OCS Study MMS 2004-024

ANIMIDA Task 2

Hydrocarbon and Metal Characterizatilon of

Sediments, Bivalves and Amphipods lin the

ANIMIDA Study Area

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Submitted by:

Exponent

2 Clock Tower Place, Suite 340

Maynard, Massachusetts

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. Contract No.t43501 ..99~CT ..30998,TO 1090:2:,

•• u.s. Department of the I".terior

Minerals ManagementService

Alaska Outer Continenta I Shelf Region
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ANIMIDA Task 2

Hydrocarbon and Metal Characterization

of Sediments, Bivalves and Amphipods in the

ANIMIDA Study Area

Final Report

John Brown, Principal Investigator

Exponent, Inc.

2 Clock Tower Place, Suite 340

Maynard, Massachusetts 01754

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

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

Anchorage, Alaska, under Contract No. 143501-99-CT-30998, TO 10902

as part ofthe MMS Alaska Environmental Studies Program.

July 2005

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

are those ofthe authors and do not necessarily reflect the views ofthe U.S. Department

ofthe Interior, nor does mention oftrade names or commercial products constitute endorsement

or recommendation for use by the Federal Government.
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Mr. John Brown, Exponent

Dr. Paul Boehm, Exponent

Ms. Linda Cook, Exponent .

Dr. John Trefry, Florida Institute ofTechnology (FIT)

Dr. Woollcott Smith, Temple University

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Table of Contents

List of Tables iv

List of Figures vi

List of Acronyms and Abbreviations : ix

Executive Summary ES-1

1.0 Introduction 1-1

1.1 Study Area 1-1

1.2 Development History in the Study Area 1-2

1.3 Current/Proposed Oil Development.. 1-2

1.3.1 Northstar : 1-2

1.3.2 Liberty 1-3,

1.4 Potential Contaminants and Disturbances ofConcern 1-3

1.5 Study Objectives 1-4

1.5.1 Task Order 2 Research Questions and Hypotheses 1-5

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 2000 Field Sampling 2-2

2.1.3 Summer 2002 Field Sampling 2-3

2.1.4 Field Sampling Procedures 2-4

2.2 Analytical Methods 2-7

2.2.1 Ancillary Parameters 2-7

2.2.1.1 Grain Size 2-7

2.2.1.2 Total Organic Carbon 2-7

2.2.2 Organic Chemical Parameters 2-8

2.2.2.1 Sample Preparation ; 2-8

2.2.2.2 Organic Instrumental Analysis 2-11

2.2.3 Inorganic Parameters 2-13

.2.2.3.1 Trace and Major Metals Analysis in Surficial Sediment.2-13

2.2.3.2 Trace and Major Metals Analysis in Organism Tissue 2-14

2.3 Quality Assurance/Quality Control 2-15

2.3.1 Quality Assurance 2-15

2.3.1.1 Dodumentation 2-15

2.3.1.2 Quality Management.. '2-15

2.3.1.3 Sample Custody, Preservation, and Tracking 2-16

2.3.2 Field QualityControl 2-18

2.3.2.1 Sample Handling 2-18

2.3.2.2 Quality Control Samples , 2-18

2.3.2.3 Documentation 2-19

2.3.3 Organic Chemistry Laboratory QualityControl.. 2-19

2.3.3.1 Data Quality Objectives and Quality Control Samples 2-19

2.3.3.2 Laboratory Records 2-21

2.3.3.3 Laboratory Data Review 2-21

2.3.4 Metals Chemistry Laboratory Quality Control : 2-21

2.4 Statistical Methods 2-23

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2.5 Database Management 2-24

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4.0

Results ' 3-1

3.1 Surficial Sediments (0-1 em) : 3-1

3.1.1. General Chemical and Physical Measurements 3-1

3.1.2 Organics 3-2

3.1.2.1 Saturated Hydrocarbons 3-2

3.1.2.2 Polynuclear Aromatic Hydrocarbons 3-3

3.1.2.3 Steranes and Triterpanes 3-4

3.1.3 Metals 3-4

3.1.4 Statistical Results - Organics 3-5

3.2 Tissues 3-6

3.2.1 Organics 3-6

3.2.2 Metals 3-6

3.3 Caged Mussel and SPMD Results 3-7

3.3.1 Caged Musse,ls 3-7

3.3.1.1 Organics 3-7

3.3.1.2 Metals 3-8

3.3.2 SPMDs 3-9

3.4 Quality Control Results 3-10

3.4.1 Field QualityControl 3-10

3.4.1.1 Equipment Blanks 3-10

3.4.1.2 Field Blanks 3-11

3.4.1.3 Field Replicates 3-11

3.4.2 Organics Quality Control 3-12

3.4.2.1 Surrogate Results 3-12

3.4.2.2 Procedural Blanks 3-13 -

3.4.2.3 Blank Spike Sample Recoveries 3-14

3.4.2.4 Laboratory Duplicates 3-14

3.4.2.5 Standard Reference Materials 3-15

3.4.2.6 Control Oil Analyses 3-16

3.4.3 Metals Laboratory Quality ControL 3-16

3.4.3.1 Procedural Blanks 3-16

3.4.3.2 Matrix Spike Sample 3-16

3.4.3.3 Lab~ratory Duplicates 3-16

3.4.3.4 Standard Reference Materials 3-17

Discussion 4-1

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

4.1.1 Grain Size : " 4-1

4.1.2 Organics (Hydrocarbons) 4-2

4.1.2.1 Hydrocarbon Sources .4-2

4.1.2.2 Sediment Quality Guidelines 4-6

4.1.2.3 Temporal and Spatial Trends 4-7

4.1.3 Metals 4-11

4.1.3.1 Sediment Quality Guidelines .4-13

4.1.3.2 Temporal Distribution of Sediment Metals 4-14

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4.2 Hydrocarbons and Metals in Organisms .4-17

4.2.1 Organics (Hydrocarbons) 4-17

4.2.2 Metals 4-18

4.3 Caged Mussels and SPMDs : 4-20

4.3.1 SPMDs ; 4-20

4.3.2 Caged Mussels 4-20

4.3.1.1 Organics : 4-20

4.3.1.2 Metals 4-21

5.0 Recommendations 5-1

6.0 References 6-1

List of Appendices

Appendix A: Grain Size and Total Organic Carbon Data

Appendix B: Organics Data

Appendix C: Metals Data

Appendix D: Field Reports

Appendix E: Journal Article

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Section 1

Table 1-1:

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 3-2:

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:

Alaska North Slope Oil and Gas Past Development and Production

MMS ANIMIDA Summer 2000 Sampling Stations

MMS ANIMIDA Summer 2002 Sampling Stations

Saturated Hydrocarbons Target List

Polynuclear Aromatic Hydrocarbon and Alkyl Polynuclear Aromatic

Hydrocarbon Target List

Sterane and Triterpane'Target List

Summary ofInstrumental Methods and Method Detection Limits for Metal

Analysis of Sediment and Organisms

Sample Containers, Preservation, and Laboratory List ,

Data Quality Objectives for SHC and Polynuclear Aromatic Hydrocarbon I

Analyses

Data Quality Objectives for SIT Analyses

Data Quality Objectives Criteria for Metals Analyses

Summary Data for Metal$, Total Organic Carbon (TOC), and Grain Size in

Sediment from the Coastal Beaufort Sea

Map Showing Beaufort Sea Monitoring Program Sampling Stations and Table of

Concentrations for Selected Organic Parameters and Grain Size in Sediment

Samples

Map Showing Northstar Sampling Stations and Table ofConcentrations 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 ofSaturated Hydrocarbons, Polynuclear

Aromatic Hydrocarbons, and Steranes and Triterpanes

Average Total Organic Parameter Concentrations in Surficial Sediments from

ANIMIDA Study Area, Alaska Marine Sediments, and Cook Inlet and Shelikof

Strait Sediments

Map ofBeaufort Sea Monitoring Program Sampling Stations and Table of

Concentrations of Selected Metals in Sediment Samples

Map ofNorthstar Sampling Stations and Table ofConcentrations for Selected

Metals in Sediment Samples

Map of Liberty Sampling Stations and Table ofConcentrations of Selected Metals

in Sediment Samples

Statistical Model Result Summary with Silt + Clay Covariate,

Statistical Model Re$ult Summary with Perylene Covariate

Statistical Model Result Summary with Aluminum Covariate

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Table 3-15:

Table 3-16:

Table 3-17:

Table 3-18:

Table 3-19:

Table 3-20:

Table 3-21:

Table 3-22:

Table 3-23:

Table 3-24:

Table 3-25:

Table 3-26:

Table 3-27:

Section 4

Table 4-1:

Table 4-2:

Map of Sampling Stations for Organisms with Table ofConcentrations for

Selected Organic Parameters

Map of Sampling Stations for Organisms and Table ofConcentrations for

Selected Metals (Cd, Cu, Hg, and Pb)

Map of Sampling Stations for Organisms and Table ofConcentrations for

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

Map of Sampling Stations for SPMDs and Caged Mussels and Table of

Concentrations for Selected Organic Parameters

Map of Sampling Stations for Caged Mussels and Table ofConcentrations for

Selected Metals on a Dry-Weight Basis

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 Al1alyses

SRMResults for Sediment Metal Analyses: MESS-2 and 1643d

SRM Results for Tissue Metal Analyses: 2976, DORM-2 and l643d

'SRM Results for Particulate and Dissolved Metal Analyses: 2704, MESS-2,

CASS-3 and SLRS-3 . .

SRM Results for Sediment Metal Analyses: MESS-2 and 1643d

SRM Results for Tissue Metal Analyses: 2976, DORM-2 and 1643d

SRM Results for Particulate and Dissolved Metal Analyses: 2704, MESS-2,

CASS-3 and SLRS-3

Values for the Effects Range Low (ERL) and Effects Range Median (ERM) from

Long et al. (1995) and Study Results

Summary ofResults for Metal/AI Ratios and Related Coefficients ofVariation

(CV) in Sediment Cores

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. Figure 4-1: Map identifies Northstar sampling sites and histograms show grain size

distribution as percent gravel (black bar), sand (red bar), silt (green bar) and clay

(yellow bar) for sediment 'samples collected during 1999 and 2000

Figure 4-2: Map identifies Northstar ~ampling sites and histograms show ~ain size

distribution as percent gravel (black bar), sand (red bar), silt (green bar) and clay

(yellow bar) for sediment samples collected during 2002 and 2000

Figure 4-3: Map identifies Liberty safupling sites and histograms show grain size distribution

as percent gravel (black bar), sand (red bar), silt (green bar) and clay (yellow bar)

for sediment samples collected during 1999 and 2000

Figure 4-4: North Slope Crude Oil- GC/FID Chromatogram (top), PAH Distribution

Histogram (middle), Triterpane Ion Chromatogram (bottom)

Figure 4-5: Northstar Oil- GC/FID Chromatogram (top), PAH Distribution Histogram

(middle), Triterpane Ion Chromatogram (bottom)

Figure 4-6: Colville River Sediment, Year 1999 - GC/FID Chromatogram (top), PAH

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

Figure 4-7: Northstar Station 6 Sedim,ent, Year 1999 - GC/FID Chromatogram (top), PAH

Distribution Histogram (fi?iddle), Triterpane Ion Chromatogram (bottom)

Map ofthe ANIMIDA Study Area

General Map ofOnshore ~nd Offshore Oil and Gas Development in the Study

Areas

Schematic of~P's Northstar Development

Map ofNorthstar 2000 Sampling Stations with Grain-Size Histograms

Grain-Size Hist<;>grams for Northstar 20q2 Sampling Stations

Map of Liberty 2000 Sampling Stations and Grain-Size Histograms

Grain-Size Histograms for Liberty 2002 Sampling Stations

Concentrations ofAl versUs Silt + Clay for Surficial Sediment Samples from

Beaufort Sea Monitoring Program, Northstar, and Liberty Stations

Concentrations ofAl vershs (a) Fe and (b)V for Surficial Sediment Samples from

the 1999,2000,2001 and 2002 Sampling Surveys

Summer 2000 and 2002 Sampling Stations

Schematic ofthe Mussel Cage and SPMD Mooring String

Section 2

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Section 3

Section 4

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Figure 4-8: Liberty Station 6 Sediment, Year 1999 - GC/FID Chromatogram (top), PAH

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

Figure 4-9: Station 3A Sediment, Year 1999 - GCIFID Chromatogram (top), PAH

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

Figure 4-10: Station L08 Sediment, Year 1999 - GCIFID Chromatogram (top), PAH

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

Figure 4-11: Station 5D Sediment, Year 1999 GC/FID Chromatogram (top), PAH

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

Figure 4-12: Northstar Station N06 Sediment, Year 2000 - GCIFID Chromatogram (top), PAH

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

Figure 4-13: Liberty Station L08 (Rep 3) Sediment, Year 2000 - GCIFID Chromatogram (top),

PAH Distribution Histogram (middle), Triterpane Ion Chromatogram (bottom)

Figure 4-14: Northstar Station N06 Sediment, Year 2002 - GCIFID Chromatogram (top), PAH

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

Figure 4-15: Canning River Sediment, Year 2002 - GCIFID Chromatogram (top), PAH

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

Figure 4-16: Scatterplot of Silt + Clay Results versus Total Polynuclear Aromatic

Hydrocarbons Less Perylene for Northstar Surficial Sediment Samples in 1999,

2000, and 2002

Figure 4-17: Total Polynuclear Aromatic Hydrocarbon less Perylene Concentrations

normalized to Fines for all 1999,2000, and 2002 Northstar stations

Figure 4-18: Pyrogenic:Petrogenic Ratios ofNorthstar Surficial Sediment Samples for 1999,

2000, and 2002

Figure 4-19: Double Ratio Source Plot ofC2D/C2P vs C3D/C3P for BSMP, Liberty,

Northstar, and River Sediment Samples for 1999, 2000, and 2002

Figure 4-20: Double Ratio Source PiotofS25/S28 vs T21/T22 for BSMP, Liberty, Northstar,

and River Sediment Samples for 1999, 2000, and 2002

Figure 4-21: Regression Plot ofTotal PAHless Perylene versus Silt + Clay for all 1999, 2000,

and 2002 Northstar, Liberty and BSMP Sediments

Figure 4-22: Regression Plot ofTotal PAH less Perylene versus Silt + Clay for all 1999, 2000,

and 2002 Northstar, Liberty and BSMP Sediments

Figure 4-23: Regression Plot ofLN Total PAH less Perylene versus Perylene for all 2000 and

2002 Northstar, Liberty and BSMP Sediments

Figure 4-24: Comparison ofRegional i999, 2000, and 2002 Total Polynuclear Aromatic

Hydrocarbon Concentrations to Sediment Quality Criteria Effects Range-Low and

Effects Range-Medium Values (Long et aI., 1995)

Figure 4-25: Concentrations of aluminum versus (a) chromium and (b) copper for sediment

. from the ANIMIDA study area

Figure 4-26: Concentrations of aluminum versus (a) nickel and (b) lead for sediment from the

ANIMIDA study area

Figure 4-27: Concentrations of aluminum versus (a) barium and (b) zinc for sediment from the

ANIMIDA study area

Figure 4-28: Concentrations of aluminum versus (a) mercury and (b) cadmium for sediment

from the ANIMIDA study area

Figure 4-29: Concentrations of aluminum vs. lead in sediment

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Figure 4-30: Vertical profiles for activities of excess 210Pb, total 21 0Pb and I37CS for sediment

cores from sites in Prudhoe Bay (PI), near Endicott development (E1) and on the

Colville River delta (6G)

Figure 4-31: Vertical profiles for concentrations and ratios to Al in sediment core from

Prudhoe Bay (station PI) for Fe and AI, Ba, Pb, Cr, V, Zn, As, total organic

carbon (TOC), and Mn

Figure 4-32: Vertical profiles for concentrations and ratios to Al in sediment core from Colville

River delta (station 6G) for Fe and AI, Ba, Pb, Cr, V, Co, Ni, Mn, and total

organic carbon (TOC)

Figure 4-33: Station 3A Astarte sp. Tissue, Year 1999 - GC/FID Chromatogram (top), PAH

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

Figure 4-34: Station 3A Astarte sp. Tissue, Year 2000 - GC/FID Chromatdgram (top), PAH

Distribution Histogram (middle), Triterpane Ion Chromatogra,m (bottom)

Figure 4-35: Station 3A Astarte sp. Tissue, Year 2002 GC/FID Chromatogram (top), PAH

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

Figure 4-36: Total Polynuclear Aromatic Hydrocarbon Less Perylene Concentrations of

Bivalves and Amphipods for BSMP, Liberty and Northstar Stations in 1999,

2000, and 2002

Figure 4-37: Mean concentrations (± standard deviation) ofBa, Cd, Cu, Pb, V and Zn in'

amphipods (Anonyx) collected from sites in the BSMP during 1986, 1989 and for

ANIMIDA during 1999,2000 and 2002. .

Figure 4-38: Mean concentrations (± standard deviation) ofAg, AI, As, Be, Co and Fe in

amphipods (Anonyx) collected for ANIMIDA during 1999, 2000 and 2002

Figure 4-39: Mean concentrations (± standard deviation) ofHg, Mn, Sb and TI in amphipods

(Anonyx) collected for ANIMIDA during 1999, 2000 and 2002

Figure 4-40: Mean concentrations (± standard deviation) ofBa, Cd, Cu, Pb, V and Zn in clams

(Astarte) collected from sites in the BSMP during 1986, 1989 and for ANIMIDA

during 1999,2000 and 2002

Figure 4-41: Mean concentrations (± standard deviation) ofAg, AI, As, Be, Co and Fe in clams

(Astarte) collected for ANIMIDA during 1999, 2000 and 2002

Figure 4-42: Mean concentrations (± standard deviation) ofHg, Mn, Sb and TI in clams

(Astarte) collected for ANIMIDA during 1999 and 2000

Figure 4-43: SPMD PAH Distribution Histograms, Northstar SPMDs (top), Reference SPMDs

(middle), Field Blank SPMDs (bottom)

Figure 4-44: Mussel I'AH Distribution Histograms, Northstar Mussels (top), Reference

Mussels (middle), Pre-Deployment Blank Mussels (bottom)

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Executive Summary

OVERVIEW

The Arctic Nearshore Impact Monitoring in the Development Area (ANIMIDA) Program was

designed to assess potential environmental contaminant inputs from oil and gas developments in

the Beaufort Sea, namely the Northstar and Liberty developments. The Phase I Report (Boehm et

a1. 2001b) presented the initial findings on the ANIMIDA Program associated with the pre-:-

Northstar construction environment. Based on Phase I results, several tasks were recommended

for implementation in Phase II and accepted by Minerals Management Service (MMS). The tasks

included Task 2- Continue Chemical Monitoring Effort: "Hydrocarbon and Metal

Characterization of Sediments, Bivalves and Amphipods in the ANIMIDA Study Area. The

resulting information from Task 2 will be used to:

• Assess environmental conditions prior to Northstar and Liberty oil development and

production activities,

• Monitor temporal and spatial changes in sediment and biota chemistry associated with

Northstar and Liberty oil development and production activities, and

• Provide information needed in post-leasing decisions to help minimize these changes. I

Phase II - Task 2 sampling activities began during the summer of2000 and were completed

during the summer of 2003. The associated Task 2 findings for the summerfield sampling

programs conducted in 1999 (Phase I), 2,000, 2001, and 2002 are reported and discussed in this

report. For Task 2, data were acquired on surficial sediments, riverine sediments and peat, biota

(clams and amphipods), semi-permeable membrane devices (SPMDs), caged mussels, and

sediment cores in the ANIMIDA study area. The results and discussion associated with the

sediment core program (2001 field program) are contained in a separate MMS Report (Brown, et

aI., 2003) and briefly addressed in this report.

Phase II was designed to monitor the spatial and temporal shifts in chemical parameters

associated with the construction and operation ofthe Northstar and Liberty developments.

Northstar construction began in late 1999, island construction was completed in early 2000, and

the first Northstar oil was produced at the end of2001. The Liberty development was delayed by

British Petroleum Exploration Alaska (BPXA) and has not been restarted as:ofthis writing.

Organic and metal parameters were anal~zed to investigate the hypothesis that there was a shift

in these parameters associated with the island construction and oil productio).1 activities at

Northstar. The summer 1999 survey data represent pre-construction activities at Liberty and

Northstar, the summer 2000 and 2001 survey data represent post-construction, pre-production

measurements at Northstar and additional pre-constructionmeasurements at'Liberty, and the

summer 2002 survey data represent post~construction, and ongoing production measurements at

Northstar and additional pre-constructioJ). measurements at Liberty. Thus, the data collected and

the results reported here represent the monitoring ofthe Northstar development during the

construction ofthe gravel island, pipeline, and facility; the monitoring ofthd Northstar

development during continued oil production; and continued pre-construction monitoring at the

Liberty prospect area.

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OBJECTIVES

The ANIMIDA Program was designed to address a series ofscientific questions concerning the

potential for shifts in environmental chemistry parameters associated with the Northstar and

Liberty developments. Each question can then be turned into a testable hypothesis, which guides

the design ofthe technical program. The key questions, which drive Task 2 ofANIMIDA, are as

follows:

Question 1. What are the background levels of chemicals of concern (i.e., the organic and trace

metal contaminants) that are known to be associated with historic oil exploration, development,

and production activities, and do,the concentrations ofthese chemicals increase as a result ofthe

Northstar and Liberty developments? '

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

as a result ofthe Northstar and Libertydevelopments, do these increases pose an ecological

"threat" or "risk"?

Task 2 addresses the first question and Task 2 along with two additional ANIMIDA Tasks (Task

6 and Task 8) are needed collectively to address the second question.

To provide the data needed to address these questions, the specific objectives ofTask 2 include:

• Perfonn annual field studies'(Fiscal Years[FYs] 1999 - 2002) to monitor sediment and/or

biota chemistry in the nearshore Bt1aufort Sea, focusing on potential contaminant inputs

from the Northstar development.

• Coordinate chemistry monitoring coupled with other ANIMIDA Phase II tasks (biology,

, sediment transport), and with ANIMIDA~coordinated studies (e.g.; physical

oceanography).

• Perfonn organic and inorganic chemical analyses and analysis of data to document any

incremental input of contaminants. ,~

It is an explicit goal ofthe ANIMIDA Pf>ogram to examin,e temporal and spatil;ll changes and to

detennine if any observed changes in concentration and/or composition are related to the

Northstar development. '

ANIMIDA TASK 2 STUDY DESIGN

To meet the objectives ofthe ANIMIDA program, the study design ofTask 2 focused on

measuring those parameters that would be leading indicators of, or related to environmental

contaminant inputs from the Northstar and Liberty oil development projects.' The elements of

primary focus included:

• Hydrocarbons and associate polycyclic aromatic hydrocarbons (PAHs), and metals as

primary contaminants of concern

• Sediment contamination

• Bioaccumulation of contaminants

• Other natural and anthropogenic sources of chemicals of concern

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The study design for Phase II built on the Phase I design (Boehm et al. 2001b) and 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 ofthe MMS

Beaufort Sea Monitoring Program (BSMP; Boehm et al. 1991)

• Location and sampling ofreference stations

• Identification ofsource samples for collection (e.g. river sediments)

• Addition of Phase II sampling stations along the pipeline route.

FINDINGS

Sediments

As part ofANIMIDA Phase II, surficial sediment samples were collected from the ANIMIDA

study area during the summers of 2000 and 2002 and sediment core sampleswere collected

during the summer of2001. All samples were analyzed for PAH, saturated hydrocarbons (SHC),

steranes/triterpanes (SIT), metals, grain size, and total organic carbon (TOC). The sediment core

samples were also analyzed for radionuclides for age-dating. This report also presents surficial

sediment sample data collected in the 1980's 'as part ofthe BSMP (Boehm et al. 1991) and in

1999 as part ofANIMIDA Phase I (Boehm et al. 200th).

Sediment Characteristics. Comparison of grain size data from 1999 with data from 2000 shows

some inter-annual shifts in the texture ofsurficial sediment throughout the study area as well as

some possible influences from Northstar Island. The largest changes in grain size distribution

occurred at nearshore stations, landward ofNorthstar Island. During 1999, surficial sediment at

stations NII-NI4 was essentially all sand and gravel. In contrast, the 2000 samples were

dominated by silt and clay (Figure 1). Although the exact mechanism for this shift is unknown,

the 1999 samples were collected after a ~~day storm with winds >25 knots that may have eroded

away finer-grained material. No such storms preceded collection ofthe 2000 samples that

probably contained finer-grained material carried in by the Kuparuk River during the spring of

2000. At stations N06 and NI0 (Figure D, both close to Northstar Island, much finer-grained

particles were collected during 1999 than 2000, possibly resulting from inputs of coarser material

at these sites in association with construction ofthe island. Most importantly, Figure 1 depicts

the marked patchiness in sediment composition and the spatial and temporal variability of

sediment in the area.

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versus 1999 with data from Northstar area (circles) Liberty Prospect (squares) and, adjacent

areas (triangles).

The largest changes in grain size distribution observed during this study occurred between 1999

and 2000. Differences in grain size distribution between the 2000 and 2002 sampling are less

than observed between 1999 and 2000.

The most important finding derived from. the grain size data is that sediments in many locations

throughout the ANIMIDA study area are regularly shifting and that the sedirrtentgrain sizes

found during one year may shift prior to sampling during'a subsequent year.. Thus, techniques

that normalize sediment chemistry to account for differences in grain size n~ed to be used.

Hydrocarbons. In contrast to a crude oil composition (Figure 2), the surficialsediments in the

Northstar area and indeed for the whole region (e.g., Figure 3) exhibit a mix~e of primarily

terrestrial biogenic hydrocarbons and lower levels of petroleum hydrocarbons. This assemblage

is clearly dominated by plant wax normal (i.e., straight-chain) alkanes in the,n-C27 through nC33 carbon range. This is further demonstrated by carbon preference index (CPI) values that

range from two to seven for most samples, which is characteristic ofsediments influenced by

terrigenous plant inputs (Wakeham and Carpenter, 1976; Boehm, 1984).

The PAR distributions for most ofthe surficial sediments (e.g.,Figure 3) show that the PAHs are

primarily of a combined fossil fuel origin (i.e., petroleum and coal) with a biogenic component

(perylene), and lesser contributions of pyrogenic or combustion-related compounds (e.g., 4-, 5-,

and 6-ring PARs). The petrogenic PAHs account for approximately 90 percent ofthe Total PAR

less perylene throughout the study area (Figure 4). Perylene was abundant in swncial sediments,

often the most abundant single PAH compound in the overall PAH distribut~on.

Concentrations ofhydrocarbons in the sediments adjacent to Northstar and Liberty are generally

within the observed historical range for these parameters in the overall study area. Background

concentrations ofTotal PARs (a sum of2 to 6 ringed parent and alkylated PAHs) in recent

Alaskan surficial sediment studies range from <10 parts per billion (Ppb) to ,1000 ppb. Typically

PAR profiles indicate significant levels of a fossil fuel-type'signature, which appears to be

sourced in organics shales brought to the sediments from river runoff and coastal peat. PAR

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compositional results (i.e., petrogenic PAHs vs. pyrogenic PAHs) (Figure 4), illustrate no

significant changes in PAH composition year over year related to Northstar construction and

production activities.

