gy

in the inner shelf sediments, Beaufort Sea: Prior and

subsequent to petroleum-related industrial developments

A. Sathy Naidu

John J. Goering

John J. Kelley

Principal Investigators

University of Alaska Fairbanks

and

M. Indira Venkatesan

University of California, Los Angeles

FinaiReport

December 2001

OCS Study MMS 2001 -061
CMI contact information

E-mail: cmi@sfos.uaf.edu

Phone: 907.474.7707

Fax: 907.474.7204

Postal: Coastal Marine Institute

School of Fisheries and Ocean Sciences

University of Alaska Fairbanks

Fairbanks, AK 99775-7220

This study was funded in part by the U.S. Department of the Interior, Minerals Management Service

(MMS), through Cooperative Agreement No. 14-35-0001-30661, Task Order No. 14195 and

Cooperative Agreement No. 14-35-01-98-CA-30909, Task Order No. 15167, between the MMS,

Alaska Outer Continental Shelf Region, and the University of Alaska Fairbanks.

The opinions, findings, conclusions, or recommendations expressed in this report or product are those

of the authors and do not necessarily reflect the views of the Minerals Management Service, nor does

mention of trade names or commercial products constitute endorsement of recommendation for use

by the Federal Government.
Institute of Marine Science

University of Alaska Fairbanks

Fairbanks, AK 99775-7220

ffsan@uaf.edu

ffijk@uaf.edu

goeringims.uaf.edu

and

M. Indira venkatesan

Institute of Geophysics and Planetary Physics

University of California

Los Angeles, CA 90095-1567

indira@uda.edu

December 2001

111

Results 7

Discussion 12

Trace element QAJQC 12

Precision and accuracy of sampling and analyses 12

Historical changes in trace elements of the Beaufort Sea nearshore 13

Regional differences in trace element abundance 14

Geochemical partitioning of elements 15

Conclusions 17

Trace Metal Tables 18-32

HYDROCARBON STUDIES 33

Introduction 33

Analytical Methods 33

Glassware 35

Reagents 35

Apparatus 35
iv

References 75
station groups formed by cluster analysis of all the data included in Table 3 29

Table 9. Time-series changes in the mean concentrations of trace elements in mud of the

nearshore region of the Beaufort Sea 30

Table 10. Activities of 210Pb (total), Ra and '37Cs with core depth (cm) in cores 3B and SL 31

Table 11. Mean concentrations of trace metals (jtg/g), Fe (wt %) and organic carbon

(OC, wt %) in muddy sediments of the study area compared with those in muds

from selected circum-arctic shelf regions 32

Table 12. Results of the QAJQC analysis of n-alkanes 52

Table 13. Results of the QAJQC analysis of PAHs 53

Table 14. Distribution (ng/g dry weight) of n-alkanes in gross sediments 54

Table 15. Distribution (ng/g) of PAHs in gross sediments 58

Table 16. Distribution (ng/g) of triterpenoids in gross sediments 67

V
vi
petroleum characteristics 40

Figure 10. TriteTpenoid distribution from sediments exhibiting a petroleum signature and an oil 41

Figure 11. Representative sterane distribution from sediments not exhibiting

petroleum characteristics 42

Figure 12. Sterane distribution from sediments exhibiting a petroleum signature,

a pristine sediment and an oil 43

Figure 13. Relative abundance of naphthalene and phenanthrene/anthracene homologs

in Beaufort Sea sediments 44

Figure 14. Dendrogram showing station groups formed by group averaging cluster analysis

of sediment hydrocarbon concentrations (14a) and location of group members on

study area map (14b) 45

Figure 15. Station plots of the results from stepwise multiple discriminant analysis 46

VI'

regional variations in natural terrestrial or industrial inputs of Hg, the methylation process, sediment

granulometry, or all three.

The molecular markers investigated in the sediments are of mixed marine and terrigenous origin.

Generally, the resolved n-alkanes are less and the total PAHS more than those found by others in the

same region a decade ago. The PAH assemblage in the surface sediments is different from that found

in Prudhoc Bay crude oil but is very similar to that observed in coastal peat and North Slope fluvial

sediments. The triterpenoid and sterane profiles reinforce the biogenic rather than the petrogenic origin

of major portions of the hydrocarbons. Only in isolated cases is a petroleum signature documented

by the presence of thermally mature hopanes and steranes in small amounts. The fingerprint of

triterpanes/steranes rather than some internal ratio parameters in the current samples helps to clearly

distinguish biogenic inputs from petrogenic sources. The composition of triterpenoids/steranes should

serve as an important diagnostic tool in future monitoring studies that follow subtle changes in

hydrocarbon inputs to the study region, especially from oil-related activities.

In summary, the environment of the study area has remained clean as far as trace metals and hydrocarbons

are concerned in spite of recent oil-related indusirial activities. Results of our investigations should serve

as a baseline for future monitoring of trace metal and hydrocarbon contamination within the study area.

1
Krantzberg et al. 2000}. For the Alaskan high arctic seas, little mformation is available on bioaccumulation of contaminants and the geochemical pathways of contaminants involving sediments. However,

several papers have been published on the concentrations of trace metals in sediments of the above region

[Sweeney and Naidu 1989; Crecelius et al. 1991; Naidu et al. 1997; Valette-Silver et al. 1999}.

Possible anthropogemc sources in the Alaskan Beaufort Sea, for example, could be industrial activities

such as the Endicott and Prudhoe Bay petroleum projects; the ongoing, projected or potential oil prospects

such as North Star, Liberty, Point Thomson, Badami, and Alpine; Outer Continental Shelf (OCS) oil and

gas development; or offshore dredging for gravel. Potential trace metal contaminants concerned with the

above projects are V, Ni, and a variety of hydrocarbons as constituents of crude oil; Cr, Cu, Zn, Ni, and

Ba (in barites) associated with drilling fluids; and Pb, Cd, Hg, and As as products of municipal and

industrial effluents. Further, several trace metals associated with subsurface sediment interstitial fluids

can be mobilized subsequent to dredging operations and eventually reaccumulate on surface sediments.

It is also possible that there have been incidental or chronic anthropogenic discharges of crude or

industrial petroleum products during the past three decades resulting from the various oil exploration,

developmental and exploitation activities. Prior to this study one could only speculate whether three

decades of ongomg activities would lead to significant trace metal and hydrocarbon contamination of

sediments in the Beaufort Sea nearshore.

Considering the potential hazards of the above metal contaminants on the health of marine organisms

in the Beaufort Sea, a study was mitiated to determine the current concentrations and temporal changes

in V, Cr, Cu, Ni, Zn, As, Cd, Pb, Ba, total and methyl Hg (THg and MeHg) and a selected group of

hydrocarbons in sediment samples from the nearshore Alaskan Beaufort Sea. The study's primary

2
aromatic hydrocarbons in gross (or bulk) sediments of the nearshore Alaskan Beaufort Sea, and to assess

if any of the changes are related to recent industrial development within the study area.

Sampling Methods

Triplicate surficial sediment samples from 21 stations and sediment core samples from two stations in

the nearshore Beaufort Sea area located within the ColvilleCanning Delta region (Figure 1, Table 1)

were collected in September 1997, using a Kynar-coated van Veen grab sampler and a gravity/Haps corer,

respectively. Of the 21 stations, 20 were at the same locations as those occupied during the Beaufort Sea

Monitoring Program (BSMP) by Battelle in 1984-1989 [Crecelius et al. 1991]. Such coverage has

provided representative sediment samples for contaminant monitoring of all major oil prospect areas in

the North Slope region of Alaska (e.g., Libeity, Alpine, Badami, Point Thomson and North Star) that

have been slated for oil development in the next four years. The purpose of collecting the triplicate

samples at each station was to check station sampling precision.

3
71° 30' 71° 00' 70° 30' 70° 00' 69° 30' 153° 

Figure 1. Study area sho

00 25 
historical changes of the contaminants in sediments by investigating stratigraphic

variations in trace metal data available for the past two hundred years from the

21°Pb-based dated sediment cores, and from comparison of time-series decadal data

including those from the present study (1997) and those collected in 1977 and 1986

[Feder et al. 1976; Naidu 1982; Sweeney and Naidu 1983; Sweeney 1984; Boebm et

al. 1987; Sweeney and Naidu 1989; Crecelius et al. 1991], and by comparing

hydrocarbon data collected during the past 25 years [Peake et al. 1972; Wong et al.

1976; Shaw et al. 1979; Venkatesan and Kaplan 1982; Steinhauer and Boehm 1992]

with those of the present study;

partial and multiple correlation coefficients [after Shine et al. 1995] to understand

interanalyte relationships;

if there is a "downstream" concentration gradient in the contaminants from potential

sources;

cluster analysis to identify grouping of stations based on analyte levels on a regional

or geographic basis;

stepwise multiple discriminant analysis of the chemical data to correlate station

group separation by cluster analysis with sediment variables. These analyses

were conducted to gain an understanding of geochemical partitioning, sources of

contaminants and extent of contamination within the study area since industrial

development began; and

level of significance of the time-series differences in V and Ba using Student's t-test.

