OCS Study MMS 2000-024

Sediment Quality in Depositional Areas

of Shelikof Strait and Outermost Cook Inlet

Final Report

Submitted by:

Arthur D. Little, Inc.

Cambridge, Massachusetts

Submitted to:

U.S. Department of the Interior

Minerals Management Service

Anchorage, Alaska

Contract No. 1435-0l -97-CT-30830

U.S. Department of the Interior

Minerals Management Service

Alaska Outer Continental Shelf Region
Sediment Quality in Depositional Areas of

Shelikof Strait and Outermost Cook Inlet

Final Report

Dr. Paul D. Boehm, Principal Investigator

Arthur D. Little, Inc.

20 Acorn Park

Cambridge, Massachusetts

02140

This study was funded by the U.S. Department of the Interior,

Minerals Management Service (MMS) Alaska Outer Continental Shelf Region,

Anchorage, Alaska, under Contract No. 1435-0l-97-CT-30830,

as part of the MMS Alaska Environmental Studies Program.

May 2001

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 U.S. Department

of the Interior, nor does mention of trade names or commercial products constitute endorsement

of recommendation for use by the Federal Government.
Project Organization

List of Authors

Executive Summary

Dr. Paul Boehm, Arthur D. Little, Inc. (ADL)

Section 1

Dr. Paul Boehm, ADL

Mr. John Brown, ADL

Section 2

Ms. Cherie Howell, ADL

Mr. John Brown, ADL

Mr. Harry Tsomides, ADL

Dr. Stephen E. Graham, ADL

Dr. John Trefry, Florida Institute of Technology (FIT)

Dr. Simone Metz, FIT

Mr. Jordan Gold, Applied Marine Sciences (AMS)

Section 3

Mr. John Brown, ADL

Ms. Cherie Howell, ADL

Dr. Paul Boehm, ADL

Ms. Linda Cook, ADL

Mr. C. Frederick Newton, ADL

Dr. Stephen E. Graham, ADL

Dr. John Trefry, FIT

Dr. Simone Metz, FIT

Dr. Woollcott Smith, Temple University

Dr. Robert Spies, AMS

Mr. Jordan Gold, AMS

Section 4

Mr. John Brown, ADL

Dr. Stephen E. Graham, ADL

Dr. John Trefry, FIT

Dr. Simone Metz, FIT

Dr. Robert Spies, AMS

Mr. Jordan Gold, AMS

Section 5

Mr. John Brown, ADL

Dr. Paul Boehm, ADL

Dr. John Trefry, FIT

Dr. Robert Spies, AMS

ArthurDLittle
Table of Contents

Page

List of Tables vii

List of Figures X

List of Acronyms and Abbreviations

Executive Summary

1 .O Introduction

1.1 Background

1.1.1 Physical Setting

1.1.2 Oceanography

1.1.3 Biology

1.2 Objectives

1.2.1 Null Hypotheses

2.0 Methods 2-l

2.1 Field Methods and Study Design 2-l

2.1.1 Study Design 2-l

2.1.2 Field Sampling 2-2

2.1.2.1 Conductivity, Temperature, and Depth Measurements 2-3

2.1.2.2 Sediment Sampling 2-3

2.1.2.3 Sediment Toxicity Sample Collection 2-6

2.1.2.4 Sediment Profile Imaging 2-7

2.1.2.5 Fish Collection 2-8

2.1.3 Source Sample Collection 2-9

2.1.3.1 Source Oils 2-9

2.1.3.2 Source Coals 2-9

2.1.3.3 Source Sediment 2-10

2.1.3.4 Aqueous Sources 2-11

2.2 Analytical Methods 2-11

2.2.1 Physical Parameters 2-11

2.2.1.1 Grain Size 2-11

2.2.1.2 Total Organic Carbon 2-12

2.2.2 Organic Parameters 2-12

2.2.2.1 Sample Preparation 2-12

2.2.2.2 Organic Extract Cleanup 2-14

i

xvi

ES-1

1-1

l-l

l-l

l-2

l-2

l-3

l-3
2.2.2.3 Internal Standard Addition for Instrumental Analysis

2.2.2.4 Instrumental Analysis

2.2.2.5 Compound Quantification/Identification

2.2.3 Inorganic Parameters

2.2.3.1 Trace and Major Metals in Sediments

2.2.3.2 Trace Metals in Tissues

2.2.3.3 Trace Metals in Aqueous and Oil Source Samples

2.2.3.4 Trace Metals in River Particulate and Coal Source

Samples

2.2.3.5 Acid-Volatile Sulfide/Simultaneously Extracted

Metals

2.2.4 Geochronology

2.2.5 Biological Parameters

2.2.5.1 Sediment Toxicity Tests

2.2.5.2 CYP1A(P4501A) Determinations

2.2.5.3 P450 Reporter Gene System Tests

2.2.5.4 Enumeration of Heterotrophs and Hydrocarbon

Degrading Microorganisms

2.2.6 Measuring, Interpreting, and Mapping Sediment Profile

Imaging Parameters

2.2.6.1 Sediment Type

2.2.6.2 Prism Penetration Depth

2.2.6.3 Small-Scale Surface Boundary Roughness

2.2.6.4 Thickness of Depositional Layers

2.2.6.5 Mud Clasts

2.2.6.6 Apparent Redox Potential Discontinuity Depth

2.2.6.7 Sedimentary Methane

2.2.6.8 Infaunal Successional Stage

2.2.6.9 Organism-Sediment Index

2.3 Statistical Methods

2.3.1 Coefficient of Variation

2.3.2 Analysis of Variance

2.3.3 Pearson Product-Moment Correlation

2.3.3.1 Sediments

2.3.3.2 Tissues

2.3.4 Analysis of Variance/Covariance

2.3.5 Random Effects Analysis of Variance

2.4 Quality Assurance/Quality Control

2.4.1 Field Quality Assurance/Quality Control

2-14

2-14

2-15

2-16

2-16

2-17

2-17

2-18

2-19

2-19

2-20

2-20

2-21 

2-22

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2-24

2-25

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2-25

2-27

2-27

2-28

2-28

2-28

2-29

2-30

2-30

2-30

2-31

2-3 1

2-32

2-32

ii
2.4.1.1 Equipment Blanks 2-33

2.4.1.2 Field Blanks 2-33

2.4.1.3 Trip Blanks 2-33

2.4.1.4 Field Source Sample 2-33

2.4.2 Organics Analysis Quality Assurance/Quality Control 2-34

2.4.2.1 Quality Assurance 2-34

2.4.2.2 Quality Control 2-34

2.4.3 Metals and TOC Analysis Quality Assurance/Quality Control 2-35

2.4.3.1 Quality Assurance 2-35

2.4.3.2 Quality Control 2-35

2.4.4 Biology Quality Assurance/Quality Control 2-36

2.4.4.1 Sediment Toxicity Test 2-36

2.4.4.2 CYPlA (P4501A) Determinations 2-36

2.4.4.3 P450 Reporter Gene System Determinations 2-37

3.0 Results

3.1 Contaminant Sources

3.1.1 Physical Measurements

3.1.2 Organics

3.1.2.1 Source Oils

3.1.2.2 Source Coals

3.1.2.3 Source Sediments

3.1.2.4 Aqueous Sources

3.1.3 Metals

3.1.3.1 Source Sediment and Suspended Solids

3.1.3.2 Source Coals

3.1.3.3 Aqueous and Oil Sources

3.2 Surface Sediments

3.2.1 Physical Measurements

3.2.2 Organics

3-1

3-l

3-l

3-l

3-2

3-3

3-5

3-7

3-8

3-8

3-9

3-9

3-9

3-9

3-10

3-11

3-12

3-13

3-13

3-16

3-16

3-18

3.2.2.1

3.2.2.2

3.2.2.3

3.2.2.4

3.2.3 Metals

3.2.3.1

3.2.3.2

Saturated Hydrocarbons

Polycyclic Aromatic Hydrocarbons

Steranes and Triterpanes

Hydrocarbon Sources in Surface Sediments

Trace and Major Elements

Acid-Volatile Sulfide/Simultaneously Extracted

Metals

3.2.4 P450 Reporter Gene System 3-18

iii
3.2.5 Sediment Toxicity Tests

3.2.6 Enumeration of Heterotrophs and Hydrocarbon Degrading

Microorganisms

3.2.7 Sediment Profile Imaging Camera

3.2.7.1 Gram Size

3.2.7.2 Surface Boundary Roughness

3.2.7.3 Prism Penetration Depth

3.2.7.4 Apparent Redox Potential Discontinuity Depth

3.2.7.5 Infaunal Successional Stage

3.2.7.6 Organism-Sediment Index

3.2.7.7 Interpretation of Sediment Profile Imaging Results

3.3 Sediment Cores

3.3.1 Geochronology

3.3.2 Physical Measurements

3.3.3 Organics

3.3.4 Trace and Major Metals

3.3.5 Statistical Results of Core Data

3.4 Fish Tissue

3.4.1 Organics (PAH)

3.4.2 Metals

3.4.3 P450 RGS Response in Extracts of Fish Liver

3.4.4 CYPlA (P4501A) Response in Different Species and Different

Tissues

3.5 Statistical Results

3.5.1 Coefficient of Variation

.3.5.1.1 Variability Within Stations (Surface)

3.5.1.2 Variability Within Zones (Surface Stations)

3.5.2 Analysis of Variance

3.5.2.1 Between-Zone Comparisons

3.5.2.2 Between-Year Comparisons

3.5.3 Pearson Product-Moment Correlations

3.5.3.1 Sediments

3.5.3.2 Fish Tissue

3.5.4 Analysis of Variance/Covariance

3.6 Quality Control Results

3.6.1 Quality Control in the Field

3.6.1.1 Trip Blank

3.6.1.2 Equipment Blanks

3.6.1.3 Field Blanks

3-19

3-20

3-20

3-20

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343

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346

iv
3.6.2 Organics Quality Control 3-46

3.6.2-l Surrogate Results 3-47

3.6.2.2 Laboratory Control Spike Summary 3-47

3.6.2.3 Procedural Blanks 3-47

3.6.2.4 Standard Reference Materials 3-47

3.6.2.5 Analysis of Control Oils 3-48

3.6.3 Metals and TOC Quality Control 3-48

3.6.3.1 Instrument Calibration and Standard Checks 3-48

3.6.3.2 SRM Analysis and Intercalibration Excercise 3-48

3.6.3.3 Duplicate Sample Analysis 3-49

3.6.3.4 Method Blank Analysis 3-50

3.6.3.5 Field Blank Analysis 3-50

3.6.3.5 Matrix Spike Analysis 3-50

3.6.4 Toxicity Test Quality Control 3-50

3.6.5 CYPlA (P4501A) Quality Control 3-51

3.6.6 P450 RGS Quality Control 3-51

3.6.7 Marine Heterotrophs and Crude Oil Emulsifier Quality Control 3-51

4.0 Discussion

4.1 Surface Sediments as Contaminant Sinks

4.2 Concentration of Pollutants Over Time

4.2.1 Geochronology of Metals

4.2.2 Geochronology of Organics

4.2.3 Statistical Analysis of Concentrations in Cores

4.3 Composition of Pollutants Over Time

4.3.1 Metals

4.3.2 Organics

4.4 Risk Associated with Pollutant Concentrations: Exposure

Assessment

4.4.1 Comparison to Sediment Quality Criteria: Metals

4.4.2 Comparison to Sediment Quality Criteria: Polycyclic Aromatic

Hydrocarbons

4-1

4-l

4-3

4-3

4-4

4-5

4-5

4-5

4-6

4-7

4-7

4-8

4.4.3 Sediment Toxicity Tests

4.4.4 P450 Reporter Gene System in Fish and Sediments

4.4.4.1 Sediments

4.4.4.2 Fish Tissue

4.4.5 CYPlA Response in Fish

4.4.6 Assessment of Ecological Risk

4-8

4-11

4-12

4-12

4-13

4-16

ArthmDLittle

V
5.0 Recommendations

6.0 References

7.0 Publications

Appendices

A

B

C

D

E

F

G

H

I

J

Grain Size and Total Organic Carbon

Organics Data

Metals Data

Geochronology Data and AVS/SEM Data

Reporter Gene System P450 Data

Fish Measurement and P450 Data

Toxicity Data

Oil-Degrading Bacteria Data

Statistical Data

1997 and 1998 Field Logistics/Sampling Plans and Cruise Reports

5-1

6-1

7-1

CD-ROM

v i
List of Tables

Chapter 2

Table 2-l:

Table 2-2:

Table 2-3:

Table 2-4:

Table 2-5:

Table 2-6:

Table 2-7:

Table 2-8:

Table 2-9:

Table 2-10:

Chapter 3

Table 3-l:

Table 3-2:

Table 3-3:

Table 3-4:

Table 3-5:

Table 3-6:

Table 3-7:

Table 3-8:

Table 3-9:

1997 and 1998 MMS Shelikof Strait and Outermost Cook Inlet Field Survey

Stations Sampled

1997-1998 Source Samples from the Outermost Cook Inlet/Shelikof Strait Region

Saturated Hydrocarbons Target Analyte List

Polycyclic Aromatic Hydrocarbons Target Analyte List

Steranes/Triterpanes Target Analyte List

Summary of Instrumental Methods and Method Detection Limits (MDLs) for

Metal Analysis of Sediment and Fish

Calculation of the Sediment Profile Imaging Organism-Sediment Index

Data Quality Objectives for Saturated Hydrocarbons and Polycyclic Aromatic

Hydrocarbons Analysis

Quality Control Summary for Sterane and Triterpane Analyses

Data Quality Objectives and Criteria for Metals and Total Organic Carbon

Concentrations of Trace Metals, Total Organic Carbon (TOC) and Grain Size in

Source Samples (Dry Weight)

Mean and Standard Deviation Values for Total PAH, Total PHC, and Total S/T

for Source Samples in Outermost Cook Inlet and Shelikof Strait

Ranges of Metal Concentrations in Susitna and Copper River Bottom Sediment

and Suspended Solids (This Study), Sedimentary, Volcanic and Plutonic Rocks

from Alaska (Los Alamos National Laboratory, 1983), and Average Continental

Crust (Wedepohl, 1995)

Concentrations of Trace Metal in Source Solutions (Wet Weight)

Means, Standard Deviations and Ranges of Values for Total Organic Carbon

(TOC), Sand, Silt and Clay for Surficial (O-2 cm) Sediments from Zones AC, 0,

1,2,3 and 4 in the Shelikof Strait

Non-Transformed Mean, Standard Deviation and Range of Total PAH, Total

PHC, and Total S/T for Surficial Sediment (O-2 cm) from Zones 0, 1,2,3, and 4

Diagnostic Ratios and Parameters of Saturated Hydrocarbons, Polycyclic

Aromatic Hydrocarbons, and Steranes and Triterpanes

Mean, Maximum, Minimum, and Student-Newman Keuls Analysis Results for

Key Organic Parameters (Non-Transformed) in 1997 and 1998

Average Total Organics Concentrations in Surficial Sediments from Zones 0, 1, 2,

3 and 4 in Outermost Cook Inlet and the Shelikof Strait, Concentrations of Alaska

Marine Sediments, and Concentrations in Cook Inlet and the Shelikof Strait from

Previous Studies

vii

AmthwDLittle
Table 3-10:

Table 3- 11:

Table 3-12:

Table 3-13:

Table 3-14:

Table 3-15:

Table 3-16:

Table 3-17:

Table 3-18:

Table 3- 19:

Table 3-20:

Table 3-21:

Table 3-22:

Table 3-23:

Table 3-24:

Table 3-25:

Table 3-26:

Table 3-27:

Table 3-28:

Table 3-29:

Table 3-30:

Means, Standard Deviations, and Ranges of Values for Metals, Total Organic

Carbon (TOC), Sand, Silt and Clay for Surficial (O-2 cm) Sediments from Zones

AC, 0, 1, 2, 3 and 4 in Outermost Cook Inlet and the Shelikof Strait

Average Metal Concentrations in Surficial Sediments from Zones AC, 0, 1, 2, 3,

and 4 in Outermost Cook Inlet and the Shelikof Strait, Average Continental Crust

(Wedepohl, 1995) and Average Concentrations for Bottom Sediment from the

Susitna and Copper Rivers

Groupings of Metals in Surficial Sediments from Zones 0, 1, 2, 3 and 4 in

Outermost Cook Inlet and the Shelikof Strait Based on Coefficient of Variation

Results of the Student Newman Keuls Statistical Test Performed on Metal/Fe

Ratios from Surficial Sediments in Zones 0, 1, 2 and 3 collected in 1997

Percent Survival of Eohaustorius estuarius in the Sediment for Toxicity Tests

Percent Survival of Ampelisca abdita in the Sediment for Toxicity Tests

Sedimentation Rates (cm/y) Determined Using Excess *?Pb and 13’Cs Age-Depth

Relationship Based on *?Pb Sedimentation Rate

Means and Standard Deviations for Total Organic Carbon (TOC), Sand, Silt and

Clay Values for Sediment Cores from Zone 0, 1, 2, 3 and 4 in Outermost Cook

Inlet and the Shelikof Strait

Mean and Standard Deviation of Total Organic Parameters for Sediment Cores

from Zones 0, 1, 2, 3 and 4

Means and Standard Deviations for Trace Metals, Total Organic Carbon (TOC),

Sand, Silt and Clay Values for Sediment Cores from Zone 0, 1, 2, 3 and 4 in

Outermost Cook Inlet and the Shelikof Strait

Analysis of Post-1963 Shifts in Organic Indices

Analysis of Post-1963 Shifts in Iron Normalized Metals

MMS Stations Where Fish Liver Tissue Samples were Collected for Chemical

Analysis

Average PAH Concentrations (in pg/g dry weight) Detected in Fish Tissue

Samples and Comparison to PAH Concentrations in Procedural Blanks

Mean Total PAH Concentrations (in pg/g dry weight) Detected in Fish Tissue

Trace Metal Concentrations in Liver Composite Samples for Halibut, Arrow

Flounder, Black Cod, Pacific Cod and Skate (Dry Weight)

Mercury Concentrations in Flesh (Muscle) Samples for Halibut (Dry Weight)

CYPlA Sscores in all Fish and Cell Types

Mean CYP1A Scores in Pacific Halibut Cell Types by Zone

Transformed Percent Survival versus Transformed Silt and Each Target Metal for

1997 Twenty-Station Sediment Data Analysis

Summary of Surrogate Percent Recoveries

Table 3-3 1: Laboratory Control Spike Recovery Summary

Table 3-32: Standard Reference Material (SRM) Summary

Table 3-33: Control Oil Summary for North Slope Crude

. . . VIII
Table 3-34: Control Oil Summary for Cook Inlet Crude

Table 3-35: Results for Standard Reference Material (SRM) BCSS-1 and MESS-2, Marine

Sediment Samples issued by the National Research Council of Canada (NRC)

Table 3-36: Results for Standard Reference Material (SRM) 1566a, an Oyster Tissue Issued by

the National Institute of Standards & Technology (NIST), SRM DORM-2, a

Dogfish Muscle Certified by the National Research Council of Canada (NRC) and

SRM TORT-2, a Lobster Hepatopancreas Standard from the NIST

Table 3-37: Results for Standard Reference Material (SRM) 1643d, a Water Sample Issued by

the National Institute of Standards & Technology (NET), SRM 2704, a River

Sediment from the NIST, SRM SIRS-3, a Riverine Water Sample Certified by

the National Research Council of Canada (NRC) and SRM MESS-2 from the

NRC

Table 3-38: RGS Fold Induction of TCDD Control

Chapter 4

Table 4-l: Data for Sediment Deposition in Outermost Cook Inlet and the Shelikof Strait

Table 4-2: Metal/Metal Ratios for Bottom and Suspended Sediment from Area Rivers

Table 4-3: Summary of Results from Model for Identifying Sediment Sources in Outermost

Cook Inlet and the Shelikof Strait

ix
List of Figures

Chapter 2

Figure 2-l: 1997 and 1998 Cook Inlet and the Shelikof Strait Field Survey Station Locations

Figure 2-2: River and Coal Sample Locations

Figure 2-3: Copper River Source Sampling Locations

Chapter 3

Figure 3-l: Cook Inlet Crude Oil Source Sample Results: GC/FID total ion chromatogram

(top), PAH distribution plot (middle), Triterpane extracted ion chromatogram plot

(bottom)

Figure 3-2: Swanson River Field Oil Source Sample Results: GC/FID total ion chromatogram

(top), PAH distribution plot (middle), Triter-pane extracted ion chromatogram plot

(bottom)

Figure 3-3: Well Creek Oil Seep Source Sample Results: GC/FID chromatogram (top), PAH

distribution plot (middle), Triter-pane extracted ion chromatogram (bottom)

Figure 3-4: Homer Spit Coal Source Sample Results: GC/FlD total ion chromatogram (top),

PAH distribution plot (middle), Triterpane extracted ion chromatogram plot

(bottom)

Figure 3-5: Homer Coal Bay Source Sample Results: GC/FID chromatogram (top), PAH

distribution plot (middle), Triter-pane extracted ion chromatogram (bottom)

Figure 3-6: Ninilchik Coal Source Sample Results: GC/FID chromatogram (top), PAH

distribution plot (middle), Triter-pane extracted ion chromatogram (bottom)

Figure 3-7: Matanuska Coal Source Sample Results: GC/FID chromatogram (top), PAH

distribution plot (middle), Triter-pane extracted ion chromatogram (bottom)

Figure 3-8: Coyote Lake Coal Source Sample Results: GC/FID chromatogram (top), PAH

distribution plot (middle), Triter-pane extracted ion chromatogram (bottom)

Figure 3-9: Beluga Coal Source Sample Results: GC/FID chromatogram (top), PAH

distribution plot (middle), Triter-pane extracted ion chromatogram (bottom)

Figure 3-10: Homer Harbor Sediments O-2 cm Depth Source Sample Results: GC/FID total ion

chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram plot (bottom)

Figure 3-l 1: Copper River Sediments O-2 cm Depth Source Sample Results: GC/FID total ion

chromatogram (top), PAH distribution plot (middle), Triter-pane extracted ion

chromatogram plot (bottom), 1997

Figure 3-12: Copper River Sediments O-2 cm Depth Source Sample Results: GC/FID total ion

chromatogram (top), PAH distribution plot (middle), Triter-pane extracted ion

chromatogram plot (bottom), 1998

Figure 3-13: Susitna River Sediments O-2 cm Source Sample Results: GC/FlD total ion

chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram plot (bottom)

Figure 3-14: Matanuska River Sediment Source Sample Results: GC/FlD chromatogram (top),

PAH distribution plot (middle), Triterpane extracted ion chromatogram (bottom)

X
Figure 3-15: Alaska Coastal Current Sediment Source Sample Results: GC/FID chromatogram

(top), PAH distribution plot (middle), Triterpane extracted ion chromatogram

(bottom)

Figure 3-16: St Augustine Island Sediment Source Sample Results: GC/FID chromatogram

(top), PAH distribution plot (middle), Triterpane extracted ion chromatogram

(bottom)

Figure 3-17: Municipal Waste Treatment Facility, Pt Woronzof Final Effluent Source Sample

Results: GC/FlD total ion chromatogram (top), PAH distribution plot (middle),

Triterpane extracted ion chromatogram plot (bottom)

Figure 3-18: Produced Water TBPF Outfall Source Sample Results: GC/FlD total ion

chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram plot (bottom)

Figure 3-19: Zone 0, Station Fl, Surface Sediment Sample 97-0-Fl-0l-00-PHC-S (rep 01)

Results: GC/FID chromatogram (top), PAH distribution plot (middle), Triterpane

extracted ion chromatogram (bottom)

Figure 3-20: Zone 0, Station F4, Surface Sediment Sample 97-0-F4-02-00-PHC-S (rep 02)

Results: GC/FID total ion chromatogram (top), PAH distribution plot (middle),

Triterpane extracted ion chromatogram plot (bottom)

Figure 3-21: Zone 0, Station F4, Surface Sediment 98-0-F4-0l-00-PHC-S: GC/FID

chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram (bottom)

Figure 3-22: Zone 0, Station F5, Surface Sediment Sample 97-0-F5-02-00-PHC-S (rep 02)

Results: GC/FID total ion chromatogram (top), PAH distribution plot (middle),

Triterpane extracted ion chromatogram plot (bottom)

Figure 3-23: Zone 0, Station F5, Surface Sediment 98-0-F5-0l-00-PHC-S: GC/FID

chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram (bottom)

Figure 3-24: Zone 1, Station R9, Surface Sediment Sample 97-l-08-0l-00-PHC-S Results:

GC/FlD total ion chromatogram (top), PAH distribution plot (middle), Triterpane

extracted ion chromatogram plot (bottom)

Figure 3-25: Zone 2, Station R8, Surface Sediment Sample 97-2-08-0l-00-PHC-S Results:

GC/FID total ion chromatogram (top), PAH distribution plot (middle), Triterpane

extracted ion chromatogram plot (bottom)

Figure 3-26: Zone 3, Station Rl0, Surface Sediment Sample 97-3-l0-0l-00-PHC-S Results:

GC/FID total ion chromatogram (top), PAH distribution plot (middle), Triterpane

extracted ion chromatogram plot (bottom)

Figure 3-27: Zone 4, Station 2, Surface Sediment Sample 98-4-F2-0l-00-PHC-S: GC/FID

chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram (bottom)

Figure 3-28: Double Ratio Plot of C2D/C2P and C3D/C3P for All Source and Surficial

Sediments (Zones 0, 1, 2, 3, and 4)

Figure 3-29: Double Ratio Plot of C2D/C2P and C3D/C3P for All Source and Zone 0 Surficial

Sediments

ArtharD Little x i
Figure 3-30: Double Ratio Plot of C2D/C2P and C3D/C3P for All Source and Zone 1 Surficial

Sediments

Figure 3-31: Double Ratio Plot of C2D/C2P and C3D/C3P for All Source and Zone 2 Surficial

Sediments

Figure 3-32: Double Ratio Plot of C2D/C2P and C3D/C3P for All Source and Zone 3 Surficial

Sediments

Figure 3-33: Double Ratio Plot of C2D/C2P and C3D/C3P for All Source and Zone 4 Surficial

Sediments

Figure 3-34: Plots Showing Fe Versus Al, Ba, and Cr for Surficial Sediments from Outermost

Cook Inlet (Zone 0) and the Shelikof Strait (Zones 0, 1, 2, 3 and 4)

Figure 3-35: Plots Showing Fe Versus Cu, Hg, and Ni for Surficial Sediments from Outermost

Cook Inlet (Zone 0) and the Shelikof Strait (Zones 0, 1, 2, 3 and 4)

Figure 3-36: Plots Showing Fe Versus Pb, Sn, and Zn for Surficial Sediments from Outermost

Cook Inlet (Zone 0) and the Shelikof Strait (Zones 0, 1, 2, 3 and 4)

Figure 3-37: Bar Graph Showing Concentrations of Simultaneously Extracted Metals (SEM)

and Acid Volatile Sulfide (AVS) for each Station

Figure 3-38 Bar Graph Showing Concentrations of Simultaneously Extracted Metals for Cu,

Ni, and Zn

Figure 3-39: Vertical Profiles Showing Activities of Excess ““Pb and 13’Cs for Sediment Core

97-Z3F2 versus Sediment Depth

Figure 3-40: Vertical Profiles Showing Activities of Excess 21”Pb and 13’Cs for Sediment Core

98-Z0Fl versus Sediment Depth

Figure 341 Vertical Profiles Showing Activities of Excess 21!Pb and 13’Cs for Sediment Core

97-Z0F5 versus Sediment Depth

Figure 3-42: Vertical Profiles Showing Activities of Excess “!Pb and 13’Cs for Sediment Core

97-Z0F6 versus Sediment Depth

Figure 343: Vertical Profiles Showing Activities of Excess 21!Pb and 13’Cs for Sediment Core

97-Z0F8 versus Sediment Depth

Figure 3-44: Vertical Profiles Showing Activities of Excess 21”Pb and 13’Cs for Sediment Core

97-ZlFl versus Sediment Depth

Figure 3-45: Vertical Profiles Showing Activities of Excess ““Pb and 13’Cs for Sediment Core

97-ZlF2 versus Sediment Depth

Figure 346: Vertical Profiles Showing Activities of Excess 21(‘Pb and 13’Cs for Sediment Core

98-ZlR3B versus Sediment Depth

Figure 3-47: Vertical Profiles Showing Activities of Excess 21”Pb and 13’Cs for Sediment Core

98-Z2F2 versus Sediment Depth

Figure 3-48: Vertical Profiles Showing Activities of Excess 21?b and 13’Cs for Sediment Core

97-Z2R16 versus Sediment Depth

Figure 3-49: Vertical Profiles Showing Activities of Excess 21?b and 13’Cs for Sediment Core

97-Z2Fl versus Sediment Depth

Figure 3-50: Vertical Profiles Showing Activities of Excess 21(‘Pb and 13’Cs for Sediment Core

97-Z3Fl versus Sediment Depth

xii
Figure 3-51: Vertical Profiles Showing Activities of Excess 21’?Pb and 13’Cs for Sediment Core

98-Z4F4 versus Sediment Depth

Figure 3-52: Vertical Profiles from Sediment Core 97-Z0Fl (Homer Harbor) for Al, Fe, Silt

Plus Clay, TOC, and Selected Trace Metals

Figure 3-53: Vertical Profiles from Sediment Core 98-Z0Fl (Homer Harbor) for Al, Fe, Silt

Plus Clay, TOC, and Selected Trace Metals

Figure 3-54: Vertical Profiles from Sediment Core 97-ZOF5 for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-55: Vertical Profiles from Sediment Core 97-ZOF6 for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-56: Vertical Profiles from Sediment Core 98-Z0F8 for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-57: Vertical Profiles from Sediment Core 97-ZlFl for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-58 Vertical Profiles from Sediment Core 97-ZlF2 for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-59: Vertical Profiles from Sediment Core 98-ZlR3B for Al, Fe, Silt Plus Clay, TOC,

and Selected Trace Metals

Figure 3-60: Vertical Profiles from Sediment Core 97-Z2Fl for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-61: Vertical Profiles from Sediment Core 97-Z2F2 for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-62: Vertical Profiles from Sediment Core 98-Z2R16 for Al, Fe, Silt Plus Clay, TOC,

and Selected Trace Metals

Figure 3-63: Vertical Profiles from Sediment Core 97-Z3Fl for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-64: Vertical Profiles from Sediment Core 97-Z3F2 for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-65: Vertical Profiles from Sediment Core 98Z4F4 for Al, Fe, Silt Plus Clay, TOC, and

Selected Trace Metals

Figure 3-66: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station Z0Fl

versus Sediment Depth (1997)

Figure 3-67: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station Z0Fl

versus Sediment Depth (1998)

Figure 3-68: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station ZOF5

versus Sediment Depth (1997)

Figure 3-69: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station ZOF6

versus Sediment Depth (1997)

Figure 3-70: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station ZOF8

versus Sediment Depth (1998)

Figure 3-71: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station ZlFl

versus Sediment Depth (1997)

hthar D Little . . . XIII
Figure 3-72: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station ZlF2

versus Sediment Depth (1997)

Figure 3-73: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station Z2Fl

versus Sediment Depth (1997)

Figure 3-74: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station Z2F2

versus Sediment Depth (1997)

Figure 3-75: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

Z2R16 versus Sediment Depth (1998)

Figure 3-76: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station Z3Fl

versus Sediment Depth (1997)

Figure 3-77: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station Z3F2

versus Sediment Depth (1997)

Figure 3-78: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station Z4F4

versus Sediment Depth (1998)

Figure 3-79: PAH distribution for Halibut Livers Zone 2, Station R14a-H2 (top) and Zone 2,

Station R14a-Hl (bottom)

Figure 3-80: Concentrations of Zn, Cu and Cd in Liver Composite Samples from Halibut

Figure 3-81: Concentrations of As, Hg, and Pb in Liver Composite Samples from Halibut

Figure 3-82: Concentrations of Zn, Cu and Cd in Liver Composite Samples from Pacific Cod

Figure 3-83: Concentrations of As, Hg and Pb in Liver Composite Samples from Pacific Cod

Figure 3-84: Zinc Concentrations in Liver Composite Samples from Halibut as a Function of

Fish Length and Fish Weight, as well as Cu Values in Liver Composite Samples

from Halibut versus Fish Weight

Figure 3-85: Concentrations of Hg in Flesh (Muscle) Samples from Halibut versus Fish Length

Figure 3-86: Ratio of Zone Coefficient of Variation to Coefficient of Variation at all Stations for

Surface Sediments Collected in 1997

Figure 3-87: P450 Reporter Gene System Response to 1 ng Tetrachlorodibenzo-p-dioxin/mL

Chapter 4

Figure 4-l: Grain Size Contour Map, MMS Shelikof Strait and Outermost Cook Inlet

Figure 4-2: Percent TOC versus Silt + Clay for Surficial Sediments for Zones 0, 1, 2, 3 and 4

Figure 4-3: Concentrations of Fe versus (a) Cr and (b) Zn in Surficial Sediments from

Outermost Cook Inlet (Zone 0) and the Shelikof Strait (Zones 1, 2, 3 and 4)

Figure 4-4: Concentrations of Fe versus (a) Pb and (b) As in Surficial Sediments from

Outermost Cook Inlet (Zone 0) and the Shelikof Strait (Zones 1, 2, 3 and 4)

Figure 4-5: Concentrations of Fe versus (a) Ba and (b) Cd in Surficial Sediments from

Outermost Cook Inlet (Zone 0) and the Shelikof Strait (Zones 1, 2, 3 and 4)

Figure 4-6: Concentrations of Fe versus (a) Ni and (b) V in Surficial Sediments from

Outermost Cook Inlet (Zone 0) and the Shelikof Strait (Zones 1, 2, 3 and 4)

Figure 4-7: Concentrations of Fe versus (a) Cu and (b) Hg in Surficial Sediments from

Outermost Cook Inlet (Zone 0) and the Shelikof Strait (Zones 1, 2, 3 and 4)

xiv
Figure 4-8: Total PAH Concentrations Contour Map, MMS Shelikof Strait and Outermost

Cook Inlet

Figure 4-9: Vertical Profiles of Pb and Hg Values in Sediment Cores versus Time (Station

identification in lower left hand comer)

Figure 4-10: Vertical Profiles of Cr and Cd Values in Sediment Cores versus Time (Station

identification in lower left hand comer)

Figure 4-l 1: Sediment Core Profile of Perylene within each Zone

Figure 4-12: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Cores Z0Fl

(Core-depth) and Sources (abbreviations are in Table 2-2)

Figure 4-13: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Cores ZOF5 (top,

Core-depth), ZOF6 (bottom, Core-depth) and Sources (abbreviations are in Table

2-2)

Figure 4-14: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Core Z0F8

(Core-depth) and Sources (abbreviations are in Table 2-2)

Figure 4-15: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Cores ZlFl (top,

Core-depth), ZlF2 (bottom, Core-depth) and Sources (abbreviations are in Table

2-2)

Figure 4-16: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Cores Z2Fl (top,

Core-depth), Z2F2 (bottom, Core-depth) and Sources (abbreviations are in Table

2-2)

Figure 4- 17: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Core Z2R16

(Core-depth) and Sources (abbreviations are in Table 2-2)

Figure 4-18: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Cores Z3Fl (top,

Core-depth) Z3F2 (bottom, Core-depth) and Sources (abbreviations are in Table

2-2)

Figure 4-19: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Core Z4F4

(Core-depth) and Sources (abbreviations are in Table 2-2)

Figure 4-20: Comparison of Minimum, Mean, and Maximum Concentrations of (a) Ag, (b) As,

and (c) Cd for Surficial Sediments from Zones 0, 1, 2, 3 and 4 to the Effects Range

Low (ERL) and the Effects Range Medium (ERM) Values (Long et al, 1995)

Figure 4-21: Comparison of Minimum, Mean, and Maximum Concentrations of (a) Cr, (b) Cu,

and (c) Hg for Surficial Sediments from Zones 0, 1, 2, 3 and 4 to the Effects Range

Low (ERL) and the Effects Range Medium (ERM) Values (Long et al, 1995)

Figure 4-22: Comparison of Minimum, Mean, and Maximum Concentrations of (a) Ni, (b) Pb,

and (c) Zn for Surficial Sediments from Zones 0, 1, 2, 3 and 4 to the Effects Range

Low (ERL) and the Effects Range Medium (ERM) Values (Long et al, 1995)

Figure 4-23: Comparison of Sediment Total PAH Concentrations to ERL, and ERM Values

(Long et al, 1995)
ACC

ADL

AMS

ANOVA

APHA

ASTM

AVS

AWQC

B WEq

BPTCP

CAB

CIRCAC

CPI

CTD

c v

CVAAS

DCM

DDW

DO

DQO

DTT

E&P

EDTA

EPA

ERL

ERM

EVS

FAAS

GC

GC/MS

GFAAS

GLM

GPC

HCl

HPLC

ICP/MS

ID

IHC

Alaska Coastal Current

Arthur D. Little, Inc.

Applied Marine Sciences

Analysis of Variance

American Public Health Association

American Society for Testing and Materials

Acid-Volatile Sulfide

Ambient Water Quality Criteria

Benzo[a]pyrene Equivalents

California State Bay Protection and Toxic Cleanup Program

Cellulose-Acetate-Butyrate

Cook Inlet Regional Citizens’ Advisory Council

Carbon Preference Index

Conductivity, Temperature, and Depth

Coefficient of Variation

Cold Vapor Atomic Absorption Spectrometry

Dichloromethane

Distilled Deionized Water

Dissolved Oxygen

Data Quality Objectives

Dithiothreitol

Exploration and Production

Ethylene Diamine Triacetic Acid

U. S. Environmental Protection Agency

Effects Range-Low

Effects Range-Medium

EVS Environment Consultants

Flame Atomic Absorption Spectrometry

Flame Ionization Detector

Florida Institute of Technology

Gas Chromatography

Gas Chromatography/Mass Spectrometry

Graphite Furnace Atomic Absorption Spectrometry

General Linear Model

Gel Permeation Chromatography

Hydrochloric Acid

High-Performance Liquid Chromatography

Inductively Coupled Plasma-Mass Spectrometry

Inner Diameter

Immunohistochemical

List of Acronyms and Abbreviations
LALK

LCS

MDL

MMS

MPN

MPS

NCS

NIST

NOAA

NODC

N/P

NRC

ocs

OS1

PAH

PCB

PERL

%REC

PHC

ppb

ppm

ppt

%

PVC

QA

QA/QC

QC

RF

RGS

RLU

RPD

rpm

RSD

S/T

SAOB

SD

SEM

Instrumental Reference Material

Lower Molecular Weight Alkanes

Laboratory Control Spike

Method Detection Limit

Minerals Management Service

Most Probable Number

Mean Percent Survival

Minimum Reporting Limit

Nitrogen-Carbon-Sulfur Analyzer

National Institute of Standards and Technology

National Oceanic and Atmospheric Administration

National Oceanographic Data Center

Naphthalene/Phenanthrene Ratio

National Research Council of Canada

Northern Testing Laboratory

Outer Continental Shelf

Organism-Sediment Index

Polycyclic Aromatic Hydrocarbon

Polychlorinated Biphenyl

Pacific Ecorisk Laboratory

Percent Recovery

Petroleum Hydrocarbons

Parts Per Billion

Parts Per Million

Parts Per Trillion

Parts Per Thousand

Polyvinyl Chloride

Quality Assurance

Quality Assurance/Quality Cointrol

Quality Control

Research Vessel

Response Factor

Reporter Gene System

Relative Light Unit

Relative Percent Difference

Revolutions Per Minute

Relative Response Factor

Relative Standard Deviation

Steranes/Triterpanes

Sulfide Antioxidant Buffer

Standard Deviation

Simultaneously Extracted Metals

xvii

%o
SFBRMP

SHC

SlM

SKM

SL

SN-K

SOD

SOP

SPI

SRM

TALK

TBPF

TCDD

TEQ

TL

TOC

TPHC

UCM

USGS

V/V

WQC

ZGFAAS

San Francisco Bay Regional Monitoring Program for Trace Sediments

Saturated Hydrocarbons

Selected Ion Monitoring

Susitna-Knik-Matanuska River System

Standard Length

Student-Newman Keuls

Sediment Oxygen Demand

Standard Operating Procedure

Sediment Profile Imaging

Standard Reference Material

Total Alkanes

Trading Bay Production Facility

Tetrachlorodibenzo-p-dioxin

Toxic Equivalents

Total Length

Total Organic Carbon

Total Petroleum Hydrocarbons

Unresolved Complex Mixture

United States Geologic Survey

Volume to Volume

Water Quality Criteria

Wastewater Treatment Facility

Zeeman Graphite Furnace Atomic Absorption Spectrometry
Executive Summary

Background

Oil and gas exploration, production, and transportation activities in Cook Inlet, Alaska have the

potential for impacting marine resources. Though these operations are well-managed and are

regulated so as to minimize the input of pollutants to the marine environment, the longer-term

accumulation of pollutants in depositional areas on the sea floor is an area of concern when

contemplating future Outer Continental Shelf (OCS) leases.

After discharge, contaminants that are in a particulate form or which are sorbed to particles after

discharge are rapidly diluted due to a large combined water flow from tidal, current, and riverine

inputs of fresh and seawater. Though at low levels in the water column, a combination of

oceanographic and sediment transport processes pointed to the lower Cook Inlet (Kamishak and

Kachemak Bays) and Shelikof Strait as potential areas for this longer-term deposition of these

sorbed pollutants.

Estimation of current impact and prediction of future environmental risk and impacts were

complicated by the existence of multiple sources of similar pollutant assemblages to the region

beyond exploration and production (E&P) operations. Natural oil seepages were common in the

area and were known to represent an important part of the hydrocarbon assemblage in the

sedimentary environments of areas of the Gulf of Alaska. Oil spillages, especially that from the

Exxon Valdez spill, were potential contributors, though no evidence of the impact of this spill, in

particular, was observed in the subtidal sediments of Cook Inlet or Shelikof Strait. Tremendous

quantities of suspended material were swept into the region from glacial runoff with associated

metals and hydrocarbons. Municipal discharges and other permitted industrial (e.g., seafood

processing) discharges contributed important quantities of wastes over time to the immediate

coastal areas and presumably to the area’s deeper depositional locations.

Study Rationale

Because of the need to definitively examine the distribution and environmental risk of

anthropogenic chemicals (i.e., metals, petroleum hydrocarbons including polynuclear aromatic

hydrocarbons [PAHs]) in advance of any future oil and gas E&P activities that could potentially

affect the lower Cook Inlet and Shelikof Strait, MMS contracted with Arthur D. Little, Inc.

(ADL) to undertake a two-year study in the region.

The objectives of the study were to:

. Evaluate the Shelikof Strait and outermost Cook Inlet as potential depositional areas or

“traps” for oil industry contaminants . Determine whether contaminant concentrations in sediments of these areas pose an

environmental risk

. Determine whether contaminants in these areas have accumulated relative to pre-industry

concentrations

ES-1

Arthur D Little
. Determine whether any increases can be correlated with specific discharge events or

activities (e.g., the Exxon Valdez oil spill) . Determine the importance of other hydrocarbon and metal sources to the sediments

The study objectives were recast in a risk assessment-type framework (U.S. EPA;

EPA/630/R-95/002, Draft Proposed Guidelines for Ecological Risk Assessment). In this

framework a formulation of the problem leads to a characterization of exposure and effects,

which in turn leads to a characterization of the risk. This program was structured to follow that

approach to meeting the goals.

In designing an investigation to meet these goals, ADL and its team members put forth several

hypotheses for scientific testing. These hypotheses were:

. Hypothesis 1: The offshore area of outermost Cook Inlet and Shelikof Strait is not a trap

for organic and metal pollutants (i.e., there is no indication of deposition) . Hypothesis 2: Concentrations of organic and metal contaminants in sediment cores do not

show increases since before offshore oil exploration and production began in Cook Inlet

(circa 1963) . Hypothesis 3: Compositions of organics and metals in sediment cores do not show

changes in composition since before offshore oil exploration and production began in

Cook Inlet (circa 1963) . Hypothesis 4: Concentrations of organic and metal contaminants in outermost Cook Inlet

and Shelikof Strait do not pose any environmental risk

The field program was designed to collect data to test these null hypotheses. Hypotheses are

stated as the null hypotheses since the null hypotheses were tested during the statistical analyses.

Field Program Design

The design of the data acquisition/field program for the two-year study focused on two facets.

The first was the deep subtidal bottom sediments of the region as the focal point of any

long-range contaminant deposition. The design was intended to obtain both chemical (i.e.,

exposure) and biological (i.e., effects) data on surface sediments. It also was directed at looking

at historical deposition in the study area through the use of dated sediment cores. The second

facet addressed the status of chemical body burdens in bottom-feeding fish and indicators of

sublethal effects. These “biomarker” measurements were made to address their exposure to

contaminants.

The field sampling design included:

. Separation of the study area into four zones, each assumed to be relatively homogeneous . The selection of a group of random sediment stations in each zone from a large number of

candidate stations, each station representing a replicate of that zone . The selection of fixed or biased stations at key locations from which we wanted to obtain

data . The selection of a limited number of stations from each zone (including the fixed

ES-2
stations) from which to take replicates to examine within-station variability . The selection of additional sampling stations in the Gulf of Alaska off the Kenai

Peninsula to represent “upstream” source material . The selection of additional stations south of Shelikof Strait to examine longer-range

transport . The field-truthing of the suitability of each station prior to sampling . The sampling of stations for surface sediments; selected locations for sediment coring;

and selected locations for obtaining fish samples . The selection and sampling of potential contaminant sources -- oil seeps; river runoff;

coal seams; and oil and gas operational discharges

Analytical Design

The analytical design centered on organic (i.e., petroleum-related) and metal parameters as

measured in sediment, sediment core, fish tissue, and source samples. The design consisted of

the following measurements:

.

.

.

.

.

Petroleum hydrocarbons (PHC), including PAHs of petroleum and other origins, and

steranes/triterpanes (S/T) in sediments and PAHs in fish tissue

The use of detailed alkylated PAHs and S/T to elucidate source characteristics of source

samples and source identification in the field samples

Major and trace metals including silver, aluminum, arsenic, barium, beryllium, calcium,

cadmium, chromium, copper, iron, mercury, potassium, manganese, magnesium, nickel,

lead, antimony, selenium, tin, thallium, vanadium, and zinc in sediments

Acid volatile sulfide/simultaneously extracted metals (AVS/SEM) in sediments (Year 1

only)

All metals except calcium, potassium, magnesium, and nickel in fish tissues

Amphipod toxicity tests in sediments

Reporter gene system (RGS) P450 measurements for sediment and fish tissue extracts

Cytochrome P450 (CYP1A) induction determinations on selected tissues

Dating of sediment cores by 21”lead and 13’cesium methods and analysis of core sections

for hydrocarbons and metals as in the surface sediments

Sediment profile imagery (SPI) of surface sediments (Year 1 only)

Findings

The analysis of the findings was used to perform tests of the study’s four hypotheses, using field

data from 1997 and 1998. The outcomes of this hypothesis testing are as follows:

. Potential for contaminant deposition in the study area. In summary, in the context of the

null hypothesis, the surface sediments of outermost Cook Inlet and the Shelikof

Strait are traps for fme-grained sediment and are potential traps for contaminants

from oil and gas production activities in upper Cook Inlet. However, based on

evaluations of the organic and inorganic data, no contamination in the surface sediments

from oil and gas production activities in upper Cook Inlet was identified. Elevated Hg

concentrations were identified in Kachemak Bay. However, the present-day Hg levels are

ES-3

AnthwDLittie
comparable to values observed throughout the twentieth century, suggesting that the Hg

results are typical for the region.

. Contaminant depositional changes over time. In summary, in the context of the null

hypothesis, the concentrations of metals and organics (i.e., PAHs) in sediments in

outermost Cook Inlet and Shelikof Strait have not increased significantly since

offshore oil exploration and production began in Cook Inlet (circa 1963).

. Compositional changes over time. In the context of the null hypothesis, the composition

(source[s]) of metals in the sediments of outermost Cook Inlet and Shelikof Strait do

not appear to have changed since offshore oil exploration and production began in

Cook Inlet (circa 1963). The composition of hydrocarbons in sediment cores shows

subtle changes in outermost Cook Inlet over the past 25 to 50 years, but these

changes do not appear to be correlated with petroleum production activities or

spills.

The study of the magnitude of sediment deposition from the major rivers in the region

(i.e., Susitna-Knik-Matanuska; Copper River) indicates that the Copper River accounts

for 10 to 20 percent of the total sediment deposited in the study area.

. Assessment of risk. The two sampling seasons have provided a picture of contaminants

and potentially toxic trace substances in the environment at very low concentrations with

an attendant low biological risk. Using multiple measures of risk that were built into the

study design, we conclude that the concentrations of organics (i.e., PAHs) and metals

do not appear to pose any immediate ecological risk to the marine environment in

the study area.

The concentrations of trace metals are consistently below the risk levels identified by

Long and Morgan (1995), except for Ni, which has a crustal abundance higher than the

designated effects range-low (ERL) and effects range-medium (ERM) concentrations, and

Cu. Concentrations of Cu exceeded the ERL in a number of cases, but source sediment

from the Susitna River along with Alaskan rocks, show that natural levels of Cu are all

close to or above the ERL value.

The concentrations of PAH detected in sediments are also below the ERL identified by

Long and Morgan (1990).

The P450 RGS results also indicated low to negligible biological risk associated with

extractable organic compounds, namely PAH, in the sediments. Sediment bioassays with

two species of amphipods indicate that sediment chemicals do not exhibit any significant

toxicity. Some low survival rates appear to be related to testing sediments with high silt

content rather than any trace chemicals in the sediments.

The levels and patterns of induction of CYP1A in cells of bottom-dwelling fish (i.e.,

Halibut and Pacific Cod) are consistent with some mild induction by contaminants, but

with weak induction in the gills they appear not to be waterborne, but rather from the diet.

ES-4
None of the measured contaminants in the fish tissues correlated with CYP1A induction,

but chlorinated hydrocarbons were not measured. Specifically, the results on the

hepatocytes and the kidney cells are consistent with some low level of enzyme-inducing

compounds in the diet of these fish. There were no significant correlations between the

CYPlA scores and the locations (i.e., zones) of the fish.

In summary, using multiparameter measures to assess potential exposure and potential risk, the

comprehensive findings of this two-year investigation indicate that the current concentrations

of metals and PAHs in the Shelikof Strait and Outermost Cook Inlet are neither linked to

oil and gas development in the upper Cook Inlet, nor to the Exxon Valdez oil spill. The

residues that are present, from a combination of natural sources -- river inputs, oil

seepages, etc. -- pose no significant risk to the biota and the benthic environment of

outermost Cook Inlet and Shelikof Strait. The degree of current risk is indeed very low and is

similar to non-impacted coastal regions in Alaska and elsewhere.

ES-5
1.0 Introduction

The Minerals Management Service (MMS) program “Sediment Quality in Depositional Areas of

Shelikof Strait and Outermost Cook Inlet,” consisted of a two-year study whose hypotheses and

objectives are explored in this report. As part of this study, a scientific crew on board the

Research Vessel (R/V) Alpha Helix, collected samples for biological, chemical, and toxicological

analyses from the program study area during two sampling surveys. The first survey was

conducted from July 7 to July 17, 1997 and the second undertaken the following year, from June

27 to July 5, 1998. In this report, the final results including the field sampling and analytical

methods are summarized, and the results and interpretation of the chemical, biological, and

physical measurements from both the 1997 and 1998 field surveys are presented.

1.1 Background

The purpose of this two-year study was to provide and update environmental information to

support future MMS oil- and gas-leasing decisions in the outermost Cook Inlet/Shelikof Strait

planning area. Such uses of this information include environmental risk assessments,

environmental impact statements, and other pre- and post-leasing decision documents. This

study was initiated to establish baseline environmental conditions prior to any oil- and gasleasing activities. The results of the entire two-year field survey data are described in this report.

The literature on the study area has been reviewed and summarized as part of this program

(Boehm et al., 1998) and an excerpt appears below.

1.1.1 Physical Setting

Cook Inlet is a large tidal estuary, 350 km long and ranging from 20 to 90 km wide. The average

water depth is approximately 60 m, varying from 100 m near the entrance to less than 20 m near

the head of the estuary (Arthur D. Little, 1995). It is bordered on the west and northwest by the

Alaska Range, on the northeast by the Talkeetna Mountains, and on the southeast by the KenaiChugach Mountains. Cook Inlet can be divided into three distinct regions: the head, consisting

of Knik and Turnagain Arms; upper Cook Inlet, extending from the Forelands to Point

Woronzof; and lower Cook Inlet, from the Porelands to the Gulf of Alaska. Outermost Cook

Inlet, as defined by the area encompassing both the Kachemak and Kamishak Bays, from Cape

Douglas to the Barren Islands in the Gulf of Alaska, is the potential depositional area on which

this study focused.

Shelikof Strait is a marine channel situated between the Kodiak Island archipelago and the

Alaska Peninsula. Shelikof Strait is approximately 200 km long and 50 km wide. A central

trough extending beyond both ends of Shelikof Strait characterizes the sea floor, which has a

gradually southwest-sloping central platform bordered by narrow marginal channels. Currents

bring sediment into the northwest end of the strait from Cook Inlet, near Cape Douglas,

depositing a covering of well stratified sediment throughout the depositional areas of the strait.

The complex oceanography and biology of the outermost Cook Inlet and Shelikof Strait are

described in detail in the literature study (Boehm et al., 1998) and summarized briefly below.

ArtharD Little

l-1
1.1.2 Oceanography

Interactions of tides and geostrophic, baroclinic, and wind-induced currents with the topography

of outermost Cook Inlet and Shelikof Strait provide a complex hydrographic regime that

determines the distribution and eventual deposition of particle-associated contaminants released

from offshore production platforms in upper Cook Inlet (Hampton et al., 1987). Vigorous, tidalinduced mixing results in strong initial dilution of contaminant inputs at their sources with

naturally derived terrigenous materials. The main sources of these natural sediments are several

large, glacially influenced rivers emptying into upper Cook Inlet, while, farther south and east in

the Inlet and in Shelikof Strait, the Copper River to the east of the study area is the predominant

source of suspended sediments. These suspended sediments are transported by the Kenai Current

(the Alaska Coastal Current [ACC]) along the Kenai Peninsula into lower Cook Inlet and

Kachemak Bay, as well as Shelikof Strait (Hampton, 1985).

The import of inshore flow to Cook Inlet-Shelikof Strait is through the Kennedy and Stevenson

Entrances, while offshore flow occurs through these passages as well as the lower end of

Shelikof Strait. With the slackening of prevailing winds during the summer months in the Gulf

of Alaska, the strong onshore convergence relaxes. As a consequence, cold, nutrient-rich water

is upwelled onto the shelf (Strickland and Sibley, 1984) and can be observed in the general area

of the passages on either side of the Barren Islands. This upwelled water supports high gross

biological productivity in the study area. A large, clockwise gyre develops in eastern Cook Inlet

offshore of Kachemak Bay, although net flow is to the southeast through outermost Cook Inlet.

In Shelikof Strait, net flow is also strongly to the southeast; however, mesoscale eddies have also

been documented in the surface waters in the northeast portion of Shelikof Strait (Schumacher et

al., 1993; Bogard et al., 1994). The main sediment deposition sites in the study areas are the

shallows of Kamishak Bay (for sediments transported down the western side of Cook Inlet),

Kachemak Bay (with a strong component of Copper River sediments), and some deeper portions

of outermost Cook Inlet and Shelikof Strait (Hampton et al., 1987). Other possible sites of

sediment deposition of platform materials from upper Cook Inlet include glacier-incised scars in

the Kodiak shelf, the shelf slope, and shallow bays on either side of Shelikof Strait. However,

local sources become increasingly important with distance from the upper Cook Inlet, and sills

limit the depths from which suspended materials may be imported.

1.1.3 Biology

The northern shelf of the Gulf of Alaska is extremely productive, and annual primary

productivity in outermost Cook Inlet is greater than 300 g C me2 (Sambrotto and Lorenzen,

1987). The intrusion of cold, nutrient-rich water brought by the ACC into outermost Cook Inlet

in late spring and summer, combined with long days, supports vigorous biological activity in the

oceanic regime from phytoplankton growth through baleen whale foraging. The Cook

Inlet/Shelikof Strait area contains a great variety of biological habitats. Shallow intertidal and

subtidal areas are predominantly unconsolidated sediments containing mainly polychaetes,

bivalves, crustaceans, and echinoderms (O'Clair and Zimmerman, 1987; Feder and Jewett, 1987).

These habitats also support a rich variety of algae and epibenthic invertebrates, and are

frequented by nekton, pelagic fishes, nearshore demersal fishes (Rogers et al., 1986), a variety of

seabirds, and several species of marine mammals. Rocky habitat is much less common in Cook

1-2
Inlet and Shelikof Strait, although it predominates on Kodiak Island. The rocky intertidal

habitats are dominated by barnacles, limpets, mussels, and snails, a rich variety of attached algae,

other invertebrates, and associated semidemersal fishes (O’Clair and Zimmerman, 1987). The

deeper neritic environments are dominated by typical pelagic and nektonic communities, and

overlay important benthic environments in the finer unconsolidated sediments, including those

expected to be depositional areas for platform-derived contaminants (Hampton et al., 1987).

Here the communities are also dominated by polychaetes, crustaceans, echinoderms, and bivalves

with a variety of demersal, semidemersal, and associated pelagic fishes. The peculiarities of

sediment transport put the main depositional areas for platform-derived contaminants in both

shallow water embayments (e.g., Kamishak Bay) and deeper open waters (deeper portions of

outermost Cook Inlet, bottom of Shelikof Strait, and shelf slope).

1.2 Objectives

Due to the need to definitively examine the distribution and environmental risk of anthropogenic

chemicals (i.e., metals, petroleum hydrocarbons) in advance of any future oil and gas E&P

activities that could potentially affect the lower Cook Inlet and Shelikof Strait, MMS established

a multi-disciplinary sediment quality evaluation program for the region. The objectives of the

overall MMS program were to evaluate:

0 The Shelikof Strait and outermost Cook Inlet depositional areas as traps for oil-industry

contaminants.

0 Whether the contaminant concentrations in sediment of these areas pose an

environmental risk.

l Whether contaminants in these areas have accumulated relative to pre-industry

concentrations and to determine whether any increases can be correlated to specific

discharge events or activities (e.g., the Exxon Valdez spill).

1.2.1 Null Hypotheses

Based on the objectives of the program, four null hypotheses were developed. These null

hypotheses were finalized at technical meetings held in May 1997 between the Arthur D. Little

team, MMS, industry and regulatory representatives (e.g., UNOCAL, Alaska Department of Fish

and Game, and U.S. Environmental Protection Agency [EPA]), and other interested parties (e.g.,

Cook Inlet Regional Citizens’ Advisory Council [CIRCAC]).

The hypotheses which form the scientific framework for the study are as follows:

l Hypothesis 1: The offshore area of outermost Cook Inlet and Shelikof Strait is not a

trap for organic and metals pollutants (i.e., there is no indication of net deposition).

l Hypothesis 2: Concentrations of organic and metal contaminants in sediment cores do

not show increases since offshore oil exploration and production began in Cook Inlet

(circa 1963).

l-3
. Hypothesis 3: Compositions of organics and metals in sediment cores do not show

changes in composition (i.e., cannot be correlated with known sources,. such as the

Exxon Valdez oil spill residues) since offshore oil exploration and production began in

Cook Inlet (circa 1963).

. Hypothesis 4: Concentrations of organic and metal contaminants in outermost Cook

Inlet and Shelikof Strait do not pose an ecological risk to marine organisms as defined

by sediment toxicology measurements (i.e., compared to reference sediments), sediment

quality criteria, and fish P-450 response.

The study design centered on the testing of these hypotheses. The first year’s effort in 1997

focused on sediment quality across the study area. Potential uptake of contaminants by bottomdwelling fish and resulting indicators of exposure to contaminants were also evaluated by

analyzing fish collected from each zone. Based on these results, a number of recommendations

were made to enhance the following year’s survey in 1998. These included additional source

sampling, expansion of the fish species collected, sampling for hydrocarbon degrading microbes,

and extending the sampling region to investigate the potential depositional area to the south of

Shelikof Strait. In this report, we evaluate the specific objectives and hypotheses based on the

entire field survey data.
2.0 Methods

In this section, the methods used in field sampling, field measurements, and laboratory analyses

are described.

2.1 Field Methods and Study Design

2.1 .1 Study Design

The program study area was identified as outermost Cook Inlet and Shelikof Strait of Alaska.

The term “outermost Cook Inlet” has been used to avoid confusion with the lower Cook Inlet

salmon district north of the study area. The study encompassed two separate field surveys, the

first undertaken in 1997 and the second in 1998. For purposes of the scientific program, five

regions or zones within the study area were defined as indicated in Figure 2-l. The first zone

(zone 0) was outermost Cook Inlet, including the region from Anchor Point across to

approximately Mt. Chinitna, and from the lower tip of Kenai Peninsula to the Barren Islands and

across to Cape Douglas. Zone 1 was defined as North Shelikof Strait, stretching from the Barren

Islands and Cape Douglas down to the mid-section of Afognak Island (Cape Paramanof) and

across the Alaska Peninsula. Zone 2 was defined as the mid-Shelikof Strait region, from the

mid-section of Afognak Island (Cape Paramanof) to Hal1o Bay on the Alaska Peninsula, and

down to Uganik Bay on Kodiak Island and Katmai Bay on the Alaska Peninsula. Zone 3 was

defined as the south Shelikof Strait region, stretching down from zone 2 to the widening area of

the strait as indicated in Figure 2-l. Finally, zone 4 was added during the 1998 survey and

extended to the south of zone 3, just southeast of Kodiak Island.

Stations for sediment sampling were composed of random and fixed stations. The locations of

the sampled random and fixed stations are provided in Table 2-l and shown in Figure 2-l. In

zones 1, 2, and 3 (Shelikof Strait), 15 random and 2 fixed stations were sampled in 1997, while 6

random and 2 fixed stations were sampled in each of these zones in 1998. In zone 0 (outermost

Cook Inlet), 8 fixed stations were sampled during each of the 1997 and 1998 surveys. Only fixed

stations were selected from outermost Cook Inlet due to the limited area where potential

depositional environments could be identified (i.e. mud or silt/clay bottom). Three fixed stations

were sampled in zone 4, exclusive to the 1998 survey.

Random stations were selected in zones 1, 2, and 3 by establishing a 5-km grid within the 50

fathom depth contour of each zone. This grid resulted in more than 100 blocks fully contained in

each zone. Each block within a zone was sequentially numbered. Random numbers were then

generated to identify the random stations within each zone. The first 15 stations randomly

identified in each zone that contained silt/clay sediment, based on historical data, were

established as the primary random stations. The station location was positioned in the center of

the random block selected. An additional 10 alternate stations in each zone were identified in the

same manner. The selection criteria for alternate stations were defined so that the next closest

alternate station was selected if sampling at any random or fixed station was unsuccessful (did

not contain silt/clay sediment). At each location, a grab sample was collected to determine if the

station sediment was acceptable for sampling. A sediment sample was considered acceptable if it

contained greater than 50 percent silt/clay (i.e., mud). The percent silt/clay was estimated by

ArthwDLittle

2-1
visual observation of the sediments. If the sediment sample was not acceptable, repeat grabs

were attempted at the station, but no more than three attempts were performed. If after repeated

grab attempts the station was deemed unacceptable, the next closest alternate station was selected

from the list in the sampling and logistics plan (Arthur D. Little, 1997a).

Several alternate stations were sampled during the course of the survey due to inappropriate

bottom substrate. In Table 2-1, the alternate stations sampled and the rationale for requiring an

alternate station selection are included. The two fixed stations in zones 1, 2, and 3 were selected

in deep “holes” that contained depositional sediment. The three fixed stations in zone 4 were

selected in deep areas where fine-grained depositional sediment was likely to occur.

The eight fixed stations in zone 0 were selected to obtain representative spatial coverage within

the zone (e.g., Kachemak Bay, Kamishak Bay, and Kennedy Entrance). The eight fixed stations

were selected from areas where historical grain-size data indicated depositional sediments

occurred. In addition, four alternate fixed stations were identified in case depositional sediment

could not be collected from any of the eight primary fixed stations.

2.1.2 Field Sampling

The 1997 field survey was conducted aboard the R/V Alpha Helix, based out of the University of

Alaska, Seward Marine Center, Alaska. The cruise was conducted from July 7 to July 17, 1997,

and coincided with the most favorable tidal and current conditions in the program study area.

The field team arrived in Seward, Alaska on July 6. Mobilization of the field team and the R/V

Alpha Helix took place on July 7, and the R/V Alpha Helix departed Seward on July 8, 1997.

Sediment and fish sampling was conducted from July 9 through July 16. The Alpha Helix

returned to Seward on July 17 for demobilization at the Seward Marine Center. Field sampling

personnel from Arthur D. Little, Inc. (ADL), the Florida Institute of Technology (FIT), Applied

Marine Sciences (AMS), EVS Environment Consultants (EVS), and MMS participated in the

survey. The scientific team and ship’s crew conducted the work on a 24-hour-a-day shift

schedule.

The 1998 field survey was also conducted aboard the R/V Alpha Helix, from June 27 to July 5,

1998. After arrival of the field team on June 25, the mobilization of the R/V Alpha Helix and the

field team occurred on June 26, followed by departure from Seward on June 27, 1998. Sediment

and fish sampling was conducted from June 27 through July 5. The Alpha Helix returned to

Seward on July 5 (one day ahead of schedule) for demobilization at the Seward Marine Center.

Field sampling personnel from ADL, FIT, AMS, and MMS participated in the survey, with the

scientific team and ship’s crew conducting the work on a 24-hour-a-day shift schedule.

The field sampling methods were conducted in accordance with the ADL Team’s Standard

Operating Procedures (SOPS). The field sampling and logistics plan (Arthur D. Little, 1997a;

Arthur D. Little, 1998a), prepared for the 1997 field survey, provides detailed explanation of the

field methods used in sample collection, equipment decontamination, subsampling of fish tissues

and sediment cores, and sediment profile imaging (SPI) film development. In this section, we

summarize the methods for station selection, field sampling, and source sample collection.

2-2
Sediment samples were collected from 14 fixed stations and 45 random stations, fish samples

were collected from 3 stations, and 12 source samples were collected from the Shehkof Strait and

outermost Cook Inlet region in 1997. During the 1998 survey, sediments were collected from 19

fixed stations and 18 random stations, fish samples were collected from 3 locations, and an

additional 12 source samples were collected. All samples were analyzed for the appropriate

chemical and physical parameters. Figure 2-l shows the field survey station locations where

surface sediment, sediment core, and fish samples were taken. The samples collected are also

listed in Table 2- 1, which summarizes the station locations and number and type of samples

collected at each location and the analyses performed. Additional information is presented in the

field survey cruise reports (Arthur D. Little, 1997b; Arthur D. Little, 1998b). The sample

analysis results are discussed in Section 3.

The sequence of events at each sampling station followed specific procedures, described in detail

in the sampling and logistics plan (Arthur D. Little, 1997a; Arthur D. Little, 1998a), including:

Identify station (latitude and longitude)

Navigate to station position within 0.2 nautical mile (nm) radius of the grid location

Review the acoustic bottom profile for likelihood of depositional sediments

Deploy seabird conductivity, temperature, and depth (CTD) and collect CTD

measurements . Collect Van-Veen grab samples . Deploy SPI camera to photograph sediments on the ocean floor (1997 cruise only) . Deploy box core or gravity core, where appropriate, and collect sediment cores

Equipment decontamination procedures were followed as described in the sampling and logistics

plan (Arthur D. Little, 1997a). Decontamination typically included a physical scrub, rinses with

seawater and distilled water, and a rinse with ethanol or isopropanol.

Replicate samples were collected as part of the field sampling design. At several locations,

sediment samples were taken in triplicate, and at other locations as seven replicates (e.g., seven

sample jars for one location). Reproducibility and range of results were demonstrated by analysis

of replicate samples.

2.1.2.1 Conductivity, Temperature, and Depth Measurements

At each station, the seabird CTD was deployed to collect data on CTD. These data were

downloaded by a data logger to a computer system where they were analyzed, graphically

displayed, and stored electronically. The CTD data were recorded in hard copy and digital

format on board the Alpha Helix.