The observation that the Northstar 1999 sediments may be depleted in hydrocarbons relative to

the other 1999, 2000 and 2002 sediments is supported by a Total PAH less perylene versus silt +

clay regression plot for all the 1999, 2000, and 2002 sediment data. In this plot (Figure 5), the

regression and 95% prediction intervals are shown for all data. The plot shows a small cluster of

Northstar 1999 samples which are below the 95% prediction interval, indicating that these

samples are significantly lower in PAH versus silt + clay than the overall population of 1999,

2000 and 2002 samples. An analysis ofthe comparison ofthe Northstar 2000 and 2002 samples

versus the BSMP and Liberty 2000 and 2002 samples resulted in no significant difference for all

bulk hydrocarbon parameters and most ofthe diagnostic ratios. The results ofthis analysis are

illustrated by a PAH regression plot (Figure 6) which shows complete overlap between the

regression lines and 95% prediction intervals,(i.e., no.significant difference) for the Northstar,

BSMP, and Liberty sediments for 2000 and 2002. No evidence of any inputs ofNorthstarrelated petroleum hydrocarbons were observed in the surface sediments. Additionally, a

comparison ofthe Total PAH from all ANIMIDA sediments from the study region in 1999,

2000, and 2002 to the Effects Range Low (ERL) and Effects Range Median (ERM) sediment

quality guidelines reveals that none ofthe Total PAH concentrations determined in this study

exceed the guidelines.

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Trace Metals. Concentrations ofmetals in sediment help identify spatial and, temporal trends in

the distribution ofpotential anthropogenic chemicals. Fourteen metals (Ag, As, Be, Cd, Co, Cr,

Cu, Hg, Ni, Pb, Sb, tl, V and Zn - element symbols are defined in Table 2-6) were analyzed in

sediment from this study because oftheir potential as pollutants. Four othermetals (AI, Fe, Ba,

and Mn) were included in the study as indicator metals because they provide insight to sediment

composition (AI in clays and Fe in iron oxide coatings), the presence of drilling discharges (Ba

in barite, a common additive in drilling fluids), and sediment redox conditions (Mn, a redoxsensitive metal). .

A spatial patchwork in concentrations ofmetals in Sediment was ob~erved as a ftmction of

variability in the distribution ofsediment texture as described above. However, concentrations

oftrace metals generally correlated well with concentrations ofAland Fe because concentrations

ofmost metals are very low in quartz sand or carbonate shell material and much higher in finegrained, metal-bearing aluminosilicates. Anthropogenic processes rarely affect Al and Fe

concentrations because these major elements are naturally present'at percent; levels in most

sediment relative to part per million (Ppm) levels for trace metals. Thus, Al and Fe provided a

valuable normalization tool for this study that incorporated the metal-controlling variables of

grain size, organic carbon'content and mineralogy. In the ideal case, a good 'linear correlation

was observed between concentrations of a trace metal aild AI and/or Fe. Significant, positive

deviations from this linear trend helped identify metal contamination. .

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Each plot has been fit with a linear regression line and a 99% prediction interval. These plots

serve as templates for identifying past and future metal contamination. Each plot reveals a

consistent pattern ofAl versus metal for the study period. For example, the Al versus Cr plot

(Figure 7a) shows that all data points fit the 99% prediction interval very well and thus no

anthropogenic inputs ofCr to the study area were encountered. The graph for Al versus Ba

(Figure 7b) shows a reasonably good fit for most ofthe data; however, sever~l data points plot at

more than 10% above the upper prediction interval. The anomalous points were from sites

where minor inputs ofBa via'runoff from land operations or from activity atNorthstar Island or

as remnants of prior exploratory drillingmay have occurred, as explained in the report. A few

other instances ofslightly elevated levels ofHg (Figure 7c), Ag, Sb and Zn were found in a total

of-1 0 instances or only 0.8% ofthe>1200 data points for metals in sediment. Although these

various anomalies are minor, and are generally identified at low levels ofAI, they do support the

sensitivity ofAl versus Ba graphs and help identify locations where future monitoring efforts can

be focused.

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(K) and Colville (C) rivers. Data for sites identified on the graphs were not included in the regression calculations.

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Biological Samples

As part ofANIMIDA Phase II, biota samples were collected from the ANIMIDA study area

during the summers of 2000 and 2002. All samples were analyzed for PAH, SHC, SIT, and

metals. This report also presents biota sample data collected in the 1980's as part ofthe BSMP

(Boehm et al. 1991) and in 1999 as part ofANIMIDA Phase I (Boehm et aL200lb).

Hydrocarbons. As with the pre-construction (1999) data, the amphipods (Anonyx) and clams

(Astarte sp.) indicate that hydrocarbons in the sediment system are not readily bioavailable as

these species exhibit little ability to bioaccumulate saturated and aromatic hydrocarbons from

sediment or from the overlying water column. PAH levels are very low, showing consistent

concentrations of contaminants over time in the study area.

Metals. Mean concentrations ofBa, Cu, Pb, V and Zn in clams (Astarte sp.) sampled during

1986, 1989, 1999, 2000, and 2002 are relatively uniform among years. Such uniformity is

encouraging with respect to using body burdens for metals as long-term indicators ofmetal

availability. This uniformity also indicates that no detectable shifts in metal levels in Astarte

occurred between 1986 and 2000. However, the standard deviation for a given metal in an

individual year is sometimes large. Such variability limits statistical discrimination of changes in

metal levels.

Among the metals for which data are available for all five years, concentrations ofCu and Zn in

the amphipod Anonyx are highest, yet, most uniform. Levels ofthese two essential metals are

controlled by osmoregulation within the ,organism and anomalous body burdens for these metals

may imply a physiological imbalance. However, the results based on these two metals indicate

no imbalance at this time. 'Concentrations ofPb, a non-essential metal, are low, yet, reasonably

uniform. The data for 1999,2000 and 2002 for Ba, Cd, Cu, Pb, V, and Zn inAnonyx (Figure 8)

as well as the other trace metals show marked similarity among years and no influence of .

anthropogenic input from the Northstar development. Overall, the metal data for the amphipods

provide a useful baseline for monitoring shifts in concentrations over time.

SPMDs

The SPMDs from the reference site and from the Northstar site showed no significant differences

in most ofthe key PAH parameters measured. The TotalPAH concentrations in the SPMDs

were low (210 - 260 ng/g). An evaluation ofthe PAH distribution in the SP~.1D samples (Figure

9) reveals composition of primarily petroleum PAH in both the Northstar and reference SPMDs,

mixed with trace levels of pyrogenic PAH.

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The caged mussels from the Northstar and reference deployments showed no significant

differences in most ofthe key hydrocarbon parameters measured. The PAHconcentrations in

the mussels were very low (13 - 17 nglg.Total PAH), however, the concentrations were I

substantially higher than the pre-deployment reference levels indicating that the mussels

bioaccumulated trace levels ofhydrocarbons. No significant differences were observed between

. concentrations ofmetals in samples from the reference site in the coastal Beaufort Sea versus

Northstar Island.

SUMMARY

Phase II sampling efforts began with the 'summer 2000 field survey and proc~eded through the

summer of 2002. Phase I sampling was conducted during the summer of 1999. During this

period, construction ofthe Northstar Island and pipeline was completed in 2000 and production

of oil began 2001.

Overall, the results ofthe ANIMIDA Phase I and II, Task 2 effort indicated that no significant

contaminant inputs from Northstar development activities were detected and that any observed

changes in the monitored environmental 'conditions were well within the natural variability ofthe

study area. At the same time, the results; coupled to increased knowledge ofthe .chemistry of

natural sources ofhydrocarbons and metals, indicated that the monitoring and data interpretation

approaches as designed are very sensitive to changes and that ifinputs were to occur, the

measurement systems set in place would be powerful and sensitive enough t<;> detect such inputs.

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1.0 Introduction

The Outer Continental Shelf Lands Act (OCSLA) Amendments of 1978 (92 Stat. 629)

established a policy for the management of oil in the Outer Continental Shelf(OeS) and for

protection ofthe marine and coastal environments. The amendments authorize the Secretary of

the Interior to conduct studies in areas of offshore 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

initially proposed for both the Northstar and Liberty sites by British Petroleum Exploration

Alaska, Inc, (BPXA) are currently underway at Northstar and halted until further notice at

Liberty. At Northstar, the oil field was developed from a gravel island and is currently

producing oil, which is transported to land-based pipelines through a sub-sea pipeline. 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

ofInterior (USDOI), Minerals Management Service (MMS; USDOI, 2002). :

In 1998, MMS decided to conduct studies to characterize the pre-construction environment near

Northstar and Liberty and to monitor selected parameters over time as part of a long-term

program to assess potential spatial and temporal changes related to oil development and

production near both 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 specifically related to construction activities and oil

recovery and transportation via pipeline from the gravel islands to the onshore pfocessing

facilities. Thus, the overall rationale ofthe program was to establish two site-specific monitoring

efforts directed at the Northstar and Liberty developments. Priorities were placed on

characterizing the pre-construction environment and establishing a scientific basis for postconstruction and production monitoring. ,The monitoring elements included: performing

chemical analyses on sediments and selected marine biota in the area; analyzing the amount and

chemistry ofthe total suspended matter in area river and sea water; obtaining information on

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

metals); and assessing bioaccumulation in select marine biota.

1.1 Study Area

The Alaskan Beaufort Sea comprises the southern part of,the Arctic Ocean; it Hes adjacent to the

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

(600 kilometers [km]) east to the Canadian border. The Alaskan Beaufort Sea extends north'

about 200 miles (~320 km) to water depths >300 feet ('..,100 meters [m]) at 73°N. The

continental shelf ofthe Alaskan Beaufort Sea is 37 to 75 miles (60 to 121 km) wide and shallow,

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

mms animidaltask 2 final reportlfinal report fileslfinal section 1 text.doc 1-1
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(1.6 to 32 kin) ofthe coast, the Beaufort Sea is characterized by nUmerous nab-ow and low relief

barrier islands. : ' , I '

The Northstat and Liherty project areas are situated in the shallow, coastal w~ters oftHe Alaskan

Beaufort Sea (Figure 1-1). The Northstar site: (Fiigure 1-1) is seaward ofthe Barrier i~l~nds ana

the Liberty site is landward oflseveral barrier islands. The Northstar develop~ent ishirid is

located about6 miles (~1 0 krn) offshore ofPointStorkersen in the Beaufort Sea in a ~ater depth

of approximately 40 feet (~12 'In). The island was constructed partly on the r~mains of Seal

Island, whichwas built by shcill Oil Company during the 1980s (lJSAEDA, 11999). tHe

proposed Lih~rty site is about miles (~ i 0 kin) offshore in Foggy Island Ba~ or 1.5 tri~les (--2

kin) west of'fern Island, wher~ water~,depths ~re abou;t 22 ~eet (~6.7 m) (Fi8lfre 1-l)~ IThis

location is 30,miles (~50 kin) ~outheast ofthe' proposed Northstar development and 7 miles (~12

kin) from the EndicottCauseway.

1.2 Development History in ithe Study Area

Over the past three decades, numerou~ onshore and offshore oil exploration a~d deve~qpment projects have icommenced in b:oth the Alaskan and Canadian Beaufort Seas. <Dver 20:discoveries

have bee.n made, including ar~~s such asEndi~ott (an:off~hore.field in state ,aters), ,

Sagavamrktok Delta North, EI~er, and Badami. Because ofthIS past development, the

ANIMIDA study area ,is not c~nsidered to be "pristine' from a chemical pers~ective. <Dperations

to the east (i.e., in Canada) ma~ represent asource oftontaminants to the Ala~kan Beahfort Sea

and hence to the Northstar and! Liberty study ~reas. A~ overview ofthe devel~pments located in

the eastern Alaskan Beaufort Sea is presented.in Figure 1"72. '

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Since 1975, 17 gravel islands have been constructed in waters less than 50 feet (15 m) tleep in

the Alaskan Beaufort Sea for ¥ploration drilling. Mbst ofthese islands remain in sotJe fonn,'

but have been abandoned by removal of all equipinent and erosion protection) Two ofthese '

gravel islands, Seal and North~tar, arewithin the Northstar unit. Natural barrier island~ have ~lso

been used for exploration drilling acti~ities and for staging areas UJSAEDA, 1999). Tkble 1-1

summarizes p~st oil an,d gas development and,production activities in the Beahfort S~al dating

back to 1949.: ' I

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1.3.1 Northstar" , ..:. I '", I '

The BPXA Northstar development project IS located about 6 mdes (~10 kIn) l10rthwest of

Prud?oe Bay. ,While the Nortltstar Island is in stat.e w~ters, 6 to 7 wells are o~ will be'if federal

waters on the OCS. The U.S. f1.nny Corps ofEngmeers (USACE) approved the Northstar

project in May 1999 and MM~ approval followed in ~eptember 1999. North~tar is t~elfirst

offshore oil production facilit)1 in the Beaufort Sea without a causeway to shote. At this site, a

sub-sea pipeline system connects the island arid d~scovered oil to onshore probessing :dcilities.

Construction ¢fthe island wasicompleted in October 2000 and first productio~ beganll~te in

2001. Reco,verable reserves a~e estimated at 1,75 inill~on barrels ofoil. A SChellmatic 6fthe

development is shown.in Figute 1-3. , I

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Northstar Island was reconstructed from the existing gravel ofitspredecessot, Seal Island, and

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

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

system and the working surface ofthe island is surrounded by sheet piling. Drilling and . I'·

.production at Northstar has taken place on the gravel island with an above-s~awater footprint of

2 . . . . . .'.. ' about 5 acres (-0.02 km ) (URS Greiner Woodward Clyde [URSGWCJ, 1998) and a seafloor

footprint designed to be 635 feet by 970 feet (allowing for uncertainties from construction, the

footprint may be up to 835 feet by 1,170 feet). Exploration drilling had take~ pla.ce at Seal

Island dating back to the 1980s.

1.3.2 Liberty

In mid-2002, BPXA announced that they' had halted their plans to develop the Liberty Prospect

in Foggy Island Bay (Figure 1-1). Liberty Prospect is located about 6 miles bast ofthe Endicott

Project. The proposed location was adjacent to Tern Island, which was the site of exploration

drilling dating back to 1982. MMS published a final EIS report for Liberty it\2002 (USDOI,

2002). However, recent information from the oil industry has indicated that there are revitalized

plans to develop Liberty by directionally drilling from a gravel pad connected to the existing

Endicott causeway complex: This scenario would greatly reduce the development logistics and

potential environmental complexities associated with an offshore production, island and pipeline

as originally proposed. The final status ofthe Liberty Prospect development will influence the

design of any future monitoring strategies for this prospect.

1.4 Potential Contaminants and Disturbances of Concern

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

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

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

sediment inputs and resulting sedimentatton, and·3) increased levels of chemicals in the

environment that may be bioavailable.

, The majority ofwastes generated during construction and developmental drilling would consist

of drill cuttings and spent muds. Drilling fluids would be disposed through onsite injection into

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

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

would be injected into a 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!f1uids entrained in

the ice roads. Entrained contamInants from vehicle exhaust, grease, antifreeze, oil; and other

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

discharges are not expected to be major; however, they would exist over the 'life ofthe field. , .

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 end withiA a few days after construction stops.' Trenching for the

mms ahimidaltask 2 final reportlfinal report fileSlfinal Section 1 text.doc 1-3
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oil pipeline at Northstar may J1ave caused resuspensi~n of existing bottom sediments. Both island

and pipeline construction may: have resulted in incorporation ofsl,1spendedl seaiment irlto sea ice.

Research findings concerning :sources, concentrations, and dispersion pathwa~s for su~pended

sediment are presented in sep~rate reports forTask 5 and Task 7 ofthe ANlt1IDA pm~am.

!

1.5 Study Objectives

, I

The ~rimary.objectivesoftheoverall ANIM!DAprogram are to characterize land mo~ft~r the

physIcal enVIronment ofthe Northstar and LIQerty development areas to evalvate poteliltlal and

actual disturbances from these major offshore oil developments. !

,

The ANIMIDA program is being implemented in two' phases. During Phase t, chemistry

measurements were made duri'ng the open-wa,ter season near the Northstar ana Libert~ sites, and

at regional Beaufort Sea Monitoring Program:(BSMP) stations. The 1999 opbn-water sampling

represented pre-construction conditiot;ls at both the Northstar and Liberty lodtions. 'The overall

objectives of Phase I were to implement a monitoring program focused on thdse measJrements

and parameters that could be u,sed to determiIW the existence, extent, and mabitude 6£ future,

environmental disturbances from the Northstar al)d Liberty oil development *ojects. , ,

I

The plans for ,Phase II evolved from: a) consideration,ofthe early results frorrl Phase I

monitoring; b) review ofthe Program by the Scientific Review Board (SRB); land c) public

comments received at the first 'Program Workshop in October 1999 in Anchorage, Ala~ka. The

ov,erall objective for Phase II Task 2 is to characterize the sediments near ongbing and broposed

offshore oil development related to potential contaminants and to serve as a etmtinuati6n ofthe

Phase I organic and inorganic chemistry monitoring program. The specific oThjectives for Phase

II Task Order2 are listed below: I'

I

• Perform annual or biannual field studies (fiscal years [FYs] 2000 to 2003j for themonitoring

ofsediment and biota chemistry in'the nearshore Beaufort Sea, focusing dn potentihl '

contaminant inputs from tHe Northstar and Liberty developments I .

• Perform organic and inorg~nic chemical analyses that are consistent with previous

measurements and .thus capable of determining incremental changes '

• Coordinate chemistrymonitoring with other ANIMIDA Ph;:tse II tasks (biblogy and sediment

transport) and with ANIMIDA-coordinated studies (e.g., physical oceano~aphy) ,

I

The results ofthepost-'Northstar construction Phase II Task 2 sediment and biota samp,ling

survey conducted in summer 2000 indicated that no organic and metal contaniinant inJ.uts from

Northstar were detected, and that any observed changes were well within the hatural \,-Jriability.

However, some hydrocarbon and sediment grain-sizetrends were observed nJar North~tar,

which warranted further investigation in 2001 Based on these observations, Phase n Task 2

sediment core sampling program was initiated in the summer of2001 to furth~r evaluate trends

of hydrocarbons and metals in ,the historical record of-sediment cores from th~ monitoring area.

The results of.the sediment core survey are presented in a separate MMS repoh (BrowA et aI.,

2003). ' , ' i

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1.5.1 Task Order 2 Research Questions and Hypotheses

The objectives ofthe ANIMIDA program address a series ofscientific questions concerning the

potential contaminant inputs from the Northstar and Liberty developments. Each question can be

turned into a testable hypothesis, which guides the design ofthe technical program. Two pairs of

questions (Q) and candidate hypotheses (H) applicable to Task 2 surficial sediments and biota

samples follow.

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 historic oil exploration, development, and

production activities, and do the concentrations ofthese chemicals increase as a result ofthe

Northstar and/or Liberty developments?

HI a. The concentrations oforganic pollutants in sediments do not show any increase as a result

ofthe development ofthe Northstar and/or Liberty units.

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

the development ofthe Northstar and/or'Liberty units.

Q2. If concentrations of organic and/or metal pollutants do increase in the en:vironment as a

result ofthe Northstar and/or Liberty developments, do the increased concentrations 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 riskto 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 bivalves and'amphipods.

H2c. Concentrations oftrace~metalpollutants 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 bivalves and.amphipods.

Incremental variations in hydrocarbons, polynuclear aromatic hydrocarbons (PARs), and metals

will be difficult to measure because ofthe known high background levels and high variability

from natural inputs - eroded shales, coals, peat, etc. These changes can onl~ be inferred from a

strategy of: 1) low-level sensitive measurements that can detect change; 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) ofthese chemicals

and contaminants, so that sources can be:fingerprinted and in tum detected and identified in

sediments. While all ofthese elements are built into this program, it is inherently limited by the

large variability and the dynamics ofthe area, which in tum impose practical limits on the

amount ofreplication that can be accomplished for a given program budget. The bottom line is

that changes in measured parameters might only be determined by factors oftwo or more, which

mms animidaltask 2 final reportlfinal report fileslfinal section 1 text.doc 1-5
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may be the lowest statistically!significant chahge that' can be detected in pre- ~nd postdevelopment hlonitoring efforts. i I

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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 .Seglan

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

Sag Delta North Offshore Oil Offshore 1982 1989 Satellite'

Schrader Bluff Onshore Oil Onshore 1969 1991 SatelliteL.

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 Satellitej

West Beach Onshore Oil Onshore 1976 1994 Field

Cascade Onshore Oil Onshore 1993 1996 Field

West Sak Onshore Oil Onshore 1969 1998 SatelliteL.

Badami Offshore Oil Onshore 1990 1998 Field

Eider Offshore Oil Offshore 1998 1998 Satellite!

Tam Onshore Oil Onshore 1991 1999 Field

Tabasco Onshore Oil Onshore 1992 1999 Satellite..!

Midnight Onshore Oil Onshore 1998 1999 Satellite4

SuniSambucca

Alpine Onshore Oil Onshore 1994 (2000) Field

Source: USDOI, 2002.

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
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Figure 1-1. Map of the ANIMIDA Study Area
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(from: http://www.bp.com/alaska/index_nstar.htm)
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2.0 Methods

This section describes the methods used in field sampling, field meastlrements, laboratory

analyses, and data 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 Bea~fort 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 ofthe shoreline whe~e regional Prudhoe

Bay oil production activities areoccurririg. Two open-water surveys were cOJ;lducted in August

2000 and in July-August 2002 under Task Order 2 of Phase II ofthe ANIMIDA program. These

surveys included collection ofsediment and biota samples and provided post·Northstar

construction sampling which correspond,s to the pre-Northstar construction samples collected in

1999 as part ofthe Phase lfield survey described in Boehm et aI., 2001b. Caged mussels and

semi-permeable membrane devices (SPMDs) were also deployed and retrievdd during the

summer 2002 survey.

The overall design ofthe field program incorporated a sampling program using 'a combination of

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

historical BSMP stations (Figure 2.,.1 [Summer 2000 and 2002 Sampling Statibns] and Boehm,

1987). The site-specific Liberty and Northstar stations were located in four radial transects

centering on the proposed prospect sites: The radials were located at 0.5, 1, 2~ and 4 km intervals

and the transects were oriented approximately North - South and East - West; (Figure 2-1). The

radial transect orientation enables statiortcomparison spatially away from theidevelopment

islands, as well as onshore offshore st~tion comparison, and East - West station comparison to

account for the prevailing East - West currents in the region. In addition, five pipeline route

stations and four 0.5 km radial stations were added in 2000 and 2002 to enharlce the sample

station resolution for the Northstar pipeline and development island. This overall design allowed

a combination ofsite·specific stations to' be sampled for sediment and biota (tissue) chemistry.

The summer 2000 and 2002 field surveys included extensive sampling at the Northstar

development to provide sufficient data tb assess potential post-construction changes. Samples

collected at the Liberty prospect and the'majority ofthe BSMP stations serve ;as additional

baseline samples for the overall ANIMIDA program (Figure 2-1). Several oflthe BSMP stations

[SF, 5D, and 5(10)] are located within 11 km ofthe Northstar development arid BSMP station SA

is within 3 km ofNorthstar; samples collected from these stations provide additional data to

assess post-construction changes at Northstar.

The summer 2002 field survey included :deployment and retrieval of paired mussel cages and

SPMDs to further investigate the bioavailability of contaminants. Three caged mussellSPMD

moorings were deployed adjacent to Northstar and 3 moorings were deployed, in a reference

location approximately 4 km southwest of Pole Island (Figure 2-1).

mms anirnida\task 2 final report\final re~or1 files\final section 2 tcxt.doc 2-1
• Collected 11 bivalve/amphipod samples

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Samples ,

The scientific crew collected samples for chefuical analyses from the program study a~ea. The

following components were successfully completed: , I

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• Collected samples at 44 stations

15 historic BSMP stations

23 Northstar and Northstar pipeline stations !

6 Liberty stations

Collected 48 surficial sedimeJ:ltsamples (0 to 1 c~ntimeter [cm]) for hydrocarbpn and metals

chemistry (triplicates at 2 stations - stations ~08 and N13) i

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2.1.2 Summer 2000 Field S~mpling I, I

The summer 2000 field sampling waliconductedfrom August 12 to August 28, 2000. ;li'he

scientific crew, aboard the MMs Vessel 1273r.collected samples for chemi~al rnd oth~rlana~ys~s

from the program stu~y area. ,The field samp~Ing methods were conducted In fccorda~ge wIth

Arthur D. Little, Inc. (ADL)/~CF Consulting (ICF) Standard Operating Procedures (SC[>Ps). The

field sampli?g and l~~istics p~an \Arthur D.Uittle, 2000) prepared: for the sU~fner 20?,0Ifield

survey provIdes detaIled expl;matIOns ofthe field methods for sample collectIOn, eqUIpment

decontamination, and subsam'pling ofsedime&t cores. Field sampling personnbl from ~DL/ICF,

Florida Institute ofTechnology (FIT), and Applied Marine Sciences (AMS) pJrticipated in the

survey. The scientific team and ship's captai~ (Mark Mertz - TEG Ocean SerJices) conbucted .

the work on an 18-hour-a~daybasis depending ort favorable operating conditio~s. A det~iled

description oftheactivities cqnducted during ithesurvey, including a log of th~ daily act~vities, is

included in the Cruise Reporti(Arthur D. Little, 2001). A summary ofthe field samplih~

activities and methods follows in this section.:' I

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Collected 5 ~ource sediment/peat samples (4 ~iver stations)

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Delivered field sampfes to analyticallaboratofies:for appropriate analyses

Several sonre,e sample,'s were c,ollected as PartiO[;he s~,mmer survey. The sour11ce samp'les • I :.' I'" • I I collected mcluded se4Iment filiI' hydrocarbon and :metals analyses, from the SagavamrI<:tok,

Kuparuk, an~ Colville Rivers. Additionally, <?ne peat 'sample was obtained'froF the b4rik ofthe

Kuparuk River. I " , :

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compl~te'ist ofthe sampliIw stations th~t ~ere occu?ie~ and.sam~led int~elstudy af9~ is

Included In Table 2-1, Table 7-1 also prOVIdes the statIOn IdentificatIon, statIOn type, latItude

and longitude, depth, date and time ofsampli4g, and t~le type of chemical and geophys~dal

analyses for :eachsample. Figure 2~1, a m~p ~fthe A~IMIDA. study area, Shots th.e l<?~ati.ons of

the summerfOOO (ancl2002) samplmg statIoI1js. AddItional daIly survey and samphng!sfatIOn

information is included in the12000 station logs contained in the Cruise Report (Arthur:}). Little,

2001). i '

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2.1.3 Summer 2002 Field Sampling

The summer 2002 field sampling was cortducted from July 27 to August 22,2002, and coincided

with a period of expected favorable ice conditions in the program study area. IThe scientific

crew, aboard the MMS Vessel 1273, collected samples for chemical and other:artalyses from the

program study area. The field sampling methods were conducted in accordance with ADL/ICF

SOPs. The field sampling and logistics plan (ICF, 2002a) prepared for the sU~l1lner 2002 field

survey provides detailed explanations ofthe field methods for sample collection, equipment

decontamination, and subsampling ofsediment cores. Field sampling personrtel from Battelle,

FIT, and Kinnetics Laboratory (KLI) participated in the survey. The scientifi? team and ship's

captain (Mark Mertz - TEG Ocean Services) conducted the work ort a 12~ to 20~hour-a-day basis,

depending on favorable operating conditiorts. A detailed description ofthe activities conducted

during the survey, including a log ofthe:daily activities, is included in the CrJise Report (ICF,

2002b). A summary ofthe field samplin:g activities and methods follows in this sectiort.