5
fraction was dried at 60°C, and then powdered using an agate mortar and pestle. It is possible that during

the process of separating the mud fraction by wet sieving the gross sediment may have hydrolyzed some

metals, or desorbed them from the sediment (or both). If this occurred then some metal portions were

thus lost to the water that was subsequently siphoned and discarded. It is assumed that the fraction of the

metals thus lost, and excluded from the analysis, was negligible. This is based on earlier results, within

the study area, of elemental analysis on sequential extracts of sediments by various chemicals [Sweeney

1984]. At the Frontier Geosciences laboratory a 0.5-g portion of the mud powder was dissolved in a

Teflon bomb by digesting it in a microwave oven in high-purity, concentrated HFHNO3 acid.

Subsequently, the dried residue of the digest was dissolved in warm 10% HNO3 and made up to 20 ml

with DDW. From this solution, the concentrations of V, Cr, Cu, Ni, Zn, Cd, Pb and Ba were analyzed.

A separate 0.1-g powder sample was dissolved at the IMS laboratory by the LiBO2 fusion-11NO3 acid

technique [Medlin et al. 1969] and the solution was analyzed for Fe and Mn at Northern Testing

Laboratories. The purpose of the Fe and Mn analyses was to gain insight into the possible geochemical

role of the oxyhydroxides of these two elements in scavenging trace metals. The above ten elements

were analyzed using either a direct injection Zeeman graphite furnace atomic absorption spectrometer

(GF-AAS, Hitachi model Z-41 10 or Z-5000) or an inductively coupled plastnalmass spectrometer

(ICP/MS, Perkin-Elmer model Elan-6000). In a separate split of the mud fraction As was analyzed by

Excaliber automated hydride generation atomic fluorescence spectrometry, using EPA method 1632.

The analyses of total Hg and the relatively more toxic methyl Hg [Bloom 1992; ATSDR 1993; Phillips

et al. 1997] were on gross sediments rather than on the mud fraction as was done for the rest of the

metals. The reason for this is that significant portions of the volatile Hg could be lost during the wet

sieving process. The analysis of Thg was by cold vapor atomic absorption spectrometry (CV-AAS). The

6
Because sediment grain size, total organic matter (OM), and carbonate generally control the trace metal

concentrations of sediment [Loring 1991; Daskalaskis and O'Connor 1995; Naidu et al. 1997], these three

variables were also analyzed. The analyses were conducted at the Institute of Marine Science in portions

of the same sediment mud fraction and gross sediment that were taken for analyses of trace metals, Hg

and hydrocarbons, respectively. The OM and carbonate contents were estimated using the stepwise loss in

powder weight subsequent to ignition at 550°C/hr and 1000°C/hr, respectively [Dean 1974]. The analyses

for gravel, sand, silt, and clay contents in gross sediments and the percentages of silt and clay in the mud

fraction were by the conventional sievepipette method [Folk 1968].

Results

The results of the analysis for QA/QC on the reference sediments (MESS-2, NIST-2709) and selected

representative mud samples from the study area for trace metals, with special reference to analytical

accuracy and precision as applicable, are shown in Table 2.

Table 3 shows the concentrations of V, Cr, Cu, Ni, Zn, As, Cd, Pb, Ba, silt, clay, carbonate and total

organic matter on a thy weight basis for the mud fraction, and MeHg on a wet weight basis of gross

sediments for the replicate samples at each of the 21 stations of the study area. The table also illustrates

the mean (geometric) concentrations and the coefficient of variations (CV) of the variables for each of the

stations. Additionally, the concentrations of T}lg (wet weight), and Fe and Mn (dry weight) are provided

for a representative sample of gross sediment and mud, respectively, for each station. The grand mean

7
mud for 1977]). By comparing elemental data on a specific size class, it is assumed that the elemental

concentrations are normalized to the sediment granulometry [Loring 1991].

Table 10 includes the specific activities of total 21% in gross sediments separated at 1-cm intervals

from the core tops of cores 3B and SL, and the activities of 6R.a and '37Cs at selected core intervals. A

comparison of the mean concentrations of a suite of trace metals in muds of the study area with the mean

concentrations of elements in muddy sediments of selected circum-arctic shelves is shown in Table 11.

8
EUQ. MeHg (nWg) 0.1 0.26 ol I 0.1 024- 6- 8- .c 10- Q. 12- 14- 16- 18- 20- 0.4 

Figure 2. Stratigraph

weight in 
9 20-

Figure 3. Stratigraphic variations in the concentration of MeHg in cores 3B and SL.

(ng/g wet weight in gross sediments)

10
7r 00

7O 30

7O 00

69 30

Figure 4. Dendrogram showing station groups formed by group averaging cluster analysis

of sediment trace metal concentrations (4a) and location of group members on

study area map (4b).

11
Figure 5. Station plots of the results from stepwise multiple discriminant analysis. Groupmgs are

determined by cluster analysis.

Discussion

Trace element QNQC

As mentioned earlier, Frontier Geosciences was the subcontractor for the trace element analysis on

sediments. Frontier Geosciences participated in the interlaboratoiy exercise conducted in 1997 by NRC

for NOAAJ1 1 to ensure that the QAJQC requirements for the analysis were met (Scott Willie, National

Research Council of Canada, personal communication; see also Table 2). The analytical precision relating

to the mdividual elements mcluded in this study was excellent. Consequently, trace element data

presented in this report can be considered to be of high quality.

Precision and accuracy of sampling and analyses

Results of the analyses of various parameters in replicate samples from a specific station (Table 3)

provide the within station variability for individual analytes in the study &ea. The results show that for

some stations there are significant variabilities (relatively high % CV) in a few analytes (especially

MeHg). The cases with high variability at any one station and a specific analyte are probably due to

large differences in the contents of silt, clay and/or OM between the replicate samples and, therefore, are

12
elements, including V andBa.

Some difficulty was encountered in attempting to match stratigraphic trends in trace elements with the

elemental trends suggested on the decadal basis (Table 9). The difficulty stems from an inability to

establish a firm geochronology for the two cores examined. Attempts to date the cores based on the

210Pb and '37Cs methods have failed because the activities of the two radionucides were extremely low

throughout the cores. For example, the activity of total 210Pb was typically between 1-2 dpm/g, which is

close to the activity of the radionucide's parent, Ra, with yields of excess 210Pb (210Pb) generally less

than 1 dpm (Table 10). Additionally, no significant down-core exponential decreases in the 210Pb were

noted in either of the cores. The activity of '37Cs was generally below 200 dpm/kg in core 3B and below

detection levels in core SL. The '"Cs dating method is based primarily on detection of a well-defined

spike, with highest activity generally noted in a subsurface section of a core and corresponding to the

years 1961-1964, which marked the maximum injection of the radionuclide into the atmosphere from

nuclear weapon testing. However, this spike was not identified in core 3B. Because of these constraining

factors, attempts to define the geochronology of the two cores failed. Despite the relatively very low

activity (<2 dpm/g) in 210Pb that is generally reported in sediments of the continental shelf region of the

Alaskan Arctic [Weiss and Naidu 1986; Baskaran and Naidu 1995; Naidu et al. 1999], it has nonetheless

been possible to use the radionuclide to estimate the sediment accumulation rates for selected sites within

the study area (e.g., Simpson Lagoon, located at the western end of the area [Weiss and Naidu 1986]).

The mean linear and mass accumulation rates (LAR and MAR respectively) for three sites within

Simpson Lagoon are 0.61 cm/yr and 0.77 g/cm2/yr, respectively [Weiss and Naidu 1986]. The three sites

are located adjacent to where core SL was collected. Assuming that the above mean LAR is applicable

generally to the entire area of our investigation (as the sediment depositional setting is comparable

throughout) and that there has been a constant rate of sedimentation, the times of elemental changes in

13
y gpy (, 

several millions of barrels), because such a large-scale discharge has not occurred. The exact source,

mode and mechanics of transport and deposition of the two recent contaminants into the sediments

of the nearshore Beaulort Sea are yet to be resolved. In spite of the trends exhibited in the increasing

concentrations of V and Ba in the muds since the start of intensified industiial activities in the North

Slope, the levels of these two elements throughout the study area are in ranges reported for unpolluted

marine nearshore sediments, especially within the circum-arctic shelf regions (Table 11). The study area

has remained a relatively clean environment as far as the elements analyzed are concerned despite the

industrialization during the past 25 years.

Regional differences in trace element abundance

As mentioned earlier, the cluster analysis dendrogram shows the presence of two predominant cluster

station groups in the study area, I and II, based on statistical analysis of all physical and inorganic

chemical data gathered (Figure 4). Most of the Group I stations are clustered in Prudhoe Bay and its

vicinity, whereas the Group II stations are located in the lagoonal regions east and west of Pnidhoe Bay.

Also as shown in Figure 5 and Table 8, the stepwise multiple discnniinant analysis (SMDA) indicates

that station grouping is defined by significantly lower concentrations of MeHg in gross sediments of

Group I (mean: 0.058 ng/g wet wt) than in Group II (mean: 0.164 ng/g wet wt). Although the THg and

Mn abundance were not included in the SMDA because of the limited number of samples analyzed (i.e.,

one analysis from each of the nine stations from each of the two groups), it is apparent that differences in

the mean concentrations in Mn and THg also exist between the two station groups. In Group I, the mean

concentrations of THg and Mn are 18.22 ng/g and 678 ig/g, respectively, whereas in Group II the mean

14
The single and multiple correlation coefficient analyses (Tables 5 and 6) provide insight into the

geochemical partitioning of the elements analyzed in this study. As suggested by the high levels of

positive correlations (Table 5), total organic matter and the clay size particles (<4 jim size) in our samples

have major roles in the partitioning of most elements. Table 5 also demonstrates that all the elements

except Cd, Fe, Mn, MeHg and Thg are, at least to an extent, partitioned in the clay size, presumably

in the adsorbed phase. Likewise, OM content also seems to be a factor (as a possible chelating agent

forming ligands) on the abundance of all trace metals except Cd, Ba, MeHg and Thg. Results of

subsequent multiple correlation coefficient analysis (Table 6) helped clarify that the amount of OM is the

more dominant factor than the amount of clay in partitioning of Cu, Ni, Zn, As and Mn, whereas Cd and

Ba appear to be partitioned in a phase(s) other than OM and clay. The lack of significant covariance

between OM and Thg and MeHg (Table 5) was surprising, as organic matter in sediments generally

serves as an important scavenger of Hg [Gagnon et al. 1997]. It is suggested that further investigations

similar to those conducted in Simpson Lagoon by Sweeney [1984] and Sweeney and Naidu [1989], using

sequential chemical extraction of sediments, will assist in better understanding the geochemical

partitioning of the elements.

The study demonstrates a net increase in concentrations of MeHg in gross sediments down the two cores

investigated (Figure 3, Tables 4 and 7). It would seem that the stratigraphic trends in Thg or MeHg in

marine regions vary widely in the world. For example, in the nearshore deep water sediments in the

Greenland ords a net up-core increase in Thg is reported [Asmund and Nielsen 2000]. The MeHg

profiles shown in our core samples generally run parallel to those repoited by Gagnon et al. [1997] for

the Saguenay Fjord, Quebec and for Thg in Lavaca Bay, Texas [Bloom et al. 1999]. However, trends for

MeHg in the cores in our study do not completely match those shown in Lavaca Bay cores. In the latter,

15
The finding of increased levels of the relatively more toxic MeHg in subsurface deeper sediments of cores

in the study area could have potential environmental implications, especially if the MeHg concentrations

were to increase significantly in the future because of elevated anthropogenic discharge. It is possible that

some of the subsurface MeHg could be mobilized into overlying water subsequent to resuspension of

bottom sediments by any of the several natural or anthropogemc sediment reworking processes (i.e., ice

gouging, stonn-induced wave-current action, dredging). Any particle-held MeHg thus mobilized during

the early freeze-up period could be encapsulated in sea ice. Several possible mechanisms have been

suggested for sediment entrainment in waters of the Beaufort Sea inner shelf [Barnes et al. 1982; Naidu

et al. 1984]. If a large flux of MeHg concentrated in sea ice were to be released suddenly into the water

during spring break up, some of it could be sequestered by primary producers and passed ultimately into

the food chain with possible deleterious effects to higher trophic levels.

16
deleterious affects to the food chain.

Cluster analysis of all data has identified two major station cluster groups. Group I

stations are located within Pnidhoe Bay and its vicinity and Group LI stations are east

and west of this area. The delineation of the two groups is determined by relatively

higher concentrations of MeHg in Group LI. These differences are either due to regional

differences in the natural terrigenous inputs and methylation process of Hg, or to

significantly higher concentrations of mud in Group II stations.

Single and multiple correlation coefficient analyses of all data suggest that most of the

V, Cu, Ni, Zn, As, Pb and Mn in mud are chelated (ligand formation) with organic

matter, whereas some of the V is also adsorbed on clays.

Although increasing concentrations in V and Ba in mud have been detected with time

during the past 30 years, the levels of these elements are below or comparable to the

values reported for unpolluted nearshore marine sediments.

In summary, the environment of the study area has remained clean as far as trace metals are concerned

despite the recent oil-related industrial activities. Results of these investigations should serve as a baseline

for future monitoring of trace metal contamination within the study area.

17
()

Longitude .(W)

Pepui(rn)

Water.(%)

Phase I/li

Station

Date

.L4itud..(N).

Long..de (YV)

Depth(m)

'!ter.).. Phase I/Il

147° 05.5'

6.2

36.0

TM+HC/

0.86 16.56

0.74 17.46

0.13 2.35

3B°

5Se p97

70° 17.9'

147° 02.3'

4.2

36.4

TM/FfC

1 0.00 20.61

2 0.00 23.58

3 0.00 24.22

Mean 0.00 22.80

SD 0.00 1.93

. 80.67 .3.59

2

3 30.82 16.68

Mean 55.75 10.14

SD 35.25 9.26

82.2

2 0.00 84.26

3 0.00 83.84

Mean 0.00 83.44 .SI) . 0.00 1.08

18

.

62.53 20.06 82.59

61.07 20.72 81.79

1.63 1.38 2.40

53.06 26.43 79.49

57.07 19.13 76.20

51.31 24.47 75.78

53.81 23.34 77.16

2.95 3.78 2.03

...04 .9.70 ..574

21.21 31.29 52.50

13.63 20.50 34.12

10.73 15.27 25.99

..12..5 ..5.20-17.78

11.21 4.53 15.74

12.22 3.94 16.16

12.00 4.56 16.56

0.71 0.63 1.08

Station

Date

4A

5Sep97

Latitude(N) 70° 18.5'

Long.tuç.! .(W) 147° 40.2'

pepth (m) 4.5

Water(%) 19.5

Phase I/li TM+FfC/

Station WPB

Date lSep7

Latitude(N) 70° 20.6'

Lcng!tude...(W) 14.8° 23.2'

P..th(m) 2.5

Water(%) 232

Phase I/il TM+FfC/
0.00

2 0.00

3 0.00

Mean 0.00

SD 0.00

0.79 49.46 49.75 99.21

5.06 58.57 36.37 94.94

2.99 49.18 47.82 97.00

2.95 52.40 44.65 97.05

2.14 5.34 : 1 2.14

1 0.00 50.79 1 38.22 10.98 49.20

2 0.00 . 50.62 . 39.93 . 9.45 49.38

3 . 0.00 63.40 29.66 6.94 36.60

Mean 1 0.00 54.94 35.94 9.12 45.06

SD 0.00 - 7.33 5.50 2.04 7.33

..0.9081.47 .14.72 381 18.53

2 0.00 83.04 20.83 1.85 22.68

3 0.00 73.17 20.35 6.48 26.83

Mean 0.00 79.23 18.63 4.05 22.68

SD 0.00 4.33 2.77 1.90 3.39

19

Station 5F

Date Sep97

Latitude (N) 70°26.5'

Longktude(W) .14849.6

Depth(m) 1.5

Water(%) 25.1

Phase i/il TM+HC/

Station SG

Date 4Sep97

Latitude .(N) 70°29.3'

LP9IK!de (W) 1480 02.6'

9.3

Water (%) 19.2

Phase i/il /TM

Station

Date

5A

4Sep97

La de (N) 70° 29.7'

1480 46.0'

epth(rn) 11.4

W1er(%).. 564

Phase I/li /TM

() 

Phase i/il TM/HC
Mean

SD

0.00 77.57 10.89 0.00

0.00 2 0.00 3 0.00

Mean 0.00

SD 0.00

0.00 2 0.00 3 0.00

Mean 0.00

SD 0.00

20

Phase i/il TM/HC

Station 60

Date 3Sep97-

Latitude 70° 44.9'

Long.tude .(W) 150° 28.5'

p9pth (m 18.4

Wter(%) 32.5

Phase i/il /TPA

16.88 : 67.36 . 15.76 83.12

50.72 40.32 8.95 49.27

18.01 63.22 18.77 81.99

28.54 56.97 14.49 71.46

15.69 11.89 4.11 15.70

5.25 72.25 22.50 94.75

5.03 73.00 21.97 94.97

8.18 72.87 18.96 91.83

6.15 72.71 21.14 93.85

1.44 0.33 1.56 1.43

Station 6G

Date 2Sep97

I atitude .(N) 70° 31 3'

gitu 149° 53.9'

Depth(m) 2.1

Water (%) 37.1

Phase i/il /TM

Station 7E

Date 3Sep97.

Latitude (N) 70° 436'

Lçgitude (W) 152° 04.4'

p9pt!1(m.. 3.3

ter.(%) 48.0

Phase i/il /TM
Table 2. Results of analysis f

and IAEA-356 refe

Sam Ic M

ng!

