoranthene, pyrene, benzofluoranthene, benzo-e-pyrene, and benzoperylene (Fig. 6). In
addition, phytane was present at low concentrations comparedwith the most abundant PAHs
34
LU
Rocky Bay; Intertidal Sediments
1989 - 1990 ( N = 5)
15
10
5
0
Figure 6.--Mean relative abundances of PAH compounds in intertidal sediments at Rocky Bay and
in Exxon I’nldez mousse collected 1 1 days after the Spill. Error bars are 95% confidence
intervals.
35
(Fig. 6). Normal alkanes larger than n-eicosane were generally near detection limits, and the
UCM was consistently low. These characteristics of bothPAHs and alkanes were consistent
among intertidal samples in both 1989 and 1990; the only years that samples werecollected ,at
Rocky Bay.
The TPAH concentration was lowest at the Olsen Bay intertidal reference station; it was
consistently below the median and usually included primarily naphthalenes. Naphthalenes were
also the most prevalent PAHs in intertidal sediments of the other reference stations;
they
accounted for more thanhalf the TPAH Concentration in over half of thesamples. The large
relative contribution of the napthalenes may also indicate a diesel source.
Shallow Subtidal Stations
The TPAHconcentration in sediments from a depth of 3m to 20 m at lightly oiled locations
and at reference locationswas generally low and did not show the EVO-PAH pattern.
Considering all reference locations together during the
3-year study period, one-half of themean
TPAH concentrations in subtidal sediments within the 3-m to 20-m depth range were below 175
ng/g and 85% were below 400 ng/g (n = 91; Fig. 5). By comparison, 61% of the mean TPAH
concentrations in subtidal sediments from moderately to heavily oiled locations were below 400
ng/g. At the remaining assessment locations where the EVO-PAH pattern wasnot observed, half
of the mean TPAH concentrations within the 3-m to 20-m depth range werebelow 100 ng/g and
86% were below 400 ng/g (n = 49).
Various PAH composition patterns wereobserved at lightly oiled assessment and reference
locations that did not show the EVO-PAH pattern. The most common patterns included: (1)
high (i.e., morethan 50%) relative proportions of naphthalenes; (2) high proportions of
unsubstituted, higher-molecular-weight PAHs; (3) patterns that differed from weathered EVO due
to low relative proportions ofchrysenes; and (4) patterns that differed from weathered EVO due
to low proportions of dibenzothiophenes (e.g.
Fig. 6).
The TNA concentrationat reference stations and at lightly oiled stations was similar to that
at moderately oiled stations (Table 9). The median TNA concentration of the former stations was
922 ng/g; 79.0% of the samples from these stations contained TNA concentration lower than
2,000 ng/g (n = 224). However, the CPI at reference stations and at lightly oiled stations was
often higher than at moderately oiled stations (Tables 7 and IO). The median CPI at the former
stations was 6.17,and 91.6% of thesamples from these stations had a CPI greaterthan 1.5 (n =
203).
The concentration of TNAvaried markedly among reference stations and lightly oiled
stations (Table 9). Mean T N A concentration was highest at Drier Bay, Eshamy Bay, Olsen Bay,
and Paddy Bay where mean concentration frequently exceeded 2,000 ng/g. Mean TNA
concentration reached levels as high as 9,730 ng/g and 13,200 ng/g in intertidal sediments at
36
.n 57
LE
5z
8PP
97
910'1
(I
L I 'OhZP9
E69
tZ
s75
S
S
C7
(EEl'OhSSL
598
LL6
(9L9'0)<01L
S
OLb'l
SI
8L7
I18
91
IZ
500l
PC6
769
(Ptl'0)rZ6S
27
S
PI
Z
I
II
01
S
cxs
.x11
S
I
S
P
8
<_Q.,%"hl
Table 9.-<Cont.)
Site
No.
Name
27
28
32
33
Paddy Bay
34
35
36
43
44
45
Rocky Boy
wpch
Dale
Sco-90
Jun-9 I
Jun-90
Jul-90
Jul-90
Jus-9 I
Jul-89
Sep-89
May-90
Jue-90
Sq-90
.Apr-9 I
Jun-91
Sep9l
May-89
sep-89
Jun-90
Sep-90
Apr-91
Sltp91
Now89
Dec-89
Juo-90
Jul-90’
Jul-89
Jun-90
Jul-90
kc-89
Jun-90
Jul-90
0 111
-
94.770.788)
200
206
s
3.15‘10.758)
13.237’(0.&9)
5 I7’(0.037)
274’(0.108)
1.880
1.727’(0.013)
285’(0.637)
581’(0.184)
229‘(0.081)
S
288
6,181’(0.046)
389‘(0.134)
3 111
448’(0.552)
699
586’(0.163)
1,035
JS.S’(O.665)
14,330’(0.144)
9,394’(0.123)
2,891’(0.108)
1.778
2,371’(0.209)
2,308’(0.299)
~~
116‘(0.311)
583’(0.355)
545
646
S
1,188’(0.268)
107’(0.671)
2.759‘(0.074)
3.895’(0.027)
1.295
1.012*(0.512)
3.004’(0.058)
1.425’(0.126)
1.803
1,0261(0.609)
Jun-90
lul-90
I50
4,988’(1.184)
717’(0.111)
2,288’(0.146)
2,016’(0.377)
715
3,314’(0.125)
40 “1
100 111
l,418‘(0.300)
1.677’(0.385)
1,764
1,351’(0.036)
S
732’(0.080)
720’(0.265)
852’(0.142)
1,599
1,4801(0.062)
1.728’(0.144)
S
1,242’(0.565)
S
S
6,662*(0.437)
3,140
7,076
3,342
S
943
1,623
1.131
355’(0.013)
730
51 l’(O.063)
478
70s
373’(0.538)
708’(0.117)
436
520’(0.069)
1,699
1,016‘(0.110)
959
605‘(0.0991
S
~~
Nd
317
194’(0.668)
61 1
20 8”
447‘(0.431)
19,448’(0.133)
198’(0.104)
539
6m
193’(0.377)
299*(0.400)
622’(0.158)
1,984
1,016L(0.27S)
1,305’(0.269)
1,176’(0.224)
S
1,150
5.444‘(0.208)
1.638’(0.288)
NW
5.1032(0.335)
1.383
38
3,127
1,448
1.201‘(0.1751
1.572’(0.199)
Other
2,57Y
L
9
LC
E
?
. . . . . .h
N
Table 10.- (Cont.)
Site
NameNo.
21
28
32
33
0m
Date
Jun-91 NA
NA
NA
S
NA
12.3
13.2
7.69
6.04
10.8
NA
11.7
NA
3 "1
6.80
5.24
20.2
I02
4! A
9.68
II I
6.14
7.86
I0 0
IO 4
S
4.51
1.25
7.03
8.53
36
43
44
45
a. I O m depth.
b. 30 rn dcptlt.
c. 55 m depth.
d. 140 o m depth
40 m
9.91
100 m
S
5.10
5.54
57.5
4.5 I
S
3.32
2.18
10.8
2.83
10.2
8.12
6.73
7.52
IO.I
4~67
S
4.86
4.96
4.15
4.62
3.86
9.07
6.88
9.17
3.59
17.9
S
4.96
1.40
4.15
4.99
4.19
5.61
4.54
10.8
11.0
4.51
9.16
9.40
18.3
8.02
NA
S
S
8.34
4.50
7.44
7.90
7.99
34
35
Depth
20
12.7
,"
6 nl
NA
8.72
12.7
71.1
NA
9.1 I
S
19.4
NA
4.47
3.58
6.00
58.1
NA
0.76
NA
Jun-91
NA
e. Sampled 28 June 1990.
T Biorcmedialion treatment sile.
R. Bioremcdiuliott reference sile.
9.55
13.2
10.3
10.9
5.26
3.41
i.A
5.07
8.85
25.6
16.2
6.35
6.14
11.5
11.8
NA
7.04
8.16
8.05
10.6
S
NA
5.51
11.9
4.67
S
11.0
8.99
6.83
40
h
I
W
3.19d
Eshamy Bay and Olsen Bay, respectively. The corresponding CPI for these sediments was 8.61
and 19.2, respectively. By contrast, the mean TNA concentration never exceeded 2,000 ndg at
Chenega Island, Ewan Bay, Green Island, Green Island 22, Iktua Bay, IktuaBay 2, Ingot Island,
Knight .Island, MacLeod Harbor, and Port Fidalgo.
DeeD Subtidal Stations
The TPAH concentrationoften tended to increase with increasing depth at particular
sampling sites. This was especially evident at reference sites (Table 8). For example, at Olsen
Bay in July 1989, the mean sediment TPAH concentration increased with depth from 25.7 4.5
ng/g (n = 3) in the low intertidal zone to 574 57.0 ng/g (n = 3) at a depth of 100 m (Fig. 7). A
similar pattern was seen at Olsen Bay in 1990 and 1991, At Rocky Bay, where the mean intertidal
TPAH of 3 16 ng/g in July 1989 wassubstantially higher than at Olsen Bay; the increase with
depth was less pronounced but still evident (Table 8; Fig. 7). At both sites, sediments from
depths 240 m had PAH composition patternstypical of deeper sediments throughout PWS (Fig.
*
*
4).
In contrast with the TPAH concentration,the TNA concentration did not show a consistent
pattern of change with depth at reference and lightly oiled sites. At some sites, the mean TNA
concentration was usually highest in intertidal and shallow subtidal sediments (e.g., Olsen Bay); at
other sites (e.g., RockyBay), just the opposite was true. At sites like Eshamy Bay, no consistent
pattern was observed in TNA concentration with depth (Table 9).
Heavilv Oiled Locations. 1990 and 1991
Concentrations of TPAH in intertidal and subtidal sediments tended to decrease or become
more variable in 1990 and 1991. The EVO-PAH pattern was frequently absent or inconsistently
present in these sediments in 1990 and 1991 at stations where it had been observed in 1989. The
EVO-PAH pattern was consistently found in shallow subtidal sediments into 1991 only at
Northwest Bay. Subtidal sediments showed the EVO-PAH pattern at 80% of the locations where
oil had come ashore (oiled locations) in 1989, 78% of oiled locations in 1990, and 57% of oiled
locations in 1991. Contamination of subtidal sediments by EVO at oiled locations reached a
depth of at least 20 m at five locations in 1989 and six locations in 1990. Two locations showed
contamination of sediments by EVO at 20 m in 1991 (Table 5).
Intertidal Stations
In 1990, the EVO-PAH pattern was found at the same locations thatit was found in 1989
including Block Island, Disk Island, Herring Bay, and Northwest Bay (Table 5). However,
because the concentrationsof oil in the intertidal region were probably markedly altered by
intensive shoreline treatment and by winter storms in 1989, some sites showed significant
decreases in concentration or exhibited more variable concentrations in 1990 and 1991 than in
1989. At Disk Island, unreplicated samples from the 0-m station contained 13 1 ng/g and 104
41
30,000
-
Disk island
10,000 :
:tt
: \
\
3.000 - \
---
Rocky Bay
,-
Olsen Bay
........l.
I
h
cn
1
CI)
c
c 1,000 7
.
.-
0
.c
\
\
v
-
2
c
K
300
P)
0
E
0"
-.
.
.-
...
....--..
----1'"'
,).
.
.
.
.
.
.
=.
=.
-.-.. .*...
100 :
.
30
.
/'*.
e..
*.--
.+
.e0
.
10
I
I
0
3
I
6
I
I
20
40
I
100
Depth (m)
Figure 7.--Depth distributionof mean concentrations of TPAHs at Disk Island, Olsen Bay and
Rocky Bay in July 1989. Error bars are one standard error of the mean.
*
42
ng/g TPAH in June and July 1990, respectively (Table 5). These concentrations were far lower
than the TPAH concentration (12,700 ndg) initially measured at Disk Island in July 1989. At
two other heavily oiled locations the intertidal TPAH concentration varied greatly between
sampling periods. Mean TPAH concentrations in intertidal sediments at Herring Bay and
Northwest Bay in 1990 varied between sampling periods, ranging from 118 f 28.6 ng/g to 949
403 ng/g (n = 3) at Herring Bay and from 166 f 30.3 ng/g (n = 3) to 4,650 ng/g (n = 1) at
Northwest Bay (Table 5). Theintertidal samples from Block Island in June and July 1990 were
the first collected at the 0-m station at that location. These samples contained mean TPAH
concentrations of 945ng/g (n = 1) and 665 f 287 ng/g (n = 2) in June and July 1990, respectively
(Table 5). The PAH composition pattern of these samples closely resembled that of sediments
from other heavily oiled beaches such as Disk Island and Northwest Bay in 1989.