For most stations, the CTD was deployed to a depth of 2 m above the ocean floor. However, the

depth required for the CTD measurements was redefined due to the extended wire time involved

for deployments at deep stations in zones 2, 3, and 4. A maximum CTD depth of 200 m was

determined to be acceptable at deep stations. As a result, CTD measurements were collected to a

depth of 200 m (or bottom, whichever was shallower) during the R/V Alpha Helix cruises.

The CTD data collected will be submitted to the National Oceanographic Data Center (NODC)

in electronic format. It was not in the scope of work under this program to analyze the collected

CTD data, therefore, no discussions nor interpretation of data are included in this report.

hthwDLittle

2-3
2.1.2.2 Sediment Sampling

Sediment sampling included the collection of surface sediments and sediment cores. During the

collection and handling of sediment samples from the grab sampler, box core, and gravity core,

extreme care was taken throughout the subsampling process to avoid contact with metals and

hydrocarbon sources. Samples were taken away from the metal sides of the box core and no

metal spatulas were used for the trace metal samples. The grab sampler, box core, and gravity

core were protected from stack smoke, grease drips from winches and wire, and other potential

airborne contaminants during the sampling process.

Surface Sediments. The modified Van-Veen grab sampler (0.1 m*), constructed of stainless steel

and Kynar coated, was the primary equipment used for surface sediment sample (0 to 2 cm

depth) collection at all stations except where sediment cores were collected. For sediment cores,

a box core was used in addition to the Van-Veen grab sampler. The grab sampler was designed

to be deployed from a vessel equipped with a power winch and A-frame or boom system and to

collect undisturbed surface sediment samples to a maximum depth of approximately 15 cm. The

operation of the grab sampler for collection of a bulk sediment sample (SOP ADL-1018) and the

collection and handling of subtidal sediment chemistry samples from the Van-Veen grab sampler

(SOP ADL-1019) are summarized below.

The grab sampler required some modifications (a shock cord dampener and adjustable stainlesssteel feet) to successfully collect samples at deep stations in the heavy seas encountered during

the survey. In addition, the order of gear deployment was modified at some stations due to

limitations in the crane wire length (i.e., the grab sampler and CTD were deployed consecutively

from the hydrowire winch at many stations).

When the grab was returned to the deck of the vessel, the sample was visually inspected to ensure

the bucket was closed and the scissors extended upright. The doors were opened and the sample

was visually inspected for sediment and overlying water in the bucket. Overlying water indicates

that the sediment sample is undisturbed and that surface sediments remain intact (i.e., there was

no leakage of water and hence fine sediment from the grab). If the grab was successful, samples

were collected; if not, the grab’s contents were discarded and the grab was redeployed.

Subsamples were removed from the grab sampler through the hinged doors on the top of the

bucket. Overlying water was removed from the grab by siphoning through a precleaned Teflon@

tube using a siphon bulb, or by carefully cracking the grab jaws to allow the water to flow out

without disturbing the sediments. If used, the Teflon@ tube was decontaminated prior to use and

stored in precleaned aluminum foil.

Sediment samples were collected from the top 2 cm of the grab, which represents recent

accumulation. Unconsolidated sediment 2 cm deep was removed from the grab with an

aluminum, Kynar-coated scoop. The 2 cm-deep scoop facilitated accurate depth collection of the

sediment. The top 2 cm were collected by several scoops up to the volume needed for

subsamples and placed directly in appropriate sample containers for organics, metals, total

organic carbon (TOC), and grain-size analyses. At stations where toxicity samples were needed,

3 to 6 grabs were necessary to obtain enough sediment volume for toxicity subsamples. Toxicity

sediments from multiple grabs were cornposited in a Kynar-coated bowl. When the appropriate

volume was reached, the sample was homogenized in the bowl and then transferred into

2-4
appropriate precleaned containers. All sampling equipment was decontaminated before use as

outlined in the field sampling and logistics plan (Arthur D. Little, 1997a). Specific subsamples

were collected from each grab into their individual container and stored in the freezer or the

refrigerator (toxicity samples), as appropriate.

Trace metal samples were removed from the grab sampler with a Teflon’ spatula, placed into

labeled 48 mL plastic vials, and refrigerated. Samples to be used for grain-size analysis were

doubled-wrapped in labeled Ziploce storage bags and refrigerated.

Sediments for acid-volatile sulfide and simultaneously extracted metals (AVS/SEM) were

collected, exclusively during the 1997 sampling event, from the top 2 to 3 cm of the grab sampler

using a 50 mL plastic syringe with the lower end cut off such that the barrel was completely

open. The syringe was carefully pushed laterally into the sediment as the plunger was pulled

back. When the syringe was full, the outer plastic of the syringe was carefully wiped clean and

the open end was covered with Parafilm@. Syringes were placed in labeled plastic bags and

frozen.

Sediments were collected for hydrocarbon degrading microorganisms (1998 field survey only).

A top 2 cm sediment subsample from the grab was collected in a pre-cleaned plastic jar and

stored refrigerated. A total of 40 samples for hydrocarbon degrading organisms were collected in

1998 and shipped on ice to the University of Alaska, Fairbanks for analysis.

After the desired subsamples were removed, an open basin was placed beneath the grab on the

grab stand. The grab jaws were then opened by releasing tension on the lifting wire and

collapsing the scissor mechanism. Any remaining sediment that fell into the basin was

discarded. The grab was rinsed with clean seawater from the deck hose and decontaminated with

distilled water and ethanol/isopropanol rinses prior to deployment at a new station.

Sediment Cores. After grab samples, CTD measurements, and SPI (1997 cruise only) were

collected, an MK III box core was used to collect sediment cores at stations where geochronology

cores were specified. In addition, two gravity cores were collected from the 1997 cruise (Table

2-l) and archived frozen for possible future analysis. One gravity core was collected from the

1998 cruise and analyzed to obtain a deep sediment profile.

The box coring device was deployed by a remotely operated winch system to the ocean floor.

Prior to deployment, the box coring device was decontaminated according to procedures in the

field sampling and logistics plan (Arthur D. Little, 1997a).

After retrieval of the box core, the overlying water was siphoned off as quickly as possible

without disturbing the surface sediment layer. The inner box containing the sediment was moved

into a covered deck area to further reduce contamination. Sediment cores were collected by

carefully pushing four premeasured, 40 cm lengths of cellulose-acetate-butyrate (CAB) tubing

down into the box core. Then, one person reached into the sediment and, placing one hand over

the lower end of the CAB tubing, pulled the core out from the sampler. Both ends of the core

were capped and taped. The cores were labeled and stored upright in a refrigerator until

subsectioning was carried out within 24 to 48 hours. The CAB tubing had been precleaned with

detergent and water, then rinsed with distilled water.

2-5
Sediment cores were subsectioned aboard ship. Cores to be used for analysis of trace metals,

organic substances, and gram size were subsectioned into 2 cm intervals over the top 10 cm (5

samples) of the core and at 5 selectively spaced 2 cm intervals over the remainder of the core to

obtain 10 samples. Subsections were obtained by placing the core upright in a fixed holder and

slowly moving a polyvinyl chloride (PVC) piston up from the bottom of the core to extrude the

sediment. Using a ruler, a 2 cm section of sediment was carefully extruded. Then the outer layer

of sediment (2 to 3 mm) in contact with the CAB tubing was removed to minimize potential

contamination from the core liner or from any smearing during sample collection and/or

extrusion. Using a stainless-steel spatula, the extruded sediment was transferred to a clean glass

jar and homogenized. After homogenization, about 10 g of sediment (wet weight) for analysis of

metals and TOC were transferred to a labeled 48 mL plastic vial and stored in a refrigerator.

Sediment in the glass jar was stored frozen to preserve organic substances. Sediment samples

obtained from the core were set aside for grain-size analysis by placing them in labeled plastic

bags and storing them in a refrigerator. During 1997, whole cores for gram- size analysis were

returned to the Maxine and Environmental Chemistry Laboratories at FIT and transferred to the

Marine Geology Laboratory at FIT. In the Marine Geology Laboratory, the cores were

subsectioned following the same sampling criteria outlined for obtaining samples for trace metals

and organic substances.

The third core from each site also was subsectioned aboard ship for determination of sediment

accumulation rates. For this core, the top 10 cm were subsectioned into 0.5 cm sections and 1

cm intervals were taken throughout the remainder of the core. Using a ruler, a 0.5 cm or 1 cm

layer was carefully extruded and the sediment in contact with the CAB tubing was removed to

avoid smearing recent sediment with older sediment during sampling and extrusion of the core.

Sampling over 0.5 cm sediment intervals over the top 10 cm was carried out to ensure that the

13’Cs record, dating back only to 1950, was observed. For example, if the sediment accumulation

rate was 0.2 cm/y, then the complete r3’Cs record would be found within the top 9.5 cm unless

extensive in situ mixing had occurred. Sediment from each interval was placed into a labeled 48

mL plastic vial and refrigerated. The fourth core from each site was archived at Arthur D. Little.

Surface sediments and core samples were shipped to the Arthur D. Little and the Marine and

Environmental Chemistry Laboratories at FIT in coolers packed with blue ice and custody sheets.

Upon receipt, each sample was logged and the samples were transferred to a refrigerator (trace

metals, age dating) or a freezer (organics, AVS/SEM). Samples collected for grain-size analysis

were transferred to the Marine Geology Laboratory at FIT.

2.1.2.3 Sediment Toxicity Sample Collection

The methods used to obtain sediments for toxicity evaluation are described in this section.

Details of the location and composition of samples are reported in their respective cruise reports

(Arthur D. Little, 1997b; Arthur D. Little, 1998b).

Sediments were collected with the Van-Veen grab and/or the MK III box core. Multiple grabs

were often required to obtain sufficient sample quantities for all measured parameters. When

this was the case, aliquots of sediments were held in a Kynar-coated stainless-steel bowl.

Between grabs, the bowl was covered with clean aluminum foil and held in the dry laboratory.

Once sufficient quantities of sediment were obtained, the sample was well mixed and aliquoted

into labeled 2 L, wide-mouth (factory-cleaned) polyethylene jars. The samples were held in a

4°C refrigerator while on board the vessel, then shipped to the analytical laboratory (Pacific Eco2-6
Risk Laboratory [PERL]). The sediments for toxicity testing were not frozen when stored and

shipped. Chain-of-custody forms accompanied the samples.

2.1.2.4 Sediment Profile Imaging

The purpose of the SPI survey was to delineate sediment type, provide information on patterns of

sediment deposition and erosion, and describe biological community characteristics in the region.

During the 1997 cruise on the R/V Alpha Helix, 57 stations were sampled by SPI. The SPI

survey was not repeated on the 1998 cruise. The sediment profile images were taken by the EVS

field crew according to the procedures described below. The complete SPI report was issued by

Arthur D. Little as a separate stand-alone document in 1998 (Arthur D. Little, 1998c).

At the beginning of the survey, the time on the SPI camera’s internal data logger was

synchronized with the internal clock on the computerized navigation system to Greenwich Mean

Time (plus 8 hours). Three replicate images were taken at each station; each SPI replicate was

identified by the time recorded on the film and on disk, along with vessel position. Even though

multiple images were taken at each location, each image was assigned a unique frame number by

the data logger and cross-checked with the time stamp in the navigational system’s computer data

file. Redundant sample logs were kept by the field crew.

Test exposures of the Kodak’ Color Separation Guide (Publication No. Q-13) were fired on deck

at the beginning and end of each survey day to verify that all internal electronic systems were

working to design specifications and to provide a color standard against which final film

emulsion could be checked for proper color balance. Charged spare batteries were carried in the

field at all times to ensure uninterrupted sample acquisition. After deployment of the camera at

each station, the frame counter was checked to make sure that the requisite number of replicates

had been taken. In addition, a prism penetration depth indicator on the camera frame was

checked to verify that the optical prism had actually penetrated the bottom to a sufficient depth to

acquire a profile image. If images were missed (frame counter indicator) or the penetration depth

was insufficient (penetration indicator), weights were added or removed and additional replicates

taken. Changes in prism weight amounts, the presence or absence of mud doors, and chassis stop

positions were noted in the log for each replicate image. All film taken was developed in the

field at the end of each survey day to verify successful data acquisition; strict controls were

maintained for development temperatures, times, and chemicals to ensure consistent density on

the film emulsion. The film was then visually inspected under magnification to determine

whether any stations needed resampling.

Following completion of field operations, the color slides were scanned and stored in photo-CD

format by ProLab@, Inc., Seattle, Washington. One hundred fifty-six digital images were

analyzed from this survey using Image Pro@ (Media Cybernetics, Inc.). Calibration information

was determined by measuring 1 cm gradations from the Kodak Color Separation Guide. This

calibration information was applied to all SPI images analyzed. Linear and area measurements

were recorded as number of pixels and converted to scientific units using the calibration

information.

Measured parameters were recorded on a Microsoft@ ExcelTM spreadsheet. These data were

subsequently checked by an EVS senior scientist (Dr. J. Germano) as an independent quality

assurance/quality control (QA/QC) review of the measurements before final interpretation was

performed.

Rrthar D Little

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2.1.2.5 Fish Collection

The methods used to capture fish for analysis are described in this section. Details of time,

location, depth, and species of fish caught were reported in their respective cruise reports (Arthur

D. Little, 1997b; Arthur D. Little, 1998b).

The primary fish species targeted by this study were Arrowtooth flounder. However, very few

were caught in 1997, so Halibut became the primary target species based on the results of the

long-line catches, though five Sablefish (black cod) and five Arrowtooth flounder were also

caught and analyzed. In 1998, Halibut and Pacific cod were caught in nearly equal numbers in all

zones fished, so both species were analyzed. In addition to these two primary species analyzed in

1998,9 Arrowtooth flounder, 4 Sablefish, 1 Aleutian skate and 1 Longnose skate were also

caught and analyzed.

Table F-l in the appendix lists all of the species caught and analyzed or discarded during both

years of the study. The two skates were analyzed in 1998 out of interest stemming from

differences in physiology and life history between elasmobranchs and teleosts (cartilagenous vs

bony fishes).

Fish were captured by long-line. The gear used for this study had approximately 200 circle

hooks with a shaft-to-point distance of 2 cm. The hooks were tied to 30 cm leaders of

approximately 200 kg breaking strength, which were attached to the main line every 2 m. The

main line was approximately 7 rmn in diameter, with a breaking strength of approximately 1,000

kg. Each end of the long-line had an anchor/buoy line attached to it, with the long-line attached

near the anchor, allowing the hooks to fish on or near the bottom. The buoys located the longline at the surface. Each hook was baited with a piece of salted herring, and the gear was

deployed for 4 to 6 hours and then retrieved (longer fishing times would have precluded

returning all unused Halibut alive, as mortality increases with time).

A large tub was filled with seawater prior to retrieving the fishing gear. As the gear was brought

on board, fish were removed from the hooks and either placed in the tub or discarded overboard.

Fish were discarded if they were not a species of interest, or if they were dead. The species of all

fish captured were documented regardless of whether they were kept for analysis. All unused

target fish were returned to the ocean alive, after their total length (TL) was measured.

The methods used for tissue sampling of captured fish are described in this section. Weight and

length were reported in the first cruise report as reported to the Alaska Department of Fish and

Game (Arthur D. Little, 1997b).

Dissections commenced as soon as the fishing gear was retrieved. Dissections were done on

several species of fish, but all were accomplished using the following protocol. Dissections were

conducted by four scientists: one to record data, one to prepare the sample containers and assist

the dissector, the third to weigh and measure, and a fourth to dissect the fish. The fish were

removed from the tub, sacrificed with a fatal blow to the head, weighed on deck using a pesola

(hanging balance), and then brought into the wet laboratory and placed on a precleaned nylon

cutting board. General observations (e.g., parasites, deformations) were recorded. The fish were

then measured (TL) and dissected.

2-8
All dissection equipment was cleaned with AlconoxO detergent and water, and then rinsed with

1 percent hydrochloric acid (HCl) and methanol prior to each dissection. The dissections were

performed “in the fish” to minimize the potential for sample contamination. This was

accomplished by placing the fish blind side up (for the flatfishes, i.e, the Halibut, flounder, and

skates) and making a cut with a cleaned stainless-steel filet knife along the lateral line from the

pelvic girdle to the caudal peduncal. Round fish (i.e., Pacific Cod and Sablefish) were laid on

their side, but otherwise dissected with the same methodology. The musculature covering the

peritoneal cavity was then cut away, and a small portion of the flesh from the caudal end of the

fish (without skin) was removed for metals analysis (FIT ancillary samples). General

observations (e.g., parasites, deformities, sex of the fish) of the peritoneal cavity were made and

then sections of liver for Reporter Gene System (RGS) P450, metals, and organic contaminant

analyses were removed and placed in precleaned glass containers. A section of liver was also

removed for immunohistochemical analysis of CYPlA (P4501A) and placed in a polyethylene

container. Finally, a section of kidney and gill were removed and placed with the liver CYPlA

sample. The liver samples for RGS-P450, metals, and organics were cornposited if sufficient

numbers of target species were obtained, or were collected as individual samples where small

numbers of individuals were caught; all samples were frozen after collection (Arthur D. Little,

1997b; Arthur D. Little, 1998b). The samples for CYPlA analysis were fixed with 10 percentneutral-buffered formalin. The muscle samples for metals analysis were placed in plastic bags

and frozen. Chain-of-custody forms accompanied the samples to each analytical laboratory.

2.1.3 Source Sample Collection

Source samples were collected in order to compare concentrations and distributions of

contaminants in the sediments to potential contaminant sources. Based on the literature review

of historical data on the outermost Cook Inlet and Shelikof Strait (Boehm et al., 1998), a number

of potential contamination sources for the depositional sediments were identified. These sources

include oil and gas activities, oil seeps, coals, municipal discharges, boat harbors, and riverine

and coastal inputs. Samples representative of these separate source types were collected as part

of the both the 1997 and 1998 sample cruises and are summarized in Table 2-2.

2.1.3.1 Source Oils

A source sample of Cook Inlet crude oil was collected from the Unocal Trading Bay Production

Facility (TBPF) in August 1997 by Northern Testing Labs (NTL). A second oil source sample

consisted of Swanson River Field oil, and was collected by UNOCAL in 1998. Finally, oil seep

samples were collected from Well Creek, which drains into Oil Bay on the Iniskin Peninsula

(Figure 2-l). The samples of seep oil were collected from the surface water of a pond adjacent to

the creek. Each oil sample was collected in a precleaned glass jar for organics and metals, then

shipped to Arthur D. Little for analysis.

2.1.3.2 Source Coals

A coal source sample was collected from the bluff area west of Homer Spit by Cook Inlet

Regional Citizens’ Advisory Council (CIRCAC), in November 1997. Five chunks of beachwashed coal were collected from the beach approximately one mile west of Bishops Beach, in

Homer, Alaska (Figure 2-l), placed in a precleaned glass jar, then shipped to Arthur D. Little for

analysis. A second coal source sample was collected from scattered pieces along Coal Bay

Beach, Homer in 1998 (Figure 2-l) following the R/V Alpha Helix cruise.

2-9
Additional coal source samples collected in 1998 included those from coal seams in Ninilchik

Bluff (Figure 2-l) and at Matanuska (Figure 2-2), one collected from a coal pocket at Coyote

Lake (Figure 2-2) and two separate samples from the Beluga Coal Fields provided by CIRCAC.

2.1.3.3 Source Sediment

Several locations were sampled during both surveys to determine the potential influence of

resuspended river sediment and coastal bottom sediment to the study area.

The Homer boat harbor sediment source samples were collected during the July 1997 R/V Alpha

Helix cruise. These sediment source samples were collected just outside the entrance of the boat

harbor to the west of the dredged channel in an area where sampling activities did not interfere

with boat traffic in the harbor. Two samples were collected from the Van-Veen grab, using a 2

cm-deep, Kynar-coated, stainless-steel scoop, at 0- to 2-cm and 4- to 6-cm intervals.

The Copper River sediment samples were collected in July 1997 by P. Boehm of Arthur D.

Little. Figure 2-3 shows the four Copper River sediment sampling locations from Round and

Long Islands (CR-2 to CR-4), and upstream near Million Dollar Bridge (CR-l). The samples

were collected on the shoreline one meter above water level, from surface sediments (0 to 2 cm)

using a stainless-steel spoon and precleaned glass sample jars. Sampling equipment was

decontaminated between sample locations by rinsing with distilled water. Additional sediment

(CR-5) was collected from the Copper River in 1998 (Figure 2-3). The sediment was placed into

glass jars (organics) and plastic vials (metals), and shipped to Arthur D. Little and FIT.

The Susitna River sediment samples were collected in July 1997 by J. Trefry of FIT (Figure 2-3).

The two Susitna River samples were taken from the northern bank of the river, 200 yards

downstream (west) of the bridge at mile 105 on George Parks Highway (Highway No. 2).

Sediment from the Susitna River was collected where there was fine-grained sediment,

approximately one meter from the shore. At the time of sampling, the Susitna River was at a

relatively high stage and the water was very turbid. The samples were collected using a stainlesssteel spoon that was rinsed well with alcohol and Susitna River water. The sediment was placed

directly into precleaned glass jars provided by Arthur D. Little. The samples were stored on ice

in a cooler and shipped frozen with blue ice to Arthur D. Little.

Other sediment source samples were collected from one location in the influence of the Alaska

Coastal Current, up-current of Cook Inlet offshore of the Kenai Peninsula, during the 1998 R/V

Alpha Helix cruise (Figure 2-l). Additional sediment samples were collected offshore of St.

Augustine Island with a Van-Veen grab sampler for grain-size and chemistry analysis (Figure 2-

1). A sediment sample was collected near Holgate Glacier (Kenai Peninsula), not for the purpose

of source influence, but to be used as a toxicity reference sample representing the fine- grained

sediment encountered in the study area (Figure 2-l). This location was selected since it

represented fine grained and glacial sediment and was up current from Cook Inlet (would not

have Cook Inlet contaminants) and inshore of the influence of the Gulf of Alaska. In May 1998,

Matanuska River sediment was collected for both metals and organic analysis (Figure 2-2).

Finally, a miscellaneous volcanic ash sample was collected from the beach of St. Augustine

Island for metals analysis only (Figure 2-l).

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2.1.3.4 Aqueous Sources

Water samples from the Susitna, Knik, Matanuska, and Copper rivers were collected in 1998

(Figures 2-2 and 2-3) using l-L, acid-washed polyethylene bottles. Each bottle was submerged,

opened, partially filled, and closed. Once closed, the bottle was shaken and the sample discarded

as an equipment rinse. Then, the closed bottle was resubmerged, opened, filled, and closed. To

minimize sample contamination, all bottles were handled using powder-free polyethylene gloves.

The bottles were double-bagged, labeled, placed in a cooler, and shipped cold to FIT for filtration

and analysis of the suspended solids.

The municipal discharge produced water source sample was collected by personnel at the Point

Woronzof, Anchorage Municipal Wastewater Treatment Facility (WWTF) in August 1997, and

shipped to Arthur D. Little for analysis. The sample of final effluent was collected after

treatment from the discharge location.

A produced water sample from the Unocal TBPF, representing oil and gas production activities,

was sampled by a Unocal contractor. The produced water samples were collected in August

1997 from a final effluent outfall at the facility (TBPF-Outfall). The samples were collected in a

precleaned glass jar for organics, and a plastic bottle for metals, and shipped on ice to Arthur D.

Little for analysis of the suspended solids.

2.2 Analytical Methods

2.2.1 Physical Parameters

2.2.1.1 Grain Size

Surface sediment samples (0 to 2 cm) for grain-size analysis were double-wrapped in Ziploce

plastic bags and kept refrigerated while at sea. A separate subcore was collected for grain size at

each of the nine coring locations during 1997 and four coring locations during 1998. Water was

siphoned from the top of the core and the core was stored in a refrigerator at sea. Surface

sediment and core samples were shipped to the Marine Geology Laboratory at FIT in coolers

packed with blue ice and a chain-of-custody sheet. Upon receipt, each sample was logged in and

prepared for analysis as described below.

Determination of grain-size distribution followed the classic method of Folk (1974). Initially, a

dispersant (2 g of sodium hexametaphosphate “Calgon@” per 1 L of distilled water) was added to

about 20 g of wet sediment to disaggregate and deflocculate the sediment. The subsample was

immersed in this solution for 24 hours, prior to wet-sieving the sample through mesh sizes No.

10 (2 mm) and No. 230 (0.063 mm) to separate the gravel, sand, and mud fractions. The gravel

and sand fractions were collected in preweighed beakers, dried in an oven at 60°C and

reweighed. The mud fraction was collected in an evaporating bowl and transferred to a 1,000 mL

cylinder. This fraction was deflocculated with a mechanical mixer for 5 minutes. Dispersant

was added to the cylinders to bring the volume to 1,000 mL. The mud subsample was soaked for

another 24 hours. Pipette analysis was performed for each cylinder using a 20 mL pipette. The

fractions were withdrawn at a depth of 20 cm after 20 seconds (silt) and at a depth of 10 cm after

2 hours (clay). The samples were placed in preweighed beakers and dried. Weights for all size

fractions were recorded in a spreadsheet for later calculations. The 2 g/L of deflocculant was

subtracted from the final weights during calculations. The final data are presented as percent

2-11
sand (2 mm to 0.062 mm), silt (0.062 to 0.004 mm), and clay (<0.004 mm). No gravel (particle

sizes greater than 2 mm) was found in any samples,

2.2.1.2 Total Organic Carbon

Sediment stored in 48 mL plastic vials was initially freeze-dried to a constant mass

(approximately 48 hours) after a 2 g portion of wet sediment had been taken for mercury (Hg)

analysis. A 0.5 to 1 g portion of the freeze-dried sediment was placed in a 10 mL Pyrex@’ beaker

and treated with 2 mL of concentrated HCl to remove any inorganic carbon present. The

sediment was dried at 60°C and reweighed to determine the increase in weight due to the

formation of calcium chloride (CaCI,) as a result of adding HCl. Then, approximately 5 to 20

mg of pretreated sediment were weighed into tin cups and combusted at 1,020°C in a CarloErbae NA1500 carbon analyzer following the manufacturer’s instructions. The TOC content of

the sediment samples was determined using a four-point calibration curve with sulfanilamide as

the standard. The TOC concentrations were corrected to account for the increase in sediment

mass following the addition of HCl. The calibration curve was checked every 10 samples by

analyzing standard reference material (SRM) BCSS-1, a marine sediment issued by the National

Research Council of Canada (NRC).

2.2.2 Organic Parameters

Arthur D. Little provided analytical chemistry services as part of the Sediment Quality in

Depositional Areas of the Shelikof Strait and Outermost Cook Inlet study. Arthur D. Little

performed selected organic chemical analyses on 302 sediment, 43 tissue, and 27 source samples.

This section describes the analytical methods that were used in performing these chemical

analyses.

The core target analytes for the sediment and source samples were saturated hydrocarbons (SHC)

as reported in Table 2-3, polycyclic aromatic hydrocarbons (PAH) as reported in Table 2-4, and

biomarkers (steranes/triterpanes [S/T]) as reported in Table 2-5. Instrumental analysis included

gas chromatography/flame ionization detection (GC/FID) for SHC determinations and gas

chromatography/mass spectrometry detection (GUMS) for PAH and biomarker determinations.

Samples were grouped together in batches of no more than 20 field samples plus associated

quality control (QC) samples. All organic sample analyses were conducted according to Arthur

D. Little analytical SOPS.

2.2.2.1 Sample Preparation

Sediment Extraction. The sediment samples were extracted based on EPA Method 3550A,

Ultrasonic Extraction, which has been modified to include orbital shaking of the sample in

extraction solvent for 1 hour following the final sonication. The following is a summary of the

procedure used:

A 50 g weight of the homogenized sediment was placed into a Teflon@ jar and dried with sodium

sulfate. Another 5 g subsample was placed into an aluminum weighing pan for dry weight

determination. The sample was serially extracted 3 times with 100 mL of dichloromethane

@CM) and acetone (1: 1, volume to volume [V/V]) , each time by sonication. The final

sonication was followed by orbital shaking for 1 hour. The surrogates were spiked into the

sample after the first addition of solvent and before the first extraction. All sediment samples

were spiked with low-level surrogates. The surrogates were: naphthalene-$, acenaphthene-d,,,

2-12
phenanthrene-d,,, and benzo[a]pyrene-d,, for PAH analysis, Sa-androstane and d,-tetracosane

for SHC analysis, and SP(H)-cholane and &-dotriacontane for biomarker analysis.

After extraction, samples were concentrated by Kudema-Danish on a hot water bath and an

extract weight was taken, if necessary. Extracts were treated with copper to remove sulfur, and

split in half. One-half was archived and the other half processed through a neutral alumina

column (optionally, silica gel High-Performance Liquid Chromatography [HPLC] fractionation

was performed in addition to the alumina cleanup).

The QC samples processed along with the sediment samples included one procedural blank, one

blank spike, and one SRM (sediment SRM 1941a) per batch. The blank spike sample was

fortified with PAH matrix spike solution and SHC matrix spike solution.

Tissue Homogenization. Each tissue sample was a composite of the livers of up to five individual

fish. Samples were homogenized in a blender prior to extraction. A 30 g aliquot was removed

from each homogenized sample, frozen, and sent to Columbia Analytical Services for RGS-P450

analysis. A 10 to 15 g aliquot of frozen liver homogenate was sent to the Marine and

Environmental Chemistry Laboratories at FIT for trace metals analysis.

Tissue Extraction. Twenty-five grams of the homogenized wet tissue sample were placed into a

Teflon’ jar and dried with sodium sulfate. Another 5 g subsample was placed into an aluminum

weighing pan for dry weight determination. The sample was then serially extracted 3 times with

100 mL of DCM by maceration using a TissuemizerO. The surrogates were spiked into the

sample after the first addition of solvent and before the first extraction. The surrogates were:

naphthalene-$, acenaphthene-d,,, phenanthrene-d,,, and benzo(a)pyrene-d,, for PAH analysis

and SP(H)-cholane and &-dotriacontane for biomarker analysis. Surrogate compounds were

spiked into all tissue samples at the low level.

After extraction and concentration the gravimetric weight (lipid weight) was recorded. Extracts

were then processed through an alumina column and a post-alumina gravimetric weight recorded

prior to cleanup on the HPLC. Percent solid determinations for the tissue samples are provided

in Appendix C.

The QC samples processed with each batch of tissue samples included one procedural blank, one

blank spike, one SRM (1974a), and one duplicate analysis. The blank spike sample was fortified

with PAH matrix spike solution.

Source Samples. Source samples included crude oils, produced water, sediments, coals, and

municipal discharge. These samples were expected to exhibit high concentrations of the targeted

analytes. As such, they were segregated from the other samples to avoid the possibility of

contaminating low-level samples. Following is a summary of the procedures used for the

preparation of source samples.

Crude Oil: A dilution was prepared from each crude oil or seep sample in DCM at an

approximate concentration of 5 mg/mL. Each dilution was spiked directly with SHC, PAH, and

S/T surrogates at the low level. Extracts were then passed through an alumina column and

prepared for instrumental analysis.

ArthwDLittle

2-13
Produced Water and Municipal Discharges: Produced water and municipal discharge samples

were extracted serially with DCM by the liquid-liquid method. These samples were spiked with

surrogates at the high level. After extraction, the combined extracts were passed through an

alumina column.

Source Sediment Samples: Source sediment samples from Homer Harbor and the Copper and

Susitna rivers were extracted by the sediment extraction procedure described in Section 2.2.2.1.

Coals: Coal source samples (approximately 5 g) were first ground to a fine particle size using a

mortar and pestle, followed by extraction using the procedure described in section 2.2.2.1. The

extracts were then passed through an alumina column and fractionated by silica gel into saturates

and aromatics.

2.2.2.2 Organic Extract Cleanup

Ahmina Column. Sediment extracts were treated with activated copper to remove sulfur and

split in half. One-half was archived, and the other half passed through a neutral alumina column.

Silica gel fractionation by HPLC was performed in addition to alumina cleanup to remove

additional interferences from the S/T extracts.

Tissue extracts were weighed and passed through a 2 percent deactivated F-20 alumina column,

and a post-alumina gravimetric weight was recorded.

High-Pet$ormance Liquid Chromatography. Tissue sample extracts were cleaned up by HPLC

using a preparative gel permeation chromatography (GPC) column. The extracts were split

according to total extract weight following the criteria in the SOP. The resulting post-HPLC

extracts were analyzed by GUMS for PAH. The pre-HPLC archive was saved for possible

biomarker analysis at a later date.

2.2.2.3 Internal Standard Addition for Instrumental Analysis

The post-alumina and post-HPLC extracts were spiked with SHC, PAH, and VI’ internal

standards as appropriate for each extract/fraction. In general, the extracts were concentrated to

approximately 250 FL before adding the internal standards. The internal standard compounds

were: chrysene-d,, and fluorene-d,, for PAH; chrysene-d,, for S/T; and d&riacontane for SHC.

The amount of SHC internal standard added to the extracts was adjusted to obtain a target

concentration of 50 ~&IL. The amount of PAH and S/T internal standard added to the extract

was adjusted to obtain a target concentration of 1 pg/mL. Aliquots (approximately 100 pL) were

removed from the spiked extracts for GC and GUMS analyses. Due to the low extract volume

all instrumental aliquots were recombined.

2.2.2.4 Instrumental Analysis

Instrumental analysis included GC/FlD and GUMS analysis of all sediment samples, and

GUMS analysis of tissue samples. A five-point calibration, an Instrumental Reference Material

(IRM), a North Slope Crude Reference, and a Cook Inlet Crude Reference were run at the

beginning of each instrumental sequence with each batch of samples.

All instruments were calibrated with analytical standards prior to the analysis of sample extracts.

Target analyte concentrations were calculated versus the internal standard compound and were

2-14
,-

corrected for recovery of the surrogate compounds. The recovery of the surrogate compounds

was calculated versus the internal standards added to the extracts prior to instrumental analysis.

Gas Chromatography/FZame Ionization Detection. Approximately 100 uL of the internal standard

containing sample extract were submitted for GUPID analysis. Sample extracts were injected

onto a 30 m long by 0.25 mm inner-diameter (ID) fused-silica capillary column with DB5

bonded phase. This column provides baseline resolution of n-alkanes from n-C, to n-C, and nC,,/pristane and n-C,,/phytane pairs. The injection port is designed for splitless injection and

includes a silanized wide-bore glass liner containing a plug of silanized glass wool to reduce

high-molecular-weight mass discrimination.

Gas Chromatography/Mass Spectrometry Analysis. The GUMS analysis of sample extracts for

PAH and biomarkers was performed in accordance with EPA Method 8270 modified to include

alkyl PAH and selected ion monitoring (SIM). The PAH and S/T analyses were performed on

sediments. PAH analyses only were performed on tissues. Approximately 100 pL of extract

were submitted for analysis. The sample extract was injected onto a 30 m long by 0.25 mm ID

fused-silica capillary column with DB5 bonded phase.

2.2.2.5 Compound Quantification/Identification

Saturated Hydrocarbons. The C, through C, normal alkanes, pristane, phytane, and selected

isoprenoids were determined in the extract per EPA Method 8015 modified (Table 2-3). Two

control oil solutions were analyzed with the samples. Quantification of the analytes was based

on the internal standard compound (d&.riacontane) which was spiked into the sample just prior

to analysis. The target analyte concentrations were corrected for surrogate recovery. The SOP

includes the acceptability criteria for the calibration, procedural blank, surrogate compound

recoveries, and matrix spike recoveries, as well as the corrective action if the criteria are not met,

reporting requirements, and method detection limit (MDL) protocols. The data quality objectives

(DQO) for this analysis are summarized in Table 2-8.

Polycyclic Aromatic Hydrocarbons. The extracts were analyzed by GUMS in the SIM mode per

modified EPA Method 8270, to determine the concentrations of parent and alkylated PAH in the

samples (Table 2-4). Two control oils and a 1: 10 dilution of SRM 1491 spiked with 250 ng/mL

of surrogates and internal standards were also analyzed with the samples.

The concentrations of the individual PAH were calculated relative to one of the two internal

standards that were spiked into the sample just prior to instrumental analysis (Table 2-4). The

analyte concentrations were corrected for their respective surrogate recoveries (Table 2-4). The

target PAH concentrations were quantified using average response factors (RFs) generated from

the five-point calibration curve. To quantify the alkyl PAH, homologues were assigned the RF of

their respective parent PAH compound.

Steranes and Triterpanes. Only sediment extracts were analyzed for steranes and triter-panes by

GUMS in the SIM mode by modified EPA Method 8270 (Table 2-5). An initial four-point

calibration was performed before each batch sequence. A control oil (approximately 5 mg/mL)

was analyzed to obtain a good biomarker signal and the identification of target compounds was

based on the retention times of this oil. There was no analysis of sediment or instrumental SBM,

since there was no recognized SRM for these compounds.

hthm D L’ittle

2-15
The concentrations of all identified S/T were calculated versus the internal standard chrysene-d,,.

All target triter-pane concentrations were quantified using the average RF of 17p(H), 21p(H)-

hopane (T23) generated from the initial SLT four-point calibration. All target sterane

concentrations were quantified using the average RF of cholestane (S 17) in the initial four-point

calibration. Analyte concentrations were corrected for surrogate recovery. Surrogate recovery of

@(f-I)-cholane was calculated relative to the internal standard. If the determination of 5p(H)-

cholane was interfered with, the extract archive was analyzed, using the alternate internal

standard triacontane-4, and the alternate surrogate dotriacontane-&. Extracted ion

chromatogrtis of m/z 191 for the diterpanes and triter-panes and m/z 217 for the steranes were

annotated with peak names and printed out for all samples.

2.2.3 Inorganic Parameters

2.2.3.1 Trace and Major Metals in Sediments

Initially, each wet sediment sample was homogenized in the original 48 mL plastic vial using a

Teflon’s’ mixing rod. Then, a portion (approximately 2 g) of each sample was transferred to a

preweighed plastic vial to determine water content. Once transferred, the wet sediment and the

vial were reweighed. In addition, approximately 2 to 4 g of sample were transferred into a

polyallomer centrifuge tube to determine the Hg content of the sediment (element symbols are

defined in Table 2-6). Samples intended for water content were frozen, freeze-dried, and

reweighed to determine the water content. The dried sediment samples were homogenized again

using a Teflon@ mixing rod.

Approximately 0.45 g of freeze-dried, homogenized sediment and standard reference sediment

(BCSS-1) were totally digested in Teflon@ beakers using concentrated, high-purity HF-HNO,-

HClO,. Total digestion of the sediments is preferred because then no doubt remains about the

absolute amount of metal associated with a sample. In the digestion process, 1 mL HClO,, 1 mL

HNO,, and 3 mL HF were added to the sediment in the Teflon’s’ beaker and heated at 50°C with a

Teflon@ watch cover in place until a moist paste formed. The mixture was heated for another 3

hours at 80°C with an additional 2 mL HNO, and 3 mL HF before bringing the sample to

dryness. Finally, 1 mL HNO, and about 30 mL distilled, deionized water (DDW) were added to

the sample and heated strongly to dissolve perchlorate salts and reduce the volume. The

completely dissolved and clear samples were then diluted to 20 mL with DDW. This technique

is 100 percent efficient with no loss of the elements studied and has been used successfully in the

FTT laboratory for many years with a variety of sediment types.

Sediment for Hg analysis was digested by heating 2 to 4 g of wet sediment in an acid-washed,

polyallomer centrifuge tube with 4 mL HNO, and 2 mL H$O,. Sample tubes were heated for 1

hour in a 90°C water bath and allowed to cool. Each tube was centrifuged at 2,000 revolutions

per minute (r-pm) and the supemate was decanted into a 25 mL graduated cylinder. The sediment

pellet was rinsed twice with 5 mL DDW, centrifuged, and decanted into the graduated cylinder

before diluting to a final volume of 20 mL with DDW.

Labware used in the digestion process was acid-washed with hot, 8N HNO, and triple-rinsed

with DDW. Two procedural blanks, two duplicate samples, and two SRMs were prepared with

each set of 40 samples. SRM BCSS-1 (trace metals except Hg) and MESS-2 (Hg), sediment

samples issued by the NBC, and 1646a (Hg), issued by the National Institute of Standards and

Technology (NIST), respectively, were used.

216
Samples, SRM, and procedural and reagent blanks were analyzed by either flame atomic

- absorption spectrometry (FAAS), Zeeman graphite furnace atomic absorption spectrometry

(ZGFAAS), cold vapor atomic absorption spectrometry (CVAAS), or inductively coupled

plasma/mass spectrometry (ICP/MS). The method used for each element and the corresponding

MDLs are presented in Table 2-6. All analytical techniques followed manufacturers’

specifications, SOPS on file at FIT, and the details provided in the QA/QC section below. These

methods are very similar to the EPA methods described for Series 7000 FAAS and ZGFAAS,

Series 7470 CVAAS, and Series 6010A ICP/MS as described in EPA 1992. Matrix interferences

were carefully monitored for all elements using the method of standard additions.

2.2.3.2 Trace Metals in Tissues

In preparation for analysis, each tissue sample was homogenized with a Teflon@ mixing rod (fish

liver-composite samples) or stainless-steel instruments (fish flesh). Then, between 0.3 to 1.5 g of

tissue were transferred to a preweighed plastic vial and reweighed to determine percent water

content (required for Hg analyses). The plastic vial was frozen, freeze-dried, reweighed, and the

water content was calculated. In addition, an additional weighed portion of each homogenized

wet tissue (approximately 1 g of liver-composite or 2 to 3 g of fish flesh) was transferred to a 50

mL polypropylene centrifuge tube to be digested for total Hg content.

_-

Liver-composite and fish flesh samples for determining concentrations of all metals except Hg

were prepared using approximately 4 g of wet sample. The samples were transferred to

preweighed, 100 mL glass digestion flasks, reweighed, frozen, freeze-dried, and the percent

water content was calculated. These freeze-dried tissues and approximately 0.5 g portions of

tissue SRM were totally dissolved by refluxing with concentrated, high-purity HNO,, H,O,,and

HCl. Once the tissue samples were completely dissolved, the clear solutions were transferred to

graduated cylinders, diluted to 20 mL with DDW rinses of the flasks, and then stored for analysis

in 30 mL polyethylene bottles.

The wet tissue samples (1 to 3 g) for Hg analysis, along with 0.2 to 0.4 g portions of tissue SRM,

were digested using high-purity HNO, and H2S04, Each sample was refluxed for 1 hour in a

90°C water bath and allowed to cool. Once cool, the solution was decanted into a graduated

cylinder, diluted to a final volume of 20 mL with DDW rinses of the centrifuge tubes, and stored

for analysis in a 30 mL polyethylene bottle.

Metal concentrations in the digested tissue samples, tissue SRM, and procedural blanks were

determined by FAAS, ZGFAAS, CVAAS, or ICP/MS in a manner compatible with the EPA

Series 200.3 techniques (EPA, 1991). The methods used for each element and the corresponding

MDL are listed in Table 2-6. In all cases, the manufacturers’ specifications were followed and

adherence to QA/QC requirements was maintained.

2.2.3.3 Trace Metals in Aqueous and Oil Source Samples

Initially, the salinity of the aqueous source samples (effluent and produced water) was obtained

using a Reichert-Jung@’ Model 10419 refractometer to help determine the appropriate analytical

technique or dilution for determining trace metal concentrations. Then, 20 mL of each sample

(effluent and produced water) was pipetted into a 30-mL polyethylene bottle. The sample was - acidified with 0.2 mL of high-purity HNO, and stored for the determination of all metal

concentrations. The liquid source samples were not shaken to resuspend particulate matter prior

to the transfer.

Arthw D Little

2-17
Subsamples of the crude oils (approximately 1 g) were transferred to glass digestion flasks and

digested by refluxing with high-purity HNO,, Hz02, and HCl for the determination of all metals

except Hg. The digested oil samples were poured into graduated cylinders and diluted to a final

volume of 15 mL with DDW rinses of the digestion flask. The Hg concentration of the crude oil

was determined using 0.2 g subsamples that were placed in polypropylene copolymer centrifuge

tubes and refluxed with high-purity HNO, and H&SO, for 1 hour in a 90°C water bath. After the

Hg digestion was complete, the sample was transferred into a graduated cylinder, diluted to a

final volume of 20 mL with DDW rinses of the centrifuge tube, and stored for analysis in 30 mL

polyethylene bottles.

Metal concentrations for the water source samples, crude oil, SRM, and procedural and reagent

blanks were determined by FAAS, ZGFAAS, CVAAS, or ICP/MS following methods

comparable with EPA Series Method 200 and 200.8 (EPA, 1992). Levels of Ba in produced

water and Zn in the crude oil were determined by FAAS using a Perkin-Elmer@ Model 4000

instrument. Concentrations of Cd (except produced water), Cr, Cu, Fe, Mn, Ni, and V were

determined by ZGFAAS using a Perkin-Elmer@ Model 4000 instrument equipped with an HGA400 graphite furnace, and an AS-40 autosampler. Levels of Ag, As, Be, and Se were determined

by ZGFAAS using a Perkin-Elmer@ Model 5100 instrument equipped with Zeeman background

correction, an HGA-600 graphite furnace, and an AS-60 autosampler. Values for Ba, Pb, Sb, Sn,

Tl, and Zn in the low-salinity effluent water and crude oil (except Zn) were determined by

ICPLMS using a Perkin-Elmer@ ELAN 5000. Dissolved concentrations of Cd, Pb, Sb, Sn, Tl, and

Zn in the high-salinity water were determined by ICPLMS using the method of standard additions.

All Hg values were determined by CVAAS using a Laboratory Data Control Model 1235

Mercury Monitor. In all cases, the manufacturers’ specifications were followed and adherence to

QA/QC requirements was maintained.

2.2.3.4 Trace Metals in River Particulate and Coal Source Samples

River water samples were vacuum filtered through polycarbonate filters (Poretics @‘, 47-mm

diameter, 0.4 pm pore size). Prior to use, the filters had been acid-washed in 5N HNO,, triplerinsed with DDW, dried, and then weighed to the nearest pg using a Sartorius@ Model M3P 6-

place electronic balance under cleanroom conditions. Vacuum filtration was carried out in a

Class-100 laminar-flow hood in the FIT cleanroom facility using acid-washed glassware. The

filters were dried and reweighed prior to digestion for trace metals analysis.

Filters with river-me particulates and milligram quantities of SRM No. 2704, a river sediment

issued by the NIST, were digested in stoppered, 15 mL Teflon@ test tubes using Ultrex II@ HNO,,

HF, and HCI. The sealed test tubes were placed in an 80°C water bath where refluxing of the

acids completely dissolved the particles on the filters. After digestion, the resultant solutions

were transferred to acid-washed, labeled 15 mL polyethylene bottles, diluted to approximately 6

mL with DDW rinses of the Teflon@ test tubes, and stored in a plastic bag until analysis. No

separate digestion was required for Hg.

Metal concentrations for the dissolved particulate samples, SRM, and blanks were determined by

FAAS, ZGFAAS, CVAAS, or ICP/MS in a manner compatible with EPA Series 7000,6010A,

and 7470 (EPA, 1992), respectively. Particulate Al, Fe, Mn, and Zn concentrations were

measured by FAAS using a Perkin-Elmer@ Model 4000 AAS. Silver, As, Be, and Se values were

determined by ZGFAAS using a Per-kin-Elmer@ Model 5 1OOPC AAS equipped with Zeeman

background correction, an HGA-600 graphite furnace, and an AS-60 autosampler.

2-18
Concentrations of Cr, Cu, Ni, and V were quantified by ZGFAAS using a Perkin-Elmer@ Model

- 4000 AAS equipped with an HGA-400 graphite furnace, and an AS-40 autosampler. Values for

Ba, Cd, Pb, Sb, Sn, and Tl were measured by ICP/MS using a Perkin-Elmer@ ELAN 5000

spectrometer. Particulate Hg levels were determined by CVAAS using a Laboratory Data

Control Model 1235 Mercury Monitor. In all cases, the instrument manufacturers’ specifications

were followed and adherence to QA/QC requirements was maintained.

Coal samples were digested and analyzed following the methods used for sediments as outlined

in Section 2.2.3.1

2.2.3.5 Acid-Volatile Sulfide/Simultaneously Extracted Metals

Approximately 4 to 9 g of wet sediment were homogenized, weighed, and analyzed for AVS

using the cold acid purge-and-trap method (Di Toro et al., 1990). The homogenized sample was

placed in a flask containing 45 mL of DDW after the system had been purged with 99.999

percent nitrogen. The sulfide in the sediment was then volatilized by injecting 45 mL of

deoxygenated 2N HCl through a septum. The flask was continuously stirred and purged with

99.999 percent nitrogen. The nitrogen was passed through an impinger containing 45 n-L of a

sulfide anti-oxidant buffer (SAOB) which acted to trap and prevent oxidation of the sulfide. The

SAOB buffer consisted of 2M NaOH, O.lM ascorbic acid, and O.lM ethylene diamine triacetic

acid (EDTA). After a reaction time of 1 hour, the SAOB solution was placed into a 100 mL

volumetric flask and brought to a final volume of 100 mL by adding the solution obtained from

rinsing the impinger flask with a 1:l solution of SAOB and DDW. The sulfide concentration of

the SAOB solution was determined using a sulfide-specific ion probe (Orion@ Model No.

9616BN). The probe was calibrated for each analysis using known concentrations of sodium

sulfide/SAOB solution with a five-point curve. The sediment/acid slurry that remained at the end

of the reaction was filtered into a 100 mL volumetric flask using Whatmar? No. 40 ashless paper

filter. The reaction flasks were rinsed with DDW and the rinse was used to bring the filtrate

volume to 100 mL. This filtrate was then stored in acid-washed polyethylene bottles until

analysis for SEM. Concentrations of Cu, Fe, and Zn were determined by FAAS using a PerkinElmer@ Model 4000 instrument. Cadmium, Ni, and Pb values were obtained by ZGFAAS using

a Perkin-Elmer@ Model 4ooO instrument equipped with an HGA-400 graphite furnace and an

AS-40 autosampler.

--

2.2.4 Geochronology

Approximately 8 to 10 g of freeze-dried sediment from each layer (0.5 to 1.0 cm thick) of the

sediment cores were ground to a fine powder using a Spex@ 8000 mixer mill. Then, each sample

was tightly packed in a 2 cm diameter, 5 cm long polycarbonate vial to a depth of 30 &l mm. A

rubber stopper was cemented in place with two-part epoxy to seal the vials and prevent leakage

of ***Rn and disruption of secular equilibrium between 226Ra and *?Pb. The samples were set

aside for at least 20 days to establish secular equilibrium. Activities of the various radionuclides

were then determined by counting using a well-type intrinsic germanium detector, “WiGe”

(Princeton Gamma Tech@ Model IGWl1023). The samples were counted for a period of 1 to 2

days or until sufficient counts of the pertinent radionuclides were obtained (greater than 1,000 net

counts for *?b).

The peaks monitored for the purposes of this study were as follows: *?F’b at 46.5 KeV, *14Pb at

295.2 KeV and 351.9 KeV, *14Bi at 609.3 KeV, and 13’Cs at 661.6 KeV. The 226Ra daughter

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isotopes 214Pb (2 peaks) and 214Bi were used to determine the activity of 226Ra. Detector

efficiency and counting accuracy were standardized using SRM sediment 4350B (13’Cs) issued by

the MST and RGU-1 (*l?b) from the International Atomic Energy Agency.

Sedimentation rates (S) in cm& were calculated using the following equations with the

reasonable assumption for these samples that sediment mixing was minimal:

For 13’cs:

s = Depth in cm at which Activity 13’Cs = maximum

(Year - 1963) in years

and/or

s =

Depth in cm at which Activity 13’Cs not detectable

(Year - 1950) in years

For 21!Pb:

s= (-) decay constant for *“?b (0.03 11 y-r)

Slope for plot of natural logarithm (In) excess *‘O Pb vs. sediment depth

The activity of excess *l?b was calculated by subtracting the mean of Am2r4, Bi-214) from AW2ro.

2.2.5 Biological Parameters

2.2.5.1 Sediment Toxicity Tests

The toxicity tests followed guidelines established by the EPA (1994) and were performed on

surface sediments collected from both the 1997 and 1998 surveys, and a “reference” sample

collected from Aialik Bay near Holgate glacier. This fine-grained sediment was tested to

evaluate the test organism’s sensitivity to fine-grained sediment.

Sediment samples from 20 locations in 1997, and 7 locations in 1998, were received at the

testing laboratory in Martinez, California. Upon receipt, the sediment samples were stored at

4°C until used to set up the test replicates for the sediment toxicity tests. The test organisms for

the 1997 sediments, Eohuustorius eswarius, were obtained from a commercial supplier

(Northwestern Aquatic Sciences, Newport, Oregon). These organisms were acclimated to the

test salinity of 34 ppt (parts per thousand). The test organisms for the 1998 sediments, Ampelisca

abdita, were obtained from a commercial supplier (John Brezina and Associates, Dillon Beach,

California).

The sediment toxicity test replicates were established on 1 day at 4 replicates for each site. Each

replicate consisted of a 1 L glass beaker to which approximately 175 ml (approximately 2 cm

deep) of sediment was added (each sediment sample was homogenized prior to loading of the test

replicate containers). Test replicates were similarly established for a “home” control treatment,

which consisted of the same sediment from which the test organisms were originally collected;

this sediment was a fine-grained sand mixture. An additional “reference” control, consisting of

sediment collected from Ailalik Bay, was included in the 1998 sediment toxicity test; this

sediment was autoclaved for 30 minutes prior to use. The overlying water consisted of 0.45 pm

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filtered seawater (collected from the U.C. Bodega Bay Marine Laboratory); approximately 800

ml of this water was carefully poured into each test replicate so as to minimize disturbance of the

sediment. These test replicates were then placed in a temperature-controlled water bath at 15OC

(20°C for the Ampeliscu) under continuous illumination from fluorescent lighting. Each test

replicate was gently aerated.

The following day, routine water qualities (temperature, pH, dissolved oxygen [DO], and

salinity) were determined for each test replicate. Then, the tests were initiated with the random

allocation of 20 randomly selected organisms, into each replicate container (aeration was shut off

until the amphipods reburied themselves, approximately 1 hour after their introduction). Each

day, for the next 10 days, the temperature, pH, DO, and salinity were analyzed. Also on each

day, a sample of the overlying water was collected from each replicate for each sediment

treatment containing the Eohaustorius, cornposited, and analyzed to determine the total ammonia

at that treatment. For the Ampelisca, water was collected on days 2 and 8 for ammonia

determination.

After 10 days’ exposure, routine water qualities (temperature, pH, DO, and salinity) were

determined for each replicate. Then the contents of each replicate beaker were sieved and

examined, and surviving amphipods were collected and counted. The resulting percent survival

data were statistically analyzed using the ToxCalc statistical software (Tide-Pool Scientific,

McKinleyville, California). Comparison of the survival data from each of the sites with the

control treatment was made using the Homoscedastic t-Test.

2.2.5.2 CYPlA (P45OlA) Determinations

Preserved sections of liver, gill, heart, and kidney were placed in cassettes in 10 percent neutral

buffered formalin, embedded in paraffin, and analyzed immunohistochemically for the presence

of CYPlA. Tissue sections (5-pm) mounted on Superfrost Plus slides (Fisher), were

deparaffinated and hydrated as before (Smolowitz et al., 1991). Matching serial sections were

incubated with 150 ~1 of 1-12-3~6 monoclonal antibody against scup CYPlA, using

modifications of Smolowitz (Smolowitz et al., 1991). Formalin-fixed tissues were embedded in

paraffin, and 5-urn sections were mounted on Superfrost Plus slides (Fisher) and analyzed

immunohistochemically for the presence of CYPlA as before (Smolowitz et al., 1991).

Matching serial sections were incubated using the ShandonTM cover-slip system for 2 hours with

two 150 uL aliquots of MAb 1-12-3~6 or with nonspecific purified mouse myeloma protein

(UPC-10, IgG2A, Organon Teknika, West Chester, Pennsylvania), each at 1.5 g/ml in 1 percent

BSA!TBS added at 0 and 60 minutes. Blocking solutions, secondary antibodies, linker, and color

developer were components of the Signet (Medford, Massachusetts) murine immunoperoxidase

kit.

Color development was achieved as described before using 2 percent 3-amino-9-ethylcarbazole

and 1 percent hydrogen peroxide. Sections were counterstained with Mayer’s hematoxylin.

Slides were examined with a Zeiss Axioskop microscope and relative staining intensities were

determined subjectively by comparing the staining of samples to that of control and highly

induced 3,3’,4,4’ tetrachlorobiphenyl-treated scup liver sections included in each run.

Nonspecific staining, if present, was determined by comparison with UPC-10 stained sections.

Staining occurrence was scored as O-no staining (or equal to UPC staining), l-rare- few cells

staining, 2-many cells staining, 3-multifocal and diffuse-all cells staining. The intensity of

staining was scored as O-none (or equal to UPC staining), l-mild, 2-moderate, 3-medium, 4-

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strong, 5-very strong. A scaled product of staining occurrence times the staining intensity was

determined for each cell type. Therefore, immunohistochemical (MC) scores (being the product

of 2 numbers, the first from 0 to 3, and the second from 0 to 5) could range from 0 to 15. In this

study, scores of l-5 are considered low, 6-10 are considered moderate, and 11-15 are considered

high.

2.253 P450 Reporter Gene System Tests

The detailed methodology used in this study has been described previously (Anderson et al.,

1995; American Public Health Association [APHA], 1996; American Society for Testing and

Materials [ASTM], 1997). The P450 Reporter Gene System (JXGS) utilizes 1OlL cells, human

hepatoma cells stably transfected with a luciferase reporter gene downstream of human CYPlAl

promoter sequences. So, CYPlA inducers also trigger a bioluminescent response in affected

cells.

Two reference toxicant solutions representing two classes of CYPlA inducers, 2,3,7,8-

tetrachlorodibenzo-p-dioxin TCCD, (a dioxin) and benzo[a]pyrene, (a PAH) and environmental

sample extracts are applied at volumes of 2 to 20 mL to replicate wells in 6-well plates

containing 2 mL of culture media. Both sediment and tissue extracts are applied in the same

manner. Both reference toxicants are commonly used when the constituent contaminants of an

environmental sample are unknown and/or are a complex mixture. Every RGS test includes an

application of at least one and normally both reference toxicants, as the performance of the test

cells varies from test to test. Use of reference toxicants in every test results in consistently

accurate comparisons of toxicity of test matrices to benzo[a]pyrene (B[a]PEq) and dioxin, the

most potent of the chlorinated hydrocarbons, (TEQ). Dioxin is an order of magnitude more toxic

to the test cells than benzo[A]pyrene. Both 6 and 16hr. exposures were tested in this study.

Duplicate plates were dosed such that one plate was incubated for 6h, and the second for 16h.

Approximately 80% of the response due to PAH’s is typically measurable after 6 hr. of exposure.

Response due to chlorinated hydrocarbons (dioxins/furans, coplanar PCB’s) is best measured

with 16 hr. exposure periods, as it typically requires 16 hours for chlorinated hydrocarbons to

fully induce test cells. Due to the unknown nature of contaminants in sediments and fish tissues

collected in this study, both exposure periods were tested. RGS response rarely results from a

single chemical contaminant, as contaminants most often occur as complex mixtures in

environmental matrices (sediment, water, or tissues). The RGS values are expressed as both

B[a]PEq and Toxic Equivalents (TEQ), since prior to chemical confirmation it can not be

determined if the response was from exposure to PAH’s (B[a]PEq) or from chlorinated

hydrocarbons (TEQ). The use of (B[a]PEq) and TEQ’s also allows comparison of relative

toxicity of environmental samples from complex mixtures of contaminants and diverse studies.

After 6h or 16h incubation with the test solutions, the cells were washed with Hank’s Balanced

Salt Solution (Mediatech, Herndon, Virginia), and lysed with 200 mL of buffer containing 1

percent Triton, 25 mM Tricine, pH 7.8, 15 mM MgS04,4 mM EDTA, and 1 mM dithiothreitol

(DlT). Cell lysates were centrifuged at 6,000 rpm for lOs, and 50 mL of the supematant was

applied to a 96-well plate, followed by 100 mL of 0.1 M potassium phosphate buffer, pH 7.8,

containing 5 mM ATP and 10 mM MgC12. Reactions were initiated by injection of 100 mL of

luciferin, dissolved in 0.1 M potassium phosphate buffer, pH 7.8. Luminescence in relative light

units (RLUs) was measured using a ML2250 Luminometer (Dynatech Laboratories, Chantilly,

Virginia). Luciferase assay buffers were purchased from PharMingen (San Diego, California).

2-22
--

With each test run, a solvent blank (using a volume of DCM equal to the sample volume being

tested) and a reference toxicant (1 ng/mL tetrachlorodibenzo-p-dioxin [TCDD]).were also

applied to two separate replicate wells. Mean fold induction of the solvent blank was set equal to

1, and the fold induction of the reference toxicant and each sample were determined by dividing

the mean RLUs produced by these samples by the mean RLUs produced by the solvent blank.

The coefficient of variation among replicates was acceptable if less than 20 percent.

Equivalency Calculations. RGS Toxic Equivalents (TEQ) are a measure of the RGS response if

the sample contained only dioxins and furans, and are calculated using the equation below.

According to previous concentration-response studies using a standard mixture of dioxins and

furans, the RGS response is equivalent to the mixture TEQ in pg/mL (calculated using Toxic

Equivalency Factors established by Safe, 1990). Dividing by 1,000 yields the TEQ in rig/g.

Where,

RGS TEQ = (fold induction/l,OOO) * ((VJVJW,)

V, = total extract volume

V, = volume of extract applied to cells

W, = dry weight of sample

Similarly, RGS Benzo[a]pyrene Equivalents (B[a]PEq) are a measure of the RGS response if the

sample contained only PAH, and are calculated in mg/g using the equation below. Based on

RGS concentration-response curves for Benzo[a]pyrene, a fold induction of 60 is produced by 1

mg/niL B[a]P.

Where,

RGS B[a]PEq = (fold induction/60) * ((VJV3/w,)

V, = total extract volume

V, = volume of extract applied to cells

W, = dry weight of sample

2.2.5.4 Enumeration of Heterotrophs and Hydrocarbon-Degrading Microorganisms

Microbial analyses were performed on surface sediments from the1998 field survey. The

analyses were for the enumeration of total heterotrophic microorganisms and

hydrocarbon-degrading microorganisms, and was a modification of the most probable number

(MPN) technique (Brown and Braddock, 1990; Braddock and McCarthy, 1996). Once the

samples arrived in the laboratory they were stored at 4°C and were all processed within a week.

First, each sample was homogenized by mixing the sample in the sample jar with a clean spatula.

Then, 10 g (k 0.1 g) sediment was diluted into 90 ml of marine Bushnell Heas Broth. These

initial dilutions were shaken by hand for one minute before further dilutions for the MPN test.

Duplicates (two separate dilution series) were prepared for each sediment. In addition, for

heterotrophs, laboratory duplicates were run on each dilution. Finally, approximately 5 to 10 g of

sediment was dried overnight at 105°C to determine dry weights for the sediment. Final values

reported were all corrected to sediment dry weight.

The cell culture plates for the MPN tests were filled with either Marine Broth (Difco) (96-well

plates for heterotrophs) or marine Bushnell Heas Broth (24-well plates for hydrocarbon

degraders). Following inoculation, one drop of autoclaved Cook Inlet crude oil was added to

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each of the wells of the hydrocarbon-degrader plates. The plates were incubated at room

temperature. After three weeks and after five weeks, the marine heterotroph plates were scored

for growth. Full growth was obtained in the plates at three weeks, confirmed by restoring the

plates at five weeks. After six weeks, the hydrocarbon degrader plates were scored for

emulsification of crude oil.

2.2.6 Measuring, Interpreting, and Mapping Sediment Profile Imaging Parameters

The SPI camera was used to photograph the surface and subsurface layers of sediment on the

ocean floor during the 1997 survey. These images can be used to describe benthic community

and benthic structure, physical setting (e.g., grain size), biochemical parameters, and depth of the

redox layer.

2.2.6.1 Sediment Type

The sediment grain-size major mode and range were visually estimated from the color slides by

overlaying a grain-size comparator that was at the same scale. This comparator was prepared by

photographing a series of Udden-Wentworth size classes (equal to or less than coarse silt up to

granule and larger sizes) with the SPI camera. Seven grain-size classes were on this comparator:

>4 @,4-3 a, 3-2 @,2-l a, 1-O a, O-(-)1 4, c -14. The lower limit of optical resolution of the

photographic system was about 62 microns, allowing recognition of grain sizes equal to or

greater than coarse silt (24 M). The accuracy of this method has been documented by comparing

SPI estimates with grain-size statistics determined from laboratory sieve analyses.

The comparison of the SPI images with Udden-Wentworth sediment standards photographed

through the SPI optical system was also used to map near-surface stratigraphy such as sand-overmud and mud-over-sand. When mapped on a local scale, this stratigraphy can provide

information on relative transport magnitude and frequency.

2.2.6.2 Prism Penetration Depth

The SPI prism penetration depth was measured from the bottom of the image to the sedimentwater interface. The average penetration depth was determined by measuring across the entire

cross-sectional image. Linear maximum and minimum depths of penetration were also

measured Maximum, minimum, and average penetration depths were recorded in the data file.

Prism penetration is potentially a noteworthy parameter; if the number of weights used in the

camera is held constant throughout a survey, the camera functions as a static-load penetrometer.

Comparative penetration values from sites of similar grain size give an indication of the relative

water content of the sediment. Highly bioturbated sediments and rapidly accumulating sediments

tend to have the highest water contents and greatest prism penetration depths.

The depth of the camera’s penetration into the bottom also reflects the bearing capacity and shear

strength of local sediments. Over-consolidated or relic sediments and shell-bearing sands resist

camera penetration. Highly bioturbated, sulfitic, or methanogenic muds are the least

consolidated, and deep penetration is typical. Seasonal changes in camera prism penetration are

typically observed at the same station and are related to the control of sediment geotechnical

properties by bioturbation (Rhoads and Boyer, 1982). The effect of water temperature on

bioturbation rates appears to be important in controlling both biogenic surface relief and prism

penetration depth (Rhoads and Germano, 1982).

2-24
.- 2.2.6.3 Small-Scale Surface Boundary Roughness

Surface boundary roughness was determined by measuring the vertical distance (parallel to the

film border) between the highest and lowest points of the sediment-water interface. The surface

boundary roughness (sediment surface relief) measured over a horizontal distance of 15 cm

typically ranges from 0.02 to 3.8 cm and may be related to either physical structures (ripples, ripup structures, mud clasts) or biogenic features (burrow openings, fecal mounds, foraging

depressions). Biogenic roughness typically changes seasonally and is related to the interaction of

bottom turbulence and bioturbational activities.

The camera must be level to take accurate boundary roughness measurements. In sandy

sediments, boundary roughness can be a measure of sand wave height. On silt-clay bottoms,

boundary roughness values often reflect biogenic features such as fecal mounds or surface

burrows.

2.2.6.4 Thickness of Depositional Layers

Because of the camera’s unique design, SPI can be used to detect the thickness of depositional

and dredged material layers. SPI is effective in measuring layers ranging in thickness from 20

cm (the height of the SPI optical window) to 1 mm. During image analysis, the thickness of the

newly deposited sedimentary layers can be determined by measuring the linear distance between

the pre- and post-disposal sediment-water interface. Recently deposited material is usually

evident because of its unique optical reflectance and/or color relative to the underlying material

representing the predisposal surface. Also, in most cases, the point of contact between the two

layers is clearly visible as a textural change in sediment composition, facilitating measurement of

the thickness of the newly deposited layer.

2.2.6.5 Mud Clasts

When fine-grained, cohesive sediments are disturbed, either by physical bottom scour or faunal

activity (e.g., decapod foraging), intact clumps of sediment are often scattered about the seafloor.

These mud clasts can be seen at the sediment-water interface in SPI images. During analysis, the

number of clasts was counted, the diameter of a typical clast was measured, and their oxidation

state (discussed below) was assessed. The abundance, distribution, oxidation state, and

angularity of mud clasts can be used to make inferences about the recent pattern of seafloor

disturbance in an area.

Depending on their place of origin and the depth of disturbance of the sediment column, mud

clasts can be reduced or oxidized. In SPI images, the oxidation state is apparent from the

reflectance (MMS, 1998). Also, once at the sediment-water interface, these mud clasts are

subject to bottom-water oxygen concentrations and currents. Based on laboratory microcosm

observations of reduced sediments placed within an aerobic environment, oxidation of reduced

surface layers by diffusion alone is quite rapid, occurring within 6 to 12 hours (Germano, 1983).

Consequently, the detection of reduced mud clasts in an obviously aerobic setting suggests a

recent origin. The size and shape of the mud clasts are also revealing. Mud clasts may be moved

and broken by bottom currents and animals (macro- or meiofauna; Germano, 1983). Over time,

large angular clasts become small and rounded.

2.2.6.6 Apparent Redox Potential Discontinuity Depth

Aerobic near-surface marine sediments typically have higher reflectance relative to underlying

AtirDLittle

2-25
hypoxic or anoxic sediments. Surface sands washed free of mud also have higher optical

reflectance than underlying muddy sands. These differences in optical reflectance are readily

apparent in SPI images; the oxidized surface sediment contains particles coated with ferric

hydroxide (an olive or tan color when associated with particles), while reduced and muddy

sediments below this oxygenated layer are darker, generally grey to black. The boundary

between the colored ferric hydroxide surface sediment and underlying grey to black sediment is

called the apparent redox potential discontinuity (RPD).

The depth of the apparent RPD in the sediment column is an important time-integrator of DO

conditions within sediment porewaters. In the absence of bioturbating organisms, this highreflectance layer (in muds) will typically reach a thickness of 2 mm (Rhoads, 1974). This depth

is related to the supply rate of molecular oxygen by diffusion into the bottom and the

consumption of that oxygen by the sediment and associated microflora. In sediments that have

very high sediment oxygen demand (SOD), the sediment may lack a high reflectance layer even

when the overlying water column is aerobic.

In the presence of bioturbating macrofauna, the thickness of the high-reflectance layer may be

several centimeters. The relationship between the thickness of this high-reflectance layer and the

presence or absence of free molecular oxygen in the associated porewaters must be considered

with caution. The actual RPD is the boundary (or horizon) that separates the positive Eh region

of the sediment column from the underlying negative Eh region. The exact location of this Eh =

0 potential can be determined accurately only with microelectrodes; hence, the relationship

between the change in optical reflectance, as imaged with the SPI camera, and the actual FWD

can be determined only by making the appropriate in situ Eh measurements. For this reason, the

optical reflectance boundary, as imaged, was described in this study as the “apparent” RPD and it

was mapped as a mean value. In general, the depth of the actual Eh = 0 horizon will be either

equal to or slightly shallower than the depth of the optical reflectance boundary. This is because

bioturbating organisms can mix ferric hydroxide-coated particles downward into the bottom

below the Eh = 0 horizon. As a result, the apparent mean RPD depth can be used as an estimate

of the depth of porewater exchange, usually through porewater irrigation (bioturbation).

Biogenic particle mixing depths can be estimated by measuring the maximum and minimum

depths of imaged feeding voids in the sediment column. This parameter represents the particle

mixing depths of head-down feeders, mainly polychaetes.

The rate of depression of the apparent RPD within the sediment is relatively slow in organic-rich

muds, on the order of 200 to 300 micrometers per day; therefore this parameter has a long time

constant (Germano and Rhoads, 1984). The rebound in the apparent RPD is also slow

(Germano, 1983). Measurable changes in the apparent RPD depth using the SPI optical

technique can be detected over periods of 1 or 2 months. This parameter is used effectively to

document changes (or gradients) that develop over a seasonal or yearly cycle, related to water

temperature effects on bioturbation rates, seasonal hypoxia, SOD, and infaunal recruitment.

Time-series RPD measurements following a disturbance can be a critical diagnostic element in

monitoring the degree of recolonization in an area by the ambient benthos (Rhoads and Germano,

1986).

The apparent mean BPD depth also can be affected by local erosion. The peaks of disposal

mounds commonly are scoured by divergent flow over the mound. This scouring can wash away

2-26
-_

fines and shell or gravel lag deposits, and can result in very thin apparent RPD depths. During

storm periods, erosion may completely remove any evidence of the apparent RPD (Fredette et al.,

1988).

Another important characteristic of the apparent RPD is the contrast in reflectance at this

boundary. This contrast is related to the interactions among the degree of organic loading, the

bioturbation activity in the sediment, and the concentrations of bottom-water dissolved oxygen in

an area. High inputs of labile organic material increase SOD and, subsequently, sulfate reduction

rates and the associated abundance of sulfide end products. This results in more highly reduced,

lower-reflectance sediments at depth and higher RPD contrasts. In a region of generally low

RPD contrasts, images with high RPD contrasts indicate localized sites of relatively high past

inputs of organic-rich material such as phytoplankton or other naturally occurring organic

detritus, dredged material, and sewage sludge.

2.2.6.7 Sedimentary Methane

If organic loading is extremely high, porewater sulfate is depleted and methanogenesis occurs.

The process of methanogenesis is indicated by the appearance of methane bubbles in the

sediment column, and the number and spatial coverage of all methane pockets is measured.

These gas-filled voids are readily discemable in SPI images because of their irregular, generally

circular aspect and glassy texture (due to the reflection of the strobe off the gas bubble).

2.2.6.8 lnfaunal Successional Stage

-

The mapping of infaunal successional stages is readily accomplished with SPI technology. These

stages are recognized in SPI images by the presence of dense assemblages of near-surface

polychaetes and/or the presence of subsurface feeding voids; both may be present in the same

image. Mapping of successional stages is based on the theory that organism-sediment

interactions in fine-grained sediments follow a predictable sequence after a major seafloor

perturbation. This theory states that primary succession results in “the predictable appearance of

macrobenthic invertebrates belonging to specific functional types following a benthic

disturbance. These invertebrates interact with sediment in specific ways. Because functional

types are the biological units of interest, our definition does not demand a sequential appearance

of particular invertebrate species or genera” (Rhoads and Boyer, 1982). This theory is presented

in Pearson and Rosenberg (1978) and further developed in Rhoads and German0 (1982) and

Rhoads and Boyer (1982).

This continuum of change in animal communities after a disturbance (primary succession) has

been divided subjectively into three stages: Stage I is the initial community of tiny, densely

populated polychaete assemblages; Stage II is the start of the transition to head-down deposit

feeders; and Stage III is the mature, equilibrium community of deep-dwelling, head-down deposit

feeders.

After an area of bottom is disturbed by natural or anthropogenic events, the first invertebrate

assemblage (Stage I) appears within days after the disturbance. Stage I consists of assemblages

of tiny tube-dwelling marine polychaetes that reach population densities of lo4 to lo6 individuals

per m2. These animals feed at or near the sediment-water interface and physically stabilize or - bind the sediment surface by producing a mucous “glue” that they use to build their tubes.

Sometimes deposited dredged material layers contain Stage I tubes still attached to mud clasts

ArthrrDLittle

2-27
from their location of origin; these transported individuals are considered as part of the in situ

fauna in our assignment of successional stages.

If there are no repeated disturbances to the newly colonized area, then these initial tube-dwelling

suspension or surface-deposit feeding taxa are followed by burrowing, head-down depositfeeders that rework the sediment deeper and deeper over time and mix oxygen from the overlying

water into the sediment. The animals in these later-appearing communities (Stage II or III) are

larger, have lower overall population densities (10 to 100 individuals per m2), and can rework the

sediments to depths of 3 to 20 cm or more. These animals loosen the sedimentary fabric,

increase the water content in the sediment, thereby lowering the sediment shear strength, and

actively recycle nutrients because of the high exchange rate with the overlying waters resulting

from their burrowing and feeding activities.

2.2.6.9 Organism-Sediment Index

The Organism-Sediment Index (OSI) is a summary mapping statistic that is calculated on the

basis of four independently measured SPI parameters: 1) apparent mean RPD depth, 2) presence

of methane gas, 3) low/no dissolved oxygen at the sediment-water interface, and 4) infaunal

successional stage. Table 2-7 shows how these parameters are summed to derive the OSI.

The highest possible OS1 is +l 1, which reflects a mature benthic community in relatively

undisturbed conditions (generally a good yardstick for high benthic habitat quality). These

conditions are characterized by deeply oxidized sediment with a low inventory of anaerobic

metabolites and low SOD, and by the presence of a climax (Stage III) benthic community. The

lowest possible OS1 is -10, which indicates that the sediment has a high inventory of anaerobic

metabolites, has a high oxygen demand, and is azoic. Based on Joe Germano’s (EVS

Environmental Consultants) mapping experience over the past 15 years, he has found that OS1

values of 6 or less indicate that the benthic habitat has experienced physical disturbance,

eutrophication, or excessive bioavailable contamination in the recent past.

2.3 Statistical Methods

2.3.1 Coefficient of Variation

The coefficient of variation (CV) was used to describe the variation in several populations of

physical and chemical sediment parameters. The CV can be expressed as a percent and is

generally defined by:

cv = 1oo*o/m

Where o is the standard deviation and m is the population mean (Snedecor and Co&ran, 1978).

The utility of the measure lies partly in the fact that within many data sets, the mean and standard

deviation tend to change in concert. The experimental design associated with the 1997 sediment

surface sampling program included three stations possessing seven replicate samples each.

Intensive sampling at selected stations was conducted for the purpose of evaluating within station

variation.

A modification of the general CV statistic of the equation above was used to describe the within

station variation for each of the measured chemical/physical parameters. The following equation

2-28
- -

was used to generate within station CVs for each measured parameter at the multi-replicate

stations:

C^v= 100 *\/(SSr +SS,... +SS,)l(df, +df2... +dfi)/F

Where,

SS,, SS,,...,SSi are the parameter-specific sums of squares at each of the stations with seven field

replicates; dfl,, df2,..., dfi are the associated degrees of freedom, and X is the grand mean of the

parameter of interest from all seven-replicate stations. All data manipulations were aided by the

Statistical Analysis System (SAS, ver. 6.12).

Within-zone variation was also explored using the general CV statistic for each zone and

chemical/physical parameter. For this analysis, all stations with greater than one replicate per

station were included in calculations. Additionally, a parameter-specific “Grand CV” was

calculated incorporating all parameter-specific information gathered at stations with greater than

one replicate. A CV ratio was then calculated by dividing the zone parameter-specific CV by the

Grand CV. Ratios less than one can be used to highlight parameters where within zone

variability is less than overall system variability.

2.3.2 Analysis of Variance

- The General Linear Model (GLM), an application of an analysis of variance (ANOVA), was used

to elucidate significant differences between zones. Under the GLM, a continuous response, or

dependent, variable (e.g., zinc) is measured under experimental conditions identified by

classification, or independent, variables (i.e., zone and year). The variation in the response is

explained as being due to effects in the classification, with random error accounting for the

remaining variation (Searle, 1971). Prior to running the GLM analyses, mean values were

generated for each of the multireplicates. This was deemed appropriate since the variability

within stations was much lower than variability between stations, and thus stations can be

considered replicates within a zone. Mean station values were subsequently used in all GLM

hypothesis testing.

A significant effect identified by the GLM statistic indicates that the classification variables (e.g.,

Zones) differ for a specific dependent variable (e.g., zinc), but the model does not tell how this

difference is manifested (i.e., which Zones are different). A Student-Newman-Keuls (SNK)

multiple range test (Steel and Torrie, 1980) was used to identify significant differences (~~0.05)

between classification variables when the associated GLM indicated a significant difference.

Simply put, the SNK test was used to separate classification variables into significantly different

groupings. These tests were performed on the following sets of data:

+

.

Surface sediments collected from 59 stations within zones 0, 1,2, and 3 in 1997,

measured for 23 organic and 26 inorganic parameters

Surface sediments collected from 35 stations within zones 0, 1,2,3, and 4 in 1998,

measured for 23 organic, 23 inorganic, and 5 biological parameters

2-29
It is well established that certain chemical/physical parameters tend to predict concentrations of

other analytes. Because of this, several GLM analyses were performed on the surface sediment

data set before and after the transformation (normalization) of metals (dividing metal

concentration by percent iron at the station) and organic compounds (dividing by percent total

organic carbon at a station).

A GLM analysis was also performed on surface sediment collected from both the 1997 and 1998

sampling periods in order to determine whether significant variance could be attributed to time of

collection/analysis. A Bonferroni multiple range test was used to identify significant differences

(~~0.05) between classification variables when the associated GLM indicated a significant

difference. The Bonferroni multiple range test is conceptually similar to the SNK, however, it is

less sensitive to problems associated with an unbalanced experimental design (unequal number

of stations, zones, and/or replicates). This test was performed on a subset of data where station

sampling and parameter analysis was repeated during both years and totaled 16 stations (14

stations for the RGS-P450 data).

2.3.3 Pearson Product-Moment Correlation

2.3.3.1 Sediments

Not all chemical, physical, and biological parameters were measured at all stations. However,

subsets of the data were collected to identify significant correlations between measurement

parameters and additional differences between zones. These subsets included the following:

.

. 20 stations in 1997 shared 37 common measurement parameters

14 stations where sampling was repeated during both the 1997 and 1998 surveys over

37 measurement parameters

Again, the correlation analyses were performed on both transformed and nontransformed

organic/inorganic data. Aquatic toxicity test results were reported as mean percent survival

(MPS) and, along with the chemical/physical measurements reported as percents, was

transformed by applying an arc sine square root to the fractional data.

Correlative analyses were performed on the separate data sets using the Pearson product-moment

which measures the strength of the linear relationship between two variables. If one variable

(e.g., length) can be expressed exactly as a linear function of another variable (e.g., weight), then

the correlation is 1 if the variables are directly related, or -1 if the variables are inversely related.

A correlation of 0 between two variables suggests that each variable has no linear predictive

ability for the other. If the values associated with the variables are normally distributed, a

correlation of 0 also means the variables are independent of one another. Again, SAS ver. 6.12

was used to perform data manipulations and analysis.

2.3.3.2 Tissues

Measurements of chemical and biological parameters, similar to those applied to sediments were

used in the examination of fish tissues at three stations. Three species of mixed size and sex

were acquired. Subsetting of tissues was necessary for microscopic analyses and not all fish

were examined for all chemical/biological parameters. Chemical analyses were performed on

composite samples of fish tissue (a requirement of chemical analytical methods), while all fish

2-30
_-

were measured or evaluated for “non-quantity dependent” variables (e.g., length). Data sets

included the following:

c In 1997, P450 measurements (Section 2.5.2) were made on 45 individuals and

chemical/biological measurements were made on 13 tissue composites.

+ In 1998, P450 measurements were made on 116 individuals and chemical/biological

measurements were made on 30 tissue composites.

By collecting data in the form of discrete (e.g., length) and composite (e.g., chemical)

measurements it was not possible to correlate measures on a one-to-one basis. To evaluate the

degree to which two or more variables were related and changed together (correlated), it was

necessary to calculate average individual measurements (e.g., length and P450) using groupings

defined by the chemical composite groupings. A Pearson’s correlation was applied to the data,

after the averaging process, and significant correlations (~10.05) were retained and reported.

2.3.4 Analysis of VarianceKovariance

GLhJ and SNK procedures were applied to both the combined chemical/biological and the P450

data sets. In general, fish length positively correlates with fish age, and fish age has been shown

to covary with several chemical and biological (P450) parameters. The tendency of one

statistical variable to change in relation to another is commonly termed as covariance. Analysis

of covariance combines some of the features of a typical regression model with analysis of

variance. Typically, a continuous variable (the covariate length in the example above) is

introduced into the analysis of variance model in an attempt to lessen the influence of the

covariate. GIN processing used length as a covariant for this reason. Additionally, since sex

was recorded for each fish sex and is known to correlate with many of the measured parameters

sex was examined as a possible covariate during the analytical process.

2.3.5 Random Effects Analysis of Variance

The basic data analysis and statistical questions center around whether there is a consistent and

statistically significant pattern associated with the oil and gas development and production

operations initiated in 1963. Although concentrations of metals and hydrocarbons associated

with post-1963 oil and gas development would be expected to differ by zone and distance from

the production sites, as detailed in Section 3.4, indicator ratios of metal and hydrocarbon

concentrations might be expected to show consistent patterns even as the absolute concentrations

decline with distance from the production site.

Since information from the cores is limited, a parsimonious statistical model was developed to

explain post-1963 shifts in metal and organic indices. This statistical analysis models the

individual cores as randomized blocks, where each core is considered as a random sample, with a

mean effect and an oil and gas development and production effect.

2-31
The statistical model for the i * core and thej * slice is

yij = p + ai+pi zij + E ij

Where a i is the core effect and Zij is the indicator variable, which is one if the core is post-1963

and zero otherwise. Within this type of model, there are two modeling approaches. First, we can

think of the oil production effect as fixed and constant between cores, thus pi = p, and test the

null hypothesis that the effect is zero. The second, and more realistic approach, is to consider the

sampled cores as a random sample of all cores, where the oil production effect is consistent, that

is, in the same direction, but variable between cores. For the second random effect model, the

null hypothesis is that the mean of the random effect differs from zero. Subsequently, the

alternate hypothesis is that there is a consistent but variable effect between cores.

Data were analyzed and plotted using the statistical package S-plus. The linear mixed effects

models within S-plus were used for the “random cores analysis.” The analysis is based on

methods developed in Laird and Ware (1982) using restricted maximum likelihood methods.

The distribution theory is approximate for small sample sizes. The P-values reported for the

random effects models are only approximated and should be used only to judge the relative

strength of the evidence for post-1963 shifts.

2.4 Quality Assurance/Quality Control

As part of our overall QNQC program, both field and laboratory QAZQC measures were taken.

Several types of field QC samples were collected during the survey, including field blanks,

equipment blanks, replicate samples, an Alpha ZZeZix reference diesel-fuel sample, and a trip

blank. These samples were collected to characterize potential influences from equipment (VanVeen grab, boxcore, core liner, fish dissection tools) and each type of sampling activity (sediment

sample collection, fish sampling, and dissection). For the field QNQC samples, one jar each

was collected for metals and organics analyses. Laboratory quality assurance (QA) measures

included maintaining detailed laboratory records and comprehensive validation of data packages.

In addition, several QC measures were implemented in conjunction with hydrocarbon and metals

analyses in order to provide a measure of analytical accuracy, precision, and potential

contamination.

2.4.1 Field Quality Assurance/Quality Control

QAZQC samples were collected during the field sampling program to assess overall accuracy and

representativeness of the sampling efforts. The number of QC samples collected for this effort is

based on the total number of field samples as established in the sampling and logistics plans

(Arthur D. Little, 1997a; Arthur D. Little, 1998). Discussion and interpretation of analytical

results for these samples are provided in Section 3.6. Quality assurance techniques were used in

sampling activities to avoid potential contamination and cross-contamination including use of:

precleaned sample containers; clean sampling equipment; decontamination protocol; and good

laboratory practices. Standard sampling procedures and protocols were followed. In this section,

the field methods used for collecting field QC samples are summarized.

2-32
,-.

Several types of field QC samples were collected during the field survey, including equipment

blanks, field blanks, and trip blanks. For all field QNQC samples, one jar each‘was collected for

metals and organics analyses.

2.4.1 .l Equipment Blanks

Three equipment blank samples were collected from rinsate of the grab sampling equipment at

locations ZOFl, ZOF8, and Z3R13 in 1997, and three similar rinsates were collected at locations

ZlR19,Z2R14A, and Z2R23 in 1998. Both the 1997 and the 1998 surveys included an

equipment blank collected from rinsate of fish dissection equipment that was used in the onboard laboratory associated with location Z2R14A. One additional equipment blank sample was

collected from rinsate of the box core sampling equipment (and core liner) at location ZOFl. The

procedure for collecting the equipment blank samples followed these steps:

.

. The equipment was decontaminated according to the SOP

The equipment was rinsed with high-purity, deionized water and the rinsate collected

directly into two clean, prelabeled water sample containers . A precleaned stainless-steel funnel was used to assist in the collection . The rinsate equipment blank sample was refrigerated at 4°C

2.4.1.2 Field Blanks

Field blanks were collected during sampling, representing atmospheric or other contamination

that the field samples may have been subject to. Three field blank samples were taken during the

collection of sediment samples. One field (deck) blank was collected during sediment sampling

in 1997 at location ZlR9 when a forest fire smoke smell was noticed in the air. The other two

field blank samples, deck blanks, were collected during sediment sampling at location Z2Fl and

location Z2R23, in 1997 and 1998, respectively.

To collect field blank samples, a clean, prelabeled sample jar of the same batch used for sample

collection was carried into the working area, opened during the collection of one sample, and

returned to the laboratory with the field samples. For each field blank, two sample containers

were collected for metals and organics analysis, respectively. The field blanks were stored under

the same conditions as their associated field samples.

2.4.1.3 Trip Blanks

A trip blank sample was prepared to accompany the samples from location ZOFl during the 1997

survey. The trip blank was a sample jar that was never opened. The trip blank was treated

similar to other field samples during storage and shipment.

2.4.1.4 Field Source Sample

A source sample of the FUV Alpha Helix diesel fuel was taken during the 1997 field survey. The

purpose of this sample was to, if necessary, be able to characterize any potential sample

contamination believed to originate from the shipboard diesel fuel (e.g., exhaust and surface

sheen). The ship’s engineer collected a sample of diesel fuel in a precleaned glass jar. The

sample was stored separately from the other samples at room temperature, and shipped packaged

in two plastic bags to prevent leaking or cross-contamination to other samples.

2-33
2.4.2 Organics Analysis Quality Assurance/Quality Control

2.4.2.1 Quality Assurance

Laboratory Records. All laboratory operations were documented and placed in three-ring binders.

Documentation included the following:

Lot number and vendors for reagents and standards

Preparation of stock solutions, standards, and spiking solutions

Sample preparation

Analytical procedures

Analytical instrument and conditions

Dates of analysis of standards

Dates of analysis of samples

Problems encountered

Corrective actions

All entries were initialed and dated by the analyst at the time of entry. Any deviations from SOP

were explained, initialed, and dated. All the raw data and chromatograms acquired on the data

systems linked with GC/FID and GC/MS instruments were archived in both hardcopy and

electronic form.

Data Validation. All chemistry data generated by Arthur D. Little’s laboratories were assembled

in data packages and validated by the designated team member in charge of each analysis to

ensure that the data quality objectives (DQOs) for accuracy and precision were met, that the data

were generated in accordance with the Laboratory Quality Assurance (QA) Plan, and that data are

both traceable and defensible. Data packages were also reviewed by the Project Manager to

ensure compliance with procedures and (DQOs) specified in the QA Plan. Data were also

reviewed for their consistency with expected petroleum hydrocarbon, PAH, or saturated

hydrocarbon distributions.

When data validation was successfully completed by each facility, all data sets were submitted to

the QA Officer for a formal audit. This formal audit included a 100 percent review on all handentered and calculated data, i.e., preparation documentation, standard amounts, weights, etc.

Approximately 20 percent of each data set that was generated by an automated system was

checked for accuracy. This involved tracking the final reported concentrations back to the raw

data. After any necessary corrections were made, the data were approved by the auditor and

forwarded to the Case Leader for review. A formal report documenting the audit findings was

generated and maintained in the QA Unit files.

2.4.2.2 Quality Control

Data Quality Requirements. DQOs are established to ensure that analytical data are of the quality

necessary to achieve project objectives. Our DQOs are designed to enhance our ability to

identify and accurately quantify source-specific oils. The DQO limits are listed in the specific

laboratory and analytical SOP. PAH and SHC DQOs and criteria are summarized in Table 2-8.

DQOs for biomarker analysis are summax-ized in Table 2-9.

Target analyte concentrations, surrogate recoveries, and QC sample results were determined at

the respective GCEID and GC/MS facilities. After careful checking and review by the facility’s

2-34
-

manager, these data were arranged in Excel spreadsheet format. Diagnostic graphics were also

generated and submitted to the program manager for review. Any subsequent changes to or

updates of the data in the spreadsheet were performed by the respective facility. The data

packages containing all the information (e.g., chain-of-custody sheets, sample preparation data)

required for QA audits were submitted to the QA data auditor.

The auditor prepared a concise audit report for each type of analysis. Comments and action items

in the audit report were addressed by the Arthur D. Little laboratory manager and instrument

facility supervisors.

2.4.3 Metals and Total Organic Carbon Analysis Quality Assurance/Quality Control

2.4.3.1 Quality Assurance

Sample Tracking Procedure. Upon receipt, each sediment, tissue, and source sample received by

the Marine and Environmental Chemistry Laboratories at FIT was carefully inspected to ensure

that it was intact and that the identification number on the sample container matched that found

on the custody sheet. All sediment and source samples were kept refrigerated (- 1 “C) and all

tissue samples were kept frozen (- 18°C) until processed for analysis.

2.4.3.2 Quality Control

-

For this project, QC measures included balance calibration, instrument calibration (FAAS,

ZGFAAS, CVAAS, ICP/MS, and NCS analyzer), matrix spike analysis for each metal, duplicate

sample analysis, SRM analysis, procedural blank analysis and standard checks. With each batch

of up to 40 samples, 2 procedural blanks, 2 SRM, 2 duplicate samples, and 2 matrix spiked

samples also were analyzed. DQOs for these QC measurements are provided in Table 2-10.

Instrument Calibration. Electronic balances used for weighing samples and reagents were

calibrated prior to each use with certified (NIST traceable) standard weights. All pipets

(electronic or manual) were calibrated prior to use. Each of the spectrometers used for metal

analysis was initially standardized using a three- to five-point calibration curve with a linear

correlation coefficient of r20.999 required before experimental samples could be analyzed.

Analysis of complete three- to five-point calibrations and/or single standard checks alternated

every 5 to 10 samples until all the analyses were complete. The relative standard deviation

(RSD) between complete calibration and standard check was required to be less than 15 percent

or recalibration and reanalysis of the affected samples was performed.

Matrix Spike Analysis. Matrix spikes were prepared for a minimum of 5 percent of the samples

analyzed and included each metal to be determined. Results from matrix spike analysis using the

method of standard additions provided information on the extent of any signal suppression or

enhancement due to the sample matrix. If necessary (i.e., spike results outside an 80 to 120

percent limit), all samples were analyzed by the method of standard additions.

Duplicate Sample Analysis. Duplicate samples from homogenized field samples (as distinct from

field replicates) were prepared in the laboratory for a minimum of 5 percent of the total samples.

These laboratory duplicates were included as part of each set of sample digestions and analyses

to provide a measure of analytical precision.

2-35
Procedural Blank Analysis. Two procedural blanks were prepared with each set of 40 samples to

monitor potential contamination resulting from laboratory reagents, glassware, and processing

procedures. These blanks were processed using the same analytical scheme, reagents, and

handling techniques as used for the experimental samples.

Standard Reference Material Analysis. A common method used to evaluate the accuracy of

environmental data is to analyze SRM, samples for which consensus or “accepted” analyte

concentrations exist. The following SRM were used: Marine Sediments, BCSS-1 and MESS-2

(NRC); Estuarine Sediment 1646a (NIST); Buffalo River Sediment 2704 (NRC); Oyster Tissue

1566a (NIST); Dogfish Muscle DORM-2 (NRC); Lobster Hepatopancreas TORT-2 (NIST),

River Water SLRS-3 (NRC) and Trace Elements in Water 1643d (NEST). Metal concentrations

obtained for the SRM were required to be within +20 percent of accepted values for greater than

85 percent of other certified analyses. When no certified values exist for a metal, matrix spikes

were used to evaluate analytical accuracy.

Filter Weighing. All weighing-related manipulation of the filters used for suspended particulate

quantification took place under cleanroom conditions, including controlled temperature and

relative humidity. Each filter was weighed twice in random order, with a minimum of 5 percent

of the filters being weighed in triplicate. Static effects during filter weighing were controlled by

placement of two ‘?o antistatic devices near the weighing pan within the balance. The standard

deviation for the mass of each filter was required to be less than 2 pg for the value to be

accepted.

2.4.4 Biology Quality Assurance/Quality Control

2.4.4.1 Sediment Toxicity Tests

The methods used in conducting these tests followed the guidelines established by the EPA

manual Methods for measun’ng the toxicity of sediment-associated contaminants with estuarine

and marine amphipods (EPA, 1994). The following methodological QA/QC criteria were met at

test initiation and validate the results obtained:

.

.

.

.

2.4.4.2

.

Adult organisms, 3 to 5 mm and in good condition, were used at test initiation; all

organisms were from the same source

Tests were started within 2 days of sediment sample receipt, well within acceptable

holding time limits

Test chambers were identical and contained the same amount of sediment and overlying

water

All instruments used for routine measurements of chemical and physical characteristics

were calibrated each day according to the instrument manufacturer’s instructions

CYPlA (P45OlA) Determinations

Internal standards were included in each staining run to ensure the consistency and

quality of a run, and to determine maximum (occurrence 3 times intensity 5=15) and

minimum (0) staining

All tissues were stained with UPC 10 to determine if nonspecific staining was present

As part of the standard Signet protocol, slides were presoaked in 3 percent H202 to

eliminate endogenous peroxidase activity

Any slides with questionable staining were rerun

2-36
- 2.4.4.3 P450 Repotter Gene System Determinations

Measures of QA/QC were taken during testing of each batch of environmental samples. The

reference inducer (TCDD) at a concentration of 1 ng/mL, and a solvent blank, typically DCM,

are each applied to replicate wells. The fold induction response, that is, the mean l&U of the

TCDD divided by the mean RLU of the DCM blank, is compared to a long-term QC chart. The

response to 1 ng/mL TCDD must be within 2 standard deviations of the running mean

(approximately 100 f 30). Calibration of the luminometer is performed monthly, using a

luciferase control kit purchased from Pharmingen.

Environmental extracts are applied to 2 (for both 6h and 16h time periods) or 3 (for only the 16h

time period) replicate exposure wells, and the CV is evaluated for each sample. A CV that is in

excess of 20 percent is unacceptable, and that extract must be re-tested. In addition, any extract

that produces a fold induction response greater than 100 percent must be diluted and retested.

Typically, an extract is diluted 1: 10 in DCM, and applied to 3 replicate wells.

2-37

ArtJurDLitUe







-

Table 2-2: 1997-1998 Source Samples from the Outermost Cook InletBhelikof Strait

Region

Homer Harbor dredged channel (59O36.37, 151’19.94) (39

Coal collected from exposed coal seam.

lib)

Susitna-03

(SR-Wl)

Matanuska-0 1

(MR-WI)

Matanuska-02

(MR-9

Coyote Lake

Sutton, AK coal 05/16/98 PM Coal collected from coal pocket.

Deshka Lauding, Surface Approximately mile 82.5 on George Parks

Susitna River Water OSll3l98 AM

HV

Matauuska River Surface

Water OS/l 3198 AM Collected at intersection of Old Glenn Hwy

and Matanuska River

Matanuska River Sediment 05113198 AM Collected at intersection of Old Glenn Hwy

and Matanuska River.
Table 2-2: 1997-l 998 Source Samples from the Outermost Cook Inlet/Shelikof Strait

Region

Collected at intersection of Old Glenn H
Table 2-3: Saturated Hydrocarbons Target Analyte List

nC9 A/l nC29 A/l

nCl0 A/l nC30 A/l

nCl1 A/l nC3 1 A/l

nC12 A/l nC32 A/l l

11380.

I

1pl-istane

nC25 A/l

nC26 Ail

nC27 A/l

Tetracosane-d,

5-a-Androstane

l/A

2/A
Table 2-4: Polycyclic Aromatic Hydrocarbons Target Analyte List

~

C2-FhoranthenedPyrenes (C2F/l?) 3, A

C3-FluoranthenedPyrenes (C3F/P) 13, A
Table 2-5: SteraneslTriterpanes Target Analyte List

Diacholestane

Diacholestane

Methvlchblestane S24

Ethvlcholestane S25

Ethvlcholestane S28

Ditemane T4

Tricyclictriterpane T9

Tricyclictriterpane TlO

Trisnorhopane (TS) Tll

Trisnorhopane (TM)

Norhowne

T12

T15

Oleanane

HoDane T19

HomohoDane T21

HomohoDane T22

Internal Standards

Chrysene-d12 c

Triacontane-d62 (Alternate)

Surrogates

SB(H)-Cholane

1 Dotriacontane-d66 (Alternate) I I
Table 2-6: Summary of Instrumental Methods and Method Detection Limits (MDL) for

Metal Analysis of Sediment and Fish

1 Ag - Silver I ZGFAAS 0.01 I ZGFAAS 0.004 I

Al - Aluminum FAAS 6 FAAS 2.3

A s - Arsenic ZGFAAS ’ 0.1 ZGFAAS 0.03

B a - Barium ICPIMS 0.1 ICPnvfS 0.006

B e - Beryllium ICP/MS 0.1 ZGFAAS 0.002

C a - Calcium FAAS 5 Not analyzed --

C d - Cadmium ICPIMS 0.02 FAAS 0.3

Cr - Chromium FAAS 1 GFAAS 0.003

Cu - Copper FAAS 2 FAAS 0.7

Fe - Iron FAAS 5 FAA.9 2.5

Hg - Mercury CVAAS 0.001 CVAAS 0.001

K - Potassium FAAS 5 Not analyzed

Mg - Mannesium FAAS 1 Not analyzed

Mn - Manganese FAAS 2 FAAS 1.1

Ni - Nickel ICPIMS 0.2 Not analyzed (Year 1) - \

Pb-Lead ICP/MS 0.1 1 ICP/MS 0.001 I

Sb - Antimony ICP/MS 0.2 ICPDJIS 0.001

Se - Selenium ZGFAAS 0.05 ZGFAAS 0.03

%-Tin ICP/MS 0.1 ICPnvlS 0.001

Tl-TlMlliUIll ICPi?vIS 0.1 ICPfMS 0.0001

V-Vanadium FAAS 10 GFAAS 0.007

I Grain-Size I Sieve and Pipet I I

I TOC -1 Carlo Exba NCS Svstem 0.1 I I

Notes:

FAAS = Flame Atomic Absorption Spectrometq

GFAAS = Graphite Furnace Atomic Absorption Specixomelry

ZGFAAS = Zeeman Graphite Furnace Atomic Absorption Spectrometry

CVAAS = Cold Vapor Atomic Absorption Spectromeny

ICPMS = inductively Coupled Plasma-Mass Spectrometry

NCS = Nitrogen - carbon - Sulfur Analyzer

TOC=TotalOrganicCarbon
Table 2-7: Calculation of the Sediment Profile Imaging Organism-Sediment Index

A. Mean RPD Depth

(choose one)

0.00 cm 0

>O-0.75 cm 1

0.76 - 1.50 cm 2

1.51 - 2.25 cm 3

2.26 - 3.00 cm 4

I 3.01 - 3.75 cm 5 I

I > 3.75 cm I 6 I

B. Successional Stage

(choose one) I I I

Oxygena

Notes:

Organism-sediment Index = Total of above subset indices (A+B+C); Range: -10 to +ll.

‘This is nbt based on a Winkler or polarigraphic electrode measurement, but on the imaged evidence of reduced, low reflectance

(i.e., high-oxygen-demand) sediment at the sediment-water interface.
Table 2-8: Data Quality Objectives for Saturated Hydrocarbons and Polycyclic Aromatic

Hydrocarbons Analyses

Initial CalibrationInitial Calibration

Continuing Calibration (CC)

Oil Reference Standard

Procedural Blank

Blank Spike

Instrument SRM (1491)

Sediment SRM (1941a)

Tissue SRM (1974a)

Duplicate Analysis

surrogate standards

Prior to every instrument sequence for

GUMS analysis and as needed for

GUFJD analysis

After every 12 samples or 16 hours,

whichever is more frequent, and at end

of instrument sequence

Two with each instrument sequence

(One North slope Crude and one Cook

Inlet Crude)

One per batch

One per batch

One per instrument sequence

Not applicable to SHC analysis

One per batch as appropriate

One per 40 field samples

Every sample

5-point curve, percent RSD < 35

percent for ah CC target analytes,

90 percent must be c 25 percent

Percent RSD < 35 percent for all

CC target analytes; 90 percent

must be < 25 percent

North Slope Crude c 35 percent D

from laboratory mean for target

compounds (use surrogate

corrected values) except for

compounds below the reporting

limit

No analyte to exceed 5X the MDL

unless sample amount is > 10X

blank amount

Recovery between 35 and 125

percent

Values must be cl5 percent

difference of true value for all

certifid analytes

Values must be within 30 percent

of the true value on average for all

analytes, not to exceed 35 percent

of true value for more than 2

analytes

RPD c 30 percent for all analytes

>lO times the MDL, Mean

RPDdO percent

Recovery between 45 and 125

percent
Table 2-9: Quality Control Summary for Sterane and Triterpane Analyses

Initial Calibration Prior to every instrument sequence Cpoint curve, percent RSD < 25

percent for all target analytes

Continuing Calibration After every 12 samples or 16 hours,

whichever is more frequent, and at end

of each sequence

Percent RSD < 25 percent for all

analytes

Oil Reference Standard (North Slope

Crude)

One with each instrument sequence c 35 percent Dif. from laboratory

mean for target compounds (use

surrogate corrected values) except

for compounds below the reporting

limit

Procedural Blank One per batch No analyte to exceed 5X the MDL

unless sample amount is > 10X

blank amount

surrogate standards Every sample Recovery between 45 and 125

percent
Table 2-10: Data Quality Objectives and Criteria for Metals and Total Organic Carbon

Initial Calibration

Continuing Calibration

Standard Reference Materials

Method Blank

Matrix Spike and Spike Method Blank

Laboratory Duplicate

Prior to every batch of samples

Must end every analytical sequence;

for flame, repeat all standards every

five samples; for graphite furnace and

ICP/MS, recheck standard after every

8 to 10 samples

One per batch of 20 samples

One per batch of 20 samples

One per batch of 20 samples

One per batch of 20 samples

3- to S-point curve depending on

the element and a blank. Standard

curve correlation coefficient

r> 0.999 for all analytes

Percent RSD < 15 percent for all

analytes

Values must be within -c 20 percent

of accepted values for > 85 percent

of the certified analytes and within

f 25 nercent for Ha

No more than 2 analytes to exceed

5X MDL unless analyte not

detected in associated sample

Analyte recoveries between 80 to

120 percent

RSD < 25 percent for 65 percent of

the analytes
3.0 Results

3.1 Contaminant Sources

Source samples were collected throughout the study area at several locations representing

potential contaminant input sources such as oil and gas activities (crude oil and produced water),

coals, municipal discharges, boat harbors, riverine and coastal inputs (Section 2.1.3). The results

were used to compare concentrations and distributions of contaminants found in the sediment

samples from zones 0, 1,2,3, and 4 to potential known contaminant sources. The source

samples from surface sediment, oil, coal, and water matrices were analyzed for organics and

metals. In addition, the source sample sediments were analyzed for grain size and TOC.

3.1 .l Physical Measurements

The TOC content for bottom sediments from the Susitna and Copper Rivers, two primary

sediment sources to outermost Cook Inlet and the Shelikof Strait, average 0.20 f 0.01

percent and 0.14 4 0.02 percent, respectively (Table 3-l). Low TOC values in sediments from

these two rivers reflect the high sand content. For example, bottom sediment from the Susitna

River has 56.2 percent sand, 37.9 percent silt and only 5.9 percent clay. The Copper River

contains 35.8 percent sand, 48.7 silt and 15.5 percent clay. In contrast, bottom sediment

recovered from Homer Harbor, also a potential source of sediment to the study area, contains 1.6 - percent TOC, 5.6 percent sand, 43.6 percent silt and 50.7 percent clay. The TOC content of a

coal sample from Homer, Alaska is 67.1 percent (Table 3-l).

3.1.2 Organics

Analyses for SHC, PAH, and S/T target analytes were conducted on the various source samples,

and included the following: crude oil from Cook Inlet; Swanson River Field oil; seep oil from

Well Creek; coals from Cook Inlet, Homer coals, Ninilchik, Matanuska, Coyote Lake, and

Beluga; sediments from the Susitna River, Copper River, Homer Harbor, Matanuska River,

Alaska Coastal Current, and Augustine Island; Trading Bay produced water; and Point Woronzof

municipal effluent. Inputs from crude oil (e.g., seeps), produced water, municipal effluent, and

coal were all considered to be the potential source(s) of organic hydrocarbons to outermost Cook

Inlet and the Shelikof Strait (Boehm et al., 1998).

Results for each source sample are summarized in Table 3-2 as total PAH, total petroleum

hydrocarbons (PHC), and total S/T concentrations. Where more than one sample was analyzed

for a source (e.g., Copper River, Susitna River, and Homer Harbor), an average is presented. For

the Cook Inlet crude oil, the source sample as well as all Cook Inlet crude “check” oils that were

analyzed with respective PAH, SHC, and SK field sample analyses were averaged together. The

complete organics results data tables are presented in Appendix B. Figures 3-l through 3-18

provide a representative GUFID chromatogram (top), PAH distribution histogram (middle), and

VI extracted ion chromatogram (bottom) for each source sample type. The GCLFID

chromatograms represent the total signal detected by the instrument (GUFID) during the sample

analysis. The extracted ion chromatogram is similar, but represents the signal of only one ion or

3-1
mass (in this case mass 19lwhich is characteristic of triter-panes) from the total signal detected by

the mass spectrometer (GCLMS) during the sample analysis.

3.1.2.1 Source Oils

Cook Zdet Crude. Results for the Cook Inlet crude oil show an average total PHC concentration

of 700,000 +- 34,000 pg/g (n=24). The Cook Inlet crude oil sample chromatogram (Figure 3-l)

reveals a predominance of resolved n-alkanes in the C8 through C34 carbon range, typical for a

fresh crude oil. An unresolved complex mixture (KM - seen as a baseline rise) extends across

the entire n-alkane range. The distribution of alkanes gradually tapers from highest

concentrations of lower molecular weight carbon alkanes (C12) down to the higher molecular

weight carbon compounds (C34). The crude oil source results may be used to typify possible

hydrocarbon contributions from fresh crude oil and/or seep areas in the Shelikof Strait and Cook

Inlet in the sediment samples.

The results of GCYMS analyses of Cook Inlet crude oil show an average total PAH concentration

of 13,000 + 1,000 pg/g (n=29), or 1.3 percent PAH. The distribution of the PAH analytes

(Figure 3-l) shows a typical petrogenic PAH signature, with an abundance of 2- and 3-ring PAH

(naphthalenes through phenanthrenes), substantially lower levels of 4-ring PAH

(fluoranthenes/pyrenes and chrysenes) and only traces of 5- and 6-ring PAH. The Cook Inlet

crude oil has a low sulfur content as indicated by the low levels of the 3-ring, sulfur-containing

dibenzothiophenes. The observed PAH distribution with the C-2 or C-3 alkyl homologues

greater than the parent PAH is also characteristic of petroleum PAH.

The steranes and triter-panes in the Cook Inlet crude averaged 510 -c 81 &g (n=21) and exhibit a

characteristic petroleum pattern dominated by the C30-triterpane, 17a(H)-hopane (Figure 3-l).

In addition, the triterpane 18a(H)-oleanane, an indicator of higher plant (e.g., angiosperm) input

to crude oils from the upper Cretaceous period and later (Peters and Moldowan, 1993), is absent.

Thus the presence of oleanane can be used as an indicator of non-Cook Inlet crude oil inputs.

Swanson River Field OZ The total petroleum hydrocarbons determined for the Swanson River

Field oil sample was comparable to the Cook Inlet crude oil, at 630,000 pg/g (Table 3-2). The

GCYFID chromatogram also portrays a virtually identical pattern of the resolved n-alkanes.

The total PAH concentration of 12,000 pg/g (Table 3-2) and overall PAH distribution (Figure 3-

2) are also similar to that determined for the Cook Inlet crude oil, i.e., an increased abundance of

alkyl homologues relative to both the parent PAH and higher molecular weight PAH.

Comparable concentrations and S/T distribution of the Swanson River Field oil with the Cook

Inlet crude oil sample (Figures 3-2 and 3-1, respectively), lend further support to the

consistencies found within each of the hydrocarbon subclasses.

WeU Creek Seep Oil. On average, the Well Creek oil samples contained 660,000 & 130,000 pg/g

(n=2) of total PHC. The sample chromatogram (Figure 3-3) exhibits a deficiency of resolved nalkanes, likely due to the fair amount of weathering expected for a sample of this type. The

UCM predominates the chromatogram and extends across the entire range of the GC/FlD

analysis.

3-2
The average total PAH for the Well Creek seep oil was 4,400 f 2,000 pg!g (n=2). As seen with

the SHC chromatogram, the PAH distribution (Figure 3-3) also shows some degree of

weathering. Losses of the low molecular weight PAH such as naphthalene, fluorene, and their

alkyl homologues are common due to their heightened solubility/volatility when compared with

the higher molecular weight compounds such as the alkylated phenanthrenes and fluoranthenes.

Steranes and triterpanes averaged 250 f 5.6 pg/g (n=2) in the Well Creek seep oil and, similar to

observations in the Cook Inlet crude oil S/T extracted ion chromatogram, is also dominated by

the C30-triterpane, 17a(H)-hopane and lacks the triter-pane 18a(H)-oleanane (Figure 3-3).

3.1.2.2 Source Coals

Hornet Spti Coal. This coal source sample was collected from a beach in the Kachemak Bay area

and contained low concentrations of total PHC (1,200 pg/g) relative to the Cook Inlet crude oil.

The GC/FD chromatogram of the coal reveals a complex mixture of hydrocarbons in the C26 to

C34 carbon range; however, there is no homologous pattern of normal alkanes observed (Figure

3-4). Although the concentrations of PHC are low, the coal represents a potentially significant

source of hydrocarbon input to the marine sediments of the region.

The PAH analysis of the coal sample reveals a substantially lower total PAH concentration (5.3

pg/g) than the Cook Inlet crude oil. The PAH distribution of the coal is comprised of 2- and 3-

ring PAH, with a predominance of alkyl naphthalenes. Perylene, a biogenic PAH, which occurs

naturally as a product of diagenesis of terrigenous organic matter in sediments, is one of the most

abundant PAH compounds. The sulfur-containing dibenzothiophenes are low relative to the

phenanthrenes, but appear to be slightly more abundant than in the Cook Inlet crude oil.

The S/T in the coal are distinctive and very different from Cook Inlet crude oil. The triterpanes

are dominated by moretane (the largest peak in Figure 3-4), which is an indicator of recent

biogenic material. In comparison, C30-hopane, the primary triter-pane in Cook Inlet crude oil, is

a relatively minor component in the coal. The large relative abundance of the C31-homohopane

22R isomer over the 22s isomer (peaks T22 and T21 in Figure 3-4, respectively) is further

evidence of the immature/recent biogenic nature of the coal.

Homer Coal This coal sample was very similar to that described above for the Homer Spit coal

in that it contained low concentrations of total PHC (660 pg/g). In addition, the GC/FID

chromatogram of the coal reveals a complex mixture of saturated hydrocarbons in the C26 to

C34 carbon range (Figure 3-5).

The total concentration of PAH is fairly low, at 2.4 pg/g, and is comprised mainly of the parent

and alkylated naphthalenes and phenanthrenes (Figure 3-5). However, the biogenic component

(perylene) is fairly large in this coal, at a concentration of 0.25 pg/g or just above 10 percent of

the total PAH.

The amount of S/T is also comparable to the Homer Spit coal, with a total S/T of 2.1 pg/g.

Additionally, the C30-hopane is present, although not dominant as was seen with the Cook Inlet

crude. The relative abundance of the C31-homohopane 22R isomer over the 22s isomer (peaks

T22 and T21 in Figure 3-5, respectively), is the reverse of that seen in the Homer Spit coal,

perhaps evidence of a more mature nature of this coal sample.

3-3
Nidchik Cod. Total PHC for this coal source (4.7 pg/g) is comparable to that of the Homer

coals (Table 3-2). The GCEID chromatogram (Figure 3-6) also illustrates the similar heightened

distribution of saturated hydrocarbons in the C26 to C34 carbon range.

The concentration of total PAH in the Ninilchik coal was also similar to the other coal source

samples, but was clearly dominated by the biogenic PAH, perylene (Figure 3-6), comprising

nearly 80 percent of the total PAH distributions.

Results for Ninilchik coal total S/T were 0.95 @g, within the range spanned by the other coal

source samples (Table 3-2). The extracted ion chromatogram shows the presence of the C30-

hopane (peak T19, Figure 3-6), in addition to a minor triterpane 18a(H)-oleanane component.

Matanuska Coal. The TPH results for the Matanuska coal are comparable to the other coals

(1,200 pg/g). The GCEID chromatogram (Figure 3-7) reveals the presence of a wider range of

the resolved n-alkanes, generally extending across the domain of the analysis (from C9 through

C36), compared with the other coal samples.

The total PAH for the Matanuska coal was the highest compared to all other coals, at 62 pg/g

(Table 3-2). The overall PAH distribution is similar to a petrogenic source, with a predominance

of the low molecular weight naphthalenes and phenanthrenes; however a clear absence of

fluorenes and dibenzothiophenes render it quite unique. There are also only trace amounts of the

4- and 5-ring PAH, in addition to a minimal biogenic PAH component (Figure 3-7).

Results for the S/T concentrations are comparable to the Homer coals, with a total S/T of 2.1

pg/g. The distribution of analytes, however, is not similar and is noted by maximums at the C31-homohopanes, with the 22s isomer dominant over the 22R isomer (Figure 3-7).

Coyote LA& Coal. The total concentration of petroleum hydrocarbons was the lowest of the coal

samples measured in this study (400 pg/g). The GC/FID chromatogram is very similar to that of

the Matanuska coal, although there appears to be a degree of weathering associated with the loss

of some of the resolved n-alkanes (Figure 3-8).

Total PAH for the Coyote Lake coal source sample was about one-third that of the Matanuska

coal (23 pg/g), but still substantially higher than the other coals (Table 3-2). The coal sample

from Coyote Lake (Figure 3-8) also exhibits similarity to the Matanuska coal (Figure 3-7)

regarding the high abundance of the alkylated naphthalenes and phenanthrenes and lack of most

other PAH measured here.

Comparable distributions of S/T, e.g., the dominance of the C-31 homohopanes, the lack of

oleanane and similarities among the other hydrocarbon analytes, lead to the conclusion that these

two source coals (Coyote Lake and Matanuska) are from the same coal-bearing formation.

Beluga Cod Results for the TPH concentration are within the range of the other coals measured

in this study (750 + 180 pg/g). The GC/FID chromatogram contains a complex mixture of

saturated hydrocarbons in the C26 to C34 range, much like that of the Homer and Ninilchik

coals, but the concentrations of the resolved n-alkanes are much lower (Figure 3-9).

3-4
-_

The Beluga coal sample contained a low concentration of total PAH (4.4 +- 0.44 pg/g) and, just as

observed with the Ninilchik coal, was dominated by the biogenic PAH perylene (Figure 3-9).

The similarities between these two coals also extend to the S/T distribution, with a dominance of

the 22s isomer of C31-homohopane and the presence of oleanane (Figures 3-6 and 3-9).

3.1.2.3 Source Sediments

Homer Harbor Sediment. Results of SHC analyses for the two Homer boat harbor sediment

source samples were very similar at the surface (0- to 2-cm) and subsurface (4- to 6-cm) depth

intervals. This sediment was a black, anoxic, silt-clay, and as expected, the SHC and other

organic hydrocarbon concentrations were approximately 3 to 10 times greater than the riverine

and surficial sediments collected throughout the study region. The average total PHC

concentration was 120 it 7.1 ug/g (Table 3-2). The SHC chromatogram (Figure 3-10) shows a

predominance of higher molecular weight alkanes in the C27 to C3 1 range and a corresponding

UCM. The assemblage of saturated hydrocarbons in these samples is predominated by the plant

wax alkanes; however, there are also indicators of weathered petroleum as well.

-.

The mean total PAH concentration in the Homer Harbor sediments is 0.78 pg /g. The PAH

distribution is comprised primarily of petroleum PAH and perylene, with a minor combustion

PAH contribution (Figure 3-10). The relative distribution within the series of alkyl naphthalenes

indicates that the petroleum PAH are moderately weathered (e.g., the C4-naphthalenes > C3-

naphthalenes > C2-naphthalenes). The predominance of perylene is indicative of recent

diagenesis of terrestrial hydrocarbons in the sediments, or alternatively may be linked to a coal

source (i.e, Homer coals, Figures 3-4 and 3-5). The abundance of the CCphenanthrenes, which

are the dominant PAH analyte in the distribution, is likely due to an interferent which may be

related to combustion sources.

The S/T distributions of the Homer Harbor sediments are clearly different from the other source

samples. An unidentified triter-pane, perhaps normoretane, is the most abundant compound,

followed by the C31-homohopane 22R isomer (Figure 3-10). C30-hopane and oleanane are only

minor components. Some similarities in the triter-pane distributions between the Homer Harbor

sediments and the Homer coals (e.g., the large relative abundance of the C31-homohopane 22R

isomer versus the 22s isomer) indicate that Homer Spit coal (Figure 3-4) may be a major

component of the observed hydrocarbon assemblage.

Copper-River Sediment. The total PHC concentrations in the Copper River sediment samples

were very low in 4 of the 5 samples and ranged from 2.6 to 68 pg/g, with an average total PHC

concentration of 18 f 28 yg/g. The SHC distributions in all the samples were dominated by

terrigenous alkanes in the C25 to C33 range (Figures 3-l 1 and 3-12). None of the samples

exhibited evidence of a petroleum hydrocarbon signature based on the GCE’ID chromatograms.

In comparison to the total PHC concentrations in the oil, coal, and Homer Harbor sediment

source samples, the PHC levels in these riverine sediments were quite low. The one exception is

the CR-l sample collected near the Million Dollar Bridge. This sample had a total PHC

concentration approximately 15 times higher than the other 4 samples (CR-2 to -5), and is likely

the result of incorporation of terrigenous/pla.nt material in this sample.

-. The total PAH concentrations from the Copper River sediments were very low, with many target

compounds below the detection limit of the method (i.e., not detected). The mean total PAH

concentrations of the Copper River sediments were 0.041 ug/g (Table 3-2). The PAH

3-5
distribution of the Copper River sediments (Figure 3-l 1) contains trace levels of petrogenic 2-

and 3-ring PAH, as well as combustion-related 4-, 5, and 6-ring PAH. Furthermore, the Copper

River sediment also contains a significant biogenic PAH component, i.e., perylene (Figure 3-12).

S/T are present at only trace levels in the Copper River sediments and many compounds were not

detected (Figures 3-l 1 and 3-12). This further supports the observation that petroleum is not a

significant component of the total hydrocarbons in the samples. Overall, the trace levels of SHC

and PAH in these river-me samples indicate that they are not likely to be a significant source of

petroleum hydrocarbon input to the Cook Inlet and Shelikof Strait region.

Susitruz River Sediment. The Susitna River sediment samples have low total PHC concentrations

(3.4 r 1.3 pg/g). The Susitna River sediment SHC distributions are similar to the Copper River

samples and are characterized by a predominance of terrigenous alkanes in the C27 to C31

carbon range (Figure 3-13). There is no evidence of petroleum hydrocarbons in these sediments

based on the GC/FlD chromatograms.

In contrast to the Copper River sediment, the PAH distribution of the Susitna River sediment

shows only trace levels of total PAH (0.0074 +- 0.00094 pg/g), composed primarily of the

combustion-related PAH (phenanthrene, fluoranthene, and pyrene) and the biogenic PAH,

perylene.

S/T are present at only trace levels in the Susitna River sediments and many compounds were not

detected (Figures 3-13). This further supports the observation that petroleum is not a significant

component of the total hydrocarbons in the samples. Overall, the trace levels of SHC and PAH

in these river-me samples indicate that they are not likely to be a significant source of petroleum

hydrocarbon input to the Cook Inlet and Shelikof Strait region.

Mafanz~ku River Sediment. Sediment collected from the Matanuska River contained low

concentrations of total PHC (6.3 pg/g). The SHC distributions are similar to the Copper and

Susitna River samples and are characterized by a predominance of terrigenous alkanes in the C24

to C31 carbon range (Figure 3-14). There is no evidence of petroleum influence in these

sediments based on the GC/F!ID results.

The PAH concentrations in these sediments were higher than the other two rivers but still less

than that of the Homer Harbor sediment (Table 3-2). The PAH distribution of the Matanuska

River sediment (Figure 3-14) contains trace levels of petrogenic 2- and 3-ring PAH, as well as

combustion-related 4-, 5, and 6-ring PAH.

S/T are present at only trace levels in the Matanuska River sediments and many compounds were

not detected (Figures 3-14). This further supports the observation that petroleum is not a

significant component of the total hydrocarbons in the samples and indicates that they are not

likely to be a significant source of petroleum hydrocarbon input to the Cook Inlet and Shelikof

Strait region.

Alaska Coastal Current Sediment. Results for the ACC sediment revealed a total PHC

concentration of 47 f 3.0 yg/g (Table 3-2). The pattern of saturated hydrocarbons extends across

the range of GCYFID analysis (Figure 3-15), with a similar distribution of the lower n-alkanes and

terrigenous C27 to C31 alkanes, as seen in Cook Inlet and Shelikof Strait sediments.

3-6
GCLMS results showed the highest PAH concentrations (1.7 + 0.06 pg/g) compared with each of

the other source sediments analyzed (Table 3-2). The distribution of PAH analytes represents a

mixture of both petrogenic (i.e., 2- and 3-ringed alkylated PAH) and typical pyrogenic (5 and 6-

ringed PAH) signatures (Figure 3-15).

The concentrations of S/T in the ACC sediments were moderately low, at 0.049 f 0.0021 pg/g.

The extracted ion chromatogram exhibits a biomarker distribution similar to that of the oils, with

a dominance of the C30-triterpane, 17a(H)-hopane (Figure 3-15), although the sediments did

contain a significant amount of oleanane. These results indicate that these sediments are likely

influenced by both “background” petroleum and pyrogenic sources of hydrocarbons.

Augustine Island Sediment. Total petroleum hydrocarbons in the Augustine Island sediments

were 12 pg/g (Table 3-2). The overall SHC (Figure 3-16) distribution reflects the influence of

terrigenous plants (C23 through C30) just as observed with each of the river sediments.

PAH concentrations for these sediments were moderate (0.17 pg/g), with a distribution reflecting

the influence of petrogenic, pyrogenic, and biogenic (perylene) PAH (Figure 3-16).

The concentration of S/T for the Augustine Island sediments was 0.019 pg/g, with a profile

containing similar dominance of the 22R isomer of C3 1-homohopane (Figure 3-16), as was

observed with the Homer Spit coal and Homer Harbor sediments (Figures 3-4 and 3-10,

respectively).

3.1.2 4 Aqueous Sources

Point Woronzof Municipal Effluent. The total PHC concentration for the Point Woronzof

(Anchorage) municipal effluent was 2,300 @L (Table 3-2). The chromatogram of the

municipal effluent sample reveals a predominance of higher molecular weight alkanes (C27 to

C34)) which are typical of terrigenous hydrocarbon sources (i.e., plant wax alkanes), and only a

trace PHC signature.

The Anchorage municipal effluent has a total PAH concentration of 6.7 pg /L, with a PAH

distribution charac.terized by a full suite of 2-, 3-, and 4-ring PAH, with considerably lower levels

of 5- and 6-ring PAH (Figure 3-17). Three of the most abundant compounds in the PAH

distribution are phenanthrene, fluoranthene, and pyrene, which are indicative of pyrogenic or

combustion-related sources (e.g., urban runoff). The effluent also contains a complete series of

Cl- through C4-alkyl naphthalenes, phenanthrenes, and dibenzothiophenes, which is

characteristic of petroleum sources.

The full suite of triter-panes, dominated by hopane (Figure 3-17), is also characteristic of PHC

material. Based on the SHC, PAH, and S/T data, the Anchorage effluent contains a mixture of

petroleum and combustion-related hydrocarbons.

Trading Bay Produced Water. Total SHC in the produced water sample from the Trading Bay

Production Facility had a concentration of 6,200 pg!L (Table 3-2). The chromatogram for the

produced water (Figure 3-18) displays a homologous series of alkanes and a UCM similar to the

Cook Inlet crude oil (Figure 3-l), although the produced water is depleted in the low molecular

weight alkanes (C9 to C14).

3-7
The total PAH concentration of 380 p/L in the TBPF produced water sample is substantially

higher than the municipal effluent, but within the range for other produced water samples from

Cook Inlet (Hyland, et al., 1995). The PAH distribution (Figure 3-18) is characterized by an

abundance (>90 percent) of naphthalene and alkyl naphthalene relative to the 3- and 4-ring PAH

(phenanthrenes and chrysenes). The observed enrichment of the naphthalenes is due to the

higher solubility of these 2-ring PAH relative to the 3-, 4-, 5-, and 6-ring PAH. The distribution

of the 3-, 4-, and 5-ring PAH and the S/I’ (Figure 3-18) in the produced water are comparable to

the Cook Inlet crude (Figure 3-l).

3.1.3 Metals

Twenty-three source samples were analyzed for trace metals and major elements including the

following: Susitna River bottom sediment (2), Copper River bottom sediment (4), Homer Harbor

bottom sediment (l), Susitna River suspended solids (2), Knik River suspended solids (2),

Matanuska River suspended solids (2), Copper River suspended solids (2), coal (5), Cook Inlet

crude oil (l), Cook Inlet produced water (l), and Point Woronzof municipal effluent (1).

Samples of sediment, water, and oil were collected during 1997 and samples of suspended solids

and coal were collected during 1997 and 1998. At the beginning of this study, river-me inputs

were hypothesized to be the dominant source of sediment and sediment metals to outermost

Cook Inlet and the Shelikof Strait (Boehm et al., 1998). Thus, the Susitna and Copper Rivers,

two primary sources of metals to the study area, were sampled for bottom sediment and

suspended solids.

3.1.3.1 Source Sediments and Suspended Solids

Results for bottom sediment from the Susitna and Copper Rivers (Table 3-l) show that

concentrations of nine metals (Al, Be, Cr, Fe, Hg, Ni, Pb, Sn, Tl, and Zn) are comparable to or

less than values for average continental crust (Table 3-3). In contrast, and again relative to

average continental crust, concentrations of As, Ba, Cd, Cu, Sb, and Zn are higher in bottom

sediment from both rivers, Ag and Se are greater in Susitna River sediments, and Mn and V are

higher in Copper River sediments (Table 3-l). However, when these metals in river sediment are

compared with native sedimentary, volcanic, and plutonic rocks from Alaska (Table 3-3), the

river sediments contain comparable or lower levels of all metals.

During 1998, suspended solids were collected from the Susitna, Knik, Matanuska, and Copper

Rivers. All concentrations of As, Cd, Cu, Fe, Hg, Mn, Sb, V, and Zn in river suspended solids

are higher than levels reported for average continental crust (Table 3-3). However, relative to

Alaskan rocks, only concentrations of Al, Cr, and Ni are higher in most samples of river

suspended solids (Tables 3-l and 3-3). This enrichment is most likely due to higher natural

levels of these three metals in the fine-grained aluminosilicate clays carried in suspension.

Maximum concentrations of Ba and Pb in suspended solids are about 30 percent higher than

Alaskan rocks for just one or two isolated instances that may be tied to natural or anthropogenic

processes. Collectively, metal values for bottom sediments and suspended solids from the

important source rivers provide one valuable frame of reference that will be used to help identify

inputs of contaminants to sediments as they are carried through Cook Inlet and on to the Shelikof

strait.

Bottom sediment from Homer Harbor also was chosen as a potential source material to outermost

Cook Inlet and the Shelikof Strait. This sediment is fine-grained, black mud (94.3 percent silt

3-8
plus clay) with 1.6 percent organic C. Despite the nature of this material, concentrations of all

metals in river suspended solids are greater than levels found in sediments from Homer Harbor. _ When Homer Harbor sediments are compared with river sediments, concentrations of Hg, V, and

Zn are elevated in Homer Harbor (Table 3-l). However, bottom sediment from the Susitna River

contains 56 percent sand and may not be representative of the material carried seaward from the

river system. At this point, Homer Harbor sediment will be considered an additional potential

source of Hg, V, and Zn to the study area. The degree of anthropogenic additions of Hg, V, and

Zn to Homer Harbor will be discussed in Section 4.1.

3.1.3.2 Source Coals

Coal is an important deposit in the drainage basin of the study area (MMS, 1996).

Concentrations of metals in five samples of coal are generally lower than in bottom sediment

from the Susitna or Copper Rivers (Table 3-l). Notable exceptions to this observation are higher

levels of Cd, Cu, and Hg in the Ninilchik coal and elevated concentrations of Sb in the

Matanuska coal relative to river bottom sediment and suspended solids. When source coals for

this study are compared with the USGS (1998) database for coal in Alaska (Table 3-l), the

following metals (samples) are above the range of observed concentrations: Al (Homer), Cd

(Ninilchik), Cr (Beluga), Cu (Matanuska and Ninilchik), Fe (Homer), Hg (Ninilchik), Mn

(Homer), Pb (Beluga and Ninilchik), and Sb (Matanuska). However, coal is unlikely to be an

important source of metals to any of the sediments in outermost Cook Inlet and the Shelikof

Strait because the highest TOC values in sediment (TOC =2 percent) are more than 30 times

lower than in coal (TOC>60 percent). Even if all the TOC in the sediment was from coal, metals

in the coal would be diluted by a factor or 30 or more. Thus, concentrations of Sb, with a 3-fold

enrichment in coal, would not be enhanced in sediment due to the presence of a small fraction

(<3 percent) of coal.

3.1.3.3 Aqueous and Oil Sources

Metal concentrations in the source sample of TBPF produced water (salinity = 25 g/L), Cook

Inlet crude oil, and final effluent from Point Woronzof WWTF (Table 3-4) are low, with

concentrations >l mg/L only for Ba and Mn in the produced water, Fe and Ni in the crude oil,

and Fe in the final effluent. At these low concentrations and discharge rates, the aqueous and oil

samples are unlikely to serve as a detectable source of metals to sediments in the study area.

Trefry et al. (1996) found no statistical differences (CX = 0.05) in concentrations of Ba, Cd, Cu,

Fe, Mn, Ni, Pb, V, or Zn in fish collected from oil production platforms in the Gulf of Mexico

where there were discharges of produced water versus non-discharging sites. Furthermore, metal

levels of produced water from the Gulf of Mexico were considerably higher than those found in

the sample from TBPF.

3.2 Surface Sediments

3.2.1 Physical Measurements

A total of 170 surficial sediments were analyzed for TOC and percent sand, silt, and clay. The

TOC values in surficial sediments range from 0.26 percent to 1.49 percent (Table 3-5). Relative

to TOC concentrations in bottom sediment from the Susitna (O.ZO&Ol percent) and Copper

(0.14ti.02 percent) Rivers, TOC levels in sediment from outermost Cook Inlet and the Shehkof

Strait are significantly higher. Average TOC values are similar in zones 0 and 1, increasing by

about 40 percent in zones 2 and 3 (Table 3-5). Highest TOC levels (~1 percent TOC) are
observed at ZOFl and ZOF14 (Homer Harbor), at selected sites in zones 2 and 3, and throughout

zone 4 (Appendix A).

Sand values in surficial sediments average about 42 percent in zone 0 and 41 percent in zone 1

(Table 3-5). However, the sand content decreases dramatically in the remaining three zones. For

example, sediment from zone 2 averages about 7 percent sand, zone 3 contains only 2 percent

sand, and zone 4 has about 1 percent sand. In contrast, the silt+ clay levels in surficial sediments

from outermost Cook Inlet and the Shelikof Strait increase from 57.9 percent in zone 0 to >97

percent in zones 3 and 4 (Table 3-5).

3.2.2 Organics

In this section, the surface sediment grab sample results and general trends in the data will be

discussed for the outermost Cook Inlet and Shelikof Strait study area as a whole, as well as

within each of the five zones.

Average concentrations of total PAH, total PHC, and total S/T were calculated for each zone by

first averaging replicates, where appropriate, to obtain a value for each station location, and then

averaging the station location values within each zone to obtain an average total concentration

for each zone. The data presented reflect concentrations on a dry sediment weight basis. The

concentrations presented for the combined years (1997 and 1998) are simply the average of the

zone for each sample period (n=2). The study area-wide grand average concentrations were

obtained by averaging the average total concentration for each zone (i.e., n=4 for 1997, n=5 for

1998, n=5 for 1997 and 1998). The range of values presented for each grand average includes

the minimum and maximum concentration values for all station locations. These calculated

means and ranges for the summary organic parameters in all zones are presented in Table 3-6.

The complete organics data for all surface sediments are included as data tables in Appendix B.

In addition, the key diagnostic parameters for the organics data, as defined in Table 3-7, which

were used in the statistical analysis of the surface sediment data for both years, are summarized

in Table 3-8.

To facilitate the presentation and discussion of the organics data, GC/FlD chromatograms, PAH

distribution plots, and triterpane extracted ion chromatograms that are representative of surface

sediments in zones 0, 1,2,3, and 4 were selected, and are presented in Figures 3-19 through 3-

27. The stations selected for presentation are as follows:

Zone 0 - Fixed station locations Fl - Kachemak Bay (sample 97-0-Fl-Ol-OO-PHC-S,

Figure 3-19), station F4 - center of outermost Cook Inlet (samples 97-0-F4-02-OO-PHCS, Figure 3-20 and 98-0-F4-Ol-OO-PHC-S, Figure 3-21), and F5 - Kamishak Bay

(samples 97-O-F5-02-00-PHC-S, Figure 3-22 and 98-0-F5-01-00-PHC-S, Figure 3-23)

Zone I - Random station 09 - North Shelikof Strait (sample 97-l-OS-Ol-00-PHC-S,

Figure 3-24)

Zone 2 - Random station 08 - Middle Shelikof Strait (sample 97-2-08-Ol-00-PHC-S,

Figure 3-25)

Zone 3 - Random station 10 - South Shelikof Strait (sample 97-3-lo-Ol-00-PHC-S,

Figure 3-26)

Zone 4 - Fixed station location F2 - Outside Shelikof Strait (sample 984-F2-Ol-OOPHC-S, Figure 3-27)

3-10
,- Surface sediments were also collected in triplicate at two embayrnent stations located within

Kodiak Island (Figure 2-l). Due to their close proximity to the shore and the presence of a sill

between them and the open strait (as indicated by the water depths of the two embayment

stations), these stations were not included in the statistical zone analysis, but are discussed

separately.

3.2.2.1 Saturated Hydrocarbons

Concentrations of total PHC in surficial sediments from outermost Cook Inlet and Shelikof Strait

ranged from 6.8 to 71.0 pg/g throughout the study area. The total PHC concentrations were

generally at low to moderate levels with average total PHC concentration across the four zones of

28.5 pg/g in the sediments collected in 1997, with a coefficient of variation (CV) of 18 percent

(Table 3-6). The total PHC concentrations for surface sediment averaged across the five zones

collected in 1998 was 28.8 pg/g, with a CV of 19 percent (Table 3-6). The grand average total

PHC for the study area over the entire sampling period was 29.4 +, 5.41 (Table 3-6). Comparison

of both sample periods reveals little variation across both years, with the CV for zones ranging

from 0.2 percent to 7.4 percent. A more detailed comparison of the analysis of variance among

measured and calculated parameters between years is presented in Section 3.5. Among samples

in each zone, the average total PHC concentration was highest in zones 3 and 4 (34.8 &g and

35.8 pg/g, respectively), with somewhat lower average concentrations in zones 0, 1, and 2 (25.5

pg/g ,24.9 yg/g, and 26.0 pg/g, respectively).

In general, the surficial sediments collected in zones 1,2,3, and 4 (GCYFID chromatograms in

Figures 3-24 through 3-27) exhibit a mixture of terrestrial and marine hydrocarbons dominated

by an assemblage of plant wax alkanes in the C27 through C33 carbon range. This is further

demonstrated by Carbon Preference Index (CPI - calculated as:

C26 + C28 + C30

C27 + C29 + C31)

values, on average, ranging from 2.3 to 3.6, and is characteristic of sediments influenced by

terrigenous plant inputs (Wakeham and Carpenter, 1976; Boehm, 1984). Traces of lower

molecular weight alkanes (LALK), indicative of petroleum, are visible in the chromatograms

only as a minor component relative to the plant wax alkanes. The GC/FID chromatograms from

three stations in zone 0 (Figures 3-19 through 3-23) show a similar distribution of terrestrial

hydrocarbons (an average CPI of 3.2 and 5.4 for 1997 and 1998, respectively), but show even

less evidence of lower molecular weight petroleum hydrocarbons.

The sediment for the two embayment stations adjoining zone 2, but within Kodiak Island sills,

contained substantially higher total PHC concentrations of SHC’s, with a mean total PHC of 71.3

+ 17.5 pg/g and 47.7 f 10.7 pg/g for stations Z2F3 and Z2F4, respectively. The composition of

SHCs however, was similar to the other zone 2 sediments although primarily influenced by

terrigenous plants. Each chromatogram (not shown) was dominated by the plant wax alkanes

along with a large corresponding UCM, and revealed low abundances of the nC9 through nC20

alkanes (LALK) relative to the entire suite of alkanes (between 18 and 23 percent), compared

with a mean abundance of 42 percent for the LALK in the zone 2 sediments.

3-11
3.2.2.2 Polycyclic Aromatic Hydrocarbons

In general, low to moderate levels of PAH were found across the study area. The-average total

PAH concentration in sediment for all four zones collected in 1997 was 0.457 vg/g (CV of 32

percent) and 0.432 pg/g (CV of 38 percent) for the five zones collected in 1998. The grand

average for total PAH in the entire study region across both years was 0.459 f 0.151 &g, with

minimal variation between the sampling period within zones (CV of 2.2 to 21 percent). In

outermost Cook Inlet (zone 0), the average total PAH concentration was 0.235 l.q$g, while the

average total PAH concentrations in Shelikof Strait (zones 1,2, 3, and 4) gradually increased

with distance from Cook Inlet (0.376 CL&/g, 0.534 ug/g, 0.548 pg/g, and 0.604 @g, respectively).

These levels of PAH are consistent with previously reported values for the Cook InletYShelikof

Strait region, as well as other Alaskan coastal sediments (e.g., Prince William Sound and the

Beaufort Sea - Table 3-9).

The PAH distributions for most surficial sediments show that the PAH are primarily of a

combined fossil fuel origin (i.e., petroleum and coal), with a somewhat variable biogenic

component (perylene) and lesser contribution of pyrogenic or combustion-related compounds

(4-, 5-, and 6-ring PAH). Perylene concentrations were relatively high in most surficial

sediments, but varied widely from zone to zone and among samples within a zone. Perylene is a

naturally occurring PAH formed during early diagenesis in sediments from biological source

precursors (Wakeham and Farrington, 1980; Wakeham, et al., 1980). It may also be found in

crude oil at very trace concentrations. In past studies, perylene was found at comparable

concentrations in the sediments of Cook Inlet and Alaska nearshore sediments (Boehm et al.,

1998).

The variations in PAH composition in the surface sediments of zone 0 are shown in PAH

distribution plots in Figures 3-19 through 3-23. In Kachemak Bay (Station ZOFl, Figure 3-19)

the PAH assemblage is dominated by perylene, with a full suite of 2-, 3-, and 4-ring petroleum

PAH, and lower levels of combustion PAIL In contrast, in the center of Cook Inlet (Station

ZOF4, Figures 3-20 and 3-21) only traces of perylene are found, and the PAH distribution is

primarily comprised of moderately weathered petroleum PAH (i.e., naphthalenes generally c

phenanthrenes), with trace combustion PAH. In Kamishak Bay (Station ZOF5, Figures 3-22 and

3-23), the PAH concentration is somewhat lower and is characterized by a full suite of petrogenic

PAH, a significant perylene component, and only trace combustion PAH.

The PAH distributions in zones 1,2,3, and 4 are generally similar throughout, and are

characterized by the presence of a full suite of relatively “unweathered” petroleum PAH (i.e.,

naphthalenes 2 phenanthrenes). Perylene is present at somewhat variable concentrations, and

does not appear to correlate with the total PAH concentrations. Trace levels of 4-, 5-, and 6-ring

combustion PAH are present, but are generally only a minor component of the overall PAH

composition.

The total PAH concentrations for sediments located within the Kodiak Island embayment area

were consistent and within the range of all zones (Table 3-8), with a mean of 0.530 f 0.043 l&g

and 0.415 -c 0.033 pg/g for the stations Z2F3 and Z2F4, respectively. The composition of PAH

were similar to the other Shelikof Strait sediments, containing a mixture of the relatively

“unweathered” petroleum PAH combined with a minor combustion PAH component similar to

that observed for the adjacent zone 2 sediments, as well as, sediments from zones 1,3, and 4

(Figures 3-24 through 3-27).

3-12
3.2.2.3 Steranes and Triterpanes

In general, the S/T appear somewhat different in zone 0 than in zones 1,2,3, and 4, where the

S/T results were generally similar. Figures 3-19 through 3-27 show the distribution of triterpanes

for surficial sediments in all 5 zones of the study area. The average total S/T concentrations for

zones 1,2,3, and 4 range from 0.016 to 0.029 ug/g (CV of 31 to 71 percent) for surface sediment

collected in 1997, while the range of average S/T concentrations for the sediment collected in

1998 was 0.016 to 0.030 pg/g (CV of 4 to 81 percent). The grand average for total S/T for all

zones across both years was 0.024 + 0.005 pg/g, with minimal year-to-year variation within

zones (CV of 0 to 23 percent).

Generally, there were low levels of S/T characteristic of petroleum found at all stations in zones

1,2,3, and 4 with C30-hopane (T19) present and often the most abundant compound in the

overall triterpane distribution. Oleanane (T18) was detected in all samples in zones 1,2,3, and

4, indicating the presence of a non-Cook Inlet post-Cretaceous/Tertiary petroleum source (i.e.,

T18 is absent in Cook Inlet crude). In addition, the relative abundance of T22 > T21 and the

presence of the moretanes are indicators of recent organic matter inputs to the surficial

sediments.

The S/T concentrations at station Z2R22 (1997) and Z3Rll (1998) were substantially higher than

all other stations, thus contributing to relatively heightened CVs for these zones (Table 3-6). A

closer evaluation of the triterpane distribution in these samples indicates the presence of a

different petroleum source (or a mixture) than in the other samples and currently suggests that

these stations may be an outlier in the data set for triterpanes (all other organic parameters were

within the range of other samples from the study area).

The S/T analyses from zone 0 (outermost Cook Inlet) stations reveal a slightly different pattern of

triterpanes, particularly in Kachemak Bay (Figure 3-19). The triter-panes from this station show

an abundance of recent biogenic triter-panes and the greater abundance of T22 versus T21 is

similar to that observed for the Homer Spit coal source sample (Figure 3-4). While a

characteristic petroleum triterpane distribution is present, it is only a minor component,

indicating that coal may be the primary source of the S/T. Three other samples taken from the

Kachemak Bay area (ZOF2,ZOF13, and ZOF14) also have similar triterpane distributions,

indicating the influence of a coal source. In general, the remaining stations in zone 0 (Figures 3-

21 through 3-23) have triter-pane patterns more similar to those observed in zones 1,2,3, and 4

(Figures 3-24 through 3-27). However, there appears to be a greater component of coal influence

as indicated by the T22 > T21 abundance. Oleanane was also present in all of the zone 0

samples, indicating a non-Cook Inlet petroleum contribution. At station ZOF6 only trace

oleanane was detected, indicating a different petroleum source (discussed below).

The total S/T concentrations for sediments located within the Kodiak Island embayment area

were similar to those measured in all zones (Table 3-8), with a mean of 0.023 & 0.003 ug/g and

0.020 & 0.005 pg/g for the stations Z2F3 and Z2F4, respectively. The composition of S/T were

similar to the other Shelikof Strait sediments, i.e., dominated by the C30-hopane and containing a

minor presence of oleanane, in addition to having a relative abundance of T22 > T21.

3.2.2.4 Hydrocarbon Sources in Surface Sediments

As mentioned previously, selected diagnostic ratios and parameters were used in the statistical

evaluation and to support the interpretation of the organics data (SHC, PAH, and S/T). The data

3-13
sets were analyzed separately by year due to the additional zone (zone 4) included in the 1998

sampling survey. The initial statistical analysis of the hydrocarbon data focused-on identifying

differences between zones for the selected diagnostic parameters, in order to evaluate potential

source trends i.e., higher concentrations of hydrocarbons closer to Cook Inlet oil and gas

production activities.

The statistical results (Student Newman-Keuls test on non-normalized data) of the organics

diagnostic parameters for the surface sediments collected in 1997 are shown in Table 3-8

(complete details of the statistical results are included in Appendix I Table H-I). Zones were not

significantly different for 8 of the 23 parameters measured. For 11 of the remaining 16

parameters, zone 0 was significantly different from zones 1,2, and 3. The remaining parameters

resulted in some overlap in significant differences between zones. Results for the 1997 surface

sediment data normalized by TOC were not substantially different, with zone 0 again statistically

separate from the other zones, which were overlapped among each other.

The statistical results (Student Newman-Keuls test on non-normalized data) of the organics

diagnostic parameters for the surface sediments collected in 1998 are also shown in Table 3-8.

Two additional parameters were introduced during this sample period, i.e., the presence of oil

degrading bacteria and mean heterotrophic bacterial population (Section 2.2.5.4). All zones were

not significantly different for 18 of the 25 parameters measured. For 2 of the remaining 7

parameters, zone 0 was significantly different from zones 1,2,3 and 4. The remaining

parameters resulted in some overlap in significant differences between zones. Results for the

1998 data normalized by TOC were, once again, not substantially different with zone 0

statistically separate from the other zones, which were themselves overlapped among each other.

Generally, these results show that zone 0 was different from the other zones due to lower

concentrations of the total or summed hydrocarbon parameters (e.g., Total PAH, petrogenic

PAH, isoprenoids, LALK). Zone 0 had significantly higher concentrations of perylene and a

higher pyrogeniclpetrogenic ratio (for the 1997 and 1998 sediments), showing that zone 0 is

more subject to biogenic and combustion inputs than zones 1,2,3, and 4. The

naphthalene/phenanthrene (N/P) ratio in zone 0 was lower in the 1997 sediment analysis,

supporting earlier observations that the PAH in zone 0 appeared more weathered than zones 1,2,

3, and 4. The Carbon Preference Index (CPI) was not significantly different between zones in the

sediment collected in 1997, while in 1998 the zone 0 sediment had a significantly higher CPI,

confirming a consistent influence of terrigenous hydrocarbon input throughout the area,

particularly in zone 0. The key petroleum source parameters (e.g., C2D/C2P, C3D/C3P,

oleanane/hopane, and Ts/Ts+TM, ) were either not different or resulted in overlap between

zones, indicating a common source of petroleum hydrocarbons to the study area. Overall, these

statistical results indicate that zone 0 was generally different from the other zones due to lower

concentrations of organic parameters, and there is no reproducible trend showing higher levels of

organics closer to Cook Inlet oil and gas production activities.

Based on a review of the key diagnostic parameters for organics, an evaluation of the petroleum

hydrocarbon sources in the surface sediments is best described by the double-ratio plot of the

alkyl dibenzothiophenes and alkyl phenanthrenes (C2D/C2P versus C3D/C3P). This double ratio

has been well documented as an accurate source indicator in other studies investigating the

sources of petroleum hydrocarbons in the environment (Brown and Boehm, 1993; Page et al.,

1996; Bence et al, 1997).

3-14
_.

A double-ratio plot of the source samples and all the surface sediment samples collected during

both surveys is shown in Figure 3-28. The plot reveals that North Slope crude oil (i.e., Exxon

Valdez crude) and Point Woronzof effluent have significantly higher ratios than any of the study

samples, effectively eliminating either of these sources as significant contributors to the surface

sediments. Four of the Copper River and both of the Susitna River source samples contained

only trace concentrations of most individual PAH, while the alkyl dibenzothiophenes and

phenanthrenes were not detected. As a result, both of these sources plot at the origin and are

likewise eliminated as a source of petroleum hydrocarbons. One of the Copper River samples,

however, did contain detectable alkyl PAH, and the subsequently calculated ratio did fall near

many of the sediment samples. As stated earlier though, the PAH levels present in this source

are insufficient to be considered as an influential contributor of PAH. Furthermore, the Well

Creek seep oil and the Matanuska and Coyote Lake coals can also be discounted as primary

sources of hydrocarbons based on their positioning within the double-ratio plot (Figure 3-28).

Several of the other source samples, the Homer Harbor sediment, St. Augustine Island sediment,

Alaska Coastal Current sediment, Homer Spit coal, Ninilchik coal, TBPF produced water, Cook

Inlet crude oil, and Swanson River Field oil, all have source ratios within the range observed for

all the surface sediments. The TBPF produced water sample has a similar ratio to the Cook Inlet

crude oil and falls within the ellipse representing 1 standard deviation (SD) around the mean of

the 29 replicate Cook Inlet crude oil analyses. In contrast, nearly all the samples appear in a

cluster above and to the right of the Cook Inlet crude (Figure 3-28), and only 4 of the surface

samples plot within the Cook Inlet crude oil ellipse.

An evaluation of the same source ratios from other studies of offshore sediments and oil seeps to

the east of the study area revealed that the sediments associated with the Katalla and Yakataga

seeps and petroleum-bearing formations have C2D/C2P and C3D/C3P ratios that are similar to

the major cluster of samples from this study (Page, et al. 1995; Page et al., 1996; Bence et al.,

1997). The Katalla production oil has C2D/C2P and C3D/C3P ratio values which are central to

the main cluster of samples, and the same ratio was determined for the deep subtidal

“background” sediments in Prince William Sound (Bence et al., 1997). Results from

“background” subtidal sediments off the Alaska Peninsula to the south of the study area have

also yielded similar C2D/C2P and C3D/C3P ratios (Manen et al., 1993). The Alaska Coastal

Current sediment sample collected east of Cook Inlet in 1998 as part of this study also has

C2D/C2P and C3D/C3P ratios which plot centrally to the main cluster of sediment samples.

These results, coupled with the known sediment transport to the area by the Alaska Coastal

Current (Boehm et al., 1998), demonstrate that petroleum hydrocarbons, likely from the Katalla

and Yakataga region formations, are the primary source of petroleum hydrocarbons in the

outermost Cook Inlet and Shelikof Strait sediments. Others have suggested that coal particles

may also represent a source of hydrocarbons to the Alaska Coastal Current sediments (Short, et

al., 1999, Hostettler, et al., 1999). However, a recent comprehensive study of Alaska Coastal

Current and Prince William Sound sediment sources, concluded that erosional sediments and

glacial flour from tertiary shales, and seep oils to the east (e.g., Katalla and Yakutaga region,

Malspina Glacier), are the primary source of hydrocarbons to the sediment loading of the Alaska

Coastal Current (Boehm, et al, 2001).

When the double-ratio plots of the surface sediments are examined by zone, a pattern of

hydrocarbon sources becomes apparent. In zone 0 the double-ratio plot reveals a greater scatter

of samples. This scatter is likely due to the influence of coal and Homer Harbor source(s)

3-15
mixing with the influx of “background” sediment and seep oil hydrocarbons (Figure 3-29). The

sediments plotting most distant from the Cook Inlet ellipse and proximal to the Homer Harbor

source samples were consistently collected from locations in or near Karnechak Bay (ZOF14,

ZOFl).

In zone 1 there is substantially less scatter of the ratio as it approaches the “background”

sediment value of seep-associated petroleum hydrocarbons with minimal coal source influence

(Figure 3-30). Four of the surface sediment samples from zone 1 occur within the Cook Inlet

crude source ellipse, indicating a possible contribution or mixing from Cook Inlet crude or

related seep oil(s) from Cook Inlet (Iniskin Peninsula). In zones 2 and 3 the sediment samples

generally cluster in the area of the “background” sediments and seep-associated hydrocarbons oil

formation (Figures 3-31 and 3-32). Many of the sediments collected from zone 4 also mirror the

calculated “background” sources, although several samples did fall outside the range of sources

measured as a part of this study (Figure 3-33).

3.2.3 Metals

3.2.3.1 Trace and Major Elements

All surficial sediments were analyzed for total concentrations of Ag, Al, As, Ba, Be, Cd, Cr, Cu,

Fe, Hg, Mn, Ni, Pb, Sb, Se, Sn, Tl, V, and Zn (Table 3-10 and Appendix C). The 1997 samples

also were analyzed for the major elements Ca, K, and Mg for use as possible indicators of

differences in composition of material from the Susitna River versus the Copper River. The

resulting data show that concentrations of Ag, Al, Be, Cd, Cr, Fe, Mir, Ni, Pb, Sn, Tl, and V in

surficial sediments from outermost Cook Inlet and the Shelikof Strait are similar to or less than

average continental crust, whereas concentrations of As, Ba, Cd, Hg, Sb, Se, V, and Zn are

enriched by a factor of 1.4 to 5 (Table 3-l 1). When average metal values for these Alaskan

sediments are compared with data for sediment from the Susitna and Copper Rivers (Table 3-l l),

only levels of Fe, Hg, Mn, Pb, Tl, V, and Zn are 16 to 50 percent higher (Table 3-l 1). Further

comparison of average metal concentrations for the surficial sediments from this study (Table 3-

11) with available values for sedimentary, volcanic, and plutonic rocks from Alaska (Table 3-3)

and river suspended solids (Table 3-l), show that average levels for all metals in these sediments

are within the range of values in potential source rocks and river suspended solids.

Average metal concentrations for surficial sediments from zones 0, 1,2,3, and 4 (Table 3-10)

are relatively uniform throughout this region which extends over approximately 350 km. For

example, the CV [CV = (standard deviation/mean) x 100 percent] for all metals in all surficial

sediments (except zone AC) range from about 9 to 35 percent. As shown in Table 3-12,14 of

the 22 metals have a CV ~20 percent. Only Ag, Hg, and Se have a CV of >30 percent. The high

CV for Hg results from high concentrations (%I. 1 pg Hg/g) in sediments from Homer Harbor.

To make inter-comparisons among sediment samples, it is often necessary to normalize metal

values to either Al or Fe, thereby removing variations in metal concentrations that result from

changes in gram size and/or mineralogy. Aluminum and Fe exhibit a strong linear relationship

when they are introduced by a common suite of aluminosilicate and/or Fe-bearing minerals to a

sedimentary basin. This trend results from progressive dilution of Al- and Fe-rich minerals with

quartz sand and/or shell carbonates that are depleted in these two elements. In addition, trace

metals tend to be enriched in aluminosilicate minerals and depleted in quartz sand and shell

carbonates, thereby showing a positive relationship with Al and/or Fe.

3-16
In contrast with typical marine sediments, no distinct relationship between Fe and Al (Figure 3-

34) is observed for surficial sediments from zones 0, 1,2,3, and 4. This lack of a simple trend

between Fe and Al suggests that more than one source (or suite) of Al- and Fe-bearing minerals

is responsible for observed concentrations of these elements. For example, abundant magnetite

(Fe-rich, Al-poor) was observed in some sediment samples. Furthermore, no strong positive

linear trends between trace metals and Al were obtained for these surficial sediments, suggesting

that Al is not a dependent variable for most trace metals. Metal/Fe plots for the surficial

sediments from zones 0, 1,2,3, and 4 showed good linear relationships (r > 0.70) for Cr, Cu, Ni,

Pb, Sb, V, and Zn (Figures 3-34,3-35, and 3-36), suggesting that Fe-bearing phase(s) are the

more important carriers of these trace metals to the sediments. Less significant trends (r < 0.70)

between Fe and the trace metals Ag, As, Ba, Be, Cd, Hg, Mn, Se, Sn, and Tl (Figures 3-34 and 3-

35) were observed, indicating that a more complex or varied suite of mineral phases carry these

metals to the study area.

Twenty-five samples of surficial sediment collected during 1997 were resampled in 1998 to

assess interannual variability. Metal concentrations in the 1997 samples agreed within +lO

percent with results from 1998 for Al, Ba, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl, and Zn.

For As, Sn, and TOC, agreement between years was within GO%. Only concentrations of Ag

and Se varied by >20 percent, at 39 percent and 23 percent, respectively.

- -

Statistical analysis (1997 Student Newman-Keuls test) of the metal/Fe ratios by zone for the

surficial sediments showed that the metals divided into three separate groups (Table 3-13). In the

first group, values for Ag/Fe, Mn/Fe, Ni/Fe, and Tl/Fe show no significant differences at = =

0.05 among the four zones in outermost Cook Inlet and the Shelikof Strait. Within the second

group, comprising As, Ba, Cr, Cu, Hg, Pb, Sb, Sn, V, and Zn normalized to Fe, two different

subgroupings (A and B) could be identified. For example, Pb/Fe and &/Fe ratios in zone 0 are

statistically different from zones 1,2, and 3, whereas Cr/Fe and Cu./Fe ratios in zone 2 differ

from zone 1, but are similar to zones 0 and 3 (Table 3-13). Beryllium, Cd, and Se normalized to

Fe make up the third group with three different groupings (A, B, and C). In this group, the

metal/Fe ratio in one zone is statistically different from two other zones (Table 3-13). For

example, the Be/Fe ratio in zone 0 is statistically different at = = 0.05 from zone 2 and 3 and

zone 2 differs from zone 3. The statistical results by zone show that the metal/Fe ratios in zones

0, 1,2, and 3 are all similar with the exception of Cd and Se in zone 0 and Be in zone 2.

Statistical analysis (1997 and 1998 Combined Student Newman-Keuls test) of the metal/Fe ratios

by zone for the surficial sediment data for 13 of the 17 metals (Ag, As, Ba, Be, Cr, Cu, Hg, Pb,

Ni, Sb, Se, Tl, and V) showed no significant differences at = = 0.05 among the four zones in

outermost Cook Inlet and the Shelikof Strait (Table 3-13). For Cd, Mn, Sn, and Zn ratioed to Fe,

two different sub-groupings (A and B) could be identified. In each case, higher metals values are

observed for zone 3 relative to zone 1, possibly the result of sediment with a greater surface area

in zone 3. However, in the cases of Cd, Sn, and Zn, standard deviations (SD) for average metal

concentrations in a given zone are often quite low (CV c 2% or absolute value of SD co.05

ug/g). Thus, relatively small absolute differences between metal values from zone to zone test as

being statistically significant. For Mn, variation may be related to differences in the degree of

Mn remobilization, as previously discussed.

Statistical results for metal/Fe ratios for 1997 versus 1998 show no annual differences (at = =

0.05) for 15 of the 17 metals (Appendix I Table I-29). In the case of Sn, the absolute difference

3-17
in mean concentrations for 1997 (1.67 + 0.07 pg/g) versus 1998 (1.46 f 0.07 pgg) was small and

is not considered to be related to any defensible shifts during the sampling periods. A similar,

small absolute difference was observed in Ag levels for 1997 (0.08 + 0.01 pg/g) versus 1998

(0.05 + 0.01 pg/g). Much of this statistical result for Ag results from an interannual difference of

0.03 pg/g for zones 0 and 3. The overall mean (a standard deviation) for Ag in all surface

samples of 0.07 + 0.02 supports no easily detectable differences in Ag levels.

3.2.3.2 Acid-Volatile Sulfide/Simultaneously Extracted Metals

Concentrations of AVS and SEM were determined for 29 samples of surficial sediment (0 to

2cm) collected during 1997. Results for AVS range from co.005 pmoles/g (the detection limit)

at four stations (ZOF6,ZOF8 [ 1 of 3 field replicates], ZlFl, and ZlR8) to 18.6 pmoles/g at

station ZOF14 (Figure 3-37). This maximum value is much higher than the next closest value of

3.1 pmoles/g (at both ZOFl and Z3R20). Only six values in the data set are >l pmole/g, the

level considered to be the threshold of applicability for the SEM-AVS technique (DiToro et al.,

1990). The overall mean value of 1.2 f 3.6 pmoles/g decreases to 0.6 st 0.8 pmole/g when the

maximum value is excluded. The six samples with >l pmole AVS/g are scattered across all

these zones with no simple trend except that the two highest values are for zone 0.

Analyses for SEM included the following metals: Cd, Cu, Ni, Pb, and Zn. Of the 5 SEM metals,

Zn is the most abundant in all cases, comprising 50 percent or more of the total SEM (Figure 3-

38 and Appendix D). Copper and Ni are the second and third most abundant metals in the SEM

summation, with typical contributions of about 10 to 35 percent of the total SEM. In contrast, Pb

and Cd account for (7 percent and cl percent, respectively, of the total SEM in all samples.

The underlying principle for this technique is to use the value for SEM minus AVS as an

interpretative tool. For these samples, values of (SEM-AVS) range from -17.5 to +2.3 pmoles/g

(Figure 3-37 and Appendix D). In the total data set, six values are negative and the remainder are

positive. In those instances where the value for (SEM-AVS) is negative, the amount of sulfide

exceeds the total amount of metal and thus these metals should all be bound in the sediments as a

sulfide phase. When the (SEM-AVS) value is positive, acid-leachable metals are present in the

sediment in other than a sulfide phase. The implications of these results are discussed in Section

4.4.

The data for SEM was used to determine the percent of total metal that is released into 2N HCl

with the following overall mean values: Cd, 88%; Cu, 40%; Ni, 20%; Pb, 44%; and Zn, 41%

(Table 3b). Cadmium is clearly the most labile of the five metals and Ni is the least labile. The

variability in the percent of total metal leached was ~40% (as a coeffkient of variance) for each

metal except Zn (Table 3b). A complementary study by Gray (1999) showed that ~3% of the

total metal was leached at pH levels of 4 (i.e., O.OOOlN HCl).

3.2.4 P450 Reporter Gene System Response in Extracts of Sediment

Twenty-seven sediment samples were analyzed by the RGS assay in 1997 and another twentyseven were analyzed in 1998. The RGS B[a]PEq ranged from 0.8 to 6.3 pg/g dry weight (a mean

of 3.2 with a CV of 54 percent) in 1997. The RGS B[a]PEq ranged from 0.6 to 3.8 pg/g dry

weight (a mean of 2.2 with a CV of 38 percent) for 1998 samples.

3-18
Values in the range of 1 to 10 ug/g dry weight are generally considered to be at background

levels in embayment areas and 1 to 5 ug/g dry weight are considered to be at background levels

in coastal marine sediments. Only two samples collected in 1997,ZlR13 and Z3R14, were

slightly above the coastal marine background with concentrations of 6.3 and 6.2 ug/g dry weight

B[a]PEq, respectively. These results are consistent with the concentrations of the PAH measured

in the surface sediment, i.e., generally low concentrations of PAH, as well as the results from the

6hr. vs. 16hr which indicate that the RGS response was due to PAH’s rather than chlorinated

hydrocarbons (dioxins/furans, coplanar PCB’s).

Examination of the trends in the mean values for the zones, including the standard deviations for

each set of data indicated that sediments from zone 0 had the lowest level of inducing

compounds in comparison to the other zones. Also, the mean values for all zones were somewhat

lower in 1998 than in 1997. The complete results of the P450 RGS sediment tests are included in

Appendix E.

3.2.5 Sediment Toxicity Tests

Amphipod toxicity tests were conducted using marine amphipods and surface sediments

collected during both sample cruises. The test organism for the 1997 sediments was

Eohaustorius estuarius, while the test organism for the 1998 sediments was Ampelisca abdita.

The percent survival of the amphipods exposed to sediment collected during the 1997 cruise is

presented in Table 3-14. Statistical analysis (using ToxCalc ~5.0 software) of the results from

the 1997 sediment bioassay conducted by PERL demonstrated that 15 of the 20 sediment samples

resulted in survival less than the control at ~~0.05. However, most laboratories conducting

sediment bioassays only indicate toxicity if the following criteria are met:

. There is a significant difference between the laboratory control and the test using a t- test,

as was done here.

. Mean organism response in the bioassay test was less than 80 percent of the laboratory

control value.

Application of the second criterion eliminates the problem of designation of toxicity based only

on comparison to controls with low replicate variance.

The 80 percent of control criterion was established by statistical analysis of many amphipod data

sets by other investigators (e.g., Thursby and Schlekat, 1993). The two criterion approach is

currently being used by the EPA’s EMAP (Schlimmel et al., 1994), by California’s State Bay

Protection and Toxic Cleanup Program (BPTCP, 1993) and by the Regional Monitoring Program

for Trace Substances in the San Francisco Estuary (SFBRMP, 1995).

Applying these criteria to the bioassay results demonstrates that only 7 of the 20 sample sites had

sediments with significantly lower survival than the controls: 2 of 8 from zone 0; 1 of 4 from

zone 2; and 4 of 4 from zone 3. None of the 4 sites in zone 1 demonstrated significantly lower

survival than the controls. A detailed analysis of the data for these toxicity tests (discussed in

Sections 3.6 and 4.4) indicates that the significantly lower survival observed in these sediments

was correlated with sediment grain size and therefore probably not due to the measured

concentrations of metals or organics.

R8thw D Little

3-l 9
Results for the toxicity tests conducted on the 7 sediment sites collected in 1998 are presented in

Table 3-15. Statistical analysis of these results from sediment bioassay demonstrated that 5 of

the 7 sediment samples resulted in survival less than the ‘home’ control at ~~0.05. However, not

one of the amphipod test exposures to surface sediment had less than 90 percent survival. In

addition, none of the exposure groups were significantly less than the Holgate Glacier

“reference” sediment, which averaged 91 percent survival. (This reference location was selected

since it represented fine grained and glacial sediment and was up current from Cook Inlet and

inshore of the influence of the Gulf of Alaska). These results support the theory that the toxicity

observed in the 1997 and 1998 sediments was not due to the measured concentrations of metals

or organics, but likely the result of grain size effects.

3.2.6 Enumeration of Heterotrophs and Hydrocarbon Degrading Microorganisms

Heterotrophic bacteria ranged from approximately 8 x lo3 to 8 x lo6 organisms per gram of dry

weight sediment. Most samples contained about lo4 to 10’ organisms per gram of dry weight

sediment. Hydrocarbon degrader populations were very low for all samples - 30 sample results

were zero and the 10 remaining results ranged from 26-300 organisms per gram of dry weight

sediment These results indicate that the petroleum hydrocarbons present in the sediment are not

readily bioavailable.

Complete information on the sample handling and the mean MPN populations are found in

Appendix H Table H-l.

3.2.7 Sediment Profile Imaging Camera

In this section, a summary of the SPI camera analyses is presented. A complete set of all the

summary data measured from each image is included in the SPI report, which was issued by

MMS as a separate stand-alone document in 1998 (MMS, 1998).

Parameters such as boundary roughness and mud clast data (number, size) provide supplemental

information pertaining to the physical regime and bottom sediment transport activity at a site.

Even though mud clasts are definitive characteristics whose presence can indicate physical

disturbance of some form, the mud clasts noted in the images from this survey were either

biogenic in origin or artifacts due to sampling (mud clumps clinging to the frame base) and not

indicative of physical disturbance or sediment transport activities. Therefore, mud clast data

were not used as individual parameters for interpretation. Rather, they were used to enhance the

overall comprehension of characteristics at the various areas sampled in conjunction with other

SPI parameters such as RPD and OSI.

3.2.7.1 Grain Size

The sediments throughout the entire area surveyed were primarily fine-grained, with very few

occurrences of any substantial amount of sand-sized particles except at 5 of the 57 stations

sampled (see Appendix Figure Al). For the majority of stations, the sediment grain-size major

mode was 24 @ (4 4 is an upper particle size limit of 0.0625 mm, or coarse silt). Appendix

Figure Al shows the spatial distribution of sediment grain-size major mode and bottom kinetic

regimes at all stations sampled. Most of the images from zone 1 and all the images from zones 2

and 3 in the Shelikof Strait displayed a grain-size major mode of silt-clay with little to no fine

sand as part of the grain-size range; Appendix Figure A2 shows a typical profile image from the

3-20
area. These well-sorted sediments are most likely derived from glacial till and are indicative of

low-energy, depositional environments.

At the northern end of the Shelikof Strait and moving into outermost Cook Inlet, evidence of

fine- to medium-sand surface layers appeared at 5 of the stations (Stations 1,3,5, and 20 in zone

1; Station F4 in zone 0); medium sand was also the grain-size major mode at 1 station in

Kachemak Bay (Station 2, zone 0; Appendix Figure A3). The cluster of these 5 stations in zones

0 and 1 represented a localized area at depths ranging from approximately 150 to 175 m that was

influenced by strong bottom transport and displayed coarser-grained sediment. Station 2 (zone 0)

presented a transitional facies of a silt-clay bottom with a 2- to 3-cm layer of fine sand at the

surface and a hint of bedforms occurring as the result of bottom currents (Appendix Figure A4).

The stations surrounding Station 2 with sandy bottoms (Appendix Figure Al) ranged from those

with a level sediment-water interface and a grain-size major mode of medium sand (Appendix

Figure A5) to stations with allochthonous surface fine-sand layers that showed evidence of active

transport (Appendix Figure A6).

Set against a background that is predominantly fine-grained glacial till, the source of sand in this

localized region was not readily apparent; however, the presence of these coarser sediments did

not appear to be related to water depths (Appendix Figure A7).

3.2.7.2 Surface Boundary Roughness

Surface boundary roughness ranged from 0.26 to 4.81 cm, principally due to fecal mounds or

burrow openings caused by infaunal activities. The large roughness features at the high end of

the range were all macro- or megafaunal burrow structures (Appendix Figure A8). Because most

of the area sampled was represented by a low-energy, depositional environment, the surface

boundary roughness elements were primarily of biogenic origin and not indicative of active

transport regimes. The locations that appeared to have active transport had surface boundary

roughness values ranging between 0.26 and 2.12 cm.

3.2.7.3 Prism Penetration Depth

With sediment grain-size fairly uniform across the entire study area, the variation in prism

penetration was a good indicator of relative sediment shear strength as a function of biological

mixing depth. The average prism penetration depth at the fine-grained stations (sediment grainsize major mode 24 a) in the study area ranged from 3.75 to 20.69 cm; the spatial distribution of

mean penetration depth at all stations sampled is shown in Appendix Figure A9. Sediments

appeared to be more consolidated (lower penetration) at those stations in outermost Cook Inlet

and the northern end of the Shelikof Strait; while this was due primarily to a shift in sediment

grain-size major mode to a coarser fraction (very fine to medium sand), there were 5 stations

(Stations 7, 8, 15, and F2, zone 1; Station F5, zone 0) in this elliptical region outlined in

Appendix Figure A9 that were fine-grained.

The typical variation in sediment water content and shear strength caused by differences in

bioturbation intensity at stations with similar gram-size distributions is dramatically illustrated by

the two example images in Appendix Figure AlO. Fine-grained sediments can be substantially

dilated through the activity of deep bioturbating infauna; for example, Station 15 in zone 3

(Appendix Figure Al 1) shows a dramatic difference in geotechnical properties compared to the

sediments shown in Appendix Figures 6 and 8, because of the burrowing activity of head-down,

deposit-feeding infauna. Low-shear-strength sediments are susceptible to erosion, and the high

3-21
frequency of stations with penetration depths in excess of 14 to 15 cm is further evidence of the

low-energy, depositional nature of most of this site.

3.2.7.4 Apparent Redox Potential Discontinuity Depth

The distribution of mean apparent Redox Potential Discontinuity depths is shown in Appendix

Figure AU; depths from individual image measurements ranged from 0.57 to 8.32 cm. The

greatest depths were found in the southern end of the Shelikof Strait. The variation in Redox

Potential Discontinuity depth was largely a function of the number, size, and type of infauna

present at a particular location; apparent Redox Potential Discontinuity depths were not related to

water depth (3 = 0.48). The lowest apparent Redox Potential Discontinuity depths were found at

those stations in the northern end of the Shelikof Strait and in outermost Cook Inlet where the

more consolidated sediments, with lower prism penetration due to lower bioturbation rates, were

found.

There was no evidence of low-oxygen stress in the overlying water or high SOD caused by

excess organic loading at any of the locations sampled. The range of apparent Redox Potential

Discontinuity depths encountered did not display any anomalous patterns or unusual variations

given the sediment type and amount of biological activity in the surveyed areas, indicating

normal sediment with appropriate natural Redox development.

3.2.7.5 lnfaunal Successional Stage

The mapped distribution of infaunal successional stages is shown in Appendix Figure A13.

There was evidence of head-down, deposit-feeding infaunal taxa (mature Stage III communities)

at all locations sampled except for Station F8, zone 0. Only one successful image was obtained

from this station, and while it is possible that deposit-feeding taxa were present at this location in

low densities, the shallow penetration depth (2.2 cm) prevented the detection of any subsurface

feeding voids. This same phenomenon of shallow penetration obscuring the detection of Stage

III communities was observed at the adjacent Station F6, zone 0 (Appendix Figure A14).

Because of their location at the sediment-water interface, Stage I taxa are ideal prey items for

demersal fish and epifaunal macroinvertebrates. Appendix Figure Al5 shows a crab at Station 1

(zone 1) that is most likely foraging on the tubicolous fauna evident at the sediment-water

interface. However, the dominant infaunal community at all of the fine-grained stations were

head-down, deposit-feeding taxa that were reworking the sediment to depths of 10 to 15 cm or

more which is generally consistent with the results of sediment core age dating (Appendix Figure

A16). Almost half the images collected (69 out of 156) showed evidence of secondary

succession (Stage I fauna recolonizing the sediment surface after Stage III communities are

established); Appendix Figure Al7 shows an example of Stage I and III taxa present at the same

location.

One unique faunal component recorded in this survey was at Station 3 in zone 3 at a depth of 279

m. Appendix Figure A18 shows a rare, in situ photograph of an obscure family of sea

cucumbers, the Chirodotidae; the oral ends of the individuals bear a striking resemblance to

coelenterates. Very little is known about the life-history of these elongate, worm-like

holothurians, but the oral ends of individuals can be seen both above the sediment-water

interface and 1 to 5 cm below the sediment surface.

3-22
3.2.7.6 Organism-Sediment Index

The spatial distribution of OS1 values throughout the study area can be seen in Appendix Figure

A19. An OS1 of 6 or less typically indicates that a benthic habitat has experienced physical

disturbances, eutrophication, or excessive bioavailable contamination in the recent past. The

four stations that had median OS1 values I 6 were quiescent locations with limited profile

information due to shallow camera prism penetration caused by coarser sediments or limited

biological reworking. The low OS1 at these four locations were attributed more to physical

factors such as coarse or overconsolidated sediments than to anthropogenic sources of

disturbance. Most OS1 throughout the site were very high, reflecting a largely undisturbed

environment with a mature biological community.

3.2.7.7 Interpretation of Sediment Profile Imaging Results

All the results from the SPI technology survey supported the conclusion that there was a largely

undisturbed, low-energy depositional basin throughout the sampled area of the Shelikof Strait.

Water depths throughout most of zones 1 through 3 ranged between 100 and 350 m, well below

the depth at which storm energy would typically be able to impact the bottom. Only nine stations

sampled at the northern end of the Shelikof Strait (Stations 1,3,5, and 20 in zone 1) and in

outermost Cook Inlet (Stations F2, F4, F6, F8, and F13) were clearly unrepresentative of a

quiescent environment. Station 2 in zone 1 was a transitional zone between the quiescent siltclay facies found at the majority of stations and the few stations that had a surface sand layer

present. Because the sand appeared primarily as a discrete stratum at the sediment surface

(Appendix Figure A20), it most likely represented a quantum input of sand-sized particles at

some point in the recent past; over time, this surface sand layer should get thoroughly mixed in

with the underlying mud by the burrowing and feeding activities of the resident infauna.

Based on the reflectance contrast of the sediment profile, there were no areas obviously suffering

from excess organic carbon loading, and no areas that appeared to have their biological

communities compromised by any form of excess chemical contamination. One of the images at

Station F2 in zone 2 (Appendix Figure A21) shows a localized patch of highly reduced sediment

at depth, but this was more likely due to some form of biogenic decomposition rather than

anthropogenic contamination. The uniform silt-clay sediment grain size, the prism penetration

depths in excess of 12 cm reflecting low-shear strength, dilated sediments, the high OSI, and the

high frequency of mature, Stage IIl infaunal assemblages at most of the stations sampled are all

attributes that would be found in a low-disturbance, depositional regime. From the

characteristics seen in the profile images, we would predict sediment organic carbon

concentrations ranging between 0.5 and 2 percent at the majority of the stations, and annual

depositional rates in the Shelikof Strait basin of between 0.2 and 1.5 cm/year.

All the data from the profile images point to both high sediment quality and bentbic habitat

values at most of the area surveyed throughout the site. From the data available from SPI

technology, there appeared to be no detectable adverse impacts to this area from any of the oil

and gas development activities in the region.

3-23
3.3 Sediment Cores

3.3.1 Geochronology

Sedimentation rates were calculated for 13 cores for which concentrations of organics and/or

metals were determined. Sediment ages were determined using the fission-produced

radionuclide 137Cs (first introduced to Earth by bomb testing during the early 1950s) in tandem

with excess *?Pb (a naturally occurring decay product of 238U; half-life *?Pb = 22.3 y). By using

two different independent radioisotopes, sedimentation rates could be verified by separate

methods. Results for 9 of the 13 cores that could be dated showed good agreement between the

two methods (Table 3-16). The sedimentation rate in the core collected from ZOFl (Homer

Harbor) in 1997 was too fast to obtain a reliable rate over the 34 cm core length and thus a

longer, 2-m gravity core was collected during 1998 with successful dating results. The cores

from ZOF8,ZlF2, and Z2Fl had discordant ages between the two methods; however, a range of

likely sedimentation rates was established using one of the two isotopes.

Results for core Z3F2 (Figure 3-39) show an ideal decay curve (natural logarithm scale) for

excess ‘l?b. The sedimentation rate calculated using the activities of excess *r?b is 0.44 cm&.

A sedimentation rate of 0.45 cm/y calculated from the 137Cs profile is in excellent agreement with

the rate determined from the excess *l“Pb profile. When the 137Cs activities for the core from

Z3F2 are compared with the year determined from excess *l”Pb (Figure 3-39), the highest peak

for 137Cs corresponds well with the 1963 date of maximum 137Cs input to the atmosphere. Thus,

the geochronology results for the core from Z3F2 are considered reliable. Results from the other

cores will be evaluated on a zone-by-zone basis below using the same perspective described here.

Sedimentation rates of about 1.3 to 1.5 cm/y are obtained for the 1998 core from Homer Harbor

(ZOFl) (Figure 3-40). Thus, a record of contaminant inputs can be traced back to at least

1900 in this 2-m core. Sedimentation rates for all three cores from Kamishak Bay (ZOF5,ZOF6,

and ZOF8) are about 0.1 to 0.3 cm/y (Table 3-16 and Figures 341,342, and 343). Two minor

discontinuities (lower activities of 21”Pb than predicted by the overall trend) in the activity profile

for core ZOF5 occur at 2 to 4 cm and 8 to 10 cm; however, they have been included in the overall

calculation of sedimentation rate using excess *?Pb because we did not identify any reason to

exclude them. The resultant sedimentation rate for the core from ZOF5 has a lower correlation

coefficient than the other sites and an associated error as large as f 25%. Results for cores from

sites ZOF6 and ZOF8 are much better (Figures 3-42 and 3-43). The activity of 137Cs decreases to

zero about 1950 in each of the cores from Kamishak Bay based on the excess *?Pb age. Such

concordance verifies the overall reliability of the sedimentation rate for these sites.

Calculated sedimentation rates for cores from zone 1 (ZlFl, ZlF2, and ZlR3B) are all similar at

about 0.2 to 0.3 cm/y (Table 3-16 and Figures 3-44,3-45, and 3-46). The profile for 137Cs in the

core from site ZlFl contains some discontinuities in the upper 5 cm that may be due to postdepositional disturbances and the excess “(‘Pb profiles support some mixing in the upper 2.5 cm

of the core. Using data from below the mixed zone, the sedimentation rates are concordant

(Table 3-16). The excess 21?b profile for the second core from zone 1 (ZlF2, Figure 3-45)

exhibits a large discontinuity at a depth of 10 cm where the activity of the 21?b decreases from

approximately 7.5 dpm/g (In = 2.0 dpm/g on Figure 3-45) to 1 dpm/g (In = 0.0 dprn/g on Figure

3-45). This large change in activity complicates calculation of a sedimentation rate. If we use

the point at which the activity of 137Cs goes to zero (12.5 + 2.5 cm), then the sedimentation rate is

3-24
about 0.27 cm/y. Thus, a general estimate of sedimentation rate can be made at this site. The

.- third core from zone 1 also contains some minor anomalies at -4 and 14 cm (Figure 3-46).

Sedimentation rates calculated using excess 21!Pb and 13’Cs for core Z2F2 (Figure 3-47) agree

well at 0.62 and 0.65 cm/y, respectively, despite evidence for some mixing at the top of the core.

The vertical profile for excess 21!Pb in the core from site Z2R16 shows clear indications of

mixing over the top 10 cm of the sediment column (Figure 348). Excluding the 0 to 10 cm

section, the calculated sedimentation rate is 0.53 cm/y relative to 0.72 cm/y using the full data

set. The 13’Cs profile also does not fit simple interpretation and the sedimentation rate is 0.76

cm/y based on the assumed peak activity at. 24.5 cm. Thus, a sedimentation rate of 0.5 to 0.7

cm/y was similar to that found for site Z2F2 and at least 3 times greater than found in zone 1. In

contrast with results for Z2F2 and Z2R16, the calculated sedimentation rate for the core from site

Z2Fl is 2 times higher at 1.3 cm/y (Table 3-16 and Figure 3-49). The slope of the excess 21!Pb

profile, along with an incomplete 13’Cs profile, supports a high sedimentation rate at site Z2Fl.

Site Z2Fl was located in a depositional basin in zone 2 that may serve as an effective trap for

fine-grained sediments.

Both cores from zone 3 (Z3Fl and Z3F2) had sedimentation rates of 0.60 and 0.44 cm/y,

respectively (Table 3-16 and Figures 3-49 and 3-50). These rates are comparable with two sites

from zone 2, but 2 to 3 times higher than found in zone 1.

The excess 21?b profile for one core collected from zone 4 during 1998 (Figure 3-5 1) may be

interpreted as having 2 different sedimentation rates. Using data from the top 20 cm, the

calculated sedimentation rate is 1 .O cm/y relative to a rate of 0.52 cm/y for the 20 to 43-cm

interval in the core. The 13’Cs profile corroborates this perspective. The peak activity for 13’Cs at

29.5 cm (1963 or 35 y BP) is consistent with 20 years of sedimentation at 1.0 cm/y and 9 cm of

sedimentation at 0.5 cm/y to yield about 38 years.

3.3.2 Physical Measurements

Concentrations of TOC in 14 sediment cores from outermost Cook Inlet (zone 0) and the

Shelikof Strait (zones 1,2,3, and 4) range from 0.21 percent to 1.24 percent (Table 3-17). The

highest TOC values are for cores from sites ZOFl (Homer Harbor-1997,1998) and Z4F4

(southernmost Shelikof Strait), whereas the lowest values for TOC are for cores from sites

ZlR3B, ZOF6, and ZOF8 (Table 3-17 and Appendix A).

In zone 0, levels of TOC in all four cores (ZOFl, ZOF5,ZOF6, and ZOF8) have remained

relatively uniform since the 1940s (Figures 3-52 through 3-56). Data for core ZlFl, with an

average of 0.62a.08 percent TOC, show that inputs of TOC to the sediment column have been

fairly constant since the turn of the century (Figure 3-57). In contrast, TOC values for core ZlF2

are more variable (Figure 3-58) since the 1950s. Prior to the 195Os, TOC concentrations

increased from 0.60 percent at about 13 cm (-1950s) to 1.01 percent at 29 cm.

-

Sediment cores from zone 2 average 0.87ti.11 percent TOC, (Z2Fl,Z2F2, and Z2R16, Figures

3-60,3-61 and 3-62). Values of TOC are relatively uniform in cores Z2Fl and Z2R16 (Figures

3-60 and 3-62), whereas in core Z2F2, TOC levels decrease gradually from 1.14 percent in the

surficial layer to 0.84 percent at 32 cm (Figure 3-61). Average values for TOC in cores Z3Fl and

Z3F2 are comparable at 0.83 percent and 0.81 percent, respectively. However, only values in

3-25
core Z3Fl are uniform throughout the entire sediment column (Figure 3-63). Values for TOC in

core Z3F2 decrease from 0.89 percent between 0 to 2 cm to 0.70 percent at 32 cm (Figure 3-64).

In zone 4, TOC values of 1.08ti.06 percent for core Z4F4 (Figure 3-65) are comparable with

those obtained for Homer Harbor (ZOFl) (Table 3-17).

Sand levels in sediment cores from Homer Harbor (1997-total length 35 cm) and zones 2,3, and

4 average 16 percent. For these sediment cores, the silt+clay content is >90 percent and values

are uniform throughout the length of the core (Figure 3-52 and Figures 3-60 through 3-65).

However, the sand content in the sediment core recovered from Homer Harbor during 1998

averages 13.029.6 percent from 20 to 235 cm (Table 3-17 and Figure 3-53). The grain-size

distribution for the upper 20 cm was not determined. In the remainder of the sediment cores

from zone 0 (ZOF5,ZOF6, and ZOF8) and those from zone 1 (ZlFl, ZlF2, and ZlR3B), the sand

content averages between 17.8 percent and 59.6 percent (Table 3-17). The silt+clay levels in

cores ZOF5,ZOF6, and ZOF8 are fairly uniform, averaging 69.425.7 percent, 49.56.9 percent

and 46.6k4.2 percent, respectively (Figures 3-54,3-55, and 3-56). Values for silt+clay in core

ZlFl vary between 50 percent and 81 percent in the upper 14 cm, but are relatively uniform over

the remaining 10 cm of the core, ranging between 67.1 percent and 71.9 percent (Figure 3-57).

Silt+clay concentrations in the sediment core recovered from ZlF2 are fairly uniform throughout

the core, with values ranging between 71 percent and 91 percent (Figure 3-58).

3.3.3 Organics

Sediment cores for organics analysis were collected from 11 of the fixed (non-random) stations

and from 1 of the random stations in the study region (5 cores from zone 0,2 cores each from

zones 1 and 3,3 from zone 2, and 1 from zone 4). The sediment cores ranged from 18 to 235 cm

in length (depth of the core). Approximately 9 to 12 separate 2-cm sediment intervals were

subsampled within a core section and analyzed for the same suite of organic target analytes as the

surface sediments (Section 2.2.2). Finer resolution of the core at station Z2R16 was desired,

therefore this core was subsectioned at separate l-cm intervals over the first 15 cm of the core.

Approximate sedimentation rates from an earlier core collected at station ZOFl indicated that

subsamples needed to be much larger than 2-cm intervals. A 230 cm core from ZOFl was

obtained during the 1998 sampling survey and was subsectioned between intervals of 5 cm and

35 cm.

The results of the sediment core analyses are summarized in Table 3-18 and detailed results

including individual analyte measurements are included in Appendix B. The average

concentrations of the three key total organic parameters measured (TPHC, total PAH, and total

S/T) are comparable to the values observed in the surface sediments from the 5 zones in the study

region (Tables 3-6 and 3-18). Core profiles for selected organic diagnostic parameters (Section

3.2.2) and TOC are shown for all 13 of the sediment cores in Figures 3-66 through 3-78. The

selected diagnostic parameters were chosen based on their capacity to show the overall trends in

total concentration, composition, and source of hydrocarbons.

In general, the core profiles do not show any clear trends that would indicate increases in the

overall petroleum hydrocarbon concentrations over time. Geochronology of the cores has

resulted in seven cores of sufficient depth to be dated to 1920 or earlier and four additional cores

that can be dated to 1950 or earlier. The established dates for these cores provide sufficient data

3-26
to evaluate the potential impact of Cook Inlet petroleum exploration and production activities,

and is evaluated statistically in Section 3.35.

The core profiles of organics from zone 0 (Figures 3-66 through 3-70) do not reveal any patterns

of analytes that are consistent between parameters. However, there are several slight patterns or

anomalies which merit discussion. In the ZOFl core (Kachemak Bay) collected in 1997 the CPI

increases by a factor of 4 at the 2 to 4 cm depth interval (Figure 3-66). This anomalous increase

in CPI is likely associated with particles of plant material (possibly from the wood chip

processing operation on Homer Spit) entrained in the sediment. The deeper core from station

ZOFl (1998) does contain a trend of increasing total hydrocarbons over the past decade; however,

the CPI is within the range of terrestrial plant influence and the corresponding PAH profile

during that time frame is decreasing (Figure 3-67). The core profiles of ZOF5 (Kamishak Bay),

ZOF6 (near Oil Bay), and ZOF8 show a recent decrease in the combustion/petroleum PAH ratio

(0 to 5 cm depth - -1970 to present), suggesting a possible shift in PAH composition (Figures 3-

68 and 3-70). However, the total PAH decreases slightly in each core at the same depth interval,

indicating that the decrease in the combustion/petroleum ratio is due to lower combustion PAH

input.

A slight increase in the C2DK2P source ratio is also apparent in the ZOF6 core at the 0 to 6 cm

depth (Figure 3-69). The C2DK2P ratio for the remainder of the core is considerably lower than

other sediments from the study. The Well Creek seep oil sample analyzed as part of this study

had a C2DK2P value of 0.046, which is substantially lower than the value at depth in the ZOF6

core (0.082). This could indicate a mixture of “background” and Well Creek sources, with a

greater Well Creek component in the past. In a study of Southern Alaska seeps, Page et al. (in

press) reported a C2DE2P ratio for an Oil Bay seep oil of 0.071. This value is close to the ratio

at depth in the ZOF6 core (0.082), further indicating that the inputs of Oil Bay seep oil are an

important local source of petroleum hydrocarbons in this area. There is also an apparent rise in

the C2DK2P ratio in the ZOF8 core (Figure 3-70) and the ZOF5 core (Figure 3-68), although at

depth the ratios are higher than ZOF6 (-0.10) and increase to a value of -0.20. The rise in the

C2DK2P ratio at the surface of these cores may indicate a greater contribution from

“background” petroleum sources more recently.

The core profiles for the six stations in zones 1,2,3, and 4 are remarkably similar (Figures 3-71

through 3-78) with some variability in parameters. The total PAH values exhibit minimal

variation, with some cores showing a slight decrease in total PAH over time to the present-day

sediment (e.g., total PAH at ZlFl increases as the core date approaches -1920). The source

parameter C2D/C2P ratio is very consistent with depth in all six cores, indicating a continuing

and unchanging source of petroleum hydrocarbons from the early 1900s to the present. This is

further supported by the Ts/Ts+Tm maturity ratio which is similarly constant throughout the core

profiles. Overall, evaluation of the core profiles does not reveal any substantial petroleum

hydrocarbon trend (either increase or decrease) which can be attributed to the onset of petroleum

exploration and production activities (circa 1963) in Cook Inlet.

3.3.4 Trace and Major Metals

Sediment cores, ranging in length from 15 to 235 cm, were collected for metal analysis from 14

sites in the study area. Two sediment cores were obtained from Homer Harbor in zone 0 (Fl), a

35-cm core in 1997 and a 235-cm core in 1998. Three additional cores were collected from zone

3-27
0 at sites F5, F6, and F8. In the Shelikof Strait, the following samples were collected: 3 cores

from zone 1 (Fl, F2, and R3B) and zone 2 (Fl, F2, and R16), 2 cores from zone-3 (Fl and F2),

and 1 core from zone 4 (F4). Approximately 5 to 12 separate l- or 2-cm sediment intervals were

subsampled from each core and analyzed for the same suite of metals as the surface samples

(Table 3-19, Appendix C).

Average metal concentrations for Al, Ag, As, Ba, Be, Cd, Mn, Pb, Sb, Sn, and Tl from each core

site (Table 3-19) are comparable with levels obtained for bottom sediments from the Susitna and

Copper Rivers (Table 3-l). For Cr, Cu, Hg, Ni, Se and V, average concentrations for all

sediment cores, except Homer Harbor (ZOFl) and ZOF4 (Hg only), also are consistent with

results obtained for bottom sediments from the Susitna and Copper Rivers. However, sediments

from Homer Harbor are about 14 to 225 percent higher for these 6 metals relative to values for

bottom sediments from the Susitna and Copper Rivers. Average Zn concentrations for all 14

cores range from 81.2 to 125 pg/g (Table 3-19). These Zn values are consistently higher than the

average Zn level of 75+4 pg/g in bottom sediments from the Susitna and Copper Rivers (Table 3-

1). However, as previously discussed (Section 3.2.3 and Table 3-3), concentrations of all metals

in suspended solids from the Susitna and Copper Rivers are higher than found in sediment cores.

Further consideration of the relative contributions of river-borne sediment from the Susitna River

versus the Copper River is presented in Section 4.1.

Sediment in cores from Homer Harbor (ZOFl) are fine-grained (>85 percent silt + clay) and

organic-rich (-1.1 percent organic C). Besides having the highest sedimentation rate (-1.4

cm/y), sediments from Homer Harbor also contain the highest levels of Fe, Ag, As, Cr, Cu, Hg,

Ni, Sb, and V (Table 3-19). With such a high sedimentation rate, the 235-cm long core from site

ZOFl collected during 1998 (Figure 3-53) records the turn of the twentieth century at - 140 cm.

During this past century, concentrations of trace metals have varied only slightly, with most

metals having a CV for the entire core of ~5 percent, except for Ag and As (-12 percent) and Se

(21 percent).

The other 3 cores collected from zone 0 (F5, F6. and F8) were all from the outer portions of

Kamishak Bay. The average silt+clay content at these 3 sites (69 percent for ZOF5,49 percent

for ZOF6, and 46 percent for ZOF8) is considerably lower than observed for Homer Harbor (87

percent). Likewise, TOC values are lower at 0.44,0.34, and 0.36 percent, respectively.

Concentrations of trace metals for these 3 cores from zone 0 also are lower than in Homer Harbor

(Table 3-19 and Figures 3-54,3-55 and 3-56); however, they are comparable to metal values for

bottom sediments or suspended solids from the Susitna and Copper Rivers. Despite sizeable

differences in gram size among these cores from zone 0 (Table 3-19), metal concentrations

generally varied by ~10 percent. Overall, metal concentrations in sediment from this study do

not show a strong positive relationship with levels of silt+clay as commonly observed in many

other shelf and slope locations. This trend suggests that the mineralogy is similar among

sediments with different grain-size distributions, and thus, only the size of the particles most

likely varies as a function of the degree of powdering by glacial activity.

The sedimentation rate of 0.10 to 0.27 cm/y for cores from zone 0 (P5, F6, and F8) facilitates

tracing the record of metal inputs back to the 1920s (Figure 3-54). Relatively minor shifts

(CVI 10 percent) in metal concentrations occur over this - 70-y time interval. However, As and

Hg levels in the top 2 cm (the 1990s) of the core (from ZOF5), are about 20 and 30 percent

higher, respectively, relative to subsurface sediment, with no significant shifts in levels of Fe, Al,

3-28
and most other metals. In core ZOF8 concentrations of TOC, Ba, Be, Cd, Hg, Sb, and Zn have

decreased by 20 to 30 percent over the past 20 years (top 5cm), yet no changes in the Fe and Al

content of these sediments was observed (Figure 3-56). Similar to core ZOF5, As levels are

about 20 percent higher in the top 2 to 5 cm of core ZOF8 and ZOF6. Concentrations of Fe, Ca,

Cd, Cu, Cr, Mg, Mn, Ni, Sb, V, and Zn (Figure 3-55 and Table 3-19) are - 30 percent lower at 4

to 6 cm in the core from ZOF6 relative to other samples from Kamishak Bay. In sharp contrast,

concentrations of Be, Sn, and Tl are 20 to 25 percent higher in the same layer. These transitions

may be related to input of volcanic material deposited during the rather large time interval of

1947 + 10 years.

Two of the three cores recovered from zone 1 (Fl and F2) have similar metal concentrations

throughout the cores (CVs 10 percent) (Table 3-19) with the exceptions of about 25 percent

higher As and Cd and about 15 percent lower Al in core ZlF2 relative to core ZlFl (Figures 3-

57 and 3-58). These three exceptions match higher TOC levels in core ZlF2 and may be related

to deposition of more As- and Cd-rich (Al-poor) organic matter in these sediments. Core ZlFl

(Figure 3-57) records about 100 years of sediment input with little change in metal levels,

except for slightly higher Cr levels (10 to 20 percent) prior to the 1920s. Higher concentrations

of Fe, Ni, Cr, V, and Zn are observed in core ZlF2 below a depth of about 15 cm, which

corresponds to the 1940s (Figure 3-58). The third core from zone 1 (R3B), has the lowest values

of As, Cr, Cu, Fe, Hg, Mi-r, Ni, Pb, Sb, Sn, Tl, V, Zn, and TOC observed throughout the study

area (Figure 3-59 and Table 3-19). These low levels of trace metals most likely result because

sediment from this core averages 60 percent sand-size particles that include extensive amounts of

volcanic ash.

Sediment cores from zone 2 (Figure 2-l) were collected near the western (Z2Fl) and eastern

(Z2F2) sides of the Shelikof Strait, respectively, whereas core Z2R16 was from a central basin.

The silt+clay content for these cores is uniform at 95 to 99 percent. No differences greater than

ti percent occur for concentrations of Fe and Al (Table 3-19). Trace metal levels also vary by

cl0 percent (CV) among these three sites with the exception of Cd (Table 3-19 and Figures 3-60,

3-61, and 3-62). Cadmium concentrations at Z2F2 vary downcore from 0.14 pg/g in the surficial

2 cm interval to 0.27 pg/g at 19 cm (Figure 3-61). A similar increase downcore also is observed

in core Z2R16, with Cd values increasing from 0.10 pg/g in the top 1 cm to 0.15 ug/g at 5 cm

(Figure 3-62). In contrast, levels of Cd were relatively uniform in core Z2Fl at 0.13+0.01 pg/g

over the entire 33 cm length of the core (Figure 3-60). Overall, in zone 2, no changes in

concentrations of trace metals, with the exception of Cd in Z2F2 and Z2R16, have occurred over

the past 50 years (Figures 3-60,3-61, and 3-62).

Two cores were recovered along a track extending north (Z3F2) to south (Z3Fl) in zone 3

(Figure 2-l). The grain-size distribution (Table 3-19, Figures 3-63 and 3-64), indicates that the

sediments in this region are very fine-grained, containing >98 percent silticlay. Average Al and

Fe for all samples from the two cores vary by ~6 percent, averaging 7.15ti.42 percent and

4.39ti.08 percent, respectively. In addition, average concentrations of Ba, Cd, Cr, Cu, Hg, Ni,

Pb, Sb, Sn, Tl, V, and Zn differ by I 10 percent for these sediment cores and about 10 to 20

percent for Ag, As, Be, Mn, and Se. Relative to the other three zones, maximum concentrations

of Ba, MIn, Sn, Tl, and Zn were found in sediments from zone 3 (Appendix C).

Sedimentation rates in cores from zone 3 were 0.60 cm/y and 0.44 cm/y. These rates indicate

that the history of metal inputs at these sites can be traced to the 1950s in core Z3Fl and the

RwthmDLittle 3-29
1920s in core Z3F2 (Figures 3-63 and 3-64). Thus, metal trends throughout these two cores,

except for Cd, show that inputs to this region have been uniform over the past 70 to 80 years

(Figures 3-63 and 3-64). Cadmium values in Z3F2 increase from 0.14 pg/g in the surficial2 cm

to 0.25 pg/g at 24 cm (Figure 3-64). The depth of peak Cd values is about the 1940s; however,

such peaks may sometimes be explained by biogeochemical processes and may not be timedependent. For example, in core Z3F1, a 50 percent increase in Mn (and As) values occurs in the

top 2 cm of sediment, most likely the result of remobilization as previously shown for Mn in the

Shelikof Strait (Massoth et al., 1979) and other depositional environments (e.g., the Gulf of

Mexico, Trefry and Presley, 1982).

Sediment recovered from zone 4 (Z4F4), has >98 percent silt+clay and an organic carbon content

of 1.08 percent (Figure 3-65), similar to that obtained for sediments collected in Homer Harbor

(Table 3-19). Sediments in core Z4F4 have the highest concentrations of Al, Mn and Pb.

Average concentrations of Al, Ba, Be, Cr, Cu, Fe, Hg, Ni, Pb, Sb, Tl, V and Zn differ by 15

percent and about 10 to 20 percent for Ag, As, Mn, Se, and Sn. Cadmium values vary downcore

and range from 0.12 pg/g to 0.20 pg/g (Pigure 3-65). The upper 2 to 5 cm of sediment show a

40-percent increase in Mn (and As) values, most likely indicative of remobilization, as

previously discussed.

3.3.5 Statistical Results of Core Data

Indices Shifts Associated with the Post-1963 Development Time Period. Trends in metals and

organic indices were analyzed to investigate the hypothesis that there was a shift in these indices

associated with post-1963 oil development. In this analysis, post-1963 core sections were

compared to pre-1963 sections for the 12 cores where appropriate dating and thus sedimentation

rates were available. These cores were taken at the fixed stations ZOFl, ZOF5,ZOF6,ZOF8,

ZlFl, ZlF2,Z2Fl, Z2F2,Z3Fl, Z3P2,Z4F4, and the random station Z2R16.

Small changes in the selected indices can also result from geochemical and biochemical

processes in the sediments as detailed in Sections 3.2 and 3.3. The major finding here is that

there are relatively small variations in the important indices with time or depth within a core and

that the empirical association with the post-1963 oil development accounts for a small percentage

of the total variation within a core. All 23 organic indices that were used to describe the spatial

patterns in the surface sediments were analyzed using a standard randomized block analysis of

variance. The results of this analysis are detailed below.

In Table 3-20, the first column gives the organic index analyzed. The second column gives the

percent of the variation within a core (after the between-core variability has been removed) that

can be attributed to the post-1963 intervention. The third and fifth columns give the mean shift

in the index that is associated with the post-1963 intervention. A negative value indicates the

index is decreasing historically to current time, a positive value indicates the index is increasing

historically to current time. Associated with each of the mean shift columns are their respective

results of the two analysis of variance tests, i.e., for the null hypothesis that the mean shift

associated with the post-1963 development is zero.

In the first analysis (columns three and four in Table 3-20), the cores are considered fixed (i.e.,

non-random samples, and the statistical test is for a mean shift associated with the 1963

intervention within these twelve fixed cores. In the second, and more realistic analysis (columns

3-30
five and six in Table 3-20), the twelve cores are considered as random samples, and the statistical

test is for a mean shift associated with the 1963 intervention for the population of all possible - sediment profiles from the study area. In this second analysis, the variation in the intervention

effect from core to core is modeled as a random effect, contributing to the statistical uncertainty

in estimating the mean intervention effect and thus increasing the P-value. P-value here is

defined as the probability (assuming no 1963 intervention effect) of obtaining a mean shift as

large or larger than the observed mean shift.

The major statistically significant feature in this table is the increase in perylene with depth in the

cores, which is clearly detected in this analysis. For perylene, the higher mean value in pre-1963

core sections is scored as a negative intervention effect. The increase in perylene concentration

with depth in all cores is due to well known biogenic processes of early diagenesis in marine

sediments (Wakeham et al., 1980).

A few of the other organic indices had statistically significant associations with the post-1963

period. The diagnostic PAH source parameters, C2DK2P and C3DK3P exhibited a positive

intervention effect and could suggest a slight shift in petroleum source with depth. A decrease in

the Ts/Ts+Tm ratio with depth could also be indicative of a shift in petroleum source over time,

with the lower TsiT.s+Tm ratios at depth indicating a greater contribution from a less-mature

petroleum source. Several other hydrocarbon parameters also showed significant increases after

1963 (pristane, TPHC, nC27+nC29+nC31, and TOC). However, increases in all of these

parameters can be associated with increases in plant wax or terrigenous hydrocarbon inputs. This

is supported by the result that there are no corresponding post-1963 significant increases in any

of the key petroleum hydrocarbon parameters (e.g., TPAH, petrogenic and pyrogenic PAH, N/P,

etc.). This suggests that the observed post-1963 increases in these parameters may be due to

increased terrigenous hydrocarbon inputs associated with terrestrial development activities (i.e.,

logging). Overall, based on this analysis, no increases in the key petroleum hydrocarbon indices

were observed that are associated with the onset of petroleum exploration and production

activities in 1963.

For post-1963 shifts in metal concentrations, the data were first normalized for iron

concentration, generally removing differences between cores due to sediment properties. Table

3-21 presents the same kind of analysis as was done for the organic indices.

Higher concentrations of Mn (normalized to Fe) in surficial sediment (top 5cm) layers are

commonly observed in marine sediments at outer continental shelf and slope environments

(Trefry and Presley, 1982). Under reducing conditions at depth in the sediment, manganese

oxides dissolve and dissolved Mn2+ ions diffuse upward until they are reoxidized near the

sediment surface. This natural processs leads to the surface sediment enrichment of MWn as seen

most clearly at the following sites from this study: ZOF6,ZlF2,Z2F2,22R16,23Fl, and Z4F4.

Concentrations of Ba (and the Ba/Fe ratio) in sediment cores show relatively uniform values (~10

percent deviation) from 1963 to the present at most sites. At two sites, ZOF8 and Z4F4, Ba levels

were distinctly lower in the surficial layers of the sediment column. No systematic reason can be

given for this trend in this study. However, barium sulfate is produced naturally in the tests of

some decaying organisms (Bishop, 1988), a portion of which is likely to dissolve at the seafloor.

In any case, the observed lower Ba/Fe ratios in surficial sediments at 2 to 3 sites is not likely to

be related to any anthropogenic inputs. Cadmium (and the Cd/Fe ratio) shows a similar and more

3-31
widespread (about 8 cores) trend of lower levels in more recent, surface layers. Cadmium is

known to be released from sediment organic matter during early chemical diagenesis (Niagu and

Sprague, 1987). However, no simple reason explains why this process may be more exaggerated

in recent times (e.g., why more Cd may be released from sediments now than in the past). A

general decrease in the input of Cd to the sediments of the Shelikof Strait is possible; however,

there are no other data to support this explanation.

In addition to more obvious lower levels of Ba and Cd in surficial sediment, decreased

concentrations of Sb, Cu and Tl were observed in surface layers from 1 or more cores, thereby

yielding a statistical trend of lower metaUPe ratios since 1963. In the case of Sb and Tl, the

actual change in concentrations is small (co.05 to 0.2 pg/g) and the generally high analytical

precision for these elements (2 0.01 to 0.04 pg/g) leads to the observation of statistically

significant changes. Overall, no increases in metal concentrations have been observed since

1963 that can be related to the anthropogenic activities.

3.4 Fish Tissue

This section documents the collection and analytical results for the fish sampled during the 1997

and 1998 R/V Alpha HeEix cruises. Time, location, depth, and fish species caught are reported in

their respective cruise reports (Arthur D. Little, 1997a; Arthur D. Little 1998a). Details of the

number collected, physical measurements (sex, length, and weight), composite information, and

the biological results for individual fish are given in Appendix F Tables F-l through F-3.

3.4.1 Organics (PAH)

During the 1997 cruise, fish samples were collected from 3 different stations across 3 zones

(zones 0,2, and 3), and 3 species of fish were collected (Halibut, Arrowtooth Flounder, and

Black Cod). Three stations across 3 different zones were also sampled in 1998 (zones 1,2, and

3), with 6 species collected (Halibut, Arrowtooth Flounder, Black Cod, Aleutian Skate, Longnose

Skate, and Pacific Cod). The catch distribution across the zones, in addition to the total samples

for each year, are presented in Table 3-22. Fish liver samples were prepared from collected

specimens and analyzed for PAH. Livers were analyzed because the highest concentrations of

PAH would accumulate and be detected in this fatty organ if the fish were exposed to petroleum

contamination.

Distributions of PAH in most fish tissue samples indicated a combination of petrogenic (e.g., C2-

alkylated naphthalenes), pyrogenic (e.g., fluoranthene), and biogenic (perylene, detected at less

than 2 pg/kg in 2 samples in 1997) hydrocarbons, all at very low concentrations. The individual

PAH concentrations in fish tissue samples are included in Appendix B. Method detection limits

(MDL), based on laboratory MDL tissue studies, range from approximately 1 to 5 pg/g (parts per

billion [ppb]) dry weight. Minimum reporting limits (MRL), based on the lowest calibration

standard, sample size, and pre-injection extract volume, ranged from approximately 2.8 ppb to 35

ppb dry weight. Values below the MRL are considered estimates and should be treated

accordingly.

The concentrations of individual PAH rarely exceeded 20 pg/kg (ppb) and values of most

individual PAH were near or below the MRL of the method (74 percent in 1997,78 percent in

3-32
1998). Most of the PAH that were detected above the MRL were associated with low ppb blank

contamination (66 percent of PAH above the MRL in 1997 tissues and 51 percent in 1998).

Naphthalene and phenanthrene concentrations were high for several fish liver samples.

However, analysis of laboratory procedural blanks revealed low concentrations of naphthalene,

Cl-naphthalenes, phenanthrene, and benzo[g,h,i]perylene (see Section 3.6.2 for complete

laboratory QA/QC results). Table 3-23 compares the PAH detected in procedural blanks to the

average PAH concentrations in fish tissue samples in zones 0, 1,2, and 3.

In most instances, the concentrations of these PAH compounds in fish tissue samples were

similar to or less than the concentrations of these compounds found in the procedural blanks.

The average phenanthrene concentrations were elevated in Halibut tissue samples from all 3

zones in 1997, with concentrations ranging from 0.027 mg/kg to 0.052 mg/kg which were greater

than the phenanthrene concentrations found in the two associated procedural blanks (0.016 and

0.006 mg/Kg). For the 13 tissue samples collected in 1997, the mean percent increase of the

detected phenanthrene concentrations relative to the mean of the two procedural blanks (for each

sample), is 55 percent. The Halibut tissues again contained the highest concentrations compared

to the other species collected in 1998, but there was a smaller difference between the lowest

blank and the tissue concentrations, in particular phenanthrene, ranging from 0.006 mg/kg to

0.009 mg/kg (Table 3-23).

The trace concentrations and distribution of PAH detected in the liver samples (Figure 3-79 and

Table 3-24) are characteristic of pyrogenic sources (e.g., primarily non-alkylated PAH), most

likely derived from atmospheric deposition, land runoff, and creosote pilings (Page et cd., 1995).

The characteristic petroleum-alkylated homologue distribution (NRC, 1985) was not observed in

any of the samples and represents clear evidence that these samples do not contain petroleumderived hydrocarbons. Due to trace concentrations of PAL-I in these samples (e.g., most of the

data were below the MRL) and the low-level blank contaminants, there are no apparent

differences between the background levels of hydrocarbons detected in the fish and the zone

from which they were collected.

3.4.2 Metals

Concentrations of trace metals were determined for 36 composite samples of liver from Halibut

and Pacific Cod from single sites in zones 0, 1,2 and 3 (Table 3-25 and Figures 3-80 to 3-83).

Overall, metal values for these fish livers are quite variable (Table 3-25). In general, fish length

and weight did not correlate well with liver metal concentrations in the Halibut, except for Hg

(Figure 3-84). Mercury concentrations in Halibut liver correlated positively with both length and

weight (r = 0.80 and r = 0.82, respectively). Concentrations of Be in all liver samples were

below the MDL (0.002 @g, dry weight).

Metal concentrations in liver samples from the Arrowtooth Flounder (3), Black Cod (2), and

skates (2) are within the range of values obtained for the Halibut livers (Table 3-25). However,

lower concentrations of Ag, As, Cd, Cu, Se, V, and Zn in Black Cod livers, Ag, Hg, Mn, Ni, and

Pb in Flounder livers, and Al, Cd, Hg, Mn, Ni, Pb, Se, Sn, V, and Zn in skate livers are observed

relative to the Halibut livers collected in the same zone. In contrast, values of Ag in skate livers

and Ag, As, and Sb in Pacific Cod livers are higher than the Halibut livers (Table 3-25).

3-33
Fifty-three samples of fish flesh (muscle) from halibut collected in zones 0,2, and 3 were

analyzed separately for total Hg content (Table 3-26). Concentrations ranged from 0.128 to 2.43

pg/g (dry weight) or 0.022 to 0.486 ug/g (wet weight). The highest levels were found in zone 2.

In general, the highest Hg levels in halibut flesh are found in longer (older) specimens (Figure 3-

85). Concern for adverse effects from Hg during human consumption of fish is based on a daily

Hg intake of 0.1 @Kg mass of human (EPA, 1999). At typical Hg levels of 0.10-0.15 ug/g, as

discussed by EPA (1999), a 70-Kg human could consume 50-70 g (2-2.5 ounces) of fish per day

or 350 to about 500 g (about 2-18 ounces) per week. All mean values for Hg in halibut flesh

from all zones in the Shelikof Strait are between 0.10 and 0.15 ug/g (wet weight). These are all

considered within the range of natural levels. One of the lowest Hg levels of concern noted by

EPA (1999) is 0.4 ug/g (wet weight); a point whereat consumption should be adjusted

accordingly. Only one sample from this study has a Hg level >0.4 ug/g (wet weight) at 0.486

ug/g (wet weight).

3.4.3 P450 RGS Response in Extracts of Fish Liver

Three replicates of 13 fish liver extracts (10 ~1) were analyzed after 16h of exposure using P450

RGS on September 29 and October 17, 1997. Of the 13 samples analyzed, only 3 samples

produced a detectable RGS response (i.e., the fold induction > 1.0). These responses were just

above background, yielding B[a]PEq of 0.9, 1.0, and 1.6 pg B[a]PEq /g lipid, which is consistent

with results from an uncontaminated environment.

Extracts of 12 fish liver samples were analyzed by P450 RGS on January 7-8 and January 11-12,

1999, with the addition of 10 FL of each extract to two replicate exposure wells for both 6h and

16h. Extracts were notably oily, and in some instances, the fold induction responses were very

low, indicating possible toxicity to the cells. Additional extract was obtained from the

CAS/Kelso laboratory, and the RGS assay was again conducted on January 18-19,1999, with the

addition of 5 PL of each extract. No evidence of toxicity occurred with this test. The wide

variation in percent lipids (2.5 to 79 percent) and percent solids (28 to 92 percent) of these

samples produced high variability in the calculated equivalency values. Most samples produced

very low responses, with 4 samples producing responses that were greater than the solvent blank

(fold induction > 1.0). The 6N16h response patterns were indicative of PAH (6h greater than 16

h). Based on the 16 h responses, these 4 samples yielded B[a]PEq from 0.3 to 6.5 pg/g lipid.

These results indicate that the livers of the fish contain little or no contamination by PAH or

chlorinated compounds, which is supported by the very low PAH levels measured in the livers

(Section 3.4.1). The complete results of the P450 RGS analyses are included in Appendix E.

3.4.4 CYPlA (P4501A) Response in Different Species and Different Tissues

1997. This section will first address all three species of fish analyzed in 1997 and then discuss the

results for Pacific Halibut (Hippoglossus stendepis) in more detail, as this was the species with

the greatest number of specimens and geographic coverage and therefore provides the best

opportunity (therefore, the most power) to contrast conditions in the three zones as they affect

CYPlA response in fish.

Allfish species--Fish were captured at 1 station each in zones 0,2, and 3 (Figure 2-l). The

majority of fish analyzed (35) were Pacific Halibut, and these were caught in each of the 3 zones.
There were 4 Arrowtooth Flounder (Atherestes stomias) captured in zone 2 and 1 captured in

zone 3. There were 5 Black Cod, or Sablefish (AnopZopomafimbriu), all caught in zone 3.

With few exceptions, CYPlA was detected in 2 organs (liver and kidney) which included

responses in 3 cell types--hepatocytes in liver, and tubules and vascular endothelium in the

kidney (Table 3-27). A few responses (l/44) were also observed in the liver vascular

endothelium and liver bile duct cells (l/44). Likewise, in the gills a few responses were seen:

pillar cells (4/44), epithelial cells (2/44), and vascular endothelium (2/44 ). In general, however,

the gills showed little or no induced CYPlA protein; only hepatocytes in the liver and both

kidney cell types were responsive.

In the hepatocytes, responses ranged from 0 to 10.5 out of a possible maximum score of 15.

Likewise, in the kidney tubules scores ranged from 0 to 10.5 out of a possible maximum score of

15. In the kidney vascular epithelium scores ranged from 0 to 12, with the same maximal score

possible.

Pacific Halibut-- Halibut were collected in zones 0,2, and 3. The specimens ranged in length

from 72 to 145 cm (standard length [SL]). Both males and females were retained. The mean

Pacific Halibut MC scores are provided by zone in Table 3-28. Although for each of the 3 cell

types in Table 3-27, there was a trend of highest mean scores in zone 0, intermediate scores in

zone 3, and lowest scores in zone 2, in only one cell type, kidney tubules, were these differences

significant across all zones (p=O.O07). The results of the Student Newman-Keuls test indicated

that for the kidney tubule, CYPlA response for zones 0 and 3 fell within the same group while

zone 2 was lower and significantly different. Sex and length did not explain a significant amount

of the variance of CYPlA response in Pacific Halibut cell types.

1998. This section will first address all 6 species of fish analyzed in 1998, and then discuss the

results for Pacific Halibut (Hippoglossus stenolepis) and Pacific Cod (also called True Cod or

Grey Cod) (Gadus macrocephalus) in more detail. Both of these latter species were collected in

larger numbers than the other species, and from all 3 sites. In 1998, heart was added to the gill,

liver, and kidney tissues analyzed for CYPlA response and histopathologies.

Allfish species--Fish were collected at 1 station each in zones 1,2, and 3 (Figure 2-l). The

majority of fish analyzed were Pacific Cod (60) and Pacific Halibut (41) which were collected in

each of the 3 zones. The sites in zone 2 (22 R14A) and zone 3 (23 RlA) were the same sites at

which Halibut were collected in 1997. There were also 4 Arrowtooth Flounder (Atherestes

stomias) collected in zone 3 and 5 collected in zone 2; 4 Black Cod (or Sablefish) (Anoplopoma

fimbria) collected in zone 3; 1 Aleutian Skate (Bathyraja uleutica) collected in zone 3; and 1

Longnose Skate (Baja rhina) collected in zone 1.

CYPlA was detected in all 4 organs analyzed (Table 3-27). The majority of the responses

(scores other than zero) were in 4 cell types--hepatocytes in liver (45/l 16), tubules in the kidney

(37/l 16), epithelial cells in the gill (30/l 16), and endothelial cells in the heart (30/l 16).

Additionally, a few responses were observed in gill pillar cells (3/l 16).

The possible range of scores for the CYPlA response in each of the cell types analyzed was from

0 to 15. Liver hepatocyte scores ranged from 0 to 4.5; kidney tubule scores ranged from 0 to 9;

AwthwDLktle

3-35
gill epithelial cell scores ranged from 0 to 4.5; heart endothelial cell scores ranged from 0 to 8;

and gill pillar cell scores ranged from 0 to 4.

Aleutian Skate--One Aleutian Skate was collected in zone 3. It was female, weighed 6.6 kg, and

was 145 cm long (SL). This skate received a liver hepatocyte score of 1.5, a gill pillar cell score

of 4, a gill epithelium score of 3, and a kidney tubule score of 9. The gill pillar cell and kidney

tubule scores were the highest scores for those cell types among all fishes collected in 1998.

Lmgnose Skate--One Longnose Skate was collected in zone 1. It was male, weighed 8.25 kg, and

was 110 cm long (SL). This skate received a liver hepatocyte score of 1.5 and a kidney tubule

score of 6.

Black Cod--Four male Black Cod were collected in zone 3. They ranged from 58 to 70 cm (SL)

and from 1.8 to 3.8 kg in weight. Black Cod received CYPlA scores ranging from 1.5 to 3 for

liver hepatocytes, 3 for gill epithelium, 1 to 2 for kidney tubules, and 4.5 to 8 for heart

endothelium. Each fish had a measurable response (above zero) for each of these cell types. The

heart endothelium scores were the highest among all the analyzed species.

Arrowtooth Flounder--Four Arrowtooth Flounder were collected in zone 3 and 5 were collected

in zone 2. The fish from zone 3 ranged from 55 to 76 cm (SL) in size and from 1.5 to 4.4 kg in

weight. The largest fish was female and the other 3 were male. Two of the fish (both males)

received CYPlA scores for kidney tubules of 5. There were no other CYPlA responses (above

zero) in these fish. Arrowtooth Flounder from zone 2 ranged from 49 to 80 cm (SL) in size and

from 0.8 to 4.4 kg in weight. One of these fish was female (61 cm/2.2 kg) and the rest were

male. As found in Arrowtooth Flounder from zone 3, those from zone 2 received CYPlA scores

only for kidney tubules. The scores ranged from 1.5 to 4.

Pacific Halibut, zone I-Twelve Halibut were collected in zone 1. They ranged from 73 to 122

cm (SL) in size and from 3.2 to 20 kg in weight. There were 4 females and 8 males, and the 2

largest fish were both female. These fish received CYPlA scores only for liver hepatocytes,

ranging from 0.75 to 1.5. Only 3 of the 12 fish from zone 1 had scores other than zero.

Pacific Halibut, zone 2--Seventeen Halibut were collected in zone 2. They ranged from 77 to

110 cm (SL) in size and from 5 to 18 kg in weight. .Five of the fish were female and 12 were

male. As in zone 1, the 2 largest fish were both female. These fish received CYPlA scores for

both liver hepatocytes and kidney tubules, though only 1 fish had a score other than zero (1.5) for

liver hepatocytes, and only 3 fish had scores other than zero (1.25 to 8) for kidney tubules. The

score of 8 for kidney tubules was the second highest kidney tubule score in 1998.

Pacific Halibut, zone 3--Twelve Halibut were collected in zone 3. They ranged from 72 to 115

cm (SL) in size and from 4 to 13.6 kg in weight. Four of the fish were female and 8 were male.

The largest fish was female. These fish received CYPlA scores only for kidney tubules, and

only 1 fish had a score other than zero (3).

Pacific Cod, zone I--Sixteen Pacific Cod were collected in zone 1. They ranged from 55 to 81

cm (SL) in size and from 1.8 to 5.2 kg in weight. Ten of the fish were female and 6 were male.

The 3 largest fish were female. Thirteen of the 16 fish received CYPlA scores for liver

hepatocytes that ranged from 1.5 to 3; 4 fish received scores for gill epithelium that ranged from

3-36
2 to 3; 10 fish received scores for kidney tubules that ranged from 1 to 4; and 7 fish received

scores for heart endothelium that ranged from 0.5 to 5.

Pacific Cod, zone 2--Twenty-nine Pacific Cod were collected in zone 2. They ranged from 55 to

81 cm (SL) in size and from 1.9 to 7.8 kg in weight. Twenty-one of the fish were female and 8

were male. The 7 largest fish were female. These fish received scores for the same cell types as

Pacific Cod from zone 1, and for gill pillar cells as well (2 fish had scores other than zero, both

scoring 3). Seventeen of the 29 fish received scores for liver hepatocytes, ranging from 1 to 4.5;

15 fish had scores for gill epithelium ranging from 0.5 to 4.5; 5 fish had scores for kidney tubules

ranging from 0.5 to 5; and 15 fish had scores for heart endothelium that ranged from 0.5 to 5.

Pacific Cod, zone 3--Fifteen Pacific Cod were collected in zone 3. They ranged from 55 to 79

cm in size and from 1.9 to 5.5 kg in weight. Eight of the fish were male and 7 were female. Five

of the 15 fish received CYPlA scores for liver hepatocytes that ranged from 1.5 to 3; 6 fish

received scores for gill epithelium that ranged from 1 to 3; 5 fish received scores for kidney

tubules that ranged from 1 to 4; and 4 fish received scores for heart endothelium that ranged from

2 to 6.

CYPlA Response by Organ--The number of responses (greater than zero) per organ (inclusive of

all species) was similar among organs; the highest was liver (0.39), followed by kidney (0.32),

gill (0.28), and heart (0.26).

CYPIA Response by Species--Considered by species, Halibut had the lowest number of responses

(greater than zero) per individual (0.2), followed by Arrowtooth flounder (0.78), Pacific Cod

(1.87), Longnose Skate (2), and Black Cod and Aleutian Skate (4).

CYPIA Response by Zone--Without consideration of species caught, zone 1 had the highest

number of responses (greater than zero) per fish (1.36 responses/fish), followed by zone 2 (1.24

responses/fish), and zone 3 (1.19 responses/fish). When Halibut collected in 1998 are considered

in a statistical analysis as was performed previously for fish collected in 1997 (see above), no

significant differences between zones were noted in any of the CYPlA responses (Appendix

Table I-40). The same followed for the Student Newman-Keuls test results for the Pacific Cod,

i.e., no differences in the CYPlA response between zones. The significance of the low to

moderate MC (CYPl A) scores measured in the fish tissues analyzed in this study is discussed in

Section 4 of this report.

3.5 Statistical Results

This section summarizes and provides highlights of the statistical analyses. Full results of

statistical analyses are provided in Appendix I. The majority of corresponding figures and tables

are also provided in Appendix I of this report.

_-

Surface sediments were collected from 59 locations and examined for 121 chemical and physical

parameters as part of the 1997 Alpha Helix survey. Sediments from 35 locations, analyzed for

118 chemical and physical parameters, comprised the 1998 statistical analysis data set (Ca, Mn,

K, and AVS/SEM were not measured in these sediments, but oil-degrading bacteria were added).

Ninety-five organic compounds in each sediment sample were analyzed. Appendix I Table I-l is

a presentation of analyte number and name. While the entire list is necessary for the

3-37

AuthwDLittle
fingerprinting of specific petroleum sources, combinations and/or ratios of individual analytes

can best describe spatial differences. For this reason, and to reduce errors associated with

multiple testing, the large organic list was reduced to 23 chemically and biologically important

groupings (Appendix I Table I-2). The statistical comparisons presented below were performed

using these critical organic compounds plus an additional 26 inorganic sediment measurements

(49 analytical values per sediment sample) for the 1997 surface sediments. Twenty-three

inorganic and five biological parameters were determined in the 1998 surface sediment, resulting

in a total of 51 analytical parameters per sediment sample.

As part of the 1997 survey, replication was varied within and between zones for the purpose of

establishing estimates of within station and within zone. Between-zone variability of parameters

of interest was modeled using sediments from both the 1997 and 1998 sampling periods in

addition to monitoring the variance associated with the years of sampling.

3.5.1 Coefficient of Variation

3.5.1.1 Variability Within Surface Stations

Three stations (ZlR15,Z2R2, and Z3R13) containing 7 field replicate surface grabs collected in

1997 each were used to assess within-station variability. The CV was used to describe the

amount of variation of each analyte measured in the 3 zones. The objective of the analysis was

to establish a means of comparison between the small-scale distribution of individual analytes at

a station with the overall variance of individual analytes in all zones. Appendix I Table I-3

presents the CVs for each of the 49 parameters of interest. Overall the variation was quite low,

ranging from 0.22 percent for Fe to a maximum of 8.07 percent for total S/T, suggesting that

overall small-scale spatial variance (e.g., within an individual station) is minimal.

3.5.1.2 Variability Within Zones (Surface Stations)

As described in Section 2.1.2,59 station locations were established and sampled over 4 zones in

1997 (Zones 0, 1,2, and 3). “Randomness” of location and the number of replicate samples

varied within each zone. Zone 0 was dominated by “fixed” stations (8 stations of 3 replicates

each), a consequence of bottom sediment type. Zones 1,2, and 3 contained 14 stations each; 11

possessing 1 replicate, 2 with 3 replicates, and 1 with 7 replicate surface samples. A fourth

analysis was conducted on a subcore taken from one sample at each of the “3 replicate stations”

(those stations where 3 distinct field replicate samples were taken). This fourth chemical

analysis was not considered to be a station replicate due to lack of independence. At best, it

could be considered a duplicate, or pseudo-replicate (Hurlbert, 1979). The information contained

in these samples is nonetheless important and has been averaged into the values of the source

replicate. Coefficient of variation was again used to address variability; however, this analysis

included all samples taken within each of the 4 sampling zones in 1997. Appendix I Table I-3

provides the CV on all parameters for each of the 4 zones and a single CV which describes the

system variability represented by all zones, stations, and replicates (105 total samples). As

expected, variability within zones was greater than within stations.

Coefficient of variation was greatest in zone 0, ranging from 8.52 (Al) to 101.51 (Perylene)

percent with only 16 of the 49 analytes having a CV of less than 25 percent. Following in

descending order of variability and ascending distance from outermost Cook Inlet: zone 1 had 28

analytes with a CV less than 25 percent (range 4.32 percent Al - 82.36 percent TALK); zone 2

had 31 analytes with a CV lower than 25 percent (range 4.24 percent Al - 107.05 percent sand);

3-38
-.

and zone 3 had 34 analytes with a CV less than 25 percent (1.88 percent Fe - 114.67 percent

sand). The range of CV calculated for all stations ranged from 6.2 percent (Al) to 114.67 percent

(sand) and had only 18 analytes with a CV lower than 25 percent.

Figure 3-86 plots in descending order the analyte CV for each of the zones normalized to the

overall analyte CV. It is obvious that zone 0 is the most variable and that zones 1,2, and 3 are

quite similar, with zone 3 exhibiting a slightly lower level of variability. The CV ratio depicted

in Figure 3-86 is also of interest in that ratios less than 1 indicate that the variability within a

zone is less than overall variability for a specific analyte. Variability appears to decrease with

increasing distance from outermost Cook Inlet with 69,20,12, and 4 percent of the analytes

displaying a CV ratio of greater than 1 in zones 0, 1,2, and 3 respectively.

3.5.2 Analysis of Variance

3.5.2.1 Between-Zone Comparisons

A General Linear Models (GLM, see Section 2.3.2) analysis was conducted to identify significant

between-zone analyte differences (p<=O.O5). Additionally, if the GLM indicated a statistically

significant difference between zones, a Student Newman-Keuls multiple range test (SNK, see

Section 2.3.2) was run to separate zones at the 0.05 level of significance. Results of the SNK

comparisons are generally arranged in descending order of the dependent variable (e.g., zinc), -

with significant differences between categorical variables (e.g., Zone) identified by a unique

letter code (e.g, A,B,C). Categorical variables sharing the same code are not significantly

different and can be considered as a group. Categorical variables that share more than one code

(e.g., AB) indicate an overlap between groups and/or individual categorical variable. When - overlap is noted, only categorical variables with unique codes differ significantly. Table 3-8

provides a summary of the 1997 and 1998 results. Appendix I Tables I-4 through I-8 summarize

the GLM/SNK results performed on the surface sediments collected in 1997. Appendix I Tables

I-16 through I-23 summarize the GLM/SNK results performed on the surface sediments collected

in 1998.

Suflace Sediments - 1997. Seventeen metals were examined for significant zone differences.

Untransformed data produced significant results for all metals, with the exception of Mn, Ni, Ag,

and Tl. In general, zones 0 and 3 are most often different and that zones 1 and 2 regularly

overlap with each other and/or with zones 0 and 3. The results of this test are given in Appendix

I, Table I-4. When metals data are transformed by dividing by the percent Fe within a sample, all

metals are different between zones except As, Mn, Hg, and Ag. Again, zones 0 and 3 are most

often identified as unique by the SNK.

Nine chemical/physical sediment parameters measured as percentages of sediment (Al, Ca, clay,

Fe, Mg, K, sand, silt, and TOC) were examined and are presented in Appendix I Table I-6. Only

Al shows no significant difference between zones. The trend in zone differences differs

somewhat from that in the trace metals analyses presented in Appendix I Table I-5. These higher

represented analytes tended to group together in pairs, with four of them combining zone 0 with

zone 1, and zone 2 with zone 3.

- Organic compounds of interest (Appendix I Table I-2) were treated in a manner similar to

sediment metals. Two sets of GLM analyses were performed on the 23 organic groupings. The

first set of statistical analyses examined untransformed data and the second examined TOC

AdurDLittIe

3-39
transformed data. Appendix I Tables I-7 and I-8 summarize the statistical results. Fifteen

organic groups showed significant difference between zones in the untransformed data set (Table

3-8), while after TOC transformation 18 groupings were indicated as having significant zone

differences. Zone 0 was most often unique; however, trends of increasing, or decreasing,

concentration with distance from outermost Cook Inlet were less frequent for this group of

chemicals than for either the trace metals or the physical sediment parameters.

Surface Sediments - 1998. The GLMLSNK zone analysis was repeated for the 1998 data set on

surface sediments measured for 17 metals. Two data sets were evaluated for differences among

the defined zones, 1 transformed by dividing each analyte by the percent Fe and 1 nontransformed. Nine of the 17 metals analyzed showed significant differences between zones using

the non-transformed data. In general, zones 0 and 1 were not different from one another on most

of the parameters, but different from the other zones (2,3, and 4) that were grouped together.

Following transformation, 6 of 19 metals were shown to have statistical difference between the

zones. The differences were less distinct among the zones, but in general, zones 0 and 1 were

unique compared with the other zones. The complete analysis results are reported in Appendix I

Tables I-16 and I-17.

Six chemical/physical sediment parameters measured as percentages of sediment (Al, clay, Fe,

sand, silt, and TOC) were examined and are presented in Appendix I Table I-18. Only Al and Fe

showed no significant difference between zones. The groupings were similar to that observed

with the trace metals, with the zone 0 and zone 1 sediments paired together and significantly

different from the other three zones which were not different from one another. Transformation

of the data by the percent iron yielded identical results (Appendix I Table I-19).

The GLlWSNK zone analysis was performed on the same 23 organic groupings measured in

1997, both transformed by TOC and non-transformed. The results are summarized in Table 3-8

(non-transformed data only) and Appendix I Tables I-20 and I-21. Only seven organic groups

showed significant difference between zones in the non-transformed data set (Table 3-8 and

Appendix Table I-20), while after TOC transformation eight groupings were indicated as having

significant zone differences. In general, zone 0 tended to be the most unique, particularly after

transformation, with differences attributed mostly due to the concentrations parameters such as

the Total PAH and Petrogenic PAH.

As part of the biological analyses, surface sediments were collected to evaluate the RGS-P450

response to corresponding extracts. Significant zone differences for both parameters (TEQ and

B[a]PEq) were detected in both the data transformed by TOC and data non-transformed. For

each analysis, the response at zone 0 was generally significantly lower than all other zones (1,2,

3, and 4). The results of this test are given in Appendix I Tables I-22 and I-23. Two new

variables were introduced in the 1998 sampling survey, i.e., heterotrophic and crude oil

emulsifiying bacteria. These were also analyzed for between-zone differences and resulted in no

differences, using either transformed or non-transformed data (Table 3-8, Appendix I Tables I-22

and I-23). The mean percent survival for the sediment toxicity tests was also assessed and the

results revealed that no significant difference in toxicity exists between zones where sediments

were collected (zones 0,2, and 3). The results for both transformed and non-transformed data

are given in Appendix I Tables I-22 and I-23.
Sqface Sediments - 1997 and 1998 Combined. A data set consisting of 16 stations, evaluated for

19 metals and 4 physical parameters and sampled during both the 1997 and 1998 surveys

(including zones 0, 1,2, and 3), was constructed to examine the zone differences over the entire

sample survey. A GLM model paired with a Bonferroni multiple comparison test was used to

establish significant differences (~~0.05) between the zones. Seven metals contained significant

differences among zones using the non-transformed data. Many of the zones were grouped

together (i.e., two groupings that overlapped one another) and followed the patterns observed

with the individual sampling year analyses. Three physical parameters were determined to be

significantly different across zones, essentially separating zone 0 from the other zones (1,2, and

3) or from zone 3. Data transformed by the percent Fe yielded 4 of the metals and 3 physical

parameters significantly different across zones, generally isolating zone 0 from the other zones or

zone 3. The complete summary for these analyses is given in Appendix I Tables I-24 and I-25.

Only where the GLM determined a significant difference were the data then subjected to the

Bonfexroni analysis and included in the summary tables.

The GLMkBonferroni model was also used to establish significant differences among the zones

using a dat set comprised of the 23 organic groupings measured at the 16 stations. For the nontransformed data set, only 6 of the organic groupings were found to contain significant

differences among the zones. As was observed with the results for the surface sediment zone

analyses performed separately above, zone 0 was distinct from the other zones mainly due to the

lower concentration of parameters such as total and petrogenic PAH, and the sum of the LALK.

The same six parameters were determined to be significantly different in the analysis of the

transformed data. The results for these data are summarized in Appendix I Tables I-26 and I-27.

The two RGSP450 biological indicators (TEQ and B[a]PEq) were statistically analyzed for

differences across zones using data normalized to TOC and non-transformed data collected at 14

common stations where measurements were performed during each sampling year. Zone 0 was

distinctly lower than zone 2 on both biological parameters, with the other zones (1 and 3) no

different from either of these two zones using the non-transformed data. After normalization to

TOC, the B[a]PEq showed similar differences to the non-transformed data (i.e., zone 0 distinct

from zone 2) while the TEQ was not statistically different across the zones. The results for these

data are summarized in Appendix I Tables I-26 and I-27.

3.5.2.2 Between-Year Comparison (1997 vs. 1998)

A data set consisting of repeated station sampling for both the 1997 and 1998 surveys was

analyzed for differences across the sampling period. The 16 stations were analyzed first using

GLM followed by a Bonferroni multiple comparison test to establish whether there were

significant differences between the sampling periods. Only where the GLM determined a

significant difference were the data then subjected to the Bonferroni analysis and included in the

summary tables.

Out of the 19 trace metals analyzed, 3 (Al, Ag, and Sn) exhibited statistical differences during the

2 sampling periods using the non-transformed data and 2 (silt and clay) of the physical

parameters showed significant differences. Following transformation, only 2 (Ag and Sn) of the

19 metals and the same 2 physical parameters were found statistically different between the years

of sampling. Results for this analysis are summarized in Appendix I Tables I-28 and I-29.

3-41
The 23 organic parameters were compiled from the 16 common stations and evaluated using the

GLM/Bonferroni model to test for yearly differences. Only 1 of the 23 organic groupings was

found to be significantly different between the years of collection (Oleanane/Hopane) using

either the transformed or non-transformed data set. A summary of this analysis is given in

Appendix I Tables I-30 and I-3 1.

Differences between years for the two RGS-P450 biological indicators (TEQ and B[a]PEq) were

evaluated using data normalized to TOC and non-transformed data that was collected from 14

common stations. There were significant differences between the sampling years for both the

transformed and non-transformed data (Appendix I Tables I-30 and I-3 1).

3.5.3 Pearson’s Product-Moment Correlations

3.5.3.1 Sediments

Twenty-Sfafion Sediment Data Analysis. Concurrent measurements for 35 physical/chemical

parameters and 2 biological indicators (Appendix I Table I-9) were made at 20 stations during

the 1997 sampling survey; 8 in zone 0 and 4 in each of zones 1,2, and 3. Six stations (zone 1,7

and 13; zone 2, 1 and 13; zone 3, 11 and 14) had a single field replicate. Three field replicates

were taken at the remaining 14 stations. To explore possible correlations between sediment

parameters of special interest (amphipod MPS, RGS-P450 toxicity equivalent, AVS

concentration, total SEM minus AVS concentration) a Pearson’s correlation was performed.

Appendix I Table I-10 presents a summary of the results of the processing of untransformed data.

The mean amphipod survival had significant (z c= 0.05) negative correlations with 15 metals,

depth, silt, and TOC, but no significant correlation was observed with SEM-AVS. RGS-P450

expressed as TEQ positively correlated with depth, silt, TOC, two metals, and three organic

compounds. SEM-AVS correlated negatively with two metals and two organics and had no

positive associations. Conversely, AVS positively correlated with three metals and two organic

compounds. However, after the percent silt effect was removed, there were few significant

differences due to metals or organic contaminants (Table 3-29).

An arc sine square root transformation was applied on all data reported as percents (e.g.,

amphipod toxicity, clay, and Fe) and the Pearson’s correlation was again performed. Appendix I

Table I-l 1 is a summary of this analysis. Amphipod toxicity negatively correlated with the same

analytes as with the untransformed data. RGS-P450 positively associated with eight analytes.

SEM-AVS and AVS remained unchanged.

Fourteen-Station Sediment Data Analysk Concurrent measurements for 30 physical/chemical

parameters and two biological indicators (Appendix I Table I-32) were made at 14 stations

during the 1997 and 1998 sampling surveys; 8 in zone 0 and 2 in each of zones 1,2, and 3. To

explore possible correlations between sediment parameters of special interest (i.e., RGS-P450

toxicity equivalent) a Pearson’s correlation was performed. Appendix I Tables I-33 presents a

summary of the results for the untransformed data.

The B[a]PEq biological parameter contained significant (pcO.05) positive correlations with 6

metals, 4 organic indices and 2 physical parameters and exhibited a significant negative

correlation with the percent sand. The TEQ had significant positive correlations with 4 metals, 2

physical parameters, and 4 organic indices in addition to containing a significant negative

3-42
correlation with the sand parameter. The complete results for this analysis are given in Appendix

I Table I-33. Following normalization, the B[a]PEq was determined to be positively correlated to

2 metals, 1 physical parameter, and 2 organic indices, while containing significant negative

correlations with 2 metals and 1 of the organic indices. After normalization, the TEQ data set

contained significant positive correlations with 2 organic indices (total PAH and petrogenic

PAH) and significant negative correlations with 2 metals (Ni and Cr). The complete results for

this analysis are given in Appendix I Table I-34.

Sediment toxicity tests were only performed on seven sediment stations collected in 1998, five of

which were repeats of stations that were collected in 1997 (therefore, ten samples are common to

both years, with the remaining sediment toxicity test results from nine stations collected in 1997).

However the organism used for each year of sampling was different, therefore effectively

eliminating any meaningful correlations between this parameter and the physical/chemical

measurements on a set consisting of both years’ data.

The seven 1998 stations where sediment toxicity to the amphipod Ampelisca was determined

were analyzed separately for correlation to the physical/chemical parameters, even though

amphipod toxicity can be considered marginal if at all (see Section 3.25). No

significant/meaningful correlations were observed between the metals and organic parameters

and the mean percent amphipod survival. For example, the only significant correlations, the total

PAH (1=0.8 1, p=O.O26), petrogenic PAH (~0.77, p=O.O41), percent clay (r=O.74, p=O.O36), and

TOC (r=O.SS, p=O.O16) were all positively correlated with the amphipod survival indicating that

mean percent amphipod survival increased with increasing PAH concentrations.

3.5.3.2 Fish Tissue

Tissues - 1997. Sixty-one fish of three species (Black Cod, Arrowtooth Flounder, and Halibut)

were collected from zones 0,2, and 3, at stations F7, 14, and 01, respectively. Tissues from

multiple fish within a station and species were cornposited to generate 13 tissue samples which

were processed for 41 organic chemicals, 18 metals, and 2 biological indices (Appendix I Table

I-12). A subset of 45 fish was measured for standard length, sexed, and sampled for P450

indicators. Two distinct data sets containing analytical results were generated, one populated

with chemical tissue concentrations and the other with length, sex, and P450 indicators. For the

purpose of correlative statistics, mean lengths and P450 indicators for unique species and their

associated composite were merged into the analytical data set containing analytical chemical

results.

The results presented in Appendix I Table I-13 show that very few meaningful, significant

correlations between the biological parameters and tissue chemical parameters were obtained.

Tissues - 1998. In 1998, one hundred sixteen individuals from six species (Black Cod,

Arrowtooth Flounder, Halibut, Aleutian Skate, Longnose Skate, and Pacific Cod) were collected

from zones 1,2, and 3. Thirty tissue composites were generated and analyzed for 41 organic

chemicals, 19 metals, and 2 biological indices. Again, individual tissue responses were averaged

in order to correspond to the appropriate chemical/physical measurement performed on the tissue

composite. The data sets compiled for Pearson’s correlation analysis included all fish regardless

of species, a Halibut subset, and a Pacific Cod subset. A summary of the analytes within each

data set is given in Appendix I Table I-35.

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The review of all significant correlates, both positive and negative, is given in Appendix I Tables

I-36 and I-37. Consideration as to the detection limits of both the biological and PAH parameters

precludes conclusions regarding the validity of the statisticaly significant correlations. The

response of the biological variables “hepatocyte” and “kidney tubules” contain the most

detections across all species (see Table 3-27) and can potentially contain the most reasonable

correlations. However, when observing these two variables’ significant correlates in the “all

fish” data set (Appendix I Table I-36), there are only 3 metals and 2 organic compounds with

positive correlations to these response variables. The significant correlations for the two organic

compounds (benzo[ghi]perylene and Total PAH) are primarily driven by the same measurement,

an exceptionally high value for the benzo[ghi]perylene in one fish composite sample (see Zone 3,

Aleutian Skate, in Table 3-24).

Tissues - 1997 ad 1998 Combined. Data from both years were combined to determine

correlations among the biological parameters with the chemical/physical measurements. Data

sets included all fish regardless of species, a Halibut subset and a Pacific Cod subset. The review

of all significant correlates, both positive and negative, is given in Appendix I Tables I-38 and I39. Results are no different than from those discussed for the individual years’ data sets, that is,

there are very few meaningful correlations between the biological and tissue chemical

parameters.

3.5.4 Analysis of VariandCovariance

Tissues - 1997. Hypothesis tests using the GWSNK procedures were applied to both the

combined P450/chemical data set and the P450 exclusive data set. The combined data set was

examined in a series of three GLM tests; 1) all fish, 2) Halibut only, and 3) Halibut only with

length as a covariant. Appendix I Table I-14 summarized the significant results of these

analyses. Zones that can be described by the SNK multiple range test possess unique letters (A

or B). It is apparent that few of the 68 chemical/biological parameters examined differ

significantly with zone.

Appendix I Table I-15 summarizes four GLM processes using only the Halibut tissue

measurements, with the P450 indicators as dependent variables, zone as the independent variable

and various combinations of sex and length as covariants. The addition of both sex and length

appears to refine the analysis and bring into closer focus differences between zones.

Tissues - 1998. Hypothesis tests using the GWSNK procedures were applied to the P450 data

set, and consisted of fish species that were collected in more than one zone, that is, the Halibut,

Pacific Cod, and Arrowtooth Flounder. Each species was investigated separately with 1) no

covariate, 2) with sex as a covariate, and 3) with length as a covariate. The results for each

species analyzed with no covariate is given in Appendix I Table I-40. Of the significant GLMs,

not one resulted in statistical separation using the SNK test. The analysis of covariance yielded

identical results, with no difference across the zones for any species.

Tiksues - 1997 and 1998. Hypothesis tests using the GLlWSNK procedures were applied to both

to a chemical data set and a P450 data set, each consisting of zones where Halibut sampling was

repeated during both years, that is zone 2 and zone 3. Analytes for the chemical data set included

the individual and total PAH, the individual metals, and the P450-RGS response variables (see

Appendix I Table I-35 for complete listing). Analytes for the P450 data set included the cellular
biological measures (Appendix I Table I-35). Classification variables in both data sets included

year, zone, and the year-zone interaction. Both sex and length were also analyzed as covariates

in the biological data GLM. The results for the GLM/SNK analysis for chemical/biological - parameters (with no analysis of covariance) are given in Appendix I Tables I-41 and I-42. Very

few of the analytical parameters exhibited significant differences across any of the classification

variables. Furthermore, any relationships observed among the biologic measures were identical

after an analysis of covariance was performed using sex and length as separate covariates (length

was noted as an insignificant covariate).

3.6 Quality Control Results

This discussion is intended to provide an evaluation of data quality and usability based on the

field and laboratory QC samples collected and analyzed during the first year of this study.

3.6.1 Quality Control in the Field

QC samples were collected in the field to assess overall precision, accuracy, and

representativeness of the sampling and analytical efforts. The number of QC samples collected

for this effort is based on the total number of field samples as established in the Field Logistics

Plans (Arthur D. Little, 1997a; Arthur D. Little, 1998). All results for these samples are

presented in Appendix B. Discussion and interpretation of the results are provided in the

following sections.

1.

The quality of the sample collection process is evaluated by means of equipment, field, and trip

blanks. These sample blanks provide valuable data by monitoring the sampling process for field

contaminants and cross-contamination. The trip blank was transported along with the empty

sample containers being taken by the sampling team into the field. Equipment and field blanks

are used to assess contamination introduced in the field environment and by sampling equipment.

When sampling is complete, the blanks are submitted along with the field samples for laboratory

analysis. In addition, replicate samples were collected to demonstrate reproducibility and to

assess precision.

3.6.1 .l Trip Blank

One trip blank was prepared and shipped along with the station ZOFl samples in 1997, but its

results can be interpreted to assess the potential cross-contamination during transportation of all

samples collected for this study. The trip blank was analyzed for PAH, SHC, and Sm. Only one

sample shipment was required. Overall, no significant concentrations of relevant analytes were

detected in this sample.

For PAH analysis, low molecular weight PAH compounds (i.e., naphthalenes and phenanthrene)

were detected at very low concentrations. These were flagged with J and B codes. This

demonstrates that values detected were below the detection limits and present on the procedural

blanks associated with this sample, and that no cross-contamination occurred during

transportation, For SHC analysis, several n-alkanes were detected between 0.026 and 0.14 pg/g.

These low concentrations are probably due to the presence of non-SHC compounds at the same

elution time or trace laboratory contamination from solvents and/or septa. No analytes were

detected for S/T. analysis.

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3.6.1.2 Equipment Blanks

A total of nine equipment blanks were prepared and submitted for analysis over the entire study

period. Three were collected from rinsate of the grab sampling equipment at stations ZOFl,

ZOFS, and Z3R13 in 1997, and three similar rinsates were collected at locations ZlR19,

Z2R14A, and Z2R23 in 1998. Both the 1997 and the 1998 surveys included an equipment blank

collected from rinsate of fish dissection equipment that was used in the on-board laboratory

associated with location Z2R14A. One additional equipment blank sample was collected from

rinsate of the box core sampling equipment (and core liner) at location ZOFl.

Low molecular weight PAH compounds (i.e., naphthalenes, phenanthrene, and

dibenzothiophene) were detected at very low concentrations in the fish dissection and rinsate

equipment blanks. These analytes were flagged with J and B codes. This indicates that the

values detected were below the detection limits, detected in the procedural blanks associated with

these samples, and that no cross-contamination occurred while using the sampling and dissection

tools. Low concentrations of midrange n-alkanes were detected (i.e., nC22 through nC31) in the

equipment blanks. In the case of samples ZOFl and ZOR13, concentrations of high-end n-alkanes

were also detected. When taking into account the differing volume levels and collection

techniques in comparing results from the equipment blanks and field samples, it can be

concluded that the potential for cross-contamination from the equipment used to the field

samples is negligible. These results are consistent with what is expected in equipment blanks

and no further data qualification is required. In addition, these analytes were also observed in

procedural blanks at comparable concentration levels. No S/T compounds were detected in the

equipment blanks.

3.6.1.3 Field Blanks

Three field blank samples were taken during the collection of sediment samples. One field

(deck) blank was collected during sediment sampling in 1997 at location ZlR9 when a forest fire

smoke smell was noticed in the air. The other two field blank samples, deck blanks, were

collected during sediment sampling at location Z2Fl and location Z2R23, in 1997 and 1998,

respectively.

Low molecular weight PAH compounds (i.e., naphthalenes, phenanthrene, and

dibenzothiophene) were detected at very low concentrations. These were flagged with J and B

codes. This indicates that the values detected were below the detection limits and present in the

procedural blanks associated with these samples, and that no contamination can be attributed to

ambient sources. Low concentrations of midrange n-alkanes were detected (i.e., nC22 through

nC3 l), probably due to laboratory contamination from solvents and/or septa. The analytes were

also observed in the procedural blanks at the same concentration levels. No S/T compounds

were detected in the field blanks.

3.6.2 Organics Quality Control

For this program QC measures for organics analysis included evaluation of surrogate compound

recoveries and analysis of procedural blank samples, laboratory control spike samples, SRM

samples, and control samples.

In addition, ADL participated in the NOAADJIST intercalibration exercises for organics in 1998,

1999 and 2000. Triplicate analyses of marine and mussel tissue were analyzed for organics

3-46
(including PAH) as part of these exercises. The results of the ADL analyses were within the top

10% of the more than 30 laboratories participating in the exercises.

3.6.2.1 Surrogate Results

Surrogate compounds were added to all samples including the tissue, sediment, and QC samples.

These compounds were added at different concentrations, depending on the matrix, to determine

the recovery efficiency during sample extraction, processing, and analysis. Recoveries of the

analytes of interest are inferred from the recoveries of the surrogates. The recovery efficiency of

all samples collected and analyzed for this study are presented in Table 3-30. In order to simplify

the presentation of the surrogate data, only the mean percent recovery, standard deviation, and

relative standard deviation were included in the table (percent recovery data for each sample are

included in Appendix B). Overall, the surrogate recovery results met the DQO for the project.

3.6.2.2 Laboratory Control Spike Summary

Laboratory control spike (LCS) samples measure the normal concentration bias due to such

issues as matrix effects and analytical method errors. For this project, LCS were analyzed on

each of the matrices (i.e., sediments, water, oil, and coal), except tissue, as shown in Table 3-31.

Fifteen sediment LCS were analyzed for PAH and 17 for SHC. Water LCS were also analyzed, 5

for PAH determination and 5 for SHC. As for the oil and “coal” matrices, only 1 LCS sample

was analyzed for both PAH and SHC. Overall, the results are acceptable and demonstrate that

the system was in control. Average recoveries were within the range specified in the Work Plan

(35 percent to 125 percent). The SD and RSD are all at acceptable levels; the only exceptions are

n-Decane for the water SHC LCS analysis with an RSD of 37 and acenaphthylene for the

sediment PAH LCS analysis with an RSD of 36 (30 is the limit). The oil and coal matrices LCS

- recoveries are acceptable for both PAH and SHC analyses.

3.6.2.3 Procedural Blanks

Twenty-nine procedural blanks were analyzed in conjunction with the organics samples. Traces

of some PAH target analytes were detected in the blanks at the low ppb concentration and were

generally below the reporting limit for the method. Naphthalene and Cl-naphthalene were

identified in all the blanks, occasionally at concentrations above the reporting limit; however,

these compounds are common contaminants associated with the solvents used during extraction

and processing. Traces of some SHC target analytes were also detected in the procedural blanks

(low ppb). Only in a few cases did the concentrations of any target SHC analyte exceed the

reporting limit of the method. S/T target analytes were detected in the low ppb in only one of the

procedural blanks analyzed. Overall, the procedural blanks met the DQO in the laboratory QA

plan for the program, and do not indicate concentrations of laboratory contamination that will

affect the quality or usability of the organics data.

3.6.2.4 Standard Reference Materials

Calibmtion Solution. SRM 1491 (a solution of certified PAH) was analyzed prior to each GUMS

sequence of samples for PAH analysis. The results of the SRM 1491 analyses are presented in

Table 3-32. The difference of the measured values from the certified values is less than the f 15

percent required in the QA plan, for all samples analyzed.

Sediment. One sediment SRM (SRM 1941a - certified for PAH) was analyzed with each batch of - sediment samples. The results of the SRM 1941a analyses are summarized in Table 3-32. The

percent difference of the measured values versus the certified values for PAH compounds was

within the acceptance criteria (+ 35 percent) for all target analytes with a few exceptions.

3-47
Naphthalene had a mean percent difference of minus 43 percent and minus 51 percent in the

1997 and 1998 analyses, respectively. Fluorene was also below the acceptance criteria at minus

43 percent in 1998 only. These results indicate that the measurement of naphthalene and perhaps

fluorene in the sediments could be biased low due to loss of these more volatile PAH during

sample processing. Average recovery of dibenzo[a,h]anthracene exceeded the certified value by

41 percent in 1998, and could indicate a high bias for measurement of this compound in

sediments.

Tissue. Four tissue SRM (SRM 1974a - certified for PAH) were analyzed along with the tissue

samples. The results of the SRM 1974a analysis are included in Table 3-32. Several analytes

(naphthalene, anthracene, and phenanthrene) are outside the acceptance criteria (less than 35

percent difference from the certified value). The high recoveries of naphthalene and

phenanthrene are likely the result of laboratory contamination as these analytes were detected in

the associated procedural blank. The results for these compounds were qualified in the

corresponding tissue samples. The high recovery of anthracene is consistent with the results

obtained for this compound in multiple (more than 20 samples) analyses of SRM 1974a over the

last three years, and is likely due to the light-sensitive nature of this analyte.

3.6.2.5 Analysis of Control Oils

Cook Inlet crude oil and North Slope crude oil samples were analyzed prior to each batch

sequence for PAH, SHC, and S/T analysis. The results of the control oil analyses are compared

to the laboratory mean values generated from multiple analyses of the oils. The results of the

control oil analyses (Tables 3-33 and 3-34) indicate that accuracy and precision of the analytical

methods for PAH, SHC, and S/T analyses are within the acceptance criteria required in the

Laboratory QA Plan for the program.

3.6.3 Metals and Total Organic Carbon Quality Control

For this project, QC measures included instrument calibration, standard checks, analysis of

standard reference materials (SRM), duplicate sample analysis, method and field blank analysis,

and matrix spike analysis for each analyte.

3.6.3.1 Instrument Calibration and Standard Checks

Before instrumental analysis by FAAS, ZGFAAS, CVAAS, ICP/MS or nitrogencarbon-sulfur

analyzer, a three- to five-point calibration was carried out and the linearity of the individual

analyte response factors checked. In all instances, the calibration curve for the standards met

with the DQO of r r 0.999. The RSDs between the initial calibration and subsequent calibration

checks were cl5 percent in all instances.

3.6.3.2 Standard Reference Material Analysis and Intercalibration Exercise

For sediment and coal samples, the accuracy of the digestion and analytical techniques was

determined by analyzing SRM BCSS-1, a marine sediment sample issued by the NRC in

duplicate with each batch of 40 field samples. A total of 18 SRM BCSS-1 samples were

analyzed. Metal concentrations obtained for the SRM BCSS-1 were within the limits specified

by the NRC, except for Sb, Sn (1997) and TOC (1998) (Table 3-35). However, Sb, Sn and TOC

values obtained for the SRM samples were within 15 percent of the concentrations reported by

the NRC (Table 3-35), well within 20 percent of the certified value required by the DQO (Table

2-10). Because SRM BCSS-1 is not certified for Hg, SRM MESS-2, a marine sediment sample

issued by the NRC, and SRM 1646a, an estuarine sediment certified by the NET, were analyzed

3-48
in duplicate with each batch of 40 field samples. Values obtained for these standards were

within the limits certified by the NRC and NET, respectively (Table 3-35).

,- To determine the accuracy for the liver and muscle tissue, SRM 1566a, an oyster tissue certified

by the NET, SRM DORM-2, a dog-fish muscle, and SRM TORT-2, a lobster hepatopancreas

standard, both issued by the NRC, were analyzed in duplicate for every 20 samples. Metal

concentrations obtained for SRM 1566a, SRM DORM-2, and SRM TORT-2 are within the limits

specified by the NIST (Table 3-36). Because no certified or reference data are available for Ba

and Be in SRM 1566a, SRM DORM-2, and SRM TORT-2, a water sample certified by the

NET, SRM 1643d, was used to check the analytical accuracy for these elements and provide

additional quality assurance for Sb, Se, and Tl. The metal values obtained for SRM 1643d are

within the range of values certified by NIST (Table 3-36) and met the specified DQO (Table 2-

10).

- -

Accuracy for suspended solids from the Susitna, Knik, Matanuska and Copper Rivers was

determined by the analysis of SRM 2704 (1998), a river sediment, and SRM 1643d (1998), a

water sample, both issued by the NTST. Metal values for both SRM are within the certified limits

specified by the NIST (Table 3-37). However, no certified reference values are available for Tl,

V, and Zn. For the remaining source samples (Cook Inlet crude oil, Cook Inlet produced water,

and the Point Woronzof municipal effluent), SRM 1643d (1997) a water sample certified by the

NIST, and SRM SIRS-3 (1997), a riverine water sample certified by NRC, were analyzed.

Results for these standards are within the limits specified by NIST and NRC, except for As, Ba,

Sb, and Se (Table 3-37). Values obtained for these SRM samples are within 12 percent of the

concentrations reported by the NIST and NRC (Table 3-37), well within specifications required

by the DQO (Table 2-10). Because SRM 1643d and SRM SIRS-3 are not certified for Hg, SRM

MESS-2 was digested and analyzed along with the Cook Inlet crude oil sample. Mercury

concentrations for this standard are within the limits certified by the NRC (Table 3-37).

Florida Institute of Technology also participated in the 1998 NRC and NOAA intercalibration

exercise for trace metals in marine sediments and biological tissues. Two samples of sediment

and two samples of tissue were analyzed in quintuplicate for 17 and 13 different metals,

respectively. The FIT laboratory was among 13 of 41 laboratories in the intercalibration effort to

be rated superior and the only laboratory to report results for 60 sets of data with no values

outside the accepted limits (Willie, 1998).

3.6.3.3 Duplicate Sample Analysis

Average analytical precision for the sediment portion of this study (including source material

from the Susitna River, Copper River, Homer Harbor, and the coal sample) was determined from

analysis of 10 duplicate samples and expressed as average of [(std. deviation/mean) x 100

percent]. The results are as follows: Ag (12 percent), Al (2 percent), As (6 percent), Ba (2

percent), Be (3 percent), Ca (4 percent), Cd (4 percent), Cr (5 percent), Cu (2 percent), Fe (2

percent), Hg (3 percent); K (0.5 percent), Mg (3 percent), Mn (2 percent), Ni (3 percent), Pb (2

percent), Sb (4 percent), Se (9 percent), Sn (5 percent), Tl(1 percent), V (5 percent), and Zn (5

percent). Results of the duplicates indicate precision is in all cases below the 25 percent required

by the DQO (Table 2-10). Analytical precision for fish liver and muscle tissue analyzed in

duplicate range from 0 to 18 percent. For the source samples, Cook Inlet crude oil, produced

water and Point Woronzof municipal effluent, analytical precision ranges from 0 to 18 percent,

except for Pb which, at low levels, averages 28 percent. Analytical precision for the river

3-49
suspended solids ranges from 0.4 to 14 percent. Thus, results for these samples are well within

the DQO (Table 2-10).

3.6.3.4 Method Blank Analysis

Two method blanks were processed and analyzed with each batch of samples to monitor

potential contamination resulting from laboratory reagents, glassware, and processing

procedures. No contamination from any of these sources was noted and concentrations of

analytes in the blanks do not exceed 5 times the MDL.

3.6.3.5 Field Blank Analysis

Six field blanks (2 Van-Veen grab rinses, 1 trip blank, 1 deck blank, 1 fish lab blank, and 1 fish

tool rinse) were analyzed for trace metals to monitor potential contamination from field

operations. No contamination from any of these possible sources was noted. Concentration of

all metal analytes in the blanks was ~5 times the MDL.

3.6.3.6 Matrix Spike Analysis

Two matrix spike samples were analyzed with each batch of 40 sediments and/or source

materials using the method of standard additions. Results from these analyses provide

information on the extent of any signal suppression or enhancement due to the matrix. Spike

results for the sediment, and source samples from Susitna River and Copper River, Homer

Harbor and the coal samples (Tables 3-35 through 3-37), are within the 80 to 120 percent range

specified in the DQO (Table 2-lo), except for Ag, Hg (1998), Se, Sn (1998), and V. Even

though the recoveries for these metals were ~80 percent, no spike corrections were made to the

results for these metals.

The percent recovery for the matrix spike samples for the fish liver and muscle samples (Table 3-

36) were within the 80 to 120 percent range specified by the DQO for all metals, except Hg and

Ni. Spike recovery for Hg averaged 60 percent for the liver-composite samples and 75 percent

for the fish flesh samples. This low recovery is commonly observed when organic-rich samples

are analyzed by CVAAS. All tissue Hg concentrations reported in Table 3-25, Table 3-26 and

Table 3-36 were corrected for their spike recoveries. The Ni values for the liver composite

samples were also spike corrected. Recovery of matrix spikes (Table 3-37) in the aqueous and

oil source samples also were within the 80 to120 percent range except for Ag, As (oil), Ba

(water), Fe (oil), Ni (water), Se, and V. Nickel values (1998) and all V concentrations were spike

corrected. Spike recovery for the river suspended solids (Table 3-37) averaged 97 + 8 percent,

well within the range required by the DQO (Table 2-10).

3.6.4 Toxicity Test Quality Control

During the conduct of the sediment toxicity tests, the established QAIQC measures were

performed and monitored to evaluate the validity of the results. The following required QAIQC

criteria were met during the performance of these tests and validate the results obtained:

. A 96.5 and 100 percent survival of amphipods in the ‘home’ control sediment for the

Eohaustorius and Ampelisca, respectively, was greater than the acceptability criteria of

90 percent at the end of the test

. A 91.25 percent survival of amphipods in the ‘reference’ control sediment was greater

than the acceptability criteria of 90 percent at the end of the test

3-50
. Salinity, pH, and ammonia in the overlying water were all within the tolerance limits of

the test species

. The time-weighted average of daily temperature readings was within f 1 “C of the

desired temperature and the instantaneous temperature was always within f 3°C of the

desired temperature

. Data used in statistical analyses and reported in Tables 3-14 and 3-15 were

independently reviewed for accuracy by a second biologist

3.6.5 CYPlA (P45OlA) Quality Control

The QC measures for the CYPlA determination included:

. Scoring of samples was performed blind (identities of samples were unknown to scorer)

. The correlation of subjectively determined CYPlA immunohistochemical staining

scores with protein immunoblotting of hepatic microsomes, an independent and

nonsubjective measurement of CYPlA, has been establihsed at the laboratory in Woods

Hole, Massachusetts (Woodin, et d., 1997)

3.6.6 P450 Repotter Gene System Quality Control

1997. From the long-term QC chart, the mean RGS fold induction response to 1 ng/mL TCDD

was 100 f 30 (Figure 3-87). The RGS fold induction responses to TCDD on all assay dates in

this study are shown in Table 3-38. These values are within two standard deviations of the

running mean, indicating that the tests were acceptable. In addition, the CV of all samples tested,

including both sediments (n = 27) and tissues (n = 13), were < 20 percent, indicating low

between-replicate variability. The luminometer was calibrated on August 22, September 22, and

October 21, 1997 and yielded linear response curves with an ? = 0.9, and a detection of 2 pg of

luciferase.

1998. The RGS fold induction responses to TCDD on all assay dates in this study are shown in

Table 3-38. These values are within two standard deviations of the running mean, indicating that

the tests were acceptable. In addition, the percent CV of all samples tested, including both

sediments (n = 27) and tissues (n = 12), were < 20 percent, indicating low between-replicate

variability. The luminometer was calibrated on September 17, 1998 as well as January 29, 1999

and yielded linear response curves with an 3 = 0.9, and a detection of 2 pg of luciferase.

3.6.7 Marine Heterotrophs and Crude Oil Emulsifier Quality Control

The QC measures for the enumeration of marine heterotrophs and crude oil emulsifiers included

dilution duplicates of each sediment sample. Agreement between the duplicates for the marine

heterotrophs was very good, indicating fairly homogeneous samples. The mean relative percent

difference (RPD) for the marine heterotrophs counts within a plate (an individual plate was

counted at three and five weeks) was 31 percent, while the mean RPD for the duplicate plate

analysis per sample was 34 percent. The counts for the hydrocarbon degrader populations were

low or barely detected among all samples. Where populations were detected on duplicate plates,

the RRD was 51 percent.

3-51
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5000

0

0.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

Analyte Profile Histogram

"97C3660:97-BB-Ol-Ol-OO-PHC-C COAL"

1600

1600

1400

. 1200

Q 1000

8

E

c 600

s

d 600

400

200

0

Compounds

D”“an”CC

3eoooo

340000

320000

300000

280000

260000

240000

220000

\

200000

? 80000

1~0000

1 .aoo*o

‘I 20000

‘( 00000

80000

eoooo

4ooocl

20000

0

36.00 38.00 40.00 42.00 44.00 46.00 48.00 50.00 52.00 54.00 se.00 58.00

Figure 3-4: Homer Spit Coal Source Sample Results: GC/FID chromatogram (top), PAH distribution

plot (middle), Triterpane extracted ion chromatogram (bottom).
,

Analyte Profile Histogram

“98D22’15: HOMER COAL”

500

450

400

350

j 300

j 250

i 200

8

150

100

50

0

Compounds

bundance

110000

100000

90000

80000

70000

60000

50000

40000

30000

20000

10000

0

36.00 36.00 40.00 42.00 44.00 46.00 48.00 50.00 52.00 54.00 56.00 58.00

Figure 3-5: Homer Coal Bay Source Sample Results: GUFID chromatogram (top), PAH distribution

plot (middle), Triterpane extracted ion chromatogram (bottom).
L

Analyte Profile Histogram

“98D2216: NINILCHIK COAL”

80000

75000

70000

65000

60000

55’000

50000

45000

40000

35000

30000

25000

20000

15000

Tl!

l-21 l-22

Jj ,4 I 48.00 50.00 52.00 54.00 56.00 58.00

Figure 3-6: Ninikbik Coal Source Sample Results: GC/FID chromatogram (top), PAH distribution

plot (middle), Triterpane extracted ion chromatogram (bottom).
0.00 ‘ I 0.00 30 .oc 40.00 50.00 60.00

Analyte Profile Histogram

“98D1407: MC-1 COAL”

9000

bundance

Compounds

55000

50000

45000

40000

35000

30000

25000

20000

15000

10000

5000

0

36.00 38.00 40.00 42.00 44.00 46.00 48.00 50.00 52.00 54.00 56.00 58.00

Figure 3-7: Matanuska Coal Source Sample Results: GC/FID chromatogram (top), PAH distribution

plot (middle), Triterpane extracted ion chromatogram (bottom).
11099832.D\FIDl A

240000 j

220000

200000

180000

160000

140000

120000

100000

80000

60000

40000

20000

0 I ” , ” I ” I “, / / “, I ” ” / “. I

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

Analyte Profile Histogram

“98D1406: CLC-I COAL”

4000

6000 -

5000 -

4000 -

3000 -

2000 -

1000 -1

T19

Q,,a, ,,,, ,,), ,,,, ,,,, ,,,

36.00 36.00 40.00 42.00 44.00 46.00 d

, 191.70): DZ7132.D

T22

00 50.00 52.00 54.00 56.00 58.00

Figure 3-8: Coyote Lake Coal Source Sample Results: GC/FID chromatogram (top), PAH

distribution plot (middle), Triterpane extracted ion chromatogram (bottom).
L

Analyte Profile Histogram

“98D2316: SSCOAL 5 COAL”

4500 ,

4000 -

3500 -.

o 3000 - H

: 2500 - B

s

2 2000 -

6 1500 -

1000 -

500

abundance

55000

50000

45000

40000

35000

30000

25000

20000

15000

10000

5000

Ion 191.00 (190.70 to 191.70): DZ7139.D

36.00 38.00 40.00 42.00 44

Figure 3-9: Beluga Coal Source Sample Results: GUFID chromatogram (top), PAH distribution plot

(middle), Triterpane extracted ion chromatogram (bottom).
leSpO"Se

70000

65000

60000

55000

5ocloo

45000

40000

35000

30000

25000

a0000

7 5000

' I 0000

5000

0

0.00 . I 0.00 20.00 30.00 40.00 50.00 60.00 70.00

Analyte Profile Histogram

“97C1257: 97-HH-Ol-Ol-OO-PHC-S SEDIMENT”

250

200

i

150

=.f

f 100

8

50

0

Compoundc

D""d"rhEO

-as000

40000

35000

30000

25000

zoooo

' I so00

2 0000

5000

0

3e.00 38.00 40.00 42.00 44.00 46.00 48.00 50.00 52.00 54.00 56.00 58.00

Figure 3-10: Homer Harbor Sediments O-2 cm Depth Source Sample Results: GC/FID

chromatogram (top), PAH distribution plot (middle), Triterpane ion chromatogram (bottom).
Figure 3-11: Copper River Sediients

(top), PAH distribution plot (middle),

O-2 cm Depth Source

Triterpane extracted

Sample Results: GC/FlD chromatogram

ion chromatogram (bottom), 1997.

ArthmDLittle
1 2

Analyte Profile Histogram

“98Dl439: CR-5 Sediment”

Compounds

1600:

14007

1200:

lOOO800 :

600 :

400 -

200 y

0

Ion 191.00 (190.70 to 1 9 70): DZ6410.D

38:00 40:00 42100 44:00 46:00 48100 !

I -. ” I’,” I * 1 ” I, ‘7 )

52.00 54.00 56.00 58.00

Figure 3-12: 1998 Copper River Sediment Source Sample Results: GC/FID chromatogram (top),

PAH distribution plot (middle), Triterpane extracted ion chromatogram (bottom).
5000

4500

4000

3500

3000

2500

2000

‘I 500

1000

0 .a

=

35.D\

UT. Sm

D2B

1

1.s

C,

IO 1o:oo 20:oo 3o:oo 40:oo 50.‘00 60:00 i-o.‘00 solo0

Analyte Profile Histogram

“97C1540: 97-S-Ol-Ol-OO-PHC-S SEDIMENT”

3.5

1

3

2.5

1200

1100

f 000

900

600

700

600

500

400

300

b1 .7-O): DY7266.D

200

100

,r, I ‘f

o~,.,..,,,,.,.,.,.,,..,‘.,.,..,,.,,,,..,,.,,.,,,..,,,,,,,..,,.,.,

36.00 36.00 40.00 42.00 44.00 46.00 46.00 50.00 52.00 54.00 66.0056.00

Figure 3-13: Susitna River Sediments O-2 cm Depth Source Sample Results: GC/FI.D chromatogram

(top), PAH distribution plot (middle), Triterpane extracted ion chromatogram (bottom).
7 6000

6000

4000

2000 L4J

IS.

1". I, I,. I ', 8, " I ', , " I ", I " 1' I

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

30

25

g 2o

s

; 15

5

i 10

5

0

Analyte Profile Histogram

“98D1438: Mntanuska River Sediment”

Compounds

2500

3 8

,on 19, .OO (190.70 to 191.70): DZ640S.0

w-J\ ,,.,,I 00 42.00 44.8

T22

a

T21

I ” ” I ‘,” I ” ” I ” ” I, “. I ” ” I ” ” I

) 46.00 48.00 50.00 52.00 54.00 56.00 58.00

Figure 3-14: Matanuska River Sediment Source Sample Results: GCYFID chromatogram (top), PAH

distribution plot (middle), Triterpane extracted ion chromatogram (bottom).
Analyte Profile Histogram

“98D2128: 98-AC-ACl-Ol-OO-PHC-S SEDIMENT”

120

Compound+

T19

T15

Figure 3-15: Alaska Coastal Current Sediment Source Sample Results: GUFID chromatogram (top),

PAH distribution plot (middle), Triterpane extracted ion chromatogram (bottom).

ArtliurDLittle
e?SPO”.5F:.

09189828.D\FIDlA

16000

14000

12000

10000

8000

6000

4000

2000

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

Analyte Profile Histogram

“98D2090: Augustine Is. Sediment”

16

1 4

1 2

j ‘O

B 8

e

f

; 6

4

2

0

Compounds

bundance

1800

1600

1400

1200

1000

800

600

400

200

0

Figure 3-16: St. Augustine Island Sediment Source Sample Results: GCYFID chromatogram (top),

PAH distribution plot (middle), Triterpane extracted ion chromatogram (bottom).
700

0

bbundance

Compounds

36.00 38.00 40.00 42.00 44.00 46.00 48.00 50.00 52.00 54.00 56.00 58.00

Figure 3-17: Municipal Waste Treatment Facility, Pt. Woronzof Final Effluent Source Sample

Results: GC/FID chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram (bottom).

ArthwDLittle
-I soooo

140000

3 30000

,200oo

3 7 0000

100000

90000

80000

70000

60000

50000

40000

30000

20000

-loo00

0

Analyte Profile Histogram

“97C2282: 97-TB-Ol-Ol-OO-PHC-PW PRODUCED WATER”

140000 , 1

120000

100000

3 60000

s?

e

d5 60000

40000

20000

Compounds

140000

130000

120000

-I 10000

100000

90000

80000

70000

60000

50000

40000

30000

20000

7 0000

T15

,1 .70): DX5194.D

19

Figure 3-18: Produced Water TBPF Outfall Source Sample Results: GC/FID chromatogram (top),

PAH distribution plot (middle), Triterpane extracted ion chromatogram (bottom).
Analyte Profile Histogram

“97C1364: 97-O-Fl-01.OO-PHC-S SEDIMENT”

100

90

60

70

5 60

:

P 50

b

: 40

d

30

20

10

0

Compounds

,bundance

25000

20000

15000

10000

5000

0

36.00 38.00 40.00 42.00 44.00 46.00 48.00 50.00 52.00 54.00 56.00 58.00

Figure 3-19: Zone 0, Station Fl, Surface Sediment Sample 97-O-Fl-Ol-OO-PHC-S (rep 01) Results:

GUFID chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram (bottom).
0 9

hr.

FlDlA

sur.

4000

3500

3000 C

2500

2000

1500

1000 ,,,, ,,,, ,,,, ,,(, ,,,, ,,~, .,,~ ,,,, ,,,,

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

Analyte Profile Histogram

“97C1341: 97-O-F4-0%OO-PHC-S SEDIMENT”

35 -

Compound*

,bu”da”co

Figure 3-20: Zone 0, Station F4, Surface Sediment Sample 97-O-F4-02-OO-PHC-S (rep 02) Results:

GC/FID chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram (bottom).
.-

:.s.

Analyte Profile Histogram

“98D2143: 98-O-Fl-Ol-OO-PHC-S SEDIMENT”

5

0

1100

1000

900

800

700

600

500

400

300

200

IOn 19, .oo (190.70 tc. 191.70): DZ6341 .D

T22

T19 I

Figure 3-21: Zone 0, Station F4, Surface Sediment 9%O-F4-Ol-00-PHC-S: GC/FID chromatogram

(top), PAH distribution plot (middle), Triterpane extracted ion chromatogram (bottom).

ArthwDLittDe
Figure 3-22: Zone 0, Station F5, Surface Sediient Sample 97-O-F5-02-00-PHC-S (rep 02) Results:

GCYFID chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion

chromatogram (bottom).
Analyte Profile Histogram

-FS-Ol-OO-PHC-S SEDIMENT”

2

Compounds

bundance

ion 19, .OO (190.70 to 191.70): DZ6342.D

2000

T22

1800

1600

1200

1000

800

600

400

200

0

Figure 3-23: Zone 0, Station F5, Surface Sediment 98-O-F5-Ol-OO-PHC-S: GC/FID chromatogram

(top), PAH distribution plot (middle), Triterpane extracted ion chromatogram (bottom).
esponse8000

7500

7000

6500

6000

5500

5000

4500

4000

3500

3000

2500

2000

1500

53.D\I

iUr.

1000

I, 1 I- ” /, s I ” 7 ’ 1 “, ,a ” I ” I ” ” I

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

50 50

H 40

2

:

lsr 30

Analyte Profile Histogram

“97C1296: 97-l-09-Ol-OO-PHC-S SEDIMENT”

Compounds

Figure 3-24: Zone 1, Station R9, Surface Sediment Sample 97-l-09-Ol-00-PHC-S Results: GC/FID

chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion chromatogram

(bottom).
1000

0.00 10.00 20.00 30.00 40.00 50.00 80.00 70.00

Analyte Profile Histogram

"97C1220:97-2.OS-Ol-00-PHC-S SEDIMENT"

7 0

6 0

Compounds

2400

2200

2000

1800

1600

-I 400

1200

1000

800

600

400

200

0

36.00 38.00 40.00 42.00 44.00 46.00 48.00 50.00 52.00 54.00 56.00 58.00

Figure 3-25: Zone 2, Station RS, Surface Sediment Sample 97-2-OS-Ol-00-PHC-S Results: GUFID

chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion chromatogram

(bottom).

ArtJurDLittle
Re: 5PO”SR c

_

7 0000

9500

9000

8500

ecoc

7500

7ccc

6500

6000

5500

5000

4500

4000

3500

3000

2500

2000

1500

3 000

0

60

bundance

083,

SW.

7,

S

-a.D\l=

UT. 1,s.

7 0.00 20.00 30.00 40.00 5c.cc 60.00 70.00 8O.CC

Analyte Profile Histogram

“97C1259: 97-3-lo-Ol-OO-PHC-S SEDIMENT”

Compoundr

1600

1400

1200

1000

600

600

400

200

Ion 191 .oo (190.70 to 19Il.7 0): DZ2370.D

Tl

?

0

36.00 36.00 40.00 42.00 44.00 46.00 46.00 50.00 52.00 54.00 56.00 56.00

Figure 3-26: Zone 3, Station RlO, Surface Sediient Sample 97-3-lo-Ol-OO-PHC-S Results: GUFID

chromatogram (top), PAH distribution plot (middle), Triterpane extracted ion chromatogram

(bottom).
? a000

7 7000

16000

-I 6000

3 4000

3 3000

7 2000

37000

? 0000

9000

8000

7000

6000

5000

4000

3000

2000

,000; lll.,~~~.,~.,~,..~./.,.,/,,,. I . . ../......,,

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

Analyte Profile Histogram

“98D2126: 98-4-FZ-Ol-OO-PHC-S SEDIMENT”

50

I -

Compounds

3500 -

3000 -

2500 -

2000 -

1500-

1000-

500 -

Ion 191 .oo (190.70 to 1531.7

0 II,, 9*.1,7s.z/1111 38:OO 40.00 42.00 44.00 46.00 48.00

0): DZ6336.D

gure 3-27: Zone 4, Station 2, Surface Sediment Sample 9%4-F2-Ol-OO-PHC-S: GCYFID

romatogram (top), PAH distribution plot (middle), Triterpane extracted ion chromatogram

(bottom).

Aithr D Little
0

-?
I

0.5

0.4

0.3

0.2

0.1

All Source and All Zone 0 (1997 & 1998) Surface Sediment ,._ _,___.___ . _..-- --.- _-__.- _...-.- ~- ~~

x=O.84,y=1.06

Port Woronzof Effluent

a x =0.62, y = 0.92

A

A l

x Homer Harbor

Sediments _ _ _ _ _ .~m----..----. _“__,_--.~-...... ~~.. .~~~. . . . .

l x Homer Spit Coal

A

Beíuga Yaí l

A A Homer Harbor

’ Sediments

N

Ir x YA

Ninilchik Coal A AK Peninsula Background

- Kalalla Oil

Coastal Current Sediment

PWS Background/St. Augustine Island Sediment _ _ _ _ . . . .

Mean Cook Inlet Crude (& 1 SD)

SusitnaICopper

River Sediment

J x Matanuska Coal

X Coyote Lake Coal

0 7 -.- I I I

0 0.1 0.2 C2WC2P 0.3 0.4 0.5

Figure 3-29: Double Ratio Plot of C2DK2P and C3D/C3P for all Source and Zone 0 Surficial Sediments.
0.5

0.4

0.3

%

0

a

G

0.2

0.1

All Source and Zone 1 1997 & 1998 Surface Sediment

x =0.62, y = 0.92

x Homer Harbor

Sediments

___....... - - . . . . . . . . - - - .--._.__. _ __._____-.._...._..~. _..... . . _ _

Homer Spit Coat X

Homer

’ Harbor

8etuga Coal x . , AK Peninsula 6ackground

Sediment

Well Creek Oil ‘\l \Y

PWS Background/St. Augustine Island Sediment

X

SusttnaICopper

River Sediment

x Homer Coal

.‘.~-------------.----..-...~.-..

Matanuska River Sediment Mean Cook Inlet Crude (* 1 SD)

J

x Matanuska Coal

X Coyote Lake Coal

0 0.1 0.2 C2WC2P o-3 0.4

Figure 3-30: Double Ratio Plot of C2DK2P and C3DK3P for all Source and Zone 1 Surficial Sediments.

0.5

0.5

0.4

0.3

a

0"

a

8

0.2

0.1

0

All Source and Zone 3 1997 & 1998 Surface Sediment -_____ --~ -.-.-.. ~ -. ~~~~~~ ~~

_” _ ._ ___....- .- ___. _ .____ . . . . . . .._ __ _ _ _ _ _ . . _ _ ..~

x -0.62, y = 0.92

Homer Harbor

X Sediments

__~___.---....-----.--~-._--~-._----..-----.------.- ~--~~~-

Homer Spit Coal X

x Homer Harbor

Sediments

Beiuga Coal x

Ninilchik Coal

_ _ ._~ _ _ _ _ _ ._.._ _ .- -..

Coastal Current Sediment

_...--_

Well Creek Oil Seep _ - I _ _ . - _

X

SusitnaICopper

River Sediment

&tanuska River Sediment ’ Mean Cook inlet Crude (f 1 SD)

J

x Matanuska Coal

X Coyote Lake Coal

0 0.1 0.2 CZWC2P o-3 0.4 0.5

Figure 3-32: Double Ratio Plot of C2DK2P and C3D/C3P for all Source and Zone 3 Surficial Sediments.
All Source and Zone 4 1998 Surface Sediment

0.3 Homer Spii Coal-X- - Sediments.

0.2

0.1

0

North Slope Crude

x=O.84,y=1.06

. . . ..__. . . . . . . . ..---------~.-...-.~.-....~............~~~~~~_____..._..77

Port Woronzof Effluent -

x =0.62, y = 0.92

X Homer Harbor

Beluga Coal

X Homer Harbor

Sediments

X

Ninilchik Coal

AK Peninsula Background

Swanfo~uga Coalx X

0x0 X Copper River Sediment

Katalla Oil

laskan Coastal Current Sediment

____._ Well Creek Oil Seep _ _ _ _

Susitna/Copper

River Sediment

PWS Background/St. Augustine Island Sediment

Mean Cook Inlet Crude (* 1 SD)

Matanuska Coal x Coyote Lake%oal

0 0.1 0.2 C2DK2P O-3 0.4

Figure 3-33: Double Ratio Plot of C2D/C2P and C3DK3P for all Source and Zone 4 Surficial Sediments.

0.5
T

a6

i ,

/ ’ Crus:al Avg.

2- I ’ /

,

0 /’

0 2 4 6

Fe (%)

8

3l ,I

6

1000

800

600

200

i

/’

/’ Crustal Avg.

/’

0 L’

0

I I I

2 4 6

Fe (%)

8 0 t I

/

6 0 Crustal Avg. /

xy’

40

/

/

,%

Y=192X-9.2

r=O.i7;n=l?2

i

, _- I

0 2 4 6

Fe (%)

Figure 3-34: Plots Showing Fe Versus Al, Ba, and Cr for Surficial

Sediments from Outermost Cook Inlet (Zone 0) and the Shelikof

Strait (Zones 0, 1,2,3 and 4). Dashed Lines Show Metals/Fe Ratios

for Average Continental Crust from Wedephol(1995). Dotted Line and

Equation for Cr are from the Linear Regression for the Surficial

Sediments. Symbols are (+) for 1997 and @) for 1998.
1

6 0 71 3

$ 40-

5

20 - Crustal I Avg. -- #-<.-- - Y = 12.4 X - 17.3

_#-- _* r=0.81;n=172 1

2 4 6

Fe (%)

-3

0.15 :

I” 0.05 i - 1

Ctustsl Avg.

0.00 L - - - -T I

0 2 4 6

Fe (%)

60 , I

/ / /

2.- CruSal Avg. ,’ /’ ($

Z 20 - I,’ : , /

I

/ Y=10.7X-9.6 - I

o/’ _’ r=0.83 n=172

0 2 4 6

Fe (%)

Figure 3-35: Plots Showing Fe Versus Cu, Hg, and Ni for

Surficial Sediments from Outermost Cook Inlet (Zone 0) and the

Shelikof Strait (Zones 0, 1,2,3 and 4). Dashed Lines Show Metal/Fe

Ratios for Average Continental Crust from Wedepohl(l995). Dotted

Lines and Equations for Cu and Ni are from the Linear Regression for

the Surficial Sediments. Symbols are (+) for 1997 and (0) for 1998.

AwtharDLittle
2 0 ,

/’ _

,

, :

,_ _

15 -

.

8 +

s

-3 10 -

E

/.

5 - <

<

<

< Y= 3.06x - 0.01 _

,cc

0 j’

r=0.79; n=l72 -

0 2 4 6

Fe (%)

3 ,

,

,-

,

2 - / _ _

s

2l

Crustal Avg. ’

. _+

-3

5

l -

/ ,

/ - -

_ 0 /_ ‘. 0

‘- Y = 0.34 x + 0.17 /_

_ i

-, r = 0.62; n = 172

0 j’

0 2 4 6

Fe (%)

200

150 -

Y =32.9 X -28.8

r=0.89;n=172 . ’

B

5

2 100 -

r5

50 - Crustal Avg. -

I__-

-x

0 ’

_*--_ -,-.- -

0 2 4 6

Fe (%)

Figure 3-36: Plots Showing Fe Versus Pb, Sn, and Zn for Surficial

Sediments from Outermost Cook Inlet (Zone 0) and the Shelikof Strait

(Zones 0, 1,2,3 and 4). Dashed Lines Show Meme Ratios for

Average Continental Crust from Wedepohl(l995). Dotted Lines and

Equations are from the Linear Regression for the Surficial Sediments.

Symbols are (+) for 1997 and +) for 1998.
Concentration of Total SEM and AVS @mole/

ZO-F4

ZO-F5

ZO-F8

ZO-F13 ..,“_ ._“” “_ -. .__,, - ZO-F14

..- ~ “-. ,” ,,_^ ‘I^ ,,, . “” ; _ ,_“_ 21-04

21-07

21-08

21-13

Zl-Fl

Zl-F2

22-01

22-13

22-14

22-22

Z2-Fl

z2m

23-08

23-10

23-11

23-14

23-20

Z3-Fl

Z3-F2 @ -

Total SEM-AVS
Concentrations @mole/g)

ZO-Fl

ZO-F2

ZO-F4

ZO-F5

zo-F8

ZO-F13

ZO-F14

21-04

n-07

21-08

21-13

Zl-Fl

Zl-F2

22-o 1

22-13

Z2- 14

22-22

Z2-Fl

Z2-F2

23-08

z3- 10

23-l 1

23-14

23-20

Z3-Fl

Z3-F2
-

ln Excess 21%b Activity (dpm/g)

-1 0 1 2 3 4

20 -

30 -

s=oA4ady -

r=O.%

4 0

137Cs Activity (dpnig)

0.0 0.1 0.2 0.3 0.4 0.5 0.6

0. I I

Peak representiug -1%3 at M-E-an

Peak representing -1950 at 2223-an

s=o.45ady

40’ I I I I

Figure 3-39: Vertical Profiles Showing Activities of Excess 210Pb

and 13’Cs for Sediment Core 97-Z3F2 versus Sediment Depth.

Calculated Sedimentation Rates (S) are Shown for each Isotope

Technique.
100

In Excess 21%‘b (dpm/g)

s=13cxdy

r=O.!B

II=5

13’cS Activity (dpnYg)

0.0 0.1 0.2

0

0.3 0.4 0.5 0.6 0.7

I 8 I I I I

20 -

Figure 3-40: Vertical Profdes Showing Activities of Excess “‘Pb

and ‘“Cs for Sediment Core 9%ZOFl versus Sediment Depth.

Calculated Sedimentation Rates (S) are Shown for each Isotope

Technique.
-

,I,J

13’c3 Activity @pm’s,

0.0 0.1 0.2 0.3 0.4 0.5 0.6

0

1 0

at’ lw’ level -1963 at 85-9.0-4m I

Initial OCCUI1’BYP 4950 at 1o.llun

s=024any

Figure 3-41: Vertical Profiles Showing Activities of Excess “‘Pb

and 13’Cs for Sediment Core 97-ZOF5 versus Sediment Depth.

Calculated Sedimentation Rates (S) are Shown for each Isotope

Technique.
In Excess “‘% Activity (dpnig)

E s = 0.10 ady

8

r=o.!w

E 30-

n=7

4 0 I I I I I

13’Cs Activity (dpnig)

0.0 0.1 0.2 0.3 0.4 0.5 0

0.6

6 I I I

Peak represent@ -1963 at 3.@3.5an

3 lo Peak representing -1950 at 5.~5.S-an

s = 0.10 crdy

2

‘L

i 20-

8

8 30-

40. I I I I I

Figure 3-42: Vertical Profiles Showing Activities of Excess ‘lOPb

and 13’Cs for Sediment Core 97-ZOF6 versus Sediment Depth.

Calculated Sedimentation Rates (S) are Shown for each Isotope

Technique.
In Excess 210Pb Activity (dpm/g)

E

‘t

& 20

2

8. I

l 30

40

S = 0.27 cm/y

r=O.!W

n=3

I ! I I I

13’Cs Activity (dpm/g)

Figure 3-43: Vertical Profiles Showing Activities of Excess 210Pb

and 13’Cs for Sediment Core 97-ZOFS versus Sediment Depth.

Calculated Sedimentation Rate (S) is Shown for Excess 210Pb.
In Excess 21%‘b Activity (dpdg)

_-2 -1 0 1 2 3 4

v 1

z IO2,

t 20-

0.0 0.1

13’Cs Activity (dpm/g)

0.2 0.3 0.4

I I

0.5 0.6

I

Peak representing -1963 at 7.0-7S-an

Peak representing -1950 at 9.0-9.5an

s=031ady

Figure 3-44: Vertical Profdes Showing Activities of Excess

210Pb and ‘“Cs for Sediment Core 97ZlFl versus Sediment Depth.

Calculated Sedimentation Rates (S) are Shown for each Isotope

Technique.
In Esrcess 21% Activity (dpm/g)

O-*;

+

t

+

+

++ + + *r

40

t I ! 0 I

lgCs Activity (dpm/g)

0.0 0.1 0.2 0.3 0.4 0.5 0.6

g lo f

0

r

Peak representing -1963 at 9.G95cm

Peak representing -1950 at l2-D-cm

S=OJ7dy

Figure 3-45: Vertical Profiles Showing Activities of Excess

210Pb and 137Cs for Sediment Core 97-ZlF2 versus Sediment Depth.

Calculated Sedimentation Rate (S) is Shown for ‘“Cs.
In Excess *!Pb (dpm/g)

s = 0.20 cm/y

r2 = 0.85

n=14

13’cs Activity @pm/g)

Peak representing 1963 at 6.0-6.5 cm

Figure 3-46: Vertical Profiles Showing Activities of Excess

210Pb and 13’Cs for Sediment Core 9%ZlR3B versus Sediment Depth.

Calculated Sedimentation Rates (S) are Shown for each Isotope

Technique.
In Excess “‘% Activity (dpm/g)

S=O.62ady

0.0 0.1

13’Cs Activity (dpm/g)

o,0.0 ,0.1 0;20.2 O;>Of 0.3 0.4 0;50.5 0.6 0.6

Peak Peak representing representiI.lg -1963 at -1963 at 21-22-an

Peak representing -1950 at Peak representing -1950 at 31-32411 31-32411

S = 0.65 udy

40’ , I I I I

Figure 3-47: Vertical Profiles Showing Activities of Excess

210Pb and 13’Cs for Sediment Core 9%Z2F2 versus Sediment Depth.

Calculated Sedimentation Rate (S) is Shown for each Isotope

Technique.
In Excess 210Pb Activities (dpm/g)

- 2

0

-1

I

0 1 2 3 4

/ ,

131”

s = 0.71 cm+

r = 0.96

v, --

l

/

s = 0.53 cm/y

r = 0.99

n=9

1

40 ’

I I I 4 I I

137Cs Activities (dpm/g)

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0 I I I I

Maximum level -1963 at 26-27-an

S = 0.76 cm/y

Figure 3-48: Vertical Profiles Showing Activities of Excess

210Pb and ‘“Cs for Sediment Core 97-Z2R16 versus Sediment Depth.

Calculated Sedimentation Rate (S) is Shown for each Isotope

Technique.
In Excess “‘% Activity (dprn/g)

137Cs Activity (dpm/g)

0.0 0.1 0.2 0.3 0.4 0.5 0.6

I # 11 I I

Figure 3-49: Vertical Profiles Showing Activities of Excess

“‘Pb and 13’Cs for Sediment Core 97-Z2Fl versus Sediment Depth.

Calculated Sedimentation Rate (S) is Shown for excess “‘Pb.

ArthwDLkttIe
In Excess 21@Pb Activity (dpm/g)

# s=o.6ocdy

l-=0.%

P

tl:; yx1=16 ,

0

g 10

s

13’Cs Activity (dpm/g)

0.0 0.1 0.2 0.3 0.4 0.5 0.6

Peak rfpwedq -1950 at W-3O-an

S = 0.61 ady

1

Figure 3-50: Vertical Profiles Showing Activities of Excess

21”Pb and 13’Cs for Sediment Core 97-Z3Fl versus Sediment Depth.

Calculated Sedimentation Rates (S) are Shown for each Isotope

Technique.
In ‘*%‘b Activity (dpm/g)

-2 -1 0 1 2 3 4

0 1 I , I

s = 1.0 cm/r

r =0.99

10 - n=8 a

/ ;

s=o52ady

r =0.99

n=5

50 I I I I

13’Cs Activity (dpm/g)

0.0 0.1 0.2 0.3 0.4 0.5 0.6

0 , HI I

1

Peak representing -1963 at 29-30-an _

s=o.s4ady

50 ’ I I I I I

Figure 3-51: Vertical Profdes Showing Activities of Excess

‘l”Pb and 13’Cs for Sediment Core 98Z4F4 versus Sediment Depth.

Calculated Sedimentation Rates (S) are Shown for each Isotope

Technique.
0 5 10

a (%) -n -0

:

0.0 0.1 0.2 0.3

01 4'. 7 1

0 20 40 60 80 100

0 20 40 60 80 100

Silt+Clay 1

.

0.0 0.5 1.0 1.5

0

10

20

30

0 500 1000 1500

0

1 0

20

30

404oi

2 c

1 ,lOfl Kl

Figure 3-52: Vertical Profiles from Sediment Core 97-ZOFl (Homer Harbor)

for Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals.

Sedimentation Rate was not Valid for this Core (See Figure 3-53

for Age Record at Site ZOFl).
0

z

g 150 .-B

v) 200

250

0 20 40 60 8 0 100

“-1

0 20 40 60 80 100

01” ” ” ” “1

200

250

0

250

0 5 10 15 20

0.0 0.5 1.0 1.5

0 500 1000 1500

0

50

100

t

----,&--

1920 ;:

150

200

250

250

Figure 3-53: Vertical Profiles from Sediment Core 9%ZOFl (Homer

Harbor) for Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals.

Dotted Line Indicates Approximate Sediment Depth for 1980 and Dashed

Lines Correspond to 1950 and 1920.
1,

5 10

i . .

Or

0.0 0.1 0.2 0.3

Hg Cd

1

0 20 40 60 80 100

0 20 40 60 80 100

0

10

20

0.0 0.5 1.0 I.5

0 t

l

t 1980

l-----l

i 1o -... .,i..- -. .

‘+ 1950

20! .L 1

20

0 500 loo0 1500

0

10

20

30

4 0

Figure 3-54: Vertical Profiles from Sediment Core 97-ZOF5 for

Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980 and Dashed Line Corresponds

to 1950.
30 Fe/Al Fe Al

t i

,t , , .‘%o’ 1

z-10 3

5

&

n 2 0 a

.-B

-0

w 3 0

40

0 20 40 60 80 100

c l

0 20 40 60 80 100

0

10

2 0

3 0

4 0

0 5 10 1.5 20

0

10

2 0

3 0

40

0 1 2

0

10

2 0

3 0

0.0 0.5 1.0 1.5

0

i 1980

f----lGgo ..-.... ?; _..__._ __ ._^._.._

10 ’ 1920

r-l

i

20 ‘\

d!

0 500 1000 1500

0

10

30 - Mn Ba

0 50 100 150 200

Figure 3-55: Vertical Profiles from Sediment Core 974OF6 for

Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980 and Dashed Lines Correspond

to 1950 and 1920.
Fe/Al Fe Al

0.0 0.1 0.2

O t -y,*

,t - *

5 10 : -., . . i. ..- . . .-.

5

E 20

> t^

----c---- z

2

l----l

Hg cd

a

& 30

0 20 40 60 80 100

0 20 40 60 80 100

O”;

10 1 I-). -

i

7

20 - - .A. -.. .- -

Silt+Clay _

0 5 IO 15 20

0 b .‘A b I

10 - ._

20 .I..-

30 -

-.

I

’ 1

.\I .

) f

‘i--. .) .____ .

4

4 *

.&-.+-.. _ _-.-

As Pb

0 500 loo0 1500

0 5 0 100 150 200

0

..i.*..

10 1950 t *

20

3 0

4 0

Figure 3-56: Vertical Profiles from Sediment Core 9%ZOF8 for Al,

Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980 and Dashed Lines Correspond

to 1950 and 1920.
0

0

0 20 40 60 80 100

0 20 40 60 80 1000 20 40 60 80 100

0

10

2 0 

3 0 

0.0 0.5 1.0 1.5

0

10

2 0

0 5050 loo 150 200 loo 150 200

01 r ‘J a ” ,

1980

1920

Figure 3-57: Vertical Profiles from Sediment Core 9741Fl for

Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980 and Dashed Lines Correspond

to 1950 and 1920.
40 t

0.0 0.1 0.0 0.1 0.2 0.3

0 *

1 ;. _ .“, .I

4 ‘r, l . _ .*

t P

p *o ! ,I.

2 .J .._. _ _

s

. ..*...

3

? 1

i

t

;

; 20 t

4

i

---...+---

B

I;

G

4 30 ;g &

0 20 40 60 80 100

0

g 1 0

x

5

fl

a

20

E

a

G+ 30

0 20 40 60 80 100

0

1 0

20

.

30

l--Ill

Silt+Clay ’

(%I

40

0

10

0 5 10 15 20

l

ë\ .t

m

$ ;

i *

20

30

40

0 1 2

0

10

20

30

40

0.0 0.5 1.0 1.5

0

t,’

7

1980 l

1 0

:/

:*

--+---

1950 t

t

20 t

1920

.<,

30

l.&-&-l

&c

(%)

40

0 500 loo0 1500

“11‘1

30 - Ba Mn -

0 50

Or---

Figure 3-58: Vertical Profiles from Sediment Core 97-ZlF2 for Al,

Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980 and Dashed Lines Correspond

to 1950 and 1920.
Fe/Al Fe Al

0.0 0.1 0.2

0 20 40 60 80 100 0 1 2

0 20 40 60 80 100

0

0.0 0.5 1.0 1.5

O’-J-=J

I0 ---<

I

1

, 1920 [

20 i

-1'

?r

TOC i

i

4. t ( ,(Pip 1

0 50 loo 150 200

I~~~

Figure 3-59: Vertical Profiles from Sediment Core 9%ZlR3B

for Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted

Line Indicates Sediment Depth for 1980 and Dashed Lines Correspond

to 1950 and 1920.

AnthwDLiWe
4 0

Fe/Al Fe Al

0.0 0.1 0.2 0.3

40-

0 20 40 60 80 100 60 80 100

Ai

---ICr

4 0

0 20 40 60 80 100

0

10

2 0

3 0

40-

0 5 10 1 5 2 0

0

wi9 5 “,

: 10 r----l!*

1 L

0 5 10 15 20

0

10

20

3 0 

4 0 4oLLLLLLLLLJ

0 1 2

0

10

2 0

3 0

4 0

301 ,,i: Be 1

40-

0 500 1000 1500

0

10

2 0

3 0

4 0

0 50 100 150 200

0

10

I

20 - 1980 : A

-i*

I ,

30 - ; “, -

Figure 3-60: Vertical Profiles from Sediment Core 97-Z2Fl for

Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980.
Fe/Al Fe Al

0 2 0 40 60 80 100

“pq----q

Ni.

/

.t.

’ Cr 1

0

1 0

20

30

0 20 40 60 80 100

(%)

.

l

.

:

~

:

.

Silt+Clay .

t

Sb Be

0.0 0.5 1.0 1.5

0

(%) ,-xl

“,

1 0 ,,*

1980 4:

20

i

.

t

,:

3. 19;o.. I.

t

TOC

40"""'

0 500 loo0 1500

0 5 0 loo 150

0

&&%9 ==,

10 I-- &f

1980 .A

20 l 4

I it

7í

3O

1950 *A

40=

Kl

Figure 3-61: Vertical Profiles from Sediment Core 97-Z2F2 for

Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980 and Dashed Line Corresponds

to 1950.
10-t :

3 *’

i

5 A

Fe/Al Fe Al

20' .

I

20 L

0

1 0

20

0 20 40 60 80 100

‘m

0 20 40 60 80 100

“-1

Silt+Clay t1:

l -.

f

f

1 0 15 20 0

0

1 0

20

0

10

20

Q

1980 .i

iA.d

Figure 3-62: Vertical Profiles from Sediment Core 9%Z2R16 for

Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980.
ooj .5 10

/’ (%)

2 . 4

10 :,-

0 I i

20* * ;

3. ;;A ..- ;, ._ .-A... ‘*, __^

4 0 _

0.0 0.1 0.2 0.3

OV]

/ g 10.. ‘\.

x

. *

8n20-T * z

s I

aw 3. -..-...... - F& . Hg

0 20 40 60 80 100

0 20 40 60 80 100 0.0 0.5 1.0 1.5

0

y., (%I

t

r-7

1980 i

10 ^ j.

4

2 0

i

.

1950 :I I ..-..

I

_.... .& _.._. .

3 0 TOC

i

1

40’ ’ A

0 500 loo0 1500

0 50 100 150 200

0 . .

. _

1980

1 0

. e

2 0 . ”

i

1950 -.*

30 .’ zn v

(Pdg/g)

4 0

Figure 3-63: Vertical Profiles from Sediment Core 97-Z3Fl for

Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980 and Dashed Line Corresponds

to 1950.
Sediment Depth (cm)

t? E f: E; 0

Sediment Depth (cm)

8m;

Sediment Depth (c

--
i

A l

0.0 0.1 0.2

I

_.

O[ ; /_

: *

0 20 40 60 80 100

0 20 40 60 80 100

0

1 0

2 0

3 0

4 0 r--------4

1

@)

10 1.5 20

0 1 2

0

1 0

2 0

3 0

4 0

10 -

20 - 1980

3 0

i

i950 ” ”

40

(%)

0 500 1000 1500

0 5 0 100 150 200

0 t 4.

; ;

. 1

10

l-----A

? +

.*

Figure 3-65: Vertical Profiles from Sediment Core 9%Z4F4 for

Al, Fe, Silt Plus Clay, TOC, and Selected Trace Metals. Dotted Line

Indicates Sediment Depth for 1980 and Dashed Line Corresponds

to 1950.
ZOFl

Total Organic Carbon (%)

0 0.5 1 1s 2

07

.1980

Total S/T (ug/g)

0 0.05 0.1 0.15 0.2

Ts/Ts+Tm

0 0.2 0.4 0.6 0.8

Total Hydrocarbons (uglg)

0 20 40 60 so 100

07

1980

C26 - C31 CPI

0 5 10 15 20

nClG/nClS+nC17

0 0.2 0.‘

Total PAH (ug/g)

0 0.2 0.4 0.6

. . . . . . . . . . . . . -,g*o

_ _

CS-DBTICP-Phen

0 0.15 0.3 0.45

2, . . . . . . . . . . . . . . . ... . . . ..I -1980

2 , ., 27

: ---:‘--:--

3033 _. _ ._.. _. -

3 6 J

Combustion/Petroleum PAH

0 0.1 0.2 0.3

Figure 3-66: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

ZOFl versus Sediment Depth (1997).
ZOFl

Total PAH (uglg)

0 0.2 0.4 0.6

0

,...........* . . . . ...1980

50

. . . . . . . . . . . . . . . . . . . . . .

z

v 100

f

2

0

g 150

2

i

,950

I......... . . . . . . . . . ..g*o

Total Organic Carbon (%)

0 0.5 1 1.5 2

Total Hydrocarbons (uglg)

0 2 0 4 0 60 8 0 100

0

5 0

-. . . . . . . . . ..I.. . . . . . u ‘. , 920

zoo

250 J 250 250 1 f

Total S/T (ug/g)

O p$i?,:*.

C26 - C31 CPI

0 2 4 6 8

% I.. . . . . . . . . .

!

------- 1980

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . .

i

,950

I.. . . . . . . . . ,920

CS-DBTICP-Phen

0 0.2 0.4

0

50 ........ ........ .......... ....... I

1990

1950

5 0 ............ ........ 1.1. ........ ........... ,950 1920 1920

200 200

250 J 250

Ts/Ts+Tm

0 0.1 0.2

0

nC16/nC15+nC17 Combustion/Petroleum PAH

0 0.1 0.2 0.3 0 0.2 0.4

54

j . . . . . . .;I”.1. . . . . . . . . . . . . . . . . . ..I ,950 1950

E 100 I........ . . . . . . . . . 1920 C

z

x

z 150

G

200

1:.

1

\

250

Figure 3-67: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

ZOFl versus Sediment Depth (1998).
ZOF5

Total Organic Carbon (%)

0 025 0.5 0.75 1

0

Total Hydrocarbons (ug/g)

oo....”

Total PAH (ug/g)

0.1 0.2 03

Oh---- 3 .I . . . . *.. . . . ..***..*I.*. ,990 3

I )

........ .... . .....a..... ,980

........i..

;.-I.

...........

........................

i I

$ 6 : t f _ zt 9 - . . . . . . . . . ..*............. 1950 0

2

.)

:I*-

1950 1950

1 5 m. . . . -1. .. .. r....... 1920

I\

15 . . . . . . . . . ,920

i f

. . . . ...” . . . . I ,920 1 5

Total S/T (ug/g)

o 1” , “.“‘,, y.;: p.p

C26 - C31 CPI

0 2 4 6 6

CP-DBTICP-Phen

0 0.1 0.2 0.3

0

.-. -mm......, , ggo 3

.I .^ -.-.- -............

‘f -......... y .. . g*. 1980

. . ..i.i... . . ..'...........a 1950

1

1950

Ts/Ts+Tm nClG/nCl5+nC17 Combustion/Petroleum PAH

0 0.2 0.4 0.6 0.9

0

0 0.2 0.4 0.6

c

P 9 - ..- .“...“...r”..,

CI

t

cy 1 2 f.-

0

3 ._ .a,.... I... .,...” . . . . . . . 1980

1950

3 . ..a.. 1-m.......

t

.“...LUI. I..“....“..,

. _.

.....-I. ...“..L”..

1990

1950

1920

0 0.05 0.1 0.15

0 .

,8 _ .-.- . .._

1980

1950

15 1920

li

. . . . ..Y..........“..,1920 1 5

16 l__.____.___...._..... ._..

Figure 3-68: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

ZOF5 versus Sediment Depth (1997).
ZOF6

Total Organic Carbon (%)

o ; y.; ,0.5, ;.;5

Total PAH (uglg)

0 0.1 0.2

0

1980

3

Total Hydrocarbons (uglg)

0 10 20 30

. . . . . . . . . . . . . . I

f 12- 0

: _

2 7 _

3 j . . . ..+............ 1980

: . . . . . . . . . . . . . . . . . . . . . ,950

6-

i i...

. . . . . . . . . . . . . . . . . . . . 1920

E g

C2-DBT/C2-Phen

1980

Total S/T (ug/g) C26 - C31 CPI

0 0.01 0.02 0 2 4 6 8 10

OJ4 -: , 07

3

6

i....... .............. ....... ................ .............. ....... k:... ....... ..... ... 1980 . . . . . . . . . . . . . ,980

. . . . . . . . . . . . . ,950

,920

1950

1920

$ g

c, 12

:

0 I5

5 12 _ _.

,”

015-..

a

5

0 19 _ _

21-

24

: i:-..

t!

0” 19

2,

24

ji.

. ._

27

Ts/Ts+Tm

o0 0.2 0.4 0.6

nC16/nC15+nC17

1 ie:980

Combustion/Petroleum PAH

0 0.05 0.1 0.15

0

. . . . . . . . . . . . . . . . . . . . . . 3

l---+-Y

,980

. . . . . . . . . . . . . . . . . . . . . . 1950

6 ..-

3 ,980

. . . . . . . . . . . . . . . . . . . . . 1920

i

g-...

5 12

:

0 15

2

6 19 t i

1920 . . . . . . . . I -2 . . . . . . . . . . . E 9 ,920

21 $ 24

27 I )

Figure 3-69: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

ZOF6 versus Sediment Depth (1997).
ZOFS

Total Organic Carbon (%)

0 0.2 0.4 0.5 0.9

0

Total Hydrocarbons (ug/g)

0 3 6 9 12

Total PAH (ug/g)

0 0.05 0.1 0.15 0.2

;ti

. . . . . . . ..-... ..* . . . . . . ,980

0

3

E

f 9

2O 12 2G ! i

. . . . . . . . . . . . . . . . . . . . I ,950

1 5

1950

18

2,

Total S/T (uglg) C26 - C31 CPI

:r

C2-DBTIC2-Phen

0 0.01 0.02 0.03 0.04

0

3

l--I+-- . . . . . . . . . . . . . . . . . . . . . . . ,980 0 .-- .-.. .-_.-_-

. . . . . . . . . . . . . . . . . ..m ,

0 . . .._ .-. .- _ ..__ .._

z

2

5

* _ _

a i $

980

a

n 12 ?

1 i

. . . . . . . . * . . . . . . . . . . . . . . 1950

CY

I.5

0

n 12 r

-1 \. rzi . . . . . . . . . ..I... * . . . . ,950

15

18

i it

,g ...... .. . ..- .... ....... -- _.._. -_ - ._._. - -

2 1 f ....... 1 ....

18

21

Combustion/Petroleum PAH

0 0.04 0.09 0.12 0.16

0

3 _. ._

6

. . . . . . . . . . . . . . ..“.., 980

1

5 g

:

O 12 2

:

IS i!

. . . . . . . . . . . . . . . . . . . . 1950

Ts/Ts+Tm nC16/nClS+nC17

0 0.1 0.2 0.5 0.1 0.9

o0 0.2 0.4 0.6

,980

5

E

5 g

:

p 12

5t.. . . . . . . .. . . .. 1950

15

18 I 9

21 I l

Figure 3-70: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

ZOF8 versus Sediment Depth (1998).
ZlFl

Total Hydrocarbons (ug/g) Total PAH jug/g)

Op....‘p., 0%

Total Organic Carbon (%)

0 0.5 1 1.5

. ...*..... . . . . . . . . . . . . . 5 I# ,9&J . . . . . . . . . . . . . . . . . . . . . . . . 5 ,980

P’O... . . . . . . . . . . ” . . . . . . . . . . . . . 1950

v

5

p 15---

I\

0

42

z . . . . . . . . . . . . . . . . . . . . . . . . 1920

0 20

2 5

1980

1950

1920

P lo 11""". . . . . . . . . . . ..i... v _ 1950

c

u" 15 _ ~~

:i'

0

e .I..... . . . . . . . . . . . . . . . . . .

0" 20

,920

25

1 i

Total S/T (uglg)

Op-“’

C26 - C31 CPI

0 5 10

CP-DBTICP-Phen

0 0.2 0.4

. . . . . . . . . . . . . . . .

0

i-7----

. . . . . . . . . . . . . . . . . . . . . . .

5

. . . . . . . . . . . . . . . . . . . . . . . ,980 5

/ Jo----

,980

P ‘O ~--~ ~-~ u . . . . . . . . . . . . . . . . . . . . . . . . ,s50 z ‘O -~~ 3 1 1 -- ~~~~~~ . . . . . . . . . . . . . . . . . . . . . . . . . 1950

r

z 15

:

t i

y........... . . . . . . . . . . . 1920

;20

i i,...

C

= 15

::

?

cj 20

1920

2 5

30 j A 301.

Ts/Ts+Tm

0 0.2 0.4 0.6 0.3

0

5

l--T---

. . . . . . . ..*................ ,980

nC16/nC15+nC17

0 0.5

0

. . . . . . . . . . . . . . . . . . . . . . . . 5

r--J-+-

,980

Combustion/Petroleum PAH

0 0.05 0.1

0-

5

t- i

............ .-: .......... ,980

210

v i 1 . . . . . . . . . . . . . . . . . . . . . . . . ..I 1950 z lo $..........J............ ,950 u

4 I

f

g 15

a

e

: 20

i. . . . . . . . . . . . . . . . . . . . . . . .

1 -.I 1920

25

i

1 2 5

30 i 30 1

Figure 3-71: Vertical Core Profdes of Selected Diagnostic Organic Parameters for Station

ZlFl versus Sediment Depth (1997).

ArthmDLkttle
ZlF2

Total Organic Carbon

ow

(%I

. . . . . . . . . . . . . . . . . . . . . 5

1 +

,990

-z lo i I

. . . . . . . . . . . .. . . . . .. . . 1950

2

Jz

= I5

:

E

-i i..

2 20

. . . . . . . . ..* . . . . . . . . . . . . ,g*o

Total S/T (ug/g)

0 0.02 0.01

0

. . . ..I......... 1980

5

z IO . . . . i.iiiiSi... ,950

v

c

g (5

0

c

2 20

ii- ...--.-.-...---..-

. . . . . . . . . . . . . . . . . . . . . . . ,920

301. -.. -. --. -..

Ts/Ts+Tm

0 0.2 0.4 0.6

0

. . . . . . . . . . . . . 1980

5

P 'O . . . . . ..." . . . . 1950

5

f

p 15 . ._ .

i. .i.-.-.

0

e

z0 20

.. . . .. . .. . . . . . . . . .. . . . 1920

Total Hydrocarbons (ug/g)

0 2 0 4 0

0

/

. . . . . , . . . . . . . . . . . . . . I ,980

5

^ 10 . . . . . . . . m.........., 1950

E

c

= 15

0"

?1

: 20

. . . . . . . . . . . . . . . . . . . . . . . ,920

25

ii-.

30 ..

C26 - C31 CPI

0 2 4 6

p (0 - . . . . . . . . ..‘....1...,...

J

c

z 15

d

z

; *o

:.-..I.:

_ . _ ._-_ ..^_ - . .

.. . .. . .. . . . . . . . . . .. . . .

25 _ _ __ ._..

30 _, _ .

nC16/nClS+nC17

0 0.25 0.5 0.75

0

r-F--

.......... ........ ,g*o

5

p 10 -. . . . . . . . . . . . . . . . . . . 1950

0

f

g ,!j-. . - .._.......

0

r

;

i I.... 20.

. . . . . . . . . . . . . . . . . . . . 1920

Total PAH (uglg)

o0 0.5 1

1 f

5

........... ........

-.........a .a.....

l--l

.

.....................

1980

1950

1920

CZ-DBTICZ-Phen

0 0.2 0.4

0

. . . . . . . . . . . . . . . . . . . 1980 5

r-r-

_ .._.. ^...... - __.__..... .

25

30

.1111.,*

I.--

..............

......

i

...

... ...... _-- .-_._ .......

....................

....

. __ ......... ...

~_~~_~.

1950

1920

Combustion/Petroleum PAH

0 0.05 0.1 0.15

0

........ ............. *

l--l-

,980

5 .~ ~._.

7 'O ----*-

... ..rn.....l ,950

u

f

2 , 5 _.. _ .-_ ._.-.

0

f

: 20 i

_.i

I........ + . . . . * . . . . . . . . . ,920

25 -.- i 1

Figure 3-72: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

ZlF2 versus Sediment Depth (1997).
Z2Fl

Total Organic CarbonTotal Organic Carbon 0 0.5 1 1.5 2

0

O*

5

Total PAH (uglg) 0 0.2 0.4 0.6

1980

Total S/T (ug/g)

0 0.02 0.04

CP-DBTICP-Phen

0 0.2 0.4

0

zr 15 ‘rd!! 20

: i -I-.. ----

. . . . . . . . . . . . . . . . . . ...* 1980980

25

30

i i......

30

35

Ts/Ts+Tm 0 0.2 0.4 0.6 0.8

0

5

10 l--i---

nC16/nC16+nCl? Combustion/Petroleum PAH 0 0.1 0.2

20 -~--

- . . . . . .

25 -

z

z 15 ‘rd

?

2 0

d

I .i..‘I....

. . . . . . . . . . . . . . . . . . . . . 1980

25

3 0

. . . . . . . . . . . . . . 1980

35 j 35 j

Figure 3-73: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

Z2Fl versus Sediment Depth (1997).
Z2F2

Total Organic Carbon (%) Tot:1 Hyiroczrbo;s (yplg) 0 0.5 1 1.5Total PAH (uglg) o i ,o;*, ,0i4, ;?ip

-I--

. ...... ...r... ....... ...

-1I................. + . . . . . . . . ..a1980 1980

. . . . . . . . .1. . . . . . . . . . . . . . . 19501950

CS-DBTICZ-Phen

0 0.2 0.4

,. _

.Y... . . . ..1.l.....l

/i_. . . . . . . . . . . . . . . . . . . . . . .

Total S/T (ug/g) C26 - C31 CPI

0 0.02 0.04

0

5

1980 1980

1950

30

nC16/nC16+nC17

0 0 . 2 6 0 . 6 0 . 7 5 

Combustion/Petroleum PAH

0 0.05 0.1

0

5

r---T

-. . . -

10 a..-...--. .-.I. 1980

Ts/Ts+Tm

0 0 . 2 0.4 0.6 0 . 6 

! j

i t

.-._.... ._......_.._..._.. .

-.......... I- . ...............

_

.......

. . ... I......... ... ..... ... .._ ... ....

. ... . ... ... ... ... . .... . . 1980

P

v

r ,5 _

‘L

zo 20 -..-

:

L)

i

25 -

... ....i -..

. . . . . . . . . . . . . . . . . 30 :~.- .-- --.. . . . . . . . --~ ~~

35 .._ _

1950 1950

35j _.

Figure 3-74: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

Z2F2 versus Sediment Depth (1997).
Z2R16

Total Organic Carbon (%)

0 0.5 1 1.5

0

4

s. . . . . . . . . . . . . . . . . . .

_ i 1980

Total Hydrocarbons (ug/g)

0 20 40 6 0 80

0

Total PAH (uglg)

0 0.4 08 1.2

0

. . . . . . . . . . . . . . . . . . . . .- !i 4

.1980

Total S/T (uglg) C26 - C31 CPI

0 2 4 6

0

d

8

z 12

f

2 $6 P

. . . . . . . . . . . . . . . . m..

i%

-1980

2

G 2 0

24

CZ-DBTICS-Phen

0 0.02 0.04 0.06 0 0.1 0.2 0.3

0 0

4

8

z 12 . . . . . . . . . . . . . . . . . . -

f

z 16

0

0

; 20

0

24

;

-1980 .1980

. . . . . . . . . . . . . . . . . . . . .

I f

-1950 28

; i

. . . . . . . . . . . . . . . . . . . -1950 _(

32 J

-1950 28

32

nC16/nC15+nC17 Corn bustion/Petroleum PAH

0 0.2 0.4 0.6 0 0.04 0.08 0.12 0.16 0

F. . . . . . . . . . . . . . . . . . .

_

Ts/Ts+Tm

0 0.2 0.4 0.6

0

-F. . . . . . . . . . . . . . . . . . . . . .

-

., 4 4

8 1980 .1980 .1980

!V,............ .I.......... -

i t

i 1 .'

,.*...... . . . . . *..*., -,g50 28 . . . . ...*... . . . . . . . . . . -1950

32 1 1

28 1950 28

32 3 32

Figure 3-75: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

Z2R16 versus Sediment Depth (1998).
Z3Fl

Total Organic Carbon

OW

(“/I Total Hydrocarbons (ug/g) Total PAH (ug/g)

0 20 40 60 30 0 0.25 0.5 0.75 0

5 ..

10 **....,., . ..I......,.‘,.

z

c ‘5

Z

d

Q *O

L

0

25

i

. . . . . . . . . . . . . . . . . . . . . . . .

. . . ...*... . . . . . . . ...*...

~ ./-..

. . . . . . . . . . . . . . . . . . . . . . . .

1980 1980 1980

25

1950 1950

3 0

i 1

35 1

Total S/T (uglg) C26 - C31 CPI

0 0.02 0.04 0 2 4 6 8 CS-DBTICS-Phen

._ __

35 1. .-- .-- .-._- ._

1980 10 1980 1980

2 5

. . . . . . . . . . . . . . ..*....... 30 i -~-.L 1950 1950

35 ._ . _

nC16/nC16+nC17

0 0.5

Ts/Ts+Tm

0 0.2 0.4 0.6 0.8

i

. . . . . . . i . . . . -< . . . . . . . . . i. 1980

Corn bustion/Petroleum

0 0.05 0.1

0

5

r--T

. _ -

10 . . ..“....w.... . . . . . .

PAH

1980

2 5 --. -- .- .-

! *g. . . . . . . . . . . . . . . . . . . . . . . . 30 :...... 35 I0

5

3 0

3 5

0

..s.-..-......1980

5

. .... _..... .............

_ ..... ............._. _

11: 1-1: ::

....................... 1950 1950

Figure 3-76: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

Z3Fl versus Sediment Depth (1997).
Z3F2

Total Hydrocarbons (uglg) Total PAH (uglg)

0 2 0 40 60 60 100 0 0.5 1

0

5

l----T

. . . . . . . . . . . . . . . . . . . . . . . . 1990

1 0

Total Organic Carbon (%)

0 0.5 1 1.5

oJ”“:“‘-I”“,

. ... . ........ ........ .

li

. .. . ...a..............

. ... ... ...*............

I’

i i

. . . . . . . . . . . . . . . . . . . . . . . 5

1980

1950

1990

1 0

P

p 15

z

a

f 20

d 25

.............. ........... I ......................... i.

u

c ‘5

z

a

o 20 2 I............ . . . . . . . . . . .

: 25 : 1.

1950

1920

1950

1920

30 i . . . . . . . . . . . . . . . . . . . . . . . . 1. ,920 30

35 35j

Total S/T (uglg)

0 0.02 0.04

C26 - C31 CPI CZ-DBTIC2-Phen

0 2 4 6 0 0.2 0.4

,g*o

1950

1920

0

5 _ ,. . . . . . . . . . . . . . . . . . . . . . . . . 10 P

z 15 Z

z 20 t

: T

4

i . . . . . . . . . . . . . . . . . . . . . . . . .

1990

1950

c 15 'L

0

O 20 ,?

:

25 25

30

F

. . . . . . . . . . . . . . . . . . . . . . . . . . 1920

3 5

Ts/Ts+Tm nC16/nC15+nC17 Combustion/Petroleum PAH

0 0.2 0.4 0 . 6 0 . 6 0 0.5 0 0 1 0.2

. . . . . . . . . . . . . . . 1g80

:4,

i ! . . . . . . . . . . . . . . . . . . . . . . 1950

30

i t

,...................... ,920

35

Figure 3-77: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

Z3F2 versus Sediment Depth (1997).

ArthmDLkttIe
Z4F4

Total Organic Carbon (%)

0 0.6 1 I.5 2

0

t 24-

: 4,

3 2 0

. . . . . . . . . . . . I . . . . . . . . . . ,950

l 40 2

Total SK (ug/g)

P

2 16

5 . . . . . . . . . . . .

2 z4 I . ..--..-I

. . . . . . . . . .

:

,980

a . .._ -.

2

32 .

I i

. . . . . . . . . . . . . . . . . . . . . . ,950

40

Ts/Ts+Tm

0 0.1 0.2 0.3 0.4 0.6

. . . . . . . . . . . . . . . . . . . . . . *.. ,980

40 -

Total Hydrocarbons (uglg)

0 15 30 45

0

8

E0 1 6

f

7

. . . . . . . . . . . . . . . . . . . . *,980

E

0

2 24- G

32

; 1 ..

. . . . . . . . . . . . . . . . . . . ..I ,g50

40

C26 - C31 CPI

0 2 4 6

0

32

I

. . . . . . . . . . . . . . . . . . . .

i.....

,950

40

nC16/nC15+nC17

0 0.2 0.4 0.6

Total PAH (uglg)

0 0.5 1

0

8

l----F

z

u 16

5 . . . . . . . . . . . . . . . .

8 1

. . . . . . 1980

:

Cl

f 24

2

3 2

40

C2-DBTICP-Phen

0 0.1 0.2 0.3

.........

s i

....... ,980

............

3 2

Combustion/Petroleum PAH

0 0.04 0.08 0.12 0.16

0

* l---l-- _

1950

u 16

c . . . . . . . . . . . . . . . . . . 1950

P

L? 24

32

:.- ..-.---I ....

. . . . . . . . . . . . . . . . . . . . . . ,950

40 -. ~ .~

32

I.- ..-. 7 ....

. . . . . . . . . . . . . . . . . . . . . . ,950

40 ~ .~

Figure 3-78: Vertical Core Profiles of Selected Diagnostic Organic Parameters for Station

Z4F4 versus Sediment Depth (1998).
.--

1997 Halibut Liver Analyte Profile Histogram

Compounds

1998 Halibut Liver Anaryte Profile Histogram

Figure 3-79: PAH distribution for Halibut Livers (ug/g dry weight). Zone 2, Station Rl4aH2 (top) and Zone 2, Station R14a-Hl (bottom).

AwthwD Little
Zn @g/g dry weight)

-I

0 5 1 0 1 5 2 0 2 5

Cu &g/g dry weight)

2 4 6 6

cd (118/g dry weight)

Figure 3-80: Concentrations of Zn, Cu and Cd in Liver

Composite Samples from Halibut.
2 0

AS (cls/g dry weight)

0.2 0.4

Hg (Wg dv weight)

0.6 0.6

0.05 0.15 0.20

Figure 3-81: Concentrations of As, Hg, and Pb in Liver

Composite Samples from Halibut.

AithwDLittle
981.23A-PC,

!wl -23A.PC2

9e-I-23A-PQ

9%1.23A-PO1

9&i?-UA-PC,

98z-14A-PC2

9s2-14A-Fu

s&2-14A.PC4

9%2.14&Fc5

982-UA-PC6

SW-lA.pcl

92-3lA-IX2

98-31~Fu

Zn (&g dry weight)

Sal-PA-PC1

98-1-23&Fc2

98-I-23ApQ

9al-23A-Pa

962-lu+Fcl

SE-2-la+c!

m-z-IIA-Fa

sa-2-14A-Fca

5%2-WA-PCS

9e-2-14AFc6

m-z-IA-PC1

9&z-lA-PC2

g&3-1AFW

0 1 0

0.50 1.00

cd Ca’s dry weight)

Figure 3-82: Concentrations of Zn, Cu and Cd in Liver

Composite Samples from Pacific Cod.
AS (c14/9 dry weight)

Q&laA-PC1

S&l-PA-KZ?

9%l-23A-PC3

9%I-PA-PC4

M-2-UA-F‘cl

9%244&Pcz

sE2-14A-PC3

9s2-14APc4

98-2.14A-PCS

982~14APcx

sex?-IA-P.3

m+lAFc2

SS3-1AFW

0.00 0.05 0.10 0.15 0.20

Hg W9 dry MiW)

0.00 0.05 0.10 0.15

Pb @g/g dry weight)

0.20 0.25

Figure 3-83: Concentrations of As, Hg and Pb in

Liver Composite Samples from Pacific Cod.
0.6

Fish Weight (kg)

r = 0.80 0

Fish Length (cm)

,

r = 0.58 -

“0 10 20 30 40 50

Fish Weight (kg)

Figure 3-84: Zinc Concentrations in Liver Composite

Samples from Halibut as a Function of Fish Length and

Fish Weight, as well as Cu Values in Liver Composite

Samples from Halibut versus Fish Weight.
1

050 100 150

Fish Length (cm)

Figure 3-85: Concentrations of Hg in Flesh (Muscle)

Samples from Halibut versus Fish Length.

AnthwDLittle
cw

0
: 66lCZR

I

66/W

66/62/L

 1

96/01/l

86/LlRC

1

: 86/91/01

f 86Rl6

f 86/81/8

;

86/O

86EZlS

86/O&/9

86/12/L

86/l&/L

l/v

86l8 c/E

86EJ1 c

L6/8 1R 1

LGISZI 11

L6/Plll

: L6IOZIOl

j

L6R

L6l6Zi6

l/8

L6/

L6/6ZIL

1 l/L

L6lL l/9

L 6iEi9

L6R LA

L6lS

L6l8Zh’

l/P

L6/ WC
0;

8

AuthwDLittle
Table 3-l: Concentrations of Trace Metals, Total Organic Carbon (TOC), and Grain Sire In Source Samples (Dry Weight)

Homer Harbor Sediment

Susitna River #l (5/97) Sediment

Susitna River #2 (Y97) Sediment I 0.18 12.3 1092 1.60 0.29 73.5 29.4 0.019 619

5.5 619 1.03 0.14 60.5 41.1 0.043 810

6.3 650 1.08 0.17 58.3 43.4 0.057 829

5.3 611 1.04 0.16 62.8 44.4 0.042 876

6.0 673 1.09 0.16 67.7 43.1 0.047 821

37.2 1050 3.44 0.49 103 46.4 0.304 995

38.5 1250 2.33 0.40 163 77.9 0.428 1140

23.8 897 0.60 0.19 119 65.5 0.267 1240

18.0 636 1.14 0.24 98 63.5 0.206 1000

11.9 514 0.97 0.19 80 53.3 0.183 961

34.8 1540 1.99 0.58 159 68.5 0.133 1180

26.1 1170 2.18 0.21 162 64.9 0.186 1050

23.1 1110 0.82 0.35 114 55.2 0.111 1050

4.7 348 0.22 0.05 5.0 19.7 0.049 423

6.1 400 1.10 0.17 75 1.5 0.112 103

3.8 384 0.74 <O.Ol 8.3 7.2 0.039 25

0.1 63 0.29 co.01 7.3 51.8 0.021 6

5.9 195 0.58 0.44 24.0 89.4 0.419 204

2-20 120- 0.2-3.2 0.02~lr.23 2.4-39 7-35 0.02-O. 12 18-290

Copper River #l (7197) Sediment

Copper River #I2 (7197) Sediment

Copper River #3 (7/97) Sediment I 0.08

Copper River #4 (7197) Sediment

Susitna River #l (5/98) Suspended Solids I 0.20

Knik River #l (5198) Suspended Solids I 0.10

Matanuska River #l (5198) Suspended Solids I 0.66

Copper River #l (5/98) Suspended Solids I 0.10

Copper River #2 (5/98) Suspended Solids I 0.07

Susitna River #2 (6/98) Suspended Solids I 0.36

Suspended Solids I Knik River #l (6/98) 0.20

Matanuska River #l (6/98) Suspended Solids 0.38

Solid 0.09

Solid 0.11

Solid 0.02

Solid 0.02

Solid 0.15

Solid 0.01-l 1

Homer Coal (1997)

Beluga Coal

Homer Coal (1998)

Matanuska Coal

Ninilchik Coal

coal (USGS, 19981
Table 3-f: Concentrations of Trace Metals, Total Organic Carbon (TOC), and Grain Size in Source Samples (Dry Weight)

Homer Harbor Sediment 33.9 11.5 1.12 0.29 1.56 0.41 114 94.3

Susitna River #I (5/97) Sediment 41.3 13.8 1.44 0.42 1.91 0.57 83.2 80.0

Susitna River #2 (5197) Sediment 38.6 13.7 1.41 0.31 1.86 0.54 90.5 73.3

Copper River #l (7/97) Sediment 35.3 9.0 0.63 <o. 1 1.36 0.24 132 70.0

Copper River #2 (7/97) Sediment 36.7 9.7 0.71 <O.l 1.50 0.27 145 76.8

Copper River #3 (7197) Sediment 37.5 9.2 0.75 <O.l 1.48 0.26 141 76.1

Copper River #4 (7/97) Sediment 36.4 9.6 0.69 <o. 1 1.91 0.29 119 79.2

Susitna River #1 (5198) Suspended Solids 48.5 16.2 1.92 N.D. 2.82 0.62 170 118

Knik River #l (5/98) Suspended Solids 57.8 32.5 2.88 N.D. 3.27 0.75 209 84.3

Matanuska River #l (5198) Suspended Solids 55.0 18.9 1.31 N.D. 2.88 0.53 202 119

Copper River #l (5/98) Suspended Solids 41.4 15.0 1.13 N.D. 2.74 0.43 176 109

Copper River #2 (5198) Suspended Solids 38.5 12.9 0.86 N.D. 2.00 0.29 145 81.9

Susitna River #2 (6/98) Suspended Solids 76.7 21.8 2.88 N.D. 3.59 0.98 197 184

Knik River #l (6198) Suspended Solids 70.9 20.8 2.55 N.D. 2.04 0.65 203 143

Matanuska River # 1 (6198) Suspended Solids 47.2 21.8 0.93 N.D. 1.22 0.57 208 267

Homer Coal (1997) Solid 8.2 2.7 1.65 0.37 0.39 0.07 12.9 3.7

Beluga Coal Solid 14.3 8.4 2.66 0.30 0.89 0.31 -- 46.3

Homer Coal (1998) SoIid 8.9 1.8 0.26 co.10 0.23 0.11 - - 7.7

Matanuska Coal Solid 4.9 3.2 10.4 0.11 0.09 0.21 -- 5.1

Ninilchik Coal Solid 14.0 7.9 0.96 <o. 10 0.53 0.54 m- 15.8

Coal (USGS, 1998) Solid 5-27 l-7 0.2-5 0.07-3.2 0.4-l .7 0.7-2 9-120 3-46
Table 3-2: Mean and Standard Deviation Values for Total PAH, Total PHC, and Total S/T for

Source Samples in Outermost Cook Inlet and Shelikof Strait

Swanson River

Field

Homer Spit Coal

Homer Coal Bay

Ninilcbik Coal

Mahumska Coal

Coyote Lake Coal

Beluga Coal

(n=2) (n=2) (n=2)

Oil 12,000 630,000 660

Solid 5.3 1,200 1.4

Solid 2.4 660 2.1

Solid 4.7 1400 0.95

Solid 62 1200 1.9

Solid 23 400 0.33

Solid 4.4 + 0.44 75Ok 180 1.5 + 0.46

Coyote Lake Coal Solid 23 400 0.33

Beluga Coal Solid 4.4 + 0.44 75Ok 180 1.5 + 0.46

(n=2) (Il=2) (n=2)

Homer Harbor Sediment 0.78 f 0.021 120 +r 7.1 0.26 a.010

(n=2) (n=2) (n=2)

Copper River Sediment 0.041 -t 0.013 18+:28 0.0016 f 0.00063

(n=5) (n=5) (n=5)

Susitna River sediment 0.0074 f o.ooo94 3.4 f 1.3 o.ooo6 f 0.00086

(n=2) (n=2) (n=2)

Matanuska River Sediment 0.19 6.3 0.0064

Alaska Coastal Sediment 1.7 f 0.06 47 + 3.0 0.049 f 0.0021

Notes:

’ dry weight for solid and sediments, wet weight for oil and waters

PAH - Polycyclic Aromatic Hydrocahons

SHC - Sahuated Hydroarbons

Sm - Steranes and Triterpaues

SD - Standard Deviation

n - Number of Samples
Table 3-3: Ranges of Metal Concentrations in Susitna and Copper River Bottom Sediment

and Suspended Solids (This Study), Sedimentary, Volcanic and Plutonic Rocks from Alaska

4% 0.07-0.20 0.07-0.66

Al 6.08-7.46% 6.61-10.13%

As 5.3 -13.7 11.9-38.5

B a 61 l-1090 514-1540

B e 1.0-1.6 0.6-3.4

Cd 0.14-0.30 0.19-0.58

C r 58-77 80-163

cu 29-44 46-78

F e 2.54-4.02% 4.40-7.01%

& 0.019-0.057 0.111-0.428

M n 602-876 961-1240

N i 35-41 38-77

P b 9-14 13-32

S b 0.6-l .4 0.9-2.9

Se co. l-0.4 4.1

Sn 1.4-1.9 1.2-3.6

Tl 0.24-0.57 0.29-0.98

V 83-145 145-209

Z n 70-80 82-267

2.67-7.81%

I

7.96%

383-l 160 I

47-84 I 126

2 5

1.59-6.66% 1 4.32%

-- 2.3

-- 0.52

55-278 9 8

96-288 6 5

Notes:

*Concentrations in pglg, except where noted.

** S-K-M = Susima - Knik - Matanuska
d8d

s8d

g8d

E5 90

zd

iz8d

88d

s8d

. s8

c;

0sddQ, 8

23d
-. Table 3-5: Means, Standard Deviations and Ranges of Values for Total Organic Carbon

(TOC), Sand, Silt and Clay for Surficial (O-2 cm) Sediments from the Alaska Coastal

Current (AC) and Zones 0, 1,2,3 and 4 in the Shelikof Strait

A C 1.13 98.6

zto.04 LA a.4

(1998)

1.09-1.16 0.95-1.62 98.4-99.4

Mean

Std. Dev.

Raise

k%V.

Rws

MeaIl

Std. Dev.

Raw3

EEev.

Range

iE%ev.

Range

EEiev.

Range

kZ%ev.

Range

&%ev.

Raw

&iiev.

Rmze

Mean

Std. Dev.

Range

0 0.62 42.1 57.9

a.32 G6.9 d6.9

(1997)

0.31-1.22 3.8-84.9 15.1-96.2

0 a.36 0.82 G8.7 48.2 60.6 58.3

(1998)

0.28-1.37 7.0-78.6 21.5-93.0

1 0.57 37.1 62.9

do.18 520.9 dO.9

(1997)

0.26-0.94 2.6-70.3 29.7-97.4

1 2% 40.8 55.6

k24.5 L22.2

(1998)

0.32-0.92 12.2-68.0 32.0-87.8

2 a.13 0.83 279 6.9 93.3

(1997)

0.48-1.05 0.1-27.2 72.8-99.9

2 A.13 0.83 2 k7.2 91.8

(1998)

0.59-1.49 1.0-23.8 76.2-99.0

3 0.94 2.1 97.9

iO.08 k3.7 k3.7

(1997)

0.79-1.16 0.19-17.7 91.5-99.8

3 0.98 1.9 97.4

&I.10 zk1.8 k3.5

(1998)

0.80-1.15 0.4-12.2 87.8-99.6

4 1.13 98.9

ko.04 ii!7 a.9

W98) 1.08-1.18 0.3-2.9 97.1-99.7

All Zon~~luding 0.81 20.5 81.7

MO.28 rt24.4 d9.1

(1997-1998) 0.26-1.49 0.1-84.9 15.1-99.9

AmthwD Little
Table 3-6: Non-Transformed Mean, Standard Deviation and Range of Total PAH, Total

PHC, and Total S/T for Surficial Sediment (O-2cm) from Zones 0, 1,2,3 and 4

Mean &D 0.269 f 0.134 25.4 iz 16.2 0.029 f 0.020

Range 0 0.120 - 0.490 9.77 - 50.0 0.009 - 0.069

Mean ztSD

1

0.422 + 0.250 26.2 2 10.6 0.016 + 0.005

Range 0.173 - 1.080 12.0 - 48.0 0.011 - 0.030

Mean &D 0.542 -e 0.221 26.1 + 10.1 0.024 2 0.017

Range 2 0.221 - 0.957 14.0 - 51.0 0.012 - 0.087

Mean &SD

3

0.595 f 0.152 36.3 + 16.1 0.022 i 0.009

Range 0.314 - 0.857 15.0 - 71.0 0.011 - 0.037

Mean iSD Grand Mean: 0.457 f 0.145 28.5 -c 5.21 0.023 f 0.005

Range 0, 1,2and3 0.120 - 1.080 9.77 - 71.0 0.009 - 0.087

I998 Results 1 ! ! I

Mean iSD

0

0.200 -c 0.119 25.5 + 18.1 0.027 + 0.022

Range 0.066 - 0.420 6.80 - 54.3 0.009 - 0.069

Mean &D 0.016 f 0.004

Range 1

0.330 f 0.198 23.6 f 8.18

0.120 - 0.730 14.0 - 39.0 0.011 - 0.021

Mean &D

2

0.525 k 0.133 25.8 + 3.58 0.021 f 0.004

Range 0.290 - 0.687 21.0 - 31.0 0.017 - 0.026

Mean &D

3

0.501 f 0.060 33.2 f 6.59 0.030 -c 0.017

Range 0.360 - 0.550 24.0 - 42.0 0.021- 0.072

Mean &D

4

0.604 f 0.060 35.8 f 6.68 0.025 f 0.001

Range 0.537 - 0.650 30.7 - 43.3 0.024 - 0.027

Mean &SD Grand Mean: 0.432 f 0.164 28.8 f 5.37 0.024 + 0.005

Range 0, 1,2,3,4 0.066 - 0.730 6.80 - 54.3 0.009 - 0.072

1997 & 1998

Mean &D 1 0 1 0.235 kO.049 1 25.5 A 0.071 I 0.028 f 0.001

Mean &SD 1 1 1 0.376 kO.065 1 24.9 f 1.84 I 0.016

Mean &SD I 2 I 0.534 f 0.012 I 26.0 -+ 0.212 I 0.023 f 0.002

Mean &SD I 3 I 0.548 f 0.066 I 34.8 -c 2.19 I 0.026 f 0.006

Mean &D I 4 I 0.604 2 0.060 I 35.8 f 6.68 I 0.025 f 0.001

Mean &D 1 GrandMean: 1 0.459 f 0.151 I 29.4 f 5.41 I 0.024 f 0.005
Table 3-7: Diagnostic Ratios and Parameters of Saturated Hydrocarbons, Polycyclic

Aromatic Hydrocarbons, and Steranes and Triterpanes

Saturated Hvdrocarbons (SHC.1

Isoprenoids

LALK

The sum of selected branched isoprenoid alkanes including: phytane, pristane, famesane

[1470], and unidentified isoprenoids at relative retention index 1380 and 1650.

Isoprenoids are abundant in petroleum and are resistant to degradation relative to the

corresponding n-alkanes.

The sum of lower molecular weight n-alkanes (nC, to nC.& generally associated with

“fresh” petroleum inputs.

TALK

PHY/PRIS

The sum of total alkanes which includes those of biogenic and petrogenic origin (nC, to

n&J.

Source of phytane (PHY) is mainly petroleum, whereas pristane (PRIS) is derived from

both biological matter and oil. In “clean” environmental samples, this ratio is very low

and increases as oil is added.

The ratio of n-alkane hexadecane (nC,,& over pentadecane (nC,,) and heptadecane (nC,,).

At “‘background” levels of total hydrocarbons nC15 and nC17 can be used as indicators

of plankton (algal) hydrocarbon inputs. As plankton productivity increases the ratio

CPI

TPHC

1 decreases.

1 Carbon preference index. Describes the relative amounts of odd-andeven-chain alkanes

within a-specific alkane boiling range. CPI of 2 - 4 indicate terrestrial plants, as oil

additions increase the CPI is lowered to near 1 .O. The equation for CPI is (n+ + n-C,

+ n-C&i-& + nG, + n-C&.

Total hydrocarbons, the sum of the resolved plus unresolved saturated and aromatic

hydrocarbons.

Polycyclic Aromatic Hydrocarbons (PAH)

N/P

C2D/C2P

C3D/C3P

Perylene

Total PAH

Pyrogenic PAH

Petrogenic PAH

PyrogenidPetrogenic

The naphthalenes (N) to phenanthrenes/anthracenes (P) ratio is diagnostic for inputs of

fresh petroleum, and as a weathering indicator. Naphthalenes are characteristic of fresh

crude oil, the ratio decreases with increased weathering. (N= Naphthalene series [CON +

ClN + C2N + C3N + C4N]; P= Phenanthrene/Anthracene Series [COP/A + ClP/A +

C2P/A + C3P/A + C4P/A]).

Ratio of C2 alkyl dibenzothiophenes (D) and C2 alkyl phenanthrenes (P) is a useful

diagnostic source ratio for petroleum.

Ratio of C3-alkyl dibenzothiophenes (D) and C3-alkyl phenanthrenes (P) is a useful

diagnostic source ratio for petroleum.

A biogenic PAH formed during the early diagenisis in marine and lacustrine sediments,

may be associated with terrestrial plant source precursors.

The sum of all PAH target analytes includes 2- through 6-ring parent PAH and Cl - C4

all@ substituted PAH. -

The sum of combustion PAH compounds (4,5-, and 6-ring PAI-I Fluoranthene, pyrene,

chrysene, benzo[a]anthracene, be&$b]fluoranthene, benz&k]fluoranthene, -

benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[l,2,3,-

c,d]pyrene.

The sum of petrogenic PAH compounds (2-, 3-, and 4 -ring PAHr naphthalenes [CO -

C4], acenaphthene, acenaphthylene, fluorene [CO - C3], phenanthrenes [CO - C4],

dibenzothiophenes [CO - C3], chrysenes [Cl - C4], and fluoranthenes/pyrenes [Cl - C31).

The ratio of pyrogenic PAH compounds to petrogenic PAH compounds is useful for

determining the relative contribution of pyrogenic and petrogenic hydrocarbons and in

differentiatinp hydrocarbon sources.

AwthwDLiie
Table 3-7: Diagnostic Ratios and Parameters of Saturated Hydrocarbons, Polycyclic

Aromatic Hydrocarbons, and Steranes and Triterpanes

Total S/T

T21fl-22

Hopane

Ts/(Ts +Tm)

Oleanane/Hopane

The sum of all sterane and triterpane biomarker tzuget analytes.

The ratio of C31-homohopane (22s) (T21) to C31-homohopane (22R) (T22), useful for

determining the contribution of recent biogenic material.

C30-Hopane (T19), commonly one of the most abundant triterpanes in petroleum.

Ratio of C27&snorhopane(Ts) to C27-trisnorhopane (Tm); used as a mahuity indicator

for petroleum, also as a source ratio for different crude oils.

The ratio of C304eanane (T18) to C30-hopane (T19) indicates the relative amounts of

oleanane, which is a marker of angiosperm (post-Cretaceous) contribution to petroleum

diagenesis.
-

Table 3-8a: Mean, Maximum, Minimum, and Student Newman-Keuls Analysis Results

for Key Organic Parameters (Non-Transformed) in 1997 Surface Sediments

~Petrogenic PAH 131171 A I 0.364 I 0.241 I 0.475 1 0.069 I 19.014 I

hi9 1 2 1 7 A 0.343 0.141 0.533 0.110 32.026

I 1 1 7 A 0.289 0.117 0.573 0.151 52.436 I -- --- r

0 8 B 0.143 0.069 0.247 0.063 44.422

Pyrogenic PAH 3 1 7 A 0.039 o-021 0.058 0.012 30.177

Wg) 0 18 A 0.036 0.011 O-082 0.030 82.134 ‘-

2 117 A 0.033 0.019 0.057 0.011 33.549

014 I 0.051 0.011 40.914 f 1 I

131 I 0.235 1 0.034 I 21.549 1

1 1 7 A 0.026 0.1

C2D/C2P 0 8 A 0.159 o.--

2 1 7 AB 0.151 0.111 0.164 0.012 8.260

3 1 7 AB 0.151 0.126 0.177 0.012 8.132

I 111171 B 1 0.137 1 0.108 I 0.164 1 0.016 1 11.992 I

C3DK3P 1 0 18 A 1 0.215 0.127 f 0.289 0.048 22.293

1 2 117 AB 0.197 0.163 1 0.250 0.024 11.990

3 117 B C 0.189 0.173 0.225 0.013 7.068

1 117 C 1 0.171 OS43 0.200 0.018 10.662 I

IN/P 121171 A 1 0.980 1 0.652 1 1.568 1 0.346 1 35.265 1

3 1 7 A 0.972 0.743 1.492 0.197 20.237

1 1 7 A 0.972 0.713 1.144 0.132 13.557

0 8 B 0.643 0.523 0.792 0.098 15.196 I I - I -~- I --- I - ---

PYROLPETRO 0 8 A 0.234 0.087 f 0.471 0.123 52.391

3 1 7 B 0.106 0.084 1 0.139 O-016 15.018

2 1 7 B 0.097 0.071 f 0.134 0.014 14.163

1 1 7 B 0.096 O-076 1 0.124 0.016 16.283

087 1 0.233 0.033 20.615

I

nC16/(nC15+nC17) 1 1 7 A 0.162 o.-- , ~__ , ~__ , ~~ .~_

3 1 7 A 0.155 0.128 1 0.176 I 0.013 I 8.470 i

2 1 7 A 0.153 0.114 I

_.-. - _.---

. m - .-.rn -- . -.-- - , -.-- . , 0.194 I 0.025 1 16.642

I 10181 B 1 0.092 1 0.027 1 0.146 1 0.043 1 46.531 1 I

Pristane 3 117 A 0.078 0.036 1 0.140 0.029 37.606

W& 2 1 7 A 0.066 0.030 0.100 0.021 32.206

1 1 7 A 0.062 0.020 0.143 0.033 53.490

0 8 B 0.024 0.010 0.041 0.012 49.369
Table 3-8a: Mean, Maximum, Minimum, and Student Newman-Keuls Analysis Results

for Key Organic Parameters (Non-Transformed) in 1997 Surface Sediments

I i 0 181 1 17.367 1 6.500 I 32.667 I 11.267 I 64.879 I \

nC15+nC17 3 17 A 0.058 0.033 0,076 0.014 23.315

oLg/g) 2 17 A 0.056 O-030 0.094 0.017 - 30-651

1 17 A 0.048 0.025 0;085- 1 ,0.020 40.499

0 8 3 0.032 0.013 .0.069; 1 0.020 63.567. 1

h1C27+nC29+nC31 I 0 I 8 1 1 0.350 1 0.116 1 0.845 1 0.240 1 68.463 1

I hadd - .d I- 121171 A 1 0.302 1 0.171 I I

1 0.490 1 0.073 1 24.228 1

I 3 I 17 I A 1 0.253 1 0.080 1 0.385 1 0.100 39.429 t

A I’m45 t

I B 1 0.101 1 0.073 1 0.136 1 0.017 16.536

I 3 I 1 7 I B 1 0.097 1 0.052 1 0.229 1 0.042 1 42.744 I I

CPI 1 1 17 A ‘3.308 1356 5.425‘. 1:. 1.333 1 40.305

0 8 . A 3.209 1.859 7.000 1.618 50.418

2 17 A 2.626 1.618 4.579:- y&698 :-C&566

3 17’ A 2.304 1.136 4.8!1.,‘1 0.854 : 37.042

ITotal SIT 1 0 181 I 0.020 1 0.iJ0a.057 1 0.017 1 81.723 1 I I

1 2 1 17 1 A 1 0.016 1 0.007 1 0.055 1 0.011 I 68.305 t I I ~~~

I I -I-I 17 I I II -~--- MI07 0.019 0.004 32.5831 -. A 0.012 -.- 0.007 0.019 0.003 26.654

2 .i171’ A 03: 0,013 1- ^&003 ‘88:&X?

2 , J I 17 I A I ( U&O1 .m@l * ^ u.001 ” ,-34689

I 1 I 17 I A I o.ooz 0.001 - OXNM‘.

1 0 181

.O.ool 37.450

A I 0-t lo2 0.001 0.004 0.001 56.307
Table 3-8a: Mean, Maximum, Minimum, and Student Newman-Keuls Analysis Results

for Key Organic Parameters (Non-Transformed) in 1997 Surface Sediments

2 17 A B 0.313 0.228 0.393 0.044 14.196

0 8 B 0.279 0.180 0.499 0.102 36.573

0.274 1 0.244 1 -0.330 1 0.028 10.094

1 17 A 0.333 0.146 0.758 0.189 56.697

0 8 B 0.160 0.057 0.422 0.115 71.931
Table 3-8b: Mean, Maximum, Minimum, and Student Newman-Keuls Analysis Results for

Key Organic Parameters (Non-Transformed) in 1998 Surface Sediments

V.““” ,

0.316 I 0.085

I

1 i

I I

Iii1

_-

A 1 0.156 1 0.137 1

I 3 A I n1Ad I

3 8 A 33.250 24.000 42.000 6.585 19.803

2 8 A 25.750 21.000 31.000 3.576 13.886

0 8 A 25.504 6.800 54.333 18.095 70.950

1 8 A 23.583 14.000 39.000 8.180 34.686
Table 3-8b: Mean, Maximum, Minimum, and Student Newman-Keuls Analysis Results for

Key Organic Parameters (Non-Transformed) in 1998 Surface Sediments (continued)

3 8 A o.-. , -.

2 8 A 0.090 1 O!

1 8 A R

3 18 A. 1 xul89 I u-145 I 0223 I ok?3 I ‘CL026 t

1 18 . A ---

.O 18 A opt

LALK 1 4 13 A 0 .

Mk) 2 8 A 0

3 8 A 0 .

1 8 A 0 .

n Q A nA02 1 0.094 1 0.866 i 0.277 i 68.963 i

3 8 B 3.598 2.890 1 4.352 0.430 1 11.953

2 8 B 3.433 2.856 5.000 0.703 1 20.487

1 8 B 3.103 1.690 4.788 0.973 1 31.346

4 3 B 3.076 2.865 3.252 0.1% I 6.376
Table 3-8b: Mean, Maximum, Minimum, and Student Newman-Keuls Analysis Results for

Key Organic Parameters (Non-Transformed) in 1998 Surface Sediments (continued)

Total S/T 181 A I 0.030 1 0.021 1 0.072 1 0.017 1 57.514

(Udf!~ Y-v _I I 0 ISI A O-027 i 0.009 i 0.069 I 0.022 i 79.961 4 s I _- I ----. ----- ----- ----- ._._--

A 0.025 0.024 0.027 0.001 4.601

2 8 A 0.021 0.017 0.026 0.004 16.911

I

1 8 A 0.016 0.011 0.021 0.004 24.246

t (UdPl~.

-de

1I

3

-J8 -13 I1

A

I

0.004

1 I

0.004

~0.rxk.l 1

0.016

fI

0.604

I 1

74.763

v-v - I 42 '& Ai 0404 ---- 0.004 o.ooo 1312 - ---- - ----- I ----- --- --

1 0.004 o.ooz 0.005- .J "-0401. -22.640

1 1 8 .: A .o.O03 .0.002 -0m4 .J aoo1 ^ 37x21.

1 .O :-,8 A 0.002 <: :O.ool 0.004: 1” ~-0Bo1’ -‘- 41322 :

Ts/fI’s+Tm~ I 1 I 8 A 0.330 0.293 0.363 I 0.021 6.442

I 1 I

2

(81 I81

A

I 0.318 0.293 1 0.259 0.167 1

0.353 I 0.034 I 10.686 1

3 A
Table 3-9: Average Total Organics Concentrations in Surficial Sediments from Zones 0,

1,2,3 and 4 in Outermost Cook Inlet and the Shelikof Strait, Concentrations of Alaska

Marine Sediments, and Concentrations in Cook Inlet and the Shelikof Strait from

Previous Studies

1 TotalPHC 1 29.4 I 0.47 - 38 I 0.9 - 69.0 I

ITotalS/T 1 0.024 NA NA I I

aPrince William sound subtidal and Beaufort Sea (Bence, ef aZ., 1996, Boehm et aZ., 1991).

bENRI - UAA, 1995, Hyland, et aZ.,1995, ADL, 1996, KLI, 1996, KLI, 1997.
Table 340: Means, Standard Devlatlons, and Ranges of Values for Metals, Total Organic Carbon (TOC), Sand, Silt and Clay -

Std. Dev.

I I

ko.23

(1998)

Ranmt 8.1 t-8.57 I

Meai

Std. Dev.

Range

Mean

Std. Dev.

Range

0 *-

At!

(1998)

6.70-7.92

1 7.46 2.21

Eta.36 HI.17

(1997)

6.57-8.16 1.87-2+91 .

MWI 1 8.02 *-

Std. Dev. kIMi

(1998)

Range 7.53-9.37

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

2 7.48 1.86

i0.23 ko.19

wm 6.66-7.74 1.49-2.18

2 7.96 -s

a.25

(1998)

6.69-8.44

3 7.17 1.75

zt0.48 HI.13

(1997)

5.64-7.64 151-1.97

Mean

Std. Dev.

Range

3 7.99 --

a.11

(1998)

7.82-8.17

Mean

Std. Dev

Range

Mean

Std. Dev.

Range

4

(1998)

Av .of 01,

2 &ad4

(&cluding AC)

7.71 --

zto.12

7.46-7.94

7.45 2.14

ko.51 kO.61

5.64-9.37 1.26-4.57

5.64-5.83

3.98

kO.64

2.79-5.3 1

3.92

a.63

2.74-4.87

3.90

a31

3.37-4.40

4.03

io.35

-1 -- 0.59 44.4 55.6

zto.19 zk22.4 *22.2

3.42-4.48 I 1 O-32-0.92 1 12.2-68.0 1 32.0-87.8

4.28

ti.24

3.764.57

4.52

a.18

3.30-4.86

4.51

kO.08

4.38-4.71

4.53

i0.15

4.18-4.65

4.33

kO.16

4.08454

4.18

a43

I_ __

1.08-1.18 0*3-2.9 97.1-99.7

1.70 1.63 0.81 20.5 81.7

kO.17 HI.20 kO,28 k24.4 kl9.1

2.74-5.3 1 1.38-2.03 I 1.t2-2.01 I 0.26- 1.49 I O,l-84.9 I 15.1-99.9

1.38-2.03 I 1.12-1.89 I 0.3t-t.22 I 3.8-84.9 I 15.1-96.2

I

1.62 1.45 0.57 32.4 62.9

ko.20 HI.17 a.17 k22.4 GO.9

l-39-2.03 I 1.21-1.82 I 0.26-0.94 I 2.6-70.3 I 29.7-97.4

1.68 1.71 0.84 6.3 93.3

kO.07 M.08 a.14 *7s 6.9

1.42- 1.88 I 1.55-1.84 I 0.48-I .a5 I 0.10-27.18 I 72.8-99.9

I

__ -- 0.95 2.6 97.4

Al.11 k3.5 k3.5

0.80-l-15 0.4-12.2 87.8-99.6

I 1.13I A I

98.9

ko.04 ko.9

&y welghtj
Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

.

I 0.3-0.4 I 4.0-4.7 682-707 1 l-O-1.1 1 0.10-0.11 1 86.9-107 1 31.3-32.3

0 0.07 10.0 758

kO.03 rt4.2 d26 A S:E

66.3 34.1

(1997)

Lk15.8 *to.5

0.04-O. 13 3.8-16.0 5 18-924 0.89-1.40 0.04-O. 11 42.8-95.3 20.3-52.0

0 A% zk4.3 8.2 *123 775

(1998)

A:;

0.09 69.0 32.5

MI.01 d5.8 do.2

0.01-0.08 2.5-14.6 571-957 1.0-l .4 0.07-O. 11 47.5-94.6 20.3-50.3

1 0.07 8.0 814 kO.01 *2.1 Ib;.:

ti7 0.10 62.4 30.6

(1997)

iO.01 k7.i 6.4

0.05-0.09 4.8-l 1.8 708-914 1.01-1.36 0.08-o. 1 4 49.1-76.4 19.9-41.1

1 0.05 8.2 783

kO.02 k2.8 *73 Ai.;

0.10 63.1 28.8

(1998)

m.04 zt12.1 i7.0

0.01-0.08 5.3-13.1 630-888 1.0-l .4 0.08-0*16 46-O-77.1 21.4-41.9

2 0.07 9.5 854 iO.02 *I .6 *32 0.12

di.:

73.4 37.7

(1997)

ko.02 ti.3 k2.9

0.05-0.10 5.7-13.7 775-916 0.96- 1.32 0.09-0.20 59.2-80.9 29.4-41.2

2 0.06 12.0 904 m.01 *1.7 0.11

2:

k29 82.1 38.8

(1998)

10.01 k5.5 It1.5

0.03-O. 10 7.4-14.0 709-964 1.0-1.4 0.10-0.18 58.7-90.0 30.0-40.8

3 HI.01 0.09 9.0 878 2i.t

O-16

k1.3

75.2

*17

37.4

(1997)

io.02 k3.6 d.5

0.08-O. 11 7.0-13.4 826-928 1.34-l .48 0.12-0.23 65.1-80.7 33.9-41.5

3 0.06

m.00

299 888

~26

Ai30

0.15 79.9 36.5

(1998)

da.02 rt4.7 k1.6

0.05-0.07 7.4-I 1.2 846-925 1.2-1.4 0.12-0.18 69.0-85.7 33.0-38-O

4 2% 8.4 850

0.15

k1.6

78.9

*22 2:;

32.7

a01

(1998)

*3.0 k1.4

0.05-0.07 6.0-11.1 808-900 1.2-1.4 0.13-0.17 7 1.8-84.0 30.9-34.4

fy$40’1, 0.07 9.1 0.14 71.0 34.5

(&cIuding AC)

St.02 ~~2.6

826 k81 Ai.:

m.00 Al.0 k6.8

0.01-0.13 2.5-16.0 518-964 0.9-l .5 0.04-0.23 44.5-95.3 19.9-52.0

0.062-0.068 1 771-808

J::

0.023-o. 125 615-1000

0.057 830

a.035 *122

0.024-0.123 610-999

0.043 846

rto.009 *109

0.022-0.067 720-l 220

0.028-0.054 1 664-1049

0.047-0.072 1 688-2140

0.056-0.066 1 687-98 1

0.065 908

kO.003 ~169

0.062- 0.068 689-1209

0.056

I

907

kO.020 k208

0.022-o. 125 564-2 140
Table 3-10: Means, Standard Deviations and Ranges of Values for Metals, Total Organic Carbon (TOC), Sane

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

0 % 11.2 0.87

i2.3 a.34

(1998)

25.9-49.9 8.0-14.0 0.48-1.53

1 30.8 12.0 0.84

k5.3 zt1.2 Ml.14

(1997)

22.9-39.9 9.6-13.7 0.63-l .08

Mean

Std. Dev.

Range

Mean

Std. Dev.

Ranee

1 32.1 11.7 0.81

ti.2 *1.3 HI.14

(1998)

26.1-38.6 10.0-13.8 0.64-1.11

2 35.1 13.7 0.98

i3.8 ti.7 iO.07

(1997)

27.7-40.7 12.0-14.9 0.80-1.11

Mean

Std. Dev.

Range

2 37.3 13.8 1.02

zt4.0 HI.7 HI.05

(1998)

29.1-41.7 11.7-14.8 0.82-l .08

Mean

Std. Dev.

Range

Mean

Std. Dev.

Range

3 38.5 14.0 1.16

*l.l HI.3 HI.03

(1997)

35.4-39.9 13.1-14.8 1.06-1.22

3 38.6 14.4 1.08

*1.4 HI.4 m.06

(1998)

35.640.1 13.6-14.8 0.95-1.14

4 37.4 14.2 1.03

k2.4

I

HI.3 a.07 I1 9011\

I I I

AVR. of 0.1, I 35.1 I 12.8 0.97

1 33.6-40.9 1 13.8-14.9 1 0.90-1.15

1 2,3and4.

(excluding AC)

6.7 il.7 ztO.22

21.6-51.4 7.3-14.9 0.47-l .74

Mean

Std. Dev.

Range

Mean

td 4 in Oui

0.36

ti.03

0.33-0.38

0.26

HI.12

0.14-0.55

0.25

iO.11

0.24

kO.07

0.13-0.33

0.38

~~0.08

0.22-0.56

0.24

it-J.11

0.10-0.42

0.25-0.42

0.24

kO.03

0.20-0.30

0.24

HI.05

0.16-0.30

0.29

kO.10

0.05-0.56

!rmost Cook-Inlet and the Shelikof St1

1.40

I

0.37

io.06 I

176

iO.01 *4

1.33-1.44 0.36-0.37 171-179

1.50 0.41 126

iO.30 io.04 ~t26

1.01-1.91 0.32-0.49 87.0-180

1.18 0.42 132

HI.31 kO.05 *23

0.71-1.53 0.34-0.5 1 89.3-173

1.62 0.42 126

kO.20 HI.03 *ll

1.14-1.96 0.34-0.48 106-141

1.38 0.41 127

do.28 a.05 I.10

1.00-l .75 0.33-0.50 Ill-145

1.73 0.47 143

MO.08 ItO. ilO

1.51-1.87 0.40-0.50 119-159

1.60 0.46

a.15 kO.02 ‘2

119

*3.1

1.38-1.80 0.39-0.50 94.3-167 85.1-124

1.83 0.47 144

m.06 iQ.02 i7

1.75-1.95 I 0.44-0.52 I 129-154

1.73 0.50 153

EtO.05 iO.02 i5

Silt and Clay

116-126

100

*20

64.8-132

93.8

i19.2

66.0-125

98.4

~~12.4

77.7-I 17

93.3

i14.5

73.8-l 18

115

*7

100-127

126

*2

122-133

121

*4

114-126

117

*4

111-123

109

i16

66.0-133
Table 3-11: Average Metal Concentrations in Surficial Sediments from Zones AC, 0, 1,2,

3, and 4 in Outermost Cook Inlet and the Shelikof Strait, Average Continental Crust

(Wedepohl, 1995) and Average Concentrations for Bottom Sediment from the Susitna

and Copper Rivers

Metal All Zones in Study Area Continental Crust Susitna and

olg/g)* Copper Rivers

1997 1998 1997-1998

& 0.08 0.05 0.07 0.07 0.12

Al 7.29% 7.75% 7.45% 7.96% 6.94%

As 9.1 8.8 9.1 1.7 8.2

Ba 823 819 826 584 789

B e 1.2 1.2 1.2 2.4 1.23

Cd 0.12 0.12 0.12 0.10 0.20

Cr 69.1 74.8 71.0 126 66.6

cu 34.5 33.6 34.5 25 38.9

Fe 4.15% 4.30% 4.18% 4.32% 3.47%

Hg 0.054 0.060 0.056 0.040 0.038

Mn 905 893 907 716 759 -

N i 34.3 37.0 35.1 56 37.6

Pb 12.6 13.0 12.8 14.8 0.8

Sb 0.96 0.94 0.97 0.30 0.94

S e 0.29 0.28 0.29 0.12 0.2

Sn 1.66 1.46 1.60 2.3 1.67

Tl 0.44 0.44 0.44 0.52 0.36

V 134 141 137 98 119

Notes:

*Concentrations in pg/g, except where noted.

ArthwDLittle
Table 3-12: Groupings of Metals in Surficial Sediments from Zones 0, 1,2,3 and 4 in

Outermost Cook Inlet and the Shelikof Strait Based on Coefficient of Variation

Coefficient of Variation Metal

s-10% Al, Ba, K, Tl

>lO-20% Be, Cr, Cu, Fe, Mg, Ni, Pb, Sn, V, Zn

>20-30% As, Ca, Cd, Mn, Sb

>30% Ag, Hg, Se
Table 3-13: Results of the Student Newman Keuls Statistical Test Performed on

Metal/Fe Ratios from Surficial Sediments in Zones 0, 1,2 and 3
Table 3-14: Percent Survival of Eohausforius estuarius in the Sediment for Toxicity

Tests

1997 *PerFTnt SurWal in Test Replicates I

,;YMSthiient

,

2%rcent

Site Rep A .‘: .Rep B RepC kepD~,,‘l ,S&+vaI

, 6; _I ,.

Home

Control 9 5 100 9 0 100 96.25

’ Statistical analysis indicates that amphipod survival at this site was significantly less than the ‘home’ control at p< 0.05.

* Sites at which mean survival was less than 80% of mean Control survival.

See Appendix A for results of grain size analyses.
Table 3-15: Percent Survival of Ampelisca abdifa in the Sediment for Toxicity Tests

Reference 1 I 90 1 90 1 95 1 91.25

Control 1

ZOFl 100 95 8 5 90 92.5+

ZOF6 I 1 85 I 95 I 90 I go+

Z2Fl 9 5 85 95 100 93.75

Z3Fl 9 5 9 0 100 95 95t

I I I I I

z3F2 I 95 I 8 5 I 90 I 95 I 91.25+

Z3Rll 1 I 90 I 90 I loo I 95

Z3R14 1 I 100 I 90 I 95 I 95i

’ Statistical analysis indicates that amphipod survival at this site was significantly less than the ‘home’ control at p< 0.05, but not

significantly different than the ‘reference’ sediment at p<o.O.C

See Appendix A for results of grain size analyses.
Table 3-16: Sedimentation Rates (cm/y) Determined Using Excess *“Pb and 137Cs. AgeDepth Relationship Based on *“Pb Sedimentation Rate

Station Se@men,tatign Rate

ID (cdy) :

Depth,.

,198O c

(cm)

I 210 Pb

97-ZO-Fl 1 ND 1 -- ~~~~ I N A

9%ZO-Fl -I- 1.3 I-- 1.5 I 2 2

97-ZO-F5 1 0.24 I

97-ZO-F6 1 0.10 I 0.10 I 2

97-ZO-FS 0.27 -- 5

97-Zl-Fl 0.24 0.21 4

97-Zl-F2” -- I 0.27

9%Zl-R3B 0.20 I 0.20 I

97-Z2-Fl -- 2 2 WI I ww

97-Z2-F2 0.62 1 0.65 1 29 I [481

98-Z2-R16 0.5-0.7 1 0.7-0.8 1 -- I

-- --

97-Z3-Fl 1 0.60~ I

0.61 7 1 0 2 8 I r371

97-Z3-F2 1 0.44 1 0.45 I

9%Z4-F4 1 .o (O-20 cm) 0.84 18 -q-z0.52 (20-43 cm)

Notes:

[ ] = depth exceeded core length

ND = not determined, sedimentation rate too fast

NA = not applicable

*Agedepth relationship based on 13’Cs sedimentation rate
Table 3-17: Means and Standard Deviations for Total Organic Carbon (TOC), Sand, Silt

and Clay Values for Sediment Cores from Zone 0, 1,2,3 and 4 in Outermost Cook Inlet

and the Shelikof Strait

97-ZO-Fl

I

1.06 6.0

HI.08 k3.3 I

43.4

r12.5 I

50.6

k11.9

9%ZO-Fl I 2iE I 13.0 I 64.7 I 22.4

kg.6 k7.8 27.6 I

97-ZO-F5

I 2:; I

30.6 I 25.6 I 43.9

A5.7 k15.0 k15.9 I

97-ZO-F6 0.34 50.5 17.1 32.4

&OS-M Hi9 212.5 k11.2

9%ZO-F8 0.36 53.5 30.2 16.3

a.03 24.2 24.7 Id.7

97-Zl-Fl 0.62 35.8 28.0 36.2

a.08 k11.0 ~16.0 k15.0

97-Zl-F2 0.75 17.8 34.7 47.6

zkO.12 ti.6 ~16.1 k12.0

9%Zl-R3B 0.31 59.6 29.5 10.9

20.09 a.1 a.6 St.1

97-Z2-Fl I 0.78 I 3.3

ko.04 k1.3

I 34.8

do.8

I 61.9

~10.8 I

97-2242 I ii.?1 I 2 I 39.0 I 60.0

A19.5 kl9.7 I

98-Z2-R16

I

0.84

I

5.1

M.04 +1.8 I

97-W-F1

I

0.83

2:; I

44.3

I

53.5

a.06 k15.3 k15.1

97-2342

I

0.81 I A I 39.3 I 59.2

HI.09 A10.4 ~10.6 I

98-Z4-F4 I dI.06 1.08 I k1.71.7 I 61.2

6.4 I 37.1 26.9 I

All Samples I 0.74 I 19.5 I 40.8 I 39.7

a.27 zk21.7 e18.6 219.2

R=lF I 0.21-1.24

I

0.2-67.8

1997-1998 I

3.1-79.4

I

4.7-83.2

I
Table 3-18: Mean and Standard Deviation of Total Organic Parameters for Sediment Cores from Zones 0, 1,2 ,3 and 4

1997 1 0 Fl 46.9 k6.71 0.316 kO.047 0.082 + 0.010 1 1.06~ 0.081

1998 1 0 1 Fl 1 40.5 f 7.51 I 0.357 *0.042 I 0.082* 0.011 I 1.04 f 0.135

1997 1 i 1 F5 1 11.0 f 3.63 I 0.127 f 0.017 I 0.016 * 0,002 ~ I 0.438 f 0.026

1997 1 0 1 F6 1 12.1 f 2.84 I 0.115 f 0.015 I 0.010 + 0.001 I 0.344 20.043

1998 1 0 1 FS 1 5.71 f 1.41 I 0.109 i 0.018 I 0.014 f 0.002 I 0.361 f 0.035

1997 1 1 1 Fl 1 19.5 f 4.95 I 0.518 4 0.114 I 0.021 f 0.005 I 0.619 -co.081

1997 1 1 f F2 1 16.6 f 2.97 I 0.595 40.079 I 0.015 f 0.002 I 0.757 AI 0.116

1997 I 2 1 Fl 1 27.1 26.08 I 0.427 kO.055 I 0.025 ~0.003 I 0.776 kOo.041

1997 1 2 1 F2 1 36.1 k5.76 I 0.684 10.055 I 0.022 *0.003 I 1.003 f 0.114

1998 I 2 I Rl6 I 30.6 f8.30 I 0.743 10.034 I 0.029 4 0.004 I 0.844 f0.038

1997 1 3 1 Fl 1 30.8 A 10.3 I 0.493 ItO. I 0.016 it: 0.004 I 0.834 + 0.081

1997 1 3 1 F2 1 24.4 A 11.9 I 0,558 iiO.069 I 0.021 f 0.004 I 0.806 f0.086

1998 1 4 1 F4 1 21.3 f 4.42 I 0.687 kO.041 I 0.029 AZ 0.002 I 1.08 f 0+061

I Range I I 4.3 - 56 I 0.074 - 0.805 I 0.008 - 0.100 I 0.28 - 1.24
a%wI IIV P6’S - OS’8 61’1 - 68’2 OS’Z - 3 PI Sf’I - PI’Z 10’1 - 10-z IZ’O - PZ’I Z-0 - 8’L9 I’!2 - P’6L L’P - 2X8

usa&q pus 8S’L 66'1 pz’tr 9L’I 99’1 PL’O 5’61 8’OP L’6E

I 80’ L'I Z'I9 I'Lf ** 8p’P Pmz-86 _- -- f1'8

K-1 f8'1 6E’P 8L’I 81'1 18'0 S'I C’6E Z’6S zd-fz%

OO’L I 28’ IP'P 9L’I I LL’ E8’0 E'Z E'PP S'fS Id%Z-L6

V8.0 I'S 9’99 C’8Z 9m-zz-86 -_ -- 8P’P -- 86’L

OE’L 59'1 ZP'P 89'1 I 6L’ 00'1 0'1 0’6E 0’09 Zd-ZZ-L6

EP’L I L6’ 'P Pf f9'1 PL’I 8L’O f’ f 8’PC 6'19 Ed-ZZ-L6

If'0 9’6s S’6Z 6'01 SKII-IZ-86 -* - - Zf'f -* L9’L

LL’9 If.2 107 86'1 9S'I SL’O 8'11 L’PE 9’LP Zd-IZ-L6

!

PL’L LI'Z ZO'P 8S'I LP’I Z9’0 8’SE 0’82 Z’9E Id-TZ-Lti

9f’0 S’fS Z'OE f-91 &I’-02-86 -- - - PS’C -* PL’L

9L’L 8f’Z 96% f8’1 ES’1 Pf'O S'OS I'LI P’ZE 96-OZ-L6

91-L 8Z’Z Z6’f EL’1 WI VP’0 9’Of 9’SZ 6’EP Sd-OZ-LC

WI O’fI WL’ P’ZZ es LL’P WOZ-86 -- _- 18'L

9.0s 16.OZ-L6

WNU!p~S Sal03 UJOJj WJOZ ‘0 1 ’ ‘2 8 pue p u! ISOUJJa~nO A003 IallJl pUe @yl iOy!lWjS t[eJlS Alp) (U#!aM

algel :61-C sueayy pU8 pJepUB~S suo!le!naa JOJ CKN3Jl ‘slelaw le$oi 3!ueBJ() uoqJe3 ‘(301) ‘PUPS lI[S pufl Ae13 sanlen JO!

I

1

F;

d3d9d3d3

d3d%d3d3

t-i 8

dfds

d3d8d3

d

;?

d

zl

I

cc,

v!

d

Pi w

z9
Table 3-20: Analysis of Post-1963 Shifts in Organic Indices

Pexylene 0.1035 -0.0026 0.0003 -0.0024 0.0027

Pristane 0.1161 0.0064 0.0001 0.0069 0.0058

Phytane 0.0403 -0.0005 0.0266 -0.0004 0.1537

TPHC 0.1303 2.7406 0 2.673 1 0.0003

T19-Hopane 0.0049 0.000 1 0.4445 0.0001 0.3604

Total PAH 0.057 -0.0157 0.008 1 -0.0174 0.1631

Petrogenic PAH 0.0454 -0.0125 0.0184 -0.0154 0.1606

Pyrogenic PAH 0.0079 -0.0006 0.3295 -0.0008 0.3093

IC2DK2P 1 0.1021 1 0.0073 1 0.0003 1 0.0067 1 0.0011

OleananeJHopane 0.0165 -0.0244 0.1583 -0.0122 0.6038

T21/T22 0.0625 0.0144 0.0055 0.0115 0.318

nC16/(nC15+nC17) 0.0002 0.0005 0.8801 -0.0008 0.8846

CPI 0.0006 0.0155 0.7848 0.0515 0.4918

Pyro/Petro 1 0.0003 1 0.0002 1 0.8573 1 0.0002 1 0.8859

ITOC 1 0.0551 1 0.0224 1 0.0109 1 0.0277 1 0.0106

Notes:

’ Negative sign indicates parameter increases with increased depth, positive sign indicates parameter decreaw with increased

depth.

’ Significance is established at pd.05
Table 3-21: Analysis of Post-l 963 Shifts in Iron Normalized Metals

.

Tin 0.0001 -0.0041 0.8999 -0.0179 0.6987

Vanadium 0.0027 0.5536 0.5752 1.1589 0.2994

Zinc 0.0249 -1.1095 0.0891 -1.031 0.3864

Notes:

’ Negative sign indicates paramem increases with increased depth, positive sign indicates parameter decreases with increased

depth.

’ Significance is established at p4.05.
Table 3-22: MMS Stations Where Fish Liver Tissue Samples were Collected for Chemical Analysis

1997 Cruise

Notes:

ns - none sampled

The numbers indicate number of fish samples collected for analysis. In most cases these samples represented liver composites, however, individual fish samples (i.e., noncomposites) were collected under circumstances where multiple individuals were not caught.
Table 3-23: Average PAH Concentrations (in pg/g dry weight) Detected in Fish Tissue

Samples and Comparison to PAH Concentrations in Procedural Blanks

Blank1 1 0.024 0.009 0.016 0.013

Blank2 1 0.033 0.005 0.006 0.020

I Halibut I

Zone 0 0.018 0.007 0.027 0.003

Zone 2 0.032 0.012 0.032 0.002

Zone 3 0.025 0.012 0.052 0.001

1 Arrowtooth Flounder I

Zone 2 0.028 I N D I 0.012 I N D

Black Cod

Zone3 1 0.020 I 0.009 I 0.014 I N D

1998 cruise

Blank 1 0.003 ND 0.002 0.013

Blank 2 0.007 0.005 0.005 0.015

Blank 3 0.010 0.005 0.002 0.014

Halibut

Zone 1 0.018 0.008 0.008 0.004

Zone 2 0.018 0.009 0.011 0.007

I Zone3 I 0.03 1 I 0.005 I 0.011 I 0.002 I

Paclific cod

Zone 1 0.008 0.008 0.005 0.002

Zone 2 0.014 0.010 0.006 0.002

Zone 3 0.007 I 0.004 I 0.004 I 0.002

Arrowtooth Flounder

Zone2 1 0.012 I ND I 0.005 I N D

I

I I I

Zone3 I 0.014 I N D I 0.005 I N D I

Skates

Zone 1 0.009 0.005 0.004 0.001

Zone3 I 0.012 0.003 0.004 2.7

Black Cod

Zone 3 0.014 I 0.006 I 0.007 I 0.001

Notes:

ND=Not Detected
Table 3-24: Mean Total PAH Concentrations (in pg/g dry weight) Detected in Fish Tissue

1997 Cruise

1 Blanks 1 2 I 0.063 I 0.002 I 0.062 - 0.064 I

Halibut

Zone 0 6 0.093 0.033 0.057 - 0.136

Zone 2 4 0.149 0.073 0.059 - 0.235

Zone 3

Arrowtooth Flounder

Zone2 1

1 I 0.143 I N A I N A

1 I 0.052 I N A I N A

Black Cod

Zone 3 1 I 0.070 I N A I N A

1998 cruise

Blanks 1 3 I 0.03 1 I 0.007 I 0.023 - 0.036

HaGbUt

Zone 1 4 0.079 I 0.022 0.056-0.110

Zone 2 5 0.106 0.042 0.060 - 0.160

Zone 3

Pacgic cod

Zone 1

Zone 2

Zone 3

Arrowtooth Flounder

Zone 2

Zone 3

3 I 0.107 I 0.098 I 0.048 - 0.220

4 0.065 0.021 0.036 - 0.085

6 0.073 0.058 0.34 - 0.180

3 0.030 0.011 0.022 - 0.042

1 0.028 NA NA

1 0.032 NA NA

SkUtCS

Zone 1 1 0.047 NA NA

Zone 3 1 2.7 NA NA

B&&Cod

Zone3 I 1 I 0.048 I N A I N A

Notes;

NA = not applicable since only one sample is considered
Table 3-25: Trace Metal Concentrations In Liver Composite Samples for tialibut, Arrow Flounder, Black Cod, Pacific Cod and Skate (dry weight)

Halibut

-~~

Mean

Std. Dev.

0

1997

(n* = 6)

0.072 15.9

kO.036 lt3.3

-+-

0.024 15.1

~0.006 *3.3

169

*71

0.074 10.5

Gto.029 *5.1

11.0 0.055 N.D. 4.1

*4.0 kO.020 *l.O

Mean

Std. Dev.

1

1998

(n* = 4)

303

*15

16.8 0.050 N.D. 6.6

Et5.5 kO.026 *I.2

0.073 4.9

ztO.018 kO.6

263

k258

Mean

Std. Dev.

2

1997

(n* = 4)

0.045 12.7

kO.013 k7.1

0.104 6.4

*to.041 k2.6

29.8 0.092 N.D. 5.0

*3.4 rto.039 *l.l

Mean

Std. Dev.

2

1998

(n* = 5)

194

A105

0.064 8.2

*0.017 k2.8

15.3 0.084 N.D. 4.3

k4.8 *0.014 kO.6

0.084 10.8

fco.043 *1.9

0.051

~~ --I Mean 3 15.3 197

1997

(n* = 1)

0.100 6.2 22.0 0.082 N.D. 4.3

Mean

Std. Dev.

3

1998

(n* = 3)

0.084

I

4.7

*0.034 kO.6

163

zt52

0.019 11.6

kO.006 k4.2

26.5 0.010 N.D. 4.3

lt7.4 *o.oo 1 kO.3

Arrowtooth Flounder

Mean 2

1997

(n* = 1)

0.044 5.9 21.4 0.078 1 N.D. 1 4.7 1 0.075 1 11.1 688

21 Mean 2 195

1998

(n* = 1)

0.023 0.024 N.D. 2.2 0.041 9.5

Mean 3 138

1998

(n* = 1)

0.024 1.5 22.6 0.011 N.D. 1.7 0.022 9.9
ds

of

d0

ifi

d3d

53

d

ob

d

\o

iid2dzi d

dQ

tid

09z

N

c!

2

a cj m d8

d5
I I )

Table 3-25: Trace Metal Concentrations in Liver Composite Samples for Halibut, Arrow Flounder, Black Cod Pacific Cod and Skate (dry weight) (cont.)

Halibut

EL-&y

0.129 3.3 0.028

io.117 kO.2 zto.009

0.003 0.134 82.4

Ito. 1 zbo.044 *9.7

0.007 6.7 0.20

*to.010 *0.3 *0.09

0.004 5.0 0.14

zto.002 f1.9 *0.05

0.158 3.3 1.18 0.050

kO.046 itO. kO.27 kO.025

0.002 0.180

*O.OOO kO.046

-t

0.004 0.283

io.00 1 to. 142

84.2

*9.9

Mean

Std. Dev.

1

1998

W = 4)

0.027 0.004 7.3 0.19

*O.Ol 1 *O.OOl lt2.9 io.05

102.7

a25.9

Mean

Std. Dev.

2

1997

(n* = 4)

0.382 4.5

*o. 197 Ito.

4.6 2.0 0.286 0.003 6.6 0.122 0.002 0.245 89.3

kO.6 *o.o *OS3 1 zko.002 kO.8 kO.052 *o.ooo *o-o44 k6.3

Mean 2

Std. Dev. 1998

(n* = 5)

Mean 3 0.026 0.003 6.7 0.22 0.003 0.224 83.1

1997

(n* = 1)

Mean 3

Std. Dev. 1998

(n* = 3)

Arrowtooth Flounder

0.181 3.7

1.5

io.2

0.034

*to.022

0.003 4.5

I I

0.090

*O.OOl *0.7 *to.057

78.7

k4.0

0.001 0.230

*o.ooo kO.024

“‘“”

Mean

Mean

Mean

2 0.096 2 . 9 0.012 0.003 8.1 0.31 0.002 0.169

1997

(n* = 1)

22 0.054 2.4

I I

0.83 0.026 0.002 2.5 0.036 0.001 0.111

1 9 9 8 

(n* = 1)

0.026 1 0.002 1 2.5 1 0.036 1 0.001 1 0.11;

3 0.049 1.9

I I

1.0 0.015 0.002 1.7 0.094 0.001 0.089

1998

(n* = 1)

72.6

~-

5 3 . 8 

5 1 . 9 
Table 3-25: Trace Metal Concentrations In Liver Compostte Samples for Halibut, Arrow Flounder, Black Cod Pacific Cod and Skate (dry weight) (cont.)

Black Cod

Mean 3 0.176 2.2 0.112 0.003 3.5 0.12 0.006 0.101 52.5

1997

(n* = 1)

Mean 3 0.099 2.4 1.0 0.040 0.004 2.5 0.02 1 0.004 0.093 46.6

1998

W = 1)

Pacific Cod

Mean

Std. Dev.

Mean

Std. Dev.

Mean

Std. Dev.

Skate

1 0.085 4.3 0.88 0.037 0.016

1998 *0.055 *1.2 kO.27 *0.024 *0.004

(n* =4)

2 0.118 3.2 1.3 0.08 1 0.020

1998 kO.055 io.9 kO.3 kO.086 io.007

(n* = 6)

3 0.094 4.4 1.2 0.023 0.015

1998 kO.02 1 zto.9 io.2 *to.009 *0.002

(n* = 3)

3.1 0.057 0.002 54.8

*l.l *to.035 *O.OOl *10.3

3.8 0.083 0.003 0.211 64.0

k1.4 kO.05 1 *to.001 kO.076 *16.6

4.3 0.072 0.003 0.178 62.3

i0.6 YO.040 *o.ooo CtO.046 *5.2

Mean 1 0.012 0.9 0.42 0.009 0.002 0.48 0.036 0.001 0,054 17.3

1998

(n* = 1)

Mean 3 0.079 1.4 0.73 0.009 0.002 0.59 0.023 0.001 0.083 24.4

1998

(n* = 3)

Flounder+

Mean Atlantic 0.31 4.8 0.33 1.4 N.D. 6.2 0.33 N.D. N.D. 116

(n* =44)

Notes:

* number of samples

+ P.J. Hanson, 1997
Table 3-26: Mercury Concentrations in Flesh (Muscle) Samples for Halibut

Halibut

Mean

Std. Dev. (n* = 4)

Range

Mean

Std. Dev. (II* = 12)

Range

Mean

Std. Dev. (n* = 4)

Range

Mean

Std. Dev. (II* = 17)

Range

Mean

std. Dev. (Il* = 4)

Range

Mean

Std. Dev. (n* = 12)

Range

Notes:

*n = number of samples

0 0.721 0.149

1997 zto.667 +0.133

0.128-1.63 0.028-0.326

1 0.561 0.113

1998 szo.405 kO.089

0.111-1.65 0.022-0.363

2 1.494 0.299

1997 +1.070 kO.214

0.345-2.43 0.069-0.486

2 0.712 0.133

1998 kO.307 *0.055

0.266-1.38 0.056-0.248

3 0.659 0.135

1997 rt0.142 kO.03 1

0.478-0.927 0.096-O. 164

3 0.629 0.121

1998 *to.353 kO.061

0.139-1.44 0.029-0.245
1 F 1 0 I 0 I 0 I 9 I 0 I 0 I 7.5 I 1 2 I

12 ? 0 1 0 1 0 1 7.5 1 0 I 0 1 9 1 9

13 1 F I 0 I 0 I 0 I 0 I 0 0 I 1 I 1 2

AlTOWtOOthl F 0 0 0 1 0 0 7.5 0

Fkmllda

2 F 2 6 0 3 0 0 4 0

3 M 0 0 0 1.5 0 0 7.5 0

4 M 0 0 0 3 0 0 6 0

zQlle3

Halibut 11 ? 0 I 0 I 0 I 0.75 I 0 I 0 I 1 I 0
1 I 121 I NIS I 0 I 0 I 0 I 0 I 2 I 0 I 0 I

Notes:

NIS - Not in Section

AMurDLittle

Table 3-28: Mean CYPlA Scores in Pacific Halibut Cell Types by Zone

I 1997 Cruise I

Zone 0 9 2.44 4.31 9.63

Zone 2 15 1.25 1.9 6.73

I Zone 3 I 7 I 1.71 I 3.93 I 5.43 I

I Probability I I NS I 0.007 I NS I

Notes:

NS - not significant
Table 3-29: Transformed Percent Survival (transformed by silt) and Each Target Metal

and AVS for 1997 Twenty-Station Sediment Data Analysis

I Silt + Clay

I AVS 0.659

I As

I Ba

I Be

I Ca

I Cd

I C r

I CU

I F e

I Hg

I K

I Mg

Mh 0.642 0.127

Ni 0.596 0.561

P b 0.601 0.463

Sb 0.629 0.187

Se 0.606 0.387

S n I 0.603 I- 0.439

V 0.229

zn
Table 3-30: Summary of Surrogate Percent Recoveries

%Rec = Percent Recovery

QC = Quality Control

n = Number of Samples

SD = Standard Deviation

RSD = Relative Standard Deviation

PAH = Polycyclic Aromatic Hydrocarbons

SHC = Saturated Hydrocarbons

S/T = Steranes and Triterpanes

na = Not Applicable

& = Qualifier is outside acceptable range

ArthwDLittle
Table 3-31: Summary of Laboratory Control Spike Recoveries

1997 Redts Sediiefii .(n+9)’ W&x @I) Oil (n=l) _’ ^

Notes:

‘n=ll for SHC

n = Number of Samples

SD = Standard Deviation

RSD = Relative Standard Deviation

%Rec = Percent Recovery

PAH = Polycyclic Aromatic Hydrocarbons

SHC = Sahmted Hydrocarbous

& = Qualifier is outside acceptable range
Table 3-31: Summary of Laboratory Control Spike Recoveries (continued)

n = Number of Samples

SD = Standard Deviation

RSD = Relative Standard Deviation

%Rec = Percent Recovery

PAH = Polycyclic Aromatic Hydrocarbons

SHC = Saturated Hydrocarbons

& = Qualifier is outside acceptable range
Table 3-32: Standard Reference Material (SRM) Summary

n = Number of Samples

’ n = 5 for iudeno[l,2,3,-c,d]pyrene, dibenzo[a,h]mhracene, benzo[g,bi]perylene

PAH = Polycyclic Aromatic Hydrocarbons

%DIF = Percent Difference

na = Not Applicable

& = Qualifier is outside acceptable range
Table 3-32: Standard Reference Material (SRM) Summary (continued)

n = Number of Samples

’ n = 6 for indeno[ 1,2,3,-c,d]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene

PAH = Polycyclic Aromatic Hydrocarbons

%DIF = Percent Difference

na = Not Applicable

& = Qualifier is outside acceptable range
Table 3-33: Control Oil Summary for North Slope Crude

PAH = Polycyclic Aromatic Hydrocarbons

n = Number of Samples

SD = Standard Deviation

RSD = Relative Standard Deviation

%DIP = Percent Difference

& = Qualifier is outside acceptable range
Table 3-33: Control Oil Summary for North Slope Crude (continued)

1n-Dodecane 1 3880 197 1 1 5.1 1 3950 144 1 1 3.6 1 4000 \ -3 1 -1.2

1 n-Tridecane 1 3700 t 220 1 5.9 1 3780 1 166 1 4.4 1 4000 1 -7.5 i -5.5 I I I I I I . I I

Isoprenoid RRT 1380 1 1050 1 74.5 1 7.1 1 1050 1 179 I 1 7 I 1000 I 5 1 5.0

n-Tetradecane 1 4030 1 388 1 9.6 1 4230 1 456 1 11 I 4200 I -4 I 0.71

Isoprenoid RRT 1470 1370 72.4 5.3 1410 144 10 1400 -2.1 0.71

n-Pentadecane 3540 210 5.9 3680 225 6.1 3700 -4.3 -0.54 I

n-Hexadecane 3210 139 4.3 3250 207 6.4 3200 0.31 1.6

Isoprenoid RRT 1650 1510 96.1 6.4 1520 204 1 3 1500 0.67 1.3

n-Heptadecane 3020 174 5.8 3150 168 5.3 3200 -5.6 -1.6

Pristane 2030 154 7.6 2120 106 5.0 2200 -7.7 -3.6

n-O&&cane 2790 141 5 2690 239 8.9 2900 -3.8 -7.2

Phvtane 1480 101 6.8 1490 131 8.8 1600 -7.5 -6.9

n-Nonademne

n-Eicosane

1 2550 1 160 I 6.3 I 2530 I 187 I 7.4 I 2600 I -1.9 I -2.7 I I I I I I I I I

1 2560 1 199 1 7.8 1 2320 I 185 I 8.0 I 2700 I -5.2 I -14

n-Heneicosane 1 2260 1 145 1 6.4 1 2340 1 99.6 1 4.2 1 2400 1 -5.8 1 -2.5 I I I I I I I I I

nDocosane 1 2120 I 115 I 5.4 I 2130 I 77.8 I 3.6 I 2200 I -3.6 I -3.2

n-Tricosane 1950 74.3 -3.8 2040 90 4.4 2m -2.5 2.0

n-Tetracosane 1790 70.4 3.9 1850 67.4 3.6 2000 -10 -7.5

n-Pentacosane 1690 74.3 -4.4- 1720 62.2 3.6 1700 -0.59 1.2

n-Hexacosane 1450 64 4.4 1440 51.5 3.6 1500 -3.3 4.0

n-Heptacosane 1080 67.6 6.2 1120 38.9 3.5 1200 -10 -6.7

n-Octacosane 859 38.3 4.4 841 36.5 4.3 880 -2.4 -4.4

n-Nonacosane 761 40.5 5.3 788 72 9.1 810 1 -6 1 -2.7

n-Triacontane 636 38.5 6 651 61.4 9.4 650 1 -2.2 1 0.15

n-Hentriacontane 555 36.4 6.6 580 41.3 7.1 580 -4.3 0.0

n-Dotriacontane 451 25.6 5.7 424 56 1 3 440 2.5 -3.6

n-Tritriacontane 390 20.4 5.2 357 38.4 1 1 400 -2.5 -11

n-Tetratriacontane 348 3 1 8.9 328 37.9 12 350 -0.57 -6.3

n-Pentatriacontane 353 20.2 5.7 372 53.3 1 4 350 0.86 6.3 I , I I

n-Hexatriacontane 223 17.5 7.8 235 14.4 6.1 230 -3 2.2

n-HeDtatriacontane 222 13.7 6.2 219 32.3 1 5 230 -3.5 -4.8 1 I I I I a I I I I

n-Octatriacontane 1 207 1 16.3 1 7.9 1 216 1 22.7 1 10 1 220 1 -5.9 1 -1.8

I n-Nonatriacontane 1 167 I 16.7 I 10 I 164 I 19.8 I 12 I 180 I -7.2 I -8.9 I I I

n-Tetracontane 173 17.2 9.9 165 19.8 12 1 190 -8.9 1 -13

Total Resolved Hvdrocarbons 205000 16000 7.8 204000 11600 5.7 I220000 -6.8 I -7.3
Table 3-33: Control Oil Summary for North Slope Crude (continued)

Notes:

S/T= Steranes and Triterpanes

n = Number of Samples

SD = Standard Deviation

RSD = Relative Standard Deviation

BDIP = Percent Difference

& = Qualifier is outside acceptable range
Table 3-34: Control Oil Summary for Cook Inlet Crude

.

Dibenzo[a,h]ant.hracene 3.17 0.32 10 3.38 0.18 5.3 3.2 -0.94 5.6

Benzo[g,h,i]perylene 4.51 0.49 1 1 4.73 0.53 1 1 4.4 2.5 7.5
Table 3-34: Control Oil Summary for Cook Inlet Crude (continued)
Table 3-34: Control Oil Summary for Cook Inlet Crude (continued)

Notes:

PAH - Polycyclic Aromatic Hydrocarbons

SHC - Saturated Hydrocarbons

VT - Steranes and Triterpanes

n - Number of Samples

SD - Standard Deviation

RSD - Relative Standard Deviation

%DIF - Percent Difference

& - Qualifier is outside acceptable range

na - Not Applicable
Table 3-35: Results for Standard Reference Material (SRM) BCSS-1 and MESS-2, Marine Sediment Samples issued by the

National Research Council of Canada (NRC)

SRM-BCSS- 1

This Study (n = 12)

1997

SRM-BCSS- 1

This Study (n = 6)

1998

SRM BCSS-1

NRC Certified

SRM MESS-2

This Study 1997

SRM MESS-2

This Study 1998

SRM MESS-2

NRC Certified

Spike Recovery (%)

1997

Spike Recovery (%)

1998

0.12 6.17 10.8

*0.02 iO.08 H.8

0.11 6.30 10.5

*to.02 io.17 zt0.3

98.7

k9.2

60.8

I I

102 94.4

d9.2 *4 zt11.8

336 1.3 0.55 0.27 113 18.8 3.31 0.035”

*7 iO.06 zto.02 *o-o1 *3 io.4 iO.08 sto.00 1

333 1.3 - - 0.25 117 18.7 3.33 --

*5 *o. 1 io.01 A7 io.5 kO.08

Notes:

Values in parenthesis are for reference only; SRM not certified by the NRC or NIST.

*SRM 1646a, issued by the National Institute of Standards and Technology ( NIST) was used for Hg, 1997 (Digest 1 and 2).

N.A. = Not Available.
/ )

Table 3-35: Results for Standard Reference Material (SRM) BCSS-1 and MESS-2 Marine Sediment Sample, Issued by the

National Research Council of Canada (NRC) (continued)

SRh4-BCSS-1

This Study (n = 12)

1997

SRM-BCSS- 1

This Study (n = 6)

1998

-

SRM BCSS-1

NRC Certified

SRM MESS-2

This Study 1997

SRM MESS-2

This Study 1998

SRM MESS-2

NRC Certified

Spike Recovery (%)

1997

Spike Recovery (%)

1998

~ 1.82 1.39 233 55.0 23.7 0.66 0.42

*to.01 *0.04 &8 *1.9 *0.4 5EO.04 *0.03

-- -- 230 53.9 23.6 0.67 0.45

*3 lt2.0 *l.l kO.05 *0.04

I

1.80 1.47 229 55.3 22.7 0.59 0.43

lto.03 *0.14 +15 k3.6 *3.4 kO.06 kO.06

-- -- -- -- -- _ _ --

I I I I I I I , -- 1 -- 1 -- 1 -- 1 -- 1 -- 1 --

2.11 0.56 94.1 114

AO.09 lto.01 k6.9 *6

2.03 0.55 91.6 111

zto.22 20.02 zt2.2 +2

-- I -- I -- I -- -- I -- I -- I -- -- 1 __ / -- 1 -_

2.12

*to.05

2.19

*0.09

2.07

*0.05

2.14

*0.03

N.A.

N.A.

Notes:

Values in parenthesis are for reference only; SRM not certified by the NRC or NIST.

*SRM 1646a, issued by the National Institute of Standards and Technology was used for Hg, I997 (Digest I and 2).

N.A. = Not Available.
Table 3-36: Results for Standard Reference Materlal (SRM) 1566a, an Oyster Tissue Issued by the National Institute of

Standatds & Technology (NW), SRM DORM-2, a Dogfish Muscle Certified by the National Research Council of Canada

SRM 1566a (n = 1)

(This Study, 1997)

1.74 I 210

I

13.8

I

ms

SRM 1566a (n = 1)

(This Study, 1998)

1.74

I

211 I 13.7 I 2.05 0.01

I

4.08 1.10 66.2 534

SRM 1566a

(NIST Certified)

-c

I

4.15

kO.38

1.43

~~0.46

66.3

*4.3

1.68 203 14.0 --

kO.15 i12.5 kl.2

-- -s cw 5 13.4 /q/L

513.4

SRM 1643d* (n = 1)

(This Study, 1997)

12.44

I

--

PFL9k

SRM 1643d* (n = 1)

(This Study, 1998)

SRM 1643d*

(NET Certified)

--

SRM DORM-2 (n = 1)

(This Study, 1997)

0.053

I

10.3

I

17.2

I

2.35 N.D.

I

N.D. 32.7 2.49 148

0.041 I lo:; I f;p I -*

Eto.013

-- I 0.043

iO.008

34.7

*5.5

2.34

&O. 16

142

*lO

SRM DORM-2

(NRC Certified)

3.51

I

23.0

I

20.6

I

1.90 0.01 I SRM TORT-2 (n = 1) 26.8 0.66 100 100

(This Study, 1998)

SRM TORT-2 106

Spike Recovery (%)

Liver (1997)

108

*l

91.4

kO.6

99.1

k1.8

Spike Recovery (%)

Liver (19981

92.9

I

94.2 I 101

lt2.2 s6 I

97.7

k3.6

99.6

I

93.8

zt7.0 zt3.6

99.6

k9.2

Values in parenthesis are for reference only; SRM not certified by the NRC or NIST.

* SRM 1643d, a water sample certified by NET.

N.D. = Not Detected.
Table 3-36: Results for Standard Reference Material (SRM) 1566a, an Oyster Tissue lissued by the National Institute of

Standards & Technology (NIST), SRM DORM-2, a Dogfish Muscle Certified by the National Research Council of Canada

aancreas Standard from the NI

-- I SRM 1566a (n = 1) 0.362 0.012

(This Study, 1997) I

0.069

I

Il.5 2.15 2.73 0.009 4.77 837

SRM 1566a (n = 1) 2.33 1 0.382 1 0.008 2.20 2.62 0.005 4.70 820

(This Study, 1998) I o*068 I 11*1

2.21

i 0.24

(3) 4.68 830

*0.15 *57

SRM 1566a

(NIST Certified)

SRM 1643d* (n = 1)

(This Study, 1997)

0.0642 12.3

*0.0067 kl.5

-1 -- I 54.6

Pfa

-- 7.45

M5

--

I

sI

SRM 1643d* (n = 1) 55.0 7.36

(This Study, 1998) I -- I --

--

__ 7.28 pg/L

*0.25

SRM 1643d*

(NET Certified) I -+ I --

SRM DORM-2 (n = 1)

(This Study, 1997)

-- I 0.068 I 0.026 1.49 0.025 0.005 0.220 24.8

-- 1 0.g 1 -- 1.40

*0.09

( 0.023) (0.004) 25.6

k2.3

SRM DORM-2

(NRC Certified)

SRM TORT-2 (n = 1)

(This Study, 1998)

1 0.28 1 12.8 2.33 0.338 0.024 5.37 0.051 0.011 I.57 181

SRM TORT-2 I 0.27 I 13.6 5.63 ( 0-w 1.64 180

ltO.67 *o-19

94.6 94.6 90.0 91.6

k3.0 f 5.9 *l.O zt2.0

Spike Recovery (%)

Liver( 1997)

93.7

k2.6

Spike Recovery (a)

Liver (1998)

92.8 100 93,5 95.0 95.9

k2.8 *7 *5.3 i4.4 k4.0

Values in parenthesis are for reference only; SRM not certified by the NRC or NIST.

* SRM 16436, a water sample certified by NIST.

N.D = Not Detected.
6'P6 9'101 '

ZOI 9'16

936 L'U

Z-96

O-E6

9'08

Z’S6

‘V’O’IN

8'06

I'9f.

ZOI

ZOI

1'86

VP1

L'P6

2'66

0'18

0'9s

‘a% 1 

--

_-

600’0r

260'0

S'S6

100'0~

980'0 I- _-

9000'0r

PEIO’O -- -- -3

IEIO'O -- -- --

Lo-or

WI

OI’Or

11-v

O’SF

9'86

9

SE1

ZZ’or

WE

8'0r ZIT

P’EZ PIP

(P%WQ.LSIN)

INIS *POLZ

91'0r

11'9 --

Eo’or

OS'1

SO’OT EI'Or Or

80-C 8S'E IEI

91

6oP

z-or

Z’VZ

EO’07

 I ZP’O ~

s?uL) ‘XPW (8661

Jws *imz u) = (z

9O'OT

SO'9

OZooo’0~ 8EOO'Or 6HM-YOr

ES810'0 sozo'o 2160'0

82000'0r LEOOO'O~

!mIO’O LWOO'O

68OO'OT

S9OS'O

EUHW)'OT

ZO950'0

LSOOOO-Or

I

(P+WXLLSIN)

Pw91MIlrlS oLz1oo'o

LZIO'O --

I '~P'W?UL) CL661

Iws =U)PWI (1 EIOO'O E900'0 PSIO'O i7060'0
:

40

s$

+I

:

I

-cj

S8

::

:

28P
Table 3-38: RGS Fold Induction of TCDD Control
4.0 Discussion

In this section the results and interpretation of the chemical and biological tests performed on the

sediments and tissues from the study are further evaluated in the framework of the null

hypotheses presented in Section 1.2. The title and subject of each of the following subsections

correspond to a particular null hypothesis, and include an assessment on the validity of the null

hypothesis.

4.1 Surface Sediments as Contaminant Sinks

Fine-grained, organic-rich sediments are the most common sink in the coastal ocean for organic

and trace metal contaminants because of the large, active surface area available for adsorption.

Contaminants introduced by municipal discharges to areas surrounding Anchorage and by oil and

gas activities to uppermost Cook Inlet will most likely be deposited with such fine-grained

sediments. The upper areas of Cook Inlet have been previously shown to contain only minor

deposits of fine-grained sediment because the shallow water, large tidal ranges and active

hydrography move sediments southward to outermost Cook Inlet and the Shelikof Strait (Sharma

and Burrell, 1970; Carlson ef al., 1977; Hampton, 1982). Thus, a primary goal of this study was

to identify and sample these potential sinks for fine-grained sediments and determine whether

they contain contaminants.

Surface sediments collected during this study help identify patterns of deposition for fine-grained

silts and clays in outermost Cook Inlet and the Shelikof Strait. A contour map of silt+clay

(Figure 4-l) shows a sharp increase in silt+clay from 30 to 40 percent in outermost Cook Inlet to

greater than 95 percent in the middle (zone 2) through the lower (zones 3 and 4) portions of the

Shelikof Strait (summary data in Table 3-10). Clearly, the trends shown on Figure 4-l support

the initial assumption of the study and identify most of the Shelikof Strait as an important sink

for fine-grained sediment. Furthermore, the observed trend supports deposition of more finegrained sediment toward the southern areas of Shelikof Strait.

The TOC content of the sediment averages about 0.75 percent for the entire study area with a

relatively limited number of sites (Homer Harbor and zone 4) containing greater than 1 percent

TOC. These concentrations of TOC compare well with values previously reported by Hampton

(1983). Concentrations of TOC tend to be highest in samples with greater than 80 percent

silt+clay (Figure 4-2), suggesting that organic matter is associated with fine-grained sediments.

A first approximation of the magnitude of sediment deposition in outermost Cook Inlet and the

Shelikof Strait is estimated here based on data for river-me discharge of sediment, as well as

sediment accumulation rates. River-me input of sediment from the Susitna-Knik-Matanuska (SK-M) River system was reported as 40 x lo6 tons/year (Feely et al., 1982; USGS, 1998). This

value is most likely a lower limit for total sediment input from the S-K-M system because the

three rivers are estimated to contribute 75 to 90 percent of the total sediment input to upper Cook

Inlet. Thus, estimates of total transport of sediment from the S-K-M system range from 44 to 53

x lo6 tons/year. Added to inputs from the S-K-M system is some fraction of the sediment

transport of 107 x lo6 tons/year from the Copper River (Reimnitz, 1966). Based on a sediment

composition model described in Section 4.3, sediment derived from the Copper River accounts
for 10 to 20 percent of the total sediment deposited in the study area. Total sediment deposition

was determined for each zone (Table 4-l). The average sediment accumulation rate was

multiplied by the area of fine-grained sediment in each zone to determine total deposition (Table

4-l). Total sediment deposition based on sediment accumulation is - 60 to 70 x lo6 tons/year for

zone 0 to zone 4. Using data for river inputs, the 44 to 53 x lo6 tons/year from the S-K-M

system is combined with a 10 to 20 percent contribution from the Copper River (i.e., 6 to 14 x

lo6 tons/year) for a total of 50 to 67 x lo6 tons/year. Thus, the two approaches to determining

total sediment deposition in the study area agree relatively well.

Are fine-grained sediments from outermost Cook Inlet and the Shelikof Strait contaminated with

trace metals? Identification of metal contamination in sediments requires knowledge of natural

levels of metals. All trace metals are present in marine sediments at some natural level that

varies as a function of the mineralogy, grain size, and organic matter content of the sample. As

previously described, concentrations of trace metals were normalized to Fe to help account for

natural variability in sediment composition and concomitant trends in concentrations of trace

metals. Metal/Fe ratios can be compared with source sediments from the Susitna and Copper

Rivers, surface sediments from pristine sites, or with older, deeper (pre-industrial) sediments

from the same site to help identify anthropogenic additions of metals over space and time. Jf a

particular metal/Fe ratio is significantly increased relative to clean, reference material from the

area, then that metal can be identified as having some fraction of the total concentration

introduced by anthropogenic sources. For example, Figure 4-3 shows a Cr/Fe plot for all surface

sediments, along with source material from the Susitna and Copper Rivers. The Cr/Fe plot

(Figure 4-3) shows that most points follow a relatively good linear trend that includes source

sediment from the Copper River. The Cr/Fe ratios for average continental crust and sediment

from the Susitna River (Figure 4-3) are comparable, yet higher than observed for the samples.

Thus, with the available data, no samples show a clear deviation from what are believed to be

natural concentrations for Cr.

In contrast with the Cr/Fe relationship described above, the ZnLFe relationship for source material

and surface sediment from the study area fit a linear trend with a slope that is about 2 times

higher than shown for average continental crust (Figure 4-3). However, this trend of higher Zn

levels in Alaskan sediments, relative to Fe, is consistent with data for Alaskan rocks (Table 3-3).

Furthermore, Zn concentrations and the Zn/Fe ratio have been constant in sediments deposited in

the study area during the past 100 years (e.g., Figures 3-52 through 3-65). Thus, the higher &/Fe

ratio for Alaskan sediments is a natural reflection of somewhat higher levels of Zn in sediments

from the study area relative to average continental crust. Like Cr, concentrations of Be, Ni, Pb,

Se, Sn, and Tl (Figures 4-4 and 4-6) follow linear trends versus Fe with a slope less than shown

for average continental crust and with no indications of anthropogenic loading. In contrast,

concentrations of Ag, As, Ba, Cd, Cu, Hg, Mn, Sb, and V versus Fe are similar to trends

described for Zn versus Fe (Figures 4-4 through 4-7). Six points on the Hg/Fe graph (Figure 4-7)

show positive deviations from the basic relationship shown for the source samples and other

surface sediments. These samples were collected from ZOFl and ZOF14, both in Kachemak Bay.

However, present-day Hg levels in Kachemak Bay (core 98ZOFl) are comparable with values

observed throughout the twentieth century, suggesting that these concentrations are typical for

the Kachemak Bay area. Thus, within the present data set, no clearly identifiable anthropogenic

inputs of sediment metals are observed between the source rivers and the sediments of outermost

Cook Inlet and the Shelikof Strait.

4-2
-

The levels and extent of PAH, from petroleum and other sources, in outermost Cook Inlet and

Shelikof Strait are shown in a contour map of the total PAH concentrations (Figure 4-8). The

total PAH concentrations generally follow the pattern observed for silt+clay (Figure 4-l), with an

increase in total PAH from approximately 0.20 to approximately 0.40 ppm in zone 0 (outermost

Cook Inlet) to approximately 0.50 to 1.0 ppm in zones 1,2,3, and 4 (Shelikof Strait).

Exceptions to this pattern were observed at stations ZOFl and ZOF14 (Kachemak Bay), which

showed elevated concentrations of PAH relative to other zone 0 surface sediments. The relative

elevation of PAH at these two stations was likely due to enrichment from local coal and

petroleum hydrocarbon inputs. Coal outcrops are a well documented feature of the nearby

Kachemak Bay shoreline, and anthropogenic petroleum hydrocarbon influences were identified

from the adjacent Homer Harbor source samples.

However, the total PAH concentrations in all zones are comparable to values reported for

background hydrocarbons in other studies from offshore coastal waters of Alaska (Boehm, et aE.,

1991; Bence et al., 1996; Page, et uZ. 1996; Boehm, et al., 1998). Therefore there does not

appear to be any identifiable enrichment of petroleum contaminants (as represented by PAH)

from anthropogenic activities, including oil and gas production in upper Cook Inlet.

In summary, in the context of the null hypothesis, the surface sediments of outermost Cook

Inlet and the Shelikof Strait are potential traps for contaminants from oil and gas

production activities in upper Cook Inlet, by virtue of the fact that Shelikof Strait is a

depositional area. Based on evaluations of the organic and inorganic data, no contamination of

the study area’s surface sediments was detected that may have originated from oil and gas

production activities in upper Cook Inlet.

4.2 Concentration of Pollutants Over Time

4.2.1 Geochronology of Metals

A 50- to NM&year chronology of metal levels in sediments from outermost Cook Inlet and the

Shelikof Strait was obtained for each zone. Concentrations of Fe, Al (Table 3-19) and/or the

Fe/Al ratio were uniform in each core (Figures 3-52 through 3-65) and thus, for convenience,

metal concentrations, rather than ratios to Fe, are used in this section.

Profiles for Pb versus time show that concentrations of Pb varied by less than 10 percent (CV)

within each core over time periods extending back as far as the late 1800s. For example, at

station ZlFl, Pb levels vary by a.7 pg/g for a mean of 12.3 pg/g (Figure 4-9). A similar trend

was observed for station Z3F2 (Figure 4-9) and each of the other sites. The overall constant and

low levels of Pb, with a maximum of 15.2 pg/g relative to 14.8 ug/g for average continental

crust, show that no detectable anthropogenic Pb has been deposited at the 14 core sites during the

past century.

Based on a total of -60 x lo6 tons of sediment deposited in the study area per year, about 60 tons

of Pb would need to be introduced to the region to observe a 1 pg/g increase in sediment Pb

levels. Previous estimates of anthropogenic Pb inputs to the area were about 2 tons of Pb

(Boehm et aZ., 1998) and are consistent with the sedimentary record. Local instances of Pb

contamination are still possible; however, none were detected.

ArthwDLittIe

4-3
In a manner similar to that described for Pb, concentrations of Ag, Ba, Be, Cu, Hg, Ni, Sb, Tl, V

and Zn, or their ratios to Fe, generally show less than 10 to 20 percent variation within a core at

all sites. Furthermore, many of the observed higher levels (or ratios to Fe) are observed deeper in

the cores (i.e., older sediments). Thus, none of these elements show discernible anthropogenic

inputs or changes in metal levels during the past 40 to 50 years of industrial activity in the area.

Concentrations of Cr in cores from sites ZlFl and ZlF2 are 20 to 30 percent higher during the

early 1900s relative to the 1940s (Figure 4-10). Uniform profiles of Cr over time are observed

for most other sites with the exception of one or two lower values each in cores from ZOF5,

ZOF6,ZlR3B, and Z3F2. Chromium was mined on the Kenai Peninsula near Seldovia at varying

times from World War I through the late 1950s. The slightly elevated Cr levels in nearby sites

ZlFl and ZlF2 may reflect inputs of small amounts of Cr tailings from this activity. No such

evidence of enrichment was found at the other sites.

Concentrations of Cd in the various cores have the greatest variability (Figure 4-lo), with an

overall range of 0.07 to 0.27 pg/g. At these levels, Cd concentrations are within the bounds of

bottom sediments from the Susitna (0.30 pg/g) and Copper (0.16 l&g) Rivers. The variations

over time are believed to be a complex function of biological inputs of Cd-rich organic matter,

diagenesis in the sediments, and variable inputs of source sediment.

Surface layers (from 1 to 6 cm thick) at stations Z2R16,Z2R2, and Z3Fl have Mn concentrations

greater than 1,000 pg/g in what otherwise are generally uniform Mn profiles at the various sites.

This surficial enrichment of Mn is most likely related to dissolution of Mn oxides in reducing

layers below 6 cm with diffusion of Mn2+ up to oxic surface sediments where it precipitated as

MnO, Massoth et al.( 1979) previously observed such remobilization of Mn in Shelikof Strait.

Arsenic follows a similar trend to that observed for Mn, suggesting that As also may follow Mn

in this diagenetic process.

4.2.2 Geochronology of Organics

The geochronology of petroleum hydrocarbons was established in 12 sediment cores from the

outermost Cook Inlet and Shelikof Strait. A chronology of 20 to 100 years was established,

based on the individual core at each station with at least one core with a SO+ year record in each

zone. In general, profiles of the concentrations of the totals for the 3 categories of organic

compounds (total PAH, TPHC, and total S/T) did not reveal any significant increases over the oil

and gas development time period. This finding was consistent between cores over time. Some

variation was noted, as the CV for total PAH and total S/T ranged between 8 and 23 percent

within each core. The CVs for TPHC were somewhat higher: 14 to 49 percent, showing greater

variability for this parameter, but no consistent trend within cores. The one exception was the

core from Z3F2, which exhibited a nearly three-fold increase (from 20 pg/g to 53 pg/g) in the

non-specific TPHC parameter between approximately 1987 and present (Figure 3-77). However,

no corresponding increase in either total PAH or total S/T was observed during the same time

interval, indicating that the ‘I’PHC increase was not related to anthropogenic or petroleum

hydrocarbon inputs over the last 10 years.

In all cores, the concentrations of PAH analytes are within the same range as the PAH levels in

the surface sediments of the corresponding zone. Perylene is an exception. Perylene

concentrations generally increased with core depth at each zone, as shown in Figure 4-l 1. The

4-4
increasing concentration of perylene with depth may be related to the well-known process

associated with perylene formation during early sediment diagenesis, or may be-related to

perylene input associated with coal.

4.2.3 Statistical Analysis of Concentrations in Cores

As discussed in Section 3.3.5, the dated sediment cores were evaluated statistically to determine

if there were any significant trends in the cores that could be associated with the onset of

petroleum exploration and production activities in upper Cook Inlet. The results of the statistical

analysis revealed that there were no significant increases in the concentration of organics and

metals in the sediments which could be correlated with the onset of petroleum activities (circa

1963). Several of the trends in specific parameters which were discussed previously (e.g.,

increasing perylene with core depth, increases in tenigenous hydrocarbon parameters near the

surface, and subtle shifts in several petroleum source ratios) were also validated by the statistical

analysis.

In summary, in the context of the null hypothesis, the concentrations of metals and organics in

sediments in outermost Cook Inlet and Shelikof Strait have not increased significantly

since offshore oil exploration and production began in Cook Inlet (circa 1963).

4.3 Composition of Pollutants Over Time

4.3.1 Metals

Average metal values for Ag, As, Ba, Be, Cd, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se, Sn, Tl, V, and Zn

or their ratios to Fe, from each core site are comparable with levels obtained for source sediments

from the Susitna and Copper Rivers. This observation is consistent with the concept that no

identifiable additions of these metals occur as sediment is being transported from the source

rivers to depositional sites in outermost Cook Inlet and the Shelikof Strait. In other words, oil

and gas operations and the Point Woronzof outfall have not had a discernible impact on

concentrations of these metals at the study sites.

Knowledge of the relative amounts of sediment in the Shelikof Strait that are derived from the SK-M system versus the Copper River has valuable scientific and management application.

Previous work by Hein et al. (1979) qualitatively identified the presence of sediments from the

Copper River in Shelikof Strait using clay mineralogy. A first approximation of the quantitative

proportions of sediment in each zone that are derived from the S-K-M system was calculated

during our study using trace metal data.

Five different mettimetal ratios were selected for this calculation. Metal ratios were used to

normalize differences in absolute concentrations of metals from various source and sediment

samples. For each ratio used, the following conditions were established: (1) the ratio for river

bottom sediment was within &lo percent of the value for river suspended solids, (2) the ratio for

the combined S-K-M system differed from that for the Copper River by greater than 30 percent.

The average values used for the S-K-M system are based on the following fractions of total

sediment transport: Susitna (83 percent), Knik (11 percent), and Matanuska (6 percent), using

sediment discharge data from the USGS (1999). Based on these criteria, the five ratios used for

the model are Ni/Be, Fe/Zn, Sn/Sb, PbITl, and V/Zn (Table 4-2).

4-5
For each surface sample and each ratio, the fraction of sediment derived from the S-K-M systen

was calculated using a simple 2-member r-nixing model with average ratios from Table 4-2.

Results for all 5 ratios were averaged for each site and the grand average for each sample is

presented as a mean ti standard deviation (95 percent confidence interval) in Table 4-3. In

zones 0, 1, and 2, the error of the estimate (95 percent confidence interval) is 24 to 30 percent

relative to 8 percent for zones 3 and 4. Alaska Coastal Current sediment collected outside the

Shelikof Strait has no discernible input from the S-K-M system. Surficial sediment from

outermost Cook Inlet and the Shelikof Strait contains an average of 81 + 22 percent sediment

from the S-K-M system. Thus, the dominant source of sediment to the study area at present is

imm the S-K-M system.

4.3.2 Organics

The sediment core profiles showed that concentrations of the primary hydrocarbon parameters

were relatively constant with depth within each core. An evaluation of diagnostic source

parameters within the cores revealed that in most cases the source(s) of these hydrocarbons was

constant over the time period studied.

As was seen in the surface sediments, double-ratio source plots of C2D/C2P versus C3D/C3P

provide a representative fine-tuned summary of the PAH sources in the core samples. Doubleratio source plots for each of the sediment cores are presented in Figures 4-12 through 4-19.

Based on an evaluation of the source ratio plots of the cores, several important trends are

observed. In the cores from ZOFl (Kachemak Bay, Figure 4-12) there is greater scatter

throughout the cores, likely related to variable local hydrocarbon source inputs (e.g., coal, Homer

Harbor sediment, runoff).

The source ratio plot of the sediment core from ZOF5 (Figure 4-13) shows some scatter of the

different core sections, with the shallower depth intervals (-1940 to present) clustering between

values for “background” sediment and coal. The deeper sections of the core show a trend

towards source values corresponding to the Well Creek seep oil value and the Oil Bay seep oil

(-1940 and earlier). This result could indicate a possible shift in the source of petroleum

hydrocarbons over time. This shift would indicate a greater influence of the Well Creek/Oil Bay

seep oil sources to the outermost Cook Inlet sediments in the past (prior to 1940), and an increase

in the contribution of the particle-bound “background” hydrocarbons from other petroleum

hydrocarbon source(s) to the east (e.g., Katalla, Yakutaga area formations) more recently (post1940). A mixture of these two “end members” is suggested by the double-ratio plot.

A similar trend is observed in the source ratio plot of the core sample from station ZQF6 (Pigure

4-13), where the deeper sections of the core (6 to 25 cm) are more closely associated with the

Well Creek seep oil and Oil Bay seep oil sources, and the shallower surface sections (0 to 6 cm)

are intermediate to “background” sediment and coal sources. The same follows for the core

sample from ZOF8, i.e., the deeper sediments (16 to 20 cm, Figure 4-14) are separated from the

cluster of upper sediments and exhibit Well Creek seep oil and Oil Bay seep oil influence.

Geochronology for the ZOF6 and ZOF8 cores confii that each of the deeper sediments within

each core is from the 1940s and earlier, establishing a source correlation between the trends

observed in these 3 zone 0 core profiles.

4-6
The source ratio plots of these three zone 0 cores (ZOF5,ZOF6, and ZOF8) all suggest a shift in

the contribution of petroleum hydrocarbon sources in the western portion of outermost Cook

Inlet around 1940, with an apparent decrease in the influence of Iniskin Peninsula petroleum

sources after 1940. A preliminary statistical evaluation of the source ratios from these three

cores was performed to test this trend in the same manner as described previously for the post1963 intervention effect, except in this analysis a 1940 intervention effect was tested. The results

of this analysis (Woollcott Smith - personal communication) show a significant increase (P

~0.05) in the C2DK2P and C3DK3P source ratios after 1940 in all three cores. Several causes

for this observed shift in petroleum hydrocarbon sources could be suggested, including

earthquake activity around 1940, which may have diminished the flow of the local Iniskin

Peninsula seeps, or a shift in the sedimentary or circulatory regime of the area. Further study

would be required to refine these theories; however, with respect to the objectives of this

monitoring program it is important note that the observed trend is only found in the western area

of outermost Cook Inlet, and occurred prior to any offshore oil exploration and production

activities in Cook Inlet.

The source ratio plots for the zone 1,2, 3, and 4 cores (Figures 4-15 through 4-19) generally

show a consistent cluster of source ratio values throughout the depth intervals sampled. This

indicates that the source of hydrocarbons to these sediments has not changed since the early

19OOs, based on the geochronologies established to date. The source ratios generally plot in the

same area as the “background” sediment, indicating that particle-bound petroleum hydrocarbons

associated with seeps and petroleum formation source(s) to the east of the study area (e.g.,

Katalla, Yakutaga, east of Prince William Sound) are likely the primary source of hydrocarbons

over this period.

Thus, in the context of the null hypothesis, the composition (source[s]) of metals in the

sediments of outermost Cook Inlet and Shelikof Strait do not appear to have changed since

offshore oil exploration and production began in Cook Inlet (circa 1963). The composition

of hydrocarbons in sediment cores a show subtle changes over the past 25 to 50 years,

but these changes do not appear to be correlated with petroleum production activities or

spills.

4.4 Risk Associated with Pollutant Concentrations: Exposure Assessment

In the context of this study multiple parameters were used to evaluate biological and ecological

risk. The following sections provide a discussion on both sediment quality and biological and

ecological effects (sediment quality criteria, sediment toxicity, CYPlA [p450] induction in fish

tissues, and RGS analyses of sediment and fish tissue).

4.4.1 Comparison to Sediment Quality Criteria: Metals

Sediment quality criteria have been used extensively worldwide to assess possible adverse

biological effects from metals and PAH. The most utilized criteria are the ERL (Effects RangeLow) and ERM (Effects Range-Medium) presented by Long et al. (1995). These guidelines are

based on field, laboratory, and modeling studies conducted in the United States that coupled

concentrations of contaminants in sediments with biological effects (e.g., Long and Morgan,

1990). The ERM is defined as the concentration of a substance in the sediment that results in an

adverse biological effect in about 50 percent of the test organisms and the ERL is defined as the

4-7
concentration of a substance that affects 10 percent of the test organisms. Thus, the general

application of the criteria has been to state that adverse biological effects are “rarely” observed

when metal or PAH levels are less than the ERL, “occasionally” observed when contaminants are

present at levels between the ERL and ERM, and “frequently” observed when concentrations

exceed the ERM.

Nine of the 17 metals investigated during this study have been assigned ERL and ERM

concentrations by Long et al. (1995) at this time. None of these 9 metals are found at levels

above the ERM in any sediment samples from this study (Figures 4-20,4-21, and 4-22).

Furthermore, 5 of the metals (Ag, Cd, Hg, Pb, and Zn) are present in sediments at levels below

the ERL at all sites (Figures 4-20,4-21, and 4-22). Concentrations of Cr exceed the ERL by less

than 20 percent at 2 sites in Kachemak Bay (ZOFl and ZOF14). In contrast, concentrations of As

exceed the ERL of 8.2 pg/g at 38 of 56 sites by less than 1 to as much as 8 pg/g (Figure 4-20).

However, the highest As concentration of 16 ug/g in sediment from ZOFl is still well below the

ERM value of 70 pg/g. Suspended solids from the Susitna River carry As levels of

approximately 36 pg/g, with no 2 sites from zone 0 having higher As concentrations than this

source material.

Concentrations of Cu exceeded the ERL of 34 pg/g at 53 of 56 sites by as much as 18 pg/g (52

pg Cu/g at ZOFl); however, the maximum Cu level in sediments from this study is well below

the ERM for Cu of 270 pg/g. Once again, source sediment from the Susitna River (31 pg Cu/g)

and the Copper River (43 pg Cu/g) along with Alaskan rock data (Table 3-3), show that natural

levels of Cu in the area are close to or above the ERL value chosen by Long et al. (1995).

Finally, all samples from this study had Ni levels that exceed the ERL of 20.9 pg/g. The average

crustal abundance of Ni is 56 p&/g (Wedepohl, 1995), a value that exceeds that ERM level of

51.6 pg/g. Similarly, the Ni content of sediment from both source rivers exceeds the ERL. Even

for Ni values greater than the ERM, only 16.9 percent mortality was recorded by Long et al.

(1995) for their database, and thus the ERL and ERM values for Ni may need to be revised in the

second iteration of these sediment quality criteria. Overall, As and Cr in 2 or 3 sites in zone 0

(mainly Kachemak Bay) are present at levels that exceed the ERL; however, these values are

comparable with results for river suspended solids and Alaskan rocks.

4.4.2 Comparison to Sediment Quality Criteria: Polycyclic Aromatic Hydrocarbons

The PAH analytes in the sampled sediments were compared to the ERL and ERM values for

organic parameters in a manner similar to the metals. The results of this comparison for the

organics were slightly different from the metals results in that the ERL for both individual and

total PAH parameters were not exceeded in any zone or any site. This comparison for organics

data is illustrated in Figure 4-23 and indicates that overall, the PAH concentrations in the study

sediments are at levels that would not be expected to result in adverse biological effects.

4.4.3 Sediment Toxicity Tests

Sediment bioassays (using amphipods) were conducted in this study to determine if sediments

from selected areas of lower Cook Inlet and Shelikof Strait had the potential to cause biological

effects. Reduced survival to amphipods may indicate the potential for biological effects to

4-8
benthic organisms. However, as the sediments have a large mixture of trace substances, it may

be difficult to determine which substance(s), if any, are responsible for the observed reduced

survival of amphipods. This portion of the report will attempt to identify possible sources of the

observed reduced survival in some of the bioassays conducted during this study.

Statistical analysis (using ToxCalc ~5.0 software) of the results from the 1997 sediment

bioassays conducted by PERL demonstrate that 15 of the 20 sediment samples resulted in

survival significantly less than the Control at pc 0.05. However, most laboratories conducting

sediment bioassays only indicate toxicity if the following two criteria are met:

1 . There is a significant difference between the laboratory control and the test using a t- test,

as was done here.

2. Mean organism response in the bioassay test was less than 80 percent of the laboratory

control value.

Application of the second criterion eliminates the problem of designation of toxicity based only

on comparison to controls with low replicate variance.

The 80 percent of control criterion was established by statistical analysis of many amphipod data

sets by other investigators (e.g., Thursby and Schlekat, 1993). The two criterion approach is

currently being used by the EPA’s EMAP Program (Schlimmel et al., 1994), by California’s

State Bay Protection and Toxic Cleanup Program (BPTCP, 1993) and by the Regional

Monitoring Program for Trace Substances in the San Francisco Estuary (SFBRMP, 1995).

Applying these criteria to the bioassay results demonstrates that at 7 of the 20 sites sampled in

1997, arnphipod survival was significantly lower than the controls: 2 of 8 from zone 0; 1 of 4

from zone 2; and 4 of 4 from zone 3. None of the 4 sites in zone 1 demonstrated significantly

lower survival than controls.

Correlating amphipod survival with the trace contaminants measured in this study is problematic

due to two factors:

1 . While pristine in comparison with sediments from many areas where amphipods have

been used as test organisms to assess sediment toxicity, the tested sediments did contain a

large mix of trace substances. In this study, we have used the Effects Range methodology

developed by Long and Morgan (1990) to relate contaminant concentrations to survival of

test organisms. This methodology defines the concentrations of contaminants which have

resulted in deleterious biological effects to test organisms (see Section 4.4.1 for a more

detailed discussion of EIU and ERM). It has been demonstrated that contaminant

mixtures may have a synergistic or additive effect on test organism survival, and that

synergistic or additive effects may not be easily elucidated based on analysis of individual

contaminant concentrations (Chapman, 1989; Schwartz, 1988,1995). Methodologies are

being developed that may more completely address additive or synergistic biological

effects of the mixture of chemicals widely found in sediment analyses, and may prove

useful in future analyses of sediments from this study (Thompson, 1998). However,

although four of the sediment metals (As, Cr, Cu, and Ni) concentrations exceeded the

4-s
ERL, where sediment concentrations are “occasionally” associated with adverse effects,

no concentrations exceeded the ERM, the level at which sediment concentrations are

“frequently” associated with adverse effects (Long and Morgan, 1990; Long et al., 1995).

Concentrations of organic chemicals in the sampled sediments show a similar result. The

ERLs for individual and total PAH were not exceeded in any zone or any site.

2. The amphipod Eohaustorius estuatius used in this study in 1997 (and widely used

elsewhere) is recognized as tolerating highly variable mixtures of grain size, ranging from

0.6 to 100 percent sand. However, it naturally inhabits sandy sediments and some

correlation between survival and grain size has been reported by Dewitt et al. (1989), and

SAIC (1993a; 1993b), with increased mortality associated with decreasing grain size

(higher percent silt) (EPA, 1994).

Statistical analysis of all chemical concentrations and amphipod survival demonstrates that

percent survival was significantly correlated to two factors in the 1997 samples: 1)

concentrations of Zn in the sediments and, 2) percent silt (fine-grained sediments). The three

stations with the greatest percent silt were also the stations where amphipods had the poorest

survival. Therefore, sediment particle size composition, as has been found previously for this

and other amphipod species, probably affected survival. While further investigations may

elucidate other factors affecting test organism survival, all indications from the samples collected

in 1997 indicate fine grain size of area sediments as the primary factor contributing to low

survival in the 1997 sediment bioassays with Eohaustorius estuarim.

Concentrations of AVS and SEM also were determined for the sediments collected in 1997 and

used in the Eohaustorius toxicity tests. As previously mentioned, the underlying principle for

using results from AVS-SEM is that metals bound (SEM) with sulfide (AVS) are not

bioavailable. Concentrations of AVS in the 27 sediment samples (0 to 2 cm) from this study

were all less than 3.1 pmole/g, except for a value of 18.6 pmole/g at station ZOF14. Only five

other sites from this study (ZOFl, ZlR13,Z2R13,Z3Rll, and Z3R20) yielded AVS levels

greater than 1 ymole/g. An AVS value of less than 1 pmole/g was considered below the limit of

applicability of the AVSISEM technique by DiToro et al. (1990). Thus, low AVS values in the

sediments from outermost Cook Inlet and the Shelikof Strait restrict use of the AVS/SEM

approach. By comparison, results for marine sediments from Long Island Sound and Sapelo

Island, Georgia, show values of AVS that ranged from less than 0.1 to about 10 pmole/g in the

top 1 cm of the sediment and 8 to 43 pmole/g over the top 10 cm of the sediment column

(DiToro et al., 1990).

For the 9 sites in outermost Cook Inlet and the Shelikof Strait where amphipod survival was less

than 80 percent, AVS levels averaged 0.7 -c 1.0 pmole/g relative to 0.4 & 0.7 FmoleIg at 10

stations where survival was greater than 80 percent (excluding the high AVS site ZOF14). Thus,

no significant correlation between AVS levels and amphipod survival was observed for the

sediments collected in 1997. Concentrations of SEM also were similar between the two survival

groups at 1.0 k 0.2 pmole SIX/g for the less than 80 percent survival group and 0.8 f 0.4 pmole

SEM/g for the greater than 80 percent survival group, again showing no relationship in toxicity

results among sites as a function of SEM levels in 1997.

4-10
A more common use of the AVS and SEM data is to subtract the AVS value from the SEM value

[i.e., SEM - AVS] and assume that a negative result means that sufficient sulfide is present in the

sediment to bind potentially toxic metals with a high sulfide affinity (Ag, Cd, Cu, Hg, Ni, Pb, and

Zn), thereby rendering the sediment less toxic. Overall, excess AVS (a negative result meaning

that metals are bound with sulfide) was found at only 4 of the 20 sites sampled in 1997 (2 with

greater than 80 percent survival and 2 with less than 80 percent survival), including the site with

the lowest percent survival (Z3Rll). The SEM-AVS value for the metal-rich site ZOF14 is -17.5

pmole/g, supporting sulfide binding of metals. Once again, no pattern between the results of the

amphipod toxicity tests and data for AVS/SEM are observed.

According to the underlying principles of the AVS/SEM test, observed positive numbers for

[SEM-AVS] at most sites would correspond with more bioavailable metals. However, in these

sediments, a sizeable amount of the SEM is most likely associated with iron oxides that also

dissolve with the 1N HCl treatment used. More than 90 pmoles Fe/g were released during the

SEM treatment, or about 100 times more metal than the total SEM value. Use of the AVS/SEM

approach in oxic sediments has been previously shown to be of limited value because of the

importance of organic matter and manganese and iron oxides in controlling metal binding

(Ankley et al., 1996). The surface few centimeters from all sites were shown by the results of

sediment profile imaging to be oxic. Coupled with the observation that most AVS values were

less than 1 pmole/g, the lack of relationship between AVS-SEM results and amphipod toxicity is

certainly consistent.

In 1998, sediment toxicity tests were conducted on sediments from the seven sites that

demonstrated significant toxicity to test organisms in 1997, and in addition, a fine-grained

sediment collected from a reference site (figure 2-l) was also tested. This fine-grained reference

sediment was tested to assess the test organism’s sensitivity to fine-grain size sediments. As

discussed in section 3, the test amphipod Eohuustorius estzw-ius (used in 1997) was replaced

with the amphipodhpelisca abdita. The site selection and change in test organisms in 1998

was based on the sediment toxicity test results from 1997, which, as discussed above, were not

significantly related to measured concentrations of metals or organic compounds. The strongest

relationship in the 1997 tests was to grain size, i.e., as grain size decreased, so did survival.

Ampelisca abdita replaced Eohaustorius estuarius in 1998 as an attempt to address the question

of the apparent grain-size effect observed with the 1997 sediment toxicity test. Ampelisca abdita

was selected as an alternative species through conversations with the bioassay laboratory and

investigations of the literature. It is thought to be less subject to grain-size effects than

Eohaustorius estuarius. No significant toxicity (i.e., less than 80 percent) was found in 1998 at

the sites with the lowest survival in 1997 or in the fine-grain size “control” site sediments

included in 1998. These results indicate that factors affecting survival of test organisms in 1997

were not present in 1998, or that differential survival of test organisms exposed to sediments

from the same sites may be explained by differing tolerances between the two amphipod species

utilized as test organisms.

4.4.4 P450 Reporter Gene System in Fish and Sediments

Previous RGS studies have demonstrated that B[a]PEq in excess of 60 pg/g are associated with

benthic degradation in sediments. Studies conducted on marine sediments from various parts of

the U.S. coastal zone for The National Oceanic and Atmospheric Administration (NOAA) have

shown that relatively uncontaminated sediments have produced a response of about 1 to 6 pg/g

4-11
of B[a]PEq (Anderson et al., 1995; Anderson et al., 1997). The Alaskan sediments analyzed in

this study therefore fall within this range of background concentrations. The low levels of

CYPlA induction in most fish tissues analyzed, especially the gills, are also consistent with the

low RGS P450 response measured in the sediment extracts and in the fish liver composite

samples.

4.4.4.1 Sediments

Petrogenic PAHs (r = 0.689) and Total PAHs (r = 0.681) were found to correlate significantly

(~~0.05) with the P450 RGS responses measured on sediment extracts. Numerous individual

hydrocarbons, which were included in the summed petrogenic PAH and Total PAH

concentrations, also showed significant correlations with the P450 RGS responses.

Total PAJX have been found in numerous NOAA Bioeffects studies to correlately highly with the

RGS responses measured in those samples from various coastal regions of the country (Anderson

et al. In Press a). These previous studies have demonstrated that RGS responses to sediments

less than about 11 mg B[a]PEq/g are not likely to be associated with biological effects. Levels

of RGS response to sediments above about 32 mg B[a]PEq/g may be associated with biological

effects, and when the measured response reaches 60 mg B[a]PEq/g and greater, there is likely to

be a deleterious impact on the organisms associated with the sediments.

The sediments tested in this investigation were all under 11 mg B[a]PEq/g, and most were

equivalent to the lowest responses measured previously from very clean portions of the U. S.

coastal zones (Northern Puget Sound and Alaska). The range of RGS responses between 0.5 and

5.0 mg B[a]PEq/g, where nearly all of these samples fell is considered to be a very clean

environment.

4.4.4.2 Fish Tissue

The data on P450 RGS responses to fish tissue were expressed on a lipid weight basis, which

always produces higher values than normalization on a dry weight basis, because a smaller

portion of the tissue is composed of lipid. Very few of the fish tissue samples tested produced

fold induction above the solvent control (1.0 fold induction). Those samples that were above 1 .O

fold produced B[a]P equivalent values of 0.3 to 1.0 mg B[a]PEq/g lipid, with one arrow tooth

flounder sample having a value of 6.5 mg B[a]PEq/g lipid.

In other studies, the highest observed RGS responses to extracts of tissues were from marine

mussels deployed in contaminated areas of San Diego Bay (Anderson et al. In Press b). These

responses were as high as 295 mg B[a]PEq/g dry weight, and the native clean mussels were at 6

mg B[a]PEq/g dry weight. In a study for the Exxon Valdez trustees the P450 RGS assay was

used on 38 samples of whole sand lance collected from various locations in Prince William

Sound in 1996, well after the oil spill (1989). These rather lipid-rich fish produced RGS values

between 1.5 and 81 mg B[a]PEq/g lipid. The majority of the samples were in the range of 1 to 5,

but approximately one-third of the samples were above 10 mg B[a]PEq/g lipid. While it is

difficult to compare sand lance directly to the species of fish collected in this investigation, it

appears that those in the present study contained much lower levels of inducing compounds.

A more recent study conducted for LGLAlaska under funding by MMS examined the levels of RGS

induction produced by fish collected from both Cook Inlet and the Shelikof Straits. The two species

that were collected in adequate numbers from each region were the Pacific sand lance and surf smelt.

4-12
Those samples of the two species collected from Cook Inlet in 1998 were found to be higher in RGS

responses than the same species collected from the Shelikof Strait.

The results of these investigations demonstrate that the use of a biomarker screening approach

provides a good estimate of the levels of inducing compounds, such as high molecular weight PAHs

in both sediment and tissue samples.

The responses (both B[a]PEq and TEQ) of the RGS assay to extracts of fish tissue in 1998 were

highly correlated with several analytes. (The RGS values are expressed as both B[a]P and Toxic

Equivalents, since without chemical confirmation it can not be determined if the response was from

exposure to PAHs [B [a]Peq] or from chlorinated hydrocarbons [TEQ]). It is not surprising that for

all fish, RGS responses were correlated with Cl-fluorenes, C2-fluorenes, and Cl-phenanthrenes,

since these compounds would be part of a suite of hydrocarbons that could induce the CYPl Al gene.

However, the correlation of RGS with copper and chromium is merely a matter of co-occurance in

the sediments. The solvent extracts applied to the RGS cells would not likely even contain metals.

For Pacific cod collected in 1998, the observed correlations of RGS with fluorenes, phenanthrenes,

and fluoranthrene would be expected as noted above. In this case two other metals (zinc and

thallium) show a correlation, but these are again merely the result of co-occurance in the samples.

In conclusion, the results of the RGS assay are in general agreement with the chemical analyses on

the same samples, and both types of measurements demonstrate that the collected sediments and

tissues are quite low in the concentrations of PAHs, and chlorinated hydrocarbons which induce the

CYPlAl gene.

4.4.5 CYPlA Response in Fish

-

The CYPlA response is considered a very sensitive biological response for assessing exposure to

a variety of organic pollution conditions, and is widely considered a useful tool for assessing

exposure to specific classes of xenobiotic compounds (e.g., PAHs, coplanar polychlorinated

biphenyls [PCBs], polychlorinated dibenzofurans, and dibenzodioxins), CYPlA genes code for

the major oxidative enzymes induced in fish and other vertebrates by PAHs and chlorinated

hydrocarbons (Stegeman and Hahn, 1994). CYPlA and other measures of induction of the

cytochrome P450 enzyme system have become common components of contaminant monitoring

and effects studies worldwide (e.g., Bucheli and Fent, 1995, Holdaway et al., 1995, McCain et

al., 1996, Wirgin and Waldman, 1998, Collier et al., 1998, and Miller et, al., 1999), and in

Alaska (e.g., Varanasi et al., 1995 and Jewett et al., 2000). Buchelli and Fent, in their 1995

review, cite 75 field studies, 93% of which showed that CYPlA induction is significantly related

to contaminant levels in the environment. When coupled with measures of histopathology, ie.,

immunohistochemistry (IHC), induction of CYPlA can identify tissue specific-patterns of

CYPlA expression to identify target sites and exposure routes for PAH’s and other inducing

compounds, and can link exposure to xenobiotic compounds to effects at the biochemical,

cellular, tissue, and physiological levels. As of yet, however, there are few studies such as this

one in which CYPlA has been measured and scored in individual cell types (IHC). This

(immunohistochemical ) approach not only relates environmental contaminant concentrations to

tissue residues and responses, but may also demonstrate the route of exposure (water, diet,

4-13
substrate) of biota to environmental contaminants (e.g. Miller etal., 1989, Spies et al., 1996, Van

Veld et. al., 1997).

One study (conducted with a nearly identical methodology) examined cellular response in

Embiotocid fish (rainbow surfperch, Hypsums caryi, and rubberlip surfperch, Rachochilus

toxodes) caught near petroleum seepage in the Santa Barbara Channel, and at control sites. In this

study, liver hepatocytes from oiled sites had mean staining indices of 5.6 and 4.2. (rainbow vs

rubberlip respectively). These MC scores have been adjusted based on maximum scores of 15 as

used in the present study, as opposed to a maximum score of 25 as used in the surfperch study

(the original scores were 9.3 and 7). While at the control sites, liver hepatocyte scores were 2.7

and 2.5 (rubberlip vs rainbow respectively). The original scores being 4.5 and 4.3 (Spies et al.,

1996). These values compare to mean values of 2.83, 1.25, and 1.7 (zones 0,2, and 3

respectively) measured in Pacific halibut (liver hepatocytes) caught in 1997, .25, -09, and 0

(zones 1,2, and 3 respectively) measured in Pacific halibut in 1998, and 0 to 1.9 measured in all

species caught and analyzed in 1998.

There have been several recent studies of hydrocarbon concentrations and effects in Alaska fish

stemming from the Exxon Valdez oil spill (EVOS). One study (Jewett et al., 2000) measured the

catalytic activity of CYPlA in the form of EROD (ethoxyresorufin O-deethylase) as well as

using the IHC approach. The measurement of EROD has been the most common means of

investigating the CYPlA response to contaminants in both field and laboratory studies up until

this point, and the authors are not aware of any other field study of fish from pristine

environments in which both approaches (IHC and EROD) were utilized. The fish sampled in the

Jewett et al., study (masked greenling, hexagrammos octogrammus, and crescent gunnel, Pholis

Zaeta) all had mean liver vascular endothelium scores of less than 1, while (with the exception of

black cod which had a mean score of 1.2 from Zone 3 in 1997) none of the species from the

present study had measurable JHC scores. Vascular endothelium is the first site of contact of

inducing compounds in tissues and organs and so should demonstrate early induction and early

loss of induction in comparison with other tissues and organs. The total lack of induction (with

the exception of black cod) in the fish from the present study indicates either that the fish from

Shelikof Strait were less (recently) exposed to inducing compounds than those from the Jewett et

al., study, or that there are significant differences between the species in terms of sensitivity to

exogenous inducing compounds and or levels of endogenous inducing compounds. Additionally,

as exposure through the diet of (metabolized) hydrocarbons lessens with increasing trophic level,

it may be expected that higher trophic level fish (halibut and cod) would demonstrate less

induction via dietary exposure than lower trophic level fish (gunnels and greenling). The high

IHC score for Black cod vascular endothelium is interesting, but difficult to interpret as only 5

fish were sampled, and the mean score of 1.2 came from a single fish with a score of 6.

While direct comparisons of data from MC versus EROD based studies are somewhat tenuous,

the lack of other IHC based studies on Alaska fish initiated the need to make comparisons from

studies utilizing other methodologies. EROD is generally considered to be a more sensitive

measure of CYPlA induction than MC. Jewett et al., 2000, utilized BROD due to the low MC

scores in fish from un-oiled sites. Unfortunately, MC and EROD were not measured in the same

fish, making direct comparisons impossible. However, the EROD scores of fish from unoiled

sites were generally lower than those from oiled sites. Another study of Alaska fish stemming

from EVOS (Varanasi et al., 1995) utilized aryl hydrocarbon hydroxylase (AHH) to measure P4-14
4501A (CYPlA) induction in fish from over 50 sites in Prince William Sound, -Lower Cook

Inlet, and embayments along the Kenai Peninsula and the Alaska Pennisula. AHH is a very

similar measure to EROD. The findings in the (Varanasi et al., 1995) study were similar to the

Jewett et al., 2000 study in that AHH levels decreased with time and distance from EVOS.

In the tissue assays conducted on fish collected in 1997, the only significant differences observed

between zones were in the CYPlA concentrations in the halibut kidney tubules, although a

similar progression between zones was seen for all three cell types. In addition, when all three

CYPlA response variables were regressed against all of the tissue contaminant concentrations,

kidney tubule response did not correlate positively with any tissue measures. Similar results

were obtained for the tissues assayed in 1998. In 1997, Halibut were the only fish species caught

in significant numbers in all sampled zones, while in 1998, both Halibut and Pacific Cod were

caught in sufficient quantities in all sampled zones to allow investigation of differences between

CYPlA scores for both species. The results, however, are similar to 1997 in that there was no

significant correlation between or within species, scores, and zones. The exception to this is

cytoplasmic vacuolation in hepatocytes, which is a non-specific response of these cells that may

in some circumstances be linked to contamination.

There is the possibility that the CYPlA responses seen in some cells, i.e, kidney tubules and

kidney vascular endothelium, could be due to unmeasured factors. Relatively high levels of

kidney cell induction have been noted in other species in circumstances where contaminants are

apparently not a factor (Stegeman, personal communication). These tissues could be responding

to natural inducers, either endogenous or exogenous.

The low to moderate levels of induction observed in the fish collected in this study could also be

a response to contaminants not measured in this study, e.g., chlorinated hydrocarbons such as the

PCB. Chlorinated hydrocarbons, especially the coplanar forms of PCB, dibenzofurans, and

dioxins, are known inducers of CYPlA in fish (Stegeman et aZ., 1992). Halibut are piscivorous,

and therefore relatively high on the marine food chain, and likely to accumulate some of these

globally ubiquitous and slowly metabolized contaminants. In addition, it is well understood that

polar, and possibly sub-polar environments, are apparently sinks for chlorinated hydrocarbons

that are transported long distances in the atmosphere from lower latitudes. Recent measurement

of chlorinated hydrocarbons in the tissues of harbor seals (Small et al., 1998) and killer whales

(Matkin et al., unpublished) have confirmed high tissue concentrations of PCBs (high parts per

million) that confirm that the Gulf of Alaska receives significant inputs of these biologically

active molecules. It is therefore almost certain that fish in the northern Gulf of Alaska ecosystem

are also contaminated with such compounds, but probably at 10 to 100 times lower

concentrations. One recent study (Ewald et al., 1997) of biotransport of organic pollutants (PCBs

and DDTs) by Alaskan Sockeye salmon to their inland spawning lakes in the copper river

drainage, found muscle lipid concentrations of PCBs of 670 rig/g and DDTs of 221 rig/g in fish

caught in the Gulf of Alaska just prior to upriver migrations. These concentrations are far below

levels of concern for human health from consumption, and are 10 times lower than reported in

Atlantic salmon from the Baltic Sea (Larsson et al., 1996), and 20 times lower than those

reported for salmonids in Lake Ontario (Oliver and Niimi, 1988).

The low induction of CYPlA in gill tissues of all three fish species would be consistent with

waterborne sources of contamination being extremely low for these bottom-dwelling fish in

4-15
lower Cook Inlet and Shelikof Strait. This finding is also consistent with the low concentrations

of PAH and the very low P450 RGS responses seen in sediment extracts in this study. On the

other hand, the responses in the liver hepatocytes and the two cell types in the kidney are

consistent with some level of inducing compounds in the diet. With the currently available data

it is not possible to assign this low to moderate level of CYPlA induction to any particular group

of compounds. While serving as a useful benchmark for measures of CYPlA induction in fish

from Shelikof Strait and other relatively pristine areas of the world, future studies of fish from

this region should attempt to collect greater numbers of fish from which to base statistical

analyses and should also collect non-migratory species from lower trophic levels, due to the

ability of fish to metabolize PAH. Additionally, other studies of fish from Alaska and other

regions intent on determining exposure to xenobiotics have included measurement of bile

hydrocarbons (Varanasi et al., 1995, Jewett et al., 2000). These measurements have proven useful

in determining recent exposures to PAH. The lack of tissue residue analysis for other CYPlA

inducing compounds in the present study hindered the authors in attempting to relate CYPlA

induction to PAH alone.

4.4.6 Assessment of Ecological Risk

Sediment and fish tissue sampling in 1997 and 1998 has provided a picture of contaminants and

potentially toxic trace substances in the environment at very low concentrations with an attendant

low biological risk. The concentrations of trace metals are consistently below the risk levels

identified by Long and Morgan (1990), except for Ni, which has a crustal abundance higher than

the designated ERL and ERM concentrations. The concentrations of PAH detected in sediments

are also below the ERL identified by Long and Morgan (1990). The P450 RGS results also

indicated low to negligible biological risk associated with extractable organic compounds,

namely PAH, in the sediments. Sediment bioassays with amphipods produced some low survival

rates, but these appear to be related to testing sediments with a high silt content rather than any

trace chemicals in the sediments, be they natural or anthropogenic in origin. The levels and

patterns of induction of CYPlA in cells of bottom-dwelling fish are consistent with some mild

induction by contaminants, but with weak induction in the gills they appear not to be waterborne,

but rather from the diet. None of the measured contaminants in the fish tissues correlated with

CYPlA induction, but chlorinated hydrocarbons were not measured.

In summary, in the context of the null hypothesis, our results indicate that the concentrations

of organic and metal parameters in the sediments of outermost Cook Inlet and Shelikof

Strait do not appear to pose any immediate ecological risk to the marine organisms in the

study area.

4-16








0 5 10 15 20

2000 1 ’ 1 ’ ’

- P b l o-cm -

1980 - ?

4

1960 - \

\

1940 ; -

.

I

1920 - i

1900 ?

ZlFl l

0.00 0.08 0.16

2000 -

1980 - Hg 2T : I _

1960 - h-‘iZk) ?-

1940 - ;’

i

1920 - \z: /

1900 - /’

,F

$1

:

ZOFl-1998 b

2600

0 5 10 15 20

1980

1960

1940

4

1920

1900

/ i

z3F2

0.00 0.05 0.10

2000 I I

- Hg ; h-%49

1980 - i

? 7

1960 - 4\ i

‘\ \

1940 - :,

ZlFl ;

I

Figure 4-9: Vertical Profiles of Pb and Hg Values in Sediment Cores

versus Time (Station identification in lower left hand corner)
0 20 40 60 80 100

2000 1 7 i 1 1 1

hk> f Cr !

1980 - i

1960 - I

1940

k - +

1920 -

1900

l ë? - ZlFl /

i:

1980

1960

1940

1920

1900

z2F2

0 20 40 60 80 100

2000 1 3 1 / I ’

- wia I cr

1

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1980 - J

4

:

i

1960 -

T 1

1940 -

1920 ‘\ - k

‘*

1900 -

ZlF2 l

1980

1960 i

\

\

b

i

‘\,

1940

./

1920

1900

i z3Fz Cd i

Figure 4-10: Vertical Profiles of Cr and Cd Values in Sediment Cores

versus Time (Station identification in lower left hand corner)
ZOFl ZOF6 ZlFl

Perylene (uglg)

0 0.06 0.12 0.19

0

. . . . . . . . . . . . . . . . .

40

. . . . . . . . . . . . . . . . .

z 80

f

g 120

0

:

; 160

l--t-

,990

,950

. . . . . . . . . . . . . . . . ,920

200

240 i f

Z2R16

Perylene (uglg)

0 0.02 0.04 0

3

6

9 g . . . . . . . . . . . . . . . .

-‘(

,2

5 15 :

0 18 h

: 2124

-1980

2 7

. . . . . . . . . . . . . . . ..a

I i’

-1950

30

33

Perylene (ug/g)

0 0.01 0.02

...... ................ il;............. ..........

................. .....

27 1

Z3F2 Z4F4

Perylene (uglg)

0 0.02 0.04

0

5

. . . . . . . . . . . . . . . . . . . . . . . . .

g

10

c 15

X

a

O 20 E

lil

o.............. . . . . . . . . .

o 25

30

. . . . . . . . . . . . . . . . . ..*......

3 5

1990

1950

1920

1990

1950

1920

Perylene (uglg)

0 0.01 0.02 0.03

0

. . . . . . . . . . . . . . . . . . . . . 5

,990

pm

v . . . . . . . . . . . . . . . . . . . . . .

f

$ 15

a

:

; 20

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1950

25

1

. . . . . . . . . . . . . . . . . . . . . . . ,920

Perylene (ug/g)

0 0.02 0.04 0.06

J---F12 -

E

z 18 - . . . . . . . . ..I I.....

a

n 24

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1990

s

o 30

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.. . . . . . .. . . .. . .. . ,950

38

42 1

Figure 4-11: Sediment Core Profile of Perylene within each Zone.
1997 Zone 0. Core Fl

0.5

0.4

0.3

%

e

P

cs

0.2

0.1

0 t

0

Homer Coal

\ +-

Mean Cook Inlet Crude (i 1 SD)

0 2

C2DK2P 0.3 0.4 0.5

0.5 -

1998 Zone 0, Core Fl

0.4 -~ _ *.-MmHomer Coal +---

+xz

0.3 -

\

%

+“;ong

Q

Beluga

e

+-+l+m

0

0.2 -

Mean Cook Inlet Crude (* 1 SD)

+ ac ~Matanuska Coals

0

0 0.1 0.2

C2DIC2P

0.3 0.4 0.5

Figure 4-12: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Cores ZOFl

(Core-depth*) and Sources (abbreviations are in Table 2-2).

* for exam& Core-12 is the results for the core section taken at the 12 centimenter interval.
1997 Zone 0, Core F5

0.5

0.4

0.3

%

Q

0

G

0.2

0.1

0

0.5

0.4

0.3

i+

Q

P

8

0 2

0.1

0

t

Homer Coal

+“sr

+-Ml

Beluga

+a* 4

Matanuska Coals

0 0.1 0.2 0.3 0.4 0.5

C2D/C2P

1997 Zone 0, Core F6

t

Homer Coal

hi ++-

+Kc1

Beluga

Mean Cook Inlet Crude (t 1 SD)

+a< eMatanuska Coals

0 0.1 0.2

C2DIC2P

0.3 0.4 0.5

Figure 4-13: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Cores ZOF5 (top,

Core-depth*), ZOF6 (bottom, Core-depth*) and Sources (abbreviations in Table 2-2).

* for example, Core-12 is the results for the core section taken at the 12 centimenter interval.
1998 Zone 0, Core F8

0.5

0.4

0.3

k

Q

4

0

0.2

0.1

0 TBeluga

Homer Coal

\ +-

+K’

+-

Mean Cook Inlet Crude (t 1 SD)

+-at Matanuska Coala

0 0.1 0.2 0.3 0.4 0.5

C2DIC2P

Figure 4-14: Double Ratio Plot of C2D/C2P versus C3DK3P for Sediment Core ZOFS

(Core-depth*) and Sources (abbreviations in Table 2-2).

* for example, Core-12 is the results for the core section taken at the 12 centimenter intend
0.5

0.4

0.3

fk

e

R

0

0.2

0.1

0

0.5

0.4

0.3

i%

Y

4

0

0.2

0.1

0

1997 Zone 1, Core Fl

Homer Coal

\

+-

+-wr

Beluga

“I; \+-

‘Mean Cook Inlet Crude (+ 1 SD)

+ aeMatanuska Coals

0 0.1 0.2 0.3 0.4 0.5

C2DIC2P

1997 Zone 1 , Core F2

Homer Coal

L+,, +-

Beluga

Cc& -b+,

\

Oil Bav \y+s9cI +”

\.

Sediment

Background .

’ Mean Cook Inlet Crude (* 1 SD)

+ CL-Z +=

-Matanuska Coals

0.2 0.3

C2DlC2P

Figure 4-15: Double Ratio Plot of CZDK2P versus C3D/C3P for Sediment Cores ZlFl (top,

Core-depth*), ZlF2 (bottom, Core-depth*) and Sources (abbreviations in Table 2-2).

* for example, Core-12 is the results for the core section taken at the 12 cent&enter interval.
1997 Zone 2, Core Fl

0.5

0.4

0.3

%

9

$2

0

0.2

0.1

0

0.5

0.4

0.3

ik

Q

P

s

0.2

0.1

0

t

Homer Coal

L+_, +-

Beluga

Oil Say

Seep Oil

Well Creek

Seep Oil

b

I

+m-a +

.CS4

‘Mean Cook Inlet Crude (+ 1 SD)

0 0.1 0 2

C2DK2P

0.3 0.4 0.5

1997 Zone 2, Core F2

Homer Coal

+-

-WC,

Sediment

Baokgrolmd

‘Mean Cook Inlet Crude (i 1 SD)

0 0.1 0.2 0.3 0.4 0.5

C2D/C2P

Figure 4-16: Double Ratio Plot of C2DK2P versus C3DK3P for Sediment Cores Z2Fl

(top, Core-depth*), Z2F2 (bottom, Core-depth*) and Sources (abbreviations in Table 2-2).

* for example, Core-31 is the results for the core section taken at the 31 centimenter interval.
0.5

0.4

0.3

f+

Y

0

8

0.2

0.1

0

1998 Zone 2, Core R16

Homer Coal

Seluga

Sediment

Background

Mean Cook Inlet Crude (i 1 SD)

+ “cd Matanuska Coals

0 0.1 0.2 0.3 0.4 0.5

C2DlC2P

Figure 4-17: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Core Z2R16

(Core-depth*) and Sources (abbreviations in Table 2-2).

* for example, Core-30 is the results for the core section taken at the 30 centimenter interval.

IhthwDLittle
0.5

0.4

0.3

%

Q

4

0

0.2

0.1

0 +

1997 Zone 3, Core Fl

Homer Coal

Seluga

“I\\- +- +*

’ Mean Cook Inlet Crude (i 1 SD)

+ “u Matanuska Coals

0 0.1 02 0.3 0.4 0.5

C2DIC2P

1997 Zone 3 , Core F2

Background

‘Mean Cook Inlet Crude (i 1 SD)

+ az ~Matanurka Coals

0.2 MDKPP

0.3

Figure 4-18: Double Ratio Plot of C2D/C2P versus C3D/C3P for Sediment Cores Z3Fl (top,

Core-depth*) Z3F2 (bottom, Core-depth*) and Sources (abbreviations in Table 2-2).

* for example, Core-OS is the results for the core section taken at the 5 centimenter interval.
1998 Zone 4. Core F4

0.5

0.4

0.3

2

0

b

0”

0.2

0.1

0 !

Homer Coal

Beluga +*81

Oil Bay

Seep Oil

4-w

K Matanuska Coals

0 0.1 0.2 0.3 0.4 0.5

C2DIC2P

Figure 4-19: Double Ratio Plot of C2DK2P versus C3DK3P for Sediment Core Z4F4

(Core-depth*) and Sources (abbreviations in Table 2-2).

* for example, Core-32 is the results for the core section taken at the 32 centimenter interval.
I Low i Mean High

4 , I

ERM

3 -

8

h

,1 2 -

8 ERL -

1;.----------------------

0’ - - ---a--’

Zone0 Zone1 Zone2 Zone3 Zone4

80 ,

60- z ?t 40 2 t

I

2 0

n”

Zone0 Zone 1 Zone 2 zone 3

10 j

ERM :

8 -

2 r ERL 1

0--

_____._____________ _____

1

Zone0 Zone 1 Zone2 Zone3 Zone4

Figure 4-20: Comparison of Minimum, Mean, and

Maximum Concentrations of (a) Ag, (b) As, and (c) Cd

for Surficial Sediments from Zones 0, 1,2,3 and 4 to the

Effects Range Low (ERL) and the Effects Range Medium

(ERM) Values (Long et al., 1995).

Em = -mm-; Em =
0 LOW n Mean High

ERM

300

55

3

2 200

6

100

0

Zone0 Zone1 Zone2 Zone3 Zone4

300 , I

0

Zone0 Zone1 Zone2 Zone3 Zone4

L

0.6 t

s

2%t 0.4

I”

0.2 .-_______.

0.0

Zone0 Zone1 Zone2 Zone3 Zone4

Figure 4-21: Comparison of Minimum, Mean, and

Maximum Concentrations of (a) Cr, (b) Cu, and (c) Hg for

Surficial Sediments from Zones 0, 1,2,3 and 4 to the Effects

Range Low (ERL) and the Effects Range Medium (ERM)

Values (Long et al., 1995).

Em = ----; Em = -
3 Low 0 Mean High

60 , I

Zone 0 Zone 1 Zone 2 Zone3 Zone4

0

Zone0 Zone1 Zone2 Zone3 Zone4

400

ERM

s 300

2J

r5,1 200

100

0

zoneo zone 1 zone2 zone3 zone4

Figure 4-22: Comparison of Minimum, Mean, and

Maximum Concentrations of (a) Ni, (b) Pb, and (c) Zn for

Surficial Sediments from Zones 0, 1,2,3 and 4 to the Effects

Range Low (ERL) and the Effects Range Medium (ERM)

Values (Long et al, 1995).

Em = ----; Em = -
10000

1000

100

10

1

Comparison of Sediment Total PAH Concentrations to ERL and ERM Values

100000 T

ERM = 44,000

ERL =4Oii -

-

Zone 0 Zone 1 Zone 2 Zone 3 Zone 4

OMin

-Max

. . ERL

- - ERM

Figure 4-23: Comparison of Sediment Total PAH Concentrations to ERL and ERM Values (Long et al., 1995).
Table 4-1: Data for Sediment Deposition in Outermost Cook Inlet and the Shelikof Strait

ArthwDLittle
Table 4-2: Metal/Metal Ratios for Bottom and Suspended Sediment from Area Rivers

Susitna River

Bottom Sediment

Suspended Sediment

340

372

1.32

1.33

24.8

23.7

1.13

1.22

25.3

23.1

Average 24.2 356 1.32 24.2 1.18

Kuik River

Suspended Sediment 28.5 582 0.98 38.1 1.81

Matanuska River

Suspended Sediment 0 318 1.83 37.0 1.06

Average S-K-M Rivers (83: 11:6) 27.3 379 1.31 26.4 1.16

Copper River

Bottom Sediment

Suspended Sediment

34.4

37.2

516 2.24 35.4 1.78

509 2.40 37.5 1.65

Average 35.8 512 2.32 36.4 1.72
- Table 4-3: Summary of Results from Model for Identifying Sediment Sources in

Outermost Cook Inlet and the Shelikof Strait

Notes:

Alaska Coastal Current Sediment

O(excldi.qZOFl)

1

2

3

4

R&2,3,4

(0)“”

78~26

75%30

81k24

87k.8

84*8

81*22

* Meau + 2 standard deviations (i.e., 95% confidence interval)

** Results suggest no inputs from S-K-M Rivers, but possible inputs from source(s) other

thin the Copper River.

RrthwDLittDe
5.0 Recommendations

Based on the results and interpretation of the samples collected from the 1997 and 1998

outermost Cook Inlet and Shelikof Strait field surveys, there are a number of recommendations

for future monitoring and scientific studies of the region.

Future Monitoring

l Based on the results of this study, future monitoring of the sediments and biota of the area

should be performed if new offshore oil exploration and production activities in the area are

planned. In the absence of any oil exploration activities, a smaller, focused sediment and

tissue program (chemistry and biology) could be performed over the next 5 to 10 years to

confirm the trends reported in this study.

l Future monitoring in the area should include both intertidal and shallow subtidal depositional

areas, and embayments (Kamishak Bay, Alaskan Peninsula, Kodiak, and Afognak) of

outermost Cook Inlet and the Shelikof Strait. This would add to the baseline data generated

for this program, which focused on the deep depositional areas.

l Future studies should include additional samples of seep oils and associated river/stream

sediments from the Iniskin Peninsula and the Alaskan Peninsula. These samples would serve

to confirm the historical hydrocarbon source relationships observed in this study and add new

potential petroleum hydrocarbon sources for evaluation.
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7.0 Publications

Sediment Quality in Depositional Areas of the Shelikof Strait and Outermost Cook Inlet.

Sediment Profile Zmaging Report. Prepared by EVS Environmental Consultants under contract

to Arthur D. Little, Inc. for U.S. Department of the Interior, Minerals Management Service,

Anchorage, Alaska. OCS Study MMS 99-0003. 40 pp.

Sediment Quality in Depositional Areas of Shelikof Strait and Outermost Cook Inlet, Final

Literature Synthesis. Prepared by Arthur D. Little, Inc. for U.S. Department of the Interior,

Minerals Management Service, Anchorage, Alaska. OCS Study MMS 97-0015. 69 pp.
The Department of the Interior Mission

As the Nation’s principal conservation agency, the Department of the Interior has responsibility for

most of our nationally owned public lands and natural resources. This includes fostering sound use of

our land and water resources; protecting our fish, wildlife, and biological diversity; preserving the

environmental and cultural values of our national parks and historical places;

and providing for the enjoyment of life through outdoor recreation. The Department assesses our

energy and mineral resources and works to ensure that their development is in the best interests of

all our people by encouraging stewardship and citizen participation in their care. The Department

also has a major responsibility for American Indian reservaiion communities and for people who live

in island territories under U.S. administration.

The Minerals Management Service Mission

As a bureau of the Department of the Interior, the Minerals Management Service’s (MMS) primary

responsibiiities are to manage the mineral resources located on the Nation’s Outer Continental Shelf

(OCS), collect revenue from the Federal OCS and onshore Federal and Indian lands, and distribute

those revenues.

Moreover, in working to meet its responsibilities, the Offshore Minerals Management Program

administers the OCS competitive leasing program and oversees the safe and environmentally sound

exploration and production of our Nation’s offshore natural gas, oil and other mineral resources. The

MMS Royalty Management Program meets its responsibilities by ensuring the efficient, timely and

accurate collection and disbursement of revenue from mineral leasing and production due to Indian

tribes and allottees, States and the U.S. Treasury.

The MMS strives to fulfill its responsibilities through the general guiding principles of: (1) being

responsive to the public’s concerns and interests by maintaining a dialogue with all potentially affected

parties and (2) carrying out its programs with an emphasis on working to enhance the quality of life for

all Americans by lending MMS assistance and expertise to economic development and environmental

protection.

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