Blank-I Blank-2 B.ank-3 Blank-4 

Blank-5 

Blank-6 Mean SD Estimated MDL MESS-2 Rep 1 MESS-2 Rep2 MESS-2 Rep3 Mean SD Certified Range NIST-2709 Certified Range 

EA-356 Rep 

IAEA-356 Rep 2 Mean SD Certified Range 3B/22+1047ng/g 

..% Recovery ,,..3B12-2 + 1.084 ng/g 

%Recovery 1RPD(%) 5(10)/3 + 1000 pg/g %Recovery 

.5(10)/3 + 1000 pglg 

% Recovery RPD(%) SL/1 + 0 970 ng/g % Recovery 

Sill + 0.944 ng/g 

....%Recovery 

RPD(%) 
sapm ie M

ng

4A/1 Rep I 4A/1 Rep2 

Mean RPD (%) 

PB/I Rep I 

,WPB/1 Rep2 

Mean 

RPD (%) 

6C/lRepl /1Rep2 

Mean RPD (%) 

SL/1 RepI SL/1 Rep 2 Mean RPD (%) Spike Level 3B..2-2 MS % Recovery Spike Level 

3B/2-2 MS 

% Recovery 

RPD (%) 

Spike Level 3B/10-10 MS % Recovery 

Spike Level 

3B/10-10 MS 

Recovery 

RPD(%) Spike Level 

WPB/1 MS 

%Recovery Spike Level, 

,WPB/1 MSD 

% Recovery RPD(%) MSA 

*Anomalous data RPD (%) 
Table 3. Chemical and granu

calculated based o

per dry weight on 

Station! Sample (1⁄4) 

OM:C

Phase 2E/1 7.0 

2E/2 9.1 2E/3 7.9 

Mean 8.0 CV% 13.34 

2F/1 2F/2 

2F/3 

Mean CV% . 

3A/1 6.1 3A/2 3A/3 4.8 

8.0 

Mean 5.8 CV% 13.07 

3B/1 3B/2 .2 

8.7 

38/3 7.5 

Mean 8.8 

' 

CV% 9.44 

4A/1 4A/2 8.9 '7

8.8 

Mean 7.7 E CV% 21.30 :1

'vPBIi 8.8 '10WPB/2 6.5 1WPB/3 Mean CV% 8.8 

8.0 1

16.44 1

5(1)/I 8.5 1

5(1)/2 8,2 15(1)13 

Mean CV% 8.3 1

2.46 
Station! OM C

Sample (%) 

5(5)/i 5.3 15(5)/2 52 I5(5)/3 5.6 

Mean 5.4 1CV% 3.24 1

5(1,9)/i 6.4 15(10)12 7.9 15(IÔ)13 6.7 1

Mean 7.0 1CV% 11.36 

SF11 5.0 5F/2 ,,,5F13 5.2 

5.7 

Mean 5.3 CV% 7.23 

SIJI 5.4 SLJ2 5.8 

,,SL/3 3.6 1

Mean 4.9 CV% 24.09 1

6B/1 5.7 ,16B/2 6.486B/3 7.7 

Mean 6.6 CV% 15.12 

6C11 7.4 6c12 8.6 46c/3 7.4 2

Mean 7.8 ' CV% 8.94 '36

Ph... ii 10/1 6.0 4

10/2 6.2 ID/3 5.9 4

Mean 6.0 4CV% 2.68 4

5(Y1 5(2)/2 9.4 1

8.8 

5(2)13 9.2 

Mean 9.1 CV% 3.48 1
Station! Sample OM(%) C

Phasell 5N1 5A/2 6.8 6.2 

5N3 7.3 

Mean 6.8 CV% 8.17 1

5G/1 5G/2 5G/3 4.0 3.6 6.1 

.......Mean CV% 29.29 4,6.9

1

6N1 6A/2 5.2 4.3 6A/3 4.7 

Mean 4.8 CV% 9.80 

60/1 8.1 

..6D/2 6.9 

60/3 7.8 

Mean 7.6 CV% 8.26 

6G/1 6.0 6G/2 5.0 6G/3 8.0 

Mean ........5.6 CV% 10.35 

7E/2 7E13 Mean CV% 4.7 4.5 4.9 4.7 3.77 . 

L 

Mean CV% 23.27 6.57

3

N 58 
26

15-16 0388 980 497 230 336 849 91 0.289 106 4708

17-18 0300 1030 471 241 363 846 82 0228 96 4359

19-20 0.285 1070 529 24 1 366 858 8 3 0209 109 494 8
Table 6. Multiple and partial correlation coefficients for regression of sediment

metal contents against organic matter, clay and iron contents.

ns - not significant (p>O.O5)

27

Metal

Partial Correlation Coefficients Multipte Correlation

Coefficient (R2) rXCI8Y,OMF. r01

MeHg ns ns ns 0.1407

Thg ns ns ns 0.0933

V 0.51 37 0.4937 ns 0.6892

Cr ns ns ns 0.4379

Cu 0.4796 ns ns 0.5229

Ni 0.4900 ns ns 0.5947

Zn 0.5020 ns Us 0.4837

As 0.5369 ns ns 0.4766

Cd ns ns ns 0.0686

Pb ns ns ns 0.4894

Ba ns ns ns 0.2876

Mn 0.6529 ns ns 0.5411
28

As

Cd

Pb

Ba

-0.670.58

077

- 076

072

084

0.65

-058
29

Stats

Columns: Predicted classifications

G roup Percent

COIThC

g.1:1

= g.2:2, =

g_3:3

p = 33333

gjl:1 100.0000 2 0 0

g_2:2 100.0000 0 9 0

g_3:3 100.0000 0 0 9

Total 100.000 2 9 9

Statistica

Discriminant

Stats

Standardized Coefficients

for Canonical Variables

Variable Root I Root 2

MeHg -1.54958 .294932

CO3 -1.33190 -.953473

Mn .99230 -.057311

Cd .96229 .248501

Eigenvatue 16.42408 2.570731

Cumulative

properties .86466 1.000000
aSW, [1984], Sweeney and Naidu [1989]

et al. [1991] and Boehm et aL [1987]

CNidu etal. [1999]

30

AB46 EPson Lagoon

x 50 10 13 32 09 9

AB68 Elson Lagoon

x 77 19 24 61 05 14
bd - below detection

31

9 1.56±0.11
Table 11. Mean concentr

compared wit

'Naiduetal. (1997] Esnough [1996] 

8h&t n 

Chukchi Sea8 12SD Beaufort Seab 12 SD Beaufort Seac 13SD Beaufort Sead 62 

(this study) SD 

Pechora Sea8 40SD 

Kara Sea8 36SD l(am Sea 16 SD 

Svalbard8 15 SD E. 10SD 

W. 22SD W. Baffin Bay" 

E. Siberian sed 24SD Laptev Sear 11SD Laptev Sea1 10SD 
and gas development in the region.

Analytical Methods

Surficial sediments from 20 stations (Figure 6) of the Beaufort Sea nearshore were sampled in 1997 for

hydrocarbon analyses. Organically clean I-CHEM jars were used for the samples. The sediments were

frozen, stored and shipped to the University of California at Los Angeles (UCLA) and kept frozen until

analyzed. During the first year (1997-98) of the project, 21 sediment samples were extracted with organic

solvents and processed; the samples consisted of triplicates from seven stations. In the second year

(1998-99), 18 sediment samples from 13 stations including one duplicate and two triplicates were

analyzed. Samples from both years were analyzed, adopting the same methodology as described below.

The wet sediments were spiked with the following surrogates: deuterated n-alkanes (for n-alkanes)

and hexamethylbenzene, dodecylbenzene and deuterated terphenyl (for PAHs) before extraction with

methanol and then with methylene chloride using a homogenizer. The extracts were concentrated in a

rotary evaporator to 2 ml and, after elemental sulfur removal, were divided into two parts. One half was

run through a silica column for isolating the saturated fraction and the other half through a silica/alumina

column to recover the aromatic fraction. The details of extraction and silica and silica/alumina colunm

chromatography are discussed in Venkatesan et al. [1987] and Venkatesan [1994]. Following

fractionation, the samples were analyzed using GC/FID and GC/MS.

Each batch of field samples was accompanied by procedure blank analysis and NIST reference sediment

and matrix spike samples. Only reagent grade chemicals were used and necessary pre-cleaning of all

reagents was performed as described below.

33
71° 30' 71° 00' 70° 30' 70° 00' 69° 30' 0 

0 25 

I I 

Figure 6. Study area sho
Precautions: To prevent inter-contamination of samples, the same glassware and syringe stayed with

a given sample throughout the processing. Separate, clearly labeled micro-syringes were dedicated

exclusively for designated surrogate or standard solutions.

Quality assurance/Quality control measures: For QA/QC measures, control samples were processed

along with field samples following an identical protocol. A procedure blank was run with every sample

set. Acceptable blank levels were below 2 x MDL. If the level of any interfering target compound

exceeded this limit, samples in that batch were re-extracted and reprocessed. A matrix spike was run

with target analytes spiked at the level of 10 x MDL. Surrogate spikes (deuterated alkanes for the

saturated fraction and hexamethylbenzene, dodecylbenzene and terphenyl for PAIl fractions) at the

level of 10 x MDL were used in evely sample.

The sediment reference material (NIST SRM #1941) with certified aromatic concentrations was analyzed

to establish control reference data for the working protocol.