*
In 1991, the TPAH concentration generally decreased in intertidal sediments at Herring Bay
and Northwest Bay; locations where theEVO-PAH pattern was found (Table 5). At Herring
Bay, the pattern was present in sediments collected in April, but not in sediments collected later in
1991. At Northwest Bay, the EVO-PAH pattern wasfound in intertidal sediments in June 1991;
the only time in 1991 that Northwest Bay was sampled.
The TNA concentration generally decreased and CPI generally increased between 1989 and
1991 at heavily oiled locations. At Northwest Bay the TNA concentration of intertidal sediments
had declined to 1,650 ng/g (Table 6) and the CPI had risen to 1.44 by June 1991 (Table 7). At
Herring Bay the mean TNA concentration ofintertidal sediments decreased from 4,080 i 1,120
ns/g (n = 3 ) in May 1989, to 419 53.0 ng/g (n = 2) in June 1991; the CPIincreased from 0.85
to 16.3.
*
Subtidal Stations
In' 1990, the EVO-PAH pattern wasconsistently present in shallow subtidal sediments at
Block Island and Northwest Bay, and TPAH concentrations were relatively high (Table 5). With
one exception (Northwest Bay, 6 m depth, September 1990), the EVO-PAH pattern was
observed in all sample replicates and at each depth sampled from 3 m to 20 m at these locations.
The mean TPAH concentration in sediments from these depthsat Block Island and Northwest
Bay ranged fr.om 227 ns/g (n = 1) to 1,850 549 n d g (n = 3) and exceeded 700 ng/g at least
twice at both locations. The TPAH concentration
usually varied with depth by a factor less than
three, and no consistent trends in TPAH concentration with depth were apparent.
*
The EVO-PAH patternwas more sporadically observed in shallow subtidal sediments at Disk
Island and Herring Bay than at Block Island and Northwest Bay in 1990 (Table 5). The EVOPAH pattern was present in two samples from 3-m and 20-m depths at Disk Island in June but
was absent at the 6-m depth in June and at all shallow depths in July. At Herring Bay Site 125 the
pattern was observed at 3 and 20 m, and at the NOAA site was present at 3 m through 20 m in
June 1990 (Table 5).
43
In 1991, the EVO-PAH pattern was found in shallow subtidal sediments mainly at Northwest
Bay. The EVO-PAH pattern was present in samples from 3 m and 20 m at Northwest Bay. The
mean TPAH concentration ranged from 375 i 57.4 ng/g (n = 3) at 20 m, to 1,710 ng/g in the
single sample analyzed from 3 m. Block and Disk Islands were not sampled in 1991. The EVO- .
PAH pattern was observed at 6 m in September 1991 at Herring Bay, but the mean TPAH
concentration was only 105 29.0 ng/g (n = 3; Table 5).
The concentration of n-alkanes in shallow subtidal sediments at heavily oiled locations
followed a temporal trend similar to that observed in intertidal sediments at these locations. At
Northwest Bay, the TNA concentration in sediments at the 3-m depth declined from 4,130f
2,470 ng/g (n = 3) in July 1989 to 719 i 44.5 ng/g in June 1991 (Table 6). The CPI increased
from 1.27 to 2.89 at 3 m during the same period. At 6 m at Northwest Bay, the TNA
concentration decreased from 2,540 392 ng/g (n = 3) in July 1989 to 78 1 264 ng/g (n = 2) in
June 1991; the CPI increased from 2.37 to 3.56. The same trend was seen at the 3-m depth in
Herring Bay (Table 6); the CPI increased from 1.55 to 6.94 between July 1989 and June 1991
(Table 7). However, at 6 m in Herring Bay a declining trend in mean TNA concentration with
time was less clearly indicated. The mean TNA concentration at 6 m in May 1989 was 879 8 1.2.
ng/g, but in April 1991 had increased to 1,480 f 695 ng/g (n = 2). In June and September 1991,
the mean TNA concentration was 237 f 29.6 ng/g and 647 k 136 ng/g (n = 3), respectively
(Table 6). The CPI at 6 m in Herring Bay increased from 2.30 in May 1989 to 6.34 in April 1991
(Table 7).
*
*
*
Moderatelv Oiled Locations. 1990 and 1991
Intertidal Stations
In 1990, the EVO-PAH pattern, though consistently present in intertidal sediments from Bay
of Isles, was less consistently observed in intertidal sediments from Sleepy Bay and Snug Harbor.
At Bay of Isles, the mean TPAH concentration in intertidal sediments ranged from 749 381 ng/g
(n = 2) to 1,480 ng/g (n = 1) in 1990 (Table 5). At Sleepy Bay, the EVO-PAH pattern was
evident only in the September 1990 samples where the mean TPAH concentration was 253 f 66.2
ng/g (n = 3; Table 5). The mean TPAH concentration was lower and more variable in samples
collected in June and July at Sleepy Bay, and the samples were either high in naphthalenes or low
in chrysenes and dibenzothiophenes compared with weathered EVO. At Snug Harbor, the EVOPAH pattern was evident only at the Snug Harbor 25 site in July 1990. The EVO-PAH pattern
was not present in samples collected in June 1990 at this site, nor in samples collected from the
Snug Harbormeiofauna site (Table 5).
*
Concentrations of TPAH werelow at the remaining assessment sites sampled in 1990; 62%
of the sediments had less than 230 ng TPAH/g. The rest of the samples had either: (1) high
proportions of unsubstituted, high-molecular-weight PAHs or (2) a PAH composition analyte
pattern that differed from weathered EVO due to relatively low concentrations of chrysenes.
Both of these analyte patterns often were observed in one replicate only.
44
In 1991, the TPAH concentration generally decreased in intertidal sediments at moderately
oiled locations where the EVO-PAH pattern was found. The EVO-PAH pattern was observed in
intertidal sediments at Sleepy Bay and Snug Harbor (Table 5). At Sleepy Bay, intertidal samples
collected in June 1991 consistently showed the EVO-PAH pattern. However. replicate samples .
collected there in May and September 1991 did not show the EVO-PAH pattern (Table 5). At
Snug Harbor, the EVO-PAH patternwas found at Site 25 and the meiofauna site. Elsewhere, the
mean TP'AH concentration in intertidal sediments was either: ( I ) less than I O 0 ng/g (80% of
remaining samples; Table 5 ) , or (2) the sediments showed one or more of thealternative PAH
composition patterns described above for intertidal sediments in 1990.
Shallow Subtidal Stations
The EVO-PAH pattern wasobserved inconsistently in shallow subtidal sediments at Bay of
Isles, Sleepy Bay, and Snug Harbor in 1990 (Table 5 ) . At Bay of Isles, the EVO-PAH pattern
was consistently present in sediments sampled from 3 m through 20 m at two sites (Bay of Isles
90 and Bay of Isles Bioremediation; Table 5). At the NOAA Bay of Isles site; however, the
pattern was evident only at 20 m in June. At Sleepy Bay, the EVO-PAH pattern was observed in
shallow subtidal samples in June and September but not July 1990, and at Snug Harbor theEVOPAH pattern was observed only at 6 m at the meiofauna site in September 1990 (Table5 ) .
The number of stations at moderately oiled locations where the EVO-PAH patternwas
observed in subtidal sediments fbrther decreased in 1991. The EVO-PAH pattern was not
observed in any subtidal sediments from Sleepy Bay in 1991. At the three stations where the
pattern was observed in Bay of Isles and Snug Harborin 1991, the highest mean TPAH
concentration was 219f 102 ng/g (n = 3; Table 5).
Variability of TPAHin Reolicate Samules
The lowest relative variability of PAH concentrations in replicated samples usually occurred
in cases where PAH accumulation was most likely attributable to relatively homogenous
deposition or generation of PAH over a wide geographic area. In these cases, PAH composition
patterns were consistent among sample replicates, and most of the observed variability among the
replicates was probably because of differences in sediment composition within the area of the
replicates. In contrast, the highest relative variability usually occurred in cases where PAH
accumulation was most likely caused by deposition from small localized sources, or to episodic
events that occurred several years prior to the EVOS. In these cases, PAH composition patterns
were usually not consistent among sample replicates, and most of the observed variability among
the replicates was probably owed to patchily distributed PAHs in the sediments.
The greatestrelative variation, as shownby the coefficient of variation (CV), of TPAH
concentration in replicate samples occurred in replicate groups from the intertidal region and
shallow subtidal depths (3-20 m) where a PAH composition characteristic of weathered EVO was
not consistently present. At reference locations, over one-half of the replicate groups forthese
45
sampling depths had a CV greater than 50%. even when the mean TPAH concentration for the
group was substantial (Fig. SA). Similarly, over one-half of the replicate groups from shallow
stations at assessment locations where theweathered EVO-PAH composition was not
consistently indicated (i.e., entries in normal type in Tables 5 and 8) had a CV greater than 50%
(Fig. 8B). Combined, the median CV of the 248 replicates from these locations was5 1.9% which
means for these replicate groups,
of two or three samples, each individual sample TPAH
concentration differed from its respectivereplicate means by more than 50% more often than not.
In addition, 21 .O% of the replicate groups had a CV greater than loo%, indicating extreme
variability.
The lowest relative variation of the TPAHconcentration occurred in replicate groups from
depths 240 m in PWS regardless of location (Fig. SC). At these depths, EVO was generally not
detected. Over 79% of the68 replicate groups from these depths(all locations included) had a
CV less than 50%; the median CV was 17.2%. This means that most (79%) of the individual
sample TPAH concentrations were within f 50% of their respectivegroup means. In addition,
none ofthe replicate groups from depths 2 40 m had a CV greater than 100%; the highest CV
was 88%.
Low relative variation between replicates was also found where the weathered EVO-PAH
composition wasconsistently present, and was comparable to the variation of replicate groups
from the 40-m and greater depths (Fig. 8D). Where this PAH pattern was identified in intertidal
and shallow subtidal sediments at assessment locations (Table 5, bold-faced type), the median CV
of the 77 observations was 36.9%; 73% of thereplicate groups had a CV less than SO%, and 3
exceeded 100% This indicates that when the PAH composition pattern characteristic of
weathered EVO was present in replicated samples; individual TPAH measurements wereusually
(i.e., more than 73% of the time) within f 50% ofthe mean TPAH concentration for the replicate
group.
Pewlene
Perylene is a naturally occurring PAH compound produceddiagenetically in marine
sediments (Venkatesan 1988) and absent from EVO. The presence of perylene in benthic
sediments is indicative of a stable sedimentary sink that retains settling particles which may have
pollutants sorbed to them. The presence of perylene was coincident with the presence of EVOin
our samples. We have found perylene to be widespread in subtidal sediments, but less so in the
intertidal sediments (Tables 11 and 12). Perylene is not found in sediments where scouring
frequently exports sediment from the site or where sedimentation is great as in glacially influenced
systems for example. Relatively stable sediments are required to provide sufficient time for
perylene to form in the surface sediments.
46
Intertidal & 3m-20m depths
Reference Locations
Intertidal & 3m-20m depths
Assessment Locations
with EVO not present
c
8
a,
2
a,
a
V
100
75
50
25
40+m depths
All Locations in PWS
0
100
75
50
Intertidal & 3m-20m depths
Assessment Locations
with weathered EVO present
25
n
"
200+
0-200
TPAH (ng/g wet wt)
Figure S.--Stacked bar graph ofthe coefticient ofvariation proportion classes i n two ranges of
mean concentration ofTPAHs for sediments in the depth range 0 to 70 111at ( A ) reference
locations and (B) assessment locations where the EVO-PAH composition pattern was not
consistently present in replicate samples and (C) at depths >40m at all locations in PWS alld (D)
at depths of0-20 111 where the EVO-PAH composition patter was consistently present among
replicate samples.