Samples

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

following components were successfully, completed: .

• Collected samples at 43 offshore'stations

15 historic BSMP stations •

22 Northstar and Northstar 'pipeline stations

6 Liberty stations

Collected 48 surficial sediment samples (0 to 1 cm) for hydrocarbon and metals chemistry

(triplicates at 2 stations - stations 5D and N03) ,

Deployed and retrieved 6 moorings, 3 adjacent to Northstar and 3 in a reference location, each

with paired mussel cages and SPMDs

• Collected 13 bivalve/amphipod samples

Collected 11 source sediment/peat samples (5 river stations)

,

Delivered field samples to analytical laboratories for appropriate analyses

l

Several source samples were collected as part ofthe summer survey. The source samples

collected included sediment and peat for hydrocarbon and metals analyses from the

Sagavanirktok, Kuparuk, Colville, and CanningRivers. ,

,

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

included in Table 2-2. Table 2-2 also pr?vides the station identification, station type, latitude

and longitude, depth, date and time ofsampling, and the type of chemical and geophysical

analyses for each sample. Figure 2-1, a map ofthe ANIMIDA study area, sh6ws the locations of

the summer 2000 and 2002 sampling stations. Additional daily survey and sdmpling station

information is included in the 2002 statibn logs contained in the Cruise Report (ICF, 2002b).

mms ailimida\task 2 final report\final re~ort files\final section 2 text.doc 2-3
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2.1.4 Field 'Sampling Proce~dures, I

Sta~d~rd satppling p~ocedure~ were followediat each sampli~g station accordi~g to th~. field

Loglstlcs an? SamplIng Plans: for the 2000 an~ 2002 MMS Field Surveys (Artfur D. L'lttle, 2000

and ICF, 2002a). : ':

The sequence of events at each sampling station followed specific ,procedures, Idescrib?d in detail

below, including: : • i , I

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• Iden#fy station (latitu~e andJongitud~)' ' " i • Navigate to stfition position within 0.2: nautical miles (nm) radius oflocation

• Deplpy amphipod tra~sii'(as requited) : I

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• Deploy cagedimussel/~PMDmooring:(asrequired) I

• Collect sedimentand bivalves using a :modified Van·:Veen grab samplet

• Retri~ve amphipod traps (as required)! ' ' !

• Retrieve cage9 musse~/SPMDimooring(as required) ,

• Navigate to next statiqn 'I I

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Photodocum'entation, station l'ogs, and field notes were recorded dl;lring the ,field survey. The

station logs for each s~mplin9 stati~n are incl~ded.in the c~ise report~ (ArthurID. Li~l~, 2001

and ICF, 2002b). Copies oftl),ecfUlse reports; are mcluded m AppendiX D. Each statlOd log

includes a description ofthe sampling location, observations, number and type(s) ofsaWples

collected, and comments.' ! , I'

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Surficial Sediment Sampling: I

Sediment satpples were colle~ted using a modified Van-Veen grab' sampler. Drring th~

collection and handling of seqi~ent samples from the grab sampler, extreme c~re was ta~en to ,

avoid contact with metal and hydrocarbon sources. Samples were taken away from the sides or: : ii' , I,I ' the grab and metal spatulas were not used for the !trace metal samples. The grab sampl~r was

protected from stack smoke, grease drips froni wi~ches and wire, and otherpoiential airfuome

contamination during the sampling process. i • '. . I..

Sediment samples werecollee,ted from the top 1 em ofthe grab to represent recent accvmulatlOn.

Unconso~idated sediment lc~ deep was rem~ve~ fro~ th~ gr~b with a stainl.e~s-steel ~crop ,

coated With Kynar® or a Teflon® spatula. Tije swop IS 1 cm m depth to faclhtate accuJjate

collection depth .ofthe sedimept. The top 1 c~ w~s colle~ted by se~eral scoopsl of th~ ~r~b, up to

the volume reqUIred for subsa:rnples, and plac~d dlrect!y m appropriate sample contamers.

Specific subsamples Were collected from each' gr~b into individual containers ~nd store'd as

indicated in Table 2-7. ' ; I' , i

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Biota Sampling , '

Bivalve and amphipod samples were collected at selected stations as part oft4e sampling survey.

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

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

Amphipods (Anonyx spp.) were collected using Nitex® mesh~lined; Kynar®-toated 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 ofthe traps. The sardine bait was placed in an enclosed Nitex®

mesh pouch to reduce the possibility of ~ardine particles becoming entrained With the

amphipods. Multiple amphipods were collected at each sampling station to obtain enough mass

for a single sample. The target sample volume was 100 milliliter (mL) for amphipods. However

due to scarcity at some sampling stations as few as 10-12 mL of amphipods ~ere collected and

submitted as a sample. In 1999 and 20nO, the scarcity of amphipodsrelative' to previous BSMP

surveys may have been related to the lack ofice in the nearshore waters ofthe survey area.

Amphipods are known to occur in areas with ice cover, and the vast stretches :of open water

encountered during these surveys may have restricted the amphipods to areas ;of denser ice cover,

offshore ofthe survey area. During the Summer 2000 survey, only 6 amphipdd samples of

sufficient size for chemical analysis were collected. However, during the summer 2002 survey,

there was greater ice cover in the nearshore waters along with a greater abund'ance of amphipods

available for sample collection at seven selected sampling stations. Amphipods were removed

from the traps, washed with clean seawater, and placed in'a clean sieve for sorting. Any isopods . I

and non-Anonyx spp. amphipods were removed with clean forceps prior to transfer ofthe sample

into the appropriate sample container. I

Bivalve samples were collected using a modified Van-Veen grab sampler (as:in previous BSMP

collections). Multiple grabs were collected and sieved through a I 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 s~mple containers using clean forceps or

spatulas. Multiple bivalves were collected at each sampling station to obtain enough mass for a

single sample. The target sample volume was 200 mL for bivalves. Generally, 20 to 40 grabs

yielded a sufficient volume of bivalves for a single sample. Bivalves were determined to be in

good condition ifthey were alive.

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

ofresuspended river sediment and coastal surficial sediment to the study areal

,

The source samples collected included sediment and peat samples from the Sagavanirktok,

Kuparuk, Colville, and Canning (summer 2002 only) Rivers for organic and inorganic analysis.

In addition, a water sample was collected during the summer 2002 survey for:suspended

sediment (inorganics only) from the Canning River, and a biogenic surface residue sample from

an adjacent tundra pond was also collected, as a potential source sample for h~drocarbons. ,

f

mms animida\task 2 final repor1\final re~ort ,files\final section 2 text.doc 2-5
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The river sediment samples for organics analysis were collected from fine-grained surfieial

sediments (0 to 2 cm) approximately one meter from the shore using a stainles~-steel sp60n and

pre-cleaned glass sample jars. The spoon was rinsed well with isopropyl alcoHol and ri~er water

prior to use.. The sampling equipmentwas decontaminated between sample lotations b~ rinsing

with isopropyl alcohol and distilled water. Metals source samples ofriverba~ sediment were

collected using a plastic scoop and spatula. Thes~ sediment samples were pladed in plaJtic bags

(forgrain size) and ~5-mL plas~ic vials (for tr~ce metal~ and methyl mercury) ~nd then' ~tored in

coolers. At the on~sIte lab, sedIment samples for orgamc, trace metal, and methyl mercttry

analyses were frozen and the grain-size samples were refrigerated until transpdrted to HT. The

peat samples were collected in the same manlier as the sediments for organics ~nd metal's,

respectively, from the river shoreline.approximately one to two meters above tater level.

SPMD andCaged Mussel Deployment and Retrieval I

During the 2002 summer survey, SPMDs and caged mussels samples were de~loyed for

approximately 21 days and then retrieved to examine potential bioaccumulatio~ of organic

compounds from the water column.

The most significant technical difficulty during this survey was obtaining the dmssels for the

mussel cage/SPMD mooring deployment. Since the deployment ofmussels re~uired thd

collection and transport ofmussels from one part .ofthe state to the other, a Copection P~rmit

and a Fish Transport Permit were required by ADF&G. During the permit application p~ocess, it

was determined by ADF&G that a populationofinussels in Port Chatham, Alakka (Ke'lJi

Peninsula) was the only feasible source ofmussds for the program. A separateicollectiob trip to

Port Chatham (via floatplane)was arranged to meet this requirement ofthe perlnit. Thelmussel

collection was planned to coincide closely with the mooring deployments to li~it stress and

potential mortality ofthe mussels. The mussels were stored on ice and shipped by airfi:e~ght to

Deadhorse within 24 hours ofcollection. The. mussels were in very good condition upod arrival

in Deadhorse, and were slowly acclimatized with Beaufort Sea water (collected from thd end of

West Dock) over the next 24 Nours. Only two mussels died prior to deploymeqt and th~eir good

condition both before and after deployment is indicative ofthe overall technidl succes's bfthe

mussel cage/SPMD effort. .

The SPMDs and caged mussels were deployed on six moorings in the study area. Three ofthe

moorings were deployed in a cluster approximately 1.5 km to the west ofNortI1star Prodfction .

Island, and three ofthe mooring.s were deployed in a reference area cluster app~oximateIiY 4 km . I . southwest ofPole Island. The mussels and SPMDs were deployed m water depths of , I

approximately 10- 15 m with a 250-pound cement-rebar anchor, and suspenddd approkimately

1.5 m from the bottom by a subsurface float. OneSPMD cage (containing 5 individual:SiPMD

membranes [91.4 cm long filled with 0.915 g triolein, each] prepared by the licbnsed di,slributor'

EST, St. Joseph, MO) was suspended approximately 1 m from the bottom ancHor on each

mooring. 0t:\-e mussel cage, containing approximately 40 mussels (MytiZus edu'Zusltross4Zus),

was suspended at the same depth as the SPMD, but attached to mooring string ~o as not to

interfere with the SPMD. There were no surface floats on the moorings to minibize ice I

entanglement, and each mooring string had an acoustic pinger and secondary ailchor with a -100

m drag line, to aid in tetrievaL The SPMD and mussel cage moorings were de~loyed at the

beginning ofthe survey and retrieved after a minimum of 21 days exposure. Upon retri~val, the I

,

mms animida\task 2 final report\finalreport!fiIeS\tinal secti(~n 2 text.doc 2~

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mussel cages and SPMDs were all intact and in good condition. At Northstar,all ofthe 120

mussels were retrieved alive and exhibited extensive byssal thread growth. At the reference

location, only 2 ofthe 120 mussels were 'found dead and the remaining mussels were alive and

exhibited extensive byssal thread growth.

The mussels remaining after deployment ofthe moorings were taken and submitted as a predeployment mussel reference sample. A set offive SPMDs, exposed during ~ach mooring

deployment and retrieval, were collected. and submitted as a field blank SPMB.reference sample.

2.2 Analytical Methods

2.2.1 Ancillary Parameters

2.2.1.1 Grain Size

Determination of grain size followed the classic method of Folk (1974) using a combination of

wet sieving and pipette techniques~ Initially, 10 to 30 grams ofwet 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 distilled-deionized w~ter (DDW) was added to the dish, clky lumps were

broken up with a gloved finger, and the wetted sample was poured into a 200-mL glass bottle

and shaken vigorously for a few minutes:. Then the sample was poured through 2 millimeter

(mm; gravel) and 63 micrometer (~m; sand) sieves and rinsed until the water ~as clear. The

sediment on each sieve was washed intobeakers #1 and #2, respectively, allowed to settle and

the overlying, clear water was decanted.. The weighed beakers were dried at 100 to 110°C and

re-weighed.

,

The glass bottle containing the muddy water «63 ~m)wasshakenfor about l5 minutes and

gently poured into a 1,000-mL cylinder. :The cylinder was stirred vigorously ~ith a stirring rod

and a timer was started as soon as the rod was removed. Dispersant was not needed in these

samples ofmarine sediment since the mud fraction dispersed extremely well. :After 20 seconds,

20 mL ofsample was withdrawn from a,depth of20 cm using a Class A pipe*e. The pipette

sample was drained into weighed beaker #3, dried at 100 to 110°C for 24 hours, and weighed for

total silt + clay. After 2 hours and 3 minutes, 20 mL ofsample was withdrawri from a depth of

10 cm using a Class A pipette. This pipette sample was drained into weighed beaker #4, dried at

100 to 110°C for 24 hours, and weighed'for total clay. All masses were detertnined to the

nearest 0.01 g. The total mass ofsample was equal to the sum ofmasses in beakers 1 + 2 + 3(x

50). The individual percentages were caJculated as follows: j

% gravel = (beaker #1 sediment/sum) x 100%

• % sand = (beaker #2 sediment/sum) 100%

• silt = {[(50 x beaker #3) - (50 x beal,cer #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 ofthe freeze-dried sediment was placed in a 10-mL Pyrex® beaker. One

(1) mL of DDW and 2 mL of concentrated hydrochloric acid (HeI) were added to remove any

mms animida\task 2 final repot1\final report files\final section 2 text.doc 2-7
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2.2.2.1 Sample Preparation

I

~norgani~ catb?n present. The sedin:ent was d:ied at 60~C and re-weighed to determine

l

the

Increase In weIght du'e to the formatIOn of calcIUm chlondeXwater (CaChx2HkO) as a'result of

adding HCI., Then, approxim;ltely 200 to 400 milligrams (mg) of pre-treated sbdiment'tere

weighed int~ ceramic boats and combusted at, 900 degrees Celsius'(OC) in a S~imadzu®1 TOC5050A carbon system with SSM-5000A solid sampling module following the tnanufacturer's

instructions.: The total organi~ carbon (TOC):corttent ofthe sediment samples Iwas det~kined '

using a four~point calibration icurve with pure; sucrose as the standard. The TOC conc~ritrations

were corrected to account for:the increase in sediment mass following the addi~ion ofHCI. The,

calibration curve was checked every 10 samples by analyzing standardreferen~e matel:i~l (SRM)

MESS-2, a marine sediment issued by the NaFonal Research Council ofCanada (NRC)J

2.2.2 Orgar'lic Chemical Pa~ameters •

Analysis for organic l(ontamiI).ants was conducted by ADLlICF's ~nvironmental chemistry

laboratoryl. The analyses were conducted in ~cc()rd~nce with the lab.oratory's!SOPs al1d

generally followed the same Rrocedures used in prevIOus BSMP studIes (Boehm et aI., 1990).

The core organic analyses fori the sediment arid source samples were: I

;' ,:: I

Saturated hYdrocarbons (SHq) by gas chromatography/flame ionization detection (GC/IHD)

PAH by gaschromatography/mass spectrome~ry detection (GC/MS) I

Geochemical biomarkers (steranes/triterpanes: [SIT]) by GC/MS I

, •.. I .

Targeted compounds are listed in Tables 2-3, Q-4, and 2-5. This section describes the analytical'

methods that were used in pe~forming the organic chemical analyses. I , I , ,

!

I Sediment Sa,mples : . . I

The sedime~t samples were prepared using a procedure based on United State~ EnvirotIfental

Protection Agency (USEPA) Method)550A, !Ultrasonic Extraction (USEPA IP93). Tpe method

modifica~io~s inclUde, orbital shaking ofthe s~m~le i~, extraction solvent. for. 1 rour folfo:wing th~

final somcatIOn to enhance reeovery oftarget ~ontamInants. The follOWIng IS a summary ofthe'

method. I

i

I

I

. .' . . i

I During the course ofthis prqgram, the prim~ contractor ADL filed for banIaJptcy pn?trction

and was subSequently sold offby division. ICF Cons~lting purchased the environmental

cons~lting a~d laboratory d~vi,sion ofADL in ~ay 20?2. :0 avoid confusion ~nd rem~+

consIstent, tho." e laoborat.Ory wIll!be referr.ed t? thro~.g~ou.t thIS ~eport ·.as the AD.UII~F labP.. latory.

The ADLlIqF laboratory performed orgamc a,halysIs on sedIment, :SPMD, and t.ISSU~ s~fples for

the A~IMIDA program unde~ Task Order 2. )fhe ADlL SOPs :",ere adopted, aSIIs, WItH: ~o .

technIcal changes by ICF. In March 2003, ICF dosed the envIrontpentallaboratory lo?ated In

Cambridge, MA. FOlitunately; all necessary s*mple analyses for th,is program ~ere completed , f • " I j ,

prior to the close ofthe laboratory. Copies of;all SOPs and the hard-copies and electropfc

instrument files for the organic chemistry data' are archived at the ICF Consultihg office located

in Lexington', MA. : • " . I

: i"

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Approximately 30 grams (wet weight) ofthe homogenized sediment were weighed into a

Teflon® jar and dried with sodium sulfate. Another 5-gram subsample was pJaced into an

aluminum-weighing pan and heated at 105°C to a constant weight, for dry w~ight determination.

The sample was serially extracted 3,timeswith 100 mL ofmethylene chloride' and acetone (1 :I,

volume to volume [VN)), each time by sonication. Orbital shaking in the exttaction solvent for

I hour followed the final sonication.

,

The surrogates were spiked into the sample after the first addition ofsolvent and before the first

extraction. All sediment samples were spiked with "low-level" surrogates (as' defi.ned by the

laboratory SOP) because target compound concentrations in the sample were hpected to be at

trace levels.

The surrogates used were: naphthalene-d8, acenaphthene-dlO, phenanthrene-dIO, and

benzo[a]pyrene-dI2 for PAH analysis, 5~-androstane and d50~tetracosane for.8HC analysis, and

5~(H)-cholane for SIT analysis.

After extraction, samples were concentr~ted using a Kuderna-Danish (K-D) cbncentrator 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-halfwas archived in a,freezer at -20°C and the other halfptocessed through a

silica gel column as described in the Extract Fractionation subsection. '

The four source sediment samples [C,olville River (2), Sagavanirktok River (1), and Kuparuk

River(1)] and one source peat sample (Kuparuk River) were extracted and analyzed using the

same procedure as for the other sediment samples. '

Biota Samples

Approximately 20 grams wet weight oftissue (if available) was prepared for yxtraction.

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 ~sing 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 dean Teflon® centrifuge tube for digestion. The

remainder ofthe homogenate, if any, wa:s re-Iabeled and stored frozen as archived samples.

Thirty (30) mL of pre-extracted 6 Normal (N) potassium hydroxide and the surrogates were

added to each homogenized tissue sample. The surrogates used were: naphth~lene-d8,

acenaphthene-dIO, phenanthrene-dIO, and benzo[a]pyrene-dI2 for PAH analYsis, 5a-androstane

and d50-tetracosane for SHC analysis, and 5B(H)-cholane for SIT analysis. Surrogate

compounds were spiked into all tissue s,!-mples at the low-level because targef compound

concentrations in the samples were expected to be at trace levels. The contaiJ;ler was then

flushed with purified nitrogen, sealed, and allowed to digest overnight in a hot water bath at

approximately 35°C. After digestion, 30 mL of ethyl ether was addedto 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 pipette and filtered through sodium sulfate into a 250-mL K-D

mms animida\task 2 final report\final report files\final !'icction 2 text.doc 2-9
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~pparatus. The etherextraction?fthe digest kasrep~ated twice, andthe ethe~ ex~ract~ ?ombim~d m the K-D apparatus, The co~nbmed ether extract from each sample was reduced m volume to '

approximately I mL by K-D and nitrogen co~centration techniques. The extrabts werd then

exchanged to methylene chloride and an aliq~ot was removed and weighed onlan elec{T6balance

for totallipia weight determi~ations. ! " 1

The tissue sample extracts were further proce~sed in ~rder to reduce potentilal 1nterferdnces. The

extracts were loaded on a 30-~m by I-em glass chromatography column fililed IWith 10igram

alumina (activated overnight at Boac prior t¢ use) and I gram anhydrous sodium sUI~a~e.

Sample extracts, containing n'o more than 30q mg of extractable organic mater~al, were loaded

onto the alumina column and :eluted with 100imL ofmethylene chloride. The extracts kbre

concentrated to 5 mL using a :K-D concentratOr. All extracts were further redu?ed in vblhme and

exchanged ipto hexane using nitrogen evaporation. A post-alumina gravimetr~c weigh;t fas

recorded prior to further processing using a si~ica gel column, as described in the Extract

Fractionatio~ subsedion. I

I

I

The tissue s~mple data for the organic analyses are reported in Appendix B ofthis report. All

tissue sampl~ data are reporte~ on a wet weigpt bilSis. For each sample, perceJt solid ~rid

percent lipid measur~ments ate provided in Appendix'B should the wet weigh~ data nee~ to be

converted to

I'

a dry or lipid weight basis.' 'i I

I

SPMD Samples , ' ,

Prior to sample extraction, the SPMDs were t~awed ahd "cleaned" with de~iodized water and lab

wipes to remove alga~ growtH and sediment. iSPMD samples (2 ofthe 5 stripsldeploY~dl- the '

remaining 3 ,were archived for possible re-analysis) were placed into glass or ]eflonja'r~ with

100 mL of hexane (more ifn~eded to comple~elycoverthe SPMD:strips). jEa~h samp(eland

blank was spiked with surrog*te solution. AI~ ~PMI? samples were spiked ,witp "low-I;erel"

surrogates because target compound concentratiOns m the samples were expected to be at trace ; I :' .' ,I I I

levels. The surrogates used were: naphthalen~-d8, acenaphthene-dlO, phenanthrene-dIO, and

benzo[a]pyryne-dI2 for PAHanalysis, 5a~an~rostaneand d50-tetracosane for SHC an4lhis, and

5P(H)-cholane for SIT analysis. The extracti6njars were tightly capped and tHe sampl¢S were

placed on a shaker table and s,haken for 24 ho~rs. The solvent was decanted irito an Ef;IJnmeyer

flask for each sample.and the ,extraction was r~peated with an additional 50-lOb mL or:~exane

and anoth~r t4 hour shake. Twen~to 50 gral;lls ofsodium sulfate 'we~e added Ito the ~rllenmeyer flasks, SWIrled, and let set for 30 mmutes to remove water. The combmed hexane extracts were

decanted into K-D concentratOrs and concent~ated. ' I I I

,

i

Field Blank~ I I

Three field blank samples co~sisting of distillbd water: rinsate ofthe grab sampller were collected

as part ofthe project quality as,su,ranee (QA) drog,ram (one in 2000, an.d two in 2002). A,I"deck" , I '. , , I I

blank was collected each year and consisted of an empty sample jar that had been left (men on

the boat deck during sampling. The deck blarik was prepared by rinsing the jat three ticles with

appro~imate~~ 10 mL ofmeth:ylene chloride. jThe me~hylene chloride rinsates rere coN~ined '

and spIked WIth low-level SH~, PAH, and SIT sUrrogates. The field blank was extracted by a

liquid-liquid: method with mdhylene chloridej Fiield ~lanks were also spiked 'tith lowll~vel

I

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prepared for instrumental analysis without further processing.

Ex"actFracuonauon I

The sediment and tissue extracts were fractionated in order to remove potential interference and

to improve the quality ofthe analysis at trace levels. The procedure used for fractionation was

similar to that used for previous BSMPinvestigations (Boehmet aL, 1990). Brior to

fractionation, the sample extrapts were exchanged from methylene chloride to hexane under

nitrogen.

The fractionation waS performed using a, 30-cm by 1~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) and preconditioned with 30 IhL methylene chli:>ride followed by

30 mL of hexane. The sample extract (which had been verified to be lesstha* 50 mg extractable

, material per 1 mL) was loaded onto the column. The sample was eluted with i18 mL of hexane

and the isolated saturate (f1) fraction was collected. This was followed by 21 imL of

hexane:methylene chloride ( 1: 1) to isolate the aromatic 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 interilal standards, as

appropriate for each extract or fraction. In general, the extracts were concentrated to I

approximately 250 microliter (flL) before adding the internal standards in order to lower

detection limits. The internal standard c~mpounds used were: chrysene~dl2 ~nd fluorene-dIO

for PAH; chrysene-dl2 for SIT; and d62~triacontane for SHe. The amount ofSHC internal

standard added to the extracts Was adjusted to obtain a target concentration o~ 50 microgram (flg)

per mL. The amount of PAH and SIT in~ernal standard added to the extract was adjusted to

obtain a target concentration of 1 flg/mIJ.

f

2.2.2.2 Organic Instrumental Analysis

Instrumental analysis ofthe sediment, ti~sue, SPMD, and source samples included SHC by

GCIFID, PAH by GC/MS, and SIT by GC/MS. The laboratory SOPs includ6 the acceptability

criteria for the calibration, procedural bHmk, surrogate compound recoveries, 'and spike

recoveries, as well asthe corrective action ifthe criteria are not met, reporting requirements, and

method detection limit (MDL) protocols; The data quality objectives {DQO) 'for these analyses

are summarized in Section 2.3. [

Saturated Hydrocarbons by Gas Chromatography/Flame Ionization Detect~on

Analysis for SHCs was performed using'a method based on USEPA Method ~015 (USEPA

1993). Target compounds for the method are SHCs, including normal alkane,S from n-C8

through n-C40, pristane, phytane, and selected isoprenoids (Table 2~3). Instrument analysis was

performed by injection of a portion ofthe prepared sample extract onto a 30-r,n long by 0.25-mm

inner-diameter (ID) fused-silica capillary column with DB~5 bonded phase. This column

provides baseline resolution of n-alkanes from n-C8 to n-C40 and n-C17Ipristane and n- I

mms animida\task 2 final report\final report tiles\final section 2 text.doc 2-11
I

C18/phytane pairs (in the n-alkane nomenclaturen-C8 refers to a straight chaibed hydtocarbon,

eight carbons in length). The. injection port i~ designed for splitless injection dnd inchides a

silanized wide-bore glass liner containing a plug ofsilanized glass wool to redhce highmolecular-weight mass discrimination. !

Qualitative identification oftarget compounds was made by comparison to a s{andard mixture o,f

calibration standards. Quantitation ofthe analytes was based on the internal st~ndard cdmpound

(d62-triacontane), which was spiked into the sample just prior to analysis. Th~ target cdmpound

concentrations were corrected based on surrogate recovery. j

• j,- I i

Polynuclear Aromatic Hydro,carbons by Gas Chromatography/Mass Spectro'metry

Analysis forPARs was performed using a method based on USEPA Method 8~70 (USEPA I ' I

1993). The method nlodifications include analysis for an expanded list ofPAEjI (Table, 2-4) and

operation in the selected ion monitoring (SIM) mode to lower detection limits.', ,' ,

I

, I

The sample extract was inject~d onto a 30-m long by O.25-mm ID fused-silica ,capillary Folumn

with DB-5 bonded phase. This column provides baseline resolution oftarget P¥\.Rs. The

inject~o~ port is desig?ed .for ~plitless injection and i~cludes a silanize~ wide-~ore. gla.s;s I.line:

contammg a plug ofsIlamzedglass wool to reduce hIgh-molecular-weIght ma~s dIscnrpinatIon.

Qualitative identification oft~rget compounds was made by comparison to a s~andard jJixture of

target PARs. Identification of alkyl PARs was made by comparison to reference oil sal~ples

analyzed with each batch ofsamples. The concentrations ofthe individual PARs were' I

calculated relative to one ofthe two internal standards that were spiked into th~ sample just prior

to instrumental analysis. The target PAR. conc~ntra!ions were quantifie~ using laverage, rFsponse

factors (RFs) generated from the five~pomt cahbratlOn curve. To quantify the alkyl P~I:I,

homologue groups were assigned the RF oftheir respective parent'PAH comp~und. Cofnpound

concentrations were corrected based on surrogate recoveries. Total PAH condmtration kas

calculated as the sum of all target and alkyl PAR 'concentrations (Table 3-5). For som~ tlata

analyses, the Total PAR concentration was modifted to exclude perylene (a bidgenic PAiR) - in I

such as case the parameter is identified as Total PAR less perylene.

Steranes and Triterplmes

Analysis fOf'S/Ts was performed by GCIMS ih the SIM mode using a method ~imilar to that

used for PAIl analysis. Qualitative identification ofthe target SITs (Table 2-5) was made by

comparison to a reference oil analyzed with each batch. :

The concentrations ofthe ideqtified SITs were calculated versus the internal st~ndard chfYsened12. All target triterpane con6ent:a~i?ns w~re q.uantified using theaverageRFlo~ 17(H)~ 21(R)-

hopane (T23) generated from the mitIal cahbratlOn. All target sterane concent1!atlOns were

quantified using the average RF of cholestane,(S17) in the initial calibration. Surrogate ¥covery

of 5b(R)-cholane was calcula~ed relative to the intern~l standard. Compound ~oncentr~ltions

were corrected based on surrogate recovery. '

I

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2.2.3 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 antl source samples

were trace and major metals. Targeted analytes and associated MDLs are listed in Table 2-6. I

This section describes the analytical methods that were used in performing the chemical

analyses.

2.2.3.1 Trace and Major Metals Analysis in Surficial Sediment

Surficial sediment samples were initially brought to room temperature, then each wet sediment

sample was homogenized in the original }5-mL plastic vial using a Teflon® mixing rod.

Approximately 20 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 fe-weighed. In

addition, about 2 to 4 grams ofsample were transferred into polypropylene-copolymer centrifuge

tubes to determine the Hg (element symbols are defined in Table 2-6) contentiofthe sediments.

Samples intended for water content measurement were frozen, freeze-dried, apd re-weighed to

determine the water content. The dried sediment samples were again homogenized using a I

Teflon® mixing rod.

About 0.45 grams offreeze-dried, homogenized sediment and SRM sediment (MESS-2) were

totally digested in Teflon® beakers using concentrated, high-purity hydrogen itlllOride (HF)-

nitric acid (HN03)-perchloric acid (HCI04). This method was chosen because it is a total

digestion and thus accounts for the entire amount ofmetal in the sample. In the'digestion

process, I mL HCI04, I mL HN03, and 2mL HF were added to the sedimentjin 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°Cwith an additional 2 mL HN03 and 3 mL HF 1

before bringing the sample to dryness. Finally, I mL HN03 and about 30 mLi 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(element symbols are defined in Table 2-6) were

digested by heating 2 to 4 grams ofwet sediment in acid-washed, polypropylene-copolymer

centrifuge tubes with 4 mL HN03 and 2 mL sulfuric acid (H2S04).' Sample tubes were heated

for I hour in a 90°C water bath and allowed to cool. Each tube was centrifug~d 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 of20 mL with DDW.

Labware used in the digestion process was acid-washed with hot 8N HN03 andrinsed three

times with DDW. Two procedural blanks, two duplicate samples, and two SRMs were prepared

with each set of 40 samples. SRM BCSS-I (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 oy flame atomic

absorption spectrometry (FAAS), graphite furnace atomic absorption spectrometry (GFAAS;

Zeeman or Continuum background correction), cold vapor atomic absorption spectrometry

(CVAAS), or inductively coupled plasm'a!mass spectrometry (ICP/MS). Merpury concentrations

mms animida\task 2 final report\final report files\finul section 2 text.doc 2-13
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were measured by CVAAS. The method used fOf each element and the corres~Onding MDLs ate

Presented inTable 2-6. All analytical techniques followed manufacturers' speCificatidnk, '. . I ."',' ,I I I laboratory SOPs, and' the det~ils provided in Section 2.3 below. These methods are based on , .•".. I.· '. I I I

USEPA methods descnbed for Senes 7000 (F;AAS and OFAAS), Senes 7470 (CVAAS~, and

Series 6010A (ICP/MS) (USEPA'1991). .

2.2.3.2 Trace and Major Metals Analysis in :Organism Tissue

Prior to acid digestiotl, the hOPIogenized tiss~e samples received from ADLlIGF were thawed

and re-mixed with a Teflon® ,stirring rod. T~e samples were then split into twb portioht one

subsa~ple .to be digested ~~t ifor Hg and .the 9th~r to ?e fre~ze-driedand di,gesfed fo~ : I

determmatIOn ofthe temammg trace metals. ;The freeze-dned subsamples also provIded the

percent water content data needed to convert ~he fIg results from a wet-weight to dry-+Jight

basis. .

, .. ~~. i· '

~he conc~nttati?ns of all metfls (ex.cept.Hg) rere determined using 4 to 6 grams of~~tiweight

tIssue weIghed mto 100-mL glass dIgestIOn fl~sks. These subsamples were fre:eze-dned,

reweighed for percent water c,ontent, and thell digested by the sequential addition of I

concentrated, high-purityHN03, hydrogen petoxide (H20 2), and HCl with gen:be reflu~ing.

Aliquots oftissue SRMs wer~ digeste~ along ~ith theexperi~ental samples. ?nce the ,issue

samples and'SRMs w,ere completely dIssolved, the clear solutIOns were transferred to graduated

cylinders, di~uted to 20 mL wtth DDW rinses lofthe digestion flasks, and then ~tored in I!abeled

30-mL polyethylene screw-cap bottles for tra~e ~etal.analysis.

M~rcury ?eterminations we~eica~ied out tisinf5 0.4 to 0.7 grams ofw~t tissue and dry ~!}Ms i

weIghed mto 50-rnL glass dIgestIOn tubes. These subsamples were dIgested b~ the addItIon of

concentrated, high-purity HN03 and I-hS04 a*d r~fluxing at 90°C for I hour i~ the sea~~d tubes.

The dissolved samples were transferred to gra,duated cylinders, diluted to 20 rnL with l)DW ,

rinses ofthe 'digestion tubes, and then stored in labeled 30-mL polyethylene sctew-cap!Hottles for I I ' 1

Hg analysis.

Metal concentrations in the dif5ested tissue saI,npl~s, SRMs, and bl~nks were dtftermin~d by

FAAS, OFAAS (Zeeman or Continuum background correction), CVAAS, or ICP-MS.; The

metho? used fo~ each,element' and thecorresp~mdin~ MI?Ls are given in TableI2-6. Ap I . anal~Ical. techm~ues followed manufacturers specIfi~atIOns, SOPs on file at FlIT, a~d :tlie detaIls

pro~Ided m SectIon 2.3 below,. These .method:s alie based on USE~A methods ?escnbeplfor, .

Senes 7000 (FAAS al;1d OFAAS), Senes 747q (CVAAS), and Senes 6010A (ICPIMS):(USEPA,

1991). ' , I

2.3 Quality Assurance/Qua'ity Control

A QA plan, which included ql!lality control (Q'C) measures, was employed for the program. This

section pres~nts the key elem~nts ofthe plan. I

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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 co,ntrol, 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 pl~n for field operations, inclUding schedlliing, staffing,

training, QC sample collection and analysis procedures, sample chain-bf-custody (COC)

specifications, and sample shipping; and '

A laboratory work plan for laboratory an'alysis, including laboratory procedures, analytical

DQOs, QC procedures, corrective action criteria, and data entry/data management.

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The supporting quality assurance documentation includes the general company policies and

procedures (hiring practices, perfonnance'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. .

2.3.1.2 Quality Management

Program

As the Program Manager, Mr. John Brown was the primary contactwith MMS for the program I

and was responsible for the communication, coordination, and scheduling of all tasks, subtasks, I

meetings, and deliverables. The Program Manager was kept apprised ofthe progmm's status by

the field sampling and analytical laboratory leaders. '

Field

John Brown also served as the Field Team Leader for the summer 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 field teams. 'He was also responsible for

implementing field QC, including issuan'ce and tracking ofmeasurement and test equipment;

proper labeling, handling, storage, and shipping ofsamples; COC procedures; and control and

collection of all field documentation. .' : ..

The field sampling team was provided a'briefing ofQA measures prior to beginning field

sampling. The field personnel were briefed on the potenti~l1 for contamination: and crosscontamination ofsamples and given guidance on techniques to minimize sucll problems. In ,

general, this included training on the use of pre-cleaned sample containers; u~e of clean sampling

equipment; use of decontamination protocols; and good handling practices. It,also included

training on the specified sampling proce~ures and protocols in accordance with SOPs.

mms animida\task 2 final repon\final report files\fiilal section 2 text.doc 2-15
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As organic 9hemistry task leaper, Ms. ~inda <;:ook wa,s ~esponsible for oversigpt ofthe (j)rganics

analyses performed by ADL/~CF's envIronmental chemIstry laboratory. Dr. J(j)hn Tref~ was the

inorganic chemistry task leader and was respqnsible for oversight ofthe inorgJnic analyses I

performed by FIT. ' I

I i

Laboratory ~nalyses were perfo~ed in accordance with the laboratories' QAMs and t\l~ projectspecific laboratory workplan.< Oversight oftlIe laboratory,QA program was th& responsibility of

the laboratory's QA manager.! Implementation of,quality pmctices was the res~onsibility ofthe

laboratory manager, who had ithe following specific responsibilities: , I ,

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• Implementing and adherillg to the QA an9 corporate policies and procedures withiil the

labo.ratory; . .. r 'j , I

Approvmg SOPs; , , 'I ' MaintainiIlg:adequate staffing; and, ,', I

Implementing intemallextem(,ll audit findings,and c09"ective actions. i '

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Prior to the start oflaboratory: analyses, the lapor~tory staffwere provided proj1ect-speqific

training, including a discussidn ofthe project bac~ground and objectives; project orgarlikation;

sample preparation and instrumental analysis procedui'es; DQOs; QC procedurbs; and J:dporting

instructions, The task leaders; provided this trflining. . , I '

2.3.1.3 Smtlple Custody, Pre·le1vation, and *ra~king. . I. . The following sectioI1 describ~s the procedur~s that were employed to ensure the integhty ofthe

samples, including prevention. of contaminatiqn in the field, ensuriIlg safe tranJport, an:d

documenting sample custody ~nd tran,sfer.;' , • I

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SampleHa~dl~ng. " .!;., ' . I .'

All field samphng eql,llpment ;was decontamlI1ated pnor to use at each samphng station;. The

equipment was: . i ' ii'

I " ' I' • Scrubbed with brushes and liquid soa~-and-water mixture to remove any accumulated

sediment; , I

~iped cl~anwith a sorbent pad; paper towel, br rrg (if ~ecessary);' I

Rmsed wIth seawater(from hose or buckets, as appropnate); I

• Rinsed with distilled \yater; j I

Rinsed with isopropaJ)ol solvent; and, i! I • Rinsed with dei~nized: water (optiona9.

• I ' 1 I

The clean.eq~ip~ent wa.s preve~ted from recOntami~a.tion prior t? sampling b~ either. : .

decontamma~lOn lmmedlatelylpnor to use or protectlOn by wrappmg securely m aluml~ttm foIl

that had been decontaminated! Precautions whe taken to ensure that clean eqJipment ~id not

contact anyt~ing other th~n th~ sample, air, or: other cle~n equi~ment. CI.ean e4uipmen:t ras

prevented from contact WIth t~le ground (except fer the ImmedIate samphng area), hands,

clothing, plastic bags, buckets;, trays, etc. ' I'

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At all times after collection, sample integrity and custody were maintained. coe procedures are

specified in formal SOPs and are followed for all sample storage and shipment activities. COC

seals and sample labels were applied to each sample container, ensuring sample integrity. All

field samples were unambiguously labeled in waterproofink with the followi~g information:

• Sample site;

• Unique field sample number;

• Date and time ofsamplecollectiGm; and,

• Details of preservation used.

The type ofsample containers used and the sample storage methods are provided in Table 2-7. . ., Pre-cleaned sample containers that had ~een certified as such by the vendor were used for the

program.

In the field, sediment, biota, and QC samples for chemical analysis were imm;ediately

inventoried and stored in a secure area after collection. Inventory included cqmlting the samples

to ensure that all samples were collected and returned to the custody area on Board, documenting

all samples in field logs, and preparing the COC form. i

Sample Shipment

Following completion ofthe cruise, samples were packed in coolersfor overnight shipment from

the Prudhoe Bay Operations Camp (PBOC) in Deadhorse, Alaska using Federal Express

airfreight courier. The samples were frozen prior to transportation and shipp~d to the appropriate

analytical laboratories (Table 2-7), either frozen, packed on dry ice, or refrige:rated 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 ADLIICF

QA practices were applied when samples were received at the laboratory. Th,e laboratory sample

custodian received all samples. Prior to opening the cooler, the cooler was cHecked for the

presence ofintact custody seals. The cooler was then opened and the internal: temperature was

measured by measuring the temperature :of a representative sample. Each sample was carefully

checked for identification, which was then cross-referenced against the COC records. Samples

were logged in and a unique laboratory identification number was assigned tq each sample.

Problems or discrepancies with the coolers,samples, or documentatIon were recorded and the

project manager was notified immediately so that issues could be resolved. i

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 ofthe refrigerators and freezerS were monitored

and recorded daily. Samples were removed and thawed for sample preparation and then returned

to frozen storage, where they were stored until completion ofthis report.

mms animida\task 2 final report\final report files\fihal section 2 tcxt.doc 2..17
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Documentation tracking samp'le possession from 'the time it is collected (inclu4ing equ'ipment

and contain~r prepar'\tion) to the point at whi~h the samples and eXtracts are d~scardedl i~

necessary to. ensure the creditJility and validity offield and laboratbry results. If'or this jpJogram,

documentatibn was accompli~hed through initiatipg a cac record.for eachsarlIple at th~ time of

its collection and carrying the: requiredpapenyork: through the final reporting ~f result~, ~nd to

the final program files.' , , i,

A COC 'form accompanied the samples as the~ were delivered from the field tJ the labpratory.

Upon receipr, the document ~as signed by the laboratory's sample tustodi~n, ~nd datel:l!as

acknowledgement ofreceipt qfthe samples, Thereafter, the laboratory internal COC pf0tocols,

described in 'the individuallaDoratory~QA program plans or simila:rdocumentatIon, werci utilize~.

Receipt at FIT :. I

Each sedime.nt, tissue', and so~rce sample received by the Marine &: Environmtbntal Chbmistry !

Laboratories! at FIT was car~fully inspected t~ ensure that itwas intact and tha~ th~ ide~l~ificatio~

number on the sample contaIner matched thatfound on the custody sheet. All sedIment knd

source samp~es were kept refr~gerated (4°C ±2°9 and all tissue samples were!kept fr~zbn at

about -20°C :until processed fC:lr analysis. i. i'

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2.3.2 Field Quality Control !

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2.3.~.1 Sample Han1lin~ i " ' . ,I. EqUIpment decontammatIOn ~rocedures were stn~tly followed durIng the samplIng. The

decontamination included a pl,lysical scrub with soap and water, rinses with seJwater ahd

distilled water, and a rinse with isopropanol. ; ,I f

2.3.2.2 Quality Control Samples t. I'. .•' . I 1

As part ofthe QA program, several types offield QC samples were collected during the survey.: , I, I ' I '

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Blanks I i , I

Blank sampl~s were collectedIto characterize pot~ntial influences fromequipm:ent and tHe

sampling act~vities.

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One field (ddck) blankwas co~lected each yeatd4ringlsediment sampling. To collect the field

blanks, a clean, prelabeled sample jar ofthe same batch used for sample collection was' darried : I \ , I l I

into the working area; openedlduring the colle~tion of,one sample, and retumed to the laboratory

with the field samples. One cbntainer was collected for each organics and met~ls blank. The

field blanks were stored und~ the same condirons as tbeassociated field sam1'es.

Equipment blanks were colleqted from rinsate: ofthe sediment sampling equipment. The

procedure for collecting an eq)lipment blank ii;1cluded the following: t

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The equipm~nt was decontaminated according to 'the SOP; i • The equipmen~ was rirj.sed with high-prrity, de,ionized water and the ridsate col~ected

directly into two clean, prelabeled water sample containers (one corrtairler eachif6r

organics and metals); i :

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A precleaned stainless-steel funnel was used to assist in the collection; and,

The equipment blank was stored under the same conditions as the associated field samples.

A sample of diesel fuel typical ofthat used in marine vessels in the Arctic wa~ ta~en during a

previous field survey and was available at ADLlICF. The purpose ofthis sample was to, if

necessary, be able to characterize any potential sample contamination believeo to originate from

the shipboard diesel fuel (e.g., exhaust and surface sheen).

Field Replicates

As a QC measure, replicate samples were collected as part ofthe field sampling design at sample

stations L08 and N13 during the summer 2000 survey and at sample stations 5D and N03 during

the summer 2002 survey. At these locations, sediment samples were collected in triplicate so

that the reproducibility and range ofresults could be evaluated.

2.3.2.3 Documentation

Throughout the field surveys, field note$ were maintained by the scientists in 'log books and on

station logs. 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 pho!o-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 ofthe

quality necessary to achieve the project ?bjectives. The DQOs were also designed to enhance

the ability ofthe methods to identify and accurately quantify source-specific <;>ils. 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 andI2~9.

For processing, samples were grouped together in batches of20 field samples, plus associated

QC samples. In general, the QC samples processed along with the sediment ~amples included

one procedural blank, one blank spike, and one SRM (Sediment SRM 1941 a), per batch. The

blank spike sample was fortified with PAH matrix spike solution and SHC matrix spike solution. I

The QC samples processed with each batch oftissue samples included one prpcedural blank, one

blank spike, one SRM (Tissue SRM 197,4a), and one duplicate analysis. The ,blank spike sample

was fortified with PAH and SHC matrix spike solutions. The QC samples processed with the

batch of SPMD samples included one procedural blank, one SPMD blank, and one blank spike.

The blank spike sample was fortified with PAH and SHCmatrix spike solutions.

There were a number of additional measures added to the'processing ofthe samples to monitor

QC and to aid in the assessment ofthe data's usability with respect to the program objectives.

An important part ofthis is the evaluatidn ofspecific QC samples for accuracy, precision, and

potential contamination. The following 'is a general description ofsome elenients.

mms animida\task 2 final rcport\final report files\final section 2 text-doc 2-19

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So.lvent andlStandard.Checks . i '. . I, . Pnor to sample analysIs, every lot ofsolvent use4 m tpe analytIcalprocess wa~ analyzyd III ,

duplicate to verify that it was Ifree of contami~ati9na~d acceptable for use. Likewise, pbor to

spiking the samples with surrogates and inte~al $tandards, all standard prepar~tion rec!o~ds were

checked. No standards were tlsed for an analrsisunle'ss they had been approvtd for usel

Instrument Calibration, i .: ., I :

Before instnImental analysis ofsample extrac~s, a multi-level calibration was analyzed and the

linearity ofthe analyte respon,se factors was eyal\ilated: A continuing calibratidn standh~d was ,

analyzed regularly to check the stability ofth~ instrument response. Ifthe relabve standard

deviations (RSDs) for the init~al calibration o~ the pertent difference (%D) ofthe daily' I

calibration did not meet the ctiteria set in the SOP, a new calibration was run abd the affected , . I' samples re-analyzed. ;., i

I I , I

Reference Samples . . ; . i .; '. i. I .

To assess the accuracy ofthe mIxture used to ~ahbrate the method, an mdepenpently v~nfied

instrument reference material i(IRM) was anal¥Zed against the calibration standard for PAlI

samples. The values ofthe arlalytes had to be; within l5 percent ofthe target v~lue for :the

calibration solution to be valid.' I , I

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In addition, a solution of an assayed crude,oil [wa~ a~alyzed with each initial c~libratiOl,1 sequenc,e

and the results were compared to a laboratoryjestabhshed mean to assess method accutaby. The

solution was also used to prmlide petroleum patte'm information and to aid in ~ualitati~el

identification oftarget compounds. I' I '

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Procedural Blank ! l i

A procedural blank w:as processed and analyzed with each analytical batch iin drder to lnonitor

potenti~l corttamination resulting from labora~ory solvents, reagents, glasswar9' and prbJessing

procedures. i! I

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I Ok I I • I Bank SPI e.. . ; . .. .! .; : . . . A blank matnx was spIked wIth representatIv~ target compounds pnor to extractIOn to assess the

effect ofthe sample processing procedure indypenden~ ofsample matrix effect '

Laboratory Duplicate . . !" .' ,i. :

A field sample was analyzed In duplIcate to assess the,preclSlon ofthe method 1m the target

matrix. i ' . I

Standard Reference Materials : . '. I,

A Standard Reference Material of a well-characterized sample of known cdncentration'was

processed through sample preparation and instrumental analysis with each batdh of sariI~les. The

results were compared to externally certified ~alues to assess method accuracyJ This pt6gram

used SRM s~mples pliOvided oyNational Insdtute of Standards and Technology (NIST): SRM

1944 for sediment samples and SRM 1974a fqr tissue samples. !

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2.3.3.2 Laboratory Records

The laboratory maintained detailed records throughout the processing ofthe 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 contains

sufficient detail so that an external audit could be performed. The documentation in the final

data package includes:

• 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. l'he assembled package was peer revi~wed 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 datawere 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. i

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 ADLlICF

Data Review SOP. The formal audit process included a 1DO-percent review df all handcalculated values and a 20~percent review of computer-generated results. Th~ process also

checked the traceability of a final result through the instrument calibration an~ to the sample

preparation steps. A formal report was issued to the facility supervisors at the completion ofthe

audit for response. Upon completion ofthe responses, the auditor released the results to the - I

Program Manager for review and reporting. The final laboratory data package and the audit

report are maintained in the laboratory fi}es. '

2.3.4 Metals Chemistry Laboratory Quality Control

Quality Control Measurementsfor Analysis

For this project, QC measures included balance calibration, instrument calibr~tion (FAAS,

GFAAS, Zeeman Graphite Furnace Atomic Absorption Spectrometry [ZGFA,AS], CVAAS,

ICP/MS, Toe analyzer, turbidimeters, .l.nd 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, 2duplicate samples

and 2 matrix-spiked samples were analyked. DQOs for these QC measurements are provided in

Table 2-10.

mms animida\task 2 final repon\fin~1 report files\final section 2 text.doc 2-21
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lnstrum~nt Calibration .. :, .' I. ' El.ectrom.c balances used for \feIghmg samp!es and rea~ents were calI?rated p~IOr to e~c~ use

wIth certIfied (NIST-traceably) standard weIghts. All pIpets (electromc or manual) wqe

calibrated prior to use. Each ofthe spectromdters used for metals analysis was

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standardized with a three- to fIve-point calibr~tion with a linear correlation codfficient:ofr

0.999 required before experiIrtental samples c~uld be analyzed. Analysis of cdmplete tHree- to ,

five-point calibrations and/or isingle standard fhecks altemat~d ev~ry 5 to 10 s~mples ~9til 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 pJrformed. ! ; I . I , I

I

Matrix. Spike Analysis ': ,I ' Matrix spikes were prepared for a minimum qf 5 percent ofthe total number ofsamples analyzed

and included ea.c~ metal t~ be,.determ,i~ed. R~sults from matrix .spike analysis.fsing th:e method

ofstandard addItIons provIde imformatIOn on the extent of any sIgnal suppressIOn or .

~nh.ance~e~~ due to the sampt.e matrix. Ifne~essary (I.e., spike res.ults out~idel80 to 1~9 percent

lImIt), spIkmg frequency was Increased to 20 percent and a correctIOn applIed ~o the metal

concentrations oftheexperim~ntal samples. I

Duplicate Sample Analysis . :

Duplicate sa)llples from homqgenized field sabples (~s distinct from field replicates) were

prepared in the laboratory for ia minimum of 5 percent ofthe total samples. Th1ese labdr~tory

duplicates were included as part of each set o~ sample digestions and analyses ~nd proyitled a

measure ofanalytical.precisioh.' i

Procedural Blank Analysis ", '.

Two procedural blanks were prepared with each ~et of 40 samples to monitor dotentiall

contamination resultiIlg f~om ~aboratory reag.~nts, glassware, and processing ~~ocedur~si These:

blanks were processed usmg the same analytIcal scheme, reagents, and handlIng technIques as

used for the experimental salllpies. ' ., !

I ' I

SRM Analysis , ;:.' . I . :

A common )llethod used to eV,aluate the accurflcyof envIronmental data IS to a~Ialyze S:RlMs,

samples for which consensus or "accepted" a~alyte c0!O-centrationsexist. The followin~ !SRMs

were used: Marine Se,diments\BCSS-l and MES~-2 (NRC); Buffalo River Se~!iment 2V~4 ,

(NIST); Mussel Tissue 2976 (NIST); and Dogfish Muscle DORM,~2 (NRC). Metal I :

concentrations obtained for th~ SRMs were requited to be within ±20 percent cif accep1;etl values

for >85 percent of other certified analyses. When no certified values existed f6r a metal! matrix' , I . I . ,

spikes weJ:1e used to evaluate a;nalytical accurapy. I'

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2.4 Statistical Methods

Organic and metal parameters were analyzed to investigate the hypothesis that there was a shift

in these parameters associated with the island construction and oil production activities at

Northstar. The datasets used in these analyses included the summer 1999, summer 2000, and

summer 2002 sediment sampling surveys. The summer 1999 sampling represented preconstruction and development activities at Liberty and Northstar, the summer' 2000 sampling

represented post-construction, pre~production measurements at Northstar and additional preconstruction baseline measurements at Liberty, and the summer 2002 sampling represented postconstruction, and ongoing production measurements at Northstar and additional pre-construction

baseline measurements at Liberty.

For the statistical analyses, a standard Analysis of Variance (ANOVA) model was constructed.

In this model, variation in the dependent variable was assumed to be dependent on four fixed

effects; these were region, phase, station, and an interaction ofregion by phase. The sediment

stations were divided into two general regions: the Northstar region and a region that combined

the Liberty stations with the BSMP stations (BSMP station 5A is located within 3 km ofthe

Northstar Island and thus was included as a Northstar region station for the statistical analyses).

The field surveys were divided into two phases: pre-Northstar construction including the summer

1999 field survey and post-Northstar construction including the summer 2000 and 2002 field

surveys. Several Liberty stations were only sampled during the summer 199~ survey and

additional Northstar stations were added for the summer 2000 and 2002 surveys. For the

reported ANOVA models, only those stations sampled all three years were included in the

analyses. The results for BSMP station 5D from the summer 1999 survey were severe outliers

and thus were excluded from the statistical analyses. Results from station 5D from the summer

2000 and 2002 surveys were not outliers but were,excluded from the statistical analysis since

only matched stations (stations sampled "all three years) were included in the statistical analyses.

The SIT key parameters were not included in the statistical analyses due to limited sample

analyses performed in 1999 for these parameters.

The organic concentration variables were log-transformed prior to analysis to nonnalize the

distribution. All organic concentration variables were adjusted for sediment tYPe by using

percent silt+clay as the covariate. Additional models were developed with log4ransformed

perylene as the covariate. Perylene is not an expected contaminant from the construction or

production activities at Northstar and is not present in Northstar or North Slope Crude oil, but is

associated with biogenic sources of hydrocarbon in the Beaufort Sea. Additional sub-models I

were also developed to evaluate the differences between the Northstar and BSMP/Liberty

regions post-construction and to evaluate the differences between the BSMPlLiberty region preand post-construction. The metal variables were adjusted for sediment type by using aluminum

as the covariate. The false discovery rateS were controlled according to the Hochberg procedure

(Benjamini and Hochberg, 1995).

Analyses were also performed to determine ifthere was a gradient effect away from Northstar

Island. The analyses were performed using only the matched Northstar stations and included the

variables Radial (distance from island in km) and construction (pre- or post-) with silt+clay or

log-normal transformed (LN) perylene as the covariate for organics and aluminum as the

mins 3nimida\task 2 firial repoJ1\final report files\final section 2 tcxt.doc 2-23
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2.5 Database Management

As part ofthe ANIMIDA program, MMS req~ired that the ANIMIDA data be incorporated into

the MMS Coastal and Offshore Resource Information System (CORIS) databa~e. This I

necessitated database design and development t~ include the various data type~ generate~ by the

ANIMIDA program into CORIS. Harvard D¢sign and Mapping (HDM - Ca~bridge, MA) is

subcontracted to ADL/ICF for implementing *ndcompleting the database design and prhgram

data management. All final ANIMIDA data will be archived in the MMS CORIS datab~se and

are also provided digitally on the Appendices compact disc (CD) accompanyiJg this rep6rt for I

non-CORIS users. : _. :

covariate" for metals. The effect ofRadial wa~ not significant in these models. iAn addit~onal

variable was al.so generated that grouped stations into three radi.al categories 0!-2 k~, ~-14 km,

and 5+ km) to mcrease the number ofsamples per category~ StIll, the effect o~RadIaI ,as not

significant. Thus, Radial was removed from the final reported models. The effect ofthe pipeline

construction at Northstar was similarly tested ,and found to be not significant, thus, this 6ffect

was removed from the final models. . . I

i ,j I , ' ANOVA models were also developed using the complete sediment dataset to determin'e ifthe

results obtained using only the matched samples were biased. Similar parame~er estim:ares and I

p-values were noted when the complete dataset was used as compared to the matched dataset.

Thus, only the results ofthe matched dataset analyses have been included in th!is report. . I

I

,

Statistical analyses were carried out using the 'sta,tistical program SPSS® 8.0.

, mms animida\task 2 final report\tinal Ti~port ~les\final section 2 text.doc 2-24

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Table 2-1: 2000 MMS Animida Stations San

I

-

3B BSMP Sed.1

4A BSMP Sed.-Gni(Annoyx,Fish)

4B BSMP Sed.1

4C BSMP Sed.!

50 BSMP Sed.-Gra(Annonyx)

51 BSMP Sed.!

5(10 BSMP Sed.laltempted biota sampling

55 BSMP Sed.1

5A BSMP Sed.1

5B BSMP Sed. "water spikina range finder"

5D BSMP Sed.l

5E BSMP Sed.

5F BSMP Sed.-Gra(Cyrtodaria)

5H BSMP Sed.-Gra(Astarte)

L01 Libertv Sed.!

L04 Libertv Sed)lttempted biota sampling

L06 Libertv Sed."

LO? Libertv Sed.

L08 Liberty Sed.-Gra(Astarte)

L09 Liberty Sed.-Gra(Astarte)

N01 Northstar Sed.1

N02 Northstar Sed.

N03 Northstar Sed.-Gr '(Annonyx)

N04 Northstar Sed.

N05 Northstar Sed. attempted biota sampling

N06 Northstar Sed.

NO? Northstar Sed.11

N08 Northstar Sed.1

N09 Northstar Sed.1

N10 Northstar Sed.l

N11 Northstar Sed.lattempted biota sampling

N12 Northstar Sed.·Gra(Annonyx)

N13 Northstar Sed.-Gr '(Annonyx)

N14 Northstar Sed.

N15 Northstar Sed.

N16 Northstar Sed.

N1? Northstar Sed.

N18 Northstar Sed.-Gr (Annonyx)

N19 Northstar Sed. i attempted biota sampling

N20 Northstar Sed.'

N21 Northstar Sed.,.

N22 Northstar Sed.i gravel from pipline "cover"

N23 Northstar Sed.i 15 feet off pipeline

SAG.Q1 Source Sed., Sagavanirktok River @ -0.5 mi. S of Mile 401

KUP.Q2 Source P Kuparuk River -2 mi. S. of bridge crossing

KUP-01 Source S Kuparuk River at bridge crossing

COL-01 Source SeColvilie River N. of Nuiqsut

COL-02 Source S Colville River S. of Nuiqsut (sed. and peat)

LOO Libertv Tis Otter trawl

BOO BSMP Tis Otter trawl

NOO Northstar Tissu Otter trawl - sed. from net

Notes:

NA =Not applicable

NS =Not sampled

Trawl sample locations are approximate

I.flll cllJJ'

"~

...

Tabla 2-' (2000).x1s7/28/2005
,I

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1111

1111

1mmI

:1::

-,;-

10o'--'"".1

(~

,..

'I

!~

~.

I'

'1

1

'

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!I
-J11ili1J... l _ ...... ~----.I!IIl.!" ......1"111- ----------

I

Table 2-2: 2002 MMS Animida Stations

3B

4A

4B

4C

5 0)

5 1)

5(10)

5(5)

5A

5B

BSMP

BSMP

BSMP

BSMP

BSMP

BSMP

BSMP

BSMP

BSMP

BSMP

Sed. Grab I

Sed.-GrablTissuenonvx collected on 7/31 and 8/20)

Sed. Grab I

Sed. Grab I

Sed.-GrablTissuPhonyx)

Sed. Grab I

Sed. Grab I

Sed. Grab I

Sed. Grab

Sed. Grab I

50 BSMP Sed. Grab I

5E

5F

BSMP

BSMP

Sed. Grab f

Sed.-GrC'lblTissueyrtodaria)

5H

L01

BSMP

Libertv

Sed.-GrablTissuAstarte)

Sed. Grab l

L04

L06

Libertv

Libertv

Sed. Grab I

Sed. GrC'lb ,ittempted Anonyx collection)

L07

L08

L09

Libertv

Libertv

Libertv

Sed. Grab I

Sed.-GrablTissuestarte) Grab rep 02 for analysis, hold reo 01

Sed.-GrablTissuestarte)

N01

N02

N03

N04

Northstar

Northstar

Northstar

Northstar

Sed, Grab ,I

Sed, Grab i

Sed.-GrablTissudnOnvx collected on 8/10)

Sed, Grab . ,Inonyx collected on 8/11)

N05 Northstar Sed. Grab I

N06

N07

Northstar

Northstar

Sed. Grab 1

Sed. Grab !

N08 Northstar Sed. Grab I

N09

N10

Northstar

Northstar

Sed. Grab I

Sed. Grab !

N11

N12

Northstar

Northstar

Sed. Grab I

Sed.-GrablTissudnonvx collected on 8/3)

N13 Northstar Sed.-GrablTissudnonvx)

N14 Northstar Sed. Grab j

N15 Northstar Sed. Grab !

N16 Northstar Sed. Grab l

N17

N18

Northstar

Northstar

Sed. Grab I

Sed.-GrablTissLidlJOnvx)

N19 Northstar Sed. Grab l

N20 Northstar Sed. Grab I

N21

N22

Northstar

Northstar

Sed. Grab (

Sed. Grab ,)t Sampled

N23 Northstar Sed. Grab !50 feet South of Northstar

3M1 Reference

3M2

3M3

Reference

Reference Mussel/SPMOVlussel CaQe n-40) and 5 SPMOs

NM1 Northstar Mussel/SPMO lAussel Caae n-40 and 5 SPMOs

NM2 Northstar Mussel/SPMO.\ilussel Caae n-40 and 5 SPMOs

Sed/Peat '~Qavanirktok River (Q) -0.5 mi. S of Mile 401

Sed/Peat f,paruk River S. of E bridge crossing

MussellSPMO,jlussel CaQe n-40 and 5 SPMOs

Source

Source

NM3 Northstar

KUP-01

SAG-01

Notes:

NA = Not applicable

Sed. !Jparuk River "Borrow Pit" sediment

Sed. jnning River sediment and water

Sed/Peat~edimentand 1 Deat sample

Sed/Sheen cpnninQ River pond sheen

Source

Source

Source

Source

Source

COL-01

CAN-01

KUP-03

CAN-02

CAN-03

Table 2-2 (2002).x1s7/28/2005
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.....,r-----------------------~-------~--------~'------~-----..,...--,

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Table 2-3. Saturated Hydrocarbons Target List

n-Octane 0 C8 A/1 n-Hexacosane C26 I

n-Nonane C9 A/1 n-He tad:osane C27

n-Decane C10 A/1 n-Octac0sane C28

n-Undecane C11 A/1 n·Nonacbsane C29

n-Dodecane C12 Al.1 n-Triacohtane C30

n-Tridecane C13 A/1 n-Hentriacontane C31

Iso renoid RRT 1380 1380 A/1 n-Dotria<1:ontane C32

n-Tetradecane C14 A/1 n·Tritriacontane C33

Iso renoid RRT 1470 1470 A/1 n-Tetrat~iacontane C34

n-Pentadecane C15 A/1 n-PentatHacontane C35

Iso renoid RRT 1650 ,1650 A/1 n~Hexat~iacontane C36

n-Hexadecane C16 Al.1 n-He tatriacontane C37 ,

n-He tadecane C17 A/1 n-Octatriacontane C38

Pristane PRIS A/1 n-Nonatriacontane C39

n-Octadecane C18 Al.1 n-Tetracbntane C40

Ph ane PHYT A/1 I

n-Nonadecane C19 A/,1 Surro ate Com ounds

n-Eicosane C20 A/1 Tetracosane-dso D50T: A/1

n-Heneicosane C21 A/1 5a-Androstane 5M 8/1

n-Docosane C22 A/1 I

n-Tricosane C23 A/1 Internal Standard

n-Tetracosane C24 A/1 Triacontane-d62 D62T·

n-Pentacosane C25 A/1 !

Internal Standard/Surrogate Reference indicates internal standard used quantitation and surroga1e compound used to

correct analytical results

Also used in reporting:

TOTRES: Total of resolved compounds in sample extract

TPHC: Total of resolved and unresolved compounds in sample extract

I mms animida,ltask 2 final reportldraft report filesldraft final section 2 tables.doc

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8/4

8/4

18/4

18/4

18/4

18/4

18/4

18/3

18/3

I 18/3

, 18/3

, 18/3

I I I

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88F

D10ACE IA/2

D8N IA/1

8EP

8KF

8Gp

8AP

C3C

D10PH IA/3

D~H

CO:C

PER

C1C

C2C

INlD

C4C

A/3:

A/3.1

A/2!

A/3:

A/3i

A/3i

A/2

A/2

A/3:

81P

COA

C3F

C3D

C2F

C1P/A

COP

C2P/A

C1F

cm

C4P/A

COD

C3P/A

COF

C2D

ACEY

ACE

C3-Dibenzothio henes

C2-Dibenzothio henes

Phenanthrene

C2-Phenanthrehes/Ant~racenes

C3-Phenanthrenes/Ant~racenes

Dibenzothio hene

C4-Phenanthrenes/Anttlracenes

Anthracene

C,-Dibenzothio henes

Cl-Phenanthrenes/Ant~racenes

Fluorene

C3-Fluorenes

C,-Fluoranthenes/P renes C1 F/P A/3: I I

Fluoranthene FLANT A/3 i D128AP I 8/4

P rene PYR A/31 I I

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Table 2-4. Polynuclear Aromatic Hydrocarbon al1ld Alkyl POlynuclear Aromatic

Hydrocarbon TargetUst ' ' I I

0Rep~!f.i,~~' 1'+lntern~1 "

. ",I' ..'Standardl ~:~ <, ..•. ,'. ...•". I'}"':"':"" '.',Su ~rogate;"

)~eference'

C2-Fluoranthenes/P rehes C2F/P A/3 1 D10F IA

C3-Fluoranthenes/P renes C3F/P A/3' Ch sene-d'2 D12C! 18

Internal Standard/Surrogate Reference indicates internal standard used for quantitatioh and surrogate bompound!Jed to

correct analytical results. ' I

I ,i

2-ring PAHs include: naplhalenes, acenaphthylene, acenaphthene, biphenyl, and f1uo(enes I

3-ring PAHs include: antl;\racenes, phenanthrenes, and di~enzl'thiophenes , i

4-ring PAHs include: f1uoranthenes, pyrenes, benzo(a)anthracene, c~rysenes, benzo(b)f1uoranthene, and

benzo(k)f1uoranthene : ; . I,

5-ring PAHs include: benzo(e)pyrene, benzo(a)pyrene, pe'ryleri,e, indeno(1 ,2,3-cd)pyrene, and dibenz(a,h)anthrac~me 8enzo(g,h,i)perylene is a 6-ring PAH I . , I'

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Table 2-5: Sterane and Triterpane Target List

'~ ..

:,~m'

iI'

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## Compound used in calibration, but not reported

'D12C

2

A

\ rt- ,L

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------------:--:---------~------------..~---~.I.~--..----"'_dd.1DIIl1ll

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0.7

0.4

0.001

0.01

0.001

iZ.3 I

0.01

0.001

0.01

0.003

0.001 I I

0.004 ! I !

0.01 I

0.002 I

0.03 I

0.01 I

FAAS

ICP-MS

ICP-MS

ICP-MS

GFMS

FMS

GFMS

ICP-MS

GFMS

CVAAS

GFMS

FMS

FMS

ZGFMS

ZGFMS

2

0.5

3

0.2

10

10

0.02

10

0.04

0.04

0.3

0.001

2.

0.2

FMS

FMS

ICP-MS

Shimadzu Garbon 0.1 %

S stem

FMS

FMS

ZGFMS

FMS

: Sieve and Pi et

, ICP~MS

.ICP-MS

,ICP-MS

,ICP-MS

.ICP-MS

: ICP-MS

'FMS

:CVMS

.FMS

'ZGFMS

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Summary of Instrumental Methods and MethodDetectio~ Limitslfor

Metal Analysis of SedimEm. and Organisms

Grain Size

TOC

Table 2-6:

Notes:

CVAAS =Cold Vapor Atomic Absorption Spectrometry

FAAS =Flame Atomic Absorption Spectrometry I

GFAAS = Graphite Furnace Atomic Absorption Spectrometry

ICP/MS ::: Inductively Coupled Plasma/Mass Spectrometry

MDL =Method Detection Limit :

ZGFAAS =Zeeman Graphite Furnace Atomic Absorption Spectrometry

I

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Frozen -20°C

I

Sediment Metals, TOC Plastic jar Frozen -20°C Flo~ida Institute of Technology

I I

Sediment Grain Size Plastic bag Stored at 4°C Florida Institute of Technology

I I

Biota (Clams and SHC, PAH, t~:, 250 mL glass Frozen -20°C ADLlICF Laboratory (homogenate

Amphipods) SIT, metals

I

wa~ sent to FIT for metals) j

,

Mussels SHC, PAH, 250 mL glass or Frozen -20o

G ADI:.tICF Laboratory

SIT pre-cleaned foil

I

;

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SPMDs SHC, PAH, ~'; ,Teflon bag or Frozen -20°C ADLlICF Laboratory

SIT pre-cleaned

;cans I

Source Samples - SHC. PAH, 250 mL glass Frozen -20°C ADl:.tICF Laboratory

Sediment, Gravel, Peat SIT I

Source Samples - Metals Plastic jar Frozen -20°C Flo~ida Institute of Technology

Sediment, Gravel, Peat

I

Source Samples Grain Size :Plastic bag Stored at 4°C Flo~ida Institute of Technology

Sediment, Gravel, Peat I

Equipment Blank! Field SHC, PAH, :250 rnL glass Frozen -20°C ADlJlCF Laboratory

Blank SIT

I

. ,

Equipment Blank! Field Metals Plastic jar Frozen -20°C Flo~ida Institute of Technology

Blank

I

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Table 2-7.. Sample Containers, Preservation, and ~aboratOry List

t()!"~fg ,;,J;1l:.;;,v

a

'm--

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%0 < 35% fOr aU target an'aMes;

90% must be < 25% . , I

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l

'ean

surrogate-correcred value~)

except for compounds below the

re ortin limit I I I

One with each instrument

sequence (N9rth Slope Crude)

j

Prior to every, instrument

sequence forPAHl analysis and

as needed for sHC analysis' !

After every 1? samples or 16

hours. whichever lis more

frequent. and: at end of

instrument sequence I '

Continuing Calibration

Oil Reference Stand~rd

(North Slope Crude)

,

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Table 2-8. Data Quality Objectives for ~aturated Hydrocarbon and pl'ynucl~ar Aromatic Hydrocarbon Analyses ' I : I

I I

Procedural Blank

Blank Spike

Instrument SRM (1491)

Sediment SRM (194:1a)/Tissue

SRM (1974a)

Laboratory Duplicate

Surrogate Recovery

One per batc~

i

I

One per batc~

One per instrument sequence

(PAH only) ,

One per batcb as [appropriate

(PAH only)

One per 40 field samples I '

Every samplel

Noanalyte toexGeed 5 times the

MOL unless sam~le amouht is >

10 times blank arount '

I ,

Recovery between 35 andi125%

for ,PAH, and 45 to 125% forI

SHC I ;

Values mustbe 115% diff~rence

of true value for all certified

analytes I

Values mustbe within 30% M

the true value onlaverage fot all

analytes. not to exceed 35f/olof

true value for moire than 30% of

the anal es I : I

Relative percent tlifference I

(RPD) < 30% forlall analytes >10

times the MOL; Mean RPD I

<30% I !

Recovery between 45 and1125%

{35% for d8-,aPra,eneJ .

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___________________________-..l.i_....... ....... __~,_1
m

4-point curve, %RSD < 25% for

all target analytes

Prior to every instrument

sequence

Initial Calibration

Table 2-9. Data Quality Objectives for Sterane ari4 Tri'terpane Analytes

m

II

Continuing Calibration After every 12 samples or 16

hours, whichever is more I ~. I

frequent, and at end of '

instrument sequence

%D < 25% for all analytes I

'~~i

ml

'

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Oil Reference Standard (North

Slope Crude)

Procedural Blank

Surrogate Recovery

One with each instrument I

,eq,enc. (North Slope crur

One per batch

Every sample

%D < 35% from laboratory mean

for target compounds (use

surrogate-correpted values)

, except for compounds below the

re ortin limit ;

No analyte to exceed 5 times the

MDL unless sample amount is >

10 times blank kmount

Recovery between 45 and 125%

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- - -

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n

d

o

o

o

3· to 5-point 'cu~e depend,in'g on

the element and a blank.

Standard C~rve borrelatiori

coefficient r ~0.9~9 for all :

analytes : ,

I

%RSD <15% forlall analytes

'I i r i'

Values must be within 20% Of : I ' , accepted values Ifor >85% [of the

certified analytes, and withfn 125%

for Hg. I: :-1

, ,

No more than 2 analytes t6

exceed 5 times rJ1DL unleis

analyte not detedted in

aS,sociated samp'les

I

%RSD 80 to 120'/0

I

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RPD <25% for 65% of the:

analytes I

Prior to everj batc;:h of samples

One per batc~ of 20 samples

i

I

I

Must end every analytical

sequence; for f1arpe. repeat all

standards every 5 samples; for

graphite furn~ce and ICP/MS ,

recheck standard after every 8 to

10 sam les! t

One per batch of 20 samples I

One per batch of i20samples

i

Ohe per batch of fO samples

Continuing Calibration

Initial Calibration

Standard Reference'Materials

Method Blank

Laboratory Duplicate

Matrix Spike and Spike Method

Blank

f

Table 2-10. Data Quality Objectives an~ C:riteria for Metals Analyses

!

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Beaufort Sea

Locus Map

Alaska

OU'" /

-",-.

'h. r::::-l ,_ . ... ...c::::.:J. -"" <-

©5(5)

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4S ,';=" _~Je'ih4etteISland

.' © "~;JS: 'Boulder Patch.)

.:~/ .:r£l;.?tOl Liberty, Pro' ~t:-stOcktonISlande , ";"'/,4p:.; : 3S--......... '--"}-'" ;:\ Cj\,( : 3M~ 03A ' z '\ LO:6 L08 L09 3MMM2 :- ,,©, v _ 0 0 . ~,~~ ~_~ , 0

5H

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SAMPLE TYPE

© MussellSPMD

@ Sediment Grab

o Sediment Grabffissue

@ SedimenUPeat

@5(1)

l48'W~1 I ~_~~~'~:, Boulder Patch

5(0) Endicott 0

Development Is.

IA~~""'" -J

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River

5S

©

OKUP;;Q1"

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l49'W

5E @

Z

it>

R

z

R

SAG-01 @

iCF ",,,,,=.J 70'N l49'W 148'W l47'W

Figure 2-1 Summer 2000 and 2002 Sampling Stations
",

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IIoonoIIIoo
SPMDCage

Mussel Cage

! Sub-surface

Float v

Secondary

Anchor

Water Surface

%" Poly Line

-13 - 27 ft.

-12 ft.

Figure 2-2. sc~ematic ofthe Mussel Cage and SPMD MoJring String
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3.0 Results

3.1.1 General Chemical and Physical Measurements "

Total Organic Carbon (TOC) and Grain Size

Surficial sediments from each site duringr2000 and 2002 were analyzed for TOC and grain size

(percent gravel, sand, silt and clay). The Toc values for Jurficial sediments bnged from·

<0.01 % in the sandy sediment at site NOI (2000) to 4.4% in a mud-rich sample from site N14

(also during 2000) (Table 3-1 and Appendix A). The meah value for TOC of 1.0 ± 0.79% for

2000 is not significantly higher than the mean of0.74 ± 0.~7% for 2002, or li.l3 ± 0.54% for

2001, because the standard deviations an~ large (Table 3-11). Considerable patchiness is found for

TOC values across the study area, partly in response to sirrtilar patchiness in the occurrence of

fine-grained sediment. Overall, the TOCiconcentrations ate typical ofvalue~ reported for Arctic

shelfsediments. For example, Carsola (1954) reported a tange ofTOC valuds from 0.2-1.2 %

for Beaufort Sea sediments. ' . :

The grain size results show similar variability to that described above for TOC. Gravel content

(>2 mm diameter particles) during the 2000 sampling peribd ranged from 0% at 26 locations to

60.3% at station N22, located above the pipeline just sout~ ofNorthstar Island. In 2002, gravel

content was 0% at 27 stations with a maximum level of Id.5% at station N121

, also near the

pipeline. Likewise, the clay cOIitent «0.002 mm) varies from about 1% at s~verallocations

during 2000 and 2002 to ~35% at stationN03 and 4A in 2boo and 58% at station 4A in 2002.

Sediment resuspension, along with across and along shelf~ransport, are dynatnic components of

the inner shelf ofthe Beaufort Sea that certainly contribute to observed variations in grain size , I

distribution in the top 1 cm ofsediment. ;

Based on the 2000 and 2002 grain size data, a few general trends are observed. In the area of

Northstar Island during 2000, gravel wasifound at levels 13% only in the saclple collected from

the pile of backfilled material above ~he ~ipeline (station.1jJ22 with 60.3~ gr~vel) (Figure 3-~).

Just a few meters to the west ofthe plpelme hump at statIOn N23, the sedIment was mostly sl1t

with no gravel or sand (Figure 3-1). Sediment to the east 6fNorthstar Island lat stations N07,

N08 and N09 was rich in sand, as was observed at station~ NOI and N15, at 4-6 km north and

south ofthe island, respectively. An ared containing mord silt and clay follo~s along a southeast

to northwest line to the south and west'ofNorthstar Islandl Some ofthis fineLgrained sediment

, ""~ ~,m• .J".""_..,,_..."." "'"..,""..oc 3-1
may have been carried in with spring runoff and not yet disturbed or moved qffshore!b1y stOlID

activity. During 2002, much less sand was fO,und at stations N06, N07, N08 ~nd N09 than during

2000 (Figure 3-2); most likely because fine-grained sediment introduced to t~at area dhring river

runoff had not yet moved farther offshore. Overall, the differences in grain s~ze distri~ution

between 2000 and 2002 were less than observed between 1999 and 2000 as discussed in

Section 4. ' I

The grain size trends for 2000 near the Liberty Prospect are more complex (Figure 3.d~ than , .• . ~. I I

observed near Northstar Island. Small amounts of gravel were collected onlYi at statIOns L09,

LOI and 4C. The highest amounts ofsand w~re recovered along a continuum from sta'tions L07,

L08 and L09, to the east of center point, as wyll as at stations 4B and 4C. A patch ofrhostly silt

and clay was found adjacent to the west and south ofthe proposed sit~ for th~ LibertY, Prospect, , : , I

at stations L12, L06 and 4A (Figure 3-3). During 2002, the sand content at s~ations 4G, 4B, L01, , : . 1 I I

L08 and L09 (Figure 3-4) was markedly greater than observed during 2000 (F;igure 3-f)' In

contrast with the Northstar area, less fine-grained material was present in the area of Liberty

Prospect during 2002 than during 2000. Bott9m sediment movement and deposition :tThroughout

the ANIMIDA region is quite dynamic as discussed in more detail in Sectnon!4. '

3.1.2 Organics

Organic parameter results for the surficial sediment samples are summarized ~n Tablesi 3-2

through 3-4. The summary results include to~al PAH (includes the sum of alII target parent and

alkyl PAHs), total petroleum hydrocarbons (TPHC; includes the sum ofthe resolved 'ahd

unresolved sa~urated hydrocarbons n-C9 throl,lghn-C40), and total SIT (inclupes the ~~m of the

sterane and tnterpane target compounds). Th~ data for each ofthese SUllll1nary param,eters are

presented on a dry-weight sediment basis and! results for field replicates are presented ~s the

mean value with the standard deviation in parentheses. The results are separated into three

regional groupings: BSMP stations (Table 3-2), Northstar stations (TableJ-~), and lfiberty

stations (Table 3-4). In addition, river and peat source sample summary data iare included in

Table 3-2. Within this report and with the associated data analyses, BSMP st~tion 5A I~was ,

designated as a Northstar station based on it's location within 4 km from the Northstar island.

Descriptions of key diagnostic parameters, which are useful in describing itheloverallo ganics

dataset and will be used for comparisons to historical data and future ANIMIDA pro~am data,

are provided in Table 3-5. The complete organics data, including concentrati~ms for individual

PAH, SHC, and SIT target compounds, are included in Appendix B.

3.1.2.1 Saturated Hydrocarbons

Concentrations ofTPHC in surficial sediments from the offshore summer 20~2 surv~~ ranged

from 0.44 to 22 mglkilogram (Kg); the summ~r 2000 survey ranged from 1.00 to 27 l:n!g/Kg; and

the summer 1999 surv,ey results ranged from 0.21 to 17 mg/Kg with one outl~er at 50 rhg/Kg.

The highest TPHC concentration in the summer 1999 survey was 50 mg/Kg detected dt station

5D. The summer 2000 and 2002 TPHC concentrations at this station droppe4 to 17 8f~d 6.2

mg/Kg, respectively, within the expected TPHC concentration range. The m~an TPHCC

concentrations for the three regions (Northstar, Liberty, and BSMP) were 10,16.0, and~.4 mg/Kg

(Tables 3-2 through 3-4), respectively, in the summer 2002 survey and 14, 8.?, and 7.~ mg/Kg in

the summer 2000 surv,ey as compared to the 1999 me.ill TPHC concentration~ of 5.3,7.1, and 7.9

\mms animida\task 2 final-report\final report files\fin!al section 3 text.tioe 3-2

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mg/Kg, respectively. The river sediment and peat sampld TPHC concentratiiOlls ranged from 9.1

to 72 mg/Kg in summer 2002 and 0.55 to 25mg/Kg in surhmer 2000 (Table ~-2). A biogenic

surface residue sample collected from the Canning River ~ad a TPHC concer1tration of 2,900

mg/Kg.

An increase in the mean regional concentration ofTPHC at Northstar is obsetved between the

summer 1999 pre-construction measurements and the corrlbined summer 20do and 2002 postco~struction measurements..Thi~ increase re~ained st~tis:ticallY significant fhen the silt+~lay vanable was used as a covanate III the regreSSIOn equatIOn. However, when the concentration of

TPHC was normalized to perylene (a PAH compound assbciated withbiogerlic but not

anthropogenic hydrocarbon sources) in the full statistical thodel, no significapt Northstar,

construction: or interactiondfects were noted (tables 3.1fand 3-11).. . : .

The compOSItion ofSHCs In the nver seqIment and peat samples was SImIlar; to the surfiCIal

sediments, indicating a common TPHC source relationship between the rive~ sediments and the

nearshore surficial sediments. For example, similar patterms are noted in the GC/FID

chromatograms for the Colville River (Figure 4-6), North~tar station 6 (Figute 4-7), Liberty

station 6 (Figure 4-8),and BSMP statioJ:?i

3A (Figure 4-9).1 Also, the composition ofthe SHCs in

surficial sediments in 20.00 and 2002 was s~milar to the 19

1

99 sediment samp/,e,,' indicating that

no new source of SHCs Impacted these sedIment samples; For example, SImIlar patterns are

noted in the GC/FID chromatograms for station N06 in 1999,2000, and 2002 (Figures 4-7, 4-12,' I .

and 4-14).

3.1.2.2 Polynuclear Aromatic Hydrocar,bons

Concentrations ofTotal PAH in surficial.sediments from the offshore summer 2002 survey . . I.' ranged from 12 to 940 J.lg/Kg; the summer 2000 survey ranged from 29 to 2,000 f.lg/Kg; ~nd the

summer 1999 survey results ranged from 6.8 to 960 f.lg/K~ with one outlier at 2,700 f.lg/Kg. The

highest Total PAH concentration in the summer 1999 su~ey was 2,700 f.lg/&g detected at station

5D. The summer 2002 and 2000 Total PAH concentratio~ at this station dropped to 270 and 630

f.lg/Kg, respectively, within the expected ITotal PAH conc~ntration range. T~e mean Total PAH

concentrations for the three regions (Northstar, Liberty, add BSMP) were 520, 290, and 200

f.lg/Kg (Tables 3-2 through 3:..4), respectively, in the sumnirer 2002 survey an~ 750, 330, and 370

f.lg/Kg in the summer 2000 survey as compared to the 19~9 mean Total PAH: concentrations of

350, 380, and 440 f.lg/Kg, respectively., ;:rhe river sediment and peat sampleiTotal PAH

concentrations ranged from 89 to 690 f.lg/Kg in summer 2b02 and 8.6 to 2009 Ilg/Kg in summer

2000 (Table 3-2). ' I .

An increase in the mean regional concen~ration ofTotal phH at Northstar w'!ls noted between the

1999 pre-construction measurements and the combined 2000 and 2002 post-construction I

measurements. This increase remained statistically significant when the silttc1ay variable was

used as a covariate in the regression equa.tion. When the ~oncentration ofTdtaJ PAH less

perylene was normalized to perylene in the full statistical bodel, no significant Northstar or

Northstar*construction interaction effects were noted (Tables 3-10 and 3-11). . .

Imms animidaltask 2 final reportlfinal report fileslfinal section 3 text.doc 3-3 I

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As noted with the SHe composition, the composition ofTotal PAH in the rivfr sedin)ent and:

peat samples was similar to the surficial sedin;Ients, indicating a common PA~ sourc~ I !

relationship between the river sediments and the nearshore surficial sediments. Also; the

comp?si.tion ofthe Total PAH in sur~cial sediments ~ol~ected from Northsta~ in 2000 ~nd 20~2

~as sImIlar to the ~999 Northstar sedIment sa~,PI.,~s, .mdIcatin,g that no new. s~urce ot:RIAH '

Impacted these sedIment samples. For exam~le, sImIlar patterns are noted m Ithe PA:p,-I

distribution histograms for station N06 in 199,9, 2000, and 2002 (Figures 4-7'14-12, apa 4-14).

" I I ' , • I I

Overall, the levels ofPAH measured during tJ;te summer 2000 and 2002 surveys are within th~

range of values reported from previous studies ofthe i~egion and other Alaska~ coastJI areas

(Table 3-6). : . '

3.1.2.3 Steranes and !riterpanes! , i

Concentrations ofTotal SIT in surficial sedi~ents from the offshore summer ~002 survey ranged

from 1.5 to 110 p,g/Kg;; the summer 2000 sunrey ranged from 2.9 to 180 Jlig/I4g; and ~~e sumrrter

1999 survey results, on a small sub-set ofthe ~tatlOns, ranged from 1.2 to 82 f.!Lg/Kg WIth one

outlier at 490 J...lg/Kg. The highest Total SIT concentration in the summer i199~9 surve~ was 490

J...lg/Kg detected at station 5D. The summer 2Q02 ,and 2000 Total SIT condenttations ~t this ,

station dropped to 38 and 100 J...lg/Kg, respecti:Vely. The mean Total SIT concentrations for the

three regions (Northstar, Liberty, and BSMP)!were 55, 29, and 20 J...lg/Kg (Tables 3-2 through:3-

4), respectively, in the summer 2002 survey <$d 78, 39, and 35 J...lg/Kgin tile ~ummerl~OOO

. survey. Regional means are not available for ~hesummer 1999 survey becauSe only akelect , , '.. .: I I subset ofthe samples was analyzed for SITs. The nver sedIment and peatsample Total SIT

concentrations ranged from 18 to 390 J...lg/Kg i~ Sl!lmmer 2002 and ~.2 to 280 ~g/Kg i:n summer

2000 (Table 3-2). . i " "i'

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3.1.3 Metals i

All surficial sediments, (top 1 cm) collected dhring 2000 and 2002 were arlalyzed forltptal I

concentrations ofAg, AI, As, Ba, Be, Cd, Cr, eu; Fe, Hg,'Mn, Ni, Pb, Sb,Se,1 Sn, TI,:\f and Zil

(Table 3-1 and Appendix C). Concentrations bfmetals show a similar degree' of patchiness I

throughout the study area a~ shown for ~OC ~nd grail1 siz~ (!abl~s 3-1: 3-:, ~-8, andI3!-9). . I

However, metal concentratIOns do vary m response to vanatlOns m gram silze land TOG as wIllbe

discussed below. The highest concentrations pf a,ll metals except Ag and Ba were fO~l1id in AI~

rich (>5.8% AI) sediments from the area ofNorthstar Island (TabJe 3-8). HoWever, th6se I

maximum concentrations are within naturallitnits for the area based on metalYAI ratiJsl and as I

discussed in Section 4. Maximum concentrations ofAg and Ba were found fJr a gra+dl-rich :

(60% gravel) sample from station N22 (2000)1 The higher levels ofmetals reported fot statiOIi

5D during 1999 were not observed during 20qO, most'likely due to being covered by p~w .

sediment or winnowed away by bottom curretits. ,I

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~n the area ofthe N?rths~ar Island, sediment.~as colle~ted from 15 stations inl1999, ~31 station~ m 2000, and 21, statIOns m 2002. These addIttona) statIOns (N 16~N23) were stted close to the

island as well as along the pipeline. The lowe:st metal concentrations in th~ N;orthstat. Jrea were

found in the sandy sediment at sites NOl, NI5;, N17 and N22 (200'0, Table 3-8) and Nql, N15,

and N20 (2002, Table 3-8). In accordance with the grain size distribution, th~ highest levels of , r!'

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metals occurred where silty sediment and >6% Al were p~esent (stations NO.4, NOS, N12, N13,

N21 and N23 during 2000 and no stations during 2002; Table 3-8). Concenttations of Fe, Zn,

Cu, Cr and Ni were slightly elevated in the gravel-rich, All_poor sediment fro~ the top ofthe

pipeline. In the immediate area of Liberty Prospect, no clbar trends in grain size or metal

distribution were observed. Highest metal levels were fo~nd at sites LOI (20'00) and the lowest

metal values were observed at site L07 (2000), L08 and L09 (2000 and 2002; Table 3-9).

The patchwork ofmetal concentrations throughout the s~by area can be unified by normalizing

metal values to either Al or Fe and thereby removing vari~tions in metal concentrations that

result from differences ingrain size, TOCand/or mineraldgy. The metallAl btios are discussed

extensively in Section 4. Figure 3-5 shows a strong, positive relationship between Al and grain

size. The finer-grained material is richerin AI-bearing clJys whereas the coarser grained

sediment contains AI-poor quartz sands and carbonate shdll fragments.

Iron concentrations correlated extrerneIyweII (r 0.94) 4th AI levels (Figute3-6). Thus, either

element can be used to normalize the other metal concentliations. By way of;introduction, just

one example of a metallAl plot is given for V in Figure 3-~ to show the effestiveness ofthe

normalization process. Additional examples for other metals, such as Ba, Plj, and Cu, are

presented in Section 4. Even though ind~vidual metal conbentrations are extremely variable from

site to site, these differences can be explained by variatiorls in grain size, TOe and/or mineralogy

when normalized to AI. Concentrations ofV and other mbtals follow Al in that higher levels are I

found in aluminosilicate clays and lower,levels are found in quartz and carbqnate sands. Thus,

plots such as shown in Figure 3-6 show the natural trend (!i.e., VIAl ratio) fOli area sediments.

Positive deviations from a prediction interval constructed laround the regress~on line can often be

related to anthropogenic inputs ofthat metal. This conceRt is developed in detail in Section 4.

3.1.4 Statistical Results

Using the statistical model described in Section 2, the null hypotheses "The concentrations of

organic pollutants in sediments do not show any increase ks a result ofthe development ofthe

Northstar unit" and "The concentrations ofmetal pollutants in sediments do hot show any

increase as a result ofthe development ofthe Northstar uryit" were tested. Tne results ofthe

statistical analyses are presented in the Tables 3-10 to 3-1~.I

In Tables 3-10 to 3-12, the first column gives the parametbr analyzed as the dependant variable

in the model. The second, third, and fourth columns give Ithe R-squared, p~v~lue, and intercept

for the entire model. The R-squared is tqe proportion of~ariance explained by the ANOVA

model. In most cases the R-squared is above 70%, indicating that the model! adequately

explained most ofthe sources pfvariation in the samplind, measurement, and analysis ofthese

sediments. The fifth and sixth columns give the parametet estimate and p-vaiue for the sediment

covariate (silt+clay, LN perylene, or aluminum). The ne~t 6 columns describe the model

estimates for the three fixed effects in the same ~ay. Thel first binary effect fS the mean effect

associated with the Northstar stations in all years 1999, 2000, and 2002. A positive (or negative)

effect along with a significant p-value (p-value S-O.OS) inaicates an increase :(or decrease) in the

parameter associated with Northstar. The second binary Jffect is the increase or decrease

associated with construction (years 2000' and 2002) at all ktatibns. The thirdleffect is the

additional increase or decrease associated with Northstar ~tations and const~ction, the

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3.2 Tissues

Bivalve and amphipod samples were collecte4 at selected ANIMIDA stations! as part :ofthe

summer 1999, 2000, 'and 2002 sampling surv~ys.• During the 1999 and 2000 ~amplinglevent:s,

amphipods were scarce likely due to a lack ofjnearshore ice thus, limiting the :numberi of i

amphipod samples col1ected. A total of five~ivalve and four amphipod sam~les wer¢ bollected

in 1999, five bivalve and sixamphipod samplb were collected in 2000, and five biva1~e and

eight amphipod samples were collected in 2002. The same five bivalve st~ltiohs were: ~ampled all

three years (i.e., 3A, 5H, L08, LQ9, and 5F). The amphipod stations variee! s9mewhat from ye'ar

to year due to amphipod scarcity. As aresult bfthe small number of biota'samples collected and I . I I I

the variability of year-to-year amphipod statiqns sampled, the biota data c2llln~t be us~<d to detect

changes at Northstar Island due to constructiop activities. Nevertheless, the b~ota datk ban be i

used as a region-wide monitoring indicator. I I

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Northstar*Construction effect. The last colurim gives the p-value' associated {.vith the two-sid~d

test ofthe null hypothesis of no Northstar*Consttuction effect. P...value ht:re is definM as the I

probability - assuming no Northstar*Construction effect ofobtaining an lestibated dffect as I • . •. • . I I I I

large or larger than the observed effect. The ~alsy dIscovery rate for thIS tl::st rvas con~mlled by

using the Hochberg procedure (Benjamini anq Hochberg, 1995). ' .

In general, the results show that there is an apparent increase in PAH and pet~oleum hXdrocarbon

concentrations associated with Northstar*Construction effect (2000+2002) e~en after Jdjusting

for grain size. However, when the data are adjusted for LN perylene (a PAH paramete~ :

associated only with the natural sources of PAH in the region) there is no si~ificant fricrease in

organic concentrations associated with North~tar*Constructioneffect. I

3.2.1 Organics I

SHC, PAH, and SIT measurements were mad~ in pooled samples of amphipoQs (Anoh,J(x sp.), .

and clams (Astarte and Cyrtodaria) at stations where sufficient organisms,co~ld be c4llected. '

The concentrations ofTotal PAH, TPHC, and!Total SIT are presented in 'Iable 3-13 a:ntl

Appendix B (wet-weight basis). In general, tlie concentrations of all organic target cJrhpounds

~n the tissue of all species were quite l.ow. Total PAHconcentrations range frbm 7.41io: 39 ~g/~g m summer 2000 and 9.6 to 25 IlglKg m summer 2002; TPHC values range upl to 26 mg/Kg m .

summer 2000 and from. 2.5 to 52 mg/Kg in sutnmer 2002; and the Total SIT c6ncentrhtions

I I I

ranged from 2.0 to 8.1/-lg/Kg in sumll}er 2000 an~ 1.0 to 3.2 in summer 2002j For stations

sampled in 1999, 2000, and 2002 for tissue sa~ples, only small differences in! concen~~ations

were observed between years (Figure 4-36). i I . .. I

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3.2.2 Met~ls . i.... i: I

ConcentratlOns ofAg, AI, As, Ba, Be, Cd, Cr,iCu, Fe, Hg, Mn, NI, Pb, Sb, Se, Sn, Tl, y and Zp

were determined for samples ofamphipods (A;nonyx sp.) and clams (Astarte) at sites where they

could be found. Concentrations ofselected metals are presented on a dry wei~t basi~ for pooled

samples in Tables 3-14 and 3-15. Data for water content are included with th~ complbte data Set

in Appendix C so that metal concentrations alfo can be calculated on a wet wtight ba~ik.

Imms an;midaltask 2 final reportlfinal report fiIE'Slfin~1 section 3 te1.d

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Four ofthe six pooled samples of amphipods (Anonyx sp. Ismail) were collected from the

Northstar area, one was collected from station 5(0) near Ehdicott Island and one from station 4A

near the Boulder Patch (see Table 3-14). ,Metal concentrations in the amphipods were

reasonably uniform for each metal with values for the coefficient of variance (CV; [standard I

deviation/mean] x 100%) $:10% for Ag, As, Be and Zn, $:25% for As, Co, crt, Hg, Mn, Ni, Pb,

Sb, Tl and V, and $:40% for AI, Ba, Cd, Cr and Fe (TableJ 3~14 to 3-15 and Appendix C). No

distinct trends were observed among maximum and minirhum concentrations ofmetals as a

function oflocation. Furthermore, mean concentrations ofmetals at the four stations from the

Northstar area were not significantly different from those !for stations 5(0) a~d 4A.

Four~pooled samples of clams (Astarte) were collected frlm sites east ofthe Endicott

development. Metal concentrations were relatively simil~r among samples (Tables 3-14 to 3-15

and Appendix C) with values for the CV that were <10% for As, Cd and Zn,<25% for Ag, Cr,

Cu, Fe, Pb and Sb, and less than about 40% for the remaiJing metals (AI, Ba, Be, Co, Hg, Mn,

Ni, Tl and V). Much ofthe observed variance among metals was related to some lower

concentrations in the pooled sample from station 3A.

3.3 Caged Mussel and SPMD Results

Transplanted caged mussels and SPMDs were added to the summer 2002 survey to augment the

tissue sample collection and further investigate the bioav~ilability of contaminants. For this

study, 6 moorings were deployed and retrieved, 3 adjacent to Northstar and in a reference

location, each with paired mussel cages and SPMDs. The !SPMDs were analyzeq for PAHs,

TPHC, and SITs and the caged mussels were analyzed fo~ PAHs, TPHC, Sirs and metals. In

addition to the Northstar and Reference site mussel samples, a subsample ofthe transplanted I .' mussels was taken as a sample prior to deployment. The pre-deployment mussel sample was

analyzed to evaluate the baseline level of organic contamrnation in the mussels and for

comparison to the exposed Northstar anq Reference site clussel samples. E~ch mussel sample

consisted of approximately 40 individual mussels compo~ited into one sample, Subsamples of

the composite samples were then prepared for the organi1 and metal analyses.

The SPMD and Mussel deployments were made for approximately 21 days due to the logistical

constraints ofthe field program. Although shorter than ad optimal exposure;period of ~30 days,

it is expected that the SPMDs were near equilibrium for sbme ofthe lower molecular weight 2-

and 3-ringed PAH which partition into the SPMD morerJadily. However, some ofthe higher

molecular weight 4- and 5- ringed PAH partition more sldwly, requiring more than 60 days to

reach equilibrium (Booij et aI., 1998), resulting in the pot~ntial enrichment ofthe lower

molecular weight PAR inthe SPMDs.

3.3.1 Caged Mussels

3.3.1.1 Organics

The concentrations ofTotal Napthalenes (Total N; sum ofnaphthalene and the alkylated

naphthalenes), Total PAR, TPHC, and Total SIT are pres~nted in Table 3-16 and Appendix B.

The results for the caged mussels are presented on a wet-~eight basis and the results for the

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SPMDs are presented as concentration per SPMD membrane (two SPMD,'membranes were ,

extracted and analyzed from each device). It should be noted that the mussels were i~1 ~ood condition when retrieved and exhibited extensive byssal thread growth, indicating th*lthey were

healthy and growing. Shell condition index measurements were not made as part ofthe mussel

deployments. However, lipid measurements were made and the mean lipia levels of hie

Northstar and Reference post deployment mussels were higher than the pre-d~ploymerit mussels

(although only significantly higher for the Reference mussels), further indicating they {,.,ere

healthy and actively feeding.· 'l

The mean Total PAH concentration ofthe Northstar sampl~s (16 Jlg/Kg, standard de,ri tion [S:D]

1.2) and the Reference samples (mean 13 Jlg/Kg, SD 1.2) were similar and were not ~iknificantly

different. The Total PAH concentration ofthe pre-deplo~ent n:ussel samply.was 7.8IJlg/~g.,

Overall, these levels ofTotal PAH very low and are consIstent WIth uncontaIlfmated areas m

Alaska (Boehm et aI., 2004) and are substanti~lly lower than the referencemussels frofu a clean

area ofthe Northeast U.S. that were used fora NOAA Mussel Watch study (Peven et:JI., 1996).

~he. distri?ution oft~e PAHs in.the Northstar, Ref~rence, .an~ pre.,deployment ~amplesl were ,

SImIlar wIth subtle dIfferences lIkely due to analytIcal vanabIhty when measunng tra¢e

concentrations at and below the minimum reporting limit (MRL; Figure 4-44). The sh-hilar PAH

distributions and concentrations in the Northstar and Reference mussel sampl~s indicafe that the

samples were exposed to similar sources and yoncentrations of petroleum hydrocarbQnk while

deployed. '

The mean TPHC concentrations ofthe Northstar,samples (2.7 mg/Kg, SD 0.3?) and tP.f

Reference samples (mean 2.7 mg/Kg, SD 0.15) were the same. The TPHC cqncentration ofthe

pre-deployment mussel sample was 3.8 mg/Kg. The distribution ofthe n-~l1k~nes in thb

Northstar, Reference, and pre-deployment samples were alike indicating a similar so~rbe of '

hydrocarbons in these samples. The higher TPHC concentration in the pre-d~ployment mussel

sample along with the similar alkane distributions indicates that the alkanes d~tected i~ the

Northstar and Reference samples were likely present in the mussels before deploymei1~ and were

not a result ofhydrocarbon uptake during deployment in the Beaufort Sea. These re~~lts also

show that the deployed samples were not exposed to sufficient concentrationsofTPHG during

deployment to raise the sample concentrations above the baseline or to alter the alkane

distribution. ' ,

The mean Total SIT concentrations ofthe Northstar samples (1.5 Jlg/Kg, SD 0.19) and the

reference samples (mean 1.5 Jlg/Kg, SD 0.19)'were the same and represent tr~ce condentration

(minimum reporting limit 1.2 Jlg/Kg). The Total SIT concentration ofthe IPre~deploynient

mussel ~ample was 1.0 Jlg/Kg. Due to the trace levels ofSIT detected, a defi1itive so,ufce

companson could not be perfonned between tp.e Northstar, Reference, and pre-deployment

mussel samples. ' ,

3.3.1.2 Metals

, i

Data for metals in mussels from the predeployment site, the reference site in the coastal Beaufort

Sea and the site near Northstar Island are presented in Table 3-17. One ofthr~ecompolsite

mussel samples for the reference site and for the Northstar site was not analyz:ed becau~e of a

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labeling error. Concentrations of Fe for all three 10cationJ are similar enough to assume that any I ,

sediment incorporation that may be in the mussel sample is similar from site:to site (Table 3-17).

Variable contributions ofsediment into the mussel can be limportant for metals that are enriched

naturally in sediments relative to mussels (e.g., Fe, Ba, Be, Cr).

No significant differences were observed between concenLations ofmetals in samples from the

reference site in the coastal Beaufort Sea:versus Northstarl Island (Table 3-1 ~). In fact, the mean

values agreed within 5% for most metals. Some shifts in concentrations were observed between

the predeployment site and the Beaufort Sea sites. For exkmple, Ba in the mussels from the predeployment site was 6.5 Ilg/gram (g) relative to 18 Ilg/g iJ the Beaufort Sea.: This difference is

probably related to differences in ambient level of dissolv~d Ba in the two systems and supports

the contention that the organisms were actively filtering water. Similar shift~ were observed for

Be and Tl (Table 3-17).

3.3.2 SPMDs

The concentrations ofTotal N and Total PAH, are presen~ed in Table 3-16 aild Appendix B. The

results for the SPMDs are presented as concentration per SPMD membrane (two SPMD

membranes were extracted and analyzed·from each devic~). In addition totlieNorthstar and I ,

Reference site SPMD samples, one set of SPMDs was coillected as :a field blank sample prior to

the deployment. The field blank SPMD was opened dUridg the deployment lmd retrieval of each

mooring to monitor potential ambient contamination in thb field. The field blank SPMD sample

was also used to assess baseline level of organic contamirlation in the SPMQs and for

comparison to the exposed Northstar and Reference site SrMD samples.

The mean Total PAH concentrations ofthe Northstar samples (510 ng/SPM!?, SD 34) and the

Reference samples (500 ng/SPMD, SD 37) were similar ~nd were not signifi:cantly different.

Overall, these PAH concentrations should be considered Ibw and are comparable to results for

relatively uncontaminated waters in Alaska (Boehm etad 2005) and are only somewhat higher

than the blanks levels of 300 - 400 ng reported by Shigen1aka and Henry (1995). The Total PAH

concentration ofthe SPMD field blank sample was 130 nW(SPMD per expo~ure) ofwhich 120

ng/(SPMD per exposure) was contributed by naphthaleneIand the alkylated Japhthalenes (Total

N). The concentrations in the SPMD fie~d blank were adjusted by the numbh offield exposures;

the field blank was opened and exposed at each ofthe six moorings. The Total N concentration

in the Northstar and Reference samples averaged 240 and 230 ng/SPMD, re~pectively. The

distributions ofthe PAHs in the Northstdr and Reference samples were simil'ar with subtle

differences likely due to analytical varia~ility whenmeas~ring trace concent~ations at and below

the MRL (Figure 4-43). The similar PAH distribution and concentrations in:the Northstar and

Reference SPMD samples indicate that the samples were:exposed to similarisources and

concentrations of petroleum hydrocarbons while deployed. !

The SHC and Total SIT analyses perfo~ed on the SPMds resulted in substcimtial matrix

interference from the triolein material within the SPMD dIembrane, which masked any potential

environmental accumulation in these saIVples. The associated data were notlusable and are not

included in this report. This contaminat~on issue will nee~'to be resolved prior to performing

future SPMD monitoring in the ANIMIDA study area; otherwise, the SHC ~nd/or Total SIT

measurements should not be performed. • I '

I

! ImlllS animidal\ask 2 final reportlfinal report fileslfinal section 3 text.doc 3-9
- - -.

~ield qc also included t~e verification offield ~nst~me~t calibrahons prior to use asldescribed

m SectIon 2.3. All field mstruments passed theIr cahbratlOn and QC checks. • , "

i

,

This section provides an evaluation ofthe quality and usability ofthe environmental data based

on the results for the field and laboratory QC ~amples collected and analyied !during ih~s j

program. Tables 3-18 through 3-20 summari~ethe organic field and laboratory QC rbJults.

Tables 3-21 through 3~27 summarize the inorganic field and laboratory QC~ results. ' , '. I : ! I

In general, no serious data quality issues werd noted that would adversely affdct the q'uality or

use ofthe organic or inorganic data. I

3.4.1 Field Quality C~>ntrol i , "

Field QC samples were collected to assess overall precision, accuracy, and representdti,veness of

the sampling and analytical efforts. The result~for the field QC sa~ple an~llyses are ~rbsented:in

Appendices A through C, along with the assoCiated environmental sample!;. Discussi'oh and :

interpretation ofthe results are provided in th~ following sections. I r ! !

, ' I

Equipment and field blanks were collected to assess potential sample cont~lmihation ihtroduced

from sample collection and handling procedu~es. ,Replicate field samples Were colledetl to ass~ss

sample representativeness and precision relatiVe to sampl,e collection procedures and kJmple

matnx. . ',I

3.4.1.1 Equipment Blanks

Three equipment blanks were collected an~s~bmitted for analysis during the ~edime~t sampling

events - one from the summer 2000 samphng ,surwey and two from the summer 2002lsurvey.

These samples were collected by rinsing the gi-absampling equipment imrilediately aft~r

decontamination ofthe equipment. PAH, SIT, SHC, and metals analyses ~ere perforlrled on '

these equipment blanks. The equipment bla~ results were evaluated to assess the po~dntial fOf

cross-contamination ofsamples due to inadequate sampling equipment decontaminati:oh. ,

Several PAH compounds including naphthale1,1e, alky;ated naphth:ilenes, b:iph~nyl, fhiJene,

phenanthrene, C1~phenanthrene/anthracenes, dibenzothiophene, alkylated dib~nzothi~~henes,

fluoranthene, pyrene, indeno(1 ,2)-cd)pyrene,'and/or benzo(g,h,i)perylene.were detectJd at

trace-level concentrations in the equipment bl~nks. These compounds were d~tected ~t!

concentrations well below the MRL; the total PAH conce1)trations in thesebl~nks ran~bd from

0.114 to 0.260 f.l~liter (L). Two SIT c~mpou~ds?Tl5~norhopaneand TI9-~0~ane, W?rf detec~ed at low concentratlOns below the MRL III the eqUipment blank collected dunng the summer 2000

survey. Trace concentrations ofseveral straigllt-chain alkanes (i.e:, n-C21,thrbugh n-~G8) wer:e

detected in the equipment blanks. These compounds were detected at concentrations Jdss than i

the MRL in two ofthe field blanks. One field blank collected in 2002 containbd alkanJs n-C25

through n-C29 at concentrations slightly abovb the MRL and several additionJI alkanb~ at trace

concentrations below the MRL. The source ofthis contamination is believed to be thb laborat6ry ; ,,: 1

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The total TPH concentrations in these equipment blanks r~nged from 220 to 450 ~g/L. Concentrations of all metal analytes in the equipment blariks were less than 5 times the MDL.

These results indicate that the decontami~ation procedurJ used on the sedirrtent sampling

equipment were adequate and would have minimized the potential for sample croSgcontamination. I

3.4.1.2 Field Blanks

One field (deck) blank sample was collected during each summer survey with the collection of

sediment samples. PAH, SIT, SHC, and 'metals analyses ~ere performed on .these field blanks.

The field blank results were evaluated to ,'assess the potent[al for atmospheric or other

contamination that the field samples may have been subjebt to during sampl~ collection.

Several PAH compounds were detected at trace-:Ievel conlentrations in the field blanks and most

ofthese compounds were also detected in the associated ~rocedural blanks. All compounds were

detected at levels well below the MRL; the total PAH conbentration in these 'blanks was 0.034

~g/L (2000) and 0.035 ~g/L (2002). Trace-level concent+tions ofseveral sttaight-chain alkanes

(i.e., n-C22 through n-C40) were detected in the equipment blanks. These compounds were

detected at concentrations less than the MRL with one exJeption - n-C2S wak greater than MRL

in 2002 field blank; the total TPH conce~trations in these ~lanks were 11 0 ~WL (2000) and 26

~g/L (2002). No SIT compounds were detected in the field blanks. The concentrations of all I

metal analytes were less than 5 times the;MDL in the field blanks.

These results indicate that the sediment samples were not subject to atmospheric or other , ,

contamination during sample collection that would adversely affect the quality or use ofthe / , '

sample data. .

3.4.1.3 Field Replicates

Four sets offield replicate samples were 'generated during the collection oftl1e sediment samples

in the form oftriplicate samples collected at sampling stations N13 and LOSliuring the summer

survey and at sampling stations 5D and N03 during the sdmmer 2002 survey. The field replicate

results were evaluated to assess analytical precision relati~e to samp1e'collec,tion procedures and

sample matrix.

For the triplicate samples collected at sampling station N13, the precision criterion ofless than

50 percent RSD for sediments was met for all PAH, SHe! and SIT results detected at

concentrations greater than 5 times the reporting limit wit~ only one exceptibn. The precision

criterion was exceeded for C4-phenantht;ene/anthracene{51%). Overall, the;field replicate

precision at sampling station N13 was considered to be adceptable. I

For the triplicate samples collected at sampling station Lds, the precision cri~erion ofless than 50 • ·1 I

percent RSD for sediments was met for all PAH, SHC, and SIT results detec~ed at concentrations

greater than 5 times the reporting limit with only two exc~ptions. The precision criterion was

Imms animidaltask 2 final reportlfihal report fileslfinal section 3 text.doc I 3-11
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exce.e~ed for S28 eth,yl~holestane (52%) ~d,', n-lriaconlane (61%,)' overall,i,the fieltl [rePlicate

preCISIOn at samplmg statIOn L08 was consIdered to be acceptable. •

For the triplicate samples collected at sampli~g stations 5D and N03 in 2002,ithe preci ion

criterion ofless than 50 percent RSD for sediments was met for all PAH, SH<c, and Sit results , .

detected at concentrations greater than 5 time$ the reporting limit without ex~eption.

3.4.2 Organics Quality Control

Laboratory QC samples were analyzed to assess precision and accuracy ofth~ sample

preparation and analytical procedures. The number and type oflaboratory Q<C samples was

based on the total number offield samples and as specified in ADL/ICF SOP~ and th6field

Sampling and Logistics Plans (Arthur D. Little 2000 and ICF 2002a). For thi~ progr~J, the

following laboratory QC samples and measures were used to evaluate accuraqy and pr~cision of

the analytical data: surrogate recoveries, procedural blanks, blank spike samples, laborktory

duplicates, standard reference materials, and oil reference standards. The resJlts for thb organic

QC samples and measures are presented in Appendix B, along with the result~ for the Associated

environmental samples. Discussion and interPretation ofthe results are provitled in thJ

following sections. . I

,

In addition to the program-specific QC, ADL/ICF participated in the National Oceani.c & • I •

Atmospheric Administration/National Institute of Standards & Technology (l'fOAA/NIST)

intercalibration exercises for organics in 1998, 1999, 2000, and 200I. Triplichte analy~es of

mari~e sediment and mussel tissue were analyzed for or~a~ics, including PA*s, as p~ry of the~e exerCIses. The results ofthe ADL/ICF analyses were wIthm the top 10 percent ofthe more than

30 laboratories participating in the exercises. ' '

The Marine & Environmental Chemistry Laboratories at FIT participated in the most:recent

NOAAlNIST Intercomparison for Trace Metals that was organized by the NR[C. FIT:rknked at

the top of 41 laboratories in the exercise. Each laboratory was given two sediinent satrlples and

two fish tissue samples to analyze for 15 trace metals including mercury, leadl coppet, !cadmium,

tin, thallium, beryllium and others. Concentrations ofsome elements.were required to be withIn , I . I .

5% of established ~onc.entrat~ons, while othe.rs were to b~ dete~ined within 'O-~O%.: [Thirteen

ofthe 41 laboratones, mcludmg FIT, were gIven a Supenor ratmg for the ana'ysIs of both

sediment and tissue samples. FIT was the only laboratory to correctly determined 60ldifferent

concentrations oftrace metals in the sediment' and tissue samples with no incdrrect val~es.

3.4.2.1 Surrogate Results

Surrogate compounds were added to all environmental and QC samples prilor ~o sample

preparation. These compounds were added to determine the efficiency ofthe !sample :ektraction

and analysis procedures. Surrogate recoveries were evaluated to assess analytical metHod

accuracy relative to sample matrix and laboratory performance. :

For the PAH analyses, all ofthe environmental and QC sample surrogate rec~:veries were within

the recovery acceptance limits, with a couple of exceptions. One ofthe six blank spikds

associated with the sediment samples had low:recoveries for all four surrogatds. The niethod

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blank and all field samples associated with this blank spik~ had acceptable surrogate recoveries

and the associated sediment SRM had acceptable target cdmpound recoveries. Thus, these low I '

surrogate recoveries in the blank spike do not adversely affect the quality or ~sability ofthe

associated environmental sample data.

The method blank and blank spike associated with the year 2000 tissue samples had low

recoveries for two surrogates ranging from 12 to 30% andlth.e method blank~ssociated with the

year 2002 tissue samples had low recoveries for three ofthe four surrogates r:anging from 20 to

44%. Tissue sample 00-4A-OI-PHC-T-AN had low reco~eries for all four sdn'ogates, ranging

from 28 to 42%. Tissue sample 02-N03-01-PHC-T-AN had a low recovery of43% for one of

the four surrogate. The tissue SRMs andiremaining field ~amples associated iWith these tissue

batches met all surrogate recovery criteria, thus, the low strrogate recoveries. in the method

blanks and blank spike do not adversely affect the qualitylor usability ofthe ~ssociated

environmental sample data. The results for tissue samples 00-4A-OII-PHC~T-AN and 02-N03-

01-PHC-T-AN are considered to be estimated values.

For the SHC analyses, all ofthe environmental and QC sample surrogate recbveries were within

the recovery acceptance limits, with one exception. A blahk spike associated with the year 2000

sediment samples had very low recoveries for both sUriog~tes (3%). The method blank and

associated field samples had acceptable surrogate recoveries indicating that t~l{: poor extraction

efficiency in the blank spike was an isolated occurrence, thus, the low surrogat,e recoveries in the

blank spike do not adversely affect the quality or usabilit~ ofthe associated ~nvironmental

sample data.

For the SIT analyses, all ofthe environm¢ntal and QC sample surrogate reco\leries were within

the recovery acceptance limits without exception. '

3.4.2.2 Procedural Blanks

A laboratory procedural blank (PB) was prepared with eaG:h sample preparation batch by

extracting a blank sample matrix (sodiuni sulfate) asifit ~ere one ofthe environmental samples.

Procedural blanks are used to assess the potential of condmination introduc~d during sample

preparation and analysis. PAH, SIT, and SHC analyses w1ere performed on each PB. I I • :

, I ' Between 2 and 18 PAH target compounds were detected at trace concentrations less than the

MRL in all ofthe tissue, water, sediment, and SPMD PBsl, with the exceptiori ofthe napthalenes,

biphenyl, and phenanthrene. A few naplithalene~ alkylate~ naphthalenes, bi~henyl, and

phenanthrene results were detected at concentratIOns greater than the MRL. ,Naphthalene was

identified in all the blanks and is a common contaminant issociated with the)solvents used

during sample preparation. Several SHe target compoun~s ranging from n-C16 to n-038 were

detected at trace concentrations less than' the MRL in aU dfthe tissue, water, Isediment and

SPMD PBs with two exceptions. Alkan~s n~C26 throughln-C29 were detect~d at concentrations

greater than the MRL in two year-2002 sediment PBs. N<D SIT target compounds were detected

in the PBs. Environmental sample results that were withih 5 times the associated PB

concentration were qualified with a "B" to indicate that tHe compound was also present in the

blank. Ofthe results that were qualified 'with a "B", none ofthese results were at concentrations

greater than 5 times the sample-specific J'v1RL. '

3-13
- • -lBil]

Overall, the PBresults met the DQOs specified in the laboratory QA plan forithe pro~am, and

do not indicate concentrations oflaboratory contamination that would advers~ly affe9tlthe .

quality or usability ofthe associated sample data. Results that were qualifiediwith a "B" may be

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 py spiking a blank

sample matrix with known concentrations ofasubsetofthe target compounds. BSs arb used to

assess the accuracy ofthe sample preparation 'and analysis procedures indepehdent ofJample

matrix effects. PAH and SHC analyses were performed on each BS; SIT analyses wed~ not

performed.

For the PAHs analyses, the recoveries ofseveral compounds in a tissue BS, a,SPMD ,~S, and in

three sediment BSs exceeded the acceptance criteria. The QC sample results ;were adjusted

based on surrogate recoveries and these high recoveries are the result oflower surroghte

• ' I . recoveries in these BS analyses. These BS recovery exceedances do not adversely affect the

quality or usability ofthe associated sample data.

For the SHC analyses, the recovery ofn-C25 andn-C30 in one sediment BS t:;xceede1 fhe ,

acceptance criteria, the recovery ofn-C10 was low in two sediment BSs, and the recoveries ofnCIO and n-C15 were low in one tissue·BS. Overall, this data quality issue do~s not a~~ersely

affect the quality or usability ofthe associated sample data since these individual alk~des

contribute only a small amount to the TPHC concentration.

3.4.2.4 Laboratory Duplicates

Laboratory duplicates were prepared with several sample preparation batches by extr~cting a

second separate aliquot of an environmental sample. Laboratory duplicates ",\ere evalJated to

assess analytical precision related to laboratory performance and sample matrix. For this project,

one laboratory duplicate was prepared and analyzed with each tissue and sedi~ent sal'Jple batch.

No laboratory duplicates were performed on the aqueous field QC samples orion the SPMD

samples due to limited sample amount. PAH,:SIT and SHC analyses were performed: dn each

laboratory duplicate. .

For the sediment and tissue PAH, SHe, and SIT analyses, good laboratory duplicate prfcision.

was noted, with relative percent differences (RPDs) less than 30 percent for all ofthe compounds

detected at concentrations above the MRL and for the majority ofthe compou~ds detedted at I

concentrations below the MRL. The mean RPDsfor each laboratory duplicatk pair wa~ less than

30 percent. The laboratory duplicate precisio~ criterion does not apply to coclpounds detected

below the ~RL (or less than 10 times the MDL) due t~ increased variability ~t low . I

concentratIOns. (RPD was calculated as the absolute dIfference between the two measurements

divided by the mean ofthe two measurements). !

Overall, the laboratory duplicate results met the DQOs specified in the labora~ory QA plan for

the program. ,

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3.4.2.5 Standard Reference Materials

Instrument SRMs were analyzed with each instrumental ahalytical sequence to assess accuracy I ,

ofthe instrument calibration (PAH only). A matrix-specific SRM was prepared and analyzed

with each sample preparation batch to assess accuracy odhe analytical trtethbd relative to sample

preparation and analysis procedures. PAH analyses were ~erformed on each] SRM. SHC and

SIT analyses were not performed on the SRMs since ther~ are no certified va,lues for these

compounds. I .

Instrument SRM. SRM 1491 (a solution of parent PAHSI in solvent with ceI;tified

concentrations) was analyzed prior to each PAH analytical sequence. The percent differences

(%Ds) ofthe measured values versus the certified values tere within 15 per<pent for all

instrument SRMs, as required in the laboratory QA plan, indicating that the instrument

calibrations were acceptable.

Sediment SRM. SRM 1941a (a freeze-dried marine sediment with certifiediconcentrations for I I . I

PAHs) was prepared and analyzed for PAHs along with each ofthe sediment sample batches.

The %Ds ofthe measured values versus the certified valu~s for the PAH co~pounds were within

the acceptance criteria of 30 percent on average per SRM land 35 percent for,the individual

compounds, with a few exceptions. The response for naphthalene in all SRMs w~s more than 30

percent lower than the certified value, indicating that the theasurement of naphthalene in the

sediment samples may be biased l~w. Acenaphthe~e and Ibiphenylwere recqve~ed low in one

SRM and benzo[k]f1uoranthene was recovered low monel SRM. Chrysene and mdeno(I,2,3-

cd)pyrene recovered high in one SRM. These SRM exceedances have a min,or impact on the

quality and usability ofthe associated sample data since tfue exceedances were not extreme and

did not result in any data being considered unusable. I

Tissue SRM. One SRM (NIST SRM 1974a- certified fot PAHs) was prepared and analyzed for

PAHs along with the year 2000 tissue samples. All ofthd compound concentrations were within

35 percent ofthe certified values, with three exceptions: daphthalene (376%0), anthracene

(234%D), and benzo[b]f1uoranthene (36.2%D). The highlrecovery ofnapht~alene and

anthracene are consistent with the results obtained for thiS compound in multiple (more than 20 : I I

samples) analyses ofSRM 1974a over the last four years by ADL/ICF. ThislQC issue does not

impact the quality or usability ofthe associated sample ddta since acceptabl~ recoveries for

naphthalene and anthracene were noted in the instrument~RM analyses, an" since it appears that

the certified values for naphthalene and anthracene in NIST SRM 1974a are :incorrect. The

benzo[b]f1uoranthene results in the tissue samples may bd biased high as indicated by the high

recovery in the tissue SRM. This SRM exceedance has a iminor impact on tltequality and

usability ofthe associated sample data sihce the exceedance was not extreme and did not result

in any data being considered unusable.

One SRM (NIST SRM 2978 - certified for PAHs) was prFpared and analyz~d for PAHs along

with the year 2002 tissue samples. The t;esponse for 11 ofthe 19 certified values recovered high,

with %Ds ranging up to 700%. The poor performance on! this SRM analysis: appears to be an

anomaly as the associated PB does not show evidence of bontamination, the :associated BS

compound recoveries Were acceptable (the BS compoundr include many oflhe SRM certified

Imms animidaltaL 2 final reportlfinal report fileslfinal section 3 text.doc
- -.1 d~.]

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compounds), the associated IRM recoveries ~ere acceptable, the'associated cpntrol o'il

recoveries were acceptable, and the surrogate,recoveries in the associated san]tples w6r~

acceptable. The SRM exceedances have a minor impact on the quality and usability bfthe ,

associated sample data since the poor perfomiance appearsto bean anomaly ~nd lim1t~d to the

SRM analysis. i" :

I

3.4.2.6 Control Oil Analyses , I

A North Slope Crude oil sample was analyzed prior to each analytical sequence for PWH, SHG:, , .! ' I ' and SIT analysis. The results ofthe North Slope Crude oiLanalyses were used to evaluate I

accuracy ofthe analytical methods, provide aichromatographic pattern for,c0tPparisoh~ with :

samples, and provide an independent check ofthe quantitation for alkyl PAHs, SITs, !ahd SHCs.

Res~lts ofthe control oil ~nalyses were comp~red to laboratory mean values generat~dl from. I,.

multIple analyses ofthe OIls. For the PAH, SHC, and SIT analyses, all ofthe results were wIthm

the acceptance limits. ' ' , ,

;

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3.4.3 Metals Laboratory Quality Control i ..,' I

Laboratory QC samples were analyzed to ass~ss preClSlon and accuracy of thy sampl~

preparation and analytical procedures. For thIS program, the following laboratory QC samples

and measures were used to evaluate accuracy ~nd precision ofthe analytic~l ~ata: PBk, matrix'

spike samples, laboratory duplicates, and SRM. A summary ofthe QC results is given in Table

3-21. The individual results for the inorganic :QC samples and measures for qifferent! matrices'

for 2000 and 2002 are presented in Tables 3-2:2 through 3-27 and AppendiceslA and t1 along:

with the results for the associated environmental samples. Discussion andinterpretatidn ofthe

results are provided in the following sections. : r ' , , I

,3.4.3.1 Procedural Blanks ,

I ;

Two method blanks were processed and analyzed with each batch ofsamplesIto monh<l>r

potential contamination resulting from laborat:ory reagents, glassware, and: processing I

procedures. No contamination from any of th~se sources was noted and c(lIllcentrati0J,ls of

analytes in the blanks do not exceed 5 times t~e MDL '

3.4.3.2 Matrix Spike Sample i ,

Matrix spike samples were analyzed with eacti ba,tch ofsediment, organism, ~nd susp~ended solids samples using tq.e method ofstandard apditions. Results from these an~lyses pi-Jvide

information on the extent of any signal suppr~ssion or enhancement due to th~ matrix;. Spike !

results for the sediment, and organism samples are shown in Tables 3-22 thro*gh 3-27, and are

within the 70 to 130 percent range specified i~ the DQOs. I

3.4.3.3 Laboratory Dl!plicates ,

Duplicate subsamples taken from individual s¢diment and water samples in the laboratory were

analyzed to estimate analytical precision. Amilyticalprecision for, sediment trletal an~lhes (n == • .' I ' 'I I

3 paIrs of duphcate samples) ranged from 0.8 percent RSD for Al to 11 perceJ}t RSD for low

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~~w'

I

I

levels ofAg. For organism tissue samples (n = 1 pair), prbcision ofduplicat~ sample analysis . ,I I

ranged from 0 percent RSD for Be, Cr, Sb and TI to 8 percent RSD for Pb. '

3.4.3.4 Standard Reference Materials

SRMs were processed and analyzed for trace metals along with the experimental samples as

described in the M~thods sectio~ (Section 2). The resultslo~these anal~ses ~re shown in Tables

3-22 and 3-25 (sedIment analysIs) and 3-23 and 3-26 (orgamsm analysIs), and 3-24 and 3-27

(suspended sediment and dissolved). The metal concentr4tions determined for each SRM, were

all within the range of certified values or within the DQO!limits ofthe referepce values provided

by the certifying agencies. ,

For TOC analyses, the marine sediment SRM MESS-2 wL used as a QA sample. This SRM is

certified for total carbon content (inorganic plus organic);ltherefore, the Toe values in Table 3-

11 are slightly below the certified total carbon value. Ne'iertheless, the TOe; values determined

for MESS-2 were consistently reproducible with percent .R.SD of 1 percent!"

I

I

Imms animidaltabk 2 final reportlfinal report fileslfinal section 3 text.doc 3-17

1

,
- .i

:0'·

" .

I

I

o.

o
":nl ,e!iiiI

-"~ =, ~--, •. cOl f C

-.-'! eI ('J (T-~l ~~~~Cl

;~""j' "(~Y ,---) .51 ':. -~'t , --') ,C' --I

Table 3-1. Summary Data by Metals, Total Organic Carbon (TOC), and Grain Size in Sediment from the Coastal Beaufort Sea

Mean ±

I 0.10I 4.13I 10.5 I 387I

1.1 I 0.22

I

7.2 I 61.6 I 20.8 I 2.36 Std. Dev. ±0.04 ±1.55 ±2.7 ±146 ±0.5 ±0.09 ±3.0 ±19.5 ±9.3 ±0.78 (n = 42)

Sediment Mean ±

I 0.12 I 4.48 I 9.3 I 460 I 1.1 I 0.26 I 9.0 I 64.4 I 21.8 I 2.30

Cores 2001 Std. Dev. ±0.05 ±0.80 ±3.2 ±60 ±0.2 ±0.10 ±2.0 ±9.6 ±6.5 ±0.44 (n = 104)

Surface Mean ± 0.08

I 3.74 I 9.3 I 408I 0.9 I 0.16I 8.3 I 55.0 I 15.4 I 2.12 Sediment Std. Dev.

2002 (n = 44) ±0.05 ±1.37 ±2.6 ±121 ±0.3 ±0.06 ±2.8 ±19.2 ±6.8 ±0.71

All data Range 0.01- I '1.1-1.3 I 4-.2-28.4 I 155-7531 0.3-2.3 I 0:03-0.82 1- 2.2-18.6 I 12.7-104 I 3.6-50.21 0.7-3.9 0.44

Surface Mean± 0.043 364 25.9 9.4 0.49 0.40 99.7 75.6 1.03 52.5 Sediment Std. Dev. ±0.021 ±137 ±9.3 ±4.3 ±0.17 ±0.16 ±35.3 ±25.9 ±0.79 ±31.9 2000 (n = 42)

Sediment I Mean ± I 0.054

I~ ±~~~ ~I 31.9 I 10.3

1-

0.62 I 0.47

1

99.7

I

91.5

Cores 2001 ~~d~ ~;;)._ ~_Q,011 ±6.3 ±2.5 ±0.12 ±O.or ±17.4 ±22.6 I±~~~ 1_ ~28~._ .__ c •• _

Surface Mean ± Std. 0.036 I 353 I 24.8 I 9.3 I 0.43 I 0.41

I

90.4

I

66.4

I

0.74 I 50.2 Sediment Dev.

±0.017 ±151 ±9.7 ±3.0 ±0.12 ±0.13 ±34.0 ±24.0 ±0.37 (n = 44) ±35.0 2002

All data Range 0.003- I 62~898 I 6.0-48.4 I 3.2-22.3 I 0.15-1.14 I 0.12-0.92 I 26.9-173 I 14.8-157 I 0.01-4.41 I, 1.0-98.8 0.20
I

,I

1

,

I

I

I

:1' .

I

I

I

"r

I

i

"

'!

-~----;i~-~' I ~-'-;--~~I!r-I ~!-J

I" I I

I,

1I m

rimI I

! I I I Ii

o

1'1

:0"

ie

o

I

W

,0

'.0-" I : ,-',f:

I"

,m

m

II

o

,- .'. ,~
'40

" "

,.; .' " .1

t

Total Srr(flg/Kg) , TOC(%) SIIt+Clay(%)

I

36 0.29 70

I

28 0.58 73

I

32 0.59 85

I

55 1.2 49

I

23 0.50 42

I

25 0.96 26

I

36 0.96 31

I

31 1.1 29 I

23 0.91 33 I

7.8 0.06 1.2

I

100 2.0 54

I

22 <0.1 46

I

48 0.51 49

I

29 0.40 25

36 (i~3) 0.71 (0.51) 44 (22)

I

27 0.42 2.4

I

280 1.8 39

I

2.2 7.4 NA

I

51 2.4 NA

I

30 2.8 NA

7.4

6.4

8.1

'16

6.1

6.5

6.5

5.6

4.7

5.9

17

3.5

7.8

4.1

4.3

25

0.55

18

6.5

7.5 (4.0)

340

320

630

420

300

380

510

440

270

26

630

260

420

180 '

140

2000

8.6

100

250

370 (160)

Station Total PAH (flg/Kg) TotalPHC (mg/Kg)

River Sources

Colville (1)

Colville (2)

Kuparuk

Kuparuk Peat

Sagavanirktok

Mean (SO)

BSMP-2000

3A

38

4A

48

4C

5(0)

5(1)

5(5)

5(10)

58

50

5E

5F

5H

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

I

, I :'I-~' Ii'

m

il

I

I

' , ': :

'I·: ,

':01'

"

III

~II

'i,1'1'·'-'· I

18

;:U

,I

II

;m

,!ft1

:11

"I
-

I:

-

-

.,. i

_I

D:

II,

n' IDooIo

0, II

,0o

ilI

0' II
,

Table 3-2 (continued). Map Showing Beaufort Sea Monitoring Program Sampling Stations

and Table of Concentrations for Selected Organic Par~meters and Grain Size in Sediment

Samples I I

BSMP - 2002 I

3A 370 7.1 35 0.86 75

I

38 390 8.0 31 0.74 84

4A 500 7.8 28 90 7.8

!

48 83 1.8 7.6 0.77 10 I

4C 12 0.44 1.5 0.30 0.78 I

5(0) 170 4.0 15 0.62 18 I

5(1) 22 0.50 2.6 0.14 3.0

I

5(5) 300 5.3 30 0.58 41

!

5(10) 110 2.1 11 0.58 21

I

58 68 3.5 6·t 0.41 4.3

501 270 (33) 6.2 (1.1) 38 (6.6) 0.96 (0.13) 70 (2.3) I

5E 46 3.8 5.~ 0.08 3.7

5F 370 8,3 49 1.26 71

I

5H 160 3,5 16 0.91 22

Mean (SO) 200 (160) I

4.4 (2.7) 2006) 0.62 (0.33) 37 (34)

River Sources - 2002 I

Canning (1) 490 9.1 23

I

Canning (2) 190 19 18

I

Canning Sheen 220 2900 NID

I _Colville 690 11 73

Colville Peat 360 50 116

I

Kuparuk (1) 89 17 89

Kuparuk (2) 160 22 146I

Kuparuk Peat (1) 140 71 92

Kuparuk Peat (2) 450 72 39b

I

Sagavanirktok 670 18 65

I

Sagavanirktok Peat 160 41 38

Note1 - Field Triplicates were collected at thi$ station. The aveJage value of the tripncates is reported with e,

the standard deviation in parentheses. ill

I:

I,I,m~,.'· f'

,m

0,11

,

"[IDIW,

!m

;11 , ..

m

i.
I ,~

;0,

D"·

D. I

1',1

I:

,0oII

I,

:1.

:I,\-:

:1:

Ii

Hi Dn

-I

. ..,

-;

. !. ..,

. I

I'

:i,

. I·

-

.,~ ,. ,

.

jttt

i_ _",_.

,. ~- , ", "

.

•
RelndCKIr I

L .... :~

, ~,

-.,. '-, ..

,.." ·.,t·

h

. " . thulli::ttMhl ,•

~~..".~~.".-.'.... ~. ~., ~. ' ,"

_. ; . .,

,/

/

Northstar lsi nd

I

Station Total PAH (llg/Kg) Total PHC (mg/Kg) Total SITI(1l9/Kg) TOC(%) SlIt+Clay(%)

Northstar - 2000 I

5A 1800 22 140 1.7 85

N01 I

80 1.5 6.8 <0.1 2.4

I

N02 370 6.3 36 1.4 68 1

N03 620 12 59 0.74 83

I

N04 2000 23 150 1.7 77

I

N05 1400 16 97 1.6 86

I

N06 480 7.1 38 0.64 30

I

N07 540 11 62 1.2 48

I

N08 580 14 48 0.34 14

I

N09 280 4.1 20 0.78 12

N10 580 26 1.4 45 I

N11 650 20 82 1.4 58

24

I

N12 1500 150 1.6 90

N131 I1100 (140) 17 (3.1) 99 ~15) 1.9 (0.3) 91 (3.9) I

N14 1100 24 150 4.4 88

N15 29 1.0 2.!9 <0.1 2.2

I

N16 600 10 63 0.86 66

I

N17 630 11 59 0.97 72

12

I

N18 870 7il 0.50 61

N19 620 10 5k 0.83 63

N20 17 I 720 79 1.7 70

I

N21 170 27 180 2.3 94

N23

I

540 10 6.8 1.8 99

Mean (SO) 810 (530) 14 (7.7) 78 (47) 1.3 (0.92) 61 (30)

Table 3-3. Map Showing Northstar Sampling Stations and Table of Concentrations for

Selected Organic Parameters and Grain Size in Sedim~nt Samples . I

!I

ra

l~l

;11" .11

.\

:~I\

::mt·

.:Ill t

II

'i~l

,m

m

llll .. III

;Gl ,II·,

:11 ;u

:im

m

II

:., Ill,

iml,

,1lfI

"II
.

i

-

".

_.

II

,I'j

,II

II

:Iln,' III

fIrI" II'
Table 3-3 (continued). Map Showing N'orthstar sarnpJg Stations and ~able of

Concentrations for Selected Organic P·arameters and Grain Size in Sediment Samples

I :

I

Note1 - Field Triplicates were collected at this station.

the standard deviation in parentheses.

I 771 0.97 92

6.4 0.30 3.45

63~~.5) 0.9~·~0~09) 82~:.3) 6d 0.58 66

9d 0.90 87

I

5q 0.73 62

26 1.0 33

5J 0.84 75

I

32 0.78 60

I

55 0.84 68

I

32 0.45 47

5111.0 80

11b 1.8 91

I

100 1.4 81

2~ 0.19 4.3

I

88 0.89 89

I

70 0.85 83

I

51 0.98 51

I

1.2

I

5.7 0.09 8.8

I

.61 1.0 87

51 0.91 , 89

'55 (?8) 0.85 (0.37) 63 (28)

The ave~age value of the triplkates is reported with

10 (5.1)

14

1.7

8.2

11 (1.4)

9.3

14

8.1

6.2

10

6.p

11

6.6

13

22

22

3.7

13

11

7.6

10

3.2

14

9.6

810

62

420

600 (77)

640

940

510

280

500

310

530

340

510

830

850

200

900

620

410

510

61

650

420

Mean (SO) 520 (250)

Northstar - 2002

5A

N01

N02

N031

N04

N05

N06

N07

N08

N09

N10

N11

N12

N13

N14

N15

N16

N17

N18

N19

N20

N21

N23

'1.-', I

I !

,:1

"1m

'il

i'l- ... I. .~

I:

1.··1'''''' 'I .

,.", "

tn'ill

il:

,1m
:;

. ,. ~:.'

.: .. ..

,.

II

-

-

,."

~..', ~.' '.-'"

' ,:1

:i

,

'-

IIII,

"IIIIIIfItiII

-I

J, '.

iClldllIII "" . . !

I·~.··"· I " ! .1

',,'m--" ,

'

I"

I

II, WW

iO,. IlllI
,

Table 3-4. Map Showing Liberty Sampling Stations and Table of Concentrations for

Selected Organic Parameters and Grain Size in sedi1ent Samples ,

Station Total PAH (~g/Kg) TotalPHC (mg/Kg) Total SIT (~g/Kg) TOC(%) Silt+Clay(%)

Liberty·2000

L01 610 12 62 1.0 66

L04 400 7.7 51 0.47 60

L06 400 11 51 0.90 94

L07 220 6.9 20 1.5 36

L081 280 (70) 12 (0) 41 (10) 0.24 (0.06) 31 (7.4)

L09 99 1.9 11 ! 0.49 5.3

Mean (SO) 340 (180) 8.6 (3.9) 39 (20) 0.76 (0.45) 49 (31)

Liberty - 2002 I

I

i

L01 150 2.9 15 i 0.59 11

L04 400 7.1

~I 0.71 53

L06 420 6.5 1.2 58

L07 340 5.9 28 0.88 49

L08 340 10 52 0.67 6.4

L09 84 3.4 11 0.18 9.7 I

Mean (SO) 290 (140) 6.0 (2.6) 29 (15) 0.70 (0.33): 31 (24)

Note' - Field Triplicates were collected at this station. The avetge value 01 the triplicates is reported with

the standard deviation in parentheses.

. .. ',

Dutil ,Ratch' 1Io.ul~~rP.nt~ . . .

1'" ..' ·,.c, I M·'.~;\.ll'~"':l!I!'!!d!lr1PJl!IIII~

.Gf$1I~\!m!,I2~'" BaiJtdii'ilc:lolil!l~

C3,P.n!)!Id~l~)~.2ll%B~I<!l'!/C!IllbI.'

'M P.r/(d!~'~:,"!O;~,l!.~I~IC:GII~~i

,

-.. ,. ... ..-

"

•

•

•

il

'I

i

m

W

I

'I'

'I' ,::

~II'

~ID

I

I

I

"I'· I' \

'"I

",I

i,1

I

.1

":!:. ..11

,I

~'I
•.

1

-.,

I!

0,:
Saturated Hydrocarbons (SHe)

The sum of lower-molecular-weight n-alkane1s (n-Cg to n-C20) generally associated with

"fresh" etroleum in uts. I

LALK

Isoprenoids The sum of selected branched isoprenoid al~anes including: phytane, pristane, farnesane

[14701, and unidentified isoprenoids at relatiJe retention indices 1380 and 1650.

Isoprenoids are abundant in petroleum and ~re resistant to degradation relative to the

corres ondin n-alkanes. I ,

Table 3-5. Diagnostic Ratios and Parameters of satJated Hydrocarbons, Polynuclear

Aromatic Hydrocarbons, and Steranes and Triterpan~s

I

I

','m

,·m

I'

TALK The sum of total alkanes, which includes thdse of biogenic and petrogenic origin (n-Cg to nC40. I

LALKITALK Diagnostic alkane compositional ratio used to determine the relative abundance of lowermolecular-wei ht alkanes, which includes thbse of bio enic ori in.

Polynuclear Aromatic Hydrocarbons (PAH) j

m

'1-' t •

PHY/PRIS

CPI

TPHC

Source of phytane (PHY) is mainly petroleuriJ, whereas pristane (PRIS) is derived from

botl) biological matter and oil. In "clean" environmental samples, this ratio is very low and

increases as oil is added. I

The ratio of n-alkane hexadecane (n-C16) over pentadecane (n-C15) and heptadecane I

(n-C17). At "background" levels of total hydrocarbons n-C15 and n-C;17 can be used as

indicators of plankton (algal) hydrocarbon inputs. As plankton productivity increases, the

ratio decreases. I

Carbon Preference Index. Describes the relative amounts of odd- and even-chain alkanes

within a specific alkane boiling range [CPI = l(n-C27+ n-C29+ n-C31)/(n-C26+ n-C28+ n-C30)1.

CPI of 2 - 4 indicates terrestrial plants; as oill additions increase, the CPI is lowered to near

1.0.

Total Saturated Hydrocarbons. The sum of the resolved plus unresolved saturated

h drocarbons. "I

NIP The naphthalenes (N) to phenanthrenes/ant~racenes (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 increasedlweathering. (N= Naphthalene series [CON +

C1 N + C2N + C3N + C4N1; P= Phenanthrene/Anthracene Series [COP/A + C1 PIA + C2P/A

+ C3P/A + C4P/A . 1 .

C2D/C2P Ratio of C2 alkyl dibenzothiophenes (D) andl C2 alkyl phenanthren~s (P) is a useful

dia nostic source ratio for etroleum.

C3D/C3P Ratio O.f C3 alkyl d.ibenzothioPhenes (D) andl C3 alkyl phenanthrenes (P) is a useful

dia nostic source ratio for etroleum.

;1

Perylene

Total PAH

Total PAH less

e lene

A biogenic PAH formed during the early diagenesis in marine and lacustrine sediments;

rna be associated with ,terrestrial lant sour~e recursors.

The sum of all PAH target analytes; includes 2- through 6-ring parent PAH and C1 - C4

alkyl-substituted PAH. I I

The sum of all PAH target analytes with the exception of perylene. •

1

Pyrogenic PAH The sum of combustionPAH compounds (41' 5-, and 6-ring PAH: fluoranthene, pyrene,

chrysene, benzo[a1anthracene, benzo[b1fluoranthene, benzo[k1fluoranthene,

benzo[a1pyrene, dibenz[a,h1anthracene, benIZo[g,h,i1perylene, and indeno[1,2,3,-

c,d rene.' I.

Petrogenic PAH The sum of petrogenic PAH compounds (2-,13-, and 4-ring PAH: naphthalenes [CO - C41,

acenaphthene, acenaphthylene, fluorene [CO - C31, phenanthrenes [CO - C41,

dibenzothio henes CO - C3 ,ch senes c11- C4 , and fluoranthenesl renes C1 - C3

:0

Pyrogenic/Petrogenic The ratio of pyrogenic PAH compounds to petrogenic PAH compounds is useful for

determining the relative contribution of pyrogenic and petrogenic hydrocarbons and in

differentiatin h drocarbon sources. I
- _.
The ratio of C30-0leanane (T18) to C30-hop~ne (T19); indicates the relative amounts of

oleanane, which is a marker of angiosperm (post-Cretaceous) contribution to petroleum

diagenesis. I

C30-Ho ane T19 ,commonl one of the mclst abundant triter ane!> it' etroleum.

Ratio of C27-trisnorhopane (Ts) to C27-trisnOrhopane (Tm); used a~ a maturity indicator for

, etroleum and also as a source ratio for diffdrent crude oils. I

Oleanane/Hopane

SteraneslTriterpanes (SIT)

Js/(Ts +Tm)

Ho ane

Total srr The sum of all sterane and triter ane biomarker tar et anal es.

I

,

I

I

I

Table 3-5 (continued). Diagnostic Ratios and paramJters of Saturated1Hydrocarbons,

Polynuclear Aromatic Hydrocarbons,and Steranes ard Triterpanes '

T21rr22 The ratio of C31-homohopane (22S) (T21) to C31·homohopane (22R) (T22); useful for

determinin the contribution of recent bio e~ic material. :

CPI - Carbon Preference Index

LALK Low-molecular-weight n-alkanes

LALKrrALK - LALK:TALK ratio

PHY/PRIS - Phytane:pristane ratio

TALK - Total n-alkanes

g

eg

'1

".,g'

"I

J

U

:0

'8;

:111 ,Ill

.... '...

iD

n~I,

1fI~

10"',!,,I

1,111

111I"

n

m

n

m

m

.0
IIm

WI omo

,II.-

:0

11

iO

,0IIo

I'I

I~
-:01

'UI

·'11

:11

:11'/

III

UI

01

II...

I~

I'

iii

I

I

:1

I

·1

'I

~I.

Table 3-6. Average Total Organic cone,ent,rations in SIUrfiCial Sediments ~rom ANIMIDA

Study Area, Alaska Marine Sediments" and Cook Inlet and Shelikof Stra}t Sediments

~'*);.~(,:k'4:~~":>~:<'~,'.":W~t':Jf~"~,,,·: '.'~', ""'" otaHS/T" I '1l~'l1~

Concentrations in Alaska I

Marine Sedimentsa 0,016 - 2.4 0.47 - 38 NA

Concentrations in Cook 0.001 _ 1.080 b9 690 0.009 0.087

Inlet and Shelikof Strait I' - .

Sedimentsb

Average (Range) 9.01 (3.2 _ 31) Concentrations for 0.54 (0.28 1.99) I i 0.059 (0.021 - 0.225)

ANIMIDA StudyArea

SedimentCoresC

Average (Range) . I

Concentrations for Phase I 0.39 (0.007 2.7) 6.6

1

(0.21 - 50) 0.025 (0.001 - 0.082)

ANIMIDA Study Area

Surficial Sedimentsd

Average (Range) I

Concentrations for Phase II 0.49 (0.012 - 2.0) 9.5 (0.44 - 27) 0.049 (0.002 - 0.176)

ANIMIDA Study Area I

Surficial Sedimentse

a Prince William Sound subtidal and Beaufort:Sea (Bence et al.:!1996; Boehm et aI., 11991).

b ENRI - UAA, 1995, Hyland, et aI., 1995; KLI, 1996; KLI, 1997; Boehm et aI., 2001a.i

C Brown et aI., 2003. '

d Boehm et al. 2001 b and this study. , .

e Results from this study. . i

f Total PHC concentrations for the ANIMIDA studies included saturated hydrocarbon's only, while Total PHC

concentrations for the other studies included ~aturated and arorhatic hydrocarbons. :

NA - not applicable.
-

I ,.

I.

_,I

rill. 11 lID 'I

~,BBIII

.~mDm

I:mI
... rt.M!Ciilllhi. II ,... - 'til: G·

l\,

~.

I~.~.

'.

t

I Station AI Ba Hgj Pb Cd

I (%) (P91g) (P919) (1=19'9) , (1=19'

9)

BSMP ·2000

'. I 3A 3.99 400 0.01 9.6 0.26

38 4.14 288 0.03' 6.3 0.17

4A 4.48 285 0.0411

6.0 0.18

48 5.43 305 0.05~ 8.9 0.17

4C 3.~9 226 0.030 4.9 0.12

5H 2.74 285 0.02~ 6.6 0.21

I

5(0) 4.20 367 0.049 9.9 0.24

I

5(1) 4.33 388 0.035 11.5 0.17

I

5(5) 4.17 372 0.039 9.9 0.22

349

I

5(10) 3.85 0.031 8.9 0.21

5A 6.98 623 0.074 17.6 0.28

I

58 1.26 164 0.003 3.9 0.03

I

50 4.03 380 0.049 9.8 0.33

I

5E 2.34 187 0.013 4.4 0.06

I

5F 3.43 349 0.029 8.2 0.18 , .

Table 3-7. Map of Beaufort SeCi Monitoring Program Sampling Stations and Table of

Concentrations of Selected Metals in Sediment Sampl~s . . I

o

'0

'I

o

,0

il

'I

I

,I

'I

,I

I

'I

I

I.

:U'

,I

'I

:0
III(I

"' ~.I!III!

mmm::;;'.."" mImmoooIooI

00oIII !
Note1 - Field Triplicates were collected at this station. The aveJage value of the triPI:icates is reported with

the standard deviation in parentheses.

0.061 12.9 0.17

0.058 14.1 0.23

0.042 11.6 0.31

0.01615.4 0.17

0.0071 4.1 0.05

0.026

1

8.4 0.14

0.025

1

6.1 0.21

0.006

1

5.3 0.07

0.060

1

' 8.6 0.13

0.021 7.3 0.12

0.049

1

11.0 0.19

0.0081

5.9 0.05

0.029 (0.004) 6.9 (1.1) 0.20 (0.03)

I 0.009

1

5.1 0.06

0.0431

8.6 0.18

BSMP - 2002

3A 4.71 512 '

38 5.03 518

4A 4.28 535

48 2.02 221

4C 1.56 165

5H 2.85 313

5(0) 3.12 363

5(1) 1.72 223

5(5) 3.47 357

5(10) 2.62 271 '

5A 5.42 538

58 1.72 221

50' 3.64 (0.25) 371 (30)

5E 1.65 203

5F 4.38 455

Table 3-7 (continued). Map of Beaufort Sea Monitoring Program Sampl ng Stations and

Table of Concentrations of Selected Metals in Sediment Samples

, I

o

h

n-.........'

,0

,In

10

in

,I

in

1m

;1

10

~n

il

'iU'

II

iU'

,I

iO
,

'

-

- ,I

'I

i

'i ,!I

!-I ; I

.,

,i

Ii

II

, I

,I

iiI

:1

Ii.'

'

-. ,II

m:

'~I

••~'I '~t

W' IWIWII

W: WmIImmmI
Rolndeerl

Northstar 1.81 nd

I Station AI Ba Hgi Pb Cd

I (%) (1.I9/9) (1.19/9) (l.Ig/g) O.l9/g)

Northstar - 2000

I N01 1.67 209 0.011 5.2 0.06

N02 I

4.93 491 0.041 12.3 0.23

N03 I

4.90 505 0.046 12.8 0.28

N04 I

5.96 476 0.055 12.5 0.26

N05 I

6.76 511 0.058 13.7 0.25

N06 I

3.79 406 0.029 8.0 0.25

N08 I

2.69 306 0.024 5.2 0.20

N09 I

2.95 227 0.020 4.4 0.15

N10 I

3.54 352 0.077 8.7 0.27

N11 I

5.05 346 0.043 8.4 0.22

N12 I

6.62 654 0.078 17.7 0.35

N13 I

6.69 465 0.065 11.6 0.25

N14 5.85 555 0.08t 17.3 0.45

N15 I

1.44 172 0.006 2.8 0.06

N16 3.64 376 0.03~ 7.6 0.22

I

N17 1.64 377 0.050 9.3 0.2

I N18 3.78 271 0.033 5.2 0.16

I

N19 4.29 437 0.053 10.7 0.24

I

N20 5.32 519 0.051 13.3 0.33 . I N21 6.64 609 0.081 17.3 0.37

N22 1.06 859 0.003 3.3 0.07

I N23 6.25 625 ·0.075 20.3 0.43

I

Table 3-8: Map of Northstar Sampling Stations and Table of Concentrations for Selected

Metals in Sediment Samples I

n

I

:0

:0

I

I

o

n

o

o

I

I

o

'I

I

n
,I! .-

,i

"ij

,.

, !' '1

II

,~

m

III1I1

.,.

IIIIl

.:

!

i

"

II

Ii

II

i

I. iiI

i.I

;.1

!

i!t

.

I.

ii

!i·
-

:0

o

o

:0

il

,I

I

I

I

I

:1

I

~n'

I

I

n

n

I

I

Table 3-8 (continued). Map of Northstar Sampling staLns and Table o} Concentrations for

Selected Metals in Sediment Samples 1

Northstar· 2002

I N01 1.73 212 0.009 6.5 0.05

N02 I

4.51 501 0.044 13.8 0.13

N03' 5.42 (0.28) 537 (23) 0.055 (0.014) 14.2 (2.8) 0.17 (0.02) I N04 4.13 422 0.048 10.3 0.14

N05 I

5.78 578 0.053 12.3 0.18

N06 I

4.85 503 0.046 12.8 0.12

N08 I

4.45 469 0.045 9.3 0.17

N09 I

3.71 402 0.036 7.3 0.16

N10 I

4.49 473 0.046 9.5 0.19

N11 I

2.73 293 0.023 8.9 0.11

N12 I

4.86 478 0.041 10.1 0.21

N13 5.58 514. 0.061 15.3 0.22

N14 I

5.72 545 0.059 11.6 0.21

N15 I

1.65 302 0.015 6.1 0.11

550'

I

N16 5.86 0.051 14.3 0.20

I

N17 5.27 518' 0.05'1 13.8 0.21

N18 4.50 476 0.045 9.1 0.19

I N19 4.60 478 0.051 9.7 0.18

I

N20 1.65 291 0.011 5.1 0.07

423: I N21 4.43 0.048 11.3 0.21

I N23 4.82 575 0.04~ 10.4 0.27

Note1 - Field Triplicates were collected at this station. The aveJage value of the triplicates is reported with

the standard deviation in parentheses.
,

I

~~~~rT,,',nlllUl~ .,

'I' m'

-';!-

.. mm

"~ mw-m

:1I

'I

I' II

'.

!¥.,'
Note1 - Field Triplicates were collected at thiS, station. The ave~llage value of the triplicates is reported with

the standard deviation in parentheses. , ' ,

Note2 - Field Duplicates were collected at this station. Both values are reported. •

Cd

(pg/g)

0.18

0.26

0.19

0.19

0.15 (0.04)

0.13

Pb

(pg/g) ,

10.7

9.0

5.7

5.5

6.4 (1.8)

9.5

Jeanettel!s.,

~, W

---","">,.,,

"' , 0

'1lO~ld_Qr 1>.*"

III l~\1!'~,BClU!dtitl¢!lti!l1_~

"Chlltt;rtl1lln~ilolIlllwCGli)1ll1

Hgi

(pg/g)

I

0.061

0.030

0.03J

I

0.045

0.025 (0.608) I

0.025

Ba'

(pg/g)

370

353

252

233

343 (80)

269

6.18

3.66

4.16

3.56

2.53 (0.23)

2.64

AI

(%)

.., .

I

2.59 259 0.021 7.2 0.10

I

3.78 385 0.036 11.6 0.16

I

4.58 486 0.044 9.3 0.19

I

4.07 437 0.041 8.0 0.19

1

1.64,3.43 415,534 0.012,0'1033 7.2,7.4 0.08,0.17

L09 2.23 243 0.019 9.5 0.10

Station

L09

•

•

Liberty - 2002

L01

L04

L06

L07

L082

Liberty - 2000

L01

L04

L06

L07

L081

I

Table 3-9. Map of Liberty Sampling Stations and Table of Concentrations of Selected

Metals in Sediment Samples I

• - I

o

,I

iQ

10

'"

'iD

'0:

'0

n

I

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II
I

,

: {;i ,.,

; ,I I

:1

iD:100I

1'"

0 .. • nIIIIII I

.'

i

0 ;.1 .", '"1 ~.:' ":y' ,fr .,.l ',~ ~~1,;, , 'j 'I I

I,
II -J l!!!!!!!!!!!!!l

_,_'_~'_~

I!!!!!!!!!!!!l':l !!!!!!!!!!!!!!II !'!!!!!!!!!!!!II) I!!!!!!!!!!!!!!: !!!!!!!!!!!!!!!11 _, I!!!!!!!!!!!!!!:: -' ---Il ==, '==-ii,( '--\i =='----II' ==:==1) == =1) ==

Table 3-10. Statistical Model Result Summary with Silt + Clay Covariate

Performed on matching data sets with 35 stations each year (includes N1-N15, six Liberty stations, and all BSMP stations except 50). Model includes

station as an additional factor and silt+c1ay as the covariate for the concentration variables.

-0.032 0.849 0.936 0.000

0.110 0.449 0.751 0.001

-0.045 0.787 0.921 0.000

0.061 0.650 0.767 0.000

0.174 0.147 0.580 0.002

0.045 0.630 0.519 0.000

0.074 0.614 0.854 0.000

-0.060 0.286 0.371 0.000

0.248 0.256 0.212 0.521

n ...." n n." n n." " Q.,7

0.012 0.002 -0.003 0.582

0.017 0.253 -0.010 0.626

-0.013 0.643 -0.119 0.004

0.000 0.992 -0.001 0.819

.0.121 0.189 --- ····--0.103 . -0.463 ... ----- --_.. _--

-0.029 I 0.661 -0.253 0.014 2

-1.144 I 0.000 0.455 0.316

.951

0.002

0.408

0.002

0.513

0.000 -0.382 0.068

0.000 -0.566 0.012

0.000 -0.438 0.014

0.000 -0.362 0.019

0.000 -0.325 0.017

0.000 -0.529 0.005

0.000 -0.202 0.024

-0.191 0.522

n no'>

0.022

0.021

2.232

0.000 4.297

0.858 0.000

0.830 --_ ......!....

......_.._-- _- _ _.

LN Petrogenic PAH (l.Ig/Kg) I

LN Pyrogenic PAH (l.Ig/Kg) I 0.857

LN Total PAH (l.Ig/Kg)

IN'TotajPAHiess """""""""""""'j ,

p~ryI~~l:l.J""9.~~9L",,____,l__ ?:~~?_+_. ?:??,?,.1,~:~.1~ __ .; _,_~:~~.~,_,,: ,_~:~~~_,,' -0.

LN Perylene (l.Ig/Kg) I ,,' ._- ;

LN TPHC (mg/Kg) 0.813 0.000 1.018 0.017 ..............H.H ••••••••••••••••••••• H ••••••••••••••H •••••••••••••••••••••••••••••••••••••••••••••j .....................__.•_

LN LALK (rilg/Kg) 0.891 0.000 -1.779 0.019 ........_...............H...._..............._._ .........H......... ..;................H......

LN TALK (mg/Kg) ! 0.834 I 0.000 -0.440 0.022

'LN ,so~~~~~i~.~~~~'..~~~J::?;~~~·_]?;??~;",_-2 .549 0.013

LN TOe (%) I 0.697 0.000 -1.410

N/~------_·,--·-------·I=-~:5~1-:-0,00-1-:-0,937-

~r;1:;;~~~~~~_~_::=:;~:~9-5·;·-;:;~~·_j """"'~~~~'~

C2D/C2P 0.464 0.041 0.293

C3D/C3P 0.488 0.018 0.353

LALKITALK 0.551 0.001 0.204

,CJ6/(Ct5+_Ct7)_ - , 0.