UCLA produced acceptable PAIl data conforming to the consensus values generated by the abovedescribed methodology in the inter-laboratory exercises conducted by NIST in 1992 and in 1999. The

relatively low values reported for acenaphthylene and l,6,7-triinethylnaphthalene in the 1999 interlaboratory exercise data set were due to the very low and unpredictable recovery of these compounds

from the SPI which was newly-installed in the GC/MS just before the 1999 inter-laboratory exercise.

However, all of the sediment from this project and the 1992 inter-laboratory exercise samples had been

analyzed previously with a Varian Grob injector which did not have this problem. In summary, the

35
calibration standard (10 ng/&l) was run to verify the response for PAHs relative to internal standards. The

daily response factor for each analyte was compared to the initial calibration curve. Analyses would

proceed only if the average daily response factor for the analyte fell within 10-15% of the calibration

curve. If it exceeded 20% of the calibration curve, a five-point calibration was repeated for the analyte in

question prior to sample analysis.

The target compounds were identified quantitatively based on relative retention time (RR1') falling within

an acceptable window. The characteristic masses of each analyte should maximize in the same or within

one scan of each other. The retention time should fall within ±12 s (peak width at half height x 3.5) of

the retention time of the authentic standard. The mass spectrometer was tuned to perfluorotributylamine

(PFTBA) criteria established by the manufacturer. The relative peak heights of the primary ion and

secondary ion masses were examined for confirming the identity of the compound.

Results

Results of the QA/QC analysis on n-alkanes are listed in Table 12 and QA/QC results for PAHs &e in

Table 13. The distributions of the n-alkanes, PAHs, triterpenoids and steroids in the gross sediments are

presented in Tables 14, 15, 16 and 17, respectively. In these tables of quantitative data, analytical values

below the MDL are not included in the summation. Total alkanes comprise from Cio to C. All parent

PAHs, including dibenzothiophene and perylene and all alkylated PAHs listed in the table were summed.

The alkanes and PAH values have been corrected for recovery based on the values obtained from the

average matiix spike data. Representative gas chromatograms of the saturated hydrocarbon fraction

in sediments, without and with petroleum characteristics are shown in Figures 7 and 8, respectively.

36
604020201040402010 6Df1 r 5(6)11 

Figure 7. Represent

characteri

30 20 30 20 
a a a a - s$-g

Figure 8. Representative gas chromatograms of the saturated hydrocarbon

fraction from sediments exhibiting petroleum characteristics.

38

0 10 50 50 4 50 50 70 50
39
100.0

191 -

Figure 9. Representative triterpenoid distribution from sediments not exhibiting

petroleum characteristics.

40

618

191.057

± 0.500
Oil Sample 'C'

(1

4443

C')

4692

4000

191.057

* 0.500

1340

191.057

* 0.500

Figure 10. Triterpenoid distribution from sediments exhibiting a petroleum signature and an oil.

41
1 D12

Si

64

S2

400Q 4054

j

Figure 11. Representative sterane distribution from sediments not exhibiting petroleum

characteristics.

42

S13

4315 4379

S15

217.065

± 0.500

4423 27

100.0 -

217 -

S4

4154
100.0 -

217 -

Oil Sample 'C'

Si

60

S2

3q97 4(6

A1 AtM',it

4148

S4

S3

S7

S12

S9

Sb

Si i

4372

S14 Si5

4474

I1*

136

217.065

± 0.500

Figure 12. Sterane distribution from sediments exhibiting a petroleum signature, a pristine

sediment and an oil.

43
Relative Abundance 0-4 - NAP 4..j I $ I I I Cl- P P/A- Cl C2 C3 C4 0 Ci NAPCl- ;;C4 Relative Abundance 0 0 0 00 0 00 0 
71 00.

70 30.

70 00.

69° 30. Figure 14. Dendrogram showing station groups formed by group averaging cluster analysis

of sediment hydrocarbon concentrations (14a) and location of group members on

study area map (14b).

45
analysis. Groupings are determined by cluster analysis.

Discussion

Triplicate analyses of the sediments in the first year provided generally concordant data for alkanes and

PAHs within the replicates from a given site. For example, triplicates from three sites (3A, 5F and 6B)

yielded internally consistent results. The maximum variation in the data among triplicates at three other

sites (2F, 4A and WPB) was a factor of only 1.5 to 2. This suggests that the sediments are reasonably

homogenous within the general area of sampling. Therefore, in the second year, the number of analyses

on duplicate and triplicate samples was reduced to enable greater area coverage by single samples.

Results of procedure blanks (Table 12) indicated that they represented less than 5% of the total alkanes

found in the samples. Procedure blank data were normalized to 80 g dry weight of sediments (average

of the sediment weight of all the samples) for direct comparison. Matrix spike recoveries of n-alkanes

from C4 to Cranged from 48 to 84%. The recovery of deuterated alkanes ranged from 47 to 87% in the

matrix spikes and from 32 to 104% in the samples. Matrix spike recoveries of PAils ranged from 22 to 99

except for dibenzothiophene which had a very low recovery due to treatment of the extract with copper to

remove elemental sulfur. The PAH surrogate spikes were recovered at the level of 30 to 126%. The

n-alkane and PAH data were corrected for recovery.

46
ggjp

samples. The dominant maximum at C and occasionally at C and the odd/even ratios ranging from

2.0 to 4.8 are clearly due to inputs from terrigenous detritus (plant wax components). This was to be

expected from the geographical location of the stations. For example, the Colville and other rivers

contribute significant amounts of particulate organic matter to the nearshore sedimentary regime in the

Alaskan Beaufort Sea [Naidu et at. 2000]. Coastal peats could be a major contributor to the n-alkane

budget in the sediments as reported previously by Yunker et at. [1991] from th& study of sediments

from the Mackenzie shellin the Canadian Beaufort Sea. Only one sample, 1D12, did not show an

odd/even preference of n-alkanes and the gas chromatogram resembles one from fresh petroleum input

(cf. triterpanes and steranes below).

Unresolved complex mixture: The unresolved complex mixture (0CM) or chromatographic "hump"

was insignificant in all of the samples. Only two samples, 5(1)11 and 5(10)11, as illustrated in Figure 8,

exhibited this hump. This is discussed later under triterpenoids and under steranes. Note that replicate

samples 5(10)12 and 5(10)/3 have a baseline resolution similar to all other samples in the current study

as illustrated by the latter sample (Figure 8). This is in contrast to the general trend in all the samples

collected and analyzed a decade ago which were reported to exhibit significant amounts of UCM

[cf. Table 4 in Boehm et al. 19871.

Isoprenoid alkanes: The isoprenoid alkanes, pristane and phytane, are present in all of the samples

(0.01 to o1E'g/g, Table 14). Although the absolute concentrations vary over a range, the overall

pristane/phytane ratio is relatively constant around 2.0 for all the samples from the different regions

studied over the two years (Tables 14 and 20). This is consistent with the findings of Venkatesan and

Kaplan [1982] and Steinhauer and Boehm [1992]. These isoprenoids are most likely of biogenic origin

47
associated with the alkane chromatogram of these two samples as noted above. Unfortunately, the

potential source components such as indigenous peat, coal, shale or oil were not analyzed concurrently in

the present study to compare their fingerprints with the surface sediment samples to infer the origin of

biomaikers precisely.

The various study regions exhibited differences in the total content of alkanes; however, the distribution

of the compounds was compositionally homogeneous, pointing towards a mixed marine and terrestrial

source of organic carbon in the entire Beaufort Sea study area.

Steranes: The sterane data are presented in representative mass fragmentograms of m/z 217 from

GC/MS analysis in Figure 11. Most of the samples are biogenic and have very little sterane content;

their fingerprints are different from that of an oil sample as shown in Figure 11 and literature data of

indigenous shales and oils from the region [Seifert et al. 1979]. Again, the only two samples showing

sterane fingerprint characteristics of oil are 5(10)/i and 5(10)/i, consistent with the alkane chromatogram

and triterpane profile confirming the presence of small amounts of petroleum in the sediment samples

(Figure ii). The replicate sample, 5(i0)/3, and also 1D/2, are almost entirely biogenic as found from their

triterpane profiles. In the future, sterane fingerprints of source materials would allow for better

comparison with the surface sediments and identification of their source.

Polycyclic aromatic hydrocarbons: Total PAils (sum of all parent and methylated PAils from two to

seven ringsnaphthlene to coronene) range from 0.06 to 2.0 ig/g of dry sediment (Table 15). We did

not find PAils above five rings in significant concentrations in any of the samples. Total PAils in the

gross sediments of the study area varied in the stations in the following order:

6G 5A > 6A > SL > 4A> 3A> ID - 6C > 2F 5F> 5(5) 6D > WPB 6B > 3B > 2E> 5G 5(10)> 5(2)> 5(1).

48
the phenanthrenes in all of the samples. Monomethyifluorenes are the major homologs of fluorenes in

most of the samples. Phenanthrene homologs with chain lengths >C3 are either absent or present only in

trace amounts (Table 15, Figure 12). This pattern is also different from that of Prudhoe Bay crude oil

where dimethyl phenathrene is the major homolog and all of the fluorene homologs are almost equally

abundant [Figure 6 in Steinhauer and Boehm 1992]. Further, parent PAils and/or monomethyl homologs

are present in higher concentrations than the higher methylated homologs of the PAHs with chain length

3 in most of the sediment samples. The PAll distribution thus indicates the possible origin from peat,

coal, other diagenetic sources and long-range atmospheric transport of combustion activities Tather than

from source rocks or crude oil from the region [LaFlamme and Hites 1978; Wakeham et al. 1980; Shaw

et al. 1979; Venkatesan and Kaplan 1982; Venkatesan 1988b; Sporstol et al. 1983].

The results from our PAll data are consistent with the n-alkane (LALK and TALK) as well as

triteipenoid/sterane distribution in the current study. It is relevant to point out that previous studies did not

analyze the sediments or the peats for triterpenoids/steranes, which would have confirmed the presence or

absence of petroleum input in their samples. When the triterpenoid data are integrated with that of PAils,

it can be concluded that some of the methyl homologs of PAils could have been derived from peat

samples as well as coal outcrops in the area and that there is no clear evidence for a significant overall

contribution from a more thermally mature source rock or fossil fuel, such as crude oil, to the organic

carbon of most of the sediments investigated here. These results are also consistent with the recent

findings of Valette-Silver et al. [1999] from their study of western Beaufort Sea sediments (i.e., especially

the diagnostic ratios of selected PAils). In addition, as evident from Table 24, there appears to be

no direct correlation between the higher abundance of LALK over TALK and naphthlenes over

phenanthrenes (N/P) and the detection of petroleum triterpanes in representative stations in the current

49
The surface sediments contain n-alkanes that are largely characteristic of biogenic sources. The low

molecular n-alkanes, present in relatively small amounts, are largely from marine productivity. The high

molecular weight n-alkanes, which are the major components of the hydrocarbon fraction, derive from

plant waxes in the coastal peats and also possibly from some coal residues.

The overall triterpenoid/sterane distribution in all of the samples comprises thermally immature

components with almost none to trace amounts of petroleum, except in isolated cases where the petroleum

signature is clearly evident as reflected by characteristic hopanes and steranes in small amounts. The

triterpenoid and sterane profiles thus reinforce the biogenic origin of the major proportion of the carbon in

the entire study area.

The PAIl assemblage in the surface sediments is different from that found in Prudhoe Bay crude oil but

is very similar to that observed in coastal peats and river sediments. This and the sediment 5'3C values of

the TOC of gross sediments are consistent with the major origin of PAils from terrestrial inputs such as

peat, coal, river sediments and, to a smaller extent, from atmospheric inputs.

In summary, the molecular markers investigated in the sediments are of mixed marine and terrestrial

origin. It is also likely that the petroleum inputs detected in the surface sediments by others a decade ago

have currently decreased to such a low level that their signature is not discernible in recent samples

collected in 1997.

50
51
n-C27 2.40 1.07 0.65 0.58

n-C28 0.81 0.35 0.28 0.57

n-C29 1.60 0.98 0.66 0.75

n-C30 0.63 0.21 0.42 0.95

n-C31 1.21 0.48 0.49 0.83

n-c32 0.57 0.20 0.44 1.03

n-C33 0.52 0.15 0.21 0.31

n-C34 0.30 rid 0.26 0.64

n-C35 rid rid rid rid

n-C36 rid rid 0.14 0.39

52

82.72 76.42 79.57

84.07 76.45 80.26

82.82 75.70 79.26

81.57 74.94 78.26

81.49 74.67 78.08

81.40 74.40 77.90

79.46 74.18 76.82

77.51 73.96 75.73

76.80 74.20 75.50

76.08 74.45 75.27

73.60 63.46 68.53

73.17 62.47 67.82

71.93 60.90 66.42

70.68 59.32 65.00

70.02 58.60 64.31

69.36 57.87 63.61

68.45 57.43 62.94

67.53 56.99 62.26

64.99 55.43 60.21

62.44 53.87 58.16
Table 13. Results of QA/QC 

- PAH fraction partially lost 

§ - % recovery of some methyla

Spikes and Standards Surrogate Recovery (%) hexarnethyibenzene n-dodecyibenzene 4-terphenyi-D14 PAH (nglg dry) naphthalene C1-naphthaienes 2-methyinaphthaiene 1-methyinaphthaiene C2-naphthaienes 2,6-dimethylnaphthaiene° C3-naphthaienes 

2,3,5-tilmethylnaphthaiene C4-naphthaienes blphenyi acenaphthyiene acenaphthene fluorene 2-methylfluorene CI-fluorenes C2-fiuorenes 

C3-fiuorenes phenanthrene 1-methyiphenanthrene anthracene C1-phenanthrenes/anthracenes C2-phenanthrenes/anthracenes 3,6-dimethylphenanthrene C3-phenanthrenes/anthracenes C4-phenanthrenes/anthracenes 2,3-benzofluorene 1,1'-blnaphthalene dlbenzothiophene# C1benzothIophenes# C2dibenzothIophenes# C3dIbenzothiophenes# C4enzothiophenes" 

fluoranthene 

pyrene CI-fluoranthenes/pyrenes C2-fluoranthenes/pyrenes 
Table 14. Distribution (ng

Sample Phase I 2FSurrogate Recovery % Deu C14 47

Deu C24 59

Deu C36 n-alkane (nglg dry) 59

18

n-dO n-Cu 30n-C12 29n-C13 38n-C14 36nCl5 43n-C18 35n-C17 44pr 28n-C18 32ph 12n-C19 41n-C20 37n-C21 64n-C22 51n-C23 112n-C24 49n-C25 136n-C26 38n-C27 230n-C28 35n-C29 202n-C30 22n-C31 160n-C32 13n-C33 46n-C34 4n-C35 9n-C36 3

Total nalkanes 1570

12-C19 302

ZC2O-C33 1201pr/ph 2oden 3LALK/TALK 0
Sample Phase I 5F1

Surrogate Recovery % Deu C14 42.8

Deu C24 53.2Deu C36 n-alkane (nglg dry) 50.7

17.

n-C10 n-Cl I 25.3n-C12 25.8n-C13 30.2n-C14 30.n-C15 34.n-C16 256

n-C17 40.pr 20.n-C18 27.8

ph 9.n-C19 45.6n-C20 35.n-C21 99.n-C22 82.n-C23 218.n-C24 90.n-C25 266.n-C26 75.n-C27 363.n-C28 65.n-C29 285.n-C30 42.n-C31 243.n-C32 21.n-C33 89.n-C34 8.n-C35 20.n-C36 2.

Total n-alkanes 23.14

,..ZC12-C19 259...I,C20-C33 1960.

prlph 2.

oddleven** 3.

LALK/TALK 0.
n-C10 n

n-Cu 3

n-C12 n

n-C13 nn-C14 0n-C15 1n-C16 0n-C17 4pr 1n-C18 1

ph 0

n-C19 3n-C20, n-C21 2

6

n-C22 9n-C23 31n-C24 59n-C25 97n-C26 114n-C27 120n-C28 88n-C29 87n-C30 50n-C31 59n-C32 30n-C33 25n-C34 n-C35 14

7

n-C36 6

Total n-alkanes 826

C12-C19 12

.,,I.c20-C33........................................ 78

pr/ph 1odd/even** 1

LALK/TALK 0

Sample Phase II 1DSurrogate Recovery % DeuCl4 57 

Deu C24 64 DeuC36 n-alkane (ng/g dry) 69 
Sample Phase II SA

Surrogate Recovery % Deu C14 78 

Deu C24 59 Deu C36 n-alkane (ng/g dry) 7496n-dO n-Cu 143n-C12 129n-C13 141n-C14 31n-C15 165n-C16 100n-C17 148pr 91n-C18 102ph 39n-C19 160n-C20 171n-C21 327n-C22 263n-C23 621n-C24 265n-C25 727n-C26 247n-C27 1165n-C28 221

n-C29 1051

n-C30 136n-C31 283n-C32 67

n-C33 293n-C34 33n-C35 30n-C36 2

Total n-alkanes 7130

C12-C19 980C20-C33 5844

pIph 2odd/even** 3LALK/TALK 0sflp1e 3A13 lost 
Table 15. Distribution (ng/

t - PAH fraction partially lost § - % recovery of some methy

Sample Phase I Surrogate Recovery (%) hexameth)lbenzene n-dodecylbenzene 4-terpheny-Dl4 PAH (nglg dry) naphthalene C1-naphthalenes 2-methylnaphthalene 1-methylnaphthalene C2-naphthalenes 2,6-dlmethylnaphthalene° C3-naphthalenes 2,3,5-trlmethylnaphthalene C4-naphthalenes blpheriyl acenaphthylene acenaphthene fluene 2-methyliluorene CI-fluorenes C2-lluorenes C3-lluorenes phenanthrene I -methyiphenanthrene anthracene C1-phenar,threnes/anthracenes C2-phenanthrenes/anthracenes 3,6-dimeth)lphenanthrene C3-phenanthrenes/anthracenes C4-phenanthrenes/ardhracenes 2,3-benzofiuorene 1,1'-bnaphthaIene dlbenzothlophene# C1dibenzothlophenes# C2benzothlophenes# C3.dlbenzothlophenes# C4-dlbenzothlophenes" fluoranthene pyrene CI-Iluoranthenes/pyrenes C2-fluorardhenes/pyrenes 
t - PAH fraction partially lost 

- % recoveiy of some methylaSample Phase I Surrogat. Recovery (%) hexameth1benzene n-dodecylbenzene 4-terphenyl-D14 PAH (ng!g dry) naphthalene C1-naphthalenes 2-methylnaphthalene I -methylnaphthalene C2-naphthalenes 2,6-dimethylnaphthalene° C3-naphthalenes 2,3,5-tr1meth1naphthaIene C4-naphthalenes biphenyl 

acenaphthylene 

acenaphthene 

fluorene 2-methyifluorene 

CI-fluorenes C2-fiuorenes 

C3-fiuorenes 

phenanthrene i-methylphenanthrene anthracene CI-phenanthrenes/anthracenes C2-phenanthrenes/anthracenes 3,6-dlmethlphenanthrene C3-phenanthrenes/anthracenes C4-phenanthrenes/anthracenes 2,3-benzofiuorene 1,1 '-blnaphthalene 

dibenzothlophene# 

C1dIbenzothIophenes# C2dIbenzothIophenes# C3ibenzothlophenes# C4dlbenzothiophenes# 

fluoranthene 

pyrene CI-fluoranthenes/pyrenes C2-fluoranthenes/pyrenes 
t - PM! fraction partially lost 

§ - % recovery of some methy

Sampi. Phase I 

Surrogat. Recov.iy (%) 

hexameth)lbenzene 

n-dodecylbenzene 4-terphenyl-D14 PAH (nglg dry) naphthalene C1-naphthelenes 2-methylnaphthalene 

I -methylnaphthalene 

C2-naphthalenes 2,6-dlmeth)lnaphthalene° C3-naphthaleries 2,3,5-ti1meth,lnaphthalene C4-naphthalenes biphenyl acenaphthylene acenaphthene 

fluorene 

2-methylfluorene CI-fluorenes C2-fiuorenes C3-fiuorenes phenanthrene 

1-niethyiphenenthrane 

anthracene CI-henanthrenes/anthracenes C2-phenathrenes/anthracenes 3,6-dimeth,lphenanthrene C3-phenanthrenes/anthracenes C4-phenanthrenes/anthracenes 2,3-benzofluorene 

1,1'-blnaphthalene 

dfbenzothophene# C1-dlbenzothlophenes0 C2-dibenzothlophenes0 C3-dlbenzothiophenes0 C4-dlbenzothlcphenes0 fluoranthene pyrene C1.fluoranthenes/pyrenes C2-fluoranthenes/pyrenes 
- PAH fraction partially lost 

§ - % recovery of some methyla

Sample Phase I Surrogate Recovery (%) hexameth,1benzene n-dodecylbenzene 

4-terphenyl-D14 

PM (nglg dry) naphthalene C1-naphthalenes 2-methylnaphthalene 

1-metIilnaphthaIene 

C2-naphthalenes 2,6-dimethylnaphthalene° C3-naphthalenes 2,3,5-tr1meth,1naphthaIene C4-naphthalenes biphenyl acenaphthylene acenaphthene fluorene 2-rnethylfluorene CI-fluorenes C2-fluorenes C3-fluorenes phenanthrene 1-rnethylphenanthrene anthracene C1-phenanthrenes/anthracenes C2-phenanthrenes/anthracenes 3,6-dimethyiphenanthrene C3-phenanthrenes/anthracenes C4-phenanthrenes/anthracenes 2,3-benzofluorene l,l'-binaphthalene dIbenzothlophene C1-dlbenzothlophenes C2-zothlophenes C3-dlbenzothlophenes C4-dibenzothlophenes fluoranthene pyrene CI-fluoranthenes/pyrenes C2-ltuoranthenes/pyrenes 
t - PAH fraction partially lost 

§ - % recovery of some methy

Sample Phase I Surrogat. R.covery (%) hexamethlbenzene n-dodecylbenzene 4-terphenyl-D14 PAH (nglg dry) nhthalene C1-naphthalenes 2-methylnaphthalene l-methylnaphthalene C2-naphthalenes 2,6-dImeth1naphthaPene° C3-naphthalenes 2,3,5-trlmeth1naphthaIene C4-naphthalenes biphenyl acenaphthylene acenaphthene fluorene 2-methyifluorene CI-fluorenes C2-fiuorenes C3-fiuorenes phenanthrene 1-methyiphenanthrene anttwacene CI-phenanthrenes/anthracenes 

C2-phenanthrenes/anthracenes 3,6-dimethyiphenanthrene C3-phenanthrenes/anthracenes C4-phenanthrenes/anthracenes 2,3-benzofluorene 1,1'-blnaphthalene dlbenzothlophene# C1.dlbenzothlophenes# C2.dlbenzothiophenes# C3dlbenzothlophenes# C4dIbenzothlophenes# fluoranthene pyrene CI-fluoranthenes/pyrenes C2-fluoranthenes/pyrenee 
Sample Phase II Surrogat. Recovery (%) hexarneth,lbenzene n-dodecylbenzene 4-terphenyl-D14 PM (nglg dry) 

naphthalene C1-naphthalenes 2-methylnaphthalene 

1-methylnaphthalene 

C2-naphthalenes 2,6-dlmethylnaphthalene° C3-naphthalenes 2,3,5-trtmethylnaphthalene C4-naphthalenes bIphen acenaphthylene acenaphthene fluorene 2-methylfluorene CI-fluorenes C2-fluorenes C3-fluorenes phenanthrene 1-methyiphenanthrene anthracene CI-phenanthrenes/anthracenes C2-phenanthrenes/anthracenes 3,6-dlmeth,lphenanthrene C3-phenanthrenes/anthracenes 

nanthrenes/anthracenes 

2,3-benzofluorene 1,1'-binaphthalene dlbenzothlophene# 

C1-dlbenzothlcphenes' C2-dlbenzothicphenes' C3-dlbenzothiophenes' 

C4-dlbenzothlcphenes' fluoranthene pyrene 

CI-fluoranthenes/pyrenes C2-&ioranthenes/pyrenes 

§ - % recovery of some methy

- PAH fraction partially lost
t - PAH fraction partially lost 

§ - % recovery of some methy

Sample Phase II Surrogate Recovery (%) hexamethylbenzene n-dodecylbenzene 4-terphenyl-D14 PAH (ng/g dry) naphthalene C1-naphthalenes 2-methylnaphthalene 

1-methylnaphthalene 

C2-naphthalenes 2,6-dimethylnaphthalene° C3-naphthalenes 2,3,5-tulmethylnaphthalene C4-naphthalenes biphenyl acenaphthylene acenaphthene fluorene 2-methylfluorene CI-fluorenes C2-fluorenes C3-fluorenes phenanthrene 

1-methyiphenanthrene 

arithracene CI-phenanthrenes/anthracenes C2-phenanthrenes/anthracenes 3,6-dimeth)lphenanthrene C3-phenanthrenes/anthracenes C4-phenanthrenes/anthracenes 2,3-benzofluorene 

1,1'-blnaphthalene dibenzothiophene# 

C1.dibenzothiophenes# C2.dlbenzothlophenes# C3dibenzothIophenes# C4dibenzothIophenes# fluoranthene pyrene C1.11uoranthenes/pyrenes C2-fiuoranthenes/pyrenes 
t - PAH fraction partially lost 

§ - % recovery of some methyl

Sample Phase II Surrogat. R.cov.ry (%) hexameth1benzene n-dodecylbenzene 4-terphenyl-D14 PAN (nglg dry) naphthalene Cl-naptdhalenes 2-methylnaphthalene 1-methylnaptdhalene C2-naptthalenes 2,6-dimethlnaphthaIene° C3-naphthalenes 2,3,5-trlmethylnaphthalene C4-naphthalenes blphenyl acenaphthylene acenaphtheno 

fluorene 

2-methytfluorene CI-fluorenes C2-fluorenes C3-fluorenes phenenthrene 1-methylphenanthrene anthracene Cl-ph nanthrenes/anthracenes C2-phenanthreneslanthracenes 3,6-dimethyiphenanthrene C3-phenanthrenes/anthracenes C4-phenanthrenes/anthracenes 2,3-benzofiuorene 1.1 '-blnaphthalene dlbenzothIophene Cl.dlbenzothlophenes# C2-dibenzothIophenes C3-dlbenzothlophenes C4-dibenzothIophenes 

fluorwthene 

pyrene CI-fluoranthenes/pyrenes C2-fluoranthenes/pyrenee 
t - PAH fraction partially lost 

§ - % recovery of some methyla

Sample Phase II Surrogate R.coveiy (%) hexameth)lbenzene n-dodecylbenzene 

4-terphenyl-D14 

PAH (nglg dry) naphthalene C1-naphthalenes 2-methylnaphthalene 

1-methylnaphthalene 

C2-naphthalenes 2,6-dimeth)lnaphthalene° 

C3-naphthalenes 

2,3,5-trlmeth)lnaphthalene C4-naphthalenes 

biphenyl acenaphthylene acenaphthene fluorene 2-methyifluorene CI-Iluorenes C2-fiuorenes C3-fluorenes phenanthrene 

1-methyiphenanthrene 

anthracene CI-phenanthrenes/anthracenes C2-phenanthrenes/anthracenes 3,6-dimeth)lphenanthrene C3-phenanthrenes/anthracenes C4-phenanthrenes/anthracenes 2,3-benzofluorene 1,1'-blnaphthalene dibenzothiophene# C1-dibenzothlophenes' C2-dlbenzothlophenes' C3-dlbenzothiophenes' C4nzothicphenes' fluoranthene pyrene CI-fluoranthenee/pyrenes C2-fiuoranthenes/pyrenes 
Table 16. Distribution (ng/g

Triterpanes (ng/g)* 17c&(H),21(H)-22. I 7(H),21 3(H)-22,29,30-trlsnorh

17a(H),21 3(H)-3O-norhopane 7J(H),21a(H)-3O-norhopane I 7J3(H),21 (H)-3O-norhopane° I 8u(H)-oleanane l7cx(H....3(H)-hopane I 7(H),21 (H)-hopane I 7J3(H),21 (H)-3O-homohopane hop-I 3(1 8)-ene hop-21 (22)..ene diploptene I 7a(H),21 (H)-22,29,30-fflsnorhI 7(H),21 J(H)-22,29,30-trIsnorh

17a(H),21 (H)-30-norhopane I 73(H),2I a(H)-30-norhopane I7(H)21(H)-3O-norhopane° I 8a(H)-oleanane 1, ),21(H)-h pane I 713(H),21 (H)-hopane i7(H),21 (H)-30-homohopane hop-I 3(1 8)-ene 21(22)-ene diploptene 

* - quantitation based on miz 1
Table 17. Distribution (ng/

Steranes (nglg)* 

5c(H)-androstane 5u(H)-pregnane 5(H)-pregnane 20-methyl-5ct(H)-pregnane 20S-5u(H),14u(H),l7cz(H)-cho2.R-5c4H),14u(H),17a(H)-chole20R-5a(H),14(H),17(H)-choIe20S 5a(H) l4(H) 17(H)-choIes20S.-5a(H).14a.(H).7a(Hergos

20R-5a(H),14c&(H)1.7a(H-ergo

9!.-5u... 

20S-5u(H),14(H),17(H)-ergos20S-5a(H),14a(H),17a(H)-stigma

...29R-5aH,14G(H..17a(H)-stlgm

20R-5u(H),14(H),17(H)-stIgma20S-5a(H),14(H),17(H)-stIgma5u(H)-androstane 5a(H)-pregnane 5(H)-pregnane 20-methyl-5a(H)-pregnane 20S-5a(H),14a(H),17a(H)-chole20R.5a(H),14a(H),17a(H)-chole20R-5a(H),14(H),17D(H)-choIe

...?OS-5a(H).!1.4(H).!17(!-I)-chole

20S-5a(H),14a(H),17a(H)-ergos20R.-5u(H),14a(H),l7cx(H)-ergo20R-5a(H),14p(H),17(H)-ergos20S-5a(H),14(H),17(H)-ergos

.)I7c..i!)-stigma

20R.c..(!1.4u.(H..,17u(H)-stigma

20R-5a(H)14(H)1,7p(H).-s.dgma20S-5a(H),14(H),17(H)-stIgma

* - quantitation based on m/z 2
69 

tq.L 61 SUJ33S pqupi UI SIn2I jj pUB Z1 

I(H)npI(H)Ds-ioz eUe1SBW6flS-(H)ZL 

eUeSB6I1S-(H)ZL i. 

eueSeW6qs-(H)z 

GUeSO6ia-(H)JLI'(H)flvI'(H)73g-9fJ 

euBsO6ie-(H)1,L 

I'(H)ntI'(H)Dg-SO GUeSO6ia-(H)2L 

i1-P-IO IIJC eUBSa,Otp1P-XL 

I'(H)nt'i'(H)Dg-iOZ eue1saIO(p-(H)2L 

eueso(H$JLI'(H)Jw(H)Dg-sO 

I'(H)wI'(H)zs-Io eUesa,otP-(H)1,L 

i1-P-SO IIC I. eueSaOqoe1p-x 

i.'(H)npI'(H)Dg-so eUe1SetO(P-(H)ZL 

i.-io IIC i aUeSeoq3e!p-L 

eUeSato(eIp-Lc.-9cJ 

sis 

V-IS 

C'S 

is £ 

is i. 

OlS 

6S 

89 

LS 

99 

99 

vs 

VS 

IS 

sauiai u, seJn8H pue u 
Table 20. Mean concentra

of sediments, ne

Station Depth Tota

(m) n-alka

Phase I 2F 1.90 1878.

3A 6.20 3071.4A 4.50 2850.WPB 2.50 743.5F 1.50 2266.SL 2.40 3917.6B 5.50 417.

Phase II 10 6.00 826.

2E 7.40 258.3B 4.20 2958.5(1) 5.80 204.5(2) 5.80 258.5(5) 6.70 1319.5(10) 8.20 586.5A 11.40 7130.5G 9.30 491.6A 3.60 5400.6B 5.50 417.6C 16.10 2244.60 18.40 754.6G 2.10 11766.
Table 21. Correlation co

nearshore, nor

Depth 

(m) n

Depth (m) 1.00 Total n-alkanes C12-C19 C20-C33 

Pr!Ph Odd/Even 4,5 PAH tPAH OM % Or % Sd % St% CI % Mud % 
Stepwise analysis - Step 2 (final step)

72

Statistica

Dlscrlmlnant

Discriminant Function Analysis Summary

Step 2 Number of vanables in model: 2 Grouping: GR3 (3 grps) Stats Wilks' Lambda: 10577 approx. F(4, 32) = 16.598 p <0.0000

N =20 Wilks'

Lambda

Partial

Lambda

F-remove

(2, 16) p-level Tolerance 1-Tolerance

(R-Square)

CL % .1871374 .5652173 6.153849 .0104165 .9752235 .0247765

tPAH .1746661 .6055740 5.210608 .0180858 .9752237 .0247763

Statistica

Dlscrlminant

Stats

Standardized Coefficients

for Canonical Variables

Variable Root I Root 2

CL %

tPAH

-.676382

-.637740

-.753600

.786571

Elgenvatue 7.781033 .076660

Cumulative

Proes .990244 1.000000

Number of vanables in model: 2

Last vanable entered: tPAH F(2, 16) = 1.676846 p <.2182

WiIks' Lambda: .1057733 approx. F(4, 32) = 16.59813 p <0.0000

Discriminant Discilminant Function Analysis Results

Stats
d 1984-1986 

References 

4 this study 

Boehm et al. 1987 

5 thIs study 

Boehm etat. 1987 

9 thIs study 

Boehm et al. 1987 this study Boehmetal. 1987 

9 this study 

Boehmetal. 1987 
Acknowledgements 

This study was funded by the Minerals Management Service, U.S. Department of the Interior through 

Cooperative Agreements 14-35-0001-30661 (Task Order 14195) and 1435-0l-98-CA-30909 (Task Order 

15 167) between the MMS Alaska OCS Region and the Coastal Marine Institute, University of Alaska 

Fairbanks. Matching fimds were provided by the Institute of Marine Science/University of Alaska 

Fairbanks; Frontier Geosciences (Seattle), Department of Wildlife Management/North Slope Borough 

(DWMINSB) (Barrow), and the University of California at Los Angeles. The Minerals Management 

Service also provided funds 

to M. Indira Venkatesan to participate in the interlaboratoiy calibration 

exercise for hydrocarbon analysis (Contract # 0199, P0 16134). We thank the NOAA/ORCA2 office 

(Silver Spring, Maryland) for providing 

two days of ship time for joint sampling. This help was arranged 

by Jawed Hameedi. We thank Scott Frue and Rion Schmidt for the collection of sediment samples and 

Bill Kopplin, Captain of the RN Annika Marie for excellent cooperation in the field. Thanks are due to 

Nicolas Bloom of Frontier Geosciences, M. Indira Venkatesan of UCLA and Mark Baskaran of Texas 

A&M (Galveston) for help under subcontracts for 

trace element, hydrocarbon and geochronologic 

analyses, respectively. Amy Blanchard and Carl Pfisterer provided assistance in statistical analysis, and 

Liying Zhao and Ricardo Lopez assisted in the laboratory. The participation of Frontier Geosciences in 

the NOAA/l 1 intercomparison exercise for trace metals in sediments was organized by Scott Willie of the 

National Research Council of Canada of behalf NOAA/ORCA2, at no cost to this project. The continued 

encouragement by Vera Alexander, Director, CMI, and the excellent cooperation of Sue Hills and Dave 

Nebert of CMI, and Dick Prentki and Cleve Cowles of MMS (Anchorage) throughout this study is 

appreciated. Thanks are also due to Olivia Merino, Terrence Northrup and Timothy Lm for technical 

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