47
2
3
Bay of lsla X6
Bay oflsles 90
4
5
Bayoflsles BR
Bay of Isles
Nov-89
Nov-89
Jun-90
Jul-90
Jul-89
Sep-89
Jun-90
JuI-90
4.51
8.95’(0.239)
Nff
S
5.00’(0.224)
1.07’(1.732)
ND‘
15.72(0.380)
J”n-91
Nov-89
Nov-89
Jua-90
JUl.90
9
I3
19
Hening Bay 53
Herring Bay I IO
Herring Bay 125
20
Herring Bay
17
18
20
Hming Bay
Jul-89
Jun-90
Jul-90
Jm-91
May-X9
Jul-89
Sep89
Jun-90
Jul-90
Sep90
Apr-91
Sew91
Nov-89
Now89
Nov-X9
Jun-90
May-X9
Jul-X9
Sep-x9
Jut-90
Jul-90
Sep90
Apr-9 I
JU.9 I
Sep-9 I
NW
ND,
l.75’(1.414)
10.5’(0.266)
23.3
4.77
NW
NW
N D‘
ND‘
ND‘
NW
NW
NW
NIs‘
NW
3.34’(0.928)
1.51’(1.732)
ND‘
VI)’
NW
ND
13.2’(1.414)
NW
~~
lX.l?(0.036)
5.65’(0.163)
3.44‘(1.414)’
13.5*(0.118)
67.3’(0.158)
NW
NW
ND’
Sep-YO
6
7
46. I
5.24’(0.974)
NIY
1.21’(1.732)
7.20
9.46’(0.268)
12.OY0.4851
24.63(1.188)
NW
NW
1.18’(1.732)
NW
16.2’(0.205)
NW
ND‘
Nff
34.4’(1.414)
NW
8.44’10.286)
,
NW
5.09‘(1.414)
NW
Nff
NW
19.0’(0.486)
5.51’(0.202)
1.17’(1.732)
S
3.90’(0.909)
6.04‘(0.522)
84.9’(0.260)
27.8’(0.048)
218‘(0.024)
38.7’(0.012)
268’(0.269)
I55’(0.038)
176’(0.101)
34.0’(0.104)‘
132’(0.179)
19.3’(0.265)
19.1
15.2’(0.109) ND’
ND‘
ND‘
Nff
N DL
NW
ZSP(0.079)
6.94’(0.078)’
14 5
.
13.2’(0.102)
13.1’(o(o.127)
31.4
IS.S‘(O.280)
NW
49.3’(0.053)
Sl.O~(O.Ol3)
19.3‘(0.274)
67.1’(0.319)
41.4*(1.414)
8.64
NW
NW
NW
Nff
4.06
6.50’(0.236)
7.09’(0.105)
NW
Nff
NW
NW
1.772(1.414)
NDJ
Nff
Nff
5.55’(0.884)
3.40’(0.935)
4.49’(0.896)
6.00
NW
4.88’(0.145)
2.87’(0.1 12)
3.41’(1.006)
48
7.70’(0.142)
6.19’(0.016)
12.5*(0.212)
14.4’(0.161)
7.68’(0.249)
4.68’
1.9xy1.414)’
NW
45.4’(0.218)
21.3’(0.216)
39.9’(0.701)
11.8
S
13.8’(0.227)
25.5’(0.626)
I1.2’(0.368)
25.2
31.2
38.9’
26.2’(0.682)
”..
No.
29
Name
Northwvesf Bay 4
Yep"
Dale
N0\49
Dec-89
Om
6.62’(0.435)
1.23’(1.732)
NW
4.69
NW
0.64’(0.887)
3m
N D‘
3.80
11.7’(0.497)
6m
17.0
14.9’(0.251)
20 111
35.4
22.9
78.7’(0.148)
6.76‘(0.054)
8.66
6.47‘(0.060)
2.99’11.414>
4.82
ND’
I1.6’(0.213)
ll.l’(O.138)
13.0*(0.005)
6.99Y0.522)
I1.6*(0.031)
32.8
72.2’( 1.074)
85.1’(0.2RI)
23.8’(0.522)
NW
NW
Nff
2.56’(0.894)
0.45’(1.732)
NW
0.44*11.414)
NW
ND‘
41
42
Snug Harlmr
Snug H h r M
SLY
NW
10.6’(0.273)
9.57
6.71’(0.339)
S.OS’(0.914)
4.71’(0.186)
4.08’(0.924)
2.45Y0.462)
100 111
Other
14.8’
65.7’(0.261)
54.0’(0.176)
81.7’(0.408)’
57.0‘(0.X60)b
50.0’(0.100)
42.8‘(0.005)
56.6’(0.056)
58.3’(0.316)
40.41(0.310)
43.9’
ND’
2.43’(0.866)
4.16’(1.036)
N D‘
ND‘
ND‘
4.77’(0.388)
ND‘
Jul-90
Jun-91
Jul-89
SCp-89
Jul-90
Ju2r91
sep-9 I
Jul-89
Szp89
Jun90
Scp-90
40 m
S
NW
l0.9’(0.251)
19.1
l.Zl’(1.732)
lll‘(l.337)
NW
4.09‘(0.870)
1.05’(1.732)
6.39’(0.234)
2.31‘(1.414)
2.19’(1.732)
2.89’(0.212)
NW
NW
ND‘
NLS
NW
NW
ND‘
ND‘
S.Ol’(0.039)
ZS.S’(0.038)
26.5’(0.231)
26.0
24.5’(0.240)
17.v(n.o46)
I3.0’(0.955)
18.7*(0.935)
5.64’(0.188)
ND“
5.40‘(0.200)
10.1
3.7G‘(0.368)
7.77’(0.120)
ND“
N D‘
27.9’(0.106)
NIY‘
34.3
2X.9’(0.079)
135’(0.183)
185’(0.021)
67.8’(0.247)
136’(0.002)
19.3’(0.372)
68.3’(0.078)
25.6’(0.018)
105
4.42
6.19’(0.342)
17.7’(0.464)
14.4’(0.146)
32.6’(0.086)
7.59‘(0.385)
49
95.1’(0.022)
S
(Z9Z.O),8'LI
KIN
S
,aN
S
#aN
7aN
.S
,CZI
,PXI
raH'""7
S
9z
IN
SZ
.KIN
AIN
oxz
PZ
CZ
zz
(8190)rEl~X
IZ
91
,aN
091
9PC
E CL
XIN
SI
,aN
PI
(9P00),96X
ZI
(6ZVO),LLI
L91
raN
II
(xfC.O)rlZL
(OZl~O)1056
,aN
KlN
(9800),O'bX
01
1
.XlN
8
,(IN
,ON
.
,aN
~~
S
27
MacLeod Harbor
28
M w s e L p Bay
32
Olsen BO,”
33
34
35
Paddy Bay
Point Helen
Pon Fidslgo
36
Rmhy Boy
43
44
TwoMoon Bay
Werl Boy
45
ZazkofBay
Jun-91
Jun.90
Jul-90
Jul-90
Jun-91
Jul-89
Srp-89
hhy-90
Jun-90
Sep.90
Apr-9 I
Jun-91
sep-9 I
May-89
Sep-89
Jut,-90
Sep-90
Apr-91
scp-9 I
Nov-89
Dec-89
Jun-90
Jul-90‘
Jul-89
Jue-90
Jd-90
Dec-89
Jun-90
Jul-90
Jun-90
Jul-90
Jundl
NIY
ND‘
5.38’(0.189)
4.84‘(0.034)
S
I 1.2’(0.206)
10.4’(0.083)
3.51’(0.923)
17.0‘(0.170)
16.3’(0.169)
1.31’(1.732)
8.24’(0.525)
2.77’(0.099)
4.59’(0.873)
1.25’(1.732)
54.0’(0.339)
3.66’(0.013)
3.58’(0.167)
12.3
25.9‘(0.262)
12.7’(0.008)
NW
I58’(0.151)
92.6’(0.120)
38 2’(0.159)
I9.R’(0.547)
211.3’(0.187)
16.8’(0.237)
383’(0.010)
ND’
7.86’(0.268)
74.7
31.6*(0.523)
13.8’(0.009)
2.60‘(0.889)
54.3’(0.134)
41.2’(0.126)
57.1’(0.281)
22.6’(0.435)
35.3’(0.257)
l5.3’(O.l8l)
43.8
l7.1’(0.622)
481’(0.069)
149’(0.129)
188’(0.198)
23.2’(0.088)
113’(0.390)
460
79.6‘(0.190)
8.22’(0.124)
35.9*(0.127)
26.1’(0.035)
4.78’(0.084)
11.0’(0.071)
85.1’(0.123)
18.7
8.89
11.2’(0.122)
41.7’(0.103)
l5.4’(0.137)
75.3’(0.137)
38.7’(0.631)
48.9’(0.838)
78.9’(0.166)
63.3’(0.099)
66.1‘(0.114)
130.9
45.9’(0.260)
26.5’(0.775)
53.9’(0.237)
55.1’(0.308)
59.5’(0.288)
22.1’(0.871)
30.6’(0.100)
23.3’(0.357)
45.9’(0.051)
17.3’(0.387)
95.6’(0.049)
97.2’(0.131)
10.2‘(0.062)
9.25’(0.0Zl)
NW
. .
S
ND‘
ND‘
4.08’(0.093)
ND‘
14.71(0.071)
N Dl
ND‘
ND’
ND‘
2.44’(0.878)
16.6’(0.417)
17.3
12.5
28.6‘(0.186)
22.7
12.7‘(0.311)
NW
16.3
17.2‘(0.272)
31.6
21.9’(0.073)
26.8*(0.042)
2.84’(0.866)
4.82
ND‘
83.1’(0.281)
5.95
29.1’(0.126)
23.8’(1.414)
46.3
22.0’(0.192)
7.82’(0.497)
51
11.6
7.11
36.9’(0.045)
26.7
29.5’(0.108)
N D‘
60.3
43.5’(0.259)
20.5’(0.266)
13.8*(0.203)
30.7’(0.138)
168‘
Geographical Distribution of Pewlene in PWS
The highest perylene concentrations inside PWS were found in subtidal sediments at sites
where perylene was widely distributed subtidally at all sampling times (Tables 1 1 and 12). These
sites included Eshamy Bay, Ewan Bay, Green Island, Iktua Bay, Iktua Bay 2, MacLeod Harbor,
Olsen Bay, Paddy Bay, Rocky Bay,
Two MoonBay, West Bay,and Zaikof Bay among those
locations where shorelines were not heavily oiled by the Spill. Mean perylene concentrations
frequently exceeded 20 ndg in subtidal sediments at these sites. and ranged up to 481 ng/g in
sediments from the6-m depth at Paddy Bay. Mean perylene concentrations were usually greatest
at intermediate (6 m to 40 m) subtidal depths, but were usually present in intertidal sediments as
well. At locations where shorelines wereheavily oiled by the Spill, the only sites where perylene
was widespread subtidally at all sampling times was the NOAA site at Northwest Bay and
Northwest Bay 5. Perylene concentrations frequently exceeded 20 ng/g in deeper sediments at
the NOAANorthwest Bay site. At two other heavily oiled shoreline sites, Northwest Bay 4 and
Block Island, we failed to detect perylene only once. All of the above sites wererelatively
sheltered from heavy wave action, and they were not immediately adjacent to marine passages
where subtidal slopes can be steep and currents may be strong.
At sites where perylene was not widely distributed, it was usually found in the deeper
sediments and at concentrations that usually increased with depth. For example, at Disk Island,
perylene was never detected in sediments from 3 m or 6 m, but it was consistently detected in
deeper sediments at concentrations that exceeded 8 ng/g at depths 2 20 m. This'pattern of
distribution of perylene was widespread, and occurred at locationswith heavily-oiled shorelines
(Bay of Isles, Foxfarm, Herring Bay, Sleepy Bay, the NOAA Snug Harbor siteand the Snug
Harbor 25 site) aswell as at reference and assessment sites with low levels of oiling such as Drier
Bay, Knight Island, Lower Herring Bay, and Port Fidalgo. The perylene concentration at these
locations was lowor undetected in intertidal and shallow subtidal sediments (to a depth of6 m),
but was substantially higher in deeper sediments. The deep stations at these locations were
probably undisturbed by strong watermovement.
Perylene was consistently low in concentration or absent at some sitesin PWS. These
sites included Applegate Island (only one sample analyzed), Chenega Island, Green Island 22,
Heather Bay, Ingot Island, the Knight Island Bioremediation site, and Smith Island. Most of these
sites were exposed to wave action and were immediately adjacent to marine passages. Heather
Bay is near Columbia Glacier and was therefore subject to deposition of glacial silt.
Stations at assessment locations where subtidal sediments showed little evidence of
weathered EVO-PAH often did not have detectable levels of perylene. At Foxfarm and Smith
Island, neither perylene nor weathered EVO-PAH was found subtidally. At Disk Island, perylene
was not detected at 3 m or 6 m. One sample (3 m, June 1990) from those depths showed the
EVO-PAH pattern, but the TPAH concentration of thatsample was very low (41.5 ng/g).
Conversely, we frequently found perylene at stations where sediments exhibited a PAH
composition pattern characteristicofweathered EVO (Table 5 , bold type). At Block Island, both
52
perylene and a weathered EVO-PAH composition pattern were consistently detected in shallow
subtidal sediments to a depth of 20m. At Northwest Bay, where the weathered EVO-PAH
composition pattern wasfrequently detected and TPAH concentrations remained relatively high in
shallow subtidal sediments to 1991, perylene was consistently observed in those sediments. At
Bay of Isles, Herring Bay, Sleepy Bay. and Snug Harbor, both perylene and the weathered EVOPAH composition pattern were frequently found in shallow subtidal sediments, but less
consistently so than at Block Island and Northwest Bay.
Variabilitv of Pewlenein Replicate Samples
The relative variability of perylene measured in replicate samples was similar to the
relative variability of: (1) TPAH measured in 40 m and deeper sediments and (2) TPAH in
sediments where aPAH composition pattern characteristic of weathered
EVO wasconsistently
present. Over 84% of the 270replicate groups wherethe mean perylene concentration exceeded
4.0 ng/g had a CV less than 50%; the median CV was 21.7%. Only 3.7% oftheseexceeded
100%. (When the mean perylene concentration was less than 4.0 ng/g, individual perylene
measurements were often below detection limits resulting in a large CV). This median CV for
perylene of 21.7% compareswith a median of 17.2% for TPAH
in sediments from depths 240m
and with a median of 36.9% for TPAH where the P A H composition characteristicof weathered
EVO was consistently found in replicate samples
Correlation of TNA and Perylene
The mean concentration of TNA was significantly correlated with perylene in subtidal
sediments. At reference and assessment stations, where the weathered EVO-PAH composition
pattern was generally absent, the concentrationsof perylene and TNA in subtidal sediments were
highly significantly correlated (r = 0.722, P < 0.001, d f = 375). Perylene exceeded minimum
detection limits in all but 5 of 209 subtidal samples containing a TNA concentration greater than
800 ng/g. Perylene concentration generally increased with increasing TNA concentration in these
samples (Fig. 9).
Variabilitv of TNAconcentrations in Redicate Samples
The relative variability of TNA concentration in replicate samples was similar to the
relative variability of perylene concentration. Over 78% of the 319 replicate groups had a CV for
TNA concentration that was less than 50% (Tables 6 and 9); the median CV was 19.8%. Only
4.4% of these exceeded 100%.
Northern Gulf of Alaska
A PAH composition patternconsistent with weathered EVO wasfound at four of the
eight locations sampled in the NGOA in summer 1989. The four locations were Chugach Bay,
Hallo Bay, Katmai Bay, and Windy Bay (Fig. 2, Table 13). At each of these locations, only
53
I
100
.
I
.
(188,154)
80
h
3
c
.
60-
0)
-
0
C
Y
I
0
t
i
(6410,155)(1960,270)
.
.
..
.
.
.
.. . .
1,000
9
.
. .
. .. .
.
2,000
3,000
4,000
TNA (ng/g wet wt)
Figure 9.--Correlationof concentrations of TNAs and perylene in subtidal sedimentsat all stations
in PWS where the weathered EVO-PAH composition pattern was generally absent.
54
SS
one of three replicates was analyzed. Of the foursamples where the weathered EVO pattern was
observed, the TPAH concentration was highest in intertidal sediments from Hallo Bay and Katmai
Bay. The concentration was 348 ng/g and 339 np/g for Hallo Bay and Katmai Bay, respectively,;
these were the highest TPAH concentrations measured in intertidal sediments anywhere outside
PWS. In addition, the weathered EVO pattern appeared in subtidal samples at 6-m and 20-m
depths at Chugach Bay (TPAH concentration = 80.6 ng/g and 362 ng/g) and at the 3-m depth at
Windy Bay (TPAH concentration = 224 ng/g). These TPAH concentrations were among the
highest found in intertidal and shallow subtidal sediments at these locations.
Elsewhere in the NGOA, TPAH concentration was consistently low in intertidal and
shallow subtidal samples from Black Bay, but were consistently high in shallow subtidal samples
from Agnes Cove (Table 13). At Black Bay, intertidal and shallow subtidal TPAH concentrations
were less than 16 ng/g. At Agnes Cove, theintertidal TPAH concentration was 54.0 ng/g, but the
concentration in shallow subtidal samples ranged from 363 ng/g to 924 ng/g. The PAH
composition in these shallow subtidal sediments was generally similar to weathered EVO except
for relatively low concentrations ofdibenzothiophenes. At Chignik Bay and at Ivanof Bay,
intertidal and shallow subtidal samples were either not analyzed or had unacceptable surrogate
recoveries (at Chignik Bay, 20 m depth).
Compared with shallow subtidal sediments, deeper (40-100 m) subtidal sediments
generally had a greater TPAH concentration atall locations in the NGOA. The highest TPAH
concentrations measured outside PWS were: 8,080 ng/g at the 40-m depth at Agnes Cove; 1,990
ng/g at the 40-m depth of Chignik Bay; and 1,580 ng/g at the 100-m depth of Ivanof Bay.
Elsewhere at 40-m, the TPAH concentration ranged from 2 1.1 ng/g to 442 ng/g, and at 100 m, it
ranged from 226 ng/g to 397 ng/g. At five of these locations (Agnes Cove,Black Bay, Chignik
Bay, Hallo Bay, and Katmai Bay), the PAH composition in 40-100-m subtidal sediments was
generally similar to weathered EVO except for relatively low concentrations of
dibenzothiophenes. At the other three locations; however, both dibenzothiophenes and chrysenes
were low in concentration or absent
Although data from outsidePWS were limited, the results forn-alkanes at sites in the
NGOA showed trends similar to those observed within the Sound. Intertidal sediment TNA
concentration,was highest at Hallo Bay (2.1 I O nglg) and Katmai Bay (1,030 ng/g) where the
weathered EVO-PAH pattern was found (Tables 13 and 14). Conversely, the CPI ofintertidal
sediments was lowest at Hallo Bay (1.55) and Katmai Bay (1.44; Table 15). The intertidal TNA
concentration elsewhere in the NGOA ranged from 183 ng/g to 842ng/g; CPI ranged from 2.I O
to 7.22.
The concentration of TNAin subtidal sediments frequently increased with increasing
bathymetric depth. At Chugach Bay, Hallo Bay, and Katmai Bay, the TNA concentration at the
3-m station ranged from 384 ng/g, to 85 1 ng/g; whereas, at 100 m, the TNA concentration ranged
from 1,830 ng/g to 2,510 ng/g. At Agnes Cove and Black Bay, this trend was absent. The
subtidal TNA concentration ranged from 328 ng/g to 1,220 ng/g at these locations, and no
56
Table 14.-Conmvalion ("pig) ofTNA in sediments from all statiotu in Ole NGOA. One replicate was analyzed at each station. S denote sumgate recoveries outside acceptable ra%e.
Depth
Site
40 m
100 "1
No.
Name
Date
Om
3 "l
6m
20 t"
416
.
969
46
Apescow
Jul-X9
398
S
976
S
440
Jul-89
X42
455
1,031
1,219
47
BlackBay
328
S
S'
48
Clligrtik Bay
Aug-89
384
508
1,658
I .X26
567
Clwgach Bay
Aug-89
1x3
49
Hallo Bay
1.839 Aug-89
1,060
2.108
796
50
3,634
2,385
2.033 4,154
5I
Ivanof Bay
Aug-89
85 I
2.506
52
I;atmai Bay
Aug-X9
1.028
630
940
1.812
1.871
S
2,924
53 842
Windy Bay
Aos-89
380
5.826
a 30 111 depth.
85
consistent trend with depth was observed (Table 14). Finally, at Windy Bay, the TNA
concentration decreased with increasing depth from 2,920 ng/g at 6 m (data from the 3-m sample
were unusable because of poor recovery of surrogate standards) to 842 ng/g at 100 m. At
Chignik Bay and Ivanof Bay, data from shallow-subtidal samples were not available for
comparison.
The CPI for subtidal sediments in the NGOA was usually well above 2.00, ranging up to
11.1 at the 20-m depth in Katmai Bay (Table 15). The CPI at one-half of the subtidal stations
was greater than 4.00. The CPI wasless than 2.00 at only four stations: Agnes Cove, 3m;
Chugach Bay, 6 m; Hallo Bay, 3 m, and Windy Bay, 20 m.
Geograuhical Distribution of Pewlene in the NGOA
The patterns of perylene distribution in the NGOA weresimilar to those inside PWS.
Perylene was not detected in intertidal sediments outside PWS (Table 16), but it was detected
subtidally at locations that were relatively sheltered or had gently sloping bottoms. These
locations were Agnes Cove, Chignik Bay, Ivanof Bay, and Katmai Bay. Perylene concentration .
increased with depth at Katmai Bay to 24.7ng/g and 26.2 ng/g at the 40 m and 100 m,
respectively. At Agnes Cove, subtidal perylene concentration ranged from 5.5 ng/g at 100 m to
144 ng/g at 40-m depth with intermediate concentration at other subtidal depths. Only the deeper
(220 m) sediment samples were analyzed from Chignik Bay and Ivanof Bay. Perylene
concentration in sediments from these bays ranged from 15.4 ng/g to 39.1 ng/g. Perylene was not
detected in subtidal sediments from theremaining locations in the NGOA.
DISCUSSlON
Bathvmetric Distribution of EVO
Locations Contaminated bv EVO
Intertidal stations
Oil became broadly distributed on beaches in PWS during the first few months after the
EVOS. Most of thespilled oil that had not evaporated or dispersed naturally into the water
column was deposited in the intertidal region and supralittoral fringe primarily in western PWS
(Wolfe et al. 1994). Lower intertidal sediments (near MLLW) at some locations were clearly
contaminated by crude oil. The concentrations ofindividual aromatic analytes in the samples from
the Disk Island 0-m station averaged usually one tothree orders ofmagnitude greater than the
baseline concentrations of thosesame analytes reported by Karinen et al. (1993) for intertidal sites
in PWS before the Spill. EVO was indicated as the source ofthe PAHs atDisk Island and
Northwest Bay by: ( I ) the close similarity between relative P A H abundances in the intertidal.
59
09
sediments and those in floating mousse collected 1 1 days after the Spill; ( 2 ) high concentration of
n-alkanes and CPI near 1 that (although not specific to EVO)indicate a petroleum source of the
alkanes; and (3) theproximity of the intertidal station to the heavily-oiled upper intertidal
shoreline where oil was visually apparent in spring 1989 (indicating oil concentrations near
percent levels).
Results from samples collected along a vertical intertidal transect in September 1989 at
Northwest Bay corroborated the July 1989 results. Every sample (collected at 2-m intervals)
along the 20-m transect was qualitatively similar to samples collected at the 0-m depth in July
1989 in PAH distribution, n-alkane concentration, and CPI. Although the TPAH concentration in
the samples collected in September 1989was lower by a factor of twoto ten compared with
samples collected in July 1989; it was much higher than intertidal TPAH concentration at
reference stations. In addition, the TPAH concentration in samples from the20-m vertical
transect at Northwest Bayin September 1989 was between 1,300 ng/g and 6,000 ndg, indicating
that the PAHs were distributed homogeneously along the transect rather thanin isolated patches
of high concentration. This corroborates the EVO transport mechanism from the heavily oiled
upper intertidal zone to the less-heavily oiled lower intertidal zone posited by Short et al. (In
press(a)), which involves widespread dispersion of fine-grained, oil-contaminated sediments.
Lower-intertidal sediments were also contaminated by EVO at otherlocations, but at a
lower TPAH concentration thaninitially found at Disk Island or Northwest Bay. The PAHs in the
intertidal sediments of at least some of the stations at these locations (except Smith Island) were
qualitatively similar to PAHs at Disk Island and at Northwest Bay in 1989. Moderate to heavy
oiling was observed in the upper intertidal zone at all of the locations. At Smith Island, intertidal
samples were not collected in December 1989, but oiling may be inferred from the PAH
distribution found in the 3-m subtidal sample and from the heavy upper-intertidal oiling that
occurred there. EVO contamination of many intertidal sediments was confirmed by an associated
high n-alkane concentration and a low CPI at stations where theTPAH concentration was also
high. At stations where theTPAH concentration was lower, the magnitudeand distribution of nalkane concentrations were often confounded by alkanes from terrigenous sourcesindicated by
higher CPI values.
TNA concentrations ranging to over 1.000 ndg from terrigenous and marine sources were
widespread in intertidal sediments at reference stations and at assessment stations where oiling in
the upper intertidal zone was low or absent. The concentrations of n-alkanes from natural
sources can dominate the TNA. The concentrations n-alkanes
of
at reference stations in the
present study were similar to those in pre-spill intertidal sediments in PWS (Karinen et al. 1993).
The alkanes wereprobably derived from terrestrial plant waxes which are characterized by higher
concentrations of odd carbon-numbered alkanes in the range C-20to C-30 and above
(Kolattukudy 1976, Eglinton and Hamilton 1967, Eglinton et al. 1962) and from marine sources
including bacteria (Oro et al. 1967), blue-green algae (Winters etal. 1969), and planktonic and
macrophytic algae (Clark and Blumer 1967, Blumer 1971) which are characterized by higher.
concentrations of odd carbon-numbered alkanes smaller than C-20 (especially C-15, C-17, and
61
C-19). The benthic sediments of boreal tjords (sensu Burrell 1988) commonly receive from
inflowing rivers and streams large amounts of terrigenous organicmaterial chiefly in the form of
plant detritus refractory to decomposition. Added to this material can be substantial amounts of
phytodetritus derived from phytoplankton production and sedimented out of the euphoticzone
(Burrell 1988). The deposition of particulate organic material from these sources can cause the
accumulation of naturally occurring hydrocarbonsin benthic sediments.
Subtidal Stations
Very little oil may have reached the bottom by direct transport from the watercolumn
immediately after the Spill (see discussion of mechanisms of transport, below). Most of the
cpntamination of subtidal sediments probably resulted from resuspension of oiled sediment
particles from contaminated beaches followed by sedimentation in the subtidal region.
Consequently, contamination of subtidal sediments by EVO wasmainly confined to shallow
bathymetric depths at locations whereshorelines were: (1) heavily oiled and (2) exposed to
wave-action or shoreline treatment, and (3) where adjacent, shallow-subtidal sediment deposits
occurred on low-gradient slopes. We found strong evidence of EVOcontamination in shallow
subtidal sediments at Block Island, Herring Bay, and Northwest Bay; locations where the above
conditions prevailed. The mean TPAH concentration in samples showing the EVO-PAH pattern
was highest, consistent among replicate samples, and persistent at these locations. The EVOPAH pattern was frequently found at depths to 20 m but rarely deeper. The EVO-PAHs were
absent from greater depthsat oiled locations probably because: (1) insufficient energy was
available from waves and currents to transport contaminated sediments far enough offshoreto
reach greater depths, and (2) as contaminated sediments spread to greater depths, they became
dispersed and intermixed with uncontaminated sediments over a broader area resulting in lower
PAH concentrations that were moredifficult to detect.
Environmental conditions wereless favorable for transport of EVO-contaminated
intertidal sediments to subtidal depths at otherheavily oiled locations. Evidence for EVO
contamination of subtidal sediments was less consistent at these locations, and the mean TPAH
concentration attributable to EVO was generally lower than at Northwest Bay, for example. The
sampling stations at Bay of Isles and Snug Harbor were moresheltered from heavy wave action.
Shorelines near some sampling stations at these locations wereless heavily oiled initially than at
Northwest Bay. Consequently, EVO was available for transport to the subtidal region and those
factors promoting the transport of intertidal sediments to subtidal depths were.less pronouncedat
these locations.
At Sleepy Bay, Smith Island, and perhaps Disk Island, shorelines were heavily oiled but
were exposed to heavy wave action which may have precluded long sediment residence times.
Concentrations of terrigenous(i.e., high CPI) 11-alkanes at the shallow subtidal depths at these
locations were generally low. The sediments were probably less stable and did not act as sinks for
terrigenous organic material. The general absence of EVO-derived PAHs in the sediments is.
consistent with this conclusion. The Smith Island and Sleepy Bay sites are surrounded by, or are
62
'
adjacent to, large passages where strong currents prevail. These conditions may have promoted
greater export ratesof suspended sediments resulting in a shorter residence time of EVOcontaminated subtidal sediments at these locations.
Locations Not Contaminatedbv EVO
Intertidal Stations
Lower intertidal sediments at reference locations and at assessment locations that received
little oil were clearly not contaminated by EVO. The TPAH concentrations at these locations
were usually less than 100 ng/g, and individual PAH analyte concentrations were similar to those
in intertidal sediments sampled during the period 1977 to 1980 in PWS (Karinen et al. 1993).
To establish baseline concentrations of petroleum hydrocarbonsin PWS in case of an oil
spill, a suite of PAHs was monitored in intertidal sediments there beginning in 1977 (when the
Trans Alaska Pipeline Terminal at Valdez began operations) and continuing until 1980 (Karinen et
al. 1993). The accuracy and precision of the analytical methods used in that study were .
comparable with those of thepresent study. Two ofthe locations monitored during thatperiod
(Olsen Bay and Rocky Bay) were alsosampled during the present study. Comparison of intertidal
sediments from these locationsshowed general agreement in PAH concentrations between the
two studies (Table 17). Several of the same PAH analytes were elevated in both studies, and the
concentrations of theelevated analytes were often quite close. MostPAH analytes were near or
below detection limits at Olsen Bay during both studies.The exception was perylene which was
present at the highest concentration of the PAHanalytes in both studies at Olsen Bay, and which
did not differ significantly in concentration between studies( P > 0.25;Table 17). At Rocky Bay,
concentrations of fluorene, phenanthrene, pyrene, chrysene and benzo-e-pyrene were substantially
greater than detectionlimits in both studies. Themeans of these concentrations did not differ
significantly between studies ( P > 0.40). Mean concentrations of theremaining 3-ring PAHs
(including dibenzothiophene) were near or below detection limits in both studies. By contrast, the
2-ring PAHs in sediments from Rocky Bay were significantly greater in concentration in the
present study because of greater concentrations at theintertidal station in 1989. The
concentration of fluoranthene was lower in the present study.
The generally close agreement of theconcentrations of PAH analytes at comparable
stations between thepresent study and Karinen et al. (1993) suggest that during theperiod 1977
through 1990 PAH concentrations changedlittle in the intertidal sediments ofPWS that were not
oiled by the EVOS. Karinen et al. (1993) found little evidence of PAH contamination at four
stations (Bligh Island, Naked Island, Siwash Bay, and Olsen Bay) that they sampled in 1977-80,
based on the general absence of peaks in the representative chromatogramsthey presented for
these stations. They found very low concentrations of PAHsat Rocky Bay and at Constantine
Harbor near the eastern entrance to the Sound. Therefore, with the exception of 2-ring PAHs,
any increases in PAH concentrations in intertidal sediments of PWS before the EVOS probably
63
Table 17.--Comparisonof PAHs in intertidal sediments at Olsen Bay and Rocky Bay during 1977 to 1980 and 1989 to 1990. Numbers in the body of the table are
means and 95% confidence intervals. Significance levels are: *, P < 0.05; **, P < 0.01
RccLi Bay
1989-1 990
This study
n=6
Naphthalene
1 -Methyl naphthalene
2-Me1hyl naphthalene
2,6 L>imethyl naphthalene
2,3,5 Trimethyl naphthalene
Biphenyl
Fluorene
Dibenzolhiophene
Phenanthrene
I -Methyl phenanthrene
Anthracene
Fluoranlhene
Ppene
Benzanth-acene
Ctuysene
Benro-e-pvrene
Benzo-a-pyrene
Pewlene
a.n=8
b.n=9
c. One sample 0.29 ng/p
d. One sample 0.58 ng/g
r.n=21
tn=15
Olsen Bav
1977-1980
Karinen et al.
n = 10
f 0.61'
12.5 f 2.63**
4.50
4.39 f 0.53*
13.1 f 1.69*
8 . 3 6 i 0.90**
G2.40
6.47 fOo.63**
9.43 0.83
2.29 f 0 . 4 9
7.74 f 1.25
4.68 0.61
*
a20
3.62 f 0.60
10.7 I .47
1.78 f 0.64
3 7 . 9 5 5.61
2.41 f 0.76b
1 .SO f 0.45
I .42
*
*
400
39.8 4.52
4.66 f 0.67
.r4.00
4.09 0.54**
9.74
11.4f 1.68
<I .40
9.7 I f 1.87
7.00f 1.13
c1.20
7.52 f 3.04**
*
*
.
__
12.6 f 2.05
1.3 I f 0.47
13.0*2.58
8.90 f 1.58
0.85 f 0.69
33.3 f 5.07
4.73
. -
64
1989-1990
.Thisstudy
n = 22
3.61 *0.62**'
0.72 f 0.21'
0.90 f 0.16'
4.40
440
-240
<2.40
c2.00
2. I 6 0.42*
I .22 0.68
4.00
1.65 *0.61
*
*
600
<I .40
0.92 f 0.31
c0.39
~2.40'
420'
10.5 1.49'
*
1977-1980
Karinen et al.
n=Y
0.36 i 0.17
0.27i0.18
0.40 f 0. I7
4.21
a.22
421'
c0.226
41.39
(1.34 f 0. I4
428
4.I6
c0.29
c0.20
c0.72
489
~.
7.60 f
I .7 I
were attributable to localized sources of PAH rather than to some large-scale, dispersed source
that contaminated PWS generally. However, a widespread source of2-ring PAHs cannot be
ruled out because these PAHs were often found in intertidal and subtidal sediments in 1989 at
both reference and assessment sites. The source of these 2-ring PAHs is not known, but diesel
fuel may have played a role at some locations.
Subtidal Stations
The general absence of EVO-derived
PAHs in subtidal sediments at reference locations
and assessment locations whereshorelines were not heavily oiled indicates that subtidal sediment
contamination by EVO was localized rather than widespread along the Spill trajectory through
PWS. The few instances where the PAH composition pattern resembled that of weathered EVO
in subtidal sediments at these locations probably resulted from mixtures of PAHs from other
sources. These few occurrences weredistributed throughout the range of the subtidal depths
sampled, and sometimes appeared at locations away from theSpill path in PWS (e.g. Olsen Bay).
When the EVO-PAHpattern was observedin shallow subtidal sediments at these locationsit was
present in one replicate only. We consider these isolated occurrences of the EVO-PAH pattern in
sediments from reference locationsand lightly oiled assessment locations to be largely spurious.
We conclude that detectablecontamination of subtidal sediments by EVO wasnot widespread
throughout the Spill path, but rather was restricted to those relatively few locations where
conditions favored subtidal accumulation. Most of the subtidal area within the Spill path escaped
detectable contamination.
Geograohical distribution of EVO
pws
The pattern ofdistribution of petroleum hydrocarbons in benthic sediments in PWS in
1989 wasgenerally consistent with the pattern expected from maps
of the trajectory of theEVOS
compiled by N O M and the Alaska Department of Environmental Conservation. We found EVO
in lower intertidal and subtidal sediments over a broad geographic range in PWS from Northwest
Bay at thenorth end of Eleanor Island to Foxfarm (intertidal sediments only) at the southern end
of Elrington Island (Fig. 1). Subtidal sediments contained EVO at eight locations where oil had
come ashore (oiled locations) in 1989. Those locations constituted80% of oiled locations studied
in 1989. Contamination of subtidal sediments by EVO at oiled locations reached a depth of at
least 20 m at five locations in 1989.
We found scant evidence of subtidal sediment contamination by EVO outsidePWS. This
result was, in part, attributable to the limited number of samples that were analyzed from the
NGOA, but it probably also reflected the relatively small proportion ofthe spilled oil that exited
the Sound and subsequently spread over the much larger area ofthe NGOA. Wolfe et al. (1994)
65
estimated that between 7 and 11% of the total spilled oil ultimately became beached in the Kenai
and Shelikof Strait areas combined. Although we found some indication of EVO in intertidal
sediments at HalloBay and Katmai Bay and in subtidal sediments at ChugachBay and Windy
Bay, only one of threereplicates was analyzed at each station at these locations. The TPAH
concentrations in these samples were low; therefore, we are substantially less confident of the
source of the hydrocarbonsin the samples. We conclude that because of the relatively small
percentage of thespilled oil that exited PWS and the extensive length of coastlinein the NGOA,
oiling of the beaches there was patchy and there was less oil available on the beaches in the
NGOA than in PWS for redistribution to subtidal sediments. Moreover, probably only in
localized areas were conditionsfavorable to the transport of beached oil to adjacent shallow
subtidal sediments (i.e., heavy initial shoreline oiling, exposure to high-energy wave action, and
conditions of minimal disturbance for subtidal sediments on slopes of shallow gradient). As a
result most subtidal sediments outside PWS probably were not detectably contaminatedby EVO.
Temporal changes in EVO contamination
The general decline from 1989 to 1991 in mean TPAH concentrations in intertidal
sediments at sites contaminatedby EVO reflects the continued action of themechanisms of
dispersion that initially transported oil-contaminated sediments from heavily oiled, upper-intertidal
shorelines to the lower intertidal zone. Shoreline treatment probably augmented the action of
high-energy waves to suspend and disperse fine-grained, oil-contaminated sediments. By 1990,
the mean TPAH concentration in lower intertidal sediments at many oiled sites had declined to
levels comparable to the background TPAH concentration(i.e., to a concentration ~ 2 0 ng/g).
0
Additional decreases in TPAH concentration wereobserved at those sites sampled in 1991.
Concentrations of petroleum hydrocarbons attributableto EVOdecreased and EVO
hydrocarbons became morelocalized in subtidal sediments, as well, after 1989. By 1990, the
EVO-PAH pattern was consistently present in shallow subtidal sediments only at Block Island and
Northwest Bay. The EVO-PAH pattern was occasionally seen in subtidal sediments at five
additional locations in 1990. No consistent trend in TPAH concentration with depth was
apparent. Additional decreases in the TPAH concentration were observed at oiled sites in 1991.
The EVO-PAH patternwas consistently present only at Northwest Bay in 1991; although, the
pattern was sporadically observed in subtidal sediments fromBay of Isles, Herring Bay and Snug
Harbor in 1991. In succeeding years the PAHs will probably continue to decline and become
more patchily distributed.
Mechanisms of tranmort of EVO tosubtidal sediments
Wolfe et al. (1994) estimated that about 12% of thespilled oil was transported to the
subtidal region by fall 1992. The accumulation of EVO in subtidal sediments could have resulted
from: (1) sinking of oil, sedimentation of oil and clay colloids or settling ofbiogenic, composite
grains directly out ofthe water column shortly after the Spill and (2) resuspension of oiled
sediment particles from contaminated beaches by wave action and cleanup activities followed by
66
sedimentation in the subtidal region. Transport of oil to subtidal sediments directly from the
water column can be mediated by three mechanisms that cause oil settling (Boehm et al. 1982).
The first involves an increase in the density of the oil through the loss of soluble, volatile fractions
to the extent that the oil density exceeds that of water causing the oil to sink. This mode of
transport can occur under some conditions when the initial oil density is close to that ofwater
(Boehm et al. 1982). The EVO probably did not sink in this way (Galt et al. 1991).
The second mode of transportcausing oil to settle involves the adsorption ofoil films onto
particulate matter, especially clay particles, which can result in the formation of spontaneous
association colloids through theprocess of flocculation by electrolytic action (Bassin and Ichiye
1977). Physicochemical flocculation can increase settling rates up to about one order of
magnitude (Drake 1976). There are apparently no definitive data on howmuch oil, associated
with particulate matter, settled to the bottom of PWS shortly after the Spill. Galt et al. (1991)
presumed that oil did not settle to the bottom to "any significant extent" as the EVO slick moved
through PWS because "there was little or no sediment-laden water near the oil slick", but they
presented no data onthe amount of suspended sediment in the water near the slick. Payne et al
(1989) measured suspended particulate material (SPM) loads in PWS during the period 12-15
April 1989. They found SPM loads in the range <0.01 to 4.57mg/L. From this, Payne et al.
(1991) expected that very little oiVSPM interaction and sedimentation occurred in the first few
weeks after the Spill.
The third mechanism of transport of oil to the bottominvolves encapsulation of oil into
feces or psuedofeces after ingestion of oil droplets by copepods or suspension-feeding benthic
invertebrates such as mussels (Conover 1971, Clark and MacLeod 1977). Biotic production of
composite grains in this way can increase settling rates up to several orders of magnitude (Drake
1976). No datahave been presented to date that would allow an assessment of the importance of
this mechanism to oil settling during the EVOS. According to Koons and Jahns (1992), the U.S.
Geological Survey concluded that the amount ofEVO that sank to the bottom during the first two
months after the Spill was insignificant, but they cite no reference.
The most likely pathway by which EVO wastransported to subtidal sediments, especially
at certain heavily oiled locations, was resuspension of contaminated beach sediments followed by
deposition nearshore. Sediments collected from sediment traps initially deployed during the
period November 1989 to June 1990 at depths of IO, 15, and 20 m near oiled and non-oiled sites
showed hydrocarbon analyte patterns consistent with EVO. Hydrocarbon concentrations in these
sediments were highest at heavily oiled sites (Sleepy Bay, Northwest Bay, and Snug Harbor)and
lowest in sediment traps placed at non-oiled sites (Port Fidalgo, Eshamy Bay, and Stockdale
Harbor; Short et al.In press(a)).
67
Other hydrocarbon sources i
m
Intertidal and shallow subtidal sediments
Our results indicate that the quantitative impact of PAHsfrom sources otherthan the
EVOS on intertidal and shallow subtidal sediments in PWS was small. The TPAH concentration
of these sources wasusually below 200 ng/g. Overall, intertidal and shallow subtidal sediments in
PWS not affected by the EVOS remained substantially free of petroleum hydrocarbons. A mean
TPAH concentration greater than 100 ng/g was occasionally found in intertidal sediments where
EVO was not indicated, but a concentration this high usually occurred sporadically among station
replicates.
The probable sources of PAHsin intertidal and shallow subtidal sediments where EVO
was absent included diesel oil and products ofpyrolysis associated with small (and often
temporary) human settlements, asphalt from storage tanks at Valdez, and forest fires. Fish
processing plants or mining facilities have beenlocated historically in Snug Harbor,Drier Bay,
and near Sleepy Bay. Relatively small areas of upper-intertidal sediments may have become
contaminated by PAHs throughhuman activity at these installations, and the contamination may
have subsequently dispersed into lower-intertidal sediments. Background PAHs could be
transported to subtidal sediments by the same mechanism that transported terrigenous n-alkanes
and EVO to thosesediments. Trace residues of California crude oil linked to storage tanks at
Valdez and Whittier that may have ruptured during the Alaska earthquake of 1964have been
reported in intertidal sediments in PWS along the path of the EVOS (Kvenvolden et al. 1993).
Finally, very large forest fires on the Kenai Peninsula have, in certain of the last 30 years,
blanketed the entire Sound with wood smoke for weeks. This provided an additional potential
source ofpyrogenic PAHs that wereinitially widely distributed in the Sound and are now
confined to localized areas.
Mixtures of PAHs from multiple sources may result in PAH composition patterns that
resemble weathered EVO at low TPAH concentrations. In particular, diesel oil derived from
North Slope crudeoil together with PAHs characteristic of deepsubtidal sediments (Fig. 4) could
result in alkyl-PAH ratios near those found in samples contaminated by EVO (e.g., floating
mousse oil collected from the oil slick 1 1 days after the Spill). Compared with EVO, the diesel oil
lacked chrysenes and the deep-sediment PAHs were low in dibenzothiophenes. Mixtures of these
two components may have contained all the PAHs at relative abundances sufficiently close to that
of EVOto satisfy the criteria we used for preliminary identification of EVO. This may account
for the isolated cases where weathered EVO-PAH assemblages were identified in subtidal
sediments at reference sites and at sites where EVO was not found in intertidal sediments. These
cases were usually single samples at a TPAH concentration less than 200 ng/g in shallow subtidal
sediments or they were samples at somewhat higher TPAH concentration in deep subtidal
sediments. Some cases were near Hinchinbrook Entrance where theconcentration of PAHswere
higher in subtidal sediments (see below).
,
68
Deeo subtidal sediments
Deep subtidal sediments were uniformly contaminated by PAHs derived from marine oil
seeps or some other natural source ofPAHs such as unburned coal (Tripp et al. 1981, Barrick et
al. 1984). The PAH composition pattern characteristic of this source differs from weathered
EVO in that the coal contains lower relative abundances of dibenzothiophenes. Page et al. (1995)
attributed this PAH composition pattern to coastal oil seeps in the eastern Gulf ofAlaska near
Katalla Island and Cape Yakataga. According to Page et al. (1995), the PAHs from the oil seeps
are adsorbed to clay particles introduced into the Gulf 0f.Alask.a by glacier-fed streams and rivers,
including the CopperRiver, and are subsequently carried into PWS throughHinchinbrook
Entrance. Once inside PWS, the current velocity slows, resulting in increased deposition of oilladen sediments. Another possible source may be microscopic coal particles eroded from
terrestrial coal beds in the CopperRiver drainage and introduced into the Alaska Coastal Current
together with other sediments transported by the CopperRiver, and are subsequently carried into
PWS through Hinchinbrook Entrance. Unburned coal and petroleum in sediments may be very
difficult to distinguish at lower concentrations on the basis of PAHanalyses (Tripp et al. 1981).
Our results are generally consistent with these explanations. The generally increasing
mean TPAH concentrationwith depth below20 m associated with the PAH composition shown
in Figure 7 was consistent with the deposition of PAH-laden sediments from natural sources.
Concentrations were greatest near Hinchinbrook Entrance where thecurrent slows on entering
the Sound. Inside PWS sediments containing these PAHs were generally restricted to deeper
subtidal sediments.
As the distance from the sourceincreases, the amount ofsuspended-sediment-bearing
hydrocarbons presumably decreases as these sediments settle out of the watercolumn. As a
result, contributions of PAHs fromnatural sources to shallow subtidal sediments would be smaller
within PWS than at Hinchinbrook Entrance. In fact, PAH concentrations were low in shallow
subtidal sediments at locations within PWS that were not directly affected by the Spill. The
concentration of TPAH in shallow subtidal sediments at locations not directly affected by the Spill
was usually less than 200 ngg. However, at some stations the TPAHconcentration in shallow
subtidal sediments contaminated by EVO often exceeded 500 ndg; this is clearly more than a
small increase on a large natural PAH background.
Comoarisons with Other Oil Spills
The proportion ofspilled oil from the EVOS that entered subtidal sediments was similar to
that entering subtidal sediments from other major spills. Wolfe et al. (1994) estimated that
between 8 and 16% ofthe -35,500 metric tons of oil spilled (9-1 8% of the unrecovered oil) from
the EVOS wastransported to subtidal sediments. Gundlach et al. (1983) estimated that 8% of the
223,000 metric tons of oil spilled from the Arnoco Cudiz was deposited in subtidal sediments. A
somewhat lower percentage wasestimated by Johansson et al. (1980) for No. 5 he1 oil
sedimented to the bottom after the Tsesis oil spill. Their estimate was 3-6% of the spilled oil (1069
15% ofthe unrecovered oil). Lower still was the estimate of Boehm et al. (1 982) of the
percentage ofspilled oil that was eventually transported to subtidal sediments near the Ixtoc
blowout site (0.5-3%). The proportion of spilled EVO transported to subtidal sediments was
similar to that transported to sediment (7-16%) in experimental releases of water-accommodated
NO. 2 fuel oil into marine microcosms (Gearing et al. 1979).
The concentrations of petroleum hydrocarbons measured in subtidal sediments after major
oil spills have varied greatly among spills. Factors contributing to this variability include the
magnitude of the spill, environmental conditions during the spill, configuration of the coastline
where oil came ashore, and the analytical techniques used to estimate oil concentration in
sediments. Nevertheless, maximum concentrations of oil in sediments after the EVOS were
usually within an order ofmagnitude of the maximum concentrations in subtidal sediments after
other major spills. We found the concentration of total hydrocarbons to range from 18 to 694
pg/g where thePAH composition pattern matched EVO in the first year of the Spill. CPAH in
these samples ranged from 0.1 to 2.7 pg/g. At embayments heavily oiled by the Amoco Cudiz oil
spill, the concentration of petroleum hydrocarbons in subtidal sediments ranged from 3 to 28,457
pg/g dry weight during the first month after the spill (Marchand and Caprais 1981). Surficial
subtidal sediments (0-5 cm) contaminated by oil from the Gulf War oil spill contained a total
hydrocarbon concentration ranging from <5 to 900 pg/g dry weight. Total PAH concentration
was in the range 1-7 pg/g (Michel et al. 1993). Concentration of total hydrocarbons in surficial
sediments (0-15 cm) near the ArgoMerchunt wreck site ranged from 0.1 to 327 pg/g dry weight
two months after the spill ofNo. 6 fuel oil from the vessel (Hoffman and Quinn 1979).
When compared with chronically polluted locations, the maximum concentration of total
hydrocarbons found in shallow subtidal sediments (3-20 m) where the PAH composition pattern
matched EVO (694 pg/g), was similar in magnitude to the middle of the concentration range of
hydrocarbons in sediments at such heavily polluted locations as New York Bight and Narragansett
Bay. Farrington and Tripp.(1977) found that the total hydrocarbon concentration ranged from 35
to 2,900 pg/g dry weight 'in sediments at a depth of 23-39 m in New York Bight. The total
hydrocarbon concentration ranged from 4 to 1,650 pg/g dry weight in sediments at a depth of555 m in Narragansett Bay (Hurtt and Quinn 1979).
Toxicological Effects of Oil in Subtidal Sediments
The toxicological effects of EVOin shallow subtidal sediments were more difficult to
identify compared with the pronounced effects observed in the intertidal region at heavily oiled
sites because in the shallow subtidal region EVO concentrations did not approach known acutely
toxic levels. None of the ZPAH concentrations in subtidal sediments where the EVO
composition pattern was present exceeded the "Effects Range-Low'' (ERL) sediment toxicity
threshold of 4,000 ppb proposed by Long and Morgan (1 990, see also Long 1992) for total
PAHs. Nevertheless, impacts on shallow (0-20 m) subtidal algae, eelgrass, and infaunal and
epifaunal invertebrates were documented at oiled locations in PWS (Dean et al. 1993, Dean and
Jewett 1993, Jewett and Dean 1993). Unequivocal attribution of the impacts to hydrocarbon
70
toxicity was often precluded because of other factors, such as cleanup activities and
bioremediation.
Oil toxicity may have been the primary cause of the apparent reduction in burrowing
amphipod densities at oiled sites compared with unoiled sites in 1990 (Jewett and Dean 1993)
despite relatively low PAH concentrations in most subtidal sediments in PWS. A comparable
situation may have prevailed after the lsesis oil spill, where the burrowing amphipod Pontoporeiu
was eliminated from some sediments for at least a year (Linden et al. 1979, Elmgren etal. 1980)
despite the absence of detectable quantities of hydrocarbons related to thespilled Tsesrs oil in
subtidal sediments (Boehm et al. 1982). Measurements of hydrocarbons in surficial sediments
may underestimate the concentration of hydrocarbons to which benthic organisms are exposed
because much of thehydrocarbon material may be in the surface floc layer which is difficult to
sample (Boehm et al. 1982). However, evidence to date for the accumulation of spilled oil in the
surface floc layer is inconclusive (Gearing et al. 1980, Boehm et al. 1987).
Reliance on acute-toxicity data to estimate or predict damage in the environment has been
problematical. Disturbance to natural communities may take place after an oil spill even though
measured sediment hydrocarbon concentrations are less than those that are acutely toxic to
individual species. Processes (feeding, reproduction, growth, molting, etc.) and species'sensitive
to oil pollution are seldom evaluated in an ecological context, in which complex interactions with
predators and competitors is taken into account. Consequently, the proposed ERL sediment
toxicity threshold proposed by Long and Morgan (1990) may be appropriate for estimating effects
on macro-invertebrates in the short term, but may be high when one considers subtle changes in
natural communities over thelong term.
Shallow subtidal communities in PWS apparently did not suffer major structural damage
unlike some heavily-oiled and heavily-cleaned intertidal areas (Houghton et al. 1993a, 1993b).
Moreover, some subtidal communities have shown evidence of recovery (Dean et al. 1993, Jewett
and Dean 1993).
Changes in the deep benthos were probably not complicated by EVO contamination. The
EVOS probably did not add significantly to the regional background levels of hydrocarbons at
240 m depths. The effect of temporal changes in factors, such as larval settlement, food
availability and predation pressure on the structure of deep benthic communities may not have
been independent of EVOS. Nevertheless, considering that EVO was generally not detected in
sediments at greater depthsit is unlikely that the EVOS had a direct impact on the deep benthos.
CONCLUSIONS
Oil from the EVOS contaminated shores over a broad geographic range in PWS in the
first months after the Spill. Contamination of low intertidal and subtidal sediments was generally
restricted to sites within the trajectory of the Spill. The bathymetric distribution of oil at
71
contaminated sites in the first summer after the Spill showed that the greatest concentration of
petroleum hydrocarbons was in the low intertidal region. In the subtidal region, petroleum
hydrocarbons exhibiting a concentration patternconsistent with EVO were restricted to shallow
depths (3-20 m). Concentrations of oil at these depths wereprobably rarely, if ever, acutely toxic
to bottom organisms, but effects of the EVOS on shallow subtidal organisms have been observed
by others. In 1990 and 1991, the intertidal and shallow subtidal hydrocarbon concentrations
showing'theEVO-PAH composition patterndeclined and fewer stations showed evidence of
EVO. Petroleum hydrocarbons at depths 240 m were probably from sources other thanEVO. In
the NGOA, a PAH composition patternconsistent with weathered EVO wasfound in intertidal
sediments from Hallo Bay and Katmai Bay and in shallow subtidal sediments from Chugach Bay
and Windy Bay in summer 1989, but the TPAH concentration was low.
12
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71
APPENDIX I. Standard operating procedures for sampling benthic sediments
INTERTIDAL SEDIMENTS
1. Choose an area of intertidal beach having a substrate as homogeneous aspossible with particle
sizes of 2 mm or less. The area must be large enough to accommodate a 30-m transect. Lay the
transect parallel to the water's edgewithin the designated area.
2. Choose eight random distances along the transectfrom a random number table or pocket
calculator.
3. Three samples of substrate will be collected at each station (= transect). Each sample will
represent a composite of eight subsamples, each subsample having been taken at one ofthe eight
randomly selected points. Using a metal core tube and spatula or metal scoop, remove
approximately 10 g of sediment from the upper 2 cm of substrate at one ofthe eight randomly
selected points on the transect and place in a properly cleaned 4 oz jar. Repeat the procedure for
two more jars,collecting IO g of sediment from adjacent patches of substrateand placing it in
each of the twoadditional jars.
4. Repeat the proceduredescribed in 3 for the seven remaining points on the transect.
5 . At one station per site, a sample blank (handled in the same way as thesediment samples
except without receiving any sediment) will be taken.
6 . Label, seal (with custody control seal), and freeze sediment samples and blank as soon as
possible after collection.
7. Proper cleaning procedure for sampling implements and jars.
Sampling implements - All sampling implements will be washed with soap and water, rinsed,
dried, rinsed with methylene chloride, and if not used immediately, wrapped in clean aluminum
foil that has been rinsed with methylene chloride. The cleaning procedure will be performed
before each transect is sampled.
Jars - If sample jars have not come from the supplier cleaned to EPAspecifications, they will be
baked for 4 hours at 440°C or rinsed with methylene chloride. Sample jars will have teflon-lined
lids rinsed with methylene chloride or will be capped with aluminum foil rinsed with methylene
chloride before thelid is replaced after sample collection.
78
SUBTIDAL SEDIMENTS
Diver collected
Sampling will be conducted as described above for intertidal sediments, with the following
modifications.
1. Lids will be closed on sample jars on the surface before divers descend to the bottom to
prevent contamination by petroleum hydrocarbons floating on the surface of the water.
2. Care must be taken to avoid contamination of dive mitts/gloves with petroleum hydrocarbons.
Remote sampling by van Veen grab or Smith-Mclntyre grab.
1. The interior surfaces of the grabmust be clean prior to deployment. The grab will be lowered
to the bottom and activated to enclose a sample of substrate and then retrieved. The surface of
the water will be checked visually for sign of contamination by petroleum hydrocarbons (suchas
an oil sheen) before the grabis lowered or retrieved through it. If any indication of oil is
observed, the vessel will be moved to a visually clean area.
2. When the grab is brought to the surface and placed on deck, care must be taken to avoid
contamination of thesurface of the grab sample with lubricants from the grabsampling equipment
and vessel exhaust. The grab sample will be subsampled with a stainless-steel core tube and
spatula. The location of the subsamples will be determined randomly. Four subsamples will be
taken from each sample and placed in a cleaned 4-02 jar. Three samples will be taken ateach
station. Subsamples of different grabs will be placed in separate jars. Samples will be labeled,
sealed, and frozen as soon as possible after being collected.
3 . Sampling implements and jars will be cleaned as described in the section on intertidal
sediments above.
19
APPENDIX II. Summary of analytical results for those blanks on which hydrocarbon analysis was performed for this study.
Table 11-1.--Percentage of analpa below MDL, mcentration oftotal aromatic Itydmcarbons a d mnmtration of alkanes in three types ofblanks collected in PWS from 1989 to 1991. A dash indicates Uut
a value was not calculated because the surrogate rmvery ofone or more aronmlic or alkane analytes (excluded analytes) fell outside the range 30-150%.
Aromatic
Site
Block Island
Bay of I d e s
Date
Depth
Blank
Type
Catalog
Aromatic
Analytes
Excluded
NO.
NO.
"gg
NO.
Total
< MDL
5.0
Alkana
100
0
a
I00
0
0
100
0
0
IO
0
gig
Water
6478
0
95.5
2.44
0
718190
3
Water
6587
0
50
167.84
7
718190
40
Air
6587
8
7.8189
3
water
6595
0
7/8/89
40
6595
8
9.10.'89
3
water
6698
0
68.2
68.76
0
85.2
64.95
67.90
3
water
6702
0
54.5
161.29
0
70.4
120.73
7'1 1'90
6
wata
6474
0
IO0
0
0
100
0
7 I 1/90
I00
Air
6474
8
0
LOO
0
0
96.3
0
100
0
96.3
0
100
0
0
I00
0
100
0
Ai1
0
Air
6477
8
Chenrga Island
613~90
6
water
6477
0
Eshamy Bay
%
Alkane
Analyles
3
6 '7 ,90
Drier B a y
Alkane
A M l p
Excluded
6/5/90
Bay of Isles 90
Disk Island
< MDL
Total
Aromatics
Analyta
97.7
IO
8.96
0
7 I3189
0
Air
6582
8
6/5/90
6
water
6478
0
7'7490
0
Air
6586
8
717'9~3
6
wa1er
6588
0
95.5
2.76
7
721'90
3
water
6591
O
45.5
197.7
7
7'2 I'90
40
Air
6590
8
0
919'90
6
Water
6585
8
7
7,15189
0
Air
6594
8
0
6/4/90
0
water
6584
0
97.7
97.7
80
1.25
1.03
7
92.6
17.92
0
11.26
86.29
9Z6
It'OZ
ZP'P99
0
988
ZL 6LP
Pf98E
O
E65
Pl'SZP
E68
l0ZZZ
0
Z8'5ZE
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60P
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('96
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962
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0s
APPENDIX 111. Origin and characteristics of contaminated samples
During the course ofthis study it was discovered that 165 ofthe 1335 (12.3%) sediment.
samples analyzed for petroleum hydrocarbons had been contaminated by an extraneous
hydrocarbon source at some time after Technical Services Study #I had taken custody of the
samples. Here we characterize the contaminated samples, present evidence for contamination as
the source ofelevated concentrations of hydrocarbons in the samples, and relate the contaminated
samples to particular analytical catalogs.
Samule Selection and Assignment to Catalogs
Sediment samples were transported to the Geochemical and Environmental Research
Group (GERG) at Texas A&M University for G C M S analysis in several shipments. Samples to
be included in a particular shipment were selected in a two-stage process. First the station where
the samples were collected was specified. Stations were selected based on their location in the
study area and on the nature of existing information on the level of hydrocarbon contamination of
sediments at the station. The sample numbers of the samples to be included in a shipment were
selected from a printed list of samples. One or more sample(s) was selected from each group of
three replicates listed at the stations of interest. A list of samples chosen to be shipped for
analysis was presented to a representative of Technical Services Study #I who would retrieve the
samples from storage in a freezer, assemble them into groups, assign a catalog number to each
sample group, and ship the samples to GERG. Usually several studies would submit lists of
samples to Technical Services Study #I at about the same time. Consequently, a particular
catalog would often contain samples from several studies. Samples from up to three studies were
included with samples from AirNater Study Number 2 in the same catalog sent to GERG.
Identification of Contaminated Cataloss
In spring 1991, we found evidence of spurious contamination in some samples collected in
1990. Indications of sample contamination were manifested as unusually high concentrations of
petroleum hydrocarbons in 165 samples, particularly from reference sites. Most of the suspect
samples were collected at 26 sites in PWS during one cruise in late June and July 1990 (Table 1111). The high concentrations of hydrocarbons in the June/July sediment samples contrasted sharply
with concentrations in sediments from the same stations collected about one month earlier (Fig.
111-I), and with samples collected from the same station at later dates. The contamination also
involved a few samples collected during sampling cruises in PWS in early June (nine samples) and
September (one sample) 1990. The samples were analyzed in December 1990.
The pattern ofcontamination showed close association with particular analytical catalogs
(Fig. 111-2). Five catalogs were judgedcontaminated on the basis of the consistently higher
concentrations of hydrocarbons reported for samples contained within them (see below; Table 1111). In most cases only one of the three replicates collected at a station was contained in a
84
I ’
contaminated catalog. This allowed paired comparisons of hydrocarbon concentrations between
samples from uncontaminated catalogs and those from contaminated catalogs within stations.
Comparisons of the concentration of TPAH (excluding perylene) in sediments revealed
significant differences between replicates contained in contaminated catalogs and those in
uncontaminated catalogs. The within-station TPAH concentration was significantly greater for
samples processed in contaminated catalogs than for those processedin uncontaminated catalogs
(paired 6-test, t = -14.082, d f = 113, P < 0.001; data were log-transformed for test). When
analytical data from all three replicates collected at a station were available for comparison (true
for most stations), the TPAH concentration in the replicate from a contaminated catalog exceeded
the TPAH concentration in at least one ofthe replicates from the uncontaminated catalog(s)
100% (n = 50) and 94% (n = 51) ofthe time for reference and oiled locations, respectively. The
TPAH concentration in the contaminated replicate exceeded that in both replicates from the
uncontaminated catalog(s) 96% and 80% ofthe time for reference and oiled locations,
respectively. Within stations, the replicate(s) from the contaminated catalog contained, on
average, a TPAH concentration 15 times greater than that for the replicates from the
uncontaminated catalog(s). The TPAH concentration of the contaminated replicate exceeded that
of the uncontaminated replicates by at least an order of magnitude at25.4% ofstations. The
magnitude ofthis increase did not differ significantly (Kruskal-Wallis test, P > 0.05) between
oiled (mean multiplication factor (MF), 8.5) and reference (MF, 22.2) locations (Table 111-1).
Evidence from field blanks tended to support the sediment sample data. Twenty-nine
percent of the blanks analyzed in contaminated catalogs showed elevated (> 100 ng/g)
concentrations of TPAH. By comparison, 24% of those blanks that came from stations where
one or more sediment samples were found to contain spuriously high concentrations of TPAH,
but analyzed in uncontaminated catalogues showed elevated concentrations of TPAH (Appendix
11). The mean TPAH concentration in blanks analyzed in contaminated catalogs was 114.4f 46.8
ng/g; i n blanks that came from stations where spurious contamination was observed, but analyzed
in uncontaminated catalogs was 88.6 46.9 ng/g. The blank data contained no evidence that the
elevated concentrations of TPAH in sediment samples analyzed in contaminated catalogs came
from contamination during collection in the field (Appendix 11).
*
Another measure we used to determine the effect of analytical results from contaminated
catalogs on estimates of hydrocarbon concentrations at sampling stations was the varianceof the
estimates when the replicates from a station included samples from contaminated catalogs
compared with the variance at stations when all samples were processed in uncontaminated
catalogs. The CV of themean TPAH concentration at stations where one or more sample(s) were
processed in a contaminated catalog tended to be greater than at stations where all replicates were
processed in uncontaminated catalogs. For example, a CV t 100% was found at 48.6% of
stations in the depth range 0-20 m atreference locations when at least one sample at each station
had been processed in a contaminated catalog. By contrast, when all samples were from
uncontaminated catalogs, a CV 2 100% was found at only 26.5% (averaged over all TPAH
ranges) of the stations (Fig. 9). The difference was even more pronounced when we considered
85
the 40-m depth at reference and oiled locations. A CV z 100% was never found at 40-m stations
where all samples were from uncontaminated catalogs (Fig. 9); whereas, a CV 2 100% was found
at 44.4% of40-m stations where at least one sample at each station had been processed in a
contaminated catalog (Table 111-1).
Our analysis of the results of the hydrocarbon chemistry on the sediment samples collected
in late spring and summer 1990 indicate that many samples were spuriously contaminated with
petroleum hydrocarbons and that the contamination occurred at some time after samples were
assembled into groups and placed in analytical catalogs. No spurious contamination was found in
1989 or 1991. Samples to be analyzed by G C M S were selected without regard to any
differences that may have existed between replicates at the same station. Because thesediment
samples were stored at the AukeBay Laboratory prior to being to sent to GERG, we wereable to
closely monitor the meticulous care with which the security of the samples was ensured. We
observed no evidence of tampering as indicated by broken custody seals. Presumably the same
care was taken at GERG, but we were unable to monitor sample security there. Assignment of
the samples to catalogs was performed by Technical Services Study # I . The catalogs to which
the samples were assigned were unknown to us until we received the analytical results from
GERG. Elevated hydrocarbon concentrations were found in one or (rarely) more of the replicate
samples from 26 sites at reference and oiled locations. When replicates were compared within
stations, the elevated concentrations were associated almost without exception with catalogs
judged contaminated. Hydrocarbon concentrations in samples processed in contaminated catalogs
appeared unrealistically high, especially for reference stations, averaging 15 times greater than
comparable replicates processed in uncontaminated catalogs. Concentrations in samples from
contaminated catalogs were an order of magnitude greater than thosein comparable replicates
from uncontaminated catalogs at hlly one-quarter of the stations affected. Replicate groups that
included samples from contaminated catalogs frequently exhibited greater within-station variance
than groups that contained only samples processed in uncontaminated catalogs. Therefore, we
believe that the patterns of contamination described above could not have resulted from
contamination of sediments during sample collection or storage before shipment of the samples to
GERG. Based on this information the results from the 165 contaminated samples were not used
in evaluating the extent of contamination by EVO of subtidd sediments in PWS in 1990.
86
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374.794
24.0
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171.566
2.5
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147.368
532.082
3.6
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6471
9.0 368.434
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677.449
0.9
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5.644
306.871
54.4
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3.503
142.075
40.6
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33.848
678.919
20.1
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76.876
770.353
10.0
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873.848
127.6
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5.537
384.855
69.5
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27.964
227.048
8.1
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158.130
251.369
1.6
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256.921
1771.506
6.9
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100
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560.023
912.040
1.6
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173.849
490.680
2.8
70.8
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144.554
550.392
87.4
3.8
20
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435.219
776.784
1.8
39.0
40
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583.375
1078.799
1.8
41.6
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294.445
822.966
2.8
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308.320
6
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227.227
343.083
1.5
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350.710
452.698
1.3
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997.015
2.6
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0
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6471
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524.941
4.4
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6474
353.500
1296.890
3.7
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6472
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817.376
45.0
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213.017
19.8
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4.6
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482.660
28.7
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87.5
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6471
121.631
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2.3
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5.4
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3.4
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100
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539.592
7.4
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250.179
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224.931
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3.3
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6474
153.222
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225.849
398.445
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78.732
402.861
5.1
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479.762
1380.265
2.9
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Pon Fidalga
Rocky Bay
Snug Harbor
89
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a i k o f Bay
100
6476
1095.993
2875.018
2.6
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7.773
453,068
58.3
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15.884
173.956
11.0
144.0
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6471
8.147
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260.9
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70.366
345.813
4.9
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40
6471
106.373
247.039
2.3
57.4
100
6471
206.764
543.962
2.6
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6471
6.672
647.137
97.0
181.6
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6471
12.809
98.153
7.7
129.3
6
6471
22.083
268.810
12.2
147.5
20
6471
45.975
452.948
9.8
139.7
40
6471
305.069
1225.736
4.0
94.0
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6471
269.502
625.676
2.3
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Nolthwest Bay
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A
h
m
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0
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8
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20
n
0
80
LB
Figure 111-1. Concentrations of (A) total dibenzothiophenes and (B) phytane in sediments from
combined 0-20-111 stations at reference and oiled sites in June and July 1990. Number of samples
is shown in parentheses. Error bars are 95% confidence intervals.
91
25
~
A
-.
200 I
150 -
200
-
OB
0
PF
40
PF
BI
100
20
Station
Figure 111-2. Concentrations of (A) dibenzothiophene, (B) total dibenzothiophenes, and (C)
phytane in sediments from the intertidal region (0 m) at Olsen Bay (OB), depths of 40 and 100 m
at Port Fidalgo (PF), and 20 m at Bay of Isles (BI). Sediment sampleswere placed in catalogs
(numbers above the bars) for hydrocarbon analysis. Catalogs numbered 6471,6472, and 6474
(solid bars) were considered to be contaminated.
92
APPENDIX IV. Concentrations of hydrocarbon analytes in sediments from all stations studied in
PWS and the Gulf of Alaska, 1989-1991, Numbers in the body of the appendix are the mean and
range of up to three replicates where the number of replicates exceeds one, except for total
aromatic where values are mean, 1.96 x the standard error of the mean. Numbers in parentheses
in the total aromatic row are thenumber of replicates used to calculate the mean total aromatic.
Samples were excluded from the calculation of mean total aromatic if the surrogate recoveriesof
one or more analytes used to calculate total aromatic fell outside the acceptable range.Excluded
from the calculation of total aromatic were concentrationsof the following analytes: C-1
naphthalenes (Clnaph), dimethylnaphthalene (Dimeth), trimethylnaphthalene (Trimeth) and 1methylphenanthrene (Mephenl). “ A indicates that the recovery of the surrogate of theanalyte
fell outside the range 30-150%. A dash indicates that the concentration of the analyte was below
MDL. The MDL for aromatic hydrocarbons was 1 ng/g, and for aliphatic hydrocarbons was I O
ng/g. “ALKANES” is the sum of all alkanes exluding the UCM.
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