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OCS Study MMS 2001-104

ANIMIDA Phase I: Arctic Nearshore

Characterization and Monitoring of the Physical

Environment in the Northstar and Liberty

Development Areas

Final Report

Submitted to:

U.S. Department of the Interior

Minerals Management Service

Anchorage, Alaska

Submitted by:

Arthur D. Little, Inc.

Cambridge, Massachusetts

Contract No.143501..99..CT..30998

IJAfS U..5. Department of the Interior

Minerals ManagementService

Alaska Outer Continental Shelf Region
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ANIMIDA Phase I: Arctic Nearshore Characterization and

Monitoring of the Physical Environment in the

Northstar and Liberty Development Areas

Final Report

Dr. Paul D. Boehm, Principal Investigator

Arthur D. Little, Inc.

20 Acorn Park

Cambridge, Massachusetts

02140

Current Address - Battelle

255 Bear Hill Road

Waltham, Massachusetts

02451

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

Minerals Management Service (MMS), Alaska Outer Continental ShelfRegion,

Anchorage, Alaska, under Contract No. 143501-99-CT-30998,

as part of the MMS Alaska Environmental Studies Program.

December 2001

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

are those ofthe 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

or recommendation for use by the Federal Government.
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List of Authors

Mr. John Brown, Battelle

Dr. Paul Boehm, Battelle

Mr. Henry Camp, Arthur D. Little, Inc. (ADL)

Ms. Linda Cook, ADL

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

Mr. Robert P. Trocine, FIT

Mr. Robert D. Rember, FIT

Mr. George Shepard, BBN Technologies (BBNT)

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Table of Contents

List of Acronyms and Abbreviations x

Executive Summary ES~1

1.0 Introduction 1~1

1.1 Environmental Description 1-1

1.1.1 Study Area · 1-1

1.1.2 Physical Environment. 1-2

1.1.3 Biological Environment 1-3

1.2 Development History in the Study Area 1-5

1.3 CurrentJProposed Oil Development 1-5

1.3.1 Northstar 1-5

1.3.2 Liberty 1-6

1.4 Potential Contaminants and Disturbances of Concern 1-6

1.5 Study Objectives 1-7

1.5.1 Research Questions and Hypotheses 1-8

1.6 Limitations of this Study, 1-10

2.0 Methods : 2~1

2.1 Field Methods and Study Design 2-1

2.1.1 Study Design 2-1

2.1.2 Summer 1999 Field Sampling 2-2

2.1.2.1 Summer 1999 Field Sampling Procedures 2-3

2.1.3 Winter 2000 Field Sampling 2~6

2.1.3.1 Winter 2000 Through-Ice Field Sampling Procedures 2-7

2.2 Analytical Methods 2-9

2.2.1 Ancillary Parameters 2-9

2.2.1.1 Grain Size 2-9

2.2.1.2 Total Organic Carbon 2-9

2.2.2 Organic Chemical Parameters 2-10

2.2.2.1 Sample Preparation 2-10

2.2.2.2 Organic Instrumental Analysis 2-12

2.2.3 Stable Carbon Isotopes (13Carbon) 2-13

2.2.4 Inorganic Parameters 2-14

2.2.4.1 Trace and Major Metals Analysis in Suspended and

Surficial Sediment 2-14

2.2.4.2 Methyl Mercury Analysis in Sediment : 2-15

2.2.4.3 Trace and Major Metals Analysis in Organism Tissue : 2-15

2.3 Quality Assurance/Quality Control 2-16

2.3.1 Quality Assurance 2-16

2.3.1.1 Documentation 2-16 '

2.3.1.2 Quality M~nagement.. 2-17

2.3.1.3 Sample Custody, Preservation, and Tracking 2-18

2.3.2 Field Quality ControL 2-20

2.3.2.1 Sample Handling 2-20

2.3.2.2 Quality Control Samples 2-20

u:lmms animidalphase I reportllinal report lileslfinal section 0- TOe and more.doc
Table of Contents (continued)

2.3.2.3 Documentation , 2-211

2.3.3 Organic Chemistry Laboratory Quality Control.. 2-21I

2.3.3.1 Data Quality Objectives and Quality Control Samples 2-21

2.3.3.2 Laboratory Records 2-22,.

2.3.3.3 Laboratory Data Review 2-23

2.3.4 Metals Chemistry Laboratory Quality Control 2-23

2.4 Database Management 2-25

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3.0 Results 3·1

3.1 Surficial Sediments (0-1 em) ~-1

3.1.1 General Chemical and Physical Measurements 3-1

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3.1.1.1 Total Organic Carbon and Grain Size 3-1

3.1.2 Organics : 3,-2

3.1.2.1 Saturated Hydrocarbons ~-2

3.1.2.2 Polynuclear Aromatic Hydrocarbons 3-3,

3.1.2.3 Steranes and Triterpanes 3-3

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3.1.3 Metals 3-3

3.2 Suspended Sediments 3,-5

3.2.1 Physical Measurements 3-5

3.2.1.1 Turbidity and Total Suspended Solids August 1999 3,-5

3.2.1.2 Turbidity and Total Suspended Solids - April 2000 3-6

3.2.1.3 Particulate Organic Carbon - August 1999 3:-7

3.2.1.4 Particulate Organic Carbon - April 2000 3~8

3.2.2 Metals 3-8

3.2.2.1 August 1999 3-8

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3.2.2.2 April 2000 3-8

3.2.3 Stable Carbon Isotopes (8C13) 3~9

3.2.4 Ice Cores 3-10J

3.3 Tissues 3-11

3.3.1 Organics 3-11

3.3.2 Metals 3-11

3.4 Quality Control Results 3-12

3.4.1 Field Quality ControL 3-12

3.4.1.1 Equipment Blanks : 3-p

3.4.1.2 Field Blanks 3-13

3.4.1.3 Field Replicates , 3-13

3.4.2 Organics Quality Control 3-14

3.4.2.1 Surrogate Results 3-!4

3.4.2.2 Procedural Blanks 3-15

3.4.2.3 Blank Spike Sample Recoveries 3-15

3.4.2.4. Laboratory Duplicates 3-16

3.4.2.5 Standard Reference Materials 3-17

3.4.2.6 Control Oil Analyses 3-17

U:\mms animidalphase I reportlfinal report fileslfinal section 0- TOC and more.doc ii

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u:\mms animidalphase I reportlfinal report fileslfinal section ()- TOe and more.doc iii

6.0 References 6-1

List of Appendices

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Metals Laboratory Quality Control ~~ 3-18

3.4.3.1 Procedural Blanks 3-18

3.4.3.2 Matrix Spike Sample 3-18

3.4.3.3 Laboratory Duplicates 3-18

3.4.3.4 Standard Reference Materials 3-18

3.4.3

4.0 Discussion ....................................................................................•.......................4-1

4.1 Surficial Sediments (0-1 :cm) .4-1

4.1.1 Metals 4-1

4.1.1.1 BSMP Elements 4-1

4.1.1.2 New ANII\1IDA Metals 4-4

4.1.2 Hydrocarbons 4-5

4.1.2.1 Hydrocarbon Sources 4-5

4.1.2.2 Spatial Variability 4-8

4.1.2.3 Temporal Variability 4-9

4.1.2.4 Sediment Quality Guidelines .4-10

4.2 Organisms 4-11

4.2.1 Metals 4-11

4.3 Suspended Sediment in Water and Ice .4-13

4.3.1 Physical Considerations 4-13

4.3.2 Chemical Considerations 4-15

Table of Contents (continued)

5.0 Recommendations and Phase II Plan Summary 5-1

5.1 Recommendations 5-1

5.2 Phasell Plan Summary 5-1

Appendix A: Grain Size and Total Organic Carbon Data

Appendix B: Organics Data

Appendix C: Metals Data

Appendix D: Suspended Sediment Data

Appendix E: Water Column Data

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List of Tables

Section 2

Table 2-1:

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:

Section 3

Table 3-1:

Table 3-1a:

Table 3-2:

Table 3-3:

Table 3-4:

Table 3-5:

Table 3-6:

Table 3-7:

Table 3-8:

Table 3-9:

Table 3-10:

Table 3-11:

Table 3-12:

Table 3-13:

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MMS ANIMIDA Summer 1999 Sampling Stations

MMS ANIMIDA Winter 2000 Sampling Stations

Saturated Hydrocarbons Target List

Polynuclear Aromatic Hydrocarbon and Alkyl Polynuclear Aromatic

Hydrocarbon Target List ./

Sterane and Triterpane Target List .

Summary of Instrumental Methods and Method Detection Limits for Me~al

Analysis of Sediment and Organisms

Sample Containers, Preservation, and Laboratory List

Data Quality Objectives for SHC and Polynuclear Aromatic Hydrocarbon

Analyses --

Data Quality Objectives forsrr Analyses

Data Quality Objectives and Criteria for Metals Analyses

Summary Data by Region for Metals, Total Organic Carbon, and Grain Size

Summary Data ShoWing Within-Site Variability for Conce:ntrations of Metals , in

Sediment Samples :

Map Showing Beaufort Sea Monitoring Program Sampling Stations and Table of

Concentrations for Selected Organic Parameters and Grain Size in Sediment

I Samples '

Map ShoWing Northstar Sampling Stations and Table of Concentrations for

Selected Organic Parameters and Grain Size in Sediment Samples :

Map Showing Liberty Sampling Stations and Table ofConcentrations for

Selected Organic Parameters and Grain Size in Sediment Samples .

Diagnostic Ratios and Parameters of Saturated Hydrocarbons, PolynUclear• Aromatic Hydrocarbons, and Steranes and Triterpanes ;

Average Total Organic Carbon in Surficial Sediments trom ANIMIDA Study

Area, Alaska Marine Sediments, and Cook Inlet and the Shelikof Strait Sediments

Map of Beaufort Sea Monitoring Program Sampling Stations and Table o:f

Concentrations for Selected Metals in Sediment Samples i

Map of Northstar Sampling Stations and Table ofConcentrations for Selected

Metals in Sediment Samples I

Map of Liberty Sampling Stations and Table of Concentrations for Select.ed

Metals in Sediment Samples . I

Map of Stations Sampled during April 2000 for Total Suspended Sediment and

Laboratory Turbidity and Table of Results

Summary Data by Region for Metals in Suspended Sediment Samples 1

Results forOCI3 in Surface and Suspended Sediment Samples from the Beaufort

Sea Monitoring Program, Northstar, and Liberty Areas and from Local RIvers 1

Summary Results for oCl3 in Surface Sediment, Suspended Sediment, arid

Source Material Samples from the Study Area

u:mms animidalphase I repo~\finaJ repo~ files\finaJ section 0 • list of figures and tables. doc iv

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List of Tables (continued) I

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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:

.' ,

Map of Sampling Stations for Organisms and Table of Concentrations for

Selected Organic Parameters

Map of Sampling Stations for Organisms and Table of Concentration for Selected

Metals (Cd, Cu, Hg, and Pb)

Map of Sampling Stations for Organisms and Table of Concentrations for

Selected Metals (As, Ba, V, and Zn)

Organic Quality Control Result Summary - Polynuclear Aromatic Hydrocarbon

Analyses

Organic Quality Control Result Summary - Saturated Hydrocarbon Analyses

Organic Quality Control Result Summary - Sterane and Triterpane Analyses

Inorganic Quality Control Result Summary - Trace-Metal Analyses

SRMs Results for BCSS-1 and MESS-2

SRM Results for Trace Metals in Mussel Tissue, Dogfish Muscle, and Water·

SRM Results for Trace Metals in River and Marine Sediment

u:mms animidalphase I teportlfinal report fileslfinal section O· list of figures and tables. doc V
List of Figures

Section 1

Figure 1-1:

Figure 1-2:

Figure 1-3:

Figure 1-4:

Figure 1-5:

Section 2

Figure 2-1:

Figure 2-2:

Section 3

Figure 3-1:

Figure 3-2:

Figure 3-3:

Figure 3-4:

Figure 3-5:

Figure 3-6:

Figure 3-7:

Figure 3-8:

Figure 3-9:

Figure 3-10:

Figure 3-11:

Figure 3-12:

I:igure 3-13:

Figure 3-14:

Map of the ANIMIDA Phase I Study Area

Drifter Tracks in the Beaufort Sea

General Map of Onshore' and Offshore Oil and Gas Development in the *udy

Areas '

• Generalized Description of Arctic Oil Developments I

Schematic of BP's Northstar Development !

Map of the ANIMIDA StUdY' Area Showing the Locations of the Sumlner 1999 I

Sampling Stations :

Map of the ANIMIDA Study Area Showing the Locations of the Winter 2000

Sampling Stations :

Map of Northstar Sampling Stations and Grain Size Histograms

Map of Liberty Sampling Stations and Grain Size Histograms

Total Organic Carbon versus Silt + Clay for Surficial Sediment Samples from

Beaufort Sea Monitoring Program, Northstar, and Liberty Stations I

Concentrations of Al versus (a) Silt + Clay and (b) Clay for Surficial Sed~ment

Samples from Beaufort Sea Monitoring Program;Northstar, and Liberty Stations

Concentrations of Al versus (a) Fe and (b) V for Surficial Sediment Samples from

Beaufort Sea Monitoring Program, Northstar, and Liberty Stations :

Concentrations of Total Hg versus Methyl Hg for Surficial Sediment Sarrlples

from 1999 ANIMIDA Study Area

Total Suspended Sediment versus Laboratory Turbidity for 1999 ANIMIDA

Study Area Samples ;

In situ Turbidity versus Laboratory Turbidity for 1999 ANIMIDA StUdy Area,'

Samples :

Vertical Profiles for In situ Turbidity for Station N13 Sampled on Three Different

Dates

Vertical Profiles for In situ Turbidity for Stations NOS, Nag, NIl, and N13

Sampled August 25, 1999 :

Vertical Profiles for In situ Turbidity, Current Velocity and Direction, Salinity,

and Temperature for Station N13 Sampled August 18,1999

Vertical Profiles for In situ Turbidity, Current Velocity and. Direction, Salinity,

and Temperature for Station N13 Sampled August 25, 1999 !

Vertical Profiles for In situ Turbidity, Current Velocity and. Direction, Salinity,

and Temperature for Station NOS Sampled August 26, 1999 •

Vertical Profiles for In situ turbidity for Stations LOS, Lll, 4B, and 3A Sampled

August 28-29, 1999

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List of Figures (continued)

Figure 4-1: Concentrations of Al versus Ba in Surficial Sediment Samples from Beaufort Sea

Monitoring Program Stations

Figure 4-2: Concentrations of Al versus Ba in Sediment Samples from (a) Beaufort Sea

Monitoring Program and Harrison Bay Stations and (b) Beaufort Sea Monitoring

Program, Northstar, and Liberty Stations

Figure 4-3: Concentrations of Al versus Fe for Sediment Samples from (a) Beaufort Sea

Monitoring Program Stations and (b) Beaufort Sea Monitoring Program,

Northstar and Liberty Stations

Figure 4-4: Concentrations of Al versuS Cr for Sediment Samples from (a) Beaufort Sea

Monitoring Program Stations and (b) Beaufort Sea Monitoring Program,

Northstar, and Liberty Stations. Concentrations of Al versus V for Sediment

Samples from (c) Beaufort Sea Monitoring Program Stations and (d) Beaufort Sea

Monitoring Program, Northstar, and Liberty Stations

Figure 4-5: Concentrations of Al versus Cu for Sediment Samples from (a) Beaufort Sea

Monitoring Program Stations and (b) Beaufort Sea Monitoring Program,

Northstar, and Liberty Stations. Concentrations of Al versus Zn for Sediment

Samples from (c) Beaufort Sea Monitoring Program Stations and (d) Beaufort Sea

Monitoring Program, Northstar, and Liberty Stations

Figure 4-6: Concentrations of Al versus Pb for Sediment Samples from (a) Beaufort Sea

Monitoring Program Stations and (b) Beaufort Sea Monitoring Program,

Northstar, and Libl1rty Stations. Concentrations of Al versus Cd for Sediment

Samples from (c) Beaufort Sea Monitoring Program Stations and (d) Beaufort Sea

Monitoring Program, Northstar, and Liberty Stations

Figure 4-7: Concentrations of Al versus (a) Ag, (b) As, (c) Hg and (d) Ni for Beaufort Sea

Monitoring Program, Northstar, and Liberty Sediment Samples

Figure 4-8: Concentrations of Al versus (a) Be, (b) Co, (c) Sb and (d) TI for Beaufort Sea

Monitoring Program, Northstar, and Liberty Sediment Samples

Figure 4-9: North Slope Crude Oil- GCIFID Chromatogram (top), PAR Distribution

Histogram (middle)"Triterpane Ion Chromatogram (bottom)

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Figure 3-16:

.Figure 3-17:

Figure 3-18:

Figure 3-19:

Figure 3-20:

Figure 3-21:

Section 4 .

'''. I' f .'

Vertical Profiles of Transmissivity for Stations 5(5), LA2, and LA3 Sampled

During April 2000

Vertical Profiles for Temperature at Stations Sampled During April 2000

Vertical Profiles for Salinity at Stations Sampled During April 2000

Vertical Profiles of Transmissivity for Stations Sampled Near Northstar During

April 2000

Concentrations of Al versus (a) Fe, (b) Ba, (c) Cu, and (d) Zn for Total Suspended

Sediment Samples

Concentrations of Al versus (a) Fe and (b) Ba for Total Suspended Sediment and

Source Material Samples

Concentrations of Al versus Fe for Ice Core Sediment, Total Suspended

Sediment, and Source Material Samples
List of Figures (continued)

Figure 4-10:

Figure 4-11:

Figure 4-12:

Figure 4-13:

Figure 4-14:

Figure 4-15:

Figure 4-17:

Figure 4-18:

Figure 4-19:

Figure 4-20:

Figure 4-21:

Figure 4-22:

Figure 4-23:

Figure 4-24:

Figure 4-25:

Figure 4-26:

Figure 4-27:

Figure 4-28:

Figure 4-29:

Colville River Sediment - GCIFID Chromatogram (top), PAH Distributi~m

Histogram (middle), Triterpane Ion Chromatogram (bottom)

Northstar Station 6 Sediment - GCIFID Chromatogram (top), PAH Distribution

Histogram (middle), Triterpane Ion Chromatogram (bottom) ;

Liberty Station 6 Sediment - GCIFID Chromatogram (top), PAH Dis.tribution

Histogram (middle), Triterpane Ion Chromatogram (bottom) ;

Station 3A Sediment - GCIFID Chromatogram (top), PAH Distribution;

Histogram (middle), Triterpane Ion Chromatogram (bottom) f

Station L08 Sediment -GCIFID Chromatogram (top),PAH Distribution;

Histogram (middle), Triterpane Ion Chromatogram (bottom) 'I

Station 5D Sediment - GCIFID Chromatogram (top), PAH Distribution:

Histogram (middle), Triterpane Ion Chromatogram (bottom)

Carbon Preference Index Plot of the Beaufort Sea Monitoring Prograim,ILiberty,

and Northstar Sediment Samples

Scatterplot of Total Organic Carbon and Silt + Clay Results versus Total:

Polynuclear Aromatic Hydrocarbon Less Perylene Concentrations for Be"aufort

Sea Monitoring Program, Northstar, and Liberty Surficial Sediment Samples

Scatterplot of Total Organic Carbon and Silt + Clay Results versus Total ,PHC

Concentrations for Beaufort Sea Monitoring Program, Northstar, and Lib~rty

Surficial Sediment Samples .

Scatterplot of Total Organic Carbon and Silt + Clay Results versus TotalPHC and

Total Polynuclear Aromatic Hydrocarbon Less Perylene Concentrations for

Beaufort Sea Monitoring Program, Northstar; and Liberty Surficial Sedirrl.ent , '. Samples ;

Regional Mean Total Polynuclear Aromatic Hydrocarbon Concentrations of

Surficial Sediment Samples for 1984, 1985, 1986, 1989, and 1999 1

Regional Mean Total PHC Concentrations of Surficial Sediment Samples for

1984,1985,1986,1989,and1999

Pyrogenic:Petrogenic Ratios of Beaufort Sea Monitoring Program Surficial

Sediment Samples for 1989 and 1999 •

Comparison of Regional Mean Total Polynuclear Aromatic Hydrocarbonl

Concentrations to SedimentQuality Criteria Effects Range-Low and Effects

Range-Medium Values "

Mean Concentrations of Ba,'Cd, Cu, Pb, V, and Zn in Clams (Astarte) Collected

from Beaufort Sea Monitoring Program Stations During 1986, 1989, and from

ANIMIDA Stations During 1999

Mean Concentrations of Ba, Cd, Cu, Pb, V, and Zn in Amphipods (Anonyx)

Collected from Beaufort Sea Monitoring Program Stations During 1986, 1989,

and from ANIMIDA Stations During 1999

Station 3A Astarte sp. Tissue - GCIFID Chromatogram (top), PAH Distribution

Histogram (middle), Triterpane Ion C~romatogram (bottom) ;

Total Polynuclear Aromatic Hydrocarbon Less Perylene Concentrations of

Beaufort Sea Monitoring Program Organisms for 1989 and 19?9 \

TPHC Concentrations of Beaufort Sea Monitoring Program Organisms for 1989 ~lm . i

Vertical Profiles for In situ Turbidity at Station N13 During August 1999

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List of Figures (continued)

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Vertical Distributioft of Sediment in lee Cores Collected During April 2000

Schematic RepresefH~tion of Release of Sediiiient from Melting Surface Ice

Concentrations of Al versus (a) Cu and (b) Cr for Total Suspended Sediment and

Source Material Samples Collected during August 1999

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Figure 4-30:

Figure 4-31:

Figure 4-32:

u:mms animidalphase I reponlfinal report fileslfinal section 0 • list 01 ligures and tables. doc ix
J

IIIIIIIIIIIIIIIIIII
List of Acronyms and Abbreviations I

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ADF&G

ADL

AMMTAP

ANIMIDA

ASTM

BBNT

BP

BPXA

BRD

BS

BSMP

°C

C

CAB

CaCl2

cm

cm/sec

CMI

COC

CORIS

COTR

CPI

CTD

CV

CVAAS

%D

DCM

DDW

DNA

DQO

DTT

EC&F

EDTA

EIS,

EPA

ERL

ERM

FAAS

FID

FIT

FY

g

GC

State of Alaska Department of Fish and Game

Arthur D. Little,Inc.

Alaska MarineMammal Tissue Archival Program

Arctic Nearshore Impact Monitoring in the Development Area

American Society for Testing and Materials

BBN Technologies

British Petroleum

British Petroleum Exploration Alaska

Biological Resource Division

Blank Spike

Beaufort Sea Monitoring Program

Degrees Celsius

Carbon

Cellulose-Acetate-Butyrate

Calcium Chloride

Centimeter

Centimeters per Second

Coastal Marine Institute

Chain of Custody

Coastal and Offshore Resource Information System

Contracting Officer's Technical Representative

Carbon Preference Index

Conductivity, Temperature, and Depth

Coefficient of Variation

Cold Vapor Atomic Absorption Spectrometry

Percent Difference

Dichloromethane

Distilled, Deionized Water

Deoxyribonucleic Acid

Data Quality Objectives

DithiothreitoI

Environmental Chemistry and Forensics

Ethylene Diamine Triacetic Acid

Environmental Impact Statement

U.S. Environmental Protection Agency

Effects Range-Low

Effects Range-Medium

Flame Atomic Absorption Spectrometry

Flame Ionization Detection

Florida Institute of Technology

Fiscal Year

Gram

Gas Chromatography

u:lmms animidalphase I reportlfinal report fileslfinal section (}.. TOe and more.doc x
List of Acronyms and Abbreviations (continued)

GCIMS

GFAAS

GPC

GPS

H20

H20 2

H2S04

HCI

HCI04

HDM

HF

RN03

HPLC

ICPIMS

ID

IRM

K-D

Kg

KLI

km

kts

L

LALK

LCS

m

MDL

mg

mL

MMS

MRL

MS

N

NIP

NBS

NCS

NIST

nm

NOAA

NODC

NRC

NSB

NTU

OCS

OCSLA

Gas ChromatographylMass Spectrometry

Graphite Furnace Atomic Absorption Spectrometry

Gel Permeation Chromatography

Global Positioning System

Water

Hydrogen Peroxide

Sulfuric Acid

Hydrochloric Acid

Perchloric Acid

Harvard Design and Mapping

Hydrogen Fluoride

Nitric Acid

High-Performance Liquid Chromatography

Inductively Coupled PlasmalMass Spectrometry

Inner Diameter

Instrument Reference Material

Kuderna-Danish

Kilogram

Kinnetic Laboratories, Inc.

Kilometer

Knots

Liter

Lower-Molecular-Weight Alkanes

Laboratory Control Spike

Meter

Method J)etection Lirilit

Milligram

Milliliter

Minerals Management Service

Minimum Reporting Limit

Mass Spectrometry

Normal

NaphthalenelPhenanthrene Ratio

National Bureau of Standards

Nitrogen~Carbon-SulfurAnalyzer

National Institute of Standards and Technology

Nautical Mile

National Oceanic and Atmospheric Administration

National Oceanographic Data Center

National Research Council of Canada

North Slope Borough

Nephelometric Turbidity Units

Outer Continental Shelf

Outer Continental Shelf Lands Act

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PAH

PAR

PB

PBOC

PCB

PDB

PHC

POC

POP

ppb

ppm

ppt

PVC

QA

QA/QC

QAM

QC

%REC

RIV

RF

RFP

RL

RLU

RPD

rpm

RRF

RSD

SIT

SAOB

SD

SDE

SHC

SIM

SOP

SQL

SRB

SRM

STP

TALK

TOC

TPHC

TSS

Organism-Sediment Index

Polynuclear Aromatic Hydrocarbon

Photosynthetic Active Radiation

Procedural Blank

Prudhoe Bay Operations Camp

Polychlorinated Biphenyl

Pee Dee Belemnite

Petroleum Hydrocarbons

Particulate Organic Carbon

Persistent OrganicPollutants

Parts Per Billion

Parts Per Million

Parts Per Trillion

Polyvinyl Chloride

Quality Assurance

Quality Assurance/Quality Control

Quality Assurance Manual

Quality Control

Percent Recovery

Research Vessel

Response Factor

Request for Proposal

Reporting Limit

Relative Light Unit

Relative Percent Difference

Revolutions Per Minute

Relative Response Factor

Relative Standard Deviation

SteraneslTriterpanes

Sulfide Antioxidant Buffer

Standard Deviation

Spatial Database Engine

Saturated Hydrocarbons

Selected Ion Monitoring

Standard Operating Procedure

Structured Query Language

Scientific Review Board

Standard Reference Material

Seawater Treatment Plant

Total Alkanes

Total Organic Carbon

Total Petroleum Hydrocarbons

Total Suspended Solids

Microgram

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List of Acronyms and Abbreviations (continued)

UCM

URSGWC

USFWS

USAEDA

USDOI

USGS

V/V

WBS

WWTF

ZGFAAS

Unresolved Complex Mixture

DRS Greiner Woodward Clyde

U.S. Fish and Wildlife Service

U.S. Army Engineering District, Alaska

U.S. Department of the Interior

United States'Geological Survey

Volume to Volume

Work Breakdown Structure

Wastewater Treatment Faci,lity

Zeeman Graphite Furnace Atomic Absorption Spectrometry

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Executive Summary

Overview • 'j

The Arctic Nearshore Impact Monitoring In the Development Area (ANIMIDA) program was

conceived and designed to monitor potential factors that might contribute to marine impacts

from offshore oil and gas development in the Beaufort Sea. In particular, the focus of this

program is British Petroleum's ongoing and planned developments - Northstar and Liberty. The

ANIMIDA program is being implemented in phases: Phase I focused on establishing preconstruction/development baselines; Phase II combines the continuation of this baseline survey

at Liberty along with initial impact monitoring at Northstar.

In the nearshore Alaskan Beaufort Sea, BP Exploration Alaska, Inc.'s (BPXA) offshore oil

development and production activities are underway at the Northstar site and as of November

2001, development is planned at the Liberty site. At each site, the oil field will be developed

from a gravel island. A sub-sea pipeline will carry oil shoreward for a land-based connection

with existing pipelines. Extensive Environmental Impact Statements (EISs) were prepared for

the Northstar area by the U.S. Army Engineering District, Alaska (USAEDA, 1999) and for the

Liberty area by the U.S. Department of the Interior (USDaI), Minerals Management Service

(MMS).

Over the past three decades, numerous onshore and offshore oil exploration and development

projects have been conducted in both the Alaskan and Canadian Beaufort Seas. Discoveries and

development include over 20 discoveries in areas such as Endicott (an offshore field in state

waters), Sagavanirktok Delta, North, Eider, and Badami. Because of these past activities, the

ANIMIDA study area cannot be considered "pristine" from a chemical perspective. Thus,

ANIMIDA was designed to both carefully define the "baseline" (pre-development) conditions

and to develop sensitive measurement programs that could detect incremental change in these

new development areas.

Phase I of ANIMIDA was designed and implemented with a focus on the 1999 late-summer,

open-water period and the winter 2000 ice-covered period. The late-summer 1999 sampling

represented pre-construction baselines at both the Northstar and Liberty areas. The winter 2000

sampling represented the first construction-monitoring period for Northstar and another preconstruction data acquisition opportunity at Liberty.

Information from this study will be used to 1) establish baseline environmental conditions prior

to oil development and production activities, 2) allow for assessment of impacts from oil

development and production activities, and 3) provide information needed in post-leasing

decisions to help minimize these impacts.

Program Objectives

The primary objectives of the ANIMIDA program are to characterize and monitor the physical

environment of the Northstar and Liberty development areas to evaluate potential and actual

impacts from these major offshore oil developments.

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The overall objectives of Phase I were to implement a measurement and monitoring program

focused on those parameters that could be used to determine the existence, extent, and:

magnitude of environmental effects from the Northstar and Liberty oil development projects.

The specific objectives for the Phase I effort are listed below: I

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I • Summarize the existing literature in the study area. This activitywas accomplished and

findings were presented in Boehm (2000). 1

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• Design and conduct data collection activities to begin to address key study questions and to

allow for later hypothesis testing. The specific data collection activities included: collection

of surface sediments, bivalves, and amphipods; collection of suspendl~d sediments and

regional source samples; and collection of acoustics data and ice cores.

• Develop recommendations for Phase II ofthe ANIMIDA program. Phase II

recommendations were developed based on the results of Phase I.

The plans for Phase II evolved from: a) consideration of the early results from Phase I \

monitoring; b) reviews of the program by the Scientific Review Board (SRB); and c) public

comments received at the first Program Workshop in October 1999 in Anchorage, Alaska.

Additional Phase II program objectives and specific study elements are described in Section 5.0

of this report. ,I,

The goals of the ANIMIDA program are to address a series of scientific questions concerning

the potential impacts of the Northstar and Liberty developments. Each question can then be

turned into a testable hypothesis, which guides the design of the technical program. A shmmary

of the five key questions used to formulate the hypotheses for the ANIMIDA program follows.

Question " 1. What are the background levels of chemicals of concern (i.e., the organic and tracemetal contaminants) that are known to be associated with oil exploration, development, and

production activities, and do the concentrations of these chemicals increase as a result of the

developments?

Question 2. If concentrations of organic and/or metal pollutants do increase in the envirbnment

as a result of the developments, do these increases pose an ecological "threat" or "risk"?!

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Question 3. Do the Northstar and/or Liberty development activities add significant amo~nts of

sediment particulate material to the waters and ice cover adjacent to the developments? '

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Question 4. If the levels of suspended particulates/sediments do increase as a result of the

developments, do these increases pose significant environmental risks to marine plants and

animals?

Question 5. Do the construction and operational activities at Northstar and/or Liberty result in

noise spectra and/or noise levels that differ from background levels? . ,

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The Developments

Northstar

The BPXA Northstar development project is located about 6 miles northeast of Prudhoe Bay.

While the Northstar island is in state waters, 6 to 7 wells are or will be in federal waters on the

Outer Continental Shelf. The project was approved by the U.S. Army Corps of Engineers in

May 1999 and by MMS in September 1999. Northstar is the first offshore oil production facility

in the Beaufort Sea without a causeway to shore and with a subsea pipeline system connecting it

to onshore processing facilities. Construction of the island was completed by October 2000 and

production drilling is underway. First production was initiated in the fourth quarter of 2001.

Recoverable reserves are estimated at 175 million barrels of oil. Production is expected to reach

a peak rate of 65,000 barrels per day in first quarter 2002.

~~ . A second BPXA-proposed project is the Liberty Prospect in F<;>ggy Island Bay, east of Prudhoe

Bay. It is located about 6 miles east of the Endicott Project. The proposed location is adjacent to

Tern Island, which was the site of exploration drilling dating back to 1982. The Minerals

Management Service published a draft EIS report for Liberty in early 2001 (USDOI, 2001); the

final EIS for Liberty is scheduled to be released in early 2002. Recoverable reserves are

estimated at 120 million barrels of oil. Drilling and production will take place on a gravel island

with a seabottom footprint of about 18 acres (-0.073 km2

), and an above-seawater footprint of

approximately 9 acres (-0.037 km2).

ANIMIDA StUdy Design

To meet the objectives of the program, the study design focused on measuring those parameters

that would be indicators of, or related to, any environmental impacts (i.e., could be used to

determine the existence, extent, and magnitude of environmental effects from the Northstar and

Liberty oil development projects, and to allow for later hypothesis testing). The elements of

primary focus included:

• Hydrocarbons and associated polynuclear aromatic hydrocarbons (PAHs) and metals as

primary contaminants of concern

• Sediment contamination

• Bioaccumulation of contaminants

• Suspended sediments - amounts and compositions - in water and in ice cores

• Other natural and anthropogenic sources of contaminants of concern

• Construction and operational noise

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The study design for Phase I involved several components:

• Design of a site specific radial array sampling grid around each development centroid

• Selection of area-wide stations that had previously been sampled as part of the lV1MS

Beaufort Sea Monitoring Program (1984-1990)

• Location and sampling of reference stations

• Identification of source samples for collection (e.g., river sediments)

Phase I sampling itself was conducted during an open-water sampling program in the late

summer (August/September) of 1999, and a "through-ice" sampling program in April/~1ay

2000. The summer 1999 field and analytical programs were intended to precede any \

construction and development activities at Northstar and called for a number of field s~pling

and related laboratory analysis elements:

.. Establishing sediment contaminant baselines following site-specific radial designs at

Northstar and Liberty areas

• Establishing contaminant baselines along the Northstar pipeline route

• Sampling historical BSMP locations previously sampled in the 1984-1986 and 1.989 annual

studies, inclUding Boulder Patch and reference locations

• Collecting surface sediments, bivalve molluscs, amphipods, and suspended sedime~ts

• Obtaining current profiles and bathymetric data .

• Collecting acoustic measurements

• Obtaining representative samples of sources and natural inputs for the chemicals (organics

and metals) of concern

• Analyzing sediment, suspended sediment, and biota samples for a full suite of diagnostic

organic and inorganic parameters 1

The "through-ice" sampling program in AprillMay 2000 was focused on initial monitoring of

Northstar construction activities on the island and pipeline corridors. Specific activities, of the

"through-ice" data collection activities were to:

• Resample a select subset of the summer 1999 stations

• Obtain current profiles and through-ice photosynth~tically active radiation (PAR)

measurements

• Conduct acoustic measurements

• Obtain and analyze suspended sediments for inorganic parameters

• Obtain and analyze ice cores for inorganic parameters

Findings

The summer 1999 and winter 2000 field sampling programs successfully obtained samples of

surficial sediments, riverine sediments and peat, biota (clams and amphipods), suspended

sediments, and ice cores in the ANIMIDA study area. Ancillary data on acoustics, currents,

PAR, and conductivity, temperature and depth (CTD) were also collected. Together, th~se data

represent the pre-production baseline for the Northstar and Liberty prospects for the ANIMIDA

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Phase I program, and will be usedforfuture comparisons to Phase IT measurements (i.e., postconstruction monitoring at Northsil:lt ftrid additional pre-proHuction baseline data for Liberty).

IJ?itial interpretations and evaluation of these baseline data have resulted in the following

preliminary summary findings:

Sediment Contaminants. Concentrations of hydrocarbons and metals in the sediments adjacent to

Northstar and Liberty are generally within the observed historical range for these parameters in

the overall study area. Typically PAR profiles indicate significant levels of a fossil fuel·type

signature, which appears to be sourced in organic shales brought to the sediments from river

runoff and coastal peat. Total natural baseline concentrations of PARs, a sum of 2- to 6-ringed

parent and alkylated PARs (40+ compounds or isomer groupings) range from <10 parts-perbillion (ppb) to 1,000 ppb. Sediment hydrocarbons, and more specifically PARs, are highly

correlated with the silt+clay content of the sediment. Anomalous PAR concentrations (i.e., levels

outside of the 95 percent confidence interval around a PAH/[silt+clay] ratio) were observed at

several stations (5D, 5E, and L08). The concentration of PAR at station 5D, near West Dock,

was 2,700 ppb. Though anomalous in composition, the PAR concentrations at stations 5E and

L08 were within the observed historical range. Further examination of station L08's detailed

PAR and saturated hydrocarbon composition revealed a diesel fuel input at this station, the

source of which is unknown.

Likewise major- and trace-metal concentrations were observed over a wide range, but the

normalization of metals to Al or Fe reduces and explains the variability of trace metals (i.e.,

potential contaminants from the developments) greatly. Anomalies (i.e., normalized data outside

of the 95 percent confidence interval) indicative of current and/or historical anthropogenic

inputs, were observed for: Ba at stations 7A, 7B, and 7G; Pb, Cd, and Cu at station 5D; Zn at

station 5R; and Pb at station 5(10).

Based on comparisons to sediment quality gUidelines introduced by Long et al. (1995), the

hydrocarbon and metal concentrations found in the sediments are lower than Effects Range-Low

(ERL) benchmarks. Thus, small incremental contaminant additions from development activities

are not likely to pose any immediate ecological harm to marine organisms in the study area.

Bioaccumulation. Concentrations of hydrocarbons and metals in the clams and amphipods are

within the range of previous studies in the region. Elevated concentrations in sediments, from

natural sources, do not appear to be readily bioavailable to marine filter-feeders and deposit

feeders.

Suspended Sediments. The concentrations and distributions of suspended sediments during the

open-water season appear to be a function of wind and wave conditions, water currents, and

depth. In the summer, concentrations of total suspended solids (TSS) and turbidity are at levels

of <5 mg/L under relatively calm conditions (wind speeds <5 knots [kts]), but turbidity can

exceed 100 mg/L under high wind speeds (>25 kts). Turbidity is about 2 times lower in more

offshore waters (water depths>10 m) relative to more nearshore, shallower water, and a nearbottom nepheloid layer with a 50 to 300 percent increase in turbidity was observed at most

locations. '

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, Concentrations of trace metals in suspended sediment collected during the open-water period of

August 1999 fit the metal~to-AI trends observed for surficial sediments. Results imply that the

metals have a similar source in aluminosilicate material that is relatively uniform in

composition. For Al versus Cu and most other metals, the data for the source bottom a~d

suspended sedimentfit the same trend as the bottom and suspended sediment from the I

ANIMIDA study area. Thus, the area's rivers are providing no distinguishable tracer among

them as far as most trace metals are concerned. !

The ice-core data from April 2000 permit calculation of the impact of sediment releases;from

melting ice on surficial sediment accumulation. Using the worst-case scenario (station LAS), the

integrated amount of sediment in the ice core is about 6 mg/cm2

• As the ice melts and ~eleases

this sediment, the impact on the seafloor is accumulation of only about 0.004 cm of sediment per

cm2

• This small impact is consistent for all ice cores collected. The net impact on sedirhent

accumulation would appear to be small in the ANIMIDA study area. l

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Acoustics. Acoustics measurements from the winter 2000 sampling event indicate that the

dominant propagation mode for Northstar Island construction noise (vibrahammer) is through

the earth and then locally into the water column. The complete methods, results and dis~ussion

of the acoustics program for ANIMIDA are incorporated in a separate report to MMS (~hepard,

et aI., 2001). I

Recommendations

. Part of the overall Phase I effort was to rapidly evaluate Phase I preliminary monitoring 'findings

and to develop a set of recommendations for the Phase II program. A suite of ANIMIDA Phase

II program objectives were evaluated and subsequently issued as eight separate Task Orders for

the Phase II program. Phase II activities are now being implemented, as follows: :

• Provide for ANIMIDA Program Coordination: Task Order 001: "The Arctic Nearshore

Impact Monitoring In the Development Area (ANIMIDA) Program (Phase II) - Core

Contractor Program Management, Logistics, Database, and Reporting" l

• Continue Chemical Monitoring Effort: Task Order 002: "Hydrocarbon and Metal j ,

Characterization of Sediments, Bivalves, and Amphipods in the ANTh1IDA Study Area" ,

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• Continue Acoustic Monitoring Effort (Augment Ongoing Studies - currently under ;,

consideration): Task Order 003: "Baseline Acoustic Monitoring: Bowhead Whale Migration

Corridor" I

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• Monitor the Subsistence Whaling Effort: Task Order 004: "Annual Assessment of

Subsistence Bowhead Whaling Near Cross Island"

• Examine the Effects of Oil Development on Suspended Particulates: Task Order 005:

"Sources, Concentrations, and Dispersion Pathways for Suspended Sediment in Areas of Oil

and Gas Development along the Coastal Beaufort Sea"

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• Conduct Biological Monitoring of Sensitive Habitats (i.e., the Boulder Patch area): Task

Order 006: "Monitoring the 'Boulder Patch' as part of the Arctic Nearshore Impact

Monitoring In the Development Area (ANIMIDA) Program (Phase II)"

• Examine Partitioning of Organics and Metals: Task Order 007: "Partitioning of Potential

Contaminants between Dissolved and Particulate Phases in Waters of the Coastal Beaufort

Sea"

• Evaluate the Levels of Contaminants and Biochemical Indices on Marine Organisms: Task

Order 008: "Baseline Characterization of Anthropogenic Contaminants in Biota Associated

with the Alaska OCS Liberty and Northstar Oil and Gas Production Units in the Nearshore

Beaufort Sea"

MMS added a new objective (with additional funding) for Phase II. This objective is to identify

multiple and cumulative exposures to anthropogenic contaminants in the study area per

Executive Order 12988 on Environmental Justice. For the Beaufort Sea coastal environment,

regionally prioritized contaminants of concern are persistent organic pollutants (POPs) and trace

metals.

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1.0 Introduction

Under the Outer Continental Shelf Lands Act (OCSLA) (67 Stat. 462) of 1953, the Secretary of

the Interior was charged with the responsibility for administering minerals exploration and

development of the Outer Continental Shelf (OCS). The OCSLA Amendments of 1978 (92 Stat.

629) established a policy for the management of oil in the OCS and for protection of the marine

and coastal environments. The amendments authorize the Secretary of the Interior to conduct

studies in areas of offshore oil leasing activities to assess potential impacts on the marine and

coastal environments resulting from oil exploration, development, and production activities.

In the nearshore Alaskan Beaufort Sea, offshore oil development and production activities are

underway at the Northstar site and development is planned as of November 2001 at the Liberty

site, both by British Petroleum Exploration Alaska, Inc. (BPXA). At each site, the oil field will

be developed from a gravel island. A sub-sea pipeline will carry oil shoreward for a land-based

connection with existing pipelines. Extensive Environmental Impact Statements (EISs) were

prepared for the Northstar area by the U.S. Army Engineering District, Alaska (USAEDA, 1999)

and for the Liberty area by the U.S. Department of Interior (USDOI), Minerals Management

Service (MMS; USDOI, 2001).

In 1998 MMS decided to conduct studies to characterize the pre-development baseline

environment and to monitor selected parameters over time as part of a long-term program to

assess potential impacts from oil development and production near the Northstar and Liberty

sites. Information generated from these studies will be considered in post-leasing decisions to

help minimize potential impacts. The program, Arctic Nearshore Impact Monitoring in the

Development Area (ANIMIDA), was initially designed to carefully monitor perturbations and

impacts specifically related to construction activities and oil recovery and transportation via

pipeline from the gravel islands to the onshore processing facilities. Thus, the overall rationale

of the program was to establish two site-specific baseline and monitoring efforts directed at the

Northstar and Liberty developments. Priorities were placed on establishing both a predevelopment baseline and a scientific basis for post-construction/development impact

monitoring. Elements included contaminants in the sediments and selected marine biota in the

area; information on the amount and chemistry of the total suspended matter; information on

other natural and anthropogenic sources of contaminants of concern (hydrocarbons and trace

metals); and impacts (bioaccumulation) on marine biota.

1.1 Environmental Description

The description of the study area and a summary of the key elements of the physical and

biological environments are reviewed briefly in this section.

1.1.1 Study Area

The Alaskan Beaufort Sea comprises the southern part of the Arctic Ocean that lies adjacent to

the northern coast of Alaska and extends from the Chukchi Sea at Point Barrow about 370 miles

(600 kilometers [krnD east to the Canadian border. The northward extent of the Alaskan Beaufort

Sea is about 200 miles (-320 krn) to water depths >300 feet (-100 meters [mD at 73°N. The

continental shelf of the Alaskan Beaufort Sea is 37 to 75 miles (60 to 121 krn) wide and shallow,

with an average water depth of only 120 feet (-37 m) (USAEDA, 1999). Within 1 to 20 miles

u:mms animidalphase I reportlfinal report fileslfiinaJ section' .doc 1-1
(1.6 to 32 kIn) of the coast, the Beaufort Sea is characterized by numerous narrow and low relief

barrier islands.

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The Northstar and Liberty project areas are situated in the shallow, coastal waters of the ~laskan

Beaufort Sea (Figure 1-1). The Northstar site is seaward of the barrier islands and the Liberty

site is landward of several barrier islands. The area of the proposed Northstar development is, !

located about 6 miles (-10 kIn) offshore of Point Storkersen in the Beaufort Sea in w:atetdepths

of 30 to 40 feet (-9 to 12 m). The island will be constructed partly on the remains of Se~l Island,

which was built by Shell Oil Company during the 1980s (USAEDA, 1999).

,

The Liberty development will be constructed about 6 miles (-10 kIn) offshore in Foggy Island

Bay or 1.5 miles (-2 kIn) west of Tern Island, where water depths are about 22 feet (-6.'7 m)

(Figure 1-1). This location is 30 miles (-50 kIn) southeast of the proposed Northstar

development and 7 miles (-12 kIn) from the Endicott Causeway. I

1.1.2 Physical Environment I

The complex elements of the Beaufort Sea's physical environment, which have a bearing on oil

development and potential impacts, include 'sea ice, ocean currents, and suspended sedi~ent

loads. The regions near the Northstar and Liberty sites are described in detail in the Progi-am

Literature Review (Boehm, 2000) and summarized briefly below. I

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The Beaufort Sea continental shelf is shallow, averaging only 120 feet (-36 meters) in depth, 1

with an average width of 44 miles (-71 kIn) (Sharma, 1979). Continentalshelf waters are icecovered for about nine months of the year, with open water season generally extending from

mid-July until September. Ice cover is a major factor influencing petroleum operations ~nd

potential impacts, as it blocks air-sea exchange processes and wind shear, significantly altering

circulatory dynamics of coastal waters. I

Sea ice is a dominant feature of the Beaufort Sea. Landfast ice extends from shore to water

depths of approximately 65 feet (20 m) from at least November through April, with a thickness

of 4 to 7 feet (1.2 to 2.1 m) (USAEDA, 1999). In shallow waters, the ice becomes bottofnfast.

In open water, the polar pack ice is mobile, with ice ridges and open-water leads. Sea ic~ can

cause hazardous conditions or damage in project areas. For example, ice-gouging, caused by the

movement of grounded ice keels in response to winds and currents, poses a significant hazard to

underwater structures in shallow regions of the Beaufort Sea (USAEDA, 1999). In the l~ndfast

sea-ice zone, this occurs most commonly during breakup and freezing. More than four decades

of data from the Northstar vicinity indicate that open-water conditions may be expected to exist . . for 60 to 86 days of the year. The offshore polar pack ice is present within 75 miles (-120 kIn)

of shore, even in summer.

General ocean circulation, wind-generated waves, storm surges, and, to a lesser degree, tides, are

the factors that most influence water movement in the Beaufort Sea near the study area c'oastal

zone. Nearshore water currents are primarily wind-driven during'the open-water season;

aligning with bathymetric contours that parallel the coast in an east-west direction. The net water

flow is to the west, as evidenced from previous drifter studies (Figure 1-2). In winter, under-ice

currents are under the primary influence of tidal movement and storm,surges.

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Several major rivers drain into the Beaufort Sea, including the Colville, Sagavanirktok, and

Kuparuk rivers. Water flow, along with very high suspended sediment loadings, from the rivers

are highly seasonal. Landfast sea ice near river deltas becomes flooded with meltwater from

inland drainage and breaks up from late-May to mid-June. Most of the river flow occurs during

a four- to six-week period in May to June. Water discharge from the Colville River is about 1 x

1012 fe/year (-3 x 1010m

3

/year) (www.waterdata.usgs.gov). In contrast with the Colville River,

water discharge from the Kuparuk and Sagavanirktok Rivers is about 10 times lower at

approximately 1 x 1011 ft3

/year (-3 x 109 m3/year).

Bottom sediments in the Northstar area consist of muddy sand and sandy mud with minor

amounts of gravel (USAEDA, 1999). Offshore of the barrier islands, the sediments are stiff silts

with scattered gravel. Typical sediment cores show 5 to 25 feet (1.5 to 7.6 m) of fine-grained

sand and silt overlying coarser-grained sand and gravel. Concentrations of total organic carbon

(TOC) are somewhat variable and generally low with a range of 0.1 to 4.0 percent (Boehm et aI.,

1990). Sediment grain-size data for the Liberty area show a very patchy distribution in grain ,

size, with surface sediments (top 1 foot) containing 10 to 90 percent silt+clay, and <1 to 30

percent gravel, with the remainder composed of various sand fractions (Montgomery Watson,

1997,1998). At depths of 8 to 9 feet (-2.4 to 2.7 meters), close to the maximum depth of

dredging, a very similar and varied distribution of grain size was found.

1.1.3 Biological Environment

The complex biology of the region near the Northstar and Liberty sites is described in detail in

the literature review (Boehm, 2000) and summarized briefly below.

Planktonic plants (phytoplankton) and animals (zooplankton) form a major source of food for

fishes, birds, and marine mammals in the Beaufort Sea coastal zone. Phytoplankton are the

primary source of carbon fixation at the base of the food web. The abundance and distribution of

these unicellular algae in the Beaufort Sea coastal zone are dependent upon light intensity,

nutrient levels, and oceanographic conditions, including degree of ice cover. Light intensity, in

turn, is related to ice cover and to suspended sediment loadings. Primary production is relatively

low due primarily to nutrient limitation. Maximum productivity and population levels occur in

July and August during the open-water period. Primary productivity is similar between

nearshore and offshore waters, ranging from 10 to 15 grams (g) of carbon/square meter annual

production. Zooplankton consist of permanent water column residents, as well as larval forms of

benthic invertebrates and fishes. Smaller zooplankton include calanoid copepod crustaceans,

which are generally dominant in biomass and numbers throughout the year in the Prudhoe

region. Meroplanktonic larvae of crabs, worms, and barnacles are prevalent during the summer

months. Larger amphipod, mysid, and euphausiid crustacea are major planktonic sources of food

for bowhead whale and ringed seal (Lowry, 1993; Frost and Lowry, 1984).

The bottom-dwelling (benthic) invertebrate community consists of animals living within the

sediments (infauna) and free-moving or attached animals living on sediments or hard, rocky

substrates (epifauna). Beaufort Sea sedimentary invertebrates are significantly affected by the

incursion of sea ice, which scours the bottom and eliminates both infaunal and epifaunal

organisms for most of the year at depths shallower than 2 to 3 m (-6.5 to 9.8 feet) (USDOI,

u:mms animida\phase I report\finaJ report files\fiinaJ section 1.doc 1-3
1990). Much of the shallowest habitat of Prudhoe Bay and Stefansson Sound is protected from

extensive ice gouging and reworking of bottom substrates by offshore shoals and barrierislands

(Dunton and Schonberg, 1981). In unprotected and deeper areas, a shear zone exists, wh~re ice

gouging disturbs the bottom sediments (USDOI, 1990), extending out to a depth of abou~ 20 m

(-:-65 feet). Benthic infaunal populations are relatively limited in this zone, increasing in;

diversity and biomass in the more-stable sediments at greater depths and distances offshqre

(Carey, 1978; Carey et aI., 1974). The motility of the sedimentary epifauna provides adaptability

to the disturbances of the nearshore zone, where they tend to be more diverse and abundant than , the infauna. The dominant species are crustaceans (amphipods, isopods, and mysids) that are

opportunistic in population development, in accord with seasonality of ice breakup and food

inputs in the summer. ,I

Within the Foggy Bay region of Stefansson Sound, a unique biological community is well

developed on cobble and boulder substrates. The cobble-boulder field, defined as the Boulder

Patch (Figure 1-1), is ideally located - seaward of shallow depths (to 3 m) that are disturbed by

ice impingement in winter, and situated inside of the barrier islands and shoals that ptoteet it

from extensive ice gouging and reworking of the bottom. The hard substrate, ranging in ~ize

from pebbles to boulders exceeding 1 meter in height, provides attachment for the doInin~nt kelp

species, Laminaria solidungula, and habitat for a large number of invertebrate species, ot which

sponges, bryozoans, sea-squirts, and cnidarians are prevalent attached fomos. Associated motile

,1

species include gastropod molluscs, nudibranchs, sea stars, and crabs.

1

Monitoring of freshwater, marine, and anadromous fishes was an integral part ofthe Endicott

Development program, providing good descriptions of the regional nearshore fauna, theit

distribution, and seasonality between 1985 and 1994 (Reub et aI., 1991; LGL 1994). Seventeen

marine, ten anadromous, and six typically freshwater species were collected during this study.

The fauna was dominated by marine species (arctic cod and fourhorn sculpin) and anadr~mous

species (arctic cisco and least cisco) (LGL et aI., 1998). These types offish typify nearshore I

brackish waters, in contrast with the offshore marine ichthyofauna (Craig, 1984). Arctic cod is

the dominant species in the Arctic Ocean, serving as an important food source for the large seal

populations (Lowry et aI., 1980, Frost and Lowry 1984, Bums and Frost, 1979, Nelson et aI.,

1985).

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1990, 1996). An estimated 10 million individual birds representing over 120 species (including

terrestrial types) use the BeaufortSe~}&eatromPoint :l3mb\-\}, Alaska to Victoria Island, '

Canada. Nearly all species are migratory, occurring in the Arctic from May through September

(LGL et aI., 1998).

1.2 Development History in the Study Area

Over the past three decades, numerous onshore and offshore oil exploration and development

projects have been undertaken in both the Alaskan and Canadian Beaufort Seas. Discoveries and

development include over 20 discoveries and include areas such as Endicott (an offshore field in

state waters), Sagavanirktok Delta, North, Eider, and Badami. Because of this past development,

the ANIMIDA study area can not be considered to be "pristine' from a chemical perspective.

Operations to the east (i.e., in Canada) may represent a source of contaminants to the Alaskan

Beaufort Sea and hence to the Northstar and Liberty study areas. An overview of these

developments is presented in Figures 1-3 and 1-4.

Since 1975, seventeen gravel islands have been constructed in waters less than 50 feet (15

meters) deep in the Alaskan Beaufort Sea for exploration drilling. Most of these islands remain

in some form, but have been abandoned by removal of all equipment and erosion protection.

Two of these gravel islands, Seal and Northstar, are within the Northstar unit. Natural barrier

islands have also been used for exploration drilling activities and for staging areas (USAEDA,

1999). Table 1-1 summarizes past oil and gas development and production activities in the

Beaufort Sea dating back to 1949.

1.3 Current/Proposed Oil Development

1.3.1 Northstar

The BPXA Northstar development project is located about six miles (-10 km) northeast of

Prudhoe Bay. While the Northstar Island is in state waters, six to seven wells are or will be in

federal waters on the OCS. The U.S. Army Corps of Engineers approved the project in May

1999 and MMS approval followed in September 1999. Northstar is the first offshore oil

production facility in the Beaufort Sea without a causeway to shore and with a subsea pipeline

system connecting it to onshore processing facilities. Construction of the island was completed

by October 2000 and production drilling is underway. First production was expected in the

fourth quarter of 2001. Recoverable reserves are estimated at 175 million barrels of oil.

Production is expected to reach a peak rate of 65,000 barrels per day in first quarter 2002. A

schematic of the development is shown in Figure 1-5.

Northstar Island wasreconstructed from the existing gravel of its predecessor, Seal Island, and

from additional gravel hauled to the island from a gravel mine site near the mouth of the

Kuparuk River. The island was surrounded by a linked concrete mat armor island slope

protection system and the working surface of the island was surrounded by sheet piling. Drilling

and production at Northstar has taken place on the gravel island with an above-seawater footprint

of about 5 acres (-0.02 km2

) (DRS Greiner Woodward Clyde [DRSGWC], 1998) and a seafloor

u:mms animidalphase I reportlfinaJ report fileslfiinal section 1,doc 1-5
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footprint designed to be 635 feet by 970 feet (allowing for uncertainties from constructi~n the

footprint may be up to 835 feet by 1170 feet). i

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The summer 1999 sampling in the ANIMIDA Phase I effort represented "pre-development," or

baseline, measurements. However, it should be noted that exploration drilling had takenlplace at

Seal Island, dating back to the 1980s. 1

1.3.2 Liberty ,

As of November 2001, a second BPXAproposed project is the Liberty Prospect in Foggy Island

Bay (Figure 1-1). It is located about six miles east of the Endicott Project. The proposed location

is adjacent to Tern Island, which was the site of exploration drilling dating back to 1982~, :M1vfS

published a draft EIS report for Liberty in early 2001 (USDOI, 2001)~ the final EIS for Liberty is • scheduled to be released in early 2002. Recoverable reserves are estimated at 120 milli~n barrels

of oil. Drilling and production will take place on a gravel island with a seabottom footprint of

about 18 acres (-0.073 km2), and an above-seawater footprint ofapproximately 9 acres (-0.037

km\ Approximately 990,000 cubic yards of gravel would be needed to construct the islands

associated with the Liberty project. BPXA proposed mining a new site from an islan;d iIi the

Kadleroshilik River flood plain. .,

j If the proposed project stays on schedule and is approved, construction could start in first quarter

2003, with the first oil production in late 2004, at the earliest. The present work (Phase I) and the

future work (Phase II) will all represent pre-development baseline information at Libert~.

1.4 Potential Contaminants and Disturbances of Concern

1

There are three potential perturbations to the physical environment that may occur due to

development activities. These impacts may be a result of: 1) changes to the physical I

environment from construction (gravel island, causeways, pipeline), 2) associated changes in

sediment inputs and resulting sedimentation, and 3) increased availability of chemicals i~ the

environment that may be bioavailable. A fourth potential impact; introduced noise, is addressed

in a separate report. :

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The majority of wastes generated during construction and developmental drilling would consist

of drill cuttings and spent muds. Drilling fluids would be disposed of.through onsiteinj~ction

into a permitted disposal well or would be transported offsite to a permitted disposal location. In

addition, domestic wastewater, soil waste, and produced waters generated during the project

would be injected into the disposal well. Solid wastes, including scrap metal, would be hauled

offsite for disposal at an approved facility.

Chronic discharges of contaminants would occur during every breakup from fluids entrained in

the ice roads. Entrained contaminants from vehicle exhaust, grease, antifreeze, oil, and 6ther

vehicle-related fluids would pass into the Beaufort Sea system at each breakup. These ;

discharges are not expected to be major~ however, they would exist over the life of the fi~ld.

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The greatest effect on water quality from gravel island and pipeline construction would be

additional turbidity caused by increases in suspended particles in the water column as a result of

island and pipeline construction. Turbidity increases from construction activities generally are

temporary and are expected to occur during the winter and end within a few days after

construction stops. Trenching for the oil pipeline may also cause resuspension of existing

bottom sediments. Both island and pipeline construction may result in incorporation of

suspended sediment into sea ice. Construction activities are not expected to introduce or add any

chemical pollutants.

1.5 Study Objectives

The primary objectives of the ANIMIDA program are to characterize and monitor the physical

environment of the Northstar and Liberty development areas to evaluate potential and actual

impacts from these major offshore oil developments.

There is much known about the potential effects of oil developments (USAEDA, 1999; USDOI,

2001) and much known about the pre-development baseline in the Beaufort Sea. As part of the

ANIMIDA program, a literature review was undertaken to set the stage for further ANIMIDA

program elements (Boehm, 2000). Using this information on the Alaskan Beaufort Sea

environment together with specific information on the planned developments, a program was

designed to monitor the physical environment in the Northstar and Liberty development areas.

The ANIMIDA Program is being implemented in two phases. Phase I was designed and

implemented with a focus on the 1999 late-summer, open-water period and the spring 2000 icepack-cover period. The late-summer 1999 sampling represented pre-construction baselines at

both the Northstar and Liberty locations (see Section 1.1.4). The Spring 2000 sampling

represented the first construction-monitoring period for Northstar and another pre-construction

data acquisition opportunity at Liberty.

The plans for Phase II evolved from: a) consideration of the early results from Phase I

monitoring; b) reviews of the program by the Scientific Review Board (SRB); and c) public

comments received at the first Program Workshop in October 1999 in Anchorage, Alaska.

Additional Phase II program objectives and specific study elements are described in Section 5.0

of this report.

Phase I Objectives

The overall objectives of Phase I were to implement a measurement/monitoring program focused

on those measurements and parameters that could be used to determine the existence, extent, and

magnitude of environmental effects from the Northstar and Liberty oil development projects.

The specific objectives for the Phase I effort are listed below:

Summarize the existing literature in the study area. This activity was accomplished and findings

were presented in Boehm (2000).

u:mms animidalphase I report\final report fileslfiinal section 1.doc 1·7
u:mms animidalphase I report\final report fileslliinal section 1.doc 1-8

Design and conduct data collection activities to begin to address key study questions and to

allow for later hypothesis testing. The specific data collection activities included:

b. Designing and conducting a "through-ice" sampling program in AprillMay 2000. Th~s

activity was geared towards initial monitoring of Northstar construction activities on the,island

and pipeline corridors. Specific activities of the "through-ice" data collection activities were to:

Q1. What are the background levels of chemicals of concern (i.e., the organic and trace-metal

contaminants) that are known to be associated with oil exploration, development, and production

activities, and do the concentrations of these chemicals increase as a result of the developments?

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Reoccupy a selected subset of the 1999 summer sampling stations

Conduct acoustic measurements '

Obtain and analyze suspended sediments

Obtain and analyze ice cores

Implement a site-specific radial monitoring design at Northstar and Liberty locations

Implement monitoring along the Northstar pipeline route

Include historical Beaufort Sea Monitoring Program (BSMP) locations previously s~pled in

the 1984 to 1986 and 1989 annual studies, including Boulder Patch and reference locations

Collect and analyze surface sediments, bivalve molluscs, benthic amphipods, and suspended

sediments

Obtain current profiles and bathymetric data

Conduct acoustic measurements

Obtain representative samples of sources of contaminants and natural inputs for the

chemicals (organics and metals) of concern

Ria. The concentrations oforganic pollutants in sediments do not show any increase asa result

ofthe development ofthe Northstar and/or Liberty units.

Rib. The concentrations ofmetal pollutants in sediments do not show any increase as a result of

the development ofthe Northstar and/or Liberty units.

Develop recommendations for Phase II ofthe ANIMIDA program. One of the initial objyctives

of the Phase I effort was to rapidly evaluate Phase I preliminary monitoring results and to

develop a set of recommendations for the Phase II program,.which was set to commence in fiscal

year (FY) 2000. Phase II program objectives are described in Section 5 of this report.

•

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a. Designing and conducting an open-water sampling program in the late summer

(August/September) of 1999. This aspect of the program was intended to precede any

construction activities at Northstar. Specific objectives of the data collection activities were to:

•

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•

•

•

•

1.5.1 Research Questions and Hypotheses

The objectives of the ANIMIDA program are to address a series of scientific questions

concerning the potential impacts of the Northstar and Liberty developments. Each question can

then be turned into a testable hypothesis, which guides the design of the technical progra'm.

These pairs of questions (Q) and candidate hypotheses (H) follow.

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Q2. If concentrations of organic ahWor metal pollutants do ihcrease in the environment as a

result of the developments, do the increasedconcentrations exceed environmental quality

guidelines (e.g., Effects Range-Lows [ERLs])?

H2a. Concentrations oforganic pollutants adjacent to the Northstar and/or Liberty

developments do not pose an ecological risk to marine organisms as determined by sediment

quality benchmarks.

H2b. Concentrations oforganic pollutants adjacent to the Northstar and/or Liberty

developments do not pose an ecological risk to marine organisms as determined by changes in

bioaccumulation by marine animals.

H2c. Concentrations oftrace-metal pollutants adjacent to the Northstar and/or Liberty

developments do not pose an ecological risk to marine organisms as determined by sediment

quality benchmarks.

H2d. Concentrations oftrace-metal pollutants adjacent to the Northstar and/or Liberty

developments do not pose an ecological risk to marine organisms as determined by changes in

bioaccumulation by marine animals.

Q3. Do the Northstar and/or Liberty development activities add significant amounts of sediment

particulate material to the waters and ice cover adjacent to the developments? .

H3a. The turbidity and suspended sediments in the water column adjacent to Northstar and

Liberty are not significantly elevated above naturally occurring, ambient levels.

H3b. The composition ofsuspended particles is not different than that occurring naturally.

H3c. Suspended sedimentsfrom construction on the Northstar and/or Liberty developments are

not incorporated into the ice matrix.

Q4. If the levels of suspended particulates/sediments do increase as a result of the developments,

do these increases pose significant biological risks to marine plants and animals?

H4a. The amounts ofsuspended sediment in the most ecologically significant locations (e.g., the

Boulder Patch community) are within the range ofnatural background and therefore do not pose

a significant risk to plants and animals.

H4b. Suspended sediments occurring in the"lce matrix from construction on the Northstar and

Liberty developments do not significantly decrease the measurable amount ofPhotosynthetic

Active Radiation (PAR) under the ice and at the seafloor in the Boulder Patch area in late

spring.

Q5. Do the construction and operational activities at Northstar and/or Liberty result in noise

spectra and/or noise levels that differ from background levels?

H5. Noise levels and related acoustic features in the study area do not differfrom background

levels as a result ofNorthstar and/or Liberty construction and operational activities.

u:mms anirnidalphase I report\finaJ report files\fiinal section I.doc 1-9
1.6 Limitations of this Study

. I

The ANIMIDA study was designed to focus on the most important potential "causative agents"

of environmental impacts. Through Phase I of the study, the program has not yet begun to focus

on impacts per se. It is envisioned that Phase II will include more direct measurements 6f

biological impacts, in tenns of sublethal effects on biological enzymatic systems, an'd di'rect

measurements in the Boulder Patch area. However, Phase I only focuses on contaminants (e.g.,

metals) and/or perturbations (e.g., suspended sediments) of concern. The results of thesJ predevelopment measurements can only serve as a baseline and as a basis for later comparisons as

part of the actual monitoring of changes. Thus, Phase I examines potential causative factors in

the sediments (polynuclear aromatic hydrocarbons [PAHs] and metals), in animals

(bioaccumulated contaminants), and in the water column (suspended sediments and their

source[sD. Direct biological measurements will come later.

Phase I is a monitoring, and not impact assessment, study. The basis for the monitoring 'and later

impact studies is only directed at the sediments. Short-tenn impacts on water quality, which may

in turn have a bearing on planktonic populations and primary productivity, will only be inferred

from total suspended solids (TSS) measurements and not directly measured.

Because of the known high ba~kground levels of hydrocarbons, PAHs, and metals in the area's

sediments, and a high variability of the same resulting largely from natural inputs - eroded

shales, coals, peat, etc., incremental changes will be difficult to measure. They can only:be

inferred from a strategy of: 1) low-level sensitive measurements that can detect chaQ.ge; 2) a

statistical sampling program that affords enough measurements to detect changes; and 3) a

sampling program that includes obtaining representative other sources (natural and

anthropogenic) of these chemicals and contaminants, so that sources can be fingerprinted and in

turn detected and identified in sediments and in the water column. All of these elements: are built

into this program. While the program is designed to accomplish this "baselining," it is inherently

limited by the large variability and the dynamics of the area, which in turn impose practical . . limits on the amount of replication that can be accomplished for a given program budget. The

bottom line is that changes in measured parameters might only bedetennined by factor~ of two

or more, which may be the lowest statistically significant change that can be detected in' a pre~

and post-development monitoring effort.

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Table 1-1. Alaska North Slope Oil and Gas Past Development and Production

Name Location Oil orGas Location of Discovery Production Category

ofField or Production Production Began

Pool Facility

South Barrow Onshore Gas Onshore 1949 1950 Field

Prudhoe Bay Onshore Oil Onshore 1967 1977 Field

Lisburne Onshore Oil Onshore 1967 1981 Field

Kuparuk Onshore Oil Onshore 1969 1981 Field

East Barrow Onshore Gas Onshore 1974 1981 Field

Milne Point Onshore Oil Onshore 1969 1985 Field

Endicott Offshore Oil Offshore 1978 1986 Field

Sag Delta Offshore Oil Onshore 1976 1989 Field

S<w; Delta North Offshore Oil Offshore 1982 1989 Satellite!

Schrader Bluff Onshore Oil Onshore 1969 1991 Satellite:l

Walakpa Onshore Gas Onshore 1980 1992 Field

Pt. McIntyre Offshore Oil Onshore 1988 1993 Field

N. Prudhoe Bay Onshore Oil Onshore 1970 1993 Field

Niakuk Offshore Oil Onshore 1985 1994 Field

Sag River Onshore Oil Onshore 1969 1994 Satellite]

West Beach Onshore Oil Onshore 1976 1994 Field

Cascade Onshore Oil Onshore 1993 1996 Field

West Sak Onshore Oil Onshore 1969 1998 Satellite:l

Badami Offshore Oil Onshore 1990 1998 Field

Eider Offshore Oil Offshore 1998 1998 Satellitel

Tarn Onshore Oil Onshore 1991 1999 Field

Tabasco Onshore Oil Onshore 1992 1999 Satellite:l

Midnight Onshore Oil Onshore 1998 1999 Satellite4

Sun/Sambucca

Alpine Onshore Oil Onshore 1994 (2000) Field

Source: USDOI, 2001.

Category DefInitions: Field - infrastructure installed to produce one or more pools. Satellite - a

pool developed from an existing pad. Pool- petroleum accumulation with defined limits.

Prospect - a discovery tested by several wells. Show - a one-well discovery with poorly defined

limits and production capacity.

Note I - Satellite associated with Duck Island production unit

Note 2 - Satellite associated with Kuparuk River production unit

Note 3 - Satellite associated with Milne Point production unit

Note 4 - Satellite associated with Prudhoe Bay production unit

u:mms animidalphase I reportlfinaJ report fileslflOsl section 1.doc
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Table 1-2. Alaska North Slope Oil and Gas Reasonably Foreseeable Future Development

and Production . '

Name Location Oil orGas Location of Discovery Category

ofField or Production Production

Pool Facility

Meltwater Onshore Oil Onshore 2000 Prospect

Nanuk Onshore Oil Onshore 1996 Prospect

Kalubik Offshore ' Oil Onshore 1992 Prospect

Pete's Wicked Onshore Oil Onshore 1997 Prospect

Sikulik Onshore Gas Onshore 1988 Pool

Thetis Island Offshore Oil Offshore 1993 Prospect

GwydyrBay Offshore Oil Onshore 1969 Pool

Mikkelson Onshore Oil Onshore 1978 Prospect

Sandpiper Offshore Gas & Oil Offshore 1986 Pool

Point Thomson Onshore Gas & Oil Onshore 1977 Pools ,

Sourdough Onshore Oil Onshore 1994 Pool

Yukon Gold Onshore Oil Onshore 1994 Prospect

Flaxman Island Offshore Oil Offshore 1975 Prospect

Stinson Offshore Oil Offshore 1990 Prospect

Hammerhead Offshore Oil Offshore 1985 Pool

Kuvlum Offshore Oil Offshore 1987 I Prospect

Source: USDOI, 2001.

Oil and gas developments are listed according to the chance and timing ofthe development

(highest/firstto lowest/last).

Category DefInitions: Pool- petroleum accumulation with defmed limits. Prospect -- a ;

discovery tested by several wells.

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- - -- - -

- .- - - 1,- - - - - - _.

FIgure 1-1. Map or the ANIMIDA PhasefStudy Area
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, ", 'I Arctic MonitorIng and Assessrrent Programme

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Figure 1-2.. Drifter Tracks in the Beaufort Sea

(from www.AMAP.nu.maps-gralshow-figure353)

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..- -- -

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PS-1 Pump Stalion #1

- Oil Pipeline

Seawater Pipeline

Proposed Pipelines

A Liberty

B Northstar

Legend

Source: USDOI. 2001

m5J HE NPR-A Study Area

_ Active Leases

WOIIField

• Gas Field

. ''Ie:, ." if;

Past Development -Prudhoe Bay

Present Development - Northstar

ReasonablelForeseeableDevelopment - Kuvlurn

Speeulative. Development -Ugnu

. .! L Alpine Group "

L NOI1hstar Group

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'Figuj~~3:Y~enerill'(Map;ofiO'nstl()re'and:[qffshoreOil:'and'Gas:Developmerif ' Inthe:Study Areas .
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A~AP Asussmen: R&Port: At:tIe ~u::bn Issu!5I. Fl.aure 10.2

.. "~:1'tr~"f~~: .....,.. ,•.. 1-.:: .'

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Figure 1-4: Generalized Description of,Arctic Oil Developments

(from http://www.amap.no/maps-gra/mg-petro.httil)

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2.0 Methods

This section describes the methods used in field sampling, field measurements, and laboratory

analyses.

2.1 Field Methods and Study Design

2.1.1 Study Design

The study area for the ANIMIDA program was defined as the nearshore Beaufort Sea bounded

by the Stockton Islands to the East, and by the Jones Islands to the West. This area encompassed

both the Liberty and Northstar prospect areas, and much of the shoreline where regional Prudhoe

Bay oil production activities are occurring. The Phase I ANIMIDA program included two field

surveys:

• An open-water survey conducted in August 1999, including sediment, biota, suspended

sediment, water column, and acoustics sampling and measurements

• A "through-ice" survey conducted in April 2000 that focused on suspended sediment, ice

core, water column, and acoustics sampling and measurements

The overall design of the field program incorporated a sampling program using a combination of

site-specific fixed stations around the Liberty and Northstar developments, and regional,

historical BSMP stations (Figure 2-1 and Boehm, 1987). The site-specific Liberty and Northstar

stations were located in four radial transects centering on the proposed prospect site. The radials

were located at 0.5, 1,2, and 4 kilometer (km) intervals and the transects were oriented

approximately North - South and East - West (17 stations per prospect - Figure 2-1). The radial

transect orientation enables station comparison spatially away from the development islands, as

well as onshore - offshore station comparison, and East - West station comparison to account for

the prevailing East - West currents in the region. This design allowed a combination of sitespecific stations to be sampled for sediment chemistry, suspended sediment chemistry, and biota

(tissue) chemistry, and resulted in four stations being located in the Boulder Patch area.

The acoustics stations were located along two transects centering on each of the Northstar and

Liberty prospects. The acoustic transects included stations along a gradient away from the

prospects at approximately 0,5, and 15 KIn intervals, running North and East of Northstar, and

East and Northwest of Liberty (Figure 2-2). Where possible, the acoustics stations were

combined with the sediment chemistry stations to enhance the overall efficiency of the field

sampling program.

The summer 1999 field survey included sampling at all stations (Liberty and Northstar stations

and BSMP stations), as this survey was to serve as the pre-development baseline for the overall

ANIMIDA program. The winter 2000, or "through-ice," sampling program design focused

primarily on the Northstar prospect; since construction activities were occurring at that time.

The "through-ice" survey included two gradient transects at Northstar and one transect at

Liberty, as well as some Northstar activity-specific sampling (Figure 2-2).

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2.1.2 Summer 1999 Field Sampling

The summer 1999 field sampling was conducted aboard the MMS Vessel 1273 from August 10

to September 1, 1999, and coincided with a period of expected favorable ice conditions in the

program study area, and the onset of the bowhead whale migration (for acoustic measurements). ,

The field sampling methods were conducted in accordance with Arthur D. Little, Inc. (ADL)

Standard Operating Procedures (SOPs). The field sampling and logistics plan (Arthur D: Little, . .

1999a) prepared for the summer 1999 field survey provides detailed explanations of the field

methods for sample collection, equipment decontamination, and subsampling of sediment cores.

Field sampling personnel from ADL, Florida Institute of Technology (m), BBN Techn?logies

(BBNT), and MMS participated in the survey. The scientific team and ship's captain (Mark

Mertz - TEG Ocean Services) conducted the work on an 18-hour.,a-day basis depending on

favorable operating conditions. A detailed description of the activities conducted during ~he

survey, including a log of the daily actiVities, is included in the Cruise Report (Arthur D.~Little,

1999b). A summary of the field sampling activities and methods follows in this section.''I

Samples '

The scientific crew collected samples for chemical analyses from the program study area: The

following components were successfully completed:

• Collected samples at 43 stations

- 15 historic BSMP stations

- 12 Northstar stations (4 stations each on 1 km, 2 km, and 4 km radials)

- 13 Liberty stations (4 stations each on 1 km, 2 km, and 4 km radials)

- 3 Northstar Pipeline route stations

• Collected 47 surficial sediment samples (0 to 1 em) for chemistry (triplicates at: 2 stationsstations 5(1) and Lll)

• Collected 10 bivalve/amphipod samples

• Collected 8 source sediment/peatsamples (4 river stations and 4 causeways)

• Collected current and turbidity profiles at 11 stations (13 total profiles)

• Collected 40 suspended sediment samples at 11 stations (corresponding to current and

turbidity profile stations)

• Collected acoustic measurements along 4 radials (2 radials from NOlthstar [NNE and ESE]

and 2 radials from Liberty [NNW andE]) for a total of 10 acoustic stations

• Delivered field samples to analytical laboratories for appropriate analyses

Several source samples were collected as part of the summer survey. Most of the source:,samples I

were collected during a period of bad weather, when offshore activities were limited. Th~ source

samples collected included water for suspended particulate analysis and sediment for organic and

inorganic analysis, from the Sagavanirktok, Kuparuk, and Colville Rivers. In addition, peat

1

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samples were obtained from the banks of the Kuparuk and Colville Rivers. A sample of the

Endicott Causeway gravel was also collected for inorganic analysis.

,

A complete list of the sampling stations that were occupied and sampled in the study area is

included in Table 2-1. Table 2-1 a,lso provides the station identification, station type, latitude

and longitude, depth, date and time of sampling, and the type of chemical, acoustics, and

geophysical analyses for each sample. Figure 2-1, a map of the ANIMIDA study area, shows the

locations of the 1999 sampling stations. Additional daily survey and sampling station

,information is included in the 1999 station logs contained in the Cruise Report (Arthur D. Little,

1999b).

2.L2.] Summer 1999 Field Sampling Procedures

Standard sampling procedures were followed at each sampling station according to the Field

Logistics and Sampling Plan for the 1999 MMS Field Survey (Arthur D. Little, 1999a).

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

below, including: .

• Identify station (latitude andlongitude)

• Navigate to station position within 0.2 nautical miles (nm) radius of location

• Deploy amphipod traps (as required)

• Acoustics (as required)

• Conductivity, temperature"and depth (CTD), current profile, and suspended sediment (as

required)

• Collect Van-Veen grab samples

• Skip dredge for bivalves - alternatively, use grab-and-sieve method (as required)

• Retrieve amphipod traps (as required)

• Navigate to next station

Photodocumentation, station logs, and field notes were recorded during the field survey. The

station logs for each sampling station are included in the cruise report (Arthur D. Little, 1999b).

Each station log includes a description of the sampling location, observations, number and

type(s) of samples collected, and comments.

Water and Suspended Sediment Measurements

In-situ profiles of seawater turbidity, CTD, current speed, and current direction were obtained

using an Aanderaa Instruments system consisting of a Model 3500 Doppler current sensor,

Model 3231 CTD sensor, and Model 3712 turbidity/temperature sensor. The raw data were

received by an Aanderaa Model 3660 Datalogger and stored in a Model 2990 data storage unit.

The raw data were transformed to appropriate units using pre·calibrated equations provided with

the Aanderaa 5059 software package. The processed data were stored on hard disk with multiple

backups on floppy diskettes.

Seawater samples for determining turbidity and TSS were collected by lowering a Teflon®-lined

Niskin sampler attached to a Kevlar® hydrowire beneath the sea surface and tripping it with a

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Teflon® messenger. After retrieval, the water samples were transferred to acid-washed 5-L

plastic containers through a Tygon® tube. The water samples were labeled, sealed in plastic

bags, packed in coolers, and taken to on-site laboratory facilities established at ARCO Prudhoe

Bay Operations Camp (PBOC). In the lab, the water samples were shaken to resusp~nd the

particulates and the turbidity of each sample was determined using a Hach® Model2100A

turbidimeter that was calibrated with sealed standards. The salinity ofeach seawater sample also

was determined using a-Reichert-Jung Model 10419 optical refractometer that was q.libr~ted

with standard seawater. Salinity was determined for selected seawater samples by inductive

salinometer upon return to FIT to validate the data obtained with the Aanderaa system an:d the

optical refractometer.

In the on-site laboratory, the water samples were vacuum-filtered through polycarbonate filters

(Poretics®, 47-mm diameter, 0.4- f.!m pore size). Prior to the field effort, thefilters were' acidwashed in 5N HN03, rinsed three times with distilled, deionized water (DDW), dried, and then

weighed to the nearestf.!g using a Sartorius® Model M3P electronic balance under "dean room"

conditions. Vacuum filtration on site was carried out in a Class-lOO laminar-flow poad using

acid-washed glassware. The particle-bearing filters were then double-bagged in plastic, and

stored until dried, and re-weighed in the Marine & Environmental Chemistry Laboratories at

FIT.

Surficial Sediment Sampling

Sediment samples were collected using a modified Van-Veen grab sampler. During the ,

collection and handling of sediment samples from the grab sampler, extreme care was taken to

avoid contact with metals and hydrocarbon sources. Samples were taken away from the sides of

the grab and no metal spatulas were used for the trace metal samples. The grab sampler was

protected from stack smoke, grease drips from winches and wire, and other potential airborne , contamination during the sampling process.

Sediment samples were collected from the top 1 cm of the grab to represent recent accumulation.

Unconsolidated sediment 1 cm deep was removed from the grab with a stainless-steel scoop

coated with Kynar. The scoop is 1 cm in depth to facilitate accurate collection depth of t~e

sediment. The top 1 em was collected by several scoops of the grab, up to the volume required

for subsamples, and placed directly in appropriate sample containers. Specific subsamples were

collected from each grab into individual containers (using a scoop or a Tef1on® spatula) ~nd

stored as indicated in Table 2-7. l

Suspended Sediment Sampling

Suspended sediments were collected using Niskin bottles at the selected depth(s) (i.e., nearsurface, mid-water, and near-bottom) as dictated by the "real~time" CTD, nephelometry, ~nd

water current data.

Biota Sampling

Bivalve and amphipod samples were collected at selected stations as part of the sampling survey.

A Fish Resource Permit was obtained from the State of Alaska Department of Fish and Game

(ADF&G) to allow for the collection of biota samples.

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Amphipods (Anonyx spp.) were collected using Nitex® mesh-lined, Kynar®-coated minnow

traps, baited with sardines. The traps were generally deployed for two to six hours (depending

on other sampling activities at adjacent stations) with an anchor and float equipped with a radar

reflector to facilitate retrieval of the traps. The sardIne bait was placed in an enclosed Nitex®

mesh pouch to reduce the possibility of sardine particles becoming entrained with the

amphipods. Only five amphipod samples of sufficient size for chemical analysis were collected

dUring the survey. The scarcity of amphipods.relative to previous BSMP surveys may have been

related to the lack of ice in the nearshore waters. Amphipods are known to occur in areas with

ice cover, and the vast stretches of open water encountered during this survey may have

restricted the amphipods to areas of denser ice cover, offshore of the survey area. Amphipods

were removed from the traps, washed with clean seawater, and placed in a clean sieve for

sorting. Any non-Anonyx spp. amphipods were removed with clean forceps prior to transfer of

the sample into the appropriate sample container.

It was originally intended that bivalves (target species:~Astarte sp., Portlandia sp., Cyrtodaria

sp., and Macoma sp.) would be collected using a modified skip dredge towed behind the boat

within the 0.2 nautical mile station radius. In practice, the clam dredge was ineffective in

collecting bivalve samples. The dredge was deployed at several stations, but the clayey bottom

substrate tended to clog the dredge. No bivalve samples were actually collected with the dredge

and instead the grab sampler was used (as in previous BSMP collections). Multiple grabs were

collected and sieved through a 1 cm Nitex® screen to isolate target species of bivalves. Target

bivalves were then carefully removed to a clean sieve, rinsed with clean seawater, and

transferred into the appropriate sample containers using clean forceps or spatulas. Generally, 20

to 40 grabs yielded a sufficient volume of bivalve samples for analysis. '

Source Sampling

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

contaminants in the sediments to potential sources, as well as to determine the potential influence

of resuspended river sediment and coastal surficial sediment to the study area.

The source samples collected included water for suspended particulate analysis and sediment for

organic and inorganic analysis from the Sagavanirktok, Kuparuk, and Colville Rivers. The

Sagavanirktok River source samples were collected south of Deadhorse, near mile 401 on the

Dalton Highway. The Kuparuk River source samples were collected -1/4 mile south of the most

southerly access road river crossing. The Colville River samples were collected via helicopter

from stations to the North and South of the village of Nuiqsut. A sample of the gravel fill from

the Endicott Causeway was also collected. Peat samples were obtained from the banks of the

Kuparuk and Colville Rivers.

Water samples were collected from the Sagavanirktok, Colville, and Kuparuk Rivers in

l-L, acid-washed polyethylene bottles. The samples were obtained by wading into the river,

waiting until disturbed sediment was washed downstream, and then opening an acid-washed l-L

polyethylene bottle below the surface of the water. When the bottle was full, it was sealed

beneath the surface, retrieved, placed in a plastic bag, labeled, and stored in a cooler for return to

the on-site laboratory facilities to be filtered.

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The river sediment samples for organics analysis were collected from fine-grained surficial

sediments (0 to 2 cm) approximately one meter from the shore using a stainless-steel spoon and

precleaned glass sample jars. The spoon was rinsed well with alcohol and river water prior to

use. The sampling equipment was decontaminated between sample locations by rinsing \.vith

distilled water. Metals source samples of riverbank sediment were collected using a plastic

scoop and spatula. These sediment samples were placed in plastic bags (for grain size) and 75-

rnillileter (mL) plastic vials (for trace metals and methyl-mercury) and then stored in coolers. At

the 'on-site lab, sediment samples for trace metal and methyl mercury analyses were frozen and

the grain-size samples were refrigerated until transported to FIT. The peat samples, from the

river shoreline approximately one meter above water level, were collected in the same m~nner as

the sediments for organics and metals, respectively. -

Acoustics Measurements

Measurement of ambient noise levels (i.e., "acoustics sampling") was performed from th~ MMS

Launch 1273 for the summer 1999 field survey. A separate report was generated for the'

acoustics portion of the ANIMIDA program based on the nature of the data. This report includes

detailed information on the field collection methods for the acoustics data. A copy of thel

acoustics report is included in Appendix F. !

2.1.3 Winter 2000 Field Sampling

The first winter season field survey was conducted from April 24 to May 1,2000, which;

coincided with a period of expected favorable weather conditionsin the study area, long ~aylight

hours, and activities associated with the Northstar Island and pipeline construction. The j

scientific crew conducted the field survey from the surface of the shorefast ice and utilized

snowmobiles to access each sampling location. Discrete samples and in situ measuremettts were t

obtained from the program study area. The field sampling methods were conducted in'

accordance with ADL SOPs. The field sampling and logistics plan (Arthur D. Little, 2000a)

prepared for the winter 2000 field survey provides descriptions of the field methods for s'ample

collection and equipment decontamination. Field sampling personnel from Kinnetic .

Laboratories, Inc. (KLI), FIT, andBBNT participated in the survey. The scientific crew /

conducted the work on a 14- to 16-hour-a~day basis depending on favorable operating

conditions. Winter activities were conducted from the surface of the ice with two snowmobiles

and freight sleds that were utilized to transport personnel and sampling equipment to each survey

location. A detailed description of the activities conducted during the survey, including alog of

the daily activities, is included in the field report (Arthur D. Little, 2000b). A summary Of the

field sampling activities and methods follows in this section.

Samples

The scientific crew·collected samples for chemical analyses and recorded acoustic measurements

from the program study area. During the 2000 ANIMIDA winter sampling survey, the fohowing

components were successfully completed: '

• Collected samples at 9 stations

- 1 historic BSMP station

- 6 Northstar stations (2 stations associated with trenching'operations and 4 at distahces of

0.2 km, 1 km, 2 km, and 4 km on a radial from the island) ,

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- 2 Liberty stations (1 in the Boulder Patch and 1 at the location of the proposed Liberty

Island)

• Collected 27 water samples (surface, middle, and bottom) at each of the sampling locations

to be analyzed for suspended particulates and a subset for chemical constituents

• Collected 9 ice cores for suspended particulate analyses

• Collected 3 source sediment/peat samples (l gravel borrow pit, 1 Northstar Island, and 1

along pipeline corridor at Stump Island)

• Collected current, turbidity, CTD, and PAR profiles at 9 stations

• Collected acoustic measurements at 8 stations (obtained in the water, ice, and air at each of

the sampling sites)

A complete list of the winter 2000 sampling stations that were occupied and sampled in the study

area is included in Table 2-2. Table 2-2 also provides station identification, station type, latitude

and longitude, depth, date of sampling, and the type of chemical, acoustics, and hydrographic

measurements at each location. Figure 2-2, the map of the ANIMIDA study area, shows the

locations of the winter 2000 sampling stations. Additional daily survey and sampling station

information is included in the 2000 station logs contained in the field report (Arthur D. Little,

2000b).

2.1.3.1 Winter 2000 Through-lee Field Sampling Procedures

Standard sampling procedures were followed at each sampling station according to the Field

Logistics and Sampling Plan for the 2000 MMS Winter Field Survey (Arthur D. Little, 2000a).

Typical sampling procedures included:

• Establish and verify sampling location with a global positioning system (GPS)

• Drill a sampling hole with a gasoline-powered,ice auger

• Collect acoustics data and CTD, PAR, and current measurements with an Aandera

CTD/doppler current meter and a SeaBird CTDIPAR in situ sampler/recorder

• Collect water and ice core samples for analysis of suspended particulates and metals (at

selected locations)

Photodocumentation, station logs, and field notes were recorded during the field survey. The

station logs for each sampling station are included in the field report (Arthur D. Little, 2000b).

Each station log includes a description of the sampling location, observations, number and

type(s) of samples collected, and comments.

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Water, Suspended Sediment and Ice-Core Measurements

To obtain seawater samples, holes were drilled in the ice using a gasoline-powered drill with a

25-cm-diameter auger. Water samples were collected by lowering a Teflon®-lined Niskin

sampler attached to a Kevlar® hydrowire through the ice into the seawater where it was tripped

using a Teflon® messenger. After retrieval, the water samples were transferred to acid-washed

5-Lplastic containers using a plastic funnel. The sample containers were sealed in plastic bags,

labeled, and placed in coolers for transport back to the onshore laboratory facilities. In the lab,

the water samples were brought to room temperature to melt any ice that had formed in the

sample containers. They were shaken to resuspend the particles and the turbidity of each sample

was determined using a Hach® Model 2100A turbidimeter. The salinity of each seawater

sample was also determined using a Reichert-lung Model 10419 optical refractometer.

In the on-site laboratory at the Seawater Treatment Plant (STP), the water samples were vacuumfiltered through polycarbonate filters (Poretics®, 47-mm diameter, OA-lJ.m pore size). Prior to

the field effort, the filters were acid-washed in 5N HN03, rinsed three times with DDW, dried,

and then weighed to the nearest Ilg using a Sartorius® Model M3P electronic balance under

"clean room" conditions. Vacuum filtration on site was carried out in a Class 100 laminar-flow . hO,od using acid-washed glassware. The particle-bearing filters were then double-bagged in

plastic, and stored until dried, and re-weighed at FIT. In-situ profiles of seawater turbidity, cm,

current speed, and direction were obtained by lowering the Aanderaa Instruments system through

the borehole in the ice.

Ice cores were collected by attaching a stainless-steel core barrel with serrated teeth to toe

gasoline-powered drill. The ice core samples were placed in sealed plastic containers, labeled,

and stored in coolers for transport to the on-site lab facilities. The ice cores were allowed to melt

in the on-site laboratory, after which the samples were shaken to resuspend the particulates and

turbidity was determined using a Hach® Model 2100A turbidimeter. The salinity ofeach

seawater sample was also determined using a Reichert-lung Model 10419 optical refractbmeter.

Acoustics Measurements

Acoustics sampling was performed in conjunction with the ice core, water column, and

suspended sediment sampling during the winter 2000 field survey. A separate report, generated

by BBNT for the acoustics portion of the ANIMIDA program, includes detailed information on

the field collection methods for the acoustics data (Shepard et aI., 2001).

Source, Suspended Sediment, and Gravel Sample Collection

Three source samples (sediment/peat) were collected during the winter 2000 field survey (l from

the gravel borrow pit, 1 from Northstar Island, and 1 along the pipeline corridor at Stump

Island). Each gravel/peat sample was collected using a plastic scoop and spatula and was placed

in a 75-mL plastic vial (for trace metals and methyl mercury) and then stored in coolers. At the

on-site lab, sediment/peat samples for trace metals and methyl mercury analyses were frozen

until transported to FIT.

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2.2 Analytical Methods

2.2.1 Ancillary Parameters

2.2.1.1 Grain Size

Detennination of grain size followed the classic method of Folk (1974) using a combination of

wet sieving and pipette techniques. Initially, 10 to 30 grams of wet sediment were placed in a

wide-mouth dish using a larger mass for sandy samples and a smaller mass for muddy samples.

A small amount of DDW was added to the dish, clay lumps were broken up with a gloved finger,

and the wetted sample was poured into a 200-rnL glass bottle and shaken vigorously for a few

minutes. Then the sample was poured through 2 rom (gravel) and 63 Jlm (sand) sieves and

rinsed until the water was clear. The sediment on each sieve was washed into beakers #1 and #2,

respectively, allowed to settle and the overlying, clear water was decanted. The tared beakers

were dried at 100 to llO°C and re-weighed.

The glass bottle containing the muddy water «63 Jlm) was shaken for about 15 minutes and

gently poured into a 1,000-rnL cyiinder. The cylinder was stirred vigorously with a stirring rod

and a timer was started as soon as the rod was removed. No dispersant was needed in these

samples of marine sediment as the mud fraction dispersed extremely well. After 20 seconds, 20

rnL of sample were withdrawn from a depth of 20 cm using a Class A pipette. The pipette

sample was drained into tared beaker #3, dried at 100 to 110°C for 24 hours, and weighed for

total silt + clay. After 2 hours and 3 minutes, 20 rnL of sample was withdrawn from 'a depth of

10 cm using a Class A pipette. This pipette sample was drained into tared beaker #4, dried at

100 to 110°C for 24 hours, and weighed for total clay. All masses were determined to the

nearest 0.01 g. The total mass of sample was equal to the Sum of masses in beakers 1 + 2 + 3(x

50). The individual percentages were calculated as follows:

% gravel =(beaker #1 sediment/Sum) x 100%

% sand =(beaker #2 sediment/Sum) x 100%

silt ={[(50 x beaker #3) - (SOx beaker #4)]/Sum} x 100%

% clay =[(50 x beaker#4)/Sum] x 100%

2.2.1.2 Total Organic Carbon

A 0.5 to 1 gram portion of the freeze-dried sediment was placed in a lO-rnL Pyrex® beaker and

wetted with 1 rnL of DDW followed by the addition of 2 mL of concentrated hydrochloric acid

(HCI) to remove any inorganic carbon present. The sediment was dried at 60°C and re-weighed

to detennine the increase in weight due to the fonnation of CaCh-2H20 as a result of adding

HCl. Then, approximately 200 to 400 mg of pre-treated sediment were weighed into ceramic

boats and combusted at 900°C in a Shimadzu® TOC-5050A carbon system with SSM-5000A

solid sampling module following the manufacturer's instructions. The TOC content of the

sediment samples was detennined using a four-point calibration curve with pure sucrose 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) :MESS-2, a marine sediment issued by the National

Research Council of Canada (NRC).

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2.2.2 Organic Chemical Parameters

Analysis for organic contaminants was conducted by ADL's Environmental Chemistry and

Forensics (EC&F) laboratory. The analyses were conducted in accordance with the labo~atory's

SOPs and generally followed the same procedures used in previous BSMP studies (Boehm et aI.,

1990). The core organic analyses for the sediment and source samples were: "

• Saturated hydrocarbons (SHC) by gas chromatography/flame ionization detection

(GCIFID)

• .PAR by gas chromatography/mass spectrometry detection (GCIMS)

• Geochemical biomarkers (steranes/triterpanes [SIT]) by GCIMS

Targeted compounds are listed in Tables2-3, 2-4, and 2-5. This section describes the anklytical

methods that were used in performing the organic chemical analyses.

2.2.2.1 Sample Preparation

Sediment Samples

The sediment samples were prepared using a procedure based on United States Environmental

Protection Agency (EPA) Method 3550A, Ultrasonic Extraction (EPA 1993). The method

modifications include orbital shaking of the sample in extraction solvent for 1 hour folloy.,ing the

final sonication to enhance recovery of target contaminants. The following is a sumrtlary of the

method. I

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Approximately 30 grams (wet weight) of the homogenized sediment were weighed into

Teflon® jar and dried with sodium sulfate. Another 5-gram subsample was placed into an

aluminum-weighing pan and heated at 105°C to a constant weight, for dry weight detern1ination.

The sample was serially extracted 3 times with 100 mL of methylene chloride and aceto~e (1: 1,

volume to volume [VN]), each time by sonication. The final sonication was followed by orbital

shaking in the extraction solvent for 1 hour. '

The surrogates were spiked into the sample after the first addition of solvent and before the first I

extraction. All sediment samples were spiked with "low-level" surrogates (as defined by the

laboratory SOP) because target compound concentrations in the sample were expected to: be at

trace levels.

The surrogates used were: naphthalene-d8, acenaphthene-dlO, phenanthrene-dlO, and

be~zo[a]pyrene-d12 for PAH analysis, 5a-androstane and d50-tetracosane for SHC analysis, and

5~(H)-cholane for SIT analysis.

After extraction, samples were concentrated using a Kudema-Danish (K-D) concentrator' on a

hot water bath. An extract weight was taken if necessary to determine general organic content

levels prior to column cleanup. Extracts were then treated with copper to remove sulfur, ~and

split in half. One-half was archived in a freezer at -20°C and the other half processed through a

silica gel column as described in the Extract Fractionation subsection.

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Biota Samples

Approximately 20 grams wet weight of tissue (if available) was prepared for extraction.

Partially thawed bivalve tissues were removed from the shells with solvent-rinsed stainless-steel

utensils and weighed on a top-loading balance. Whole amphipod samples and shucked bivalve

samples were completely homogenized using a Tissumizer. An aliquot of each homogenized

sample was removed for dry weight determination, and the remaining sample (approximately 10

grams wet weight) was transferred to a clean Teflon® centrifuge tube for digestion. The

remainder of the homogenate, if any, was re-Iabeled and stored frozen as archived samples.

Thirty (30) mL of pre-extracted 6N potassium hydroxide and the surrogates were added to each

homogenized tissue sample. The surrogates used were: naphthalene-d8, acenaphthene-dlO,

phenanthrene-dlO' and benzo[a]pyrene-dI2 for PAR analysis, 5a-androstane and d50-tetracosane

for SHC analysis, and 5B(H)-cholane and d66-dotriacontane forsrr analysis. Surrogate

compounds were spiked into all tissue samples at the low-level because target compound

concentrations in the samples were expected to be at trace levels. The container was then

flushed with pUrified nitrogen, sealed, and allowed to digest overnight in a hot water bath at

approximately 35°C. After digestion, 30 rnL of ethyl ether was added to each sample and the

mixture was agitated on an orbital shaker for 5 minutes. The samples were then centrifuged at

2,000 revolutions per minute (rpm) for 5 minutes to facilitate phase separation. The ether layer

was removed using a Pasteur pipet and filtered through sodium sulfate into a 250-mL K-D

apparatus. The ether extraction of the digest was repeated twice, and the ether extracts combined

in the K-D apparatus. The combined ether extract from each sample was reduced in volume to

approximately 1 mL by K-D and nitrogen concentration techniques. The extracts were then

exchanged to dichloromethane and an aliquot was removed and weighed on an electrobalance for

total non-saponifiable lipid weight determinations.

The tissue sample extracts were further processed in order to reduce potential interferences. The

extracts were loaded on a 30-cm by I-em glass chromatography column filled with 10 gram

alumina (activated overnight at l30°C prior to use) and 1 gram anhydrous sodium sulfate.

Sample extracts, containing no more than 300 mg of extractable organic material, were loaded

onto the alumina column and eluted with 100 mL of methylene chloride. The extracts were

concentrated to 5 mL using a K-D concentrator. All extracts were further reduced in volume and

exchanged into hexane using nitrogen evaporation. A post-alumina gravimetric weight was

recorded prior to further processing using a silica gel column, as described in the Extract

Fractionation subsection.

Source Samples

The four source sediment samples [Colville River (2), Sagavanirktok River (1), and Kuparuk

River(1)] and the two source peat samples (Colville River and Kuparuk River) were extracted

and analyzed using the same procedure as for the other sediment samples.

Field Blanks

One field blank sample consisting of distilled water rinsate of the grab sampler was collected as

part of the project quality assurance (QA) program. A "deck" blank, which consisted of an

empty sample jar that had been left open on the boat deck during sampling, was also collected.

The deck blank was prepared by rinsing the jar three times with approximately 10 mL of

u:mms animidalphase I reportlfinal neport fileslfinal section 2.doc 2-11
methylene chloride. The methylene chloride rinsates were combined and spiked with low-level

SHC, PAH, and SIT surrogates. The field blank was extracted by a liquid-liquid method with

methylene chloride. This sample was also spiked with low-level SHC, PAH, and SIT surrogates.

The two field blank extracts did not require column cleanup and were prepared for instrumental

analysis without further processing.

Extract Fractionation

The sediment and tissue extracts were fractionated in order to remove potential interference and

to improve the quality of the analysis at trace levels. The procedure used for fractionation was

similar to that used for previous BSMP investigations (Boehm et aI., 1990). Prior to .

fractionation, the sample extracts were exchanged from methylene chloride to hexane under

nitrogen.

The fractionation was performed using a 30-cm by l-cm column that was wet-packed in

methylene chloride with 100 percent activated silica gel/5 percent deactivated alumina/activated

copper (approximately 11: 1:2 g) and preconditioned with 30 mL methylene chloride followed by

30 mL of hexane. The sample extract (which had been verified to be less than 50 mg extractable

material per 1 mL) was loaded onto the column. The sample was eluted ,with 18 mL of hexane

and the isolated saturate (fl) fraction was collected. This was followed by 21 mL of

hexane:methylene chloride (1:1) to isolate the aromatic (f2) fractions.

Internal Standard Addition

The extracts (or extract fractions) were reduced to a measured final volume under a stream of

nitrogen. The final sample extracts were spiked with SHC, PAH, and SIT internal standards, as

appropriate for each extract or fraction. In general, the extracts were concentrated to ,

approximately 250 flL before adding the internal standards in order to lower detection limits.

The internal standard compounds used were: chrysene-d12 and fluorene-dlO for PAH; chrysened12 for SIT; and d62-triacontane for SHe. The amount of SHC internal standard added to the

extracts was adjusted to obtain a target concentration of 50 flglmL. The amount of PAHand SIT

internal standard added to the extract was adjusted to obtain a target concentration of 1 flglmL.

2.2.2.2 Organic Instrumental Analysis

Instrumental analysis of the sediment and tissue samples (including the source samples) included

SHC by GC/FID and PAH by GC/MS. In addition, selected samples were analyzed for SIT by

GC/MS. The water samples were analyzedfor SHC and PAH.

The laboratory SOPs include the acceptability criteria for the calibration, procedural blank,

surrogate compound recoveries, and spike recoveries, as well as the corrective action if the

criteria are not met, reporting requirements, and method detection limit (NroL) protocols; The

data quality objectives (DQO) for these analyses are summarized in Section 2.3.

Saturated Hydrocarbons by Gas Chromatography/Flame Ionization Detection

Analysis for SHCs was performed using a method based on EPA Method 8015 (EPA 1993).

Target compounds for the method are SHCs, inclUding normal alkanes from n-C8 through nC40, pristane, phytane, and selected isoprenoids. Instrument analysis was performed by injection

of a portion of the prepared sample extract onto a 30-m long by 0.25-mm inner-diameter (ID)

u:mms animidalphase I reportlfinal report fileslfinal section 2,doc 2-12

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fused-silica capillary column with DB-5 bonded phase. This column provides baseline

resolution ofn-alkanes from'in-C8 to n-C40 and n-C17/pristane and n-C18/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.

Qualitative identification of target compounds was made by comparison to a standard mixture of

calibration standards. Quantitation of the analytes was based on the internal standard compound

(d62-triacontane), which was spiked into the sample just prior to analysis. The target compound

concentrations were corrected based on surrogate recovery.

Polynuclear Aromatic Hydrocarbons by Gas Chromatography/Mass Spectrometry

Analysis for PARs was performed using a method based on EPA Method 8270 (EPA 1993).

The method modifications include analysis for an expanded list of PAR and operation in the

selected ion monitoring (SIM) mode to lower detection limits.

The sample extract was injected onto a '30-m long by 0.25-mm ill fused-silica capillary column

with DB-5 bonded phase. This column provides baseline resolution of target PAHs. 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.

Qualitative identification of target compounds was made by comparison to a standard mixture of

target PARs. Identification of alkyl PARs was made by comparison to reference oil samples

analyzed with each batch of samples. The concentrations of the individual PARs were

calculated relative to one of the two internal standards that were spiked into the sample just prior

to instrumental analysis. The targetPAH concentrations were quantified using average response

factors (RFs) generated from the five-point calibration curve. To quantify the alkyl PAR,

homologue groups were assigned the RF of their respective parent PAR compound. Compound

concentrations were corrected based on surrogate recoveries.

Steranes and Triterpanes

Only selected sediment and tissue samples were analyzed for SITs. Analysis for SITs was

performed by GC/MS in the selected ion monitoring (SIM) mode using a method similar to that

used for PAR analysis. Qualitative identification of the target SITs was made by comparison to

a reference oil analyzed with each batch.

The concentrations of the identified SITs were calculated versus the internal standard chrysened12. All target triterpane concenttations were quantified using the average RF of 17(H), 21(R)-

hopane (T23) generated from the initial calibration. All target sterane concentrations were

quantified using the average RF of cholestane (S 17) in the initial calibration. Surrogate recovery

of 5b(R)-cholane was calculated relative to the internal standard. Compound concentrations

were corrected based on surrogate recovery.

2.2.3 Stable Carbon Isotopes C3Carbon)

A portion of the sample treated with HCl for TOC was used for determining values for ol3C. A

weighed portion of the treated and dried sample was processed using a Finnigan-MAT 251

isotope ratio mass spectrometer. The external precision of 0.02 per mil for ol3C was determined

u:mms animidalphase I reportlfinal report fileslfinaJ section 2.doc 2-13
by replicate analysis of a laboratory internal standard of calcite. The data were corrected for the

usual isobaric interferences using the equations ofCraig (1957), as modified for a triple collector

mass spectrometer. All isotopic data are reported in per mil unitsrelative to the Pee Dee.

Belemnite (PDB) reference.

2.2.4 Inorganic Parameters ,

Analysis for inorganic parameters was conducted by FIT. The analyses were conducted in

accordance with FIT's SOPs. The core inorganic analyses for the sediment and source samples

were trace and major metals. Targeted analytes and associated MDLs are listed in Table2-6.

This section describes the analytical methods that were used in perfonning the chemical

analyses.

2.2.4.1 Trace and Major Metals Analysis in Suspended and Surficial Sediment

Filters bearing suspended sediment and milligram quantities of SRM #2704, a river sediment

SRM issued by the National Institute of Standards and Technology (NIST), were digested in

stoppered, 15-mL Teflon® test tubes using Ultrex II® nitric acid (RN03), hydrogen fluoride

(HF) and HCl. 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, 15-mL polyethylene bottles, diluted to approximately 6 mL

with DDW rinses of the Teflon® test tubes, and stored in a plastic bag until analyzed.

Metal concentrations for the dissolved particulate samples, SRMs, and blanks were detennined

by flame atomic absorption spectrometry (FAAS), graphite furnace atomic absorption

spectrometry (GFAAS), or inductively coupled plasma/mass spectrometry (ICPIMS) in a manner

compatible with EPA Methods Series 7000, 601OA, and 7470 (EPA 1991), respectively. ,

Particulate AI, Fe, and Zn concentrations were quantified by FAAS using a Perkin-Elmer®

Model 4000 AAS (element symbols are defined in Table 2-6). Concentrations of Cd, Cr, Cu,

and Pb were quantified by GFAAS using a Perkin-Elmer® Model 4000 AAS equipped with an

HGA-400 graphite furnace and AS-40 autosampler. Values for Ba were determined by I~PIMS

using a Perkin-Elmer® ELAN 5000 spectrometer. In all cases, the instrument manufacturers'

specifications were followed and adherence to quality assurance/quality control (QAlQC)

requirements was maintained.

For sediment metal analysis, samples were initially brought to room temperature, then each wet

sediment sample was homogenized in the original 75-mL plastic vial using a Teflon® mixing

rod. Then, a portion (- 2 grams) of each sample was transferred into a pre-weighed plastic vial

to determine water content. Once transferred, the wet sediment and the vial were re-weighed. In

addition, about 2 to 4 grams of sample were transferred into polypropylene-copolymer centrifuge

tubes to determine the Hg content of the sediments. Samples intended for water content:

measurement were frozen, freeze-dried. and re-weighed to determine the water content. The

dried sediment samples were again homogenized using a Teflon® mixing rod.

About 0.45 grams of freeze-dried, homogenized sediment and SRM sediment (BCSS-l) were

totally digested in Teflon® beakers using concentrated, high-purity HF-HN03-perchloric acid

(HCI04). This method was chosen because it is a total digestion and thus accounts for the entire

u:mms animidalphase I reporllfinal reporl files\final section 2,doc 2-14

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l(~?" ; 'I. 'Jamount of metal in the sample. In the digestion process, 1 mL HCI04, 1 mL HN03, and 3 mL

HF were added to the sediment in the Teflon® beaker, covered with a Teflon® watch cover, and

heated at 50°C until a moist paste formed. The mixture was heated for another 3 hours at 80°C

with an additional 2 mL HN03 and 3 mL HF before bringing the sample to dryness. Finally, 1

mL HN03 and about 30 mL DDW were added to the sample and heated strongly to dissolve

perchlorate salts and reduce the volume. The completely dissolved and clear samples were

diluted to 20 mL with DDW.

Sediment samples to be analyzed for Hg were digested by heating 2 to 4 grams of wet sediment

in acid-washed, polypropylene~copolymer centrifuge tubes with 4 mL HN03 and 2 mL sulfuric

acid (H2S04), Sample tubes were,heated for 1 hour in a 90°C water bath and allowed to cool.

Each tube was centrifuged at 2,000 rpm and the supernatant 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 HN03 and rinsed three

times with DDW. Two procedural blanks, two duplicate samples, and two SRMs were prepared

with each set of 40 samples. SRM BCSS-l (trace metals except Hg) and :MESS-2 (Hg),

sediment samples issued by the NRC, were used.

Sediment samples, SRMs, and procedural and reagent blanks were analyzed by FAAS, GFAAS

(Zeeman or Continuum backgroUlld correction), cold vapor atomic absorption spectrometry

(CVAAS) or ICPIMS. Mercury concentrations were measured by CVAAS using a Laboratory

Data Control Model 1235 Mercury Monitor. The method used for each element and the

corresponding MDLs are presented in Table 2-6. All analytical techniques followed

manufacturers' specifications, laboratory SOPs, and the details provided in Section 2.3 below.

These methods are based on EPA ,methods described for Series 7000 (FAAS and GFAAS),

Series 7470 (CVAAS), and Series 6010A (ICPIMS) (EPA 1991).

2.2.4.2 Methyl Mercury AnalysiS in Sediment

Concentrations of methyl mercury were determined Dr. Y. Cai at Florida International

University using GC with atomic fluorescence spectrometry following aqueous derivatization

with sodium tetraphenylborate as described in Cai, et al. (2000).

2.2.4.3 Trace and Major Metals Analysis in Organism Tissue

Prior to acid digestion, the homogenized tissue samples received from ADL were thawed and remixed with a Teflon® stirring rod. The samples were then split into two portions, one

sUbsample to be digested wet for Hg and the other to be freeze-dried and digested for

determination of the remaining trace metals. The freeze-dried subsamples also provided the

percent water content data needed to convert the Hg results from a wet-weight to dry-weight

basis.

The concentrations of all metals (except Hg) were determined using 4 to 6 grams of wet-weight

tissue weighed into 100-mL glass,digestion flasks. These subsamples were freeze-dried,

reweighed for percent water content, and then digested by the sequential addition of

u:mms animidalphase I report\finai report files\final section 2.doc 2-15
concentrated, high-purityRN03, hydrogen peroxide (H20 2), and HCl with gentle reHuxing.

Aliquots of tissue SRMs were digested along with the experimental samples. Once the tissue

samples and SRMs were completely dissolved, the clear solutions were transferred to graduated

cylinders, diluted to 20 mL with DDW rinses of the digestion flasks, and then stored in labeled

30-mLpolyethylene screw-cap bottles for trace metal analysis.

Mercury determinations were carried out using 0.4 to 0.7 grams of wet tissue and dry SRMs

weighed into 50-mL glass digestion tubes. These subsamples were digested by the a~dition of

concentrated, high-purity HN03 and H2S04 and refluxing at90°C for 1 hour in the sealed tubes.

The dissolved samples were transferred to graduated cylinders, diluted to 20 mL with DDW

rinses of the digestion tubes, and then stored in labeled 30-mL polyethylene screw-cap bottles for . . t

Hg analysIs. '

Metal concentrations in the digested tissue samples, SRMs, and blanks were determined by

FAAS, GFAAS (Zeeman or Continuum background correction), CVAAS, or ICPIMS. The

method used for each element and the corresponding MDLs are given in Table 2-6. All "

analytical techniques followed manufacturers' specifications, SOPs on file at FIT, and th~ details . . . provided in Section 2.3 below. These methods are based on EPA methods describe~:for ,Series

7000 (FAAS and GFAAS), Series 7470)(CVAAS), and Series 6010A (ICPIMS) (EPA 1~91). j

2.3 Quality Assurance/Quality Control

A QA plan, which included quality control (QC) measures, was employed for the prograJ?l. This

section presents the key elements of the plan. . ,

2.3.1 Quality Assurance

2.3.1.1 Documentation

The procedures for monitoring the activities of key staff, meeting contract requirements, '

submission of all deliverables, budget control, and communications are detailed in the various

documents that together compose the project management plan: i

• A detailed work breakdown structure (WBS) for all tasks, designating primary task leader

and responsibilities for key personnel and staff;'

• A field sampling and logistics plan for field operations, including scheduling, staffing,

training, QC samp~e collection and analysis procedures, sample chain-of-custody

specifications, and sample shipping; and

• A laboratory work plan for laboratory analysis, including laboratoryprocedures, analytical

DQOs, QC procedures, corrective action criteria, and data entry/data. management..

The supporting quality assurance documentation includes the general company policies and

procedures (hiring practices, performance evaluations, program management and control tools,

and technical review procedures), the Quality Assurance Manual (QAM) for the respective

laboratories, and SOPs for field and laboratory operations. '

u:mms animida\phase I feportlfinaJ report files\final section 2.doc 2-16
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2.3.1.2 Quality Management

Program

As the ADL Program Manager, Dr. Paul Boehm was the primary contact with MMS for the

program and was responsible for the communication, coordination, and scheduling of all tasks,

subtasks, meetings, and deliverables. The Program QAlQC Officer, Dr. Judi Harris, was

responsible for the overall QAlQC activities of the project, including oversight of the record

keeping for the program. The Program Manager was kept apprised of the program's status by the

Field Sampling and Analytical Laboratory Leaders.

Field

Mr. John Brown served as the Field Team Leader for the sediment and benthic tissue collection

surveys and, as such, was responsible for completion of all field activities in accordance with the

field sampling and logistics plans and communication with the Program Manager and the field

team. He was also responsible for implementing field QC, including issuance and tracking of

measurement and test equipment; proper labeling, handling, storage, and shipping of samples;

chain-of~custody procedures; and control and collection of all field documentation. '

The field sampling team was provided a briefing of QA measures prior to beginning field

sampling. The field personnel were briefed on the potential'for contamination and crosscontamination of samples and given guidance on techniques to minimize such problems. In

general, this included training on the use of pre-cleaned sample containers; use of clean sampling

equipment; use of the decontamination protocols; and good handling practices. It also included

training on the specified sampling procedures and protocols in accordance with SOPs.

Laboratory

As organic chemistry task leader, Mr. John Brown was responsible for oversight of the organics

analyses performed by ADL's EC&F laboratory. Dr. John Trefry was the inorganic chemistry

task leader and was responsible for oversight of the inorganic analyses performed by FIT.

Laboratory analyses were performed in accordance with the laboratories' QAMs and the projectspecific laboratory workplan. Oversight of the laboratory QA program was the responsibility of

the laboratory's QA manager. Implementation of quality practices was the responsibility of the

laboratory manager, who had speCific responsibilities for:

• Implementing and adhering to the QA and corporate policies and procedures within the

laboratory

• Approving SOPs

• Maintaining adequate staffing

• Implementing internal/external audit findings corrective actions

Prior to the start of laboratory analyses, the laboratory staff were provided project-specific

training, which included a discussion of the project background and objectives; project

organization; sample preparation and instrumental analysis procedures; data quality objectives;

QC procedures; and reporting instructions. The task leaders provided this training.

u:mms animidalphase I reportlfinaJ report fileslfinal section 2.doc 2-17
2.3.1.3 Sample Custody, Preservation, and Tracking

The following section describes the procedures that were employed to ensure the integrity of the

samples, including prevention of contamination in the field, ensuring safe transport, and;

documenting sample custody and transfer.

Sample Handling

All field sampling equipment was decontaminated prior to use at 'each sampling station. !The

equipment was:

• scrubbed with brushes and liquid soap-and-water mixture to remove any accumulated

sediment '

• wiped clean with a sorbent pad, paper towel, or rag (if necessary)

• rinsed with seawater (from hose or buckets, as appropriate)

• rinsed with distilled water

• rinsed with isopropanol solvent

• rinsed with deionized water (optional)

The clean equipment was prevented from recontamination prior to sampling by either

decontamination immediately prior to use or protection by wrapping securely in aluminum foil

that had been decontaminated. Precautions were taken to ensure that clean equipment did not

contact anything other than the sample, air, or other clean equipment. Clean equipment was

prevented from contact with the ground (except for the immediate sampling area), hands:

clothing, plastic bags, buckets, trays, etc.

At all times after collection, sample integrity and custody were maintained. Chain-of-custody

(CaC) procedures are specified in formal SOPs and are followed for all sample storage and

shipment activities. Chain-of-custody seals and sample labelswere applied to each sample

container, ensuring sample integrity. All field samples were unambiguously labeled in ,

waterproof ink with the following information:

• Sample site

• Unique field sample number

• Date and time of sample collection

• Details of preservation used

The type of sample containers used and the sample storage methods are provided in Tabl~ 2-7.

Pre-cleaned sample containers that had been certified as such by the vendor were used for the

program.

In the field, sediment, biota, and QC samples for chemical analysis were immediately

inventoried and stored in a secure area after collection. Inventory included counting of all the

samples to ensure that all samples were collected and safely returned to the custody area on

board, documenting all samples in field logs, and preparing the chain-of-custody form.

,

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Sample Shipment

Following completion of the cruise, samples were packed in coolers for overnight shipment from

the PBaC in Deadhorse using Federal Express airfreight courier. The samples were frozen prior

to transportation and shipped to the appropriate analytical laboratories (Table 2-7), either frozen

packed on dry ice or refrigerated packed with frozen blue ice via overnight service. Custody

seals were used on all shipping coolers to maintain custodial security while the samples were in

the possession of a third party (i.e., airfreight courier).

Receipt at ADL

Quality assurance practices were applied at the moment samples were received at the laboratory.

The laboratory sample custodian received all samples. Prior to opening the cooler, the cooler

was checked for the presence of intact custody seals. The cooler was then opened and the

temperature of the samples was measured by measuring the temperature of a representative

sample. Each sample was carefully checked for identification, which was then cross-referenced

against the cac records. Samples were logged in and a unique laboratory identification number

was assigned to each sample. Problems or discrepancies with the coolers, samples, or

documentation were documented and the project manager was notified immediately so that

issues could be resolved.

After samples were received into the laboratory and a unique identification number assigned, the

samples were placed in a secure, uniquely identified storage area until extraction. As is the

practice by the laboratory, temperatures of all of the refrigerators and freezers were monitored

and recorded daily. Samples were removed and thawed for sample preparation and then returned

to frozen storage, where they will be stored for a period of at least two years.

Documentation tracking sample possession from the time it is collected (including equipment

and container preparation) to the point at which the samples and extracts are discarded is

necessary to ensure the credibility and validity of field and laboratory results. For this program,

documentation was accomplished through initiating a cac record for each sample at the time of

its collection and carrying the required paperwork through the final reporting of results, and to

the final program files.

A cac form accompanied the samples as they were delivered from the field to the laboratory.

Upon receipt, the document was signed by the laboratory's sample custodian, and dated as

acknowledgement of receipt of the samples. Thereafter, the laboratory internal cac protocols,

described in the individual laboratory QA program plans or similar documentation, were utilized.

Receipt at FIT

Each sediment, suspended solids, tissue, and source sample received by the Marine &

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 (4°C ±2°C) and all tissue

samples were kept frozen (-20°C) until processed for analysis. Suspended solids samples were

dried under cleanroom conditions and stored at room temperature until analysis.

u:mms animidalphase I reportlfinal report fileslfinaJ section 2.doc 2-19
2.3.2 Field Quality Control

2.3.2.1 Sample Handling

Equipment decontamination procedures were strictly followed during the sampling. The,

decontamination included a physical scrub with soap and water, rinses with seawater and

distilled water, and a rinse with isopropanol.

2.3.2.2 Quality Control Samples

As part ofthe QA program, several types of field QC samples were collected during the survey.

Blanks

Blank samples were collected to characterize potential influences from equipment and the

sampling activities.

One field (deck) blank was collected during sediment sampling. To collect the field blank, a

clean, prelabeled sample jar of the same batch used for sample collection was carried1into the

working area, opened during the collection of one sample, and returned to the laboratory 'with the

field samples. One container was collected each for organics and metals. The field blank was

stored under the same conditions as the associated field samples.

i

An equipment blank was collected from rinsate of the sediment sampling equipment. The

procedure for collecting the equipment blank 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 (one container each for"

organics and metals)

• A precleaned stainless-steel funnel was used to assist in the collection

• The equipment blank was stored under the same conditions as the associated field samples . ,

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A sample of diesel fuel typical of that used in marine vessels in the Arctic was taken durirg a

previous field survey and was available at ADL. 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). I

Field Replicates

As a QC measure, replicate samples were collected as part of the field sampling design a~ sample

stations 5(I) and Lil. At these locations, sediment samples were collected in triplicate so that

the reproducibility and range of results could be evaluated.

Turbidimeter Calibration

The Bach turbidimeter was calibrated prior to each use with the standards provided by the . .,

manufacturer. The instrumental blank was determined using a glass cuvette filled with nnw. ,

The Aanderaa turbidity sensor was calibrated by the manufacturer prior to delivery arid c~ecked

in air (zero turbidity) and with the sensor blocked (full-scale turbidity) prior to use. '

u:mms animidalphase I report\tinaJ report files\tinaJ section 2.'doc 2-20

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Salinity Calibration

The Reichert-Jung Model 10419 optical refractometer was calibrated prior to each use with

Standard Seawater (Ocean Scientific International, salinity::::: 34.998) and DDW. The Aanderaa

conductivity sensor was calibrated by the manufacturer prior to delivery and checked against

DDW and samples of known salinity prior to use. Salinity samples were also collected in the

field and shipped to the Marine & Environmental Chemistry Laboratories at FIT, where their

salinities were determined using a PortaSal® Model 8410 salinometer as a cross-check on the

field instruments.

2.3.2.3 Documentation

Throughout the field surveys, field notes were maintained by the scientists in log books and in a

station log. Biota (bivalve and amphipod) sampling information was also recorded on log forms.

Exceptions to procedures specified in the sampling and analysis plans, if any, were recorded on

the forms.

Film and digital media were used to photo-document the surveys. This documentation recorded

specific samples, sampling procedures, and unusual sediment types.

2.3.3 Organic Chemistry Laboratory Quality Control

2.3.3.1 Data Quality Objectives and Quality Control Samples

A set of DQOs was established for the program to ensure that the analytical data would be of the

quality necessary to achieve the project objectives. The DQOs were also designed to enhance

the ability of the methods to identify and accurately quantify source-specific oils. The DQOs

were adapted from the specific laboratory analytical SOPs and were included in the laboratory

workplan specific for the program. They are included here as Tables 2-8 and 2-9.

For processing, samples were grouped together in batches of 20 field samples, plus associated

QC samples. In general, 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.

The QC sample$ processed with each batch of tissue samples included one procedural blank, one

blank spike, one SRM (Tissue SRM 1974a), and one duplicate analysis. The blank spike sample

was fortified with PAH and SHC matrix spike solutions.

There were a number of additional measures added to the processing of the samples to monitor

QC and to aid in the assessment of the data's usability with respect to the program objectives.

An important part of this is the evaluation of specific QC samples for accuracy, precision, and

potential contamination. The following is a general description of some elements.

Solvent and Standard Checks

Prior to sample analysis, every lot of solvent used in the analytical process was analyzed in

duplicate to verify that it was free of contamination and acceptable for use. Likewise, prior to

spiking the samples with surrogates and internal standards, all standard preparation records were

checked. No standards were used for an analysis unless they had been approved for use.

u:mms animidalphase I reportllinal report filesllinal section 2.doc 2-21
Instrument Calibration

Before instrumental analysis of sample extracts, a multi-level calibration was analyzed and the

linearity of the analyte response factors was evaluated. A continuing calibration standard was

analyzed regularly to check the stability of the instrument response. If the relative st~ndard

deviations (RSDs) for the initial calibration or the percent difference of the daily calibration did

not meet the criteria set in the SOP, a new calibration was run and the affected samples reanalyzed.

Reference Samples :

For PARs, to assess the accuracy of the mixture used to calibrate the method, an independently

verified instrument reference material (IRM) was analyzed against the calibration standa~d. The

values of the analytes had to be within 15 percent of the target value for the calibration s<;>lution

to be valid. I

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In addition, a solution of an assayed crude oil was analyzed with each initial calibration sequence

and the results were compared to a laboratory-established mean to assess method accura~y. The

solution was also used to provide petroleum pattern information and aid in qualitative

identification of target compounds.

Procedural Blank

A procedural blank was processed and analyzed with each analytical batch in order to monitor

potential contamination resulting from laboratory solvents, reagents, glassware, and proc~ssing

procedures.

Blank Spike ,

A blank matrix was spiked with representative target compounds prior to extraction to as~ess the

effect of the sample processing procedure independent of sample matrix effects.

Laboratory Duplicate

A field sample was analyzed in duplicate to assess the precision of the method in the target

matrix. I

Standard Reference Materials

A Standard Reference Material of a well-characterized sample of known concentration was

processed through sample preparation and instrumental analysis with each batch of samples. The

results were compared to externally certified values to asseSs method accuracy. This program

used SRM samples provided by NIST: SRM 1944 for sediment samples and SRM 1974a for

tissue samples.

2.3.3.2 Laboratory Records

The laboratory maintained detailed records throughout the processing of the samples. All raw

instrumental data were archived electronically. Completed records or copies of forms were

collated into a binder for final archive storage. The final laboratory data package contain~,

u:mms animidalphase IreportlfinaJ report files\final sectiOn 2..dOC 2-22

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sufficient detail so that an external audit could be performed. The documentation in the final \~- " .( data package includes: ' . r

• Lot numbers, vendor, and preparation records for reagents and standards

• Sample preparation records

• Analytical procedures used that are not documented in laboratory SOPs

• Instrument analysis records

• Instrument raw data hardcopy

• Documentation of observations or deviations encountered

2.3.3.3 Laboratory Data Review

The following describes the process of data reporting and review by the laboratory. The

chemistry data for each analysis were reduced and reviewed by the laboratory staff and then

assembled into the final data package. The assembled package was peer reviewed and checked

to ensure that the DQOs were met, that the analyses met the program objectives, and that the data

were traceable and defensible. The data were also reviewed for compliance with the documented

procedures and quality objectives in the work plan. Data were also reviewed for internal

consistency and against expected or known values.

After the final laboratory data package review, it was subjected to a formal audit. The audit

process is coordinated by the QA Manager and follows the procedure outlined in the ADL Data

Review SOP. The formal audit process included a 100-percent review of all hand-calculated

values and a 20-percent review of computer-generated results. The process also checked the

traceability of a final result through the instrument calibration and to the sample preparation

steps. A formal report was issued to the facility supervisors at the completion of the audit for

response. Upon completion of the responses, the auditor released the results to the Program

Manager for review and reporting. The final laboratory data package and the audit report are

maintained in the laboratory files.

2.3.4 Metals Chemistry Laboratory Quality Control

Quality Control Measurements for Analysis

For this project, QC measures included balance calibration, instrument calibration (FAAS,

GFAAS, Zeeman Graphite Furnace Atomic Absorption Spectrometry [ZGFAAS], CVAAS,

ICPIMS, TOC analyzer, turbidimeters, and in-situ instrument sensors), 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 SRMs, 2 duplicate samples

and 2 matrix-spiked samples were analyzed. Data Quality Objectives 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 (National Bureau of Standards [NBS]-traceable) standard weights. All pipets

(electronic or manual) were calibrated prior to use. Each of the spectrometers used for metals

analysis was initially standardized with a three- to five-point calibration with a linear correlation

coefficient of r 0.999 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

u:mms animidalphase I reportlfinal report fileslfinaJ section 2.doc 2-23
samples until all of the analyses were complete. The RSD between complete calibration and

standard check was required to be <15 percent or recalibration and reanalysis ofthe affected

samples was perfonned.

Matrix Spike Analysis

Matrix spikes were prepared for a minimum of 5 percent of the total number of samples analyzed

and included each metal to be determined. Results from matrix spike analysis using the method

of standard additions provide infonnation on the extent of any signal suppression or

enhancement due to the sample matrix. If necessary (i.e., spike results outside 80 to 120 percent

limit), spiking frequency was increased to 20 percent and a correction applied to the metal

concentrations of the experimental samples.

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 and provided a , measure of analytical precision. :

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.

SRM Analysis .

A common method used to evaluate the accuracy of environmental data is to analyze SRMs,

samples for which consensus or "accepted" analyte concentrations exist. The '

following SRMs were used: Marine Sediments BCSS-l and MESS-2 (NRC); Buffalo River

Sediment 2704 (NIST); Mussel Tissue 2976 (NIST); Dogfish Muscle DORM-2 (NRC); and

Trace Elements in Water 1643d (NIST). Metal concentrations obtained for the SRMs were

required to be within ±20 percent of accepted values for >85 percent of other certified analyses.

When no certified values. existed 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

210pO anti-static devices near the weighing pan within the balance. The standard deviation for the

mass of each filter was required to be <2 ~g for the value to be accepted.

u:mms animidalphase 'I reponltinaJ repon filesltinal section 2,doc 2-24

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2.4 Database Management

As part of the ANIMIDA program, MMS requested that the ANIMIDA data be incorporated into

the MMS Coastal and Offshore Resource Information System (CORIS) database. This required

database design and development to include the various data types generated by the ANIMIDA

program into CORIS. Harvard Design and Mapping (HDM - Cambridge, MA) is subcontracted

to ADL for completing the database design and data submission. Thus far, a study of the CORIS

database design and structure has been performed. The CORIS structure has been expanded to

include data for acoustics, water, sediments, peat, particles, and tissue chemistry. These data

have been separated into tables with both field definitions and names that follow the existing

CORIS structure. CORIS's metadata tables are being added to the metadata information from

this environmental survey. An Entity Relationship diagram is being created to show how the

environmental chemistry and acoustics data relate to each other and can be related to the

metadata tables in CORIS. Spatial Database Engine (SDE) layers and scripts have been created

for acoustics, water chemistry, and dry chemistry data. We will work closely with MMS to

finalize our database design. Once the database design and structure are finalized, tables will be

created using Oracle Structured Query Language (SQL) scripts. In addition, primary keys,

foreign keys, sequence numbers, indices, and a data dictionary will be created prior to CORIS

database submission of all ANIMIDA data. All final ANIMIDA data will be archived in the

MMS CORIS database.

u:mms animidalphase I reportlfinal report files\final section 2,dOC 2-25
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Table 3-1a. Summary Data Showing Within-Site Variability for Concentrations of Metals in Sediment Samples

AI Ba Cr Hg Pb Zn

Sample

(%\ Cuala\ Cuala\ Cuala\ (UWg\ CUa/a\

Replicates 99-5(1)-01 1.81 232 17.6 0.000 5.8 27.3

99-5(1)-02 1.82 237 18.1 0.005 5.8 23.0

99-5(1)-03 1.89 247 29.7 0.0004 5.9 26.9

CV (%) 2.4 3.2 31.4 12.3 1.0 31.4

Replicates 99-L11-01 2.36 289 32.0 0.024 6.4 34.0

99-L11-02 3.31 355 46.1 0.028 8.9 50.6

99-L11-03 2.61 307 32.4 0.018 7.4 38.2

. 17'-8 10.8 .

21.8 21.6 16.6' CV (%) 21.1

Coefficient ofvariation (CV) = [standard deviation/mean] x 100%.

- ~_ ...._, ...1.' ._
---~-~-~-----~-~~~~

Table 3-1. Summary Data by Region for Metals, Total Organic Carbon, and Grain Size

~egl,on (~~9L AI As Ba Be Cd Co Cr Cu Fe

-.- -~ . _..,..,..~- --.- (%). .- -(~g'g)- . • (~g'g) , -(~g'g) ~. -- (~g'g). (~g'g) ' . . ~- (~g'g) .. . .(~g'g) .._. (%)

Mean Beaufort Sea 0.11 3.41 11.7 360 1.24 0.24 7.6 49.0 17.4 2.06

Stct;Oev. Monitoring· ±0.09 ±1.74 ±6.2 :i:177 ±O:OO ±0.19 ±4.6 ±26:9 ±12.9 ±O:96 pr~am

Range (B P) 0.06-0.44 1.33-6.43 5.2-27.3 155-753 0.40-2.30 0.05-0.79 2.20-18.3 15.1-91.1 4.0-46.9 0.72-3.47

Mean Northstar 0.12 3.68 11.9 448 1.25 0.22 7.1 53.6 17.3 2.07

Std. Dev. Prospect :1:0.07 :1:2.10 :1:5.8 :1:169 :1:0.61 :1:0.11 :1:3.6 :1:29.9 :1:12.5 :1:1.14

Range 0.04-0.13 1.13-7.26 4.2-22.7 164-712 0.60-2.30 0.Q7-0.43 2.70-13.1 12.7-104.3 12.5-37.6 ,0.74-3.89

Mean Liberty 0.10 3.76 11.1 418 1.13 0.18 6.9 54.2 16.2 1.98

Std. Dev. Prospect :1:0.03 :1:1.27 :1:3.3 :1:124 :1:0.38 :1:0.10 :1:2.0 :1:19.0 :1:7.9 :1:0.67

Range 0.03-0.16 2.36-6.32 6.8-17.3 289-674 _.0.50-2.00 0.07-0.37 4.50-11.4 27.8-86.5 7.4-30.9 0.72·3.47

Mean Avermor 0.11 3.61 11.5 407 1.23 0.21 7.6 52.1 17.0 2.03

Std. Dev. BS , :1:0.07 :1:1.71 :1:5.2 :1:160 :1:0.60 :1:0.14 :1:4.6 :1:25.3 :1:11.2 :1:0.93

Northstar and

Range Liberty 0.03-0.44 1.13-7.26 4.2-27.3 155-753 0.40-2.30 0.05-0.79 2.2-18.3 12.7-104.3 4.0-46.9 0.72-3.89

Average Continental Crust

0.Q7 7.96 1.7 584 2.4 0.1 24 126 25 4.32

(Wedepohl, 1996)

Region (~~?g) Mn NI Pb Sb TI V Zn TOC Silt + Clay (~g'g) (~g/g) (1-I9/g) (~g/g) (~g/g) (l-Ig/g) (~g/g) (%) (%)

Mean Beaufort Sea 0.04 287 22.0 9.8 0.50 0.36 82.1 63.0 0.41 35.2

Std. Dev. Monitoring :1:0.05 :1:144 :1:13.5 :1:6.1 :1:0.30 :1:0.22 :1:45.0 :1:39.2 :1:0.38 :1:35.1 pr~am

Range (B P) 0.003.{).20 89.8-545 6.0-48.4 3.2-22.3 0.15-1.14 0.12-0.92 26.9-153 14.8-124 0.05-1.3 1.7-98.7

Mean Northstar 0.04 272 22.5 9.7 0.44 0.37 88.9 63.9 0.70 44.6

Std. Dev. Prospect :1:0.03 :1:167 :1:12.6 :1:6.4 :1:0.23 :1:0.21 :1:55.1 :1:41.8 :1:0.66 :1:40.6

Range O.OO8'{).OO 62.4-006 7.1-43.0 3.2-20.3 0.22-0.84 0.15-0.75 28.1-173 16.7-131 0.01-1.93 1.0-98.8

Mean Liberty 0.03 245 22.2 10.0 0.52 0.41 83.8 63.8 0.79 50.7

Std. Dev. Prospect :1:0.02 :1:70 ±8.0 ±3.6 :1:0.18 :1:0.14 :1:28.0 :1:24.9 ±0.76 :1:26.5

Range 0.01-0.07 170-397 12.4-39.3 6.40-18.2 0.33-1.01 0.29-0.81 51.0-133 34.0-108 0.27-3.42 2.1-93.3

Mean Aver~of 0.04 269 22.2 9.9 0.49 0.38 84.8 63.5 0.62 43.1

Std. Dev. BS , ±0.04 :1:133 :1:11.5 :1:5.4 ±0.24 :1:0.19 :1:43.4 :1:35.5 :1:0.62 :1:34.4

Northstar and

Range Liberty 0.003.{).02 62-006 6.0-48.4 3.2-22.3 0.15-1.14 0.12-0.92 26.9-173 14.8-131 0.01-3.42 1.0-98.0

Average Continental Crust

0.04 716 56 14.8 0.30 0.52 98 65 - - (Wedepohl, 1996)
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For TOe analyses, the marine sediment SRM MESS-2 was used as a QA sample. This SRM is

certified for total carbon c'ontent (inorganic plus organic); therefore, the TOe values in Tables

3-21 and 3.:.23 are slightly below the certified total carbon value. Nevertheless, the TOe values

determined for MESS-2 were consistently reproducible with percent RSD of - 1 percent.

u:\mrns animidalphase I report\linal report files\linal section 3 text.doc 3-19
3.4.3 Metals Laboratory Quality Control

Laboratory QC samples were analyzed to assess precision and accuracy of the sample

preparation and analytical procedures. For this program, the following laboratory QC samples

and measures were used to evaluate accuracy and precision of the analytical data: procedural

blanks, matrix spike samples, laboratory duplicates, and standard reference materials. The

results for the inorganic QC samples and measures are presented in Tables 3~20 through 3-23

and Appendices A and C, along with the results for the associated environmental samples.

Discussion and interpretation of the results are provided in the following sections.

3.4.3.1 Procedural Blanks

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.

3.4.3.2 Matrix Spike Sample

Matrix spike samples were analyzed with each batch of sediment, organism, and suspended

solids samples 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, organism, and suspended solids samples are shown in Tables 3~21

through 3-23, and are within the 80 to 120 percent range specified in the DQOs (Table 2-10),

except for sediment Ag and V, and organism Co and Hg. In response, the spiking frequency was

increased for these four metals in their respective matrices and a spike correction applied to the

sample metal concentrations.

3.4.3.3 lAboratory Duplicates

Duplicate subsamples taken from individual sediment and water samples in the laboratory were

analyzed to estimate analytical precision. Analytical precision for sediment metal analyses (n =

4 pair of duplicate samples) ranged from 0.5 percent RSD for Cu to 7.7 percent RSD for Ag. For

organism tissue samples (n =1), precision of duplicate sample analysis ranged from 0 percent

RSD for Co to 15.7 percent RSD for Tl. In the case ofTl, the high percent RSD is due to the

very low concentrations of Tl present (0.012 and 0.015 IJ-g/g dry weight in the duplicate

samples). The percent RSD for duplicate TSS concentrations averaged 1.9 percent RSD in the

summer sampling (n = 7). In the winter sampling only one duplicate was obtained: the TSS RSD

from this duplicate sample was 28.6 percent RSD,(which results from the very low TSS

concentrations found under the ice). The percent RSD in suspended solids metal concentrations

ranged from 0.4 percent (AI) to 6.2 percent (Pb) for the summer sampling (n =1), and 0 percent

(Fe) to 6.1 percent (Cd) during the winter sampling (n = 1). Analytical precision of particulate

TOe analyses averaged 12.4 percent for both sampling periods (n =6).

3.4.3.4 Standard Reference Materials

SRMs were processed and analyzed for trace metals along with the experimental samples as

described in the Methods section (Section 2). The results of these analyses are shown in Tables

3-21 (sediment analysis), 3~22 (organism analysis), and 3-23 (suspended solids analysis). The

metal concentrations determined for each SRM, were all within the range of certified values or

within the DQO limits of the reference values provided by the certifying agencies.

u:\mms animidalphase I reportlfinaJ report frleslfinaJ section 3 teXl.doc 3·18

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3.4.2.5 Standard Reference Materials

Instrument SRMs were analyzed with each instrumental analytical sequence to assess accuracy

of the instrument calibration (PAR only). A matrix-specific SRM was prepared and analyzed

with each sample preparation batch to assess accuracy of the analytical method relative to sample I

preparation and analysis procedures. PAR analyses were performed on each SRM. SHC and

srr analyses were not performed on the SRMs since there are no certified values for these

compounds.

Instrument SRM. SRM 1491 (a solution of parent PAHs in solvent with certified

concentrations) was analyzed prior to each PAR analytical sequence. The percent differences

(%Ds) of the measured values versus the certified values were within 15 percent for all

instrument SRMs, as required in the laboratory QA plan, indicating that the instrument

calibrations were acceptable.

Sediment SRM. Three SRMs (SRM 1941a - a freeze-dried marine sediment with certified

concen~rations for PARs) were prepared and analyzed for PARs along with the sediment

sample? The %Ds of the measured values versus the certified values for the PAH compounds

were within the acceptance criteria of 30 percent on average per SRM and 35 percent for the

individual compounds, with a few exceptions. The response for naphthalene in all three SRMs

was m~re than 30 percent lower than the certified value (-39% D, -36% D, and -54% D). These

results indicate that the measurement of naphthalene in the sediment samples may be biased low

by approximately 40 percent, possibly due to loss of this more-volatile PAR during sample

preparation. Responses greater than 30 percent higher than the certified values were noted for

dibenzo(a,h)anthracene in two SRMs and for benzo(b)fluoranthene in one SRM. The results for

these compounds in the associated sediment sample may be biased high. These QC issues have a

minor impact on the quality and usability of the associated sample data since the exceedances

were not extreme and did not result in any data being considered unusable.

TissueSRM. One SRM (NIST SRM 1974a - certified for PAHs) was prepared and analyzed for

PAHs along with the tissue samples. All of the compound concentrations were within 35 percent

of the certified values, with one exception. Anthracene's concentration was 130 percent greater

than the certified value. The high recovery of anthracene is consistent with the results obtained

for this compound in multiple (more than 29 samples) analyses of SRM 1974a over the last four

years by ADL. This QC issue does not impact the quality or usability of the associated sample

data since acceptable recoveries for anthracene were noted in the BS and instrument SRM

analyse~, and since it appears that the certified value for anthracene in NIST SRM 1974a is

incorrect.

3.4.2.6 Control Oil Analyses

A North Slope Crude oil sample was analyzed prior to each analytical sequence for PAH, SHC,

and srr analysis. The results of the North Slope Crude oil analyses were used to evaluate

accuracy of the analytical methods, provide a chromatographic pattern for comparisons with

samples, and provide an independent check of the quantitation for alkyl PAHs, srrs, and SHCs.

Results of the control oil analyses were compared to laboratory mean values generated from

multiple analyses of the oils. For the PAH, SHC, and srr analyses, all of the results were within

the acceptance limits.

u:\mms animidalphase I reportlfina! report files\final section 31ext.doc 3·17
Overall, the laboratory duplicate results met the DQOs specified in the laboratory QA plan for

the program. f " ,:h! .

For the sediment SHC analyses, good laboratory duplicate precision was noted, with RPDs less

than 30 percent for the majority of the compounds, including compounds detected below the RL.

The mean RPD for each laboratory duplicate pair was less than 30 percent. Of the two

compounds that had RPDs greater than 30 percent, all of the concentrations were less than 10

times the associated MDL.

sample data since the response for internal standard d12-benzo(a)pyrene was significantly greater

and within acceptance limits in the associated samples. The internal standard response for d12-

benzo(a)pyrene ranged from 77 to 123 percent of the daily calibration response in the associated

environmental samples, while the responses in the BS analyses,were 49 percent, 49 percent, and

60 percent.

.,

u:\mms animidalphase I report\finaJ report files\linaJ s~on 3 tex!.doc 3-16

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For the tissue SHC analyses, all of the compound concentrations were less than 10 times the

associated MDL. RPDs are typically calculated to assess laboratory duplicate precision;

however, due to the low reported concentrations and the increased variability of quantitation at

concentrations near the RL, the RPDs would not be an accurate measure of analytical precision

for this laboratory duplicate evaluation. Instead, the absolute difference of the duplicate

measurements was used to assess analytical precision. These absolute differences were all less

than the RLs and were within the accepted margin of error of the analyticalmethod.

For the sediment and tissue PAH analyses, good laboratory duplicate precision was noted, with

RPDs less than 30 percent for the majority of the compounds, including compounds detected at

concentrations below the RL. The mean RPD for each laboratory duplicate pair was less than 30

percent. Of the four compounds that had RPDs greater than 30 percent, all of the concentrations

were less than 10 times the associated MDL. The laboratory duplicate precision criterion does

not apply to compounds detected at concentrations less than 10 times the MDL due to increased

variability at low concentrations. (RPD was calculated as the absolute difference between the

two measurements divided by the mean of the two measurements.)

For the SHC analyses, all of the tissue and sediment BS recoveries were within the recovery

acceptance limits, with two exceptions. Decane (nClO) recovered below the acceptance limits in

two of the sediment BSs, indicating that the n-ClO results in the associated environmental

samples may be biased low. Overall, this data quality issue has a negligible impact on data

quality and usability since n-ClO is not a key compound in data evaluation and decane

contributes only a small amount to the total PHC concentration.

3.4.2.4 Laboratory Duplicates

Laboratory duplicates were prepared with several sample preparation batches by extracting a

second separate aliquot of an environmental sample. Laboratory duplicates were evaluated to

assess analytical precision related to laboratory performance and sample matrix. For this project,

one laboratory duplicate (99-5F-OI-PHC-CY) was prepared and analyzed with the tissue samples

and two laboratory duplicates were prepared and analyzed with the sediment samples (99-DUPOl-PHC-S and 99-L05-0l-PHC-S). PAH and SHC analyses were performed on each laboratory

duplicate. SIT analyses were not performed on the laboratory duplicates.
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For the PAM analyses, all of the environmental and QC sample surrogate recoveries were within

the rec~very acceptance limits, with one exception. The method blank associated with the tissue

samples had two of the four surrogates with low recoveries. The blank spike associated with this

method!blank had acceptable surrogate and spike recoveries and all of the associated samples

had acceptable surrogate recoveries. Thus, these low surrogate recoveries in the method blank

do not ~dversely affect the quality or usability of the associated environmental sample data. ,

• For the SHC and srr analyses, all of the environmental and QC sample surrogate recoveries

were within the recovery acceptance limits without exception.

3.4.2.2 'Procedural Blanks

A laborktory procedural blank (PB) was prepared with each sample preparation batch by

extractihg a blank sample matrix (sodium sulfate) as if it were one of the environmental samples.

Procedural blanks are used to assess the potential of contamination introduced during sample

preparation and analysis. For this project, two PBs were prepared and analyzed with the tissue

samples and three PBs were prepared and analyzed with the sediment samples. PAH and SHC

analyse~ were performed on each PB. srr analyses were not performed on the PBs.

PAH target compounds were detected at trace concentrations less than the RL in all of the tissue

and sediment · PBs. Between 5 and 18 PAH target compounds were detected in each of the PBs.

Naphthalene was identified in all the blanks and is a common contaminant associated with the

solvents used during sample preparation. Several SHC target compounds ranging from n-C16 to

n-C34 were detected at trace concentrations less than Yz the RL in the tissue and sediment PBs. ,

Environmental sample results that were within 5 times the associated PB concentration were

qualified with a "B" to indicate that the compound was also pres'ent in the blank. Of the results

that we~e qualified with a "B", none of these results were at concentrations greater than 5 times

the sample-specific RL.

Overall; the PB results met the DQOs specified in the laboratory QA plan for the program, and

do not indicate concentrations of laboratory contamination that would adversely affect the , quality or usability of the associated sample data. Results that were qualified with a "B" may be I

biased high or may be false positives.

3.4.2.3 !Blank Spike Sample Recoveries

. A blank spike sample (BS) was prepared with each sample preparation batch by spiking a blank

sample matrix with known concentrations of a subset of the target compounds. BSs are used to

assess t~e accuracy of the sample preparation and analysis procedures independent ofsample

matrix effects. For this project, one B~ was prepared and analyzed with the tissue samples and

three BSs were prepared and analyzed with the sediment samples. PAH and SHC analyses were

performed on eachBS. srr analyses were not performed on the BSs.

For the!?AHs analyses, all of the tissue BS recoveries were within the recovery acceptance

limits. For sediments, the recoveries of several compounds - benzo(b)fluoranthene,

benzo(k)fluoranthene, indeno(1,2,3-cd)pyrene, dibenzo(a,h)anthracene, and benzo(g,h,i)perylene

- exceeded the acceptance limits. The recoveries for these compounds were raised apparently

due to the low response of the associated internal standard (d12-benzo[a]pyrene) in the BS • analyse~. This QC issue does not adversely affect the quality or usability of the associated

u:lmms animida\phase I report\Iinal report files\linal section 3 text.doc 3~15
ranged from 0.02 to 2.17 IlglKg. These absolute standard deviations are less than or equal to 2

times the reported RLs and are within the accepted margin of error of the analytical method.

Thus, acceptable precision was achieved for the PAH analyses of the field replicate samples

collected at sampling station Lll.

No field replicate analyses were performed for the SIT analys~s since only a limited number of

samples were selected for SIT analysis.

Field triplicates were collected and analyzed for surficial sediment (2 sets) and suspended

sediment (1 set). The average relative standard deviation (RSD =[(std. deViation/mean) x 100

percent]) for the sediment samples was 18.3 percent for sample Lll and 14.8 percent for sample

5(1) for the 18 metals studied. These values are larger than the RSD results for laboratory

duplicates presented below because the sediments are quite patchy with respect to grain-size and

metal composition at many stations. However, by ratioing trace metal concentrations to AI, as

described previously, this variability is normalized and the resulting ratios are considerably more

uniform than the absolute values. In this manner, concern for variability introduced by variations

in grain-size is minimized. The RSD for the field triplicate for suspended sediment was 6.6

percent for the 8 metals studied. This value is more in line with the laboratory RSD presented

below because the particles in suspension are more uniformly mixed in the water column.

3.4.2 Organics Quality Control

Laboratory QC samples were analyzed to assess precision and accuracy of the sample

preparation and analytical procedures. The number and type of laboratory QC samples was

based on the total number of field samples and as specified in ADL SOPs and the Field Sampling

and Logistics Plans (Arthur D. Little 1999a, and Arthur D. Little 2000a). For this program, the

following laboratory QC samples and measures were used to evaluate accuracy and precision of

the analytical data: surrogate recoveries, procedural blanks, blank spike samples, laboratory

duplicates, standard reference materials, and oil reference standards. The results for the organic

QC samples and measures are presented in Appendix B, along with the results for the associated

environmental samples. Discussion and interpretation of the results are provided in the

following sections.

In addition to the program-specific QC, ADL participated in the National Oceanic &

Atmospheric AdministrationlNational Institute of Standards & Technology (NOANNIST)

intercalibration exercises for organics in 1998, 1999, and 2000. Triplicate analyses of marine

sediment and mussel tissue were analyzed for organics, including PAHs, as part of these

exercises. The results of the ADL analyses were within the top 10 percent ofthe more than 30

laboratories participating in the exercises.

3.4.2.1 Surrogate Results

Surrogate compounds were added to all environmental and QC samples prior to sample

preparation. These compounds were added to determine the efficiency of the sample extraction

and analysis procedures. Surrogate recoveries were evaluated to assess analytical method

accuracy relative to sample matrix and laboratory performance.

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One field (deck) blank sample was taken during the collection of sediment samples. PAH, SHC,

and metals analyses were performed on this field blank. The field blank results were evaluated

to assess the potential for atmospheric or other contamination that the field samples may have

been subject to during sample collection.

The concentrations of all metal analytes were less than 5 times the MDL and no PAHs or SHCs

were detected in the field blank, indicating that samples were not subject to atmospheric or other

contamination during sample collection.

3.4.1.3 Field Replicates

Two sets of field replicate samples were generated during the collection of the sediment samples

in the form of triplicate samples collected at sampling stations 5(1) and L11. The field replicate

results were evaluated to assess analytical precision relative to sample collection procedures and

sample matrix.

For the triplicate samples collected at sampling station5(l), the majority of the PAH and SHC

results were detected at concentrations near or below the sample-specific RL and no PAH or

SHC results were reported at concentrations greater than 5 times the RL. There is increased

uncertainty in the quantitation of results that are reported at concentrations near the RL. Relative

standard deviations are typically calculated to assess field replicate precision; however, due to

the low reported concentrations and the increased variability of quantitation at concentrations

near the RL, the RSD values are not an accurate measure of analytical precision. Instead, the

absolute standard deviation of the triplicate measurements was used to assess comparability of

the field replicate results. The absolute standard deviations for the PAH analyses ranged from 0

to 1.45 ~glKg and the absolute standard deviations for the SHC analyses ranged from 0 to 0.039

mg/Kg for the n-alkanes and was 0.006 mg/Kg for the total PHC. These absolute standard

deviations are less than 2 times the reported RLs and are within the accepted margin of error of

the analytical methods. Thus, acceptable precision was achieved for the PAH and SHC analyses

of the field replicate samples collected at sampling station 5(1).

For the triplicate samples collected at sampling station L11, the majority of the SHC results were

detected at concentrations near or below the sample-specific RL and no SHC results were

reported at concentrations greater than 5 times the RL. Due to the low reported concentrations,

the absolute standard deviation of the triplicate measurements was used to assess comparability

of the field replicate results. The absolute standard deviations for the SHC analyses ranged from

oto 0.07 mglKg for the n-alkanes and was 2.02 mg/Kg for the total PHC. These absolute

standard deviations are less than 2 times the reported RLs and are within the accepted margin of

error or'the analytical method. Thus, acceptable precision was achieved for the SHC analyses of

the field; replicate samples collected at sampling station L11.

For the triplicate PAH analyses at sampling station Lll, the RSD was used to assess field

replicate precision when 2 of the 3 measurements were at or above 5 timesthe RL. If 2 or more

of the measmements were below 5 times the RL, the absolute standard deviation was used to

assess p"recision. The RSD values ranged from 30.3 percent to 45.6 percent and are within the

accepted field replicate precision criteria of 50 percent RSD for sediments. The absolute

standard deviations for the PAH analyses (with 2 or more concentrations below 5 times the RL)

u:\mms animidalphase I report\final report files\finaJ section 3lexl.doc 3~13
second clam species (Cyrtodaria) was analyzed as a lab duplicate with precision better than 10

percent (as a coefficient of variation [CV]) for each element.

3.4 Quality Control Results

This section provides an evaluation of the quality and usability of the environmental data based

on the results for the field and laboratory QC samples collected and analyzed during this

program. Tables 3-17 through 3-19 summarize the organic field and laboratory QC results.

Tables 3-20 through 3-23 summarize the inorganic field and laboratory QC results.

In general, no serious data quality issues were noted that would adversely affect the quality or

use of the organic or inorganic data. All reported data are usable for project objectives.

3.4.1 Field Quality Control

Field QC samples were collected to assess overall precision, accuracy, and representativeness of

the sampling and analytical efforts. The results for the fieldQC sample analyses are presented in

Appendices A through E, along with the associated environmental samples. Discussion and

interpretation of the results are provided in the following sections.

Equipment and field blanks were collected to assess potential sample contamination introduced

from sample collection and handling procedures. Replicate field samples were collected to assess

sample representativeness and precision relative to sample collection procedures and sample

matrix.

Field QC also included the verification of field instrument calibrations prior to use as described

in Section 2.3. All field instruments passed their calibration and QC checks.

3.4.1.1 Equipment Blanks

One equipment blank was collected and submitted for analysis during the sediment sampling

event. This sample was collected from a rinse of the grab sampling equipment at station N15

after decontamination of the equipment. PAH, SHC, and metals analyses were performed on this

equipment blank. The equipment blank results were evaluated to assess the potential for crosscontamination of samples due to inadequate sampling equipment decontamination.

Two PAH compounds, naphthalenes and biphenyl, were detected at very low concentrations in

the equipment blank. Both of these compounds were detected at concentrations below the

reporting limit (RL) and less than 5 times the MDL; the total PAH concentration in this blank

was 0.16/-lgIL. Trace concentrations of several straight-chain alkanes (i.e., n-C26, n-C27, n-C28,

and n-C36) were detected in the equipment blank. These compounds were detected at

concentrations less than 1/10 the RL and less than 5 times the MDL; the total SHC concentration

in this blank was 99 /-lgIL, less than 14 the RL. Concentrations of all metal analytes in the

equipment blank were less than 5 times the MDL.

These results indicate that the decontamination procedures used on the sediment sampling

equipment were adequate and would have minimized the potential for sample crosscontamination.

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ice cores are consistent with the composition of suspended particles collected from the open

water dJlring August 1999. The green hexagons (Figure 3-21) are mainly for samples collected

from the lower layers of the ice cores, where suspended sediment was derived from the under-ice

enviro~ment. Sediment from deeper il! the ice cores has a Fe/AI ratio that is consistent with the

under-ice suspended particles (gray circles in Figure 3-21). These results strengthen the

argument that the under-ice particles are more Fe-rich. Particles coated with iron hydrous oxides

can adsorb very large quantities of various metals, such as Pb and Cd, among others. Such

under-i~e geochemical processes provide an interesting scenario for overall cycling of metals in

the coastal Beaufort Sea that will be discussed briefly in Section 4 and studied in more detail

during phase II using scanning electron microscopy, energy-dispersive x-ray analysis, and more

sample$ of water and suspended particles.

3.3 Tissues , '

3.3.1 qrganics

SHC arid PAH measurements were made in pooled samples of amphipods (Anonyx spp.), and

clams (Astarte and Cyrtodaria) at stations where sufficient organisms could be collected.

Sterane: and triterpane measurements were also determined for four of the biota tissue samples.

The co~centrations of Total PAH, Total PHC, and Total SIT are presented in Table 3-14 (wetweight basis). In general, the concentrations of all organic target compounds in the tissue of all

species:were quite low. Total PAR concentrations range from 13 to 80 JAg/Kg, Total PHC values

were m~asured between 1 and 18 mglKg, and the Total SIT cOl1,centrations in the four samples

analyzed ranged from 5.5 to 18 JAg/Kg.

3.3.2 Meta,ls

Concentrations of Ag, AI, As, Ba, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Se, Sn, Tl, V and Zn

were determined for samples of amphipods (Anonyx) and clams (Astarte and Cyrtodaria) at

stations, where they could be found. Concentrations of selected metals are presented on a dryweight pasis for pooled samples in Tables 3-15 and 3-16. Data for water content are included

with the complete dataset in Appendix C so that metal concentrations can also be calculated on a

wet-we~ghtbasis.

Metal concentrations in the three pooled samples of amphipods (Anonyx sp. small) from the

Northst~ and Liberty areas were very similar (Tables 3-15 and 3-16 and Appendix C) with

values for the RSD values that were <10 percent for Ag, Cu, Mn, Tl, V, and Zn and <25 percent

for As, Ba, Be, Cd, Co, Fe, Hg, Ni, Pb and Sb. In contrast, the larger amphipods (Anonyx sp.

large) from offshore station 5Bhad 2 to 3 times lower levels of Ag, Ba, Co, Cu, Fe, Mn, Pb, and

V, yet to 3 times higher levels of As, Cd, Cr, Hg, and Zn (Tables 3-15 and 3-16). Station 5B is

in deeper water (-15 m) on the open shelf relative to the other stations at water depths <8 m.

With only a single sample of the larger Anonyx,'attempts at explaining observed differences in

metal levels would be premature. ' ,

Metal cpncentrations in the four pooled samples of clams (Astarte) from the Northstar and

LibertYiarens also were relatively similar among samples (Tables 3-15 and 3-16, and Appendix

C), with values for the coefficient of variation ([standard deviation/mean] x 100%) that were <15

percent'for As, Ba, Hg, P,b, Tl, V, and Zn and <25 percent for Ag, Cd, Fe, Mn, and Sb. The

u:\mms animidalphase I reportlfinal report lileslfinal section 3 text.doc 3-11
surlicial sediment) at about ~28 to -31 per mil (Table 3-12). The river suspended sediment had

OCl3 values closer to the values for suspended sediment from the coastal Beaufort Sea, whereas

the river sediment had oCl3 values closer to those for surlicial 'sediment from the coastal

Beaufort Sea (Table 3-12).

The carbon isotope data can be used to help identify the sources of organic carbon to surficial

and suspended sediments in the area. The potential sources inClude terrigenous and marine

materials (Table 3-13). The terrigenous component can be characterized isotopically using peat

and grass (oCl3 = - 28.5 ± 1.3 per mil) and river suspended sediment (oCl3 =-30.3 ± 0.5 per

mil) and the marine component can be defined using amphipods (OCI3 = - 19.1 ± 0.6 per mil)

and plankton (oCl3 =-22 ± 2 per mil). The eSC l3 data for peat, 'grass and plankton are taken from

earlier work by Schell (1983) and therefore may not be exactly comparable with the new values

reported here. Collection of peat and plankton samples is planned for the ANIMIDA study to

ensure an internally consistent data set. The suspended sediment collected from the study area

during August 1999, with a oCl3 =-29.2 ± 4.5 per mil, seems to have a predominantly

terrigenous source, with OCl3 values that are more in line with river suspended sediment, peat,

and grass. In contrast, surlicial sediment from the study area has a carbon isotope signature that

is much closer to values found for marine amphipods and plankton than terrigenous peat and

grass (Table 3-13). This information will be used to discuss the overall cycling of sediment, ,

metals, and carbon later in the discussion section.

3.2.4 Ice Cores

Ice cores were collected at all nine stations during the April 2000 sampling expedition. As

specified in the sampling plan, each core was subdivided into 2 to 3 sections. Each core was

thawed upon return to the field laboratory, the volume measured, and the particles in the core

obtained by filtration. Concentrations of particles in the ice cores were highly variable, ranging

from 1.2 to 248 mgIL. In general, concentrations of particles were lowest in the deeper portions

of each core. At depths>100 cm in the cores, the mean concentration of particles was 4.2 mgIL,

with only one value >3 mgIL. In contrast, the mean value for, particles in the upper 100 cm of

the cores was 54 mgIL. At station LA2, for example, the values for sediment in the ice cores

were as follows: 205 mgIL (0 to 55 cm), 2.6 mgIL (55 to 95 cm) and 1.8 mgIL (95 to 155 cm).

Even at a more-offshore station (NA2), the same trend was obs,erved with 11 mgIL (0 to 35 cm),

3.6 mgIL (35 to 70 cm) and 1.8 mgIL (70 to 150 cm).

The distribution of sediment in the ice cores is consistent with the pattern of formation of this sea

ice. The top layer (as sampled) forms first and freezes the suspended sediment in the ambient

water into the ice matrix. Storms during the fall seasons can keep the TSS at levels of>10 to

100 mgIL. Some time after the top layer of ice forms, the energy of the underlying water is

dramatically decreased and suspended particles slowly settle out such that the later ice that forms

from the water below contains considerably lower levels of sediment.

Data for Fe and Al in sediment from the ice cores provide some additional insight into

differences between the composition of particles during the open-water and under-ice seasons

(Figure 3-21). The blue hexagons in Figure 3-21 are for samples from the top layers of the ice

cores, where sediment loading w~s higher and where ice had frozen with ambient particles

suspended during late summer and fall. The Fe/AI ratios fdfihese sediments recovered from the

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the suspended sediment under the ice averaged 4.07 ± 0.76 percent and 4.45 ± 1.09 percent,

respecti~ely. The mean Fe content of the particles collected under ice was almost the same as

the mean Fe level of 3.92 percent found during the open-water period. However, the Al content

of the under.:.ice particles was about 40 percent lower than the mean value of 7.48 percent Al

during the open-water period. The decrease in the Al content of the particles collected under ice

is partially explained by dilution of aluminosilicate material with organic matter because the

concentration , . of particulate organic matter (-3 times the organic carbon level) increased from -7

percent to -30 percent. At the same time, the Fe content of the particles remained the same.

Assuming that the Fe levels were not impacted by contamination during sampling, the data

suggest ~hat a separate, more Fe-rich phase was associated with the under-ice particles. When

the FelAl ratios for particles collected under ice are compared with data from the open-water

sampleS;(Figure 3-20), the under-iceparticles contain Fe at levels that are 1.5 to 2.5 percent (of

TSS mass) higher than the open-water samples. Adsorption of iron hydrous oxides on these finegrained particles may account for the observed shift in the FelAl ratio (Figure 3-20).

Furthennore, organic-rich (12.5 percent organic carbon) suspended sediment from the Kuparuk

River, collected during August 1999, was enriched with Fe, as shown with the two inverted,

orange triangles in Figure 3-20.

Concentrations of Ba in the suspended sediment collected under the ice also show enrichment

relative ~o AI, as shown for Fe (Figure 3-20). The organic-rich samples from the Kuparuk River

also sho~ this trend. One possible explanation for this trend is that a fine-grained, almost

colloidal Fe fraction is present in the water column at all times, and can only be easily

discriminated at very low levels of TSS. Concentrations of the other trace metals are more

variable; however, the same general trend of higher levels of Cd, Cu and Pb are observed relative

to Al in the under-ice samples. In some cases where TSS levels were low «0.2 mgIL), some

concern for sample contamination exists. For example, dissolved Pb levels were determined for

4 samples, to help assess the possibility for sample contamination due to a gas-powered auger

and the difficulties of collecting and transferring samples out on the ice. In two cases, dissolved

Pb level~ we;re 0.009 J.t gIL and seem reasonable; the suspended sediment samples also contained

plausible levels of Pb at 36and 56 J.ti/g. In the other two instances, the dissolved Pb levels were

0.049 arid 0.084 J.tgIL and the particles contained Pb at 184 and 297 J.tg/g. Considering that

previously, no data were available for TSS under the ice, a solid increase in knowledge has

occurred. However, these data indicate that as Phase II evolves, extreme caution needs to be

exercised in the field and the field laboratory to minimize contamination. Furthermore,

concentratiqns of dissolved metal levels should be made in tandem with particle metal

determinations to help to better assess data quality.

3.2.3 Stabi,e Carbon Isotopes (OC13)

The l3e/12C ratio was determined for samples of surficial sediment, suspended sediment, and

source material from throughout the.study area. The results are expressed as OCI3 , where

~CJ3, ={[ (

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C)sample l (l3C/

12C)PDB standard] - 1} x 1000 .

and the standard is PDB. Values for oCl3 in surficial sediment average about -23 per mil (Table

3-12) for all three areas (BSMP, Northstar, and Liberty). Relative to the surficial sediment, the

oCl3 in ~amples of suspended sediment were more negative (richer in 12C relative to l3C than the

u:\mms animidalphase I reportlfinaJ report fileslfinaJ section 3 text.doc 3-9
average 580 ± 420 f.lg/L, ranging from 130 f.lg/L in the calm waters of station N13 on August 18

to 1,300 f.lg/L in a near-bottom sampl(f from NIl after the sto~.

3.2.1.4 Particulate Organic Carbon - April 2000

Concentrations of POC averaged 10 ± 3 percent of the TSS throughout the study area with a

range of about 8 to 14 percent. Average organic carbon values for these suspended sediments

from under the ice are about 4 times greater than the mean level for the suspended sediment

during August 1999 and about 16 times greater than values of 0.6 percent in surficial sediments

from the area. When the POC values are expressed in f.lg/L, they average about 80 ± 50 f.lg/L,

ranging from 24 f.lg/L at station NA6 to 164 f.lg/L at station NT!. These levels are about 5 to 50

times lower than determined during August 1999. Thus, the particles under the ice are somewhat

more organic-rich, but far less abundant.

3.2.2 Metals

3.2.2.1 August 1999

Concentrations of metals in suspended sediment samples collected during August 1999 were

very uniform throughout the area, with the values for the RSD [(standard

deviationlmean)*100%] for the complete data set less than or equal to 10 percent for AI, Ba, Cr,

Fe, and Zn (Table 3-11). Somewhat higher values for the RSD for Cd (45 percent), Cu (19

percent), and Pb (24 percent) result from one or more anomalous values, as discussed below.

The spatial uniformity in metal concentrations is further demonstrated in Table 3-11 with

separate summary data for the BSMP, Northstar, and Liberty stations. .

When compared with values for surficial sediment, metal concentrations in suspended particles

are 2.0 ± 0.2 times higher, with the exception of Cd with levels that are 3 times higher in

suspended sediment (Table 3-11) than surficial sediment (Table 3-1). Despite these higher

absolute values for metals in suspended sediments, the ratios of the various metals to Al are

consistent with the previously discussed results for surficial sediments (Figure 3-19). All of the

data for Fe, Ba, Cr, and Zn plot within the 99 percent prediction intervals established for these

metals versus Al from the sediment results (Table 3-11). However, these data are all skewed

toward high Al and metal levels because fine-grained clays that are naturally rich in Al and trace

metals dominate the suspended sediment.

Two suspended sediment data points for Cu (stations N13 and N14) plot above the upperprediction interval in the Al versus Cu plot (Figure 3-19c). Surficial sediment from these

stations was not enriched with Cu; however, sediment from nearby station 5D did have high Cu

levels. The same sample of suspended sediment from station N14 that was enriched with Cu

also contained high levels of Pb, at 43 f.Lglg.

The most distinct behavior for metals in suspended sediment was found for Cd, with

concentrations that ranged from 0.3 to 1.4 f.Lglg in suspended sediment relative to 0.05 to 0.8 in

surficial sediment. Cadmium is often taken up at high levels naturally in plankton. This process

and other scenarios are discussed later in Section 4.

3.2.2.2 April 2000 ,

Concentrations of metals were determined in some suspended sediment samples collected during

April 2000, even though the levels of TSS were extremely I~W.: 'The Fe and Al concentrations of

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3-10), where the overall average value for TSS was 0.25 ± 0.06 mg/L. The vertical profiles for

transmissivity show >80 percent light transmittance, consistent with low and relatively uniform

turbidity throughout the water column (Figure 3-15).

Temper~tures were very uniform and near freezing at -1.8°C at each station, except in the

slightly 'more-saline water at station LA2 (Figures 3-16 and 3-17). Likewise, salinity values

were relatively uniform from station to station, excluding the more-saline water at station LA3

and soniewhat lower salinity at station 5(5). A minor increase in salinity was observed at total

depths (ice+water) >11 meters (m) at stations NA5 and NA6. Current movement was at 1 to 4

cmlsec, and generally from the northwest or southeast. Under-ice currents tend to be tidally

influended and follow the contours of the adjacent islands with diurnal shifts in direction. No

simple t,elationship was observed between turbidity and current speed at the low levels of both

parameters.

Backfilling of the pipeline trench from Northstar to the mainland was ongoing during the April

2000 sampling trip. Although the winter sampling plan was designed to determine background

levels of turbidity and TSS under ice, water sampling was carried out at 5 locations in the

Nqrthstar area to investigate the influence of the backfilling process on turbidity. Station NTI

was about 200 meters east and downstream of the backfilling operation. The transmissivity data

show a marked decrease in light transmission at total depths >8 m (Figure 3-18). Turbidity in

the sample c;ollected at 9 m (ice + water) was 1.35 NTU, about 3 to 4 times greater than found at

more distant areas. Concentrations of TSS were 2.0 and 1.5 mg/L at a total depth of 9 m at

station NTl, about 5 to 8 times greater than apparent background levels. Due to a minor

instrument malfunction, the transmissometer data shown were collected on the day following

water colurrm sampling. At station NT2, about 300+ m northwest of the backfilling operation,

transmissivity was lower than background levels, but rather uniform between 3 and 10 m.

Values for TSS were elevated at 0.5 mg/L at a total depth of 3 m, but somewhat higher than

background: levels of 0.25 mg/L, at 6 m (0.38 mg/L), and 9 m (0.35 mg/L). Current velocities at

stations/NTI and NT2 averaged about 2 cmlsec.

At incre,ased distances from Northstar Island (NA3, -500m; NA5, -1 km; and NA6, -2 km),

values for ToSS averaged 0.32 ± 0.15 mg/L and were comparable with background levels. The

transmi~sivityprofiles show uniform and high transmissivity throughout most of the water

column;with a small, apparent near-bottom nepheloid layer that is possibly an artifact of

samplin'g. However, bottom currents were as high as 4.6 cm/sec. In addition, reduced

transmi~sivity was also observed at a total depth of about 4 m at station NA3.

3.2.1.3 'Particulate Organic Carbon - August 1999

Concentrations of particulate organic carbon (POC) averaged 2.4 ± 0.9 percent of the TSS

throughout the study area, with a range of 1.2 to 4.8 percent. Although all POC values >4

percent :were obtained for surface water samples, the overall average of surface samples versus

subsurface samples was only 2.6 percent relative to 2.2 percent. Average organic carbon values

for thes~ su~pended sediments are about 4 times greater than the mean level of 0.6 percent in

surficial sediments from the area. Higher organic carbon levels in suspended sediment are most

likely ttie combined result of the presence of plankton in the water column and re~uspension of

finer-grained, more organic-rich sediments. When the POC values are expressed in Ilg/L, they

u:lmms animidalphase I report\final report files\final section 3 text.doc 3-7
>25 knot (kt) winds from the northeast. Immediately after the storm subsided, in situ turbidity

levels on August 25 were as high as 80 NTU, decreasing to about 40 NTU two days later on

August 27 (Figure 3-9). Thus, the maximum and minimum turbidity and TSS levels were

recorded at the same station, one week apart. Under relatively calm winds «5 kts) during late

summer, turbidity levels are likely to be <3 NTU (TSS <5 mg/L) and under high winds (>25 kts),

turbidity may be in excess of 80 NTU.

One spatial view of turbidity in the area of the Northstar Prospect is obtained using the data from

August 25, 1999 (Figure 3-10). At stations N05 and N08, where water depths are about 11 m,

the vertical profiles for in situ turbidity are very similar with a gradual increase from about 10

NTU at the surface to about 20 NTU near the bottom (Figure 3-10). In somewhat shallower

water, about 2 km closer to shore, the turbidity in the surface water is closer to 20 NTU,

increasing to 50 NTU near bottom (7.5 m). Finally, at station N13 (water depth -4 m), the

turbidity was markedly higher.

Shifts in turbidity are clearly related to wind and water current velocities. Recent data from Dr.

Tom Weingartner's (University of Alaska at Fairbanks) year-long deployment of a current meter

and transmissometer arrays will help to develop a clearer seasonal picture relating turbidity with

water movement. Our single-point-in-time measurements at station N13 show a current velocity

of 20 ern/sec and less on August 18, 1999, just prior to the storm (Figure 3-11). Following the

storm, after the wind speed and wave height had already decreased greatly, current velocities still

approached 40 ern/sec (Figure 3-12). In each case, water flow was parallel to the adjacent barrier

islands. The infusion of colder, offshore water during the storm also was evident in the August

25 profiles (Figure 3-12). During the upcoming year, we will collaborate with Dr. Tom

Weingartner to fill in the details on current velocities and link his transmissometer data with our

nephelometer and TSS results.

Hydrography data for station N05 (Figure 3-13) show that current velocities of 10 to 20 em/sec

are coincident with in situ turbidity values of 12 to 21 NTU. Similar water conditions were

observed at stations N08 and NIl. Data for TSS also are available for these stations, with

concentrations of about 20 to 30 mg/L at most depths, excluding a TSS level of 56 mg/L in a

near-bottom nepheloid layer at station NIl.

Vertical profiles for in situ turbidity in the area of the Liberty Prospect (L05, L08 and L11) were

similar, with levels of 5 to 10 NTU throughout most of the water column and increasing to about

. 20 NTU on approach to the water-sediment interface (Figure 3-14). Current velocities at these

three stations ranged from 5 to 15 ern/sec. Turbidity levels at 4B were significantly greater than

at the other stations, most likely in response to greater current velocities of 30 to 40 ern/sec.

Station 3A, in the lee of Pole Island, had turbidity levels similar to those near Liberty Prospect

and lower than the open waters at station 4B.

3.2.1.2 Turbidity and Total Suspended Solids - April 2000

Turbidity (laboratory) and TSS during the ice-covered period of April 2000 ranged from 0.15 to

1.35 NTU and 0.14 to 2.0 mg/L, respectively. These levels are 10 to >100 times lower than

values obtained during the open-water period of August 1999 and provide a good overview of

turbidity and TSS under the 1.6- to 2.4-m thick layers of sea ice (Table 3-10). The lowest levels

of turbidity and TSS were observed at the more-offshore stations of NA2, 5(5), and LA2 (Table ~;

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also correlate relatively well with grain-size (Figure 3-3) and AI, thereby supporting the utility of

Al as a normalizing element.

Iron concentrations correlated extremely well (r =0.97) with Al levels (Figure 3-5). Thus, either

element'can be used to normalize the other metal concentrations. One example of a metal/AI

plot is given for V (Figure 3-5b) to show the effectiveness of the normalization process. Even

though individual metal concentrations are extremely variable from station to station, these

differences can be explained by variations in grain-size, TOC, and/or mineralogy when

normalized to AI. Concentrations of V and other metals follow Al in that higher levels are found

in aluminosilicate clays and lower levels are found in quartz and carbonate sands. Thus, plots

such as shown in Figure 3-5 show the natural trend (i.e., VIAl ratio) for area sediments. Positive

deviations from a prediction interval constructed around the regression line can often be related

to anthropogenic inputs of that metal. This concept is developed in detail in Section 4.

Concentrations of methyl Hg were determined for a subset of 30 sediment samples. Mean

concentrations of methyl Hg were 0.37 ± 0.36 ng/g with a range of <0.01-1.41 ng/g (Appendix

C). The percent of total Hg that was methyl Hg averaged 0.7 ± 0.4 percent with most sediments

having <1 percent of the total Hg present as methyl Hg (Figure 3-6).

3.2 Suspended.Sediments

3.2.1 Physical Measurements

3.2.1.1 ,Turbidity and Total Suspended Solids - August 1999

Concentrations of suspended particles in the water column were determined during open-water

(August 1999) and under-ice (April 2000) conditions by the following three methods: vertical

profiles of in situ turbidity (nephelometric), laboratory analysis of turbidity using discrete

samples, and filtration of water for TSS (Appendices D and E). Interrelationships among the

three techniques were good. Values for laboratory turbidity (in nephelometric turbidity units, or

NTU) correlated well with values for TSS (Figure 3-7); both measurements were made using the

same discrete sample. For ease of comparison, values for TSS in mg/L are approximately equal

to twice the turbidity in NTU (Figure 3-7). Direct comparison of laboratory turbidity with in situ

turbidity is more complicated because of the greater sample depth (z) integrated by the water

bottle (about 1 m) versus the vertical path width of the in situ turbidimeter «1 cm). However,

the in situ and laboratory turbidity values compare well at levels <50 NTU (Figure 3-8). Only

two data points at high turbidity levels show an inconsistency with the linear trend. Additional

data are needed at these higher levels to expand the trend presently identified in Figure 3-8.

Overall; each of the three independent measures of water clarity can be calculated from one of

the other measurements.

Turbidity (laboratory) and TSS during the open-water period of August 1999 ranged f~om 1.8 to

75 NTU and 2.9 to 119 mg/L, respectively, with the large variations due mostly to changes in

wind conditions. The overall variation in turbidity is best explained using in situ data from

station N13 for three different dates (Figure 3-9). During the first sampling at station N13 on

August 18, 1999, the wind was almost calm «5 knots) and there was a sizeable amount of

nearshore floating ice. Turbidity (in situ) levels during these calm conditions were about 2 to 3

NTU at stations N13 (Figure 3.,.9) and N14, the only two locations to be sampled before 6 days of

~,\mms animidalphase I repor1lJinal report files\final section 3 texl.doc 3·5
Concentrations of metals show a similar degree of patchiness throughout the study area to that

shown above for TOC and grain-size (Tables 3-1, 3-7, 3-8, and 3-9). One way to demonstrate

this variability is to compare calculated values of [maximum/minimum] for each metal for all

sediment samples from throughout the study area. For Ba, the, value for [maximum/minimum] is

lowest at -5 (753/155), whereas for Cd, the value for [maximum/minimum] is greatest at -16

(0.79/0.05). Overall, for all 18 metals studied during 1999 in sediment from the ANIMIDA

study area, the average value for [maximum/minimum] is -8. ,This average of an 8-fold range

for metals values in sediments shows the large variation in absolute concentrations for metals in

sediment. Fortunately, metal concentrations vary in response to variations in grain-size and

TOC; thus a predictable normalization process can be developed to simplify comparisons among

samples. This process will be discussed in Section 4.1.

Within the data set, the highest concentrations of Cd, Hg, and Pb were found at station 5D near

West Dock (Table 3-7). The highest concentrations of Ag, As, Co, Cu, and Ni in sediments also

were found at station 5D (see Appendix C). Nearby at station 5(10), the highest concentrations

of Ba and an elevated level of Pb were determined (Table 3-7). Station 5A was also

characterized by higher concentrations of Hg and Pb (Table 3-7). The area around West Dock

was certainly active during 1999 and this area may warrant more detailed monitoring during

future efforts.

In the area of the Northstar Prospect, the lowest metal concentrations were found in the sandy,

nearshore sediment at stations N12, N13, N14, and N15 (Table 3-8). In accordance with the

grain-size distribution, the highest levels of metals occurred in, a cluster of stations (N03, N04,

N05, and N06) with silty sediment (Table 3-8). In the immediate area of Liberty Prospect, no

clear trends in grain-size or metal distribution were observed. The highest metal levels were

found at stations L02, L03, and L06 and the lowest metal valu~s were observed at nearby station

L04 (Table 3-9).

Some variability is also observed in metal concentrations for sediment samples collected from

the same location during separate deployments of the grab sampler. Triplicate grab samples

were collected from stations 5(1) and Lll during 1999. At station 5(1) in 1999, concentrations

of Al were very uniform with a coefficient of variation (CV =[standard deviation/mean] x 100

percent) of only 2.4 percent (Table 3-1a). In contrast with station 5(1), concentrations of Al at

station Lll were more variable (Table 3-1a). The observed variability among samples from the

same station is related to variations in sediment grain-size. As described below, and in more

detail in Section 4, these variations can be normalized. Direct comparisons of absolute

concentrations of metals in sediments should be avoided in preference for normalized values

(metals ratioed to AI).

The patchwork of metal concentrations throughout the study area can be unified by normalizing

metal values to either Al or Fe and thereby removing variations in metal concentrations that

result from differences in grain-size, TOC, and/or mineralogy. :For example, Figure 3-4 shows a

strong, positive relationship between Al and grain-size, expressed either as percent silt + clay or

just percent clay. The finer-grained material is richer in AI-bearing clays, whereas the coarsergrained sediment contains AI-poor quartz sands and carbonate shellfragments. The TOC data

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histograms for the Colville River (Figure 4-10), Northstar Station 6 (Figure 4-11), Liberty

Station 6 (Figure 4-12), and BSMP Station 3A (Figure 4-13).

3.1.2.2 Polynuclear Aromatic Hydrocarbons

. In gener~, low to moderate levels of PAH were encountered across the study area. The mean

Total PAR concentrations at both the Liberty and Northstar regions were comparable and are

consider~d in the low range for marine sediments (330 /-lg/Kg and 380 /-lg/Kg, respectively;

Boehm et a1., 1998). The Total PAR concentrations measured at the BSMP stations were

generally within the same range, with means of 290 /-lg/Kg and 340 /-lg/Kg for the Foggy Island

and Endicott Regions, respectively. When compared to the other BSMP regions, the Kuparuk

River Bay region had an elevated mean Total PAR concentration (760 /-lg/Kg) due to the high

PAR cOlppound concentrations at station 5D. Station 5D had a total PAR concentration (2,700

/-lg/Kg) ryearly an order of magnitude higher than the means for the other regions. When the

results for S~ation 5D are excluded, the regional mean Total PAR concentration for the Kuparuk

River Bay region is 270 /-lg/Kg. (Station 5D also had high Total PHC and SHC results.) This

result suggests that there may be PAH contamination at this station, which is adjacent to an area

of high construction and development activity (i.e., West Dock). Overall, the levels of PAR

measured are well within the range of values reported from previous studies of the region and

other Alaskan coastal areas-(Table 3-6).

The total PAH concentrations in the Colville River sediment and peat samples are also nearly an

order of magnitude higher than those for the Northstar, Liberty, and BSMP regional means

(Tables 3-2 through 3-4). Similar to the SHCs, the enrichment in PARs is associated with the . .

higher organic material content in these samples as supported by the higher TOC values. The

exceptions to this trend are the Kupanik River sediment and peat samples and the Sagavanirktok

River sediment sample, which have lower total PAH concentrations with a corresponding high

organic 9arbon content.

3.1.2.3 ~teranes and l'riterpanes

Biomar~er analyses were only performed on a selected subset of samples, so no regional means

have been generated for comparisons; however, the SrI' concentrations in the surficial sediment

samples'are quite low. The total SIT concentrations range from 6.5 /-lg/Kg at station N14 to 490

. /-lg/Kg at sta~ion 5D. With the exception of station 5D, total SIT concentrations were less than

100 /-lg/Kg for all analyzed samples. The total SIT concentrations in the river and peat are

somewh~t higher, but are at levels expected to correspond to the other measured organic

paramet¢rs.

I

3.1.3 Metals

All surficial'sediments, (top 1 cm) were analyzed for total concentrations of Ag, AI, As, Ba, Be,

Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, $e, Sn, TI, V, and Zn (Table 3-1 and Appendix C). The

resulting data show that average concentrations for each metal in sediment from throughout the

study area ate similar to or less than values for average continental crust, except for Ag, Cd, and

Sb, with concentrations that are enriched by a factor of 1.5 to 2 (Table 3-1). These apparent

enrichments, appear to be natural for the area and are discussed in Section 4. ;

u:lrnms animidalphase I reportlJinal report fileslfinal section 3 text.doc 3-3
Prospect (Figure 3-2). Once again, sediment from the more-offshore locations (e.g., 4C, 4B, and

LOl) contained predominantly sand. These trends will help focus future sampling efforts for

both surficial and suspended sediment.

A good, positive relationship was found for TOC versus silt + clay as higher surface area

sediment can adsorb larger amounts of organic matter (Figure 3-3). This trend is consistent with

similar patchiness in the distribution of both grain-size and TOe. At silt + clay levels >SO

percent, a wider range in concentrations of TOC is observed, effectively from about 0.7 to 2

percent, plus the one higher value at 3.4 percent. Variability ip TOC levels and grain-size

distribution throughout the area is certainly consistent with similar variability in the presence and

abundance of benthic organisms such as amphipods and clams.

3.1.2 Organics

Organic parameter results for the surficial sediment samples are summarized in Tables 3-2

through 3-4. The summary results include total PAH (PAH - which includes the sum of all

parent and alkyl PAHs), total petroleum hydrocarbons (TPHC- the sum of the resolved and

unresolved saturated hydrocarbons n-C9 through n-C40), and total steranes and triterpanes (Total

srr- the sum of the sterane and triterpane target compounds). The data for each of these

summary parameters are presented on a dry-weight sediment basis and results for field replicates

are presented as the mean value with the standard deviation in parentheses. The results are

separated into three regional groupings: BSMP stations (Table 3-2), Northstar stations (Table 3-

3), and Liberty stations (Table 3-4). Within the BSMP station results, regional means for three

historical BSMP-defined regions (Foggy Island, Endicott Field, and Kuparuk River) are provided

for comparison to historical data. In addition, river and peat source sample summary data are

included. Descriptions of key diagnostic parameters, which are useful in describing the overall

organics dataset and will be used for comparisons to historical data and future ANIMIDA

program data, are provided in Table 3-5. The complete organics data, including concentrations

for individual PAH, SHC, and srr target compounds, are included in Appendix B.

3.1.2.1 Saturated Hydrocarbons

Concentrations of TPHC in surficial sediments from the offshore study ranged from 0.21 to 50

mglKg. The TPHC concentrations were generally at low levels for most stations, with two

, notable exceptions: station 5D at 50 mglKg, and station LOS at 17 mg!Kg. The TPHC levels

across the study area regions (Northstar, Liberty, and the three BSMP regions) are similar (mean

TPHC concentrations of 2.3 to 7.1 mg!Kg), with the exception of the Kuparuk River BSMP

region, which had a mean concentration of 15 mglKg (Tables 3-2 through 3-4). The mean TPHC

was elevated in the Kuparuk River region relative to the other regions due to the higher

concentration found at station 5D, which substantially raised the regional mean. The river

sediment and peat samples were found to have TPHC levels substantially higher than the

surficial sediments (Table 3-2). The high TPHC levels (ranging from 5.S to 36 mg!Kg for all the

river and peat samples) are likely due to the higher organic material content in these samples, as

supported by the higher TOC values for these samples. Nonetheless, the composition of SHCs in

the river sediment and peat samples was similar to the surficial sediments, indicating a common

TPHC source relationship between the river sediments and the nearshore surficial-sediments.

For example, similar patterns are noted in the GC/FID chromatograms and PAH distribution

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This section presents the results for the general chemistry, organic, and inorganic analyses for the

surficial sediment, suspended sediment, and ice core samples collected from the ANIMIDA

study area in August 1999 and April 2000.

3.1 Surficial Sediments (0-1 cm)

The results and general trends in the TOC, grain~size, organic, and inorganic data from the

surficial sediment samples collected during the summer 1999 ANIMIDA field survey are

presented in this subsection. Results from the organic analyses of the river source samples are

also discussed.

3.1.1 General Chemical and Physical Measurements

3.1.1.1 Total Organic Carbon and Grain Size

Surficial sediments from each station were analyzed for TOC and grain-size (percent gravel,

sand, silt, and clay). The TOC values for surficial sediment samples range from 0.01 percent in

the sandy sediment at station NOl to 3.42 percent in a mud-rich sample from station L06a (Table

3-1 and Appendix A). The mean value for TOC of 0.62 percent more closely represents the

overall data set as most TOC values are <1 percent and only one value is >2 percent (Table 3-1).

Considerable patchiness is found for TOC values across the study area, partly in response to

similar patchiness in the occurrence of fine-grained sediment, as described below. Overall, the

TOC concentrations are typical of values reported for Arctic shelf sediments. For example,

Carsola (1954) reported a rangeofTOC values from 0.2 to 1.2 percent for Beaufort Sea

sediments.

The grain-siZe results show similar variability to that described above for TOC. Gravel content

(>2 mm) ranges from 0 percent at 30 locations to 46.9 percent at nearshore station N13

(Appendix A). Likewise, the clay content «0.062 mm) varies from about lpercent at several

locations to 53.7 percent at station N06. Sediment resuspension, along with across- and alongshelf transport, are dynamic components of the inner shelf of the Beaufort Sea that certainly

contribute to observed variations in grain-size distribution in the top 1 cm of sediment.

Based on the 1999 grain-size data, a few general trends can be observed. In the western portion

of the study area, gravel was found at five locations, three of which (N12, N13, and N14) are just

seaward of Gwydyr Bay and close to the inner line of islands (Figure 3-1). Most of the shallowwater, nearshore stations west of Endicott are dominated by sand, with little or no silt or clay

(Figure 3-1). These locations are characterized by grounded ice during the winter and/or very

active flushing during spring runoff. In the immediate area of the Northstar Prospect, just

seaward of the stations with sand and gravel, the sediment is predominantly silt and clay (Figure

3-1). This area most likely represents at least a temporary depositional area for finer-grained

sediments introduced during river runoff. At more-offshore stations such as N01, 5B, and 5E,

the surficial sediment is again dominated by sand.

The trends in the area of the Liberty Prospect are more complex (Figure 3-2); however, several

of the same general features can be observed. Gravel was collected at nearshore stations 4A and

L12 and more sand was found nearer to shore than in the immediate area of the Liberty Prospect.

A patchof mostly silt and clay was found near and to the east of the proposed site for the Liberty

u:\mms animidalphase I reportlfinal report fileslfinal section 3 text.doc 3-1
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analyte not detected in

associated samples

%RSD 80 to 120%

RSD <25% for 65% of the

analytes

u:mms animidalphase I repMlfinaJ report fileslfinaJ section 2lables.doc

One per batch of 20 samples

Must end every analytical

sequence; for flame, repeat all

standards every 5 samples; for

graphite furnace and ICP/MS

recheck standard after every 8 to

10 sam les

One per batch of 20 samples

One per batch of 20 samples

One per batch of 20 samples

j

'" ."'"

Initial Calibration

r

j;,.

Continuing Calibration

t

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,

Standard Reference Materials

\

Method Blank ,

Matrix Spike and Spike Method

Blank

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La?oratory Duplicate

Table 2-10. Data Quality Objectives and Criteria for Metals Analyses

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Table 2~9. Data Quality Objectives for Sterane and Triterpane Analyses

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%0 < 25% for all analytes

%0 < 35% from laboratory mean

for target compounds (use

surrogate-corrected values)

except for compounds below the

re ortin limit

Recovery b~tween 45 and 125%

No analyte to exceed 5 times the

MOL unless sample amount .is >

10 times blank amount

After every 12 samples or 16

hours, whichever is more

frequent, and at end of

instrument sequence

u:mms animidalphase I reportllinaJ report filesllinaJ section 2 tables.doc

One per batch

One with each instrument .

sequence (North Slope Crude)

Every sample

Continuing Calibration

Oil Reference Standard (North

Slope Crude)

Procedural Blank

Surrogate Recovery
Recovery between 35 and 125%

for PAH, and 45 to 125% for

SHC

5-point curve, %RSD < 35% for

all target analytes; 90% must be

<25%

%D < 35% for all target analytes;

90% must be < 25%

%D < 35% from laboratory mean

for target compounds (use

surrogate-eorrected values)

except for compounds below the

reoortina limit

No analyte to exceed 5 times the

MDL unless sample amount is >

10 times blank amount

Recovery between 45 and 125%

(35% for dB-naphthalene)

Values must be <15% difference

of true value for all certified

analytes

Values must be within 30% of

the true value on average for all

analytes, not to exceed 35% of

true value for more than 30% of

the analytes

RPD < 30% for all analytes >10

times the MDL; Mean RPD

<30%

One per batch

One per 40 field samples

Every sample

One per batch

One with each instrument

sequence (North Slope Crude)

After every 12 samples or 16

hours, whichever is more

frequent, and at end of

instrument sequence

One per instrument sequence

(PAH only)

One per batch as appropriate

(PAH only)

u:mms animidalphase I report\linaJ report files\linaJ section 2 tables.doc

Co~tinuing Calibration

Laboratory Duplicate l

i

Surrogate Recovery ,

Procedural Blank ;

Initial Calibration Prior to every instrument

sequence for PAH analysis and

as needed for SHC analysis

Sediment SRM (1941 a)/Tissue

SRM (1974a)

Instrument SRM (1491)

Blank Spike

Oil Reference Standard

(North Slope Crude)

Table 2-8. Data Quality Objectives for Saturated Hydrocarbon and Polynuclear

Aro,matic Hydrocarbon Analyses

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Table 2-7. Sample Containers, Preservation, and Laboratory List

u:mms animidalphase I report\linaJ report files\linaJ section 2 tables,doc I

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Arthur D. Little

Florida Institute of Technology

Arthur D. Little

Florida Institute of Technology

Arthur D. Little

Florida Institute of Technology

Florida Institute of Technology

Florida Institute of Technology

Arthur D. Little (homogenate was

sent to FIT for metals)

Florida Institute of Technology

Florida Institute of Technology

Florida Institute of Technology

Acidified Florida Institute of Technology

Frozen -20°C

Frozen -20°C

Frozen -20°C

Plastic jar

Metals Plastic container None

\

SHC, PAH, 250 mLglass Frozen ·20°C

srr, metals

SHC, PAH, 250 mL glass Frozen ·20°C

srr

Metals Plastic jar Frozen ·20°C

Grain Size Plastic bag Frozen ·20°C

Metals Plastic jar Acidified

Metals Plastic container None

SHC,PAH 250 mL glass Frozen ·20°C )

Metals Plastic jar Frozen ·20°C

Metals

Grain Size Plastic bag

Metals, TOC, Plastic jar

Grain Size

Biota (Clams and

Amphipods)

Source Samples -

Sediment, Gravel, Peat

Equipment Blank

.' Sample'\Type':' ...., ',',:<Analysis .':' :',~',Pr~clea,ned " ,.,'.,,'. " 'C 'I' . "~' ',;\ "'.""",~". ",., :'., , ona~ller, " , •.,., "j.,""" ....,'< .... ",' "

Source Samples -

Sediment, Gravel, Peat

Source Samples -

Sediment, Gravel, Peat

Equipment Blank

Sediment

Sediment

Suspended Sediment

(aqueous phase)

Sediment SHC, PAH, 250 mL glass

srr

Suspended Sediment

(filtrate)

Source Sample -

Suspended Sediment

(filtrate)

Source Sample -

Suspended Sediment

(aqueous phase)
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Table 2-6:· Summary of Instrumental Methods and Method Detection Limits for

Metal Analysis of Sediment and Organisms

AI- aluminum FAAS 10 FAAS 2.3

As -arsenic ZGFAAS 0.2 ZGFAAS 0.03

Sa - barium ICP-MS 1 ICP-MS 0.Q1

Be -bervllium ICP-MS 0.1 ZGFAAS 0.002

Cd-'cadmium ICP-MS 0.02 GFAAS 0.001

Co -'cobalt ICP-MS 0.5 GFAAS 0.3

Cr - chromium FAAS 1 GFAAS 0.01

Cu -copper FAAS 2 FAAS 0.7

Fe-iron FAAS 10 FAAS 2.5

Ha -'mercury CVAAS 0.001 CVAAS 0.001

Mn .-: manaanese FAAS 3 FAAS 1.1

Ni - nickel ICP-MS 0.5 GFAAS 0.01

Pb - lead ICP-MS 0.2 ICP-MS 0.003

Sb - antimony ICP-MS 0.1 ICP-MS 0.001

TI - thallium ICP-MS 0.05 ICP-MS 0.001

v- vanadium FAAS 10 GFAAS 0.01

Zn - zinc FAAS 2 FAAS 0.4

Other Parameters .. '. .' '., ...... " ,', ....•. ',,; .' .. ' .'

Grain Size Sieve and Pipet

TOC,: Shimadzu Carbon 0.1

System

Notes:

CVAAS =Cold Vapor Atomic Absorption Spectrometry

FAAS = Flame Atomic Absorption Spectrometry

GFAAS = Graphite Fumace Atomic Absorption Spectrometry.

ICP/MS = Inductively Coupled Plasma/Mass Spectrometry'

MDL == Method Detection limit

ZGFAAS = Zeeman Graphite Fumace Atomic Absorption Spectrometry

u:mms animidalphase I reportlfinal report fileslfinal section 2 tables,doc
u;mrns animidalphase I reportlfinaJ report fileslfinaJ sec1ion 2 tables.doc

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A

2

D12C

D66

58

Chrysene-d"

Internal Standards

## Sa,14a,17a-cholestane(20R S17 A/1

## 17b(Hl,21 b(Hl-hopane T23 AJ1

18a(Hl-22,29,30-trisnorhopane TSl T11 A/1

Sa,14a,17a,24-ethylcholestane(20Sl S25 AJ1

Sa,14a,17a,24-methylcholestane(20R) S24 AJ1

Sa,14a,17a,24-ethvlcholestane(20Rl S28 AJ1

17a H ,21 b H)-30-norhopane T15 AJ1

22R-17a(H ,21b(H)-30-homohopane T22 AJ1

22S-17a(H ,21b(Hl-30-homohooane T21 AJ1

17a H ,21b Hl-hopane T19 AJ1

13b,17a-diacholestane 20R) S5 AJ1 5b H)-cholane

17a(Hl-22,29,30-trisnorhooane TMl T12 AJ1

18a H -oleanane T18 AJ1

C~ Tricyclictriterpane T9 A/1

C Tricvclictriteroane T10 A/1

C~ Diterpane T4 A/1 Surroaate Comoounds

13b,17a-diacholestane(20Sl S4 AJ1 n-Dotriacontane-d

## Compound used in calibration, but not reported

Internal Standard/Surrogate Reference indicates internal standard used for quantitation and surrogate compound used to

correct analytical results

Table 2-5: Sterane and Triterpane Target List
u:mms animidalphase I reportllinal report filesltinal section 2 tables.doc

B/3

B/3

B/4

B/3.

B/3

B/4

B/3

B/4

B/4

B/4

B/4

B/4

B/4

BAA B/3

C2C

C3C

COC

C1C

C4C

BKF

BBF

PER

DAH

BGP

BEP

BAP

IND

C -Chrysenes

C -Chrvsenes

Benzo eIpvrene

C ·Chrysenes

Pervlene

Benzo a Ipyrene

Chrvsene

Dibenzo[a,hlanthracene

C -Chrvsenes

Benzo k fluoranthene

Indeno 1,2,3-c,d]pvrene

Benzo[Q,h,ilperylene

Benzo b fluoranthene

Surroaate Comoounds

Naphthalene-d DaN AJ1

Acenaphthene-d D10ACE AJ2

Phenanthrene-d," D10PH AJ3

Benzo a)pvrene-d.. D12BAP B/4

Internal Standard

Fluorene-d D10F A

Chrysene-d" D12C B

AJ3

AJ3

AJ3

AJ3

AJ2

AJ3

AJ3

AJ3

AJ3

AJ2

AJ3

AJ3

AJ2

AJ2

AJ2

AJ3

AJ2

AJ3

AJ3

AJ3

AJ3

'AJ2

ACE

C1F

C3P/A

C2P/A

COP

C4P/A

C1P/A

C3F

C2D

BIP

COF

C1F/P

C3D

C2F

ACEY

COA

COD

C1D

FLANT

C3F/P

C2F/P

PYR

C -Fluorenes

C -Naphthalenes C4N AJ2

C,-Dibenzothiophenes

Pyrene

Phenanthrene

C1 ~Naphthalenes C1 N AJ2

Naphthalene CON' AJ1 Benzo[a]anthracene

C,-Naphthalenes C3N AJ2

C -Phenanthrenes/Anthracenes

Acenaphthene

C -Dibenzothiophenes

C -Fluoranthenesl 'yrenes

Anthracene

C -Phenanthrenes/Anthracenes

Fluorene

C -Dibenzothiophenes

C,-Phenanthrenes/Anthracenes

C -Fluorenes

Biphenvl

C,-Fluorenes

Acenaphthylene

C -Fluoranthenesl 'yrenes

C -Phenanthrenes/Anthracenes

C -Naphthalenes C2N AJ2

Fluoranthene

C -Fluoranthenesl 'Yrenes

Dibenzothiophene

Table 2-4. Polynuclear Aromatic Hydrocarbon and Alkyl Polynuclear Aromatic

Hy~rocarbon Target List

Internal Standard/Surrogate Reference indicates internal standard used for quantitation and surrogate compound used to

correct analytical results.

2-ring PAHs include: napthalenes, acenaphthylene, acenaphthene, biphenyl, and fluorenes

3-ring PAHs include: anthracenes, and phenanthrenes

4-ring PAHs include: fluoranthenes, pyrenes, benzo(a}anthracene, chrysenes, benzo(b)fluoranthene, and

benzo(k)f1uoranthene

5-ring PAHs include: benzo(e)pyrene, benzo(a)pyrene, perylene, indeno(1,2,3-cd)pyrene, and dibenz(a,h)anthracene

Benzo(g,h,i)perylene is a 6-ring PAH

o

o

o

o

o

o

o

o

o

o

o

o

o

o

o

o

o

o

o
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8/1

A/1

D62T

C36 A/1

C34 A/1

C35 A/1

D50T

C30 A/1

C39 A/1

C26 A/1

C31 A/1

C28 A/1

C40 A/1

C29 A/1

C37 A/1

C38 A/1

5AA

C33 A/1

C32 A/1

C27 A/1

Internal Standard

Surroaate Comoounds

Tetracosane-d<"

Triacontane-d~

5a-Androstane

I .

u:mms animidalphase I report\tinaJ report fileslfinaJ section 2 tables,doc

'.

\::I

Pristane PRIS A/1 n-Nonatriacontane

, ,

Phytane PHYT A/1

n-Tricosane C23 A/1

n-Eicosane C20 A/1

n-Docosane C22 A/1

n-Nonadecane C19 A/1

n-Pentacosane C25 A/1

n-Tetracosane C24 A/1

n-Octadecane C18 A/1 n-Tetracontane

n-Heptadecane C17 A/1 n-Octatriacontane

Isoprenoid RRT 1380 1380 A/1 n-Dotriacontane

n-Undecane C11 A/1 n-Nonacosane

n-Hexadecane C16 A/1 n-Heptatriacontane

n-Decane C10 A/1 n-Octacosane

n-Tridecane C13 A/1 n-Hentriacontane

n-Heneicosane C21 A/1

Isoprenoid RRT 1650 1650 A/1 n-Hexatriacontane

n-Octane (optional) C8 A/1 n-Hexacosane

n-Dodecane C12 A/1 n-Triacontane

n-Pentadecane C15 A/1 n-Pentatriacontane

Isoprenoid RRT 1470 1470 A/1 n-Tetratriacontane

n-Nonane C9 A/1 n-Heptacosane

n-Tetradecane C14 A/1 n-Tritriacontane

Also used in reporting:

TOTRES: Total of resolved compounds in sample extract

TPHC: Total of resolved and unresolved compounds in sample extract

Intemal Standard/Surrogate Reference indicates intemal standard used for quantitation and surrogate compound used to

correct analytical results

Table 2-3. Saturated Hydrocarbons Target List
- --._. --

- -- - -- ------

Table 2-2. Winter 2000 MMS ANIMIDA Stations Sampled.

LA2 6.0

LA3 700 16.778 1470 33.529 6.1

NS-Trench1 Northstar 700 28.806 1480 41.607 9.7

NS-Trench2 Northstar 700 29.144 1480 42.197 10.4

NA2 Northstar 700 30.817 1480 36.351 10.8

NA3 Northstar 700 29.569 1480 41.460 11.5

NA5 Northstar 700 29.889 1480 40.734 11.8

NA6 Northstar 700 30.372 1480 39.911 12.4

Note: All latitudes and longitudes in NAD83 datum.

Final Table 2-2XLS

1.6

1.6 4/28/00

1.6 4/25/00

1.6 4/25/00

1.7 4/26/00

2.4 4/26/00

1.8 4/29/00

1.8 4/29/00

I122/rn
Page

1 of1

Table 2-1. 1999 MMS Animida Stations Sampled

cou

3A ~";:.BSMP Sed.-GrabslTiss·ue-·Astarte 70°17.000 147°05.513 20 8/26/99 1435-1720

1

1

1 NA

3B BSMP Sed. Grabs; 70°17.905 14~02.574 15 8/26/99 1405-1420

1 NA NA NA

4A BSMP Sed. Grabs' 70°18.472 147°40.297 15 8/29/99 1000-1014

1 NA NA NA

48 BSMP Sed. Grabs' 70°21.019 147°39.952 20 8/29/99 1248-1350

1 NA'

I

1 NA

4C BSMP Sed. Grabs 70~6.142 147°42.914 32 8/29/99 1440-1450

1 NA NA NA

50 8SMP Sed. Grabs' 70~.766 148°00.366 17 8/31/99 0949-1023

1 NA

1 NA attempted biota sampling

51 BSMP Sed. Grabs 70~5.021 148°03.552 20 8/31/99 0845-0930

3 NA .~ NA

1 Deck Blank/attempted biota sampling

510 BSMP Sed. Grabs' 70~7.317 148°29.9n 25.4 8/16/99 2004-2024 ',,22 NA NA NA attempted biota sampling

55 BSMP Sed.-Grabsfrissue-Annon 70°26.108 148°18.119 22.5 8/16/99 1655-1920 1 1 AirlWate(: NA NA Tissue for metals onl

5A BSMP Sed. Grabs 70°29.710 148°46.107 35 8/25/99 1630-1644

1

1 NA NA NA

5B BSMP Sed.-GrabsfrissLie-Annon 70°34.889 148°55.041 49 8/17/99 1350-1645

1

1 NA NA NA

I 5D BSMP Sed. Grabs 70°24.484 148°33.610

8 8/25/99 0845-0905

1

1 NA NA NA

5E BSMP Sed. Grabs 70OS8.910 149°16.540 62.4 8/17/99 1530-1545 ·11 NA NA NA

5F BSMP Sed.-GrabslTissue- rtodaria 70°26.482 148°49.556 4-6 8/27/99 1509-1638 .1

1 NA NA NA

5H BSMP Sed.-Grabsfrissue-Astarte 70°22.205 147°47.741 22 8/31/99 1055-1207 J1

1 NA NA NA

I L01 Libe Sed. Grabs 70°18.933 147°32.870 23 8/29/99 1200-12--

1

1 NA NA NA Future biota stationltoo rough this time

L02 Libe Sed. Grabs 70°17.829 147°33.027 21 8/29/99 1130-1146

1

1 NA NA NA

L03 Libe Sed. Grabs 70°17.338 147°33.257 21 8/29/99 1103-11-- 1 1 NA NA NA

L04 Libert Sed.-Grabsfrissue-Annon 70°17.034 14~39.892 16 8/29/99 1032-1045

1

1 NA NA NA

I L05 Libert Sed. Grabs' 70°16.925 147°36.657 17 8/28/99 1720-1757 ,1

1 NA

1 NA

L06 Libert Sed. Grabs 70°16.882 147°33.991 21 8/28/99 1432-1446

1

1 NA NA NA

L06a Libert Sed. Grabs 70°16.850 147°35.113 21 8/28/99 1700-1708 1 1 NA NA NA

L07 Libert Sed. Grabs 70°16.788 147°31.958 21 8/28/99 1415-1420

1

1 NA NA NA Future biota station

I L08 Libert Sed.-Grabsfrissue-Astarte 70°16.703 147°30.299 20 8/28/99 1258 1 1 NA

1 NA

L09 Libert Sed.-Grabsfrissue-Annon 70°16.572 14r27.127 21 8/28/99 1204-1249 1 1 NA NA NA

L10 Libert Sed. Grabs 70°16.243 147°33.594 21 8/28/99 1430-1438 1 1 NA NA NA Future biota station

L11 Libe Sed. Grabs 70°15.730 147°33.761 19 8/28/99 1450-1547 3 3 NA

1 NA attempted biota sampling

I L12 Libert Sed. Grabs 70°14.589 147°34.184 18 8/28/99 1406-1414

1

1 NA NA NA

LAl Libert Acoustics Onl 70°23.424 147°46.907 24 8/26/99 2332-0003 NS NS AirlWater

1 NA

lA2 Libert Acoustics Onl 70°18.970 14r37.928 20 8/26/99 2140-2219 NS NS AirlWater.' NA NA

I LA3 Libe Acoustics Onl 70

0

16.n8 147°33.529 21 8/26/99 2015-2050 NS NS AirlWater

1 NA

LA4 Libe Acoustics Onl 70°16.582 147°25.499 20 8/26/99 1850-1935 NS NS AirlWater

1 NA

N01 Northstar Sed. Grabs 70°31.647 148°41.239 40 8/25/99 1753-1800 1 1 NA NA NA

N02 Northstar Sed. Grabs 70°30.518 148°41.414 42 8/25/99 1812-1828

1 NA NA NA

I N03 Northstar Sed. Grabs 70°30.002 148°41.571 40 8/25/99 1835-1843

1

1 NA NA NA

N04 Northstar Sed. Grabs 70°29.673 148°48.145 32 8/25/99 1655-1718

1

1 NA NA NA

N05 Northstar Sed. Grabs' 70°29.621 148°44.705 37 8/25/99 1508-1906

1

1 NA1 NA attempted biota sampling

N06 Northstar Sed. Grabs 70°29.537 148°43.194 37 8/25/99 1418-14321

1 NA NA NA

I N07 Northstar Sed. Grabs 70°29.544 148°40.140 37 8/25/99 1915-1922

1

1 NA NA NA

N08 Northstar Sed. Grabs 70°29.409 148°38.440 36 8/25/99 1925-2015

1

1 NA

1 NA attempted biota sampling

N09 Northstar Sed. Grabs 70°29.322 148°35.220 33 8/25/99 2035-2100

1

1 NA NA NA

N10 Northstar Sed. Grabs' 70°28.998 148°41.742 32 8/25/99 1310-1400

1 NA NA NA attempted biota sampling

I N11 Northstar Sed.-Grabsfrissue-Annon 70°28.428 148°41.907 25 8/25/99 1150-1240

1

1 NA

1 NA

N12 Northstar Sed.-Grabsfrissue-Annon 70°27.320 148°42.078 19.5 8/18/99 1710-1805

1

1 NA NA NA

N13 Northstar Sed. Grabs 70°27.004 148°43.597 14.5 8/18/99 1547-1655

1

1 NA1 NA

N13 Northstar Sed. Grabs 70°26.908 148°43.928 14 8/25/99 0956-1025 N.S NS NA

1 NA

I N13 Northstar Water 70°26.920 14~43.897 14 8/27/99 1709-1735 N.S NS NA

1 NA

N14 Northstar Sed. Grabs' 70°25.978 148°40.450 10.5 8/18/99 1300-1448

?

2 NA1 NA attempted biota sampling

N15 Northstar Sed. Grabs 70°26.711 148°44.576 7.2 8/25/99 1030-1115

3

3 NA 1 1 Grab Rinse/Equipment Blank

I NA1 Northstar Acoustics ani 70°36.674 148°30.212 75 8/17/99 1815-1951 NS NS AirlWatef

1 NA

NA2 Northstar Acoustics ani 70

0

31.n9 148°37.734 43 8/17/99 2050-2140 NS NS AirlWater

1 NA

NA3 Northstar Acoustics Onl 70°29.552 148°41.459 40 8/17/99 2215-2307 NS NS AirlWater1 NA

NA4 Northstar Acoustics Onl 70°28.240 148°34.618 28 8/16/99 2048

c2150 NS NS AirlWater

1 NA

.1 Notes:

NA=Not applicable

NS

=Not sampled

II Final Table2-1.XLSll22J02
- - - -

1

f.

I

i

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-

, -

. . -' ,....,.-~:;.,':!'"--,~..... -

,..

- .. .. .. "'.- - - - -

; ,

-

o·",t· ,~

-

-. ..

-
" '~ ---.........

NalVUl811sland .......... - .....

<> V) ,

'l-__~" ~~ne'lY-ISland "--..."' .....

~. ...... Boulder Patch '~" '0-< (-.-J _-4........- 0 . '. Karluk Island o \.. ..... ~<'(j" J

o rty Prospect

"...-----....

NAZ---' _ .... -/--........ , _------- ............. , Nortfistar Prospect-- " NA Cross Island ....(J/:-

.,.... Reindeer Island -1~o

J "-"'''-

Table 3-2. Map Showing Beaufort Sea Monitoring Program Sampling Stations and Table of

Concentrations for Selected Organic Parameters and Grain Size in Sediment Samples

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Foggy Island

3A 480 7.6 49 1.0 90

38 470 7.9 0.90 84

4A 410 5,3 0.54 33

4B 110 0.90 9.0 0.12 14

4C 21 0.40 0.10 1.8

5H 270 4.8 0.49 31

Mean (SO) 290 (190) 4.5 (3.2) 0.53(0.38) 42 (37)

Endicott Field

5(0) 440 6.4 0.58 39

5(1) 27 (16) 0.52 (0.01) 0.093 (0.031) 2.2 (0.17)

5(5) 170 1.4 21 0.30 22

5(10) 710 12 1.3 88

Mean (SO) 340(300) 5.1 (5.3) 0.57(0.53) 38 (37)

Kuparuk River Bay

SA 700 11 Not analyzed 99

58 24 0.25 0.050 1.7

50 2,700 50 490 0.16 58

5E 170 11 26 0.45 18

5F 180 1.9 0.24 12

Mean (SO) 760 (1,100) 15 (20) 0.22 (0.17) 38 (40)

River Sources

Colville (1) 2,600 36 340 1.6

Colville (2) 2,200 31 2.4

Kuparuk 100 11 72 4.7

Sagavanirktok 320 5.8 25 2.0

Colville Peat 1,900 32 180 13

Kuparuk Peat 110 21 61 27
I

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.1II

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'IIII

I'I

~II

'III
Table 3-3. Map Showing Northstar Sampling Stations and Table of Concentrations for

Selected Organic Parameters and Grain Size in Sediment Samples

1.0

63

90

90

94

97

12

17

59

99

2.1

21

15

6.8

1.9

45(41)

5 Kilometers

2.5 Nautical Miles

0.01

0.48

1.5

1.9

0.90

1.5

0.09

0.50

0.44

1.5

0.09

0.30

0.51

0.27

0.05

0.67 (0.64)

;'i;;;-

5(10)

16

6,5

82

0.21 1.2

6.2

11

9.8

7.8

13

0.45

0.74

6.0

11

0.26

2.6

3.5

0.63

0.21

4.9 (4.7)

N02

2km

N13~

N15 -+ ,;: ~,,~ Spoils Disposal '"'"'\

....

8.6

470

680

500

600

960

57

100

370

720

17

150

160

47

6.8

\

330 (320)

5F.-$- Gwydyr Bay

Mean (SO)

Northstar Prospe

N01

----

m

Northstar

N01

N02

N03

N04

N05

N06

N07

NOB

N09

N10

N11

N12

N13

N14

N15

I

,I

\1

I.

I

I

II

I

11-

II

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r

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II

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I
'IIII

.1

I,IIIIIIIIIIII

,I
Table 3-4. Map Showing liberty Sampling Stations and Table of Concentrations for

Selected Organic Parameters ard Grahi Size in Sediment Samples

-

. ,

51 (26)

2.1

86

93

50

32

69

54

68

36

60

31 (8.4)

31

.1·...... . . 2.5 Nautical'Miles ,

.5.Kilometers

0.61 (0.21)

0,45

0.78

1.1,

OA5

0.48

0.93

0.52

0.44

0.50

0.63

0.54 (0.28)

0.49

Prospect

o '

o

/'

/"

SCALE

Jeanette Island

'iP"''i~~,

~~..

1,

J

Karluk Island

53

33

33

45

7.1 (4.8)

5.0

7.5

16

5.7

1.8

8.6

6.9

17

4.7

5,2

2.6 (2.0)

3.8

360

490

860

400

130

450

450

300

260

340

230

260

380 (180)

'\

/

Mean (SO)

-$-

, (;H

Liberty

L01

L02

L03

L04

L05

L06

LO?

L08

L09

L10

L11

L12

I,

I

I

U

I

I

I

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~I

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I

,II

'IIIII

I,IIII

I,

,IIIII
I

I

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I

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Table 3-5. Diagnostic Ratios and Parameters of Saturated Hydrocarbons, Polynuclear

Aromatic Hydrocarbons, and Steranes and Triterpanes

Parameter Relevance in Environmental Samples

Saturated Hydrocarbons (SHe)

Isoprenoids The sum of selected branched isoprenoid alkanes including: phytane, pristane, farnesane

[1470], and unidentified isoprenoids at relative retention indices 1380 and 1650.

Isoprenoids are abundant in petroleum and are resistant to degradation relative to the

corresponding n-alkanes.

LALK The sum of lower~molecular-weightn~lkanes (n-Cg to n-C20) generally associated with

"fresh" petroleum inputs.

TALK The sum oftotal alkanes, which includes those of biogenic and petrogenic origin (n-Cg to nC4Q). .

LALKfTALK Diagnostic alkane compositional ratio used to determine the relative abundance of lower~

molecular-weight alkanes, which includes those of biogenic origin.

PHY/PRIS 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 oillis added.

n-C1s1(n-C15 +n-Cn) The ratio of n-alkane hexadecane (n-C16) over pentadecane (n-C15) and heptadecane

(n-Cn). At" bac:kground" levels of total hydrocarbons n-C15 and n-Cn can be used as

indicators Of plankton (algal) hydrocarbon inputs. As plankton productivity increases, the

ratio decreases.

CPI Carbon Preference Index. Describes the relative amounts Of odd- and even~hain alkanes

within a specific, alkane boiling range [CPI = (n-C2]+ n-C29+ n-C31)/(n-C26+ n-C28+ n-C30)].

CPI Of 2 - 4 indicates terrestrial plants; as oil additions increase, the CPI is lowered to near

1.0.

TPHC Total Saturated :Hydrocarbons. The sum Of the resolved plus unresolved saturated

hydrocarbons.

Polynuclear Aromatic Hydrocarbons (PAH)

N/P 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 +

C1 N + C2N + C3N + C4N]; P= Phenanthrene/Anthracene Series [COP/A + C1 PIA + C2P/A

+ C3P/A + C4P/Al). .

C2D/C2P Ratio of C2 alkyl dibenzothiophenes (D) and C2 alkyl phenanthrenes (P) is a useful

diagnostic soun::e ratio for petroleum.

C3D/C3P Ratio Of C3 alkyl dibenzothiophenes (D) and C3 alkyl phenanthrenes (P) is a useful

diaQnostic source ratio for petroleum.

Perylene A biogenic PAH formed during the early diagenesis in marine and lacustrine sediments;

may be associated with terrestrial plant source precursors.

Total PAH The sum of all PAH target analytes; includes 2- through 6-ring parent PAH and C1 - C4

alkyl-substituted PAH.

Pyrogenic PAH The sum of combustion PAH compounds (4-,5-, and ~ring PAH: f1uoranthene, pyrene,

chrysene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene,

benzo[a]pyrene; dibenz[a,h]anthracene, benZo[g,h,i]perylene, and indeno[1,2,3,-

c,d]pyrene.

Petrogenic PAH The sum of petrogenic PAH compounds (2-, 3-, and 4-ring PAH: naphthalenes [CO - C4],

acenaphthene, acenaphthylene, fluorene [CO C3j, phenanthrenes [CO - C4],

dibenzothiophenes rCO - C31, chrysenes rC1 - C41, and f1uoranthenes/pvrenes rC1 - C3l).

PyrogeniclPetrogenic The ratio of pyrogenic PAH compounds to petrogenic PAH compounds is useful for

determining the relative contribution of pyrogenic and petrogenic hydrocarbons and in

differentiating hydrocarbon sources.

\
I

I

Total 8fT The sum of all sterane and tritercane biomarker target analvtes, i

SteraneslTriterpanes·(SIT) .. f

Parameter Relevance in Environmental Samples I

I

I

I

I

i

!

.

I

I

C30-Hopane (T19), commonly one 'of the mostabundant triterpanes in ,petroleum. I

The ratio of C3D-Oleanane (T18) to C30-hopane (T19); indicates the relative amounts of

oleanane, which!s a marker of angiosperm (post-Cretaceous) contribution to petroleum

diagenesis. . - 1

Ratio of C27-trisnorhoparie (Ts) to C27-trlsnorliopane (Tm); used as a maturity indicator for

petroleum and also as a source ratio fordifferent crude oils.' I .

Olea~ane/Hopane

Hocane

Ts/(Ts +Tm)

Table 3-5 cont. Diagnostic Ratios and Parameters of Saturated Hydrocarbons,

Polynuclear Aromatic Hydrocarbons,and Steranes and Tiiterpanes

T21fT22 The ratio of C31-'homohopane (228) (T21) to C31-homohopane (22R) (T22); useful for

determining the contribution of recent bioaenic material: I

CPI- Carbon Preference Index

LALK - Low-molecular-weight n-alkanes

LALKfTALK ... LALKTALK ratio

PHY/PRI8 - Phytane:pristane ratio

TALK - Total n-alkanes

I

I

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I

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I

I
I

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Table 3-6. Average Total Organic Carbon in Surficial Sediments from ANIMIDA Study Area,

Alaska Marine Sediments, and Cook Inlet and Shelikof Strait Sediments

Organic Average (Range) Concentrations in Concentrations in

Parameter Concentraticms for Alaska Marine Cook Inlet and

ANIMIDA Study Area Sediments Shelikof Strait

Surficial Sediments (J.Lglg)a Sediments

(J.Lglg) (J.Lglg)b

Total PAH 0.39 (0.007 - 2.7) 0.016 - 2.4 0.001 -1.080

Total PHCc 6.6 (0.21 - ~O) 0.47 - 38 0.9 -69.0

Total SIT 0.029 (0.001-0.081) NA 0.009 - 0.087

a Prince William Sound subtidal and Beaufort Sea (Bence, et al., 1996; Boehm et aI., 1991).

bENRI- UAA, 1995, Hyland, et al.,1995; ADL, 1996; KLI, 1996; KLI, 1997; Boehm et aI., 1999).

C Total PHC concentrations for the ANIMIDA study included saturated hydrocarbons only, while Total PHC

concentrations for the other studies included saturated and aromatic hydrocarbons.

NA - not applicable.
IIIIIIIIIIIIIIIIIII
, .

,

Highlighted numbers are maximum values found during,the 1999 sampling period.

Tabfe3-7. Map of Beaufort Seal, Monitoring Program Sampling Stations and Table of

Concentrations of Selected Me~alS in Sediment Samples

,., .......-..... , ..._-------_....-----..........

58

5.99 e25, 0.075 16.1 ,0.26"

5.36 527 0.063 ' 13 0.22

3.76 279 .0.032 7.4 0.16

418 1.67 170 0.015' 4.5 0.12

4C 1.46 155 0.005 3.2 N.D.

5H 3.59 358 0,025 8.8 0.20

5(0) 2.93 2~7 0.026 6.3 0.29

'5(1) 1.81 232 0.005 5.8 0.05

5(5} 3.00 391 0.022 7.9 0.17

5(10) 6.43 0.088 21.5 0.41 '.

5A 4.96 334 0.012 17.6 0.29

58 1.33 176 0.003 3.9 N,D.

50 1.33 569 0:2011 e2.~ b.7~

'5E 4.83 256 0',030 6.5 0:05

5F 2.28 292 0.022 5.2 0.12

5E

-+

,

., - ------~ ..

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" ,

Table 3-8. Map of North~tarSampling,Stations and Tabi'e of Concentrations for Selected

Metals in Sediment Samples I .

.\

0.".

iN.D.

0.20

0.30

0.32

0.31

0.43

0.14

0.15

0.26

0,29

0.07

0.08

0.08

, N,D;

N.D.

i

5 Kilomelers

2.5 Naulica'i Miles

4.7

9.8

16.2

18.1

16,0

20.3

4.0

3.8

11.0

19.9

3.2

5.6

5.0

4.3

3,7

-$-

5(10)

e--"!

o

0:008'

0,035

0.073

0.085

0.054

0.077

0.023

0.019

0.037

0.082

0.010

0.013

0,010

0.009

0.008

253

425

577

601

612

712

269

247

452

683

164

486

458

519

284

1:43

4.29

5.70

5.73

5:82

7.26

2.47

2.38

4.76

6.59

1.54

2.12

2.06

1.35

1.13

\

5F~.

Northstar Prospe

N01

N02

N03

N04

N05

N06

N07

N08

N09

N10

N11

N12

N13

N14

N15

GwydyrBay

.-----

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Table 3-9. Map of Liberty Sampling Stations and Tab'le of Concentrations of Selected

Metals in Sediment Samples '

Jeanette Island

'U9"'~~~

'" 1

)'I"

J

Karluk Island

. ;

"". i

,5 Kilorreters

2.5 Nautical Miles

Prospect

o

o

/"

,/

------ seALE I'±S;;;;

LOt 4.01 388 0.028 8.6 0.17

L02 6.32 674 0:052 18.2 0.31

L03 5~82 554 0.053 14.7 0.26

L04 3.13 307 0.022 8.8 0.12

LOS 2.51 315 O.OtO 6.8 0,08 L06 5.10 538 0,060 14.2 0.34

L07 3.82 419 0.042 8.6 0.21

LOa 2.83 564 0.023 8.3 0.15

LOg 3.26 341 0.035 10.0 0.16

L10 3.91 437 0.037 8.5 0.21

L11 2.36 289 0.024 6.4 0.07

L12 3.03 335 0.021 9.0 0.15

m

m

m

I

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m

m

m

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m

m

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Table 3-10. Map of Stations Sampled During April 2000 for Total Suspended Sediment and

Laboratory Turbidity and Table :of Results

.............._----,)

0.25 0.35 0.28 0:23 0.26 0.44 1.2 0.41

±0.04 ±0.14 ±'0.18 fO.05 ±0.11 ±0.23 ±0.5 ±0.08

0:4 0.4 0.4 0:3 0.3 0.4 0.4 0.8 0.2

±0.2 ±0.2 ±0.1 ±0.1 ±0.05 ±0.3 ±0.1 ±O.6 ±0.05

.'1'1
I

-II

I-IIIIIIIIIIIIIII
.- - - - - - - - ..- - -..- - .- -

.. _. - -

Table 3-11. Summary Data by Region for Metals in Suspended Sediment Samples

AI Ba Cd Cr Cu Fe Pb Zn

Region (%) (lIg/g) (lIg/g) (lIglg) (llg/g) (%) (lIglg) (lIg/g)

Beaufort Sea

Mean Monitoring 7.28 700 0.44 87.2 36.8 3.81 19.7 123

Std. Dev. Program :1:0.38 :1:36 :1:0.11 :1:11.2 :1:2.6 :1:0.22 :1:3.5 :1:10

(BSMP)

Mean Northstar 7.42 700 0.72 92.6 41.3 3,94 21.9 137

Std. Dev. :1:0.44 :1:43 :1:0.33 :1:8.4 :1:9.3 :1:0.23 :1:6.6 :1:11

Prospect

Mean Liberty 7.85 73B 0.67 97.4 37.6 3.98 21.5 . 143

Std. Dev. :1:0.29 :1:28 :1:0.23 :1:5.0 :1:2.9 :1:0.00 :1:2.3 :1:14

Prospect

Mean Average of 7.48 708 0.64 92.2 39.1 3,92 21.3 135

Std. Dev. BSMP, :1:0.44 :1:41 :1:0.29 :1:9.1 :1:7.4 :1:0.21 :1:5.2 :1:14

Northstar and

Range Liberty

Surface Sediment 3.61 407 0.21 52.1 17.0 2.03 9.9 63.5 Average for ANIMIDA :1:1.71 :1:160 :1:0.14 :1:25.3 :1:11.2 :1:0.93 :1:5.4 :1:35.5 Sid. Dev.

Average Continental Crust

7.96 584 0.1 126 25 4.32 14.8 66

(Wedepohl, 1996)
Table 3-12. Results fQr BC13 in Surface and Suspended Sediment Samples from th~

Beaufort Sea Monitoring Program, Northstar, and Liberty Areas and from Local Rivers

I

I

8C13 (per mil) I

Sample Type Location •i

1

Surface Sediment BSMP -23.1 ±2.0 Ij

I

; \ I Surface Sediment Northstar -23.5 ± 1.1 i

·j

Surface Sediment Liberty -23.2 ±2.8 I

i

,

Suspended Sediment BSMP -30.8 ±2.5 I

•I

I

1

Suspended Sediment Northstar -29.0 ±5.0 ·j

,

!

Suspended Sediment Liberty -27.9 ±4.3 !

t

" I

River Sediment Colville, Kuparuk, and -24.5 ±0.4 I

Sagavanirktok Rivers 1

I

River Suspended Sediment Colville, Kuparuk, arid .;30.3 ± 0.5 ,

i

Sagavanirktok Rivers t

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Table 3-13. Summary Results for 8C13 in SUrface Sediment, Suspended Sediment, and

Source Material Samples from the Study Area

Sample Type Loccrtion 8C13 (per mil)

Surface Sediment BSMP, Northstar, and Liberty -23.3 ± 2.5

Suspended Sediment BSMP, Northstar, and Liberty -29.2 ± 4.5

River Sediment Colville, Kuparuk, and -24.5± 0.4

Sagavanirktok Rivers

River Suspended Sediment COlville, KuparUk, and -30.3 ± 0.5

Sagavanirktok Rivers

Peat and Grass Coastal Beaufort Sea -28.5 ± 1.3*

Amphipods Coastal Beaufort Sea -19.1±0.6*

Plankton Coastal Beaufort Sea -22 ± 2*

* Schell (1983)

-----------------~~-----~---------------~--------
iI

,

,

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III,II!r,IIII11iI

-~~--~-,I. . .'

I;

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"1

'IIIII

Ii

,I' I

,III

'III
--........ .... ,

' ............... _IO'U1'10101S ....

-.............

...................

• ""Cnlltl!l'.ml

....--..... ..... ....---.......... ----- ' ..._--------

58

-1t3A Astarte 13 1,0 '18

5H Astarte 17 1.2

58 Anoilyx 19 18

5F Cyrtodaria 36 1.4 5,6

L04 Anoiiyx 80 8,7

L08 Ast~rte 15 1,1 9.0

L09 Astarte 20 9.6

N11 Anot:lYX 15 3.2

N12 Anot:lYx 15 2.0 5:5 ....

Table 3-14. Map of Sampling Stations for Organisms with Table of Concentrations for

Selected Organic Parameters

I,:" , ••.• e

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II

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III

(I:-

III

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Table 3-15. Map of Sampling Stations for O~ganisms and Table of Concentrations for

Selected Metals (Cd, Cu, Hg, and Pb)

5B

........-" ... --_....... ' ....._----- ... -~_lonnoO ..$ " __ "'"

..................

-..........

N11 A'nonyx, small DAD 't28 0.045

N12 Anonyx, small 0045 120 0.045 .,:-

L04 Anonyx, small 0.63 134 0.056

58 Anonyx, large 1.3 51.5 0.085

LOS Astarte 6.8 15.5 0.065 0.76

LOg Astarte 7.2 13.1 0.056 0.71

3A Astarte 9.8 11.5 0.059 0.69

5H Astarte 8.9 23.9 0.052 0.62

5F Cyrtodaria 1.3 26.0 0.043 0.62

Anonyx (an amphipod), Astarte (a clam), Cyrtodaria.(ap'ICim).
,.

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Table 3-16. Map of Sampling, Stations for Organisms with Table of Concentrations for

Selected Metals (As, Sa,V, and Zn)

58

+ ......................

..., ...... - __ lor~"'tOIfS .. _

.............. " .........

N11 AnonyX, small 7.0 1'8.9' 1.6 93.0

N12 Anon~, .sl'T'lall 6.0 20.2' 1.5 92.9

L04 Anonyx, small 7.8 25.1 1.7 91.2

58 Anonyx, large 14.9 7.4 1.1 215

l;O8 Astarte 11.6 16,0 2.8 82.6

L09 Astarte 9.2 16.1 3.8 68.8

3A Astarte 11.0 14.0 3.7 70.0

5H Astarte 9.7 19;8 3.5 82.8

5F Cyrtodaria 6;6 9.1 2.5 68.0

Anonyx (an amphipod), Astarte (aclal'T'l), Cyrtod~ri~ (a clam); ..
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ilIII
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Table 3-17. Organic Quality Control Result Summary - Polynuclear Aromatic Hydrocarbon

Analyses

QCSampleor Acceptance Criteria Quality Control Result Impact to Data Quality

Measurement Type Summary and Usability

Equipment Blank No compound to exceed 5 All criteria were met. None

times the MDL

Field Blank No compound to exceed 5 All criteria were met. None

times the MDL

Field Replicate RSD < 50% for all All criteria were met. None

compounds >5 times the RL

Initial Calibration %RSD <25% for all All criteria were met. None

compounds (up to 10% of

compounds can be >25%,

but <35%)

Continuing Calibration %D <25% for all compounds All criteria were met. None

(up to 10% of compounds

can be >25%, but <35%)

Surrogate Recoveries 45 to 125% recovery All criteria were met, with the None. Surrogate

(35 - 125% for exception of two low recoveries were

dB-naphthalene) recoveries in a procedural acceptable in the

blank. associated samples.

Procedural Blank No compound to exceed 5 All criteria were met. Several Minor. Results within 5

times the MDL unless PAHs were detected at trace times the blank result

sample amount is >10 times concentrations, but less than were qualified "B" and

blank amount 5 times the MDL. may be biased high or

false positives.

Blank Spike Sample 35 to 125% recovery for All criteria were met for the None. The IS responses

Recoveries spiked compounds tissue BS. Several PAHs in the samples were all

were recovered at >125% in significantly greater than

the sediment BSs due to low the BS; thUS, the

response of the associated quantitation of the

internal standard. sample results was not

impacted.

Laboratory Duplicate RPD <30% for all All criteria were met. None

compounds >10 times the

MDL; mean RPD <30%

Instrument SRM (1491) Measured values must be All criteria were met. None

within 15% of true value for . all certified compounds

Sediment SRM (1941a) Measured values must be All criteria were met for the Minor. The naphthalene

within 30% of the true value sediment SRMs, with the results in the sediment

on average for all exception of low responses samples may be biased

compounds, not to exceed for naphthalene. low by apprOXimately

35% of true value for more 40%.

than 30% of the compounds

Tissue SRM (1974a) Measured values must be All criteria were met for the None. The certified value

within 30% ofthe true value tissue SRM, with the for anthracene in SRM

on average for all. exception of a high response 1974a appears to be

compounds, not to exceed for anthracene. incorrect based on

35% of true value for more consistently high

than 30% of the compounds anthracene results in

repeated analyses over

the past four years.

Oil Reference Standard %D <35% for' compounds All criteria were met. None

(North Slope CrUde) above the RL
Table 3-18. Organic Quality Control Result Summary - Saturated Hydrocarbon An~IYses

I

QCSampleor Acceptance Criteria Quality Control Result Impact to Data Quality

Measurement Type Summary and Usability <

I

Equipment Blank No compound to exceed 5 All criteria were met. None ,

times the MOL ,

Field'Blank No compound to exceed 5 All criteria were met. None I

times the MOL \

Field Replicate RSO < 50% for all All criteria were met. None

compounds >5 times the RL I

Initial Calibration %RSO <25% for all All criteria were met. None "

, compounds (up to 10% of \

compounds can be >25%,

but <35%)

Continuing Calibration %0 <25% for all compounds All,criteria were met. None I

(up to 10% of compounds ,

\

can be >25%, but <35%)

Surrogate Recoveries 45 to 125% recovery All criteria were met. None ,

,

ProceduralBlank No compound to exceed 5 All criteria were met. Several Minor. Results within 5

times the MOL unless SHCs were detected at trace times the associated

sample amount is >10 times concentrations less than 5 . blank result were

blank amount times the MOL. qualified with a UB"and

may be biased high or

may be false positives.

All qualified results were

less than 2 times the

reporting limit.

Blank Spike Sample 35 to 125% recovery for All criteria were met for the Minor. The decane

Recoveries spiked compounds tissue BS. Oecane was results in the associated

recovered at less than 35% samples may be biased

in two sediment BSs. low. I

Laboratory Duplicate RPO <30% for all All criteria were met. None ,

compounds >10 times the I

MOL; mean RPO <30% I

Oil Reference standard %0 <35% for compounds All criteria were met. None

(North Slope Crude) above the RL ,

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Table 3-19. Organic Quality Control Result Summary - Sterane and Triterpane Analyses

l;

,

QC Sample or Acceptance Criteria Quality Control Result Impact to Data Quality

Measurement Type Summary and Usability

Equipment Blank No compound to exceed 5 An equipment blank was not

times the MOL analyzed With the associated

samples.

Field Blank No compound to exceed 5 A field blank was not

times the MOL analyzed with the associated

samples.

Field Replicate RSO < 50% for all Field replicates were not

compoundS >5 times the RL analyzed With the associated

samples.

Initial Calibration %RSO <25% for all All criteria were met. None

compounds

Continuing calibration %0 <25% for all compounds All criteria were met. None

Surrogate Standards 45 to 125% recovery All criteria were met. None

Procedural Blank No compound to exceed 5 A procedural blank was not

times the MOL unless analyzed with the associated

sample amount is >10 times samples.

blank amount

Oil Reference Standard %0 <35% for compounds All criteria were met. None

(North Slope Crude) above the RL
Table 3-20. Inorganic Quality Control Result Summary - Trace..;Metal Analyses

QCSampleor Acceptance Criteria Quality Control Result Impact to Data' Quality

Measurement Type Summary and Usability

Equipment Blanks No trace-metal All criteria were met. None ,

I

concentration to exceed 5 i times the MDL ,

Field Blanks No trace-metal All criteria were met. None j

concentration to exceed 5 I

times the MDL ,

,

Field Replicates RSD <50% for all trace All criteria were met. None ,

metal concentrations >5 I

. times the MDL ,

Initial Calibration Standard Curve All criteria were met. None

correlation coefficient r

0.999 for a 3 to 5 point ,

, curve for all trace metals :

Continuing Calibration %D <15% for all trace All criteria were met. None

metals or repeat Initial j

Calibration and sample j

analvses

Matrix Spike Recoveries 60 to 125% recovery for All criteria were met. None

all trace metals I.

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Procedural Blanks No trace metal All criteria were met. None . concentration to exceed 5

times the MDL unlessthe ,

sample amount is >10

times the blank

concentration f

Laboratory Duplicates RSD <25% for all trace All criteria were met. None

metal concentrations >10 i

times the MDL; mean

RSD<25% !

Sediment SRMs Measured values must be All criteria were met. None

(MESS-2. 2704, 1643d) within 20% of the certified i

or reference values for

>85% of the SRM

analyses.

Tissue SRMs Measured values must be All criteria were met. None t

(DORM-2, 2976, 1643d) within 20% of the certified ,

or reference values for (

>85% of the SRM ,

analyses. ,

Dissolved SRMs Measured values must be All criteria were met. None , (CASS-3) within 20% of the certified , or reference values for

>85% of the SRM

analyses.

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- - - - - 

_ - .1- _-__-__ -_

Table 3-21. SRM Results for BCSS-1 and MESS-2

Sample 10 Ag AI As Ba Be Cd Co Cr Cu Fe

(Ug/g) (%) (Ug/g) (Ug/g) (Ug/g) (Ug/g) (Ug/g) (Ug/g) (ug/g) (%)

SRM-BCSS-1 0.09 6.13 12.1 317 1.5 0.25 11.1 111 18.1 3.21

This Study, 1999 (n = 2) ±O.O ±0.12 ±0.5 ±11 ±O.2 ±0.01 ±0.4 ±O ±0.6 ±0.01

SRM BCSS-1 0.11 6.26 11.1 (330) 1.3 0.25 11.4 123 18.5 3.29

NRC Certified ±0.03 ±O.22 ±1.4 ±0.3 ±0.04 ±2.1 ±14 ±2.7 ±0.10

- SRM MESS-2 -- -- -- -- -- -- -- -- -- .: -- This StudY, 1999 (n = 4)

SRM MESS-2 -- -- -- -- - - -- -- -- -- NRC Certified

Spike Recovery (%) 68.0 106.0 99.6 106.3 96.7 109.2 100.6 100.0 109 99.0

1999 ±6.1 ±2.1 ±8.4 -- -- -- -- ±4.2 ±O ±7.1

Sample 10 Hg Mn Ni Pb Sb TI V Zn TOC

(Ug/g) (Ug/g) (Ug/g) (ualg) (Ug/g) (Ug/g) (Ug/g) (Ug/g) (%)

SRM-BCSS-1 -- 226 52.1 22.8 0.65 0.53 97.1 111 - This Study, 1999 (n =2) ±4 ±2.0 ±0.4 ±0.02 ±0.01 ±2.1 ±1

SRM BCSS-1 -- 229 55.3 22.7 0.59 (0.6) 93.4 119 2.19

NRC Certified ±15 ±3.6 ±3.4 ±0.06 ±4.9 ±12 ±0.09

_SRM MESS-2 0.092 -- -- -- -- -- -- - -- This Study, 1999 (n =4) ±0.004

SRM MESS-2 0.092 -- -- -- -- - -- -- 2.14

NRC Certified ±0.009 ±0.03

Spike Recovery (%) 85.9 99.5 91.4 95.7 108.6 109.2 124 94.5 NA

1999 ±6.6 ±6.4 -- -- -- - ±4.7 ±0.6 .. Notes: Values In parenthesIs are for reference only; SRM not certified by the NRC.

Mean results .:t standard deviation are presented.

Marine sediment SRMs issued by NRC.
Table 3-22. SRM Results for Trace Metals in Mussel Tissue, Dogfish Muscle, and Water

Standard Reference Ag AI As Ba Be Cd Co Cr Cu

Material (~g/g) (~g/g) (~g/g) (~g/g) (~g/g) (~g/g) (~g/g) (~g/g) (Jig/g)

SRM 2976 0.008 150 13.1 0.63 0.009 0.81 0.63 0.63 3.95

This Study, 1999 (n = 1)

SRM 2976 (0.011) (134) 13.3 -- -- 0.82 (0.61) (0.50) 4.02

NIST Certified (±O.005) (±34) ±1.8 ±O.16 (±O.02) (±O.l6) ±O.33

SRM DORM-2 0.040 9.5 17.8 2.24 0.007 0.047 0.189 30.9 2.43

This Study, 1999 (n = 1)

SRM DORM-2 0.041 10.9 18.0 -- -- 0.043 0.182 34.7 2.34

NRC Certified ±O.O13 ±1.7 ±l.l ±O.008 ±O.031 ±5.5 ±O.16

SRM 1643d -- -- -- 509.3j.1.g/L 12.50 j.l.g/L -- -- -- -- This Study, 1999 (n = 1)

.SRM 1643d -- -- -- 506.5 j.l.g/L 12.53 j.l.g/L -- -- -- -- NIST Certified ±8.9 ±O.28

Spike Recovery (%) 92.3 96.6 92.6 101.6 100.4 103.7 130.0 91.7 101.5

1999 (Tissue) -- -- -- -- -- - -- - -- . . Notes: Values In parenthesIs are for reference only;SRM not certified by the NRC. Mean results :t standard deViation are presented.

SRM 2976 - Musseltissue issued by NIST; SRM DORM-2 - Dogfish Muscle certified by NRC; SRM 1643d - Trace Metals in Waters issued by NIST

- - - - - - ,- -------- - -, -..
____ 

: i_ _1,_ _ ___

Table 3-22 (continued). SRM Results for Trace Metals in Mussel Tissue, Dogfish Muscle, and Water

Standard Reference Fe Hg Mn NI Pb Sb TI V Zn

Material (Ug/g) (Ug/g) (Ug/g) (Ug/g) (ug/g) (Ug/g) (Ug/g) (Ug/g) lug/g)

SRM 2976 172 0.063 34.5 0.95 1.09 0.012 0.003 0.82 144

This Study, 1999 ±O.OOI

(n '" 1/2)

SRM 2976 171.0 0.061 (33) (0.93) 1.19 -- (0.001) -- 137

NIST Certified ±4.9 ±O.0036 (±2) (±O.12) ±O.l8 ±13

SRM DORM·2 137 -- 3.77 17.4 0.071 0.026 0.005 0.25 24.3

This Study, 1999

(n '" 1)

(0.004) -' ~- ......

SRM DORM-2 _ _ 142 4.64 3.66 19.4 0.065 -- -- 25.6

NRC Certified flO ±O.26 ±O.34 ±3.l ±O.007 ±2.3

SRM 1643d -- -- -- -- -- 54.6 j.lgIL 7.45j.lgIL 34.2 j.lgIL -- This Study, 1999

(n'" 1)

SRM 1643d -- -- -- -- -- 54.1 j.lgIL 7.28 j.lgIL 35.1 j.lgIL -- NIST Certified ±l.l ±O.25 ±1.4

Spike Recovery (%) 104.9 62.3 97.7 95.8 91.3 99.4 100.5 91.9 100.1

1999 (Tissue) -- ±2.9 -- -- -- -- -- -- --

Notes: Values in parenthesis are for reference only; SRM not certified by the NRC or NIST.
Table 3-23. SRM Results for Trace Metals in River and Marine Sediment

Standard Reference AI Sa Cd Cr Cu Fe Pb Zn TOC

Material (%) (l1g/g) (l1g/g) (l1g/g) (l1g/g) (%) (l1g/g) (l1g/g) (%)

SRM 2704 6.19 421 3.45 132 101 4.15 161 443 -- This Study, 1999 (n ... 4) ±O.07 ±7 ±O.l5 ±l ±1.7 ±O.07 ±4 ±4

SRM 2704 6.11 414 3.45 135 98.6 3.45 161 438 -- NIST Certified ±O.l6 ±l2 ±O.22 ±5 ±5.0 ±O.22 ±l7 ±l2

SRM MESS-2 -- -- -- -- -- -- -- -- 1.95

This Study, 1999 (n" 8) ±O.02

SRM MESS-2 -- -- -- -- -- -- -- - 2.14*

NRC Certified ±O.03

Spike R&covery (%) 101.0 100.1 97.1 93.2 105.2 100.3 97.2 96.9 101.0

1999 ±5.2 ±O.9 ±7.3 ±l.l ±3.8 ±2.4 ±3.2 ±1.8 ±1.2

Notes: Values in parenthesis are for reference only; SRM not certified by NISI.

*Total Carbon (organic plus inorganic).

Mean results:!: standard deviation are presented.

SRM 2704 - River Sediment issued by NIST; SRM MESS-2 - Marine Sediment certified by NRC

........... _ _ __ _. _...,. _ •.• _. .~~ _ ... _ • • __ _ _ .....v. __ .... _~.__._ .••.. _ ....... ,~____ __,.... ,.... ~. , '.~ .~

__ _ :< i i__: i ' _ ..
'OOlL: so ;5(0)

° I os 9 C

'OO~'OO !

50'5(1) "!~''5H I I, 0' I ' , .

osse G'o,ase

i

5Kilometers

2.5 Nautical Miles

-t

5(10)

Northstar Prospect

"OLh 5(10),

" Ii

° aos~ OIl! r.1

':tJ=G S S'C

,..........,

o

'] ~.~. aLLos s c

4km

----- ("---~'~-~~r/

I

aSSC100.l.k' so '~'.N14 , , ° . a s S'c

,OO~ N,13 ° "

°

,:~:e

os s c

N13~

N15

n:

'\Spoils Disposal '''''~...

5F~_

'001 fL" '1i:. os s c

GwydyrBay

m NOI

Northstar Prospe

"

''0

"lOll: . ,

. i 5E

50' , , 100

° aSSe ':~ os s c

~\

.-----

II

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I- Figure 3-1. Map of Northstar Sampling Stations and Grain-Size Histogram

Histograms show grain-size distribution as percent gravel-(black bar); sand (red bar), silt (green bar), and clay (yellow ~~ .

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.1IIIIIII

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Figure 3-2. Map of Liberty Sampling Stations and Grain-Size Histograms

GSSC

IOOl13A

" ,

o

lOOUh, ' 38

"

o - Q sse

Liberty Prospect

Prospect

0""""" 5 Kllomete...

0~""""!!5'~~5iiliiil;;;;;;;Z~2~.5~N'UtiC'1 Miles

4km

Jeanette Island ~'iJ

-=-=-~<>:::,,~Il..

J

Karluk Island

....- r

./

.-/ SCALE

G'SSC

"

"O~4A

"

0_ 0 : 5

100" . 100

'\

/

-s-, <.iH

""Lt ,

",,4C 50 .,

o ' G sse

Histograms show grain-size distribution as percent gravel {black bar), sand (red bar), silt (green bar), and clay (yellow

bar).

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,IIIIIIIIIII
'f

. ,

IF1i,glUire 3-3. Total Organic Carboo ;~ers<u.sSiif"'~ Ci~y for Surficial Sediment Samples from

IBeaufort Sea Monitoring Program, Northstar,<.and Lib~rtyStatiorls

t999 BSMP samples (blue triangles), Northstar sampl~~s(red triangles), and Liberty samples (green triangles)

Time line,equation, and correlation coefficient (r)are from a linear r~gres~ion calcul?rtion. The maximum value of 3A2%

TOC ;atIsilt + c1ay]= 87% isnbt'shown on the figureorincllided in the"regressibncalculationbecause it is presently treated as an anomalouspoiiif - . '. .

100

2.0

Y = 60.6x + 6.8

r = 0.84 o~=~,,---",_A=··':..L--~_..L....---"-.JL....-_--'-~_--'-__-'--_---J

0.0 0.5 1.0 1.5

To~al Organic Ca'rbon(°A»

40

60

20

80

.:>.

()

+

.-

1...:...0

·0.....

-

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'IIIII

'IIIIII
"

. .'

7 8

r = 0.93

4 5 6

AI (%)

2 3

A

A.

A

A.

r =0.91

2 3 4 5 6 7 :B

AI (% )

1

ol.--,---J!~~~---'-_.l...--,-,--~L-..L.--.L.....----'-_..L-----'---l._-'---.J

o

25

100

a. .-... 75 "#.

-->.

ro

c..> 50

+

-

en

100

b.

75

.-...

0

-->. 50 ro

c..>

25

BSMP samples (blue triangles), Northstar samples (red triangles), and Liberty samples (gr,een tnangles)

The !'ine and correlation coefficient (r) are from linear regression calculations.

Figure 3-4. Concentrations of AI versus (a) Silt + Clay and (b) Clay for Surficial Sediment

Samples from Beaufort Sea Monitoring Program, Northstar, and Uberty Stat;ions .

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-----,

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Figure 3-5. Coricentrationsof AI versus ,(a) Fe ~U'id (b) V for Surficial Sediment Samples

from Beaufort Sea Monitoring Prog'ram, Nbrthstar, and liberty Stations r ._. •

1989 BSMP samples (yellow circles), 1999 BSMP samples (blue triangles), Northstar samples (red triangles), and

Liberty samples (green triangles)

The lines, equations, correlation coefficients (r)and 99% Iprediction intervals are from Iihear regression and related

statistical calculations.

10

8 10

Y = 28.9X - 13.8

r = 0.96

8

Y = 0.52X + 0.27

r = 0.97

6

6

,AI (%)

AI (%)

4

2 4

o

o

8

a.

6

-

-

Q) 4

LL

2

300

250 b.

- 200

0>

-0>

:::L 150

>

100

50

0

0 2

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. IIIIIIII

,IIIII

I,III
Figure 3-6. Concentrations of Total Hg versus Methyl Hg for Surficial Sediment Samples

from 1999 ANIMIDA Study Area

+

I

150 200

"

MeHg-l% Total"JoJi" ~,III'"",,,,

,,~"

I J

100

Total Hg (nglg)

50

ta

2.00

0.00

eJJ 1.00

=E

0.50

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Figure 3-8. In situ TUrbidity versus Laboratory Turbidity for 1999 ANIMIDA Study Area

Samples

120

80 100

o

90

o

60

r =0.96

In siitu =1.2 Lab +0,2

60

TSS (mg/L)

40

30

20

In Situ Turbidity (NTU)

a

o

a

o

TSS = 2 x Turbidity + 1.4

r=0.99

80

I'" ".

60

40

-a

.c

"-

:::J

20

.c

co

....J

Figure 3-7. Total Suspended Solids versu~LaboratoryTurbidity for 1999 ANIMiI'DA Study

Area Samples

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IIIIIIIIIIIIIIIIIII
Figure 3-9. Vertical ProfHes ~()r In situ Tumidityfc)r Station N13 Sampled on Three Different

Dates

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'In Situ Turbidity (NTU)

o 20 4060 80 100

o " II.

.......... 1

---

E t .

.c:

-Q. 2

t\' OJ

Cl

s- 3 JB

• \ \.

4 .

t-a.•;••••'••,. '. '••'.:••• a lilt ....... 1it ••.IiI.;i

N13

! 8/18/99

A 8/25/99

A 8/27/99

~r-' _............ - - .

....' ,

;~ ...

, r'

. ,
IIIIIIIIIIIIIIIII
-.-"

NOS

9

3

6

In Situ Turbidity (NTU)

o 20 40 60 80 100 0,,-.-.......---.--...---,.--.---,-........-,

In Situ Turbidity (NTU)

0 20 40 60 80 100 0

2

I

.t: 4 a -------------- Q)

0

LJ!l 6 <ll •

8

N13 ... 10

NOS

\

N11

In Situ Turbidity (NTU)

o 0r---._2:;,.:0:.......,.......:,40r=--,.--:6:,::0-,-..:,.80:......,..-;.,;100

6

9

3

6

9

In Situ Turbidity (NTU)

o 20 40 60 80 100 o ,.,.-r----.-......-.--..---.---r--r--,

3

Figure 3-10. Vertical Profiles for In sifuTurbidity for Stations N05, NOS, N11, and N13

5amipled on August 25, 1999

. -

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Station N13, August 18, 1999

In Situ Turbidity (NTU) Cu~rent Velocity (em/sec)

0 20 40 60 80 100 0 20 40 60 0 0

2260

:[ 3 :[ 3 2680

± .c 1------------- .c 1------------- 2780

'5. '5. Q) 6 Q)

Cl Cl 6

j lii

1;j

9 9

N13 N13 12 12

Salinity (ppt) Temperature (OC)

0 10 20 30 40 Q 2 4 6 8 10 0

\

Q

g 3 :[ 3 ( .c ------------ .c ------------ '5. '5.

6 6 ...

J!! lii III 1;j

9 .~ 9

N13 N13 12 12

'Figure 3-11. Vertical Profiles for/nsitu TurbiditYI Current Velocity and Direction, SaJiliiity,

and Temperature for Station N13 Sampled August 18;. 1999

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'III

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Station N13, August 25, 1999

In Situ TUrbi,dity (NTU)

o 20 40 60 80 100

o

3

6

9

NI3<l2

Salinity (psu)

o 10 20 30 40

o

3

6

9

Nl!-02

Velocity (cm/s)

0 20 40 60

0

/ 2780

3 2580

2320

6

9

N13-{)2

Temperature (C)

0 2 4 6 8 10 0

3 (

6

9

N13-02

Figure 3-12. Vertical Profilesfor,n situ T~rbid'ity, Current Velocity and Direction, Salinity,

an~ Temperature for Station N13Sa1m.,led Aug'ust 25, 1999
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51:

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t , ,

. of

"

In Situ Turbidity (NTU) Current Velocity (em/sec)

0 20 40 60 80 100 0 20 40 60 0 0

E 3

E 3 317"

.c

15.

Cll R

6 Cll 0 0 6 .... .... 2700

2

l'll

9 9

2900

------------NOS ----------"N05

12 12

Salinity (ppt) Temperature ("C)

0 10 20 30 40 2 4 6 8 10 0

E 3

E 3

.c .c C. C. Cll

0 6 6 .... ....

9 9

1"2 - - - - - - - - - - _. NOs"" • - - - - - - - - - - - 'Nos12

Station NOS, August 26, 1999

Figu~ 3..13. Vertical Profiles for In sltu,Turbidity, Current Velocity and Direction, Salinity,

and Temperature for Station N05'Sampl~d Aug'ust 26,1999

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,'I- f

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'''''':

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In Situ Turbidity (NTU) Turbidity (NTU)

0 10 20 30 40 50 0 10 20 30 40 50 0 0

g 2

E 2

.c

11

Ql R

4 Ql Cl Cl 4 ... ... Ql ------------ m f6 ------------- 6 6

L05 L11

8 8

In Situ Turbidity (NTU) In Situ Turbidity (NTU)

0 10 20 30 40 50 0 10 20 30 40 50 0 0

E 2

E 2

R .c

11

4 Ql ·.1

Cl 4 ... ... f6 ------------ f6

6 6 1---------------

48 3A

8 8

Fligure 3-14.. Vertical Profiles for In situ TurbiditY for StationsiL05, Lt1,4:B, and 3A S:am!pled

August 28-29, 1999

....'

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,

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Figure 3-16. Vertical Profiles for Temperature at Stations Sampled During April 2000

Figure 3-15. Vertical PrOfiles of Transmissivity for Stations 5(5), LA2, and LA3 Sampled

During April 2000 (Top 2 mwere a layer of ice.)

-1.5

40 60 80 100

Transmissivity (%)

Tern peratu re (OC)

-1.9 -1.8 -1.7 -1.6

20

2

4

6

-2.0

o

12

14

16

10

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F1i,gure 3-18. Vertical Profiles of Transmissivity for Stations Sampled Near Northstar During

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linear regression fit to sediment data with 99% prediction intervals.

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4.0 Discussion

The Summer 1999 and Winter 2000 field sampling programs successfully obtained data on

surficial sediments, riverine sediments and peat, biota (clams and amphipods), suspended

sediments, and ice cores in the ANIMIDA study area. Ancillary data on currents, PAR, and

CTD were also collected. Together, these data represent the pre-production baseline for the·

Northstar and Liberty prospects for the ANIMIDA Phase I program, and will be used for future

comparisons to Phase II (post-production) measurements. In this section of the report the results

will be further evaluated for general trends and relationships, and comparison to previous BSMP

studies. Statistical comparisons of the data for the purpose of hypothesis testing will be

performed as part of the ANIMIDA Phase II program, once post-development data are collected.

4.1 Surficial Sediments (0-1 cm)

·4.1.1 Metals

4.1.1.1 BSMP Elements

Concentrations of AI, Ba, Cd, Cr, Cu, Fe, Pb, V, and Zn were also determined during the 1989

BSMP supported by MMS. The earlier data are combined here with the 1999 results to

introduce a series of templates for identification and future tracking of possible metal

contamination. The proposed normalization process is first introduced here in some detail using

data for Ba. Then, the proposed approach is applied to the other metals.

In each case, concentrations of the trace metal of interest are plotted versus AI, as shown for Ba

in Figure 4-1. The naturally occurring levels of trace metals can vary as a function of sediment

grain size, organic carbon content, and mineralogy. For example, most trace metals, and the

major metal AI, are present at very low levels in quartz sand or carbonate. In contrast,

concentrations of most trace metals and Al are much higher in fine-grained aluminosilicates.

Aluminum is rarely introduced by anthropogenic processes and is present at percent levels in

most sediment relative to paits-per-million (ppm) levels for trace metals. Thus, Al often

provides a valuable normalization tool that can incorporate the metal-controlling variables of

grain size, organic carbon content; and mineralogy. In the ideal case (Figure 4-1), a good linear

correlation is observed between concentrations of a trace metal and AI. At low levels of Al and

Ba, the sediment is rich in quartz sand. At higher levels of Al and Ba, the sediment is clay-rich.

A 99 percent prediction interval has been drawn on Figure 4-1 for the line determined from

linear regression. Natural sedimentfrom the Beaufort Sea is thus predicted to follow the trend

presented in Figure 4-1. Any positive deviations in Ba levels, above the upper prediction limit,

will suggest the presence of anthropogenic inputs of Ba such as might occur from the discharge

of drilling mud containing barite. The trends in Figure 4-1 support the conclusion that no

discernible anthropogenic inputs of Ba can be detected in sediment from the BSMP stations in

the Prudhoe Bay area during 1989 and 1999. The value for Ba in average continental crust is

slightly below the lower 99 percent confidence interval developed from the BSMP data (Figure

4-1); however, this crustal value is a grand average with a relatively large standard deviation.

Recent studies in the Shelikof Strait, Alaska, found background levels of Ba (pre-1900 from

sediment in cores) at comparable Allevels to be about 800 I-tg/g (Boehm et aI., 2001). Future

efforts in the Beaufort Sea will use sediment cores to determine if metal values for predevelopment sediment fit the "modem" prediction interval.

u:lmms animidalphase I reportllinaJ report fileslfinaJ section 4 text.doc 4-1
To demonstrate how normalization to Al can be used to identify sediment metal contamination,

the 1989 data from the western portion of Harrison Bay, where some drilling mud has b~en

discharged in the past, are added to the previous plot (Figure 4-2a). Concentrations of Ba are

clearly above the upper 99 percent prediction interval for 3 samples from stations 7A, 7B, and

7G, but not for samples from the other two stations (7C and 7E). Based on the strong linear

relationship for sediment from other locations, the evidence supports an anthropogenic source for

some of the Ba in the samples identified as anomalous in Figure 4-2a. The sensitivity of. this

approach is amplified by realizing that the excess Ba in the most anomalous sample point in

Figure 4-2a (1,100 /-lg!g - 700 /-lg!g 7400 /-lg/g) can be explained by the presence of barite at

only 0.07 percent of the total sediment mass (pure barite contains Ba at 588,000 /-lg/g). [

To complete this initial overview, the sediment data for the new stations in the Northstar. and

Liberty areas were added to the Al versus Ba plot (Figure 4-2b). Four points plotted slightly

above the 99 percent prediction interval (Figure 4-2b). These deviations are smaller tha~ those

previously shown for Harrison Bay (Figure 4-2a) and three of them (from stations N12, N13, and

N14)plot in a manner similar to that found for the nearby Kuparuk River, a minor comp~exity in

the Ba data that is discussed in a later section on source sediment. ,. "

This approach of normalizing metal concentrations to Al or Fe has been used successfully in a

number of other environments to identify sediment metal contamination (e.g., Trefry and

Presley, 1976; Schropp et aI., 1990). Metal concentrations in sediments from the coastaf

Beaufort Sea may also be normalized using Fe based on the very good relationship for Al versus

Fe (r =0.96 for the BSMP stations; Figure 4-3). When the 1999data for the Northstar aAd

Liberty areas are added to the Al versus Fe plot for the BSMP stations, all of the additional . " . , points plot within the 99 percent prediction interval. Concentrations of neither Al nor Fe were

determined in sediments co,11ected for the 1986 MMS study and thus the 1986 data are n<?t used

in this initial evaluation of potential contamination. However, Crecelius et al. (1991) did

normalize metal concentrations to V for the 1986 data, thereby providing a possible link with the

1989 and 1999 results, a link that will be investigated duringthe upcoming Phase II study.

,

The metallAl approach for identifying sediment with potential anthropogenic inputs was 'applied

to each of the other metals studied by first evaluating those elements for which data from' 1989

are available. For Cr and V (Figure 4-4), the linear regression equatiOns and the 99 perc~nt

prediction intervals were determined using the 1989 and 1999 data from the BSMP stations and

then validated by adding the 1999 data from the Northstar and Liberty areas. All points plot

within the 99 percent prediction interval, thereby showing the potential utility of these templates

for identifying natural sediment levels of Cr and V. The cumulative results also support the

absence of any discernible anthropogenic inputs of Cr or V to area sediments. The average

crustal abundance values for Cr (FigureA-4a) and Fe (Figure4-3a) from Wedepohl (1995) fit the

Beaufort Sea sediments; however, the crustal value for V is considerably lower than that found in

area sediments. Background levels of V in sediment from Shelikof Strait with comparable Al

concentrations are about 140 to 150 /-lg/g and closer to values from the Beaufort Sea. Onbe

again, a historical Rerspective for trace metals using sediment cores should be checked during

Phase II of the ANIMIDA program.

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Sediment quality "guidelines" for Cr also have been added to Figure 4-4b. Such criteria have

been used extensively worldwideif~rnniii~l assessineilt of possible adverse biological effects

from trace metals andPAH in sediments. One set of criteria introduced by Long et aI. (1995)

uses an Effects Range-Low (ERL) and Effects Range-Medium (ERM). These guidelines are

based on field, laboratory, and modeling studies conducted in the United States that coupled

concentrations of contaminants in sediments with adverse 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. The ERL is

defined as the concentration of a substance that affects 10 percent of the test organisms. For

general application, the criteria have been applied as follows: adverse biological effects are

"rarely" observed when metal or PAH levels are <ERL, "occasionally" observed when

contaminants are present at levels between the ERL and ERM, and "frequently" observed when

concentrations are >ERM. Nine of the 17 metals investigated during this study have been

assigned ERL and ERM concentrations by Long et al. (1995). Concentrations of Cr in quite a

few sediment samples and in average continental crust exceed the value for the ERL (Figures

4-4a and 4-4b). Similar observations are regUlarly made for Cr, most likely because the database

compiled by Long et al. (1995) used Cr concentrations from an acid leach of the sediment rather

than a total digestion. Only a small fraction «25 percent) of the total Cr is removed by a strong

acid leach (Trefry and Presley, 1976; Sinex et aI., 1980). Thus, a leachable Cr value equal to the

ERL level of 82 Jlglg is more likely comparable with a total Cr level of >200 Jlglg, a value

considerably higher than Cr values for continental crust or any samples from this study. The

ERL and ERM values for Cr may need to be revised in the second iteration of these sediment

quality criteria. No data points exceed the established ERM for Cr.

Concentrations of Cu and Zn also follow a strong linear relationship versus Al for the BSMP

stations sampled during 1989 and 1999 (Figures 4-5a and 4-5c). As the template for each metal

was being developed, one point on each plot was clearly above any 99 percent prediction interval

that was constructed and therefore one point from each of the template plots using the BSMP

data was rejected from the linear regression and prediction interval calculations. The anomalous

Cu and Zn values were for stations 5D (near West Dock) and 5H (near Endicott), respectively.

To validate each template, the 1999 data for the Northstar and Liberty areas were plotted in

Figures 4-5b and 4-5d. One or two points (e.g., N04 for Cu) are just slightly above the upper

limit of the 99 percent prediction interval. Similar to the results for Cr, several points on the Al

versus Cu plot exceed the present ERL; however, the ERL is very close to the average crustal

abundance and below natural levels for many sediments. In contrast, all data points from this

study fall below the ERL for Zn (Figure 4-5d). Zinc is more easily leached from sediments with

strong acid and thus the resulting ERL values may be more applicable. In summary, a

reasonable predictive tool appears to be available for Cu and Zn and, at present, one station has

an elevated level of Cu (5D) and one station has an elevated level of Zn (5H). No values exceed

the ERL or ERM for Zn and no values exceed the ERM for Cu. The ERL for Cu needs to be

reevaluated for application to total Cu concentrations.

Plots of Al versus Pb and Cd using the 1989 and 1999 BSMP data do not show the strong linear

relationships found for Cr, V, Cu, and Zn, as discussed above (Figures 4-6a and 4-6c). Some of

the discrepancy results from very low concentrations for each metal and some from scatter in the

1989 data. To construct a template for future use, the point for sample 5D was rejected from

u:lmms animdalphase I reportlfinaJ report files\tinaJ section 4 text.doc 4-3
both data sets and the point for sample 5(10) was rejected from the Pb data set because these

points far exceeded any 99 percent prediction level that was constructed. The resulting linear

regression lines have broad 99 percent prediction intervals and show that station 5D for Pb and

Cd and station 5(10) for Pb exceed the upper limit. Values for average continental crust plot

within the prediction interval for each metal (Figures 4-6a and 4-6c). '

If the 1999 data for sediment from the Northstar and Liberty areas are added to the Pb and Cd

plots, and the 1989 BSMP data are removed, the correlation coefficients are greatly increased

and the width of the 99 percent prediction interVal is narro~ed considerably (Figures 4-6b and 4-

6d). The 1989 and 1999 data were produced by the same l;lboratory (Florida Institute of

Technology); however, analysis for Pb and Cd in 1989 wa~carried out by GFAAS, whereas

ICPIMS was used in 1999. The ICPIMS data seem to be niore precise at low levels for these two

metals. '.

With either template, concentrations of both Pb and Cd are above the 99 percent prediction

interval at station 5D. No data points for either Pb or Cd exceed the ERL or the ERM. Overall,

the sediments of the area appear to have low and natural levels of both metals, with one

exception. A final choice of templates for Pb and Cd will be made following analysis of the

2000 samples and some pre-development samples from sediment cores.

4.1.1.2 New ANIMIDA Metals

Concentrations of the remaining nine metals (Ag, As, Be, Co, Hg, Mn, Ni, Sb, and TI) were

determined only for the 1999 samples. Sediment quality criteria are presently available for four

(Ag, As, Hg, and Ni) of these nine metals. Concentrations of Ag are low and somewhatyariable,

with most values <0.1 Ilg/g and in close agreement with the value for average continental crust

(Figure 4-7a). The resulting template for the AI,versus Ag plot has a relatively wide prediction

interval (Figure 4-7a), with one data point for station 5D exceeding the upper interval an'd no Ag

values above the ERL or ERM. The Al versus As and Hg plots (Figures 4-7b and 4-7c) provide

good templates for future assessments, with each graph ide~tifying one point, for station 5D, as

possibly having a small anthropogenic contribution of As and Hg. No points exceed or are close

to the ERL for As; however, the Hg value for station 5D is about double the expected levels and

exceeds the ERL, but not the ERM. Similar to results for Cr and Cu, many points on the Al

versus Ni plot exceed the present ERL; however, the ERL is less than the average crustal

abundance and below natural levels for many sediments. One station (5D) has an elevated level

of Ni and the ERL and ERM for Ni need to be reevaluated.

Concentrations of Be, Co, Sb, and TI correlated well with Al (Figure 4-8). The linear regression

equations and the prediction intervals for these metals were obtained using the complete 1999

data set. The data for average continental crust fit within the prediction intervals for Be and TI;

however, the crustal value is lower for Sb and higher for Co relative to Beaufort Sea sediments.

Overall, the results show slightly elevated values for Co and Sb at station 5D and for Co at

station 4A.

In summary, a series of Al versus metal plots have been developed and fit with linear regression

equations and 99 percent prediction intervals. Each plot serves as a template for monitoring

future trends in sediment metal concentrations in the study area. Where possible, the plots were

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developed with the 1989 and 1999 d.atCifrom the BSMP and then validated with data from the

1999 surveys of the Northstar and :tJIB~rty stations. Reg1on.iWide, the sediments contain natural

levels of the 16 metals studied (Ag, As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Tl, V, and

Zn), with only minor exceptions. These exceptions, identified by positive anomalies on the

metal/AI plots, are extremely limited and include the following: station 4A (Co), station 5D (Ag,

As, Cd, Co, Cu, Hg, Pb, and Sb), and station 5H (Zn). The strong correlation coefficients for the

metal/AI graphs show that natural levels of metals can be predicted with good reliability and

therefore the outlook for identifying inputs of contaminant metals to sediments during future

years is good.

4.1.2 Hydrocarbons

The hydrocarbon dataset for surficial sediments includes SHC, PAH, and SIT data. These data

are analyzed in part using a suite of diagnostic parameters and ratios (Table 3-5). Some of the

general trends observed in these data for several areas of interest are evaluated in this section.

These areas include: 1) sources of hydrocarbons, 2) spatial variability, or comparisons between

stations, 3) temporal variability, Of comparisons between years, and 4) comparisons to sediment

quality benchmarks or "guidelines." The results of these data evaluations will be used as the

foundation for future statistical applications of the data to test hypotheses after the development

of the Northstar and Liberty prospects during Phase II of the program.

To facilitate the presentation and discussion of the organics data, GCIFID chromatograms from

the SHC analysis, PAH distribution plots, and triterpane extracted ion chromatogram profiles for

representative samples throughout the study area were selected and are presented in Figures 4-9

through 4-15. The samples selected for presentation are as follows:

• North Slope Crude Oil - composite pipeline sample (Figure 4-9)

• Colville River sediment (Figure 4-10)

• Station N06 - Northstar sediment (Figure 4-11)

• Station L06 - Liberty sediment (Figure 4-12)

• Station 3A -- BSMP sediment station near Stockton Islands (Figure 4-13)

• Station L08 - Liberty sediment (Figure 4-14)

• Station 5D - BSMP sediment station near Stump IshindlWest Dock (Figure 4-15)

4.1.2.1 Hydrocarbon Sources

Saturated Hydrocarbons

In general, the surficial sediments (GCIFID chromatograms in Figures 4-10 through 4-15)

exhibit a mixture of primarily terrestrial biogenic hydrocarbons and lower levels of petroleum

hydrocarbons (Figure 4-9 shows a North Slope Crude Oil reference). This assemblage is clearly

dominated by plant wax normal (i.e., straight-chain) alkanes in the n-C27 through n-C33 carbon

range. This is further demonstrated by carbon preference index (CPI) values that range from two

to seven for most samples (Figure 4-16), which is characteristic of sediments influenced by

terrigenous plant inputs (Wakeham and Carpenter, 1976; Boehm, 1984). Four samples have CPI

ratios of less than two (5B, 5E, N01, and N15). With the exception of 5£, the lower CPI ratios at

these stations are due to the fact that the SHC concentrations are very low (i.e., trace levels), with

corresponding low TOC and high sand content, factors which all contribute to CPI ratio

u:lmms animidalphase I repor1\Iinai repor1 files\final section 4 text.doc 4-5
uncertainty and potential inaccuracy. However, the CPIratio of 1.25 at station 5E, with a

corresponding TPHC concentration of 11 mglKg, is characteristic of a petroleum component

present in this sample. '

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Traces of lower-molecular-weight alkanes (LALK - n-C9 through n-C20 alkanes), indicative of

a petroleum source, are visible as more minor components relative to the plant wax alkanes in

the sediment and river samples (Figures 4-10 through 4-15). This clearly visible petroleum

alkane signature in the sediments has been well documented by previous studies in the rbgion

(Boehm, et aI., 1987; Steinhauer and Boehm, 1992; and Boehm et aI., 1990). The clear I

exception to this trend is station L08 (Figure 4-14), which has a GC/FID chromatogram :with a

distinct unresolved complex mixture (UCM) or "hump" in the n-CIO through n-C24 carbon

range. The GCIFID pattern observed in this sample is characteristic of a diesel fuel hYdtocarbon

source. The diesel fuel pattern is slightly weathered, indicating a recent source of diesel fuel

contamination at this station. The absence of any similar diesel fuel signatures in adjacent

samples suggests a very limited or patchy area of sediment contamination. This result clearly

warrants further evaluation of the sediments from this station in future field surveys.

Polynuclear Aromatic Hydrocarbons

The PAH distributions for most of the surficial sediments show that the PAHs are primarily of a

combined fossil fuel origin (i.e., petroleum and coal) with a somewhat variable biogenic

component (perylene), and lesser contributions of pyrogenic or combustion-related compounds

(e.g., 4-,5-, and 6-ring PARs). The petrogenic PARs account for approximately 90 per~ent of

the Total PAH less perylene throughout the study area. Perylene was abundant in surficial

sediments, often the most abundant single PAH compound in the overall PAH distribution

(Figures 4-10 through 4-15). Perylene is a naturally occurring PAH formed during early

diagenesis in sediments from biological source precursors (Wakeham and Farrington, 1~80;

Wakeham, et aI., 1980). It may also be found in crude oil at very trace concentrations. In past

studies, perylene was found at comparable concentrations in the BSMP sediments (Boehm et aI., l

1990). '

\

The variations in PAH composition of representative surficial sediments from the region are

shown in the PAH distribution plots in Figures 4-10 through 4-15. For comparison, the PAH

distribution plot of a North Slope Crude oil is shown in Figure 4-9. The PAR distributions are

generally similar throughout all the regions of the study area and are characterized by thb

presence of a full suite of relatively "unweathered" petroleum PAHs (i.e., naphthalenes

phenanthrenes) similar to the PAH distribution seen in the North Slope Crude oil. 'As noted

previously, perylene dominates the overall PAH distribution as one of the most abundant

individual PAHs in the samples. Perylene is found at equal or greater relative abundance in the

river sediments and peat (Figure 4-10), which suggests the relationship ofthe rivers as a source

of the hydrocarbons in the nearshore sediments, as rioted previously for the SHCs.

Low levels of 4-, 5-, and 6-ring combustion PARs are also present, but are generally only a

minor component of the overall PAH composition in the sediments. The 4-, 5-, and 6-ring

combustion PAHs appear slightly enriched in the peat samples relative to the sediments, but are

still a minor contributor to the overall PAH composition.

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The PAH distribution in station L08 sediment (Figure 4-14) shows a clear increase in the

abundance of 2- and 3-ring petroleum PARs, particularly with the naphthalenes, relative to the

other sediment saIilples. This further supports the GCIFID evidence of diesel fuel contamination

in this sample. The other two samples that were identified as being enriched in petroleum based

on SHC results (5D and 5E) do not show evidence of a corresponding enrichment in PAR or

change in PAH distribution. This result suggests that the source of the hydrocarbon enrichment

may be depleted in PAH versus SHC, relative to the regional petroleum hydrocarbon background

already present in the sediments (e.g., coal and lubricating oil-range products).

Triterpanes

In general, the triterpane distributions in the sediment samples are indicative of a petroleum

pattern (Figures 4-10 through 4-15), with varying abundances of a suite of recent organic

material triterpane markers. For example, a characteristic petroleum triterpane pattern

dominated by norhopane (TI5) andC30-hopane (TI9) is shown in Figure 4-9 for the North

Slope Crude oil. The triterpane distributions for most sediment samples comprise a mixture of

these characteristic petroleum triterpanes, along with recent organic or biogenic markers such as

diploptene (the large peak to the left of the T21 and T22 doublet - Figure 4-11) and other

unnamed triterpanes (the large peaks which elute prior to T15 and in the 45- to 47-minute range

- Peters and Moldowan, 1993). In addition, the relative abundance of T22 at much greater levels

than T21 in some samples provides further evidence of substantial recent organic matter inputs to

the surficial sediments. Many of the sediment samples contain trace levels .of oleanane (TI8),

indicating the presence of a non-North Slope Crude, post-CretaceouslTertiary petroleum source;

i.e., T18 is absent in bulk North Slope Crude oil (Bence et aI., 1996). The origin of this

petroleum signal is unknown, but it is likely from regional background inputs. Seep oils from

from Kavik and Angun may have trace oleananes, as part of their biodegraded biomarker

signature. The presence of oleanane has also been reported in Canadian McKenzie Delta crude

oils far to the west of the study area (Banet, 1995).

The triterpane distributions of the Colville River sediments and peat (Figure 4-10) have the same

mixture of recent organic matter and petroleum hydrocarbon patterns as observed in many of the

sediment samples (for example, station N06 - Figure 4-11). This similarity suggests that there is

a strong link between Colville River hydrocarbon sources - mostly erosional inputs of coal shale,

peat, etc. (i.e., natural background) and the sediments. However, given the documented current

transport regime of East to Westin the study area, it is likely that the surficial sediments are also

influenced by rivers to the East, as well as the Colville River.

The Kuparuk and Sagavanirktok River sediments contain many of the same recent organic

matter triterpane markers, but generally have different distributions than the Colville River

sediments. In particular, the ratio of T211T22, where T22 is an order of magnitude higher than

T21, is characteristic of an immature or recent hydrocarbon source, possibly indicative of coal.

This predominant T22 pattern is also found in three of the surficial sediment samples - 5(5) to

the West of the Sagavanirktok River delta, and N14 and 5D near the mouth of the Kuparuk River

- indicating the influence of these rivers to the deposition of surficial sediments at these stations.

The presence of the predominant T22 pattern at station 5D (Figure 4-15) is of particular interest,

since the SHC and PAH data show evidence of petroleum hydrocarbon contamination at this

u:\mms animidalphase I reportlfinaJ report fileslfinaJ section 4leXl.doc 4-7
station. The observed T22 pattern indicates that coal particles, possibly from the Kuparuk River,

may be one of the sources of the hydrocarbon enrichment.

Two other surficial sediment samples have distinctly different triterpane distributions. Both 5E

and L08 (Figure 4-14) have triterpane distributions more characteristic of a petroleum source,

i.e., a predominance of hopanes (T15 and TI9). In the case of L08, this is not surprising since

other organic data clearly indicate diesel fuel contamination. However, the abundance of

petroleum triterpanes also indicates a petroleum product "heavier" than diesel, as triterp~nes are

typically removed from diesel-range fuels during the distillation process. This result indicates

that the observed petroleum contamination at L08 is a complex mixture of hydrocarbons

including diesel and heavier hydrocarbons such as No.6 fuel oil or crude oil. This could be the

result of drilling mud/cutting residues from historical adjacent exploratory drilling (i.e., iTem

Island), as the standard practice at the time allowed disposal of used drill muds on the ice during

winter drilling. ,This is further supported by the elevated b~um levels (when normalize~ to AI)

observed in the sediment from L08. The petroleum triterpanes in the surficial sediment at 5E

further confirm the presence of low levels of a "heavy" petroleum hydrocarbon source s~own by

the SHC and PAH results, but the specific origins of these "contaminants" are not known. , '

4.1.2.2 Spatial Variability

In examining the spatial variability, or variability between stations, one useful technique involves

examining the relationship between the organic parameter of interest and TOC content or

alternatively, the percent silt + clay. The natural background concentrations of organics;will

often vary as a function of fine-grained sediment (silt + clay) and TOC. Thus, samples enriched

in organics from anthropogenic sources can be identified by normalizing the target organic

parameter and generating a linear regression line and prediction interval on a cross-plot.:

Two plots of total PAH minus perylene versus TOC and silt+ clay are shown in Figure 4-17.

The Total PAH less perylene is usedto reduce variability introduced to the Total PAH by

perylene and can vary by sediment type. Total PAH less perylene has been used in other studies

in evaluating sediment PAH in Cook Inlet (Hyland, et aI., 1995; Boehm et aI., 2001). In, both

plots, a good linear correlation is established between concentrations of PAH and both TOC and

silt + clay (R2=0.76 and 0.83, respectively - 5D was determined to be a statistical outlier and

was not included in the regression 9alculation). This regression defines the natural

geological/geochemical background. In both cases, the data point from station 5D is clearly well

outside the calculated 99 percent prediction interval of the regression line. This result indicates

that 5D sediment is enriched in Total PAH relative to the expected background for the rbgion.

As noted previously, station 5D sediments were identified as being contaminated with '

hydrocarbons, although the source of this contamination is ~till unclear (i.e., coal versus;

petroleum) and will need to be examined more closely in ~hase II work. -

Similar plots for TPHC versus TOC and silt + clay (Figure 4-18) result in a slightly lower

regression correlation coefficient than for the Total PAHgraphs (R2=0.53 and 0.69, respectively

- once again calculated without the 5D outlier). However, the same trend is observed, with

sediment from 5D showing a clear enrichment of TPHC relative to the regional background (99

percent prediction interval), further supporting the previously noted hydrocarbon contamination.

In the TPHC plots two other samples, L08 and.5E, were found to slightly exceed the upper limit

u:1mms animidalphase I report\finaJ report files\finaJ section 4 text.doc 4·8

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of the 99 percent prediction interval (L08 only versus TOC, and L08 and 5E for silt + clay).

Based on the analytical data, these'lW6santples were also'pt~'viously identified as being enriched

in petroleum hydrocarbons. Diesel contamination with possible crude oil was identified in L08

and a "heavy" hydrocarbon product depleted in PAR was identified in 5E.

Another approach in identifying potential anthropogenic inputs to the sediments involves

examining the relationship ofTPHC versus Total PAR (Figure 4-19). In this plot, a linear

regression and 99 percent prediction intervals are calculated without sample 5D, since the vast

separation of 5D from the main cluster of samples can be misleading when determining linear

relationships. However, in the plot the calculated regression is high even without 5D (R2 ::: 0.71

and 0.72, respectively, for Total PAH and Total PAR less perylene versus TPHC). Two of the

samples that previously showed enrichment in petroleum hydrocarbons by the other techniques

(L08 and 5E) also fall above the 99 percent prediction interval in these plots, further

corroborating the presence of hydrocarbon contaminants. Of particular interest is that station 5D

falls within the expected range of Total PAH versus Total PHC for the regional hydrocarbon

background. This could indicate a coal source, as suggested earlier, but does not rule out a

mixed petroleum source with a saturate to aromatic ratio similar to the sediments.

Overall, these techniques provide a sensitive baseline process to measure anthropogenic inputs

into the system from Northstar and Liberty activities, given radial sampling design around the

prospects and regional BSMP station coverage.

4.1.2.3 Temporal Variability

Comparisons of the 1999 sediment data to 1989 and earlier BSMP and earlier data are limited to

SHC and PAH parameters, as samples were not analyzed for SrI's before 1999. Additionally,

only generalized comparisons of Northstar and Liberty regional data can be made to historical

sediment data since these stations were not sampled in previous studies. A comparison of the

total PAH concentrations in sediments between 1999 and the 1984 - 1986 and 1989 BSMP data

is shown in Figure 4~20. Regional means are provided for Foggy Island, Kuparuk River,

Endicott, Northstar, and Liberty. The 1989 West Camden Bay regional mean is also included for

comparison as a background or reference region. The 1999 regional mean Total PAR

concentrations are within the same rarige measured in the earlier BSMP programs. The 95

percent confidence intervals for the regional means overlap between years within each region

(performed on log-transformed data), indicating no significant temporal trends in Total PAH. It

should be noted that the 1999 mean for the Kuparuk River region is strongly influenced by the

high Total PAH concentration from station 5D; the mean is a factor of two lower when 5D is not

included. The Northstar and Liberty regional means for Total PAH fall within the range

measured for the three other BSMPregions and both are less than the 1989 West Camden Bay

reference value.

The comparison of the ANIMIDA 1999 Total PHC regional means versus the BSMP total PHC

means is shown in Figure 4~21. As observed for PAH, the 1999 Total PHC means are within the

same range as previous BSMP values. However, there is greater variability between years than

observed for the PAH data. This is likely an artifact of changes in the GC/FID analytical

techniques used to measure SHCs, and the same trend was documented for the 1989 sediments

(Boehm et aI., 1990). The mean Total PRe concentration for Northstar is less than the 1989

u:lmms animidalphase I reportlfinaJ report fileslfinaJ section 4 text.doe 4-9
West Camden Bay reference value (4.89 mg/Kg versus 5.39 mg/Kg, respectively) while' Mean

Total PHC for Liberty is somewhat higher (7.06 mg/Kg). However, the 95 percent confidence

intervals for the regional means substantially overlap between years, within each region;

suggesting there are no temporal differences in Total PHC (performed on log-transformed data). ,

I

Although no temporal trends were observed in the Total PAR, substantial differences in, the ratio

of pyrogenic to petrogenic PAH were observed for the 1999 and 1989 BSMP sediment data

(Figure 4-22). The calculated ratios in 1999 are higher than in 1989 (mean ratios of 0.096 and

0.038, respectively) at all possible stations. The ratio could not be determined for station 5E in

1989 due to non-detected pyrogenic PAR in that year. Reanalysis of several 1989 arch~ved

sediment samples according to the current analytical protocols indicates that this shift in' the

pyrogenic/petrogenic ratio may be related entirely to differences in the 1989 vs. 1999 analytical

methods. Specifically, the shift is likely due to a difference in quantitating the alkyl PAHs. The

pyrogenic/petrogenic ratios of the three recently analyzed 1989 archived sediment sampies

showed a significant increase in the ratios. (The reanalysis of the 1989 sediments will be

presented with the Phase II analytical results.) The impact of this finding will be evaluated in

Phase II of the ANIMIDA program. ;

4.1.2.4 Sediment Quality Guidelines l

Sediment quality criteria have been developed to assess possible adverse biological effects from

metals, polychlorinated biphenyls (PCBs), pesticides, and PAR. The commonly utilized criteria

are the ERL and ERM presented by Long et al. (1995). The general applications of the j

guidelines have been to state that adverse biological effects are "rarely" observed when PAR

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.

ERL and ERM values have been developed for 13 individual PAH compounds and three classes

of PAR (low- and high-molecular-weight PAH, and Total PAH). A comparison of the Total

PAR from all ANIMIDA sediments by study region to the ERL and ERM criteria is shOWn in

Figure 4-23. None of the Total PAR concentrations determined in this study exceed the'ERL.

Station 5D, which had the highest measured Total PAR at 2,700 IJ.g/Kg, was still well bdlow the

ERL value of 4,022 IJ.g/Kg. The mean Total PAH values from each study region were generally

an order of magnitude lowerthan the ERL. Similarly, the individual PAH concentrations did not

exceed the ERL for the 13 PARs listed, which could be compared directly. The sum of the two

methyl naphthalene isomers at station 5D (130 IJ.g/Kg - the sum of two isomers) was higher than

the ERL value listed for the single 2-methyl naphthalene isomer (70 IJ.g/Kg). However, the value

would be less than the ERL using an estimate of 50 percent contribution of 2~methyl naphthalene

to the sum of the methyl naphthalene isomers. In summary, based on sediment quality criteria,

the concentrations of PAH found in the study area sediments are not likely to pose immediate

ecological risk to marine organisms in the area. '

u:\mms animidalphase I reportlfinal report fileslfinal section 4 teXl.doc 4-10

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4.2 Organisms

4.2.1 Metals

Data from 1986, 1989 and 1999 are available for Ba, Cd, Cr, Cu, Fe, Pb, V, and Zn in clams

(Astarte) and amphipods (Anonyx) from four stations in the area of the BSMP that is being

studied during the ANIMIDA program. These results provide a temporal perspective for

monitoring trends in body burdens of selected metals over time. During 1999, concentrations of

ten additional metals (Ag, AI, As, Be, Co, Hg, Mn, Ni, Sb, and Tl) were determined in the same

three species of organisms to broaden the spectrum of analytes.

Mean concentrations ofBa, Cu, Pb, V, and Zn in clams sampled during 1986, 1989, and 1999

are remarkably uniform among years (Figure 4-24). Such uniformity is encouraging with respect

to using body burdens for metals as a long-term indicator of metal availability. This uniformity

also could be used to state that no detectable shifts in metal levels in Astarte have occurred

between 1986 and 1999. However, the standard deviation for a given metal in an individual year

is sometimes large. Such variability limits statistical discrimination of changes in metal

concentrations. For example, the RSD for the six pooled samples of Astarte for 1989 was -50

percent for Ba and Pb and 75 percent for Cd. In contrast, the RSDs for the four pooled samples

of Astarte from 1999 were 15 percent for Ba, 9 percent for Pb, and 17 percent for Cd. Some

anomalous points that led to high values for the RSD can be partially explained, whereas others

may be due to natural variability, as described below. In any case, some additional effort will

need to be devoted to the organism portion of the monitoring effort to increase its future utility.

One factor that introduces variability into concentrations of some elements in clams is the

amount of sediment contained in the gut. Because sediment in the gut may be passed up to the

next trophic level, it is not usually an issue in risk analysis; however, variable amounts of

sediment can contribute to some of the higher values observed for the RSD in the clam data. For

example, the large RSD for Ba in the 1989 data for Astarte (Figure 4-24) is partly due to a Ba

level of 40.4 /-lg/g (overall mean was 24 flg Ba/g) in one sample from station 6D, where the Fe

concentration was 80 percent higher than the average for the other samples. If half of this Fe in

the Astarte is due to sediment in the gut, then Ba associated with sediment can account for >40

percent of the Ba in the clam. The same sample from station 6D also contained V at levels

almost double those in the other five samples and this excess V is most likely bound to sediment.

The elements influenced by excess loading of sediment are those that are present at very low

levels in the organism relative to the sediment. In this study, the metals most affected by

sediment are Ba, Be, ~o, Pb, Sb, TI, and V. For most of the remaining elements (Ag, As, Cd,

Cu, Hg, Mn, and Zn), natural metal levels in the clam are high enough to minimize the influence

of excess amounts of sediment. The sediment/clam issue will be further addressed during Phase

II in order to maximize the screening capabilities of the clam data.

Comparison of the 1986, 1989 and 1999 data for metals in clams also may be limited by

geographical differences in sample location because Astarte were collected at only two common

stations during 1989 and 1999 (stations 3A and 5H). Finally, the small numbers of pools of

samples also limits the statistical power of the data. All of these factors that influence the utility

of using the data for metals in Astarte will be more rigorously evaluated during Phase II of the

ANIMIDA program. More-detailed discussion of the 10 new metals in the study also will be

u:\mms animidalphase I reportlfinai report fileslfinai section 4 text.doc 4-11
reserved until the samples collected during August 2000 are analyzed. However, the RSDs for

the new elements for 1999 are generally encouraging: Ag (17%), Al (13%), As (11 %), Be (9%),

Co (35%), Hg (9%), Mn (24%), Ni (30%), Sb (19%), and TI (7%).

Average concentrations of metals in the amphipod Anonyx are more variable from year,to year

than observed for the clam Astarte (Figure 4-25). In the case of the amphipods, excess sediment

is not an important issue because Fe levels are low, at 200 to 400J!g1g relative to 1,000 'to 2,000

J!g1g in the clam. Furthennore, the values for the RSD in the 1999 data are quite low, ~ith many

metals having RSDs <15 percent, as previously described. Only one of the seven stations where

amphipods were collected in 1989 was also occupied in 1999. The arnphipod data for the ten

new metals are also quite encouraging, withthe following values for the RSD in the small

Anonyx: Ag (2%), Al (26%), As (13%), Be (16%), Co (16%), Hg (13%), Mn (6%), Ni (14%), Sb

(15%), and TI (8%). When the 1999 data for clams and amphipods are combined with results

from samples collected at the same stations during August 2000, a more valid and useful . 1

framework for using these organisms as sentinels of possible future metal contamination can be

proposed and tested. ·

Hydrocarbons ,

The GCIFID chromatogram, PAH distribution plot, and triterpane extracted ion chromatogram

profile of a representative tissue sample (station 3A Astarte) are shown in Figure 4-26. :

The GCIFID results show trace levels of terrigenous plant wax hydrocarbons in the n-C24

through n-C32 range, a pattern similar to the surficial sediments. The PAH distributions show

trace levels of a mixture of petrogenic PAHs (e.g., 2- and 3-ring PAH and alkyl PAH) and

pyrogenic PAHs (e.g., 4-,5-, and 6-ring PAH), and perylene. The low levels ofPAH found in

the tissue samples result in "truncated" PAH patterns, where alkyl PAH compounds are below

the detection limit of the analytical method. Nonetheless, the pattern of PAHs in the tis~ues is

generallysimilar to the surficial sediments when the influence of detection limits is accbunted

for. The one sample with the highest Total PAH concentration (L04 - Anonyx at 80 J!gt;Kg)

shows a predominance of several pyrogenic PAHs (i.e., phenanthrene, fluoranthene, and pyrene)

that was not observed in any of the other tissue samples.

The SfTs in the tissue samples were near the detection levels in most samples, making ,

interpretation of the patterns more difficult. In some samples, the presence of interferences from

the natural fats and oils of the tissue matrix were also encountered. Nevertheless, the triterpane

distributions in the tissue samples generally corresponded to the patterns observed in the

sediments, with a predominance of both biogenic and recent organic matter triterpane markers.

Overall, the organic data set for the tissue samples revealsthe presence of trace levels of

hydrocarbons, generally similar in distribution to the sediments, indicating a positive relationship

between the background sediment hydrocarbons and the body burdens of the clams and:, amphipods.

;

The limited overlap stations for tissue samples collected in both 1999 and 1989 enable only

precursory evaluation of temporal data trends. A comparison of the PAH data in the 1989 and

1999 tissues, where stations and organism type coincide, shows a trend of lower Total PAH less

perylene concentrations in 1999 than in 1989 (Figure 4-27). A similar trend is observed for the

u:\mms animidalphase I reporllfinaJ report fileslfinal section 4 textdoc 4-12

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Total PRC concentrations, with the exception of the Anonyx at 'station SB, where the Total PRC

concentration was approximately f6ui'Yimes higher in 199~Hhan in 1989 (Figure 4-28). The '

observed higher value may be due to natural fat or oil interferences in this sample or could be

related to the different species ofAnonyx comprising sample (station SB Anonyx were noted as

being the "large" variety in the field records). Differences for certain metal analytes were also

noted in the 5B Anonyx sample relative to the samples composed of small individuals, suggesting

the size of the organisms may be the source of the observed differences. Additional tissue data

corresponding to the 1999 sampling locations are clearly necessary to further evaluate the

hydrocarbon relationships in the bivalves and amphipods, and their possible use as sentinel

organisms for bioaccumulation of hydrocarbon contaminants.

4.3 Suspended Sediment in Water and Ice

4.3.1 Physical Considerations

After the spring runoff from rivers subsides, the concentrations and distribution of suspended

sediment dUring the open-water season in the ANIMIDA study area appear to be a function of

wind conditions, water currents, and water depth. Data have been collected and evaluated for

only one open-water period thus far in the ANIMIDA program (August 1999). The database will

be expanded during Phase II of the study. Results obtained before and after the August 1999

stonn (Figure 4-29) helped to establish the overview described in Section 3.2. In summary, a

preliminary descriptive picture for mid-summer is as follows: 1) concentrations of TSS and

turbidity are at levels of <3 NTU «5 mgIL) under relatively calm conditions (wind speeds <5

kts), 2) concentrations of TSS and turbidity can exceed 80 NTU (and 100 mgIL) under high wind

speeds (>25 kts), 3) turbidity may be about two times lower in more-offshore waters (water

depths >10 m) relative to more-nearshore, shallower water, and 4) a near-bottom nepheloid layer

with a 50 to 300 percent increase in turbidity may be observed at most locations. The TSS data

also can be used to integrate the total mass of suspended sediment in the water column (in g/m2

),

as shown for station N13 in Figure 4-29 as follows:

Integrated TSS (g/m2

) = Integrated '[(TSS in g/m3

) x (water column depth in m)]

where TSS (g/m3

) =TSS (mg/L) x (1 g/1000 mg) x (1000Um3)

or Integrated TSS (g/cm2

) =Integrated TSS (g/m2

)/1O,000.

The integrated amounts of suspended sediment in the water column can be converted to a layer

thickness of surficial sediment that, if resuspended, would produce the observed TSS levels in

the water column as follows:

Resuspended sediment layer (em) = Integrated TSS (g/cm2

) x (1 cm3

/1.6 g wet sediment)

and thus

Resuspended sediment layer (N13, 8/18/99):::: (0.003 g/cm2

) x (0.625 cm3

/g):::: 0.002 em

u:\mms animidaIPhase I repOrtllinaJ report ftIes\finaJ section 4 text.doc 4-13
The calculations show that a layer of fine-grained sediment equal to only 0.002 Cm wo~ld need

to be resuspended to provide enough suspended sediment to produce the background c~nditions

observed at station N13 on August 18,1999. In the post-storm water column, the thicIq1ess of

the layer of sediment that would needto be resuspended at N13 increases to 0.03 cm. These,

results show how sensitive these shallow waters are to resuspension events and infer that very

high TSS levels may be observed during storm conditions. Current velocities typically 'ranged

from about 5 to >40 em/sec during the August 1999 sampling trip.

The under-ice data for suspended sediment also provide a valuable and previously unav,ailable

baseline for identifying potential impacts during winter construction activities. The lowest levels

of turbidity and TSS were observed at the more-offshore stations of NA2, 5(5), and LA2, where

the overall average value for TSS was 0.25 ± 0.06 mg/L, about 10 to >100 times lower than

values obtained during the open-water period of August 1999. The transmissivity data suggest

that a small nepheloid layer is present at each station.

Although the winter sampling plan was originally designed only to determine backgrouhd levels , of turbidity and TSS under ice, water sampling was carried out at 5 locations in the NOI1hstar

area to investigate the influence of the backfilling process on turbidity. The previously described

results show that about 200 m downstream of the backfilling operation, transmissivity decreased

at depths >8 m. Concentrations of TSS were 2.0 and 1.5 mg/L at a water depth of 9 m at station

NT1, about 5 to 8 times greater than apparent background levels. Just upstream of the !

backfilling operation, transmissivity was lower than background levels, but rather uniform

between 3 and 10 m. Current velocities near the backfilling operation averaged about 2 cm/sec.

At increased distances from Northstar Island (NA3, -0.5 km; NA5, -1 km; and NA6, -2 km),

values for TSS averaged 0.32 ± 0.15 mg/L and were comparable with background levels.

Collectively, the turbidity and TSS data from open-water and under-ice conditions have' greatly

enhanced our understanding of the concentrations and distributions of suspended sediment in the

ANIMIDA area.

r

The complementary ice-core data for suspended sediment may possibly be used to 1) sh'ow a

record of whether the ice formed under turbid- or clear-water conditions and 2) determine the

amount of sediment that will be released to the water column when the ice melts. The ;

distribution of sediment in the ice cores is consistent with the pattern of formation of this sea ice.

The top layer (as sampled) forms first and freezes in the suspended sediment in the ambient

water (Figure 4-30). Storms during the fall seasons can keep the TSS at levels of>10 to 100

rngIL. Some time after the top layer of ice forms, the energy of the underlying water is .

dramatically decreased and suspended particles slowly settle out such that the later ice that foims

from below contains considerably lower levels of sediment (Figure 4-30). The actual p~tterns of

sediment distribution in the ice cores may be more complex than the simple picture described

above, depending on ice rafting and other processes. More detailed sub-sampling of the ice

cores may improve the record of events recorded in the ice. .

The ice-core data from April 2000 does permit calculation of the impact of sediment releases

from melting ice on surficial sediment accumulation. Using the worst-case scenario (station

LAS), the integrated amount of sediment in the ice core is about 6 mg/cm2 (Figure 4-31). As the

ice melts and releases this sediment, the impact on the seafloor is an accumulation of only about

u:lmms animidalphase I reportlfinal report fileslfinal section 4 text.doc • 4-14

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0.004 cm of sediment per cm2 (FigG~~ 4-31). This small impact is consistent for all ice cores

collected. Certainly, increased loading may be possible at some locations; however, the net

.impact on sediment accumulation would appear to be small in the ANIMIDA study area.

4.3.2 Chemical Considerations

Concentrations of trace metals in suspended sediment collected during the open-water period of

August 1999 fit the metal-to-Al trends observed for surficial sediments (Figure 4-32). However,

most points on the metal/AI graphs for suspended sediment plot at higher levels of each metal

because the suspended sediment is richer in fine-grained aluminosilicates and contains little or

no carbonate or quartz. These results imply that the metals have a similar source in

aluminosilicate material that is relatively uniform in composition. For Al versus Cu and most

other metals (Figure 4-32), the data for the source bottom and suspended sediment fit the same

trend as the bottom and suspended sediment from the ANIMIDA study area. Thus, the area

rivers are providing no distinguishable tracer among them as far as most trace metals are

concerned. Values for Fe, Ba, and Cr were elevated, relative to AI, for the Kuparuk River

(positive anomalies shown with inverted orange triangles on Figure 4-32b). The Kuparuk River

sample was taken at a time of low TSS and may be relatively richer in a fine-grained iron oxide

phase than the other samples, similar to observations made in samples collected from under the

ice. Overall, no distinct elemental signature for different sources ofsediment to the ANIMIDA

study area has yet been identified.

u:lmms animida\phase I repOrtlfinaJ report fileslfinaJ section 4 text.doc 4·15
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Figure 4-1. Concentrado"nsofAI ver'susBainStJrfjcial'S~(JrmentSamples:from·Beaufort Sea Monitoring Program Stations

eSM"'statiohs'[3A,3B, 4A:-C, SA, 58, 5D-H, and 5(0, 1, 5, 10)] from 1989 (yellow circle$)~nd from 19'99 (blue triangles) and average continental crust (brown diamond,

from Wedepoht. 1995); .

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Figure 4.,2. Concentrations of·Alversus Ba in Sediment SCimplesfrom,(a) Beaufort Sea Monitoring Program and Harrison Bay

Stations and'(b) BeauforfSea Monitoring P..ogramJ~NorthstarJ and,liberty Stations

BSMP stations (yellow circles for 1989, blue triangles for 1999), 1989 Harrison Bay stations (red squares), Northstar stations (red triangles), and Liberty stations (green

triangles).

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A1(%) A1(%)

Figure 4-3. Concentrations ofAI versus Fe for Sediment Samplesfromla) Beaufort Sea Monitoring Program Stations and (b)

Beaufort Sea' Monitoring;Progr-am, Northstar,and Liberty Stations

BSMP stations (yellow circles for 1989, bluE! triangles for 1999), Northstar stations (red triangles), and Liberty stations (green triangles). Brown diamond shows value for

average continental crust (from Wedepohl, 1995). Linear regressiQn lines. equations, ~nd 99% prediction intervals displayed.
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Figure 44. Concentrations of AI versus Cr.for SedimentSamples from (a) Beaufort Sea Monitoring Program Stations and (b)

Bea~fortSea·Monitoring'Progl'am, Northstar,arid.Lib~rtYStati'ons;:Concentratio~s·OfAI versus V for Sediment Samples from (e)

Beaufort· sea· Monitoring Program Stations:and (d) BeaufonSea Monitoring'Program, Northstar, and Liberty Stations

BSMP stations (yellow circle!?Jor 1989, blue triangles for 1999), Nortlistar stations (red triangles), and Liberty stations (green triangles). Brown diamond shows value for

average continental crust (from Wedepohl, 1995). Linear regression lines, equations, 990/0' prediction intervals, and ERL and ERM values displayed.
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Beaufort.Sea Monitoringp'rogram, Northstar, and l.,ibti!'rty Stations.' Concentrations of AI vers4sZn for Sediment Samples from

(c) Beaufort Sea'. Monitoring 'Program Stations and (dfeeaufQrtSea'M6riitoring, Program, Northstar, and Liberty Stations

BSMP stations (yellow circles,'for 1989, blue triangles for 1999), Noi'thstar stations (red triangles), and Liberty stations (green triangles), Brown diamond shows value for

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Beaufort S~a Monitoring Program, Northstar,.arid Lib~r-tY Statjons.. Concentrations of AI versus Cd for Sediment Samples from

(c) BeaufortSea:Monitoring Program Stations and'(d)'SeaLifdrt Sea Monitoring Program, Northstar, and liberty Stations

BSMP stations (yellow circlesJor 1989, blue triangles for 1999), NorthstEir stations (red triangles), and Liberty stations (green triangles). Brown diamond shows value for

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Liberty. Sediment Samples

BSMP stations (blue triangles for 1999), Northstar stations (red triangle~),and Liberty _stations (green triangles). Brown diamond shows value for average continental

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Liberty SedimentSamples

BSMP stations (blue triangles for 1999), Northstar stations (red triangles), and Li,bertystations (green triangles). Brown diamond shows value·for average continental

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Figure 4-17. Scatterplot of Total Organic Carbon andS'ilt + Clay Results versus TQtal

Polynuclear Aromatic Hydroca'rbons Less Per)dene Concentrations for Beaufort Sea

Monitoring Program, Northstar, and LibertY Sul11icialSediiment Samples

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Petroleum-Hydrocarbon Concentrations for Beaufort Sea Monitoring Program, Northstar,

and Liberty SurficialSe'diment Samples

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Figur~ 4-23. Comparison of Regio,nal Mean Total Polynuclear Aromatic Hydrocarbon Concentrations to Sediment Quality Criteria

Effects Range~Lo\N and Effects Range~Medjum Values (Long et a!., 1995) Note: y-axis is present on a logarithmic scale,
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0 0

1986 1989 1999 1966 1969 1999

Figure 4-24. Mean Concentrations of Sa, Cd, Cu, Pb, V, and Zn in Clams (Astarte) Collected from Beaufort Sea Monitoring

Program Stations During 1986 and 1989, and from ANIMIDA Stations During 1999

Error bars set at ± standard deviation.
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Figure 4-25. Mean Concentra~ions Qf Sa, Cd, Cu, Pb, V, and Znin Amphipods (Anonyx) Collected from Beaufort Sea Monitoring

Program Stations During 1986 and.1989,and from ANIMIDASt~ltions During 1999

Error bars set at ± standard deviation.
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Figure 4-26. Station 3A Astarte sp. Tissue - GC/FJD Chromatogram (top), PAH Distribution

Histogram (middle), Triterpanelon Chromatogram (bottom)

Response_

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Organisms for 1989 and 1999
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Figure 4-28. Total Petroleum Hydrocarbon Concentrations of Beaufort Sea Monit~ring Program Organisms for 1989 and 1999
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Figure 4-29. Vertical P,r:ofiles for In situ rurbidityat Station N13 During August 1999

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Figure 4-31. Schematic Representation of Release of Sediment from Melting Surface Ice

In the following steps:

1. Integrated amount of ~edimentin the ice core as determined from core data

2. -Release of sediment to seafloor when ice melts

3. Calculated depth of sediment layer formed from sediment in sea ice

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Figure 4-32. Concentrations of AI versus (a) Cu and (b) Or for Total Suspended Solids and Source Material Samples Collected

During August 1999

TSS samples collected during August 1999 (Northstar - red, Liberty - green, and BSMP - blue triangles). Source material sample collected during August 1999 (inverted

orange triangles), Lines show linear regression fit to sediment data with 99% prediction intervals,
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5.0 Recommendations and Phase II Plan Summary

5.1 Recommendations

Based on the results and preliminary interpretation and discussion of the samples collected from

the summer 1999 and winter 2000 field programs, there are a number ofrecommendations for

future ANIMIDA Phase IT studies. The preliminary recommendations provided here focus on the

sediment, suspended sediment, and biota sampling and analysis components ofthe ANlMIDA

program. Subsequent recommendations related to the overall ANIMIDA Phase IT program tasks

are included in the Phase IT Plan Summary.

• Collect sediment cores at selected stations to further evaluate historical trends in

hydrocarbon and metal concentrations, and determine rates of sediment accumulation in

the study area

• Perform replicate sampling at stations 5D, 5£, L08, and 5(10) (or adjacent sampling at new

stations) to confirm contamination observed in the 1999 sediments

• Focus efforts on collection of tissue samples (clams and amphipods) to increase overall

replication and power of intetpretation (collect additional Astarte near Liberty)

• Obtain additional data on sediment transport pathways through targe~ aerial photography

and/or satellite photos

• Analyze additional source samples, including field oils from different production

wells/formations, additional river sediment samples, and coal formations

• Analyze all future sediment and tissue samples for SITs

• Analyze several historical 1989 BSMP sediments for QCcomparisons

5.2 Phase II Plan Summary

Phase IT of the ANIMIDA program commenced with the 2000 summer program and will

continue through FY 2004. The recommendations for the Phase IT effort began to evolve at the

ANIMIDA Phase I program's annual meeting in October 1999, when a draft, "strawman" plan

was discussed. Subsequent discussions with the SRB and :MMS led to the issuance of Requests

for Proposals (RFPs) for eight different tasks. :MMS added a new objective (with additional

funding) for Phase ll. This objective is to identify multiple and cumulative exposures to

anthropogenic contaminants in the study area per Executive Order 12988 on Environmental

Justice. For the Beaufort Sea coastal environment, regionally prioritized contaminants of

concern are persistent organic pollutants (POPs) and trace metals. This section summarizes the

statements of work for the eight tasks (the recommendations for the Phase IT program).

Additional refinements, stemming from actual field experience and comments received at the

Annual Program Meeting held in October 2000 (and subsequent annual meetings), are

u:mms animidalphasel report\final report files\final section 5.doc 5.1
anticipated. The background and objectives of the eight proposed Phase IT Task Orders are

presented below.

Provide for ANIMIDA Program Coordination: Task Order 001: "The Arctic Nearshore

Impact Monitoring In the Development Area (ANIMIDA) Program (Phase II) - Core '

Contractor Program Management, Logistics, Database, and Reporting"

The Phase IT work will involve a number of tasks. Recommendations made by ADL and

endorsed by MMS included work by a "core contractor" to coordinate and manage logistics and

data management elements. This work will be accomplished during the period of FYs 2000

through 2004.

Background: Both offshore and onshore oil and gas development and production activities are

planned for the coming years at the Northstar and Liberty sites in the nearshore Beaufort Sea.

Coastal indigenous peoples are concerned about the long-term effects of these developments, as

well as long-term effects of any development associated with offshore lease sales. Historical data

in the region have been collected over several decades. However, the sensitivity of the r~gion

adjacent to Northstar and Liberty, and the highly variable and complex environmental conditions,

make further monitoring necessary. In response to interagency reviews ofrelated EISs aJ?d

development and production plans, the ANIMIDA Phase I program was initiated as a

comprehensive long-term program for monitoring potential impacts of Northstar and Liberty.

ANIMIDA Phase I was started in June 1999, and will continue into FY 2001. During Phase I,

chemistry and acoustic measurements were made during August 1999 and April 2000 near both

the Northstar and Liberty sites.

Objectives: The ANIMIDA Phase IT Core Contractor Support Task is intended to provide overall

program management and logistics supportfor future tasks associated with Phase IT of the

ANIMIDA program. '

The specific objectives of the core contractor will include:

1. Provide annual updates to the ANIMIDf\, Phase I literature review.

I

2. Provide logistics support and field personnel for future Phasell field programs, including

coordination of field activities, communications, transportation, and proViding a skipper for

the MMS Launch 1273. !

3. Hold annual Public Workshops in October with MMS, other Phase IT contractors, thi SRB,

and other government/academic representatives. The meetings will also include provisions

for public involvement (local residents, industry, environmental and other public gro~ps,

etc.). The SRB will meet the following two days. A second two-day SRB meeting will be

assumed to take place in February each year, in Seattle. '

4. Develop and implement communication/involvement plan for North Slope residents.

u:mms animida\phase I report\final report files\final section S.llee 5-2 •

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5. Develop Phase II database design and analysis tools, import fOlms and metadata source file

and integrate with the MMS CORIS database.

6. Overall Phase II program management, including program management plan, data

management plan, coordination of Phase II contractors, presentation slides, and quarterly

progress reports.

7. Prepare annual Phase nreports, including annual reports, final report, technical summary,

and journal article.

8. Compile individual task reports into single annual or final report, adding introduction and

executive summary.

9. Provide draft annual or draft final reports to SRB and Contracting Officer's Technical

Representative (COTR) two weeks prior to annual Public Workshop. Provide revised reports

to SRB and COTR prior to annual February SRB meetings.

Continue Chemical Monitoring Effort: Task Order 002: "Hydrocarbon and Metal

Characterization of Sediments, Bivalves, and Amphipods in the ANIMIDA StUdy Area"

This work will be accomplished during the period of FYs 2000 through 2004.

Background: The MMS initiated an environmental monitoring program in the Beaufort Sea in

1984 to assess the potential area~wide or cumulative effects of gas and oil exploration and

development. The program was designed to detect and quantify long-term changes in the

concentrations of metals and hydrocarbons in sediments and animal tissues. Its design is based

on recommendations from a workshop conducted by MMS and NOAA in 1983. The initial

phase of the monitoring study was a three-year program, with field sampling and analyses taking

place in 1984, 1985, and 1986. Subsequent sampling was recommended for every third year, but

took place only in 1989. Some data are also available from a MMSlUniversity of Alaska

Fairbanks, Coastal Marine Institute (Crill) study that sampled nearshore sediment stations in the

vicinity in 1997 and from a BPXA study that sampled nine sediment stations near the proposed

Northstar Development and pipeline route in February 1999.

The sensitivity of the region adjacent to Northstar and Liberty, and the highly variable and

complex environmental conditions, make further monitoring necessary. Because current practice

is to not discharge muds, cuttings, and formation waters during development and production,

environmental concerns are shifting toward gravel-construction effects, such as may have

occurred at Endicott, and to pre-potential spill baselines. During Phase I, chemistry

measurements were made during the open-water season near the Northstar and Liberty sites, and

at BSMP stations. A winter sampling program was also conducted under Phase I to collect data

under ice-covered conditions.

u:mms animidalphase I reportlfinal report fileslfinal section 5.doc 5,.3
Objectives: This task will characterize the sediments near ongoing and proposed offshore oil

development related to potential contaminants and will serve as a continuation of the Ph~se I

organic and inorganic chemistry monitoring program. The specific objectives of the cherrustry

monitoring program include:

• Perform annual or biannual field studies (FYs 2000 to 2003) for the monitoring of:

sediment and biota chemistry in the nearshore Beaufort Sea, focusing on potential impacts

from the Northstar and Liberty developments

--......

• Coordinate chemistry monitoring with other ANIMlDA Phase II tasks (acoustics, biology,

and sediment transport), and with ANIMlDA-coordinated studies (e.g., physical

oceanography)

• Perform organic and inorganic chemical analyses that are consistent with previous'

measurements and thus capable of determining any o~served incremental impacts '

,

In addition, it is recommended that studies (i.e., sampling, analyses, and data analyses) ~e

undertaken to help interpret the findings, presented in this report, oftemporal changes (e.g.,

those changes in PAR composition - Section 4) observed to have occurred between the 1989

and 1999 samplings.

Continue Acoustic Monitoring Effort (Augment Ongoing Studies): Task Order 003:

"Baseline Acoustic Monitoring: Bowhead Whale Migration Corridor"

This work is currently under consideration for FYs 2000 through 2003.

Background: Both offshore and onshore oil and gas development and production activi~ies are

planned for the coming years at the Northstar and Liberty sites. Coastal indigenous peoples are

concerned about the long-term effects of noise and vibration on nearshore biota. Historical data

in the region have been collected over several decades. However, the highly variable and

complex environmental conditions make site-specific evaluation the most reliable and robust

approach. During Phase I, acoustic and vibration measurements were made in August 1999 and

April 2000, at locations near both the Northstar and Liberty sites. Since ANIMIDA Phase I was

initially designed, BPXA has undertaken a comprehensive noise and noise-effects monitoring

program in the study area.

Objectives: The primary objective of this task is to augment the BPXA design for acoust~c

monitoring of the bowhead migration offshore of Northstar by adding one to two seafloo~

recorder systems further offshore ofBP recorders. Task 7 of Technical Plan for Marine Mammal

and Acoustic Monitoring during Construction ofBP's Northstar Oil Development in the Alaskan

Beaufort Sea, 2000, dated August 20, 1999, presents the design for BP'sefforts.

A high degree of coordination with the BP industrial team is recommended.

u:mmsanimidalphase I report\final report files\final section 5.doc 5-4

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Monitor the Subsistence Whaling Effort: Task Order 004: "Annual Assessment of

Subsistence Bowhead'Whaling Near Cross Island" ....,

This work will be accomplished during the period of FYs 2000 through 2004.

Background: The effects that offshoredeve1opment may have on subsistence activities,

particularly bowhead whaling at and near Cross Island, are of primary concern to the Village of

Nuiqsut. Therefore, an effort should be made to monitor the subsistence whaling effort and its

success.

Objective: To provide an annual narrative report showing the subsistence bowhead Whaling

activities, resources, and harvest on and near offshore Cross Island. The effort should focus on

where whalers go and where they have strikes.

Examine the Effects of Oil Development on Suspended Particulates: Task Order 005:

"Sources, Concentrations, and Dispersion Pathways for Suspended Sediment in Areas of

Oil and Gas Development along the Coastal Beaufort Sea"

This work will be accomplished during the period of FYs 2000 through 2004.

Background: A primary concern regarding oil and gas development in the coastal Beaufort Sea

is increased turbidity during and after construction of offshore islands and pipelines. Suspended

sediment may be released from storage areas on the ice (after the ice melts), from erosion of

seafloor piles of sediment (removed from pipeline trenches) and/or from the island. Inputs of

suspended sediment from these sources could increase turbidity, decrease the amount of available

lightfor growth of marine plants, and/or increase sediment accumulation rates and thus alter

benthic habitats. However, the sources and dispersion pathways for suspended sediment are not

well d~fined and the annual contribution of suspended sediment to the study area from river

inputs is not well known. Various, limited data sets for TSS and turbidity are available for openwater periods, with less information available for ice-covered periods. One model for dispersion

of suspended matter has been run for the Liberty area. Some TSS data from Endicott waterquality monitoring are available from BPXA for inshore of the Liberty area. (Endicott currently

monitors effluent TSS, but not ambient TSS). No data on chemical signatures exist that would

help identify sources of suspended sediment The FY 1999 effort of the ANIMIDA project made

a first attempt at tracing sources of suspended sediment. Studies of upcoming activities at the

Northstar and Liberty sites provide valuable opportunities to validate present models of sediment

dispersion and to establish the spatial and temporal extent of suspended sediment dispersion.

Objectives: The overall objectives of this task is to detect changes to the quantity and quality of

suspended particulates from oil development.

u:mms animidalphase I report\final report files\finaJ section 5,doc 5-5
The specific objectives for this task are to:

1. Determine concentrations of suspended sediment at varying distances from constructionrelated deposits of gravel and related material during open-water and ice-covered periods

and as a function of time during and after construction I

2. Help validate previous models of dispersion pathways and distances for suspended

sediment in the study area.

3. Ddetermine sources of suspended sediment in the areas of the Northstar and Liberty

projects and to discriminate among various sources.

4. Ccontribute to an effort to determine the amount of sediment introduced to the coastal

Beaufort Sea from rivers

5. Use data from the Northstar and Liberty studies to predict net and cumulative chahges in

suspended sediment levels from additional offshore islands and pipelines

,

Conduct Biological Monitoring of Sensitive Habitats (i.e., the Boulder Patch area): Task

Order 006: "Monitoring the "Boulder Patch" as part of the Arctic Nearshore Impact

Monitoring In the Development Area (ANIMIDA) Program (Phase II)" , ,

This work will be accomplished during the period ofFYs 2000 through 2004.

Background: The "Boulder Patch" area in Stefansson Sound, adjacent to the proposed Liberty

development, is characterized by a diverse'arctic kelp community in patchy areas where boulder

cover greater than 10 percent is found. With the expected construction ofthe Liberty production

island adjacent to the "Boulder Patch," there is increased potential for impacts and effects on this

biological community. '

Objective: The objective of this task is to conduct a program to monitor the potential effects of

the Liberty island and pipeline construction on the Boulder Patch community. .

Examine Partitioning of Organics and Metals: Task Order 007: "Partitioning of Potential

Contaminants between Dissolved and Particulate Phases in Waters of the Coastal

Beaufort Sea"

This work will be accomplished during the period of FYs 2000 through 2003.

Background: Considerable interest has been expressed in selected metal and organic

contaminants in waters of the coastal Beaufort Sea. These contaminant metals and org~ic

substances may be particulate, colloidal, or dissolved in form, with the dissolved contaminants

generally being more biologically available. During resuspension of bottom sediments by storm

u:mms animidalphase I report\linal report filesllinal section 5.doc 5-6

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events, some contaminants may be released from sediment particles and added to the water

column, while others may be adsorbed to particles and removed from the water column. Little or

no data are available on dissolved contaminants in the coastal Beaufort Sea. No data are

available to predict and model the behavior and uptake or release of contaminants from

resuspended sediments. One ongoing MM:S CMI study, Kinetics and Mechanisms ofSlow PAH

Desorption from Lower Cook Inlet and Beaufort Sea Sediments, IS examining longer-term

kinetics (1 to 180 days) for PAH.

Objectives: The specific objectivesfor this task are the following:

1, To determine concentrations of selected metals and organic substances in dissolved and

particulate forms in waters of the coastal Beaufort Sea

2. To determine partition coefficients (particulate/dissolved) for selected metals and organic

substances in waters of the coastal Beaufort Sea

3. To determine the equilibrium kinetics for release or uptake of selected metals and organic

substances during sediment resuspension events

Evaluate the Levels of Contaminants and Biochemical Indices on Marine Organisms:

Task Order 008: "Baseline Characterization of Anthropogenic Contaminants in Biota

Associated with the Alaska OCS Liberty and Northstar Oil and Gas Production Units in

the Nearshore Beaufort Sea"

This work will be accomplished during the period ofFYs 2000 through 2003.

Background: Biomarker and contaminant analyses of marine mammals, birds, and fish provide

an opportunity to learn more about the effects of bioaccumulation of anthropogenic compounds

in Arctic food chains. Anthropogenic contaminants of Arctic concern are POPs and metals. The

POPs include polycyclic and polyhalogenated aromatic hydrocarbons and are globally

distributed. However, due to their chemical characteristics and atmospheric transport, rates of

deposition are much greater than rates of production in the Arctic. Some POPs are poorly

metabolized, and may bioaccumulate or biomagnify in tissue. Although PAHs can be

metabolized in mammal tissues, lessening their concentrations, PAH concentrations in edible

tissue are still a concern, because of subsistence use and potential local or regional oil industry or

spill sources.

Some aromatic compounds found in the Arctic induce enzyme P4501A in fish, birds, and marine

mammals. The induction of this enzyme facilitates metabolism of aromatic compounds and the

intermediate reaction products can react with cellular molecules, such as deoxyribonucleic acid

(DNA), causing cellular damage. Measurement of P4501A may proVide evidence of exposure to

these compounds, their metabolism, and the subsequent risk to induced animals. In addition,

analyses of a variety of tissues and cell types can indicate the route of uptake and exposure.

u:mms animidalphase I reportllinal report filesllinal section 5.doc 5.-7
Strandings of both beluga and pilot whales in temperate climates have shown that induc~d

cytochrome P4501Al occurs in cetacean liver. Recently a correlation was described between

hepatic CYPIA content and the content of co-planar PCBs in the blubber of beluga whales

consistent with an environmental chemical induction in these animals. The extent of such

induction in extrahepatic organs of cetaceans was not known until recently, when a variety of

tissues from stranded pilot whales were collected, analyzed, and found to have P4501 in~uction.

If correlations of P4501A induction were to be found with the concentrations of polyhalogenated

aromatic hydrocarbons in Arctic whales, seals, birds, or fish, for example, then these compounds

are the most likely proximate cause of such effects. i

Regional studies of contaminants in marine mammals in the Beaufort Sea are presently being

performed by the North Slope Borough (NSB) and by the Alaska Marine Mammal Tissue

Archival Program (AMMTAP). The USGS Biological Resource Division (BRD) has co~lected

and stored blood samples from polar bears for several years, as well as from common eiders,

oldsquaw, and nonviable eggs from common eiders in the ANIMIDA area and adjoining'

shoreline, starting in 1999.

Objectives: The objective of this task is to detect changes or impacts from oil development and

other contaminant sources.

Specific objectives include: I

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1. Determine baseline levels of anthropogenic compounds and contaminant biomarkers in

representative upper-trophic biota (e.g., whales, seals, birds, and/or fish). Include both

waterfowl (common eider and/or oldsquaw) and one or more important subsistence species.

Include at least some analyses of PAH in subsistence food (tissue).

2. Evaluate whether the concentration of contaminants and contaminant biomarkers indicates

significant risks to associated biota and/or health risks to subsistence consumers of chosen

biota.

3. Coordinate the field and analytical aspects of this task a) with the biological contaminant

studies presently being conducted by the NSB ,AMMTAP, U.S. Fish and Wildlife Service

(USFWS), and BRD and b) with community residents (Barrow and Nuiqsut) to identify

species of local subsistence interest.

4. Develop a strategy for longer-term, upper-trophic contaminant monitoring.

u:mms animidalphase I reportlfinal report fileslfinal section 5.doc 5-8

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6.0 .References

't~4, ~,. ~- ,f;J~'

Arthur D. Little, Inc. 1999a. 1999 Field Sampling and Logistics for the Minerals Management

Service ANIMIDA Field Survey. Prepared for Minerals Management Service. August.

Arthur D. Little, Inc. 1999b. Summer 1999 Cruise Report for the Minerals Management Service

ANIMIDA Field Survey. Prepared for Minerals Management Service.

Arthur D. Little, Inc. 2000a. Winter 2000 Field Sampling and Logistics for the Minerals

Management Service ANIMIDA Field Survey. Prepared for Minerals Management Service.

April.

Arthur D. Little, Inc. 2000b. Winter 2000 Field Report for the Minerals Management Service

ANIMIDA Field Survey. Prepared for Minerals Management Service.

Banet, Arthur c., Jr., 1995. A comparison of Crude Oil Chemistry on America's North Slope:

Chuckchi Sea - McKenzie Delta, BLM - Alaska Technical Report No. 16.

Bence, A.E., K.A. Kvenvolden, and M.S. Kennicutt, II. 1996. Organic Geochemistry Applied to

Environmental Assessments of Prince William Sound, Alaska, after the Exxon Valdez Oil Spill.·

Org. Geochem. 24:7-42. January.

Boehm, P.D. 1984. Aspects of the saturated hydrocarbon geochemistry of recent sediments in the

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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 historicalplaces;'·

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 intemsts of

all our people by encouraging stewardship and citizen participation in their care. The Department

also has a major responsibility for American Indian reservation 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 reSOUrCE!S. 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 concems 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 envirOnml:lntal

protection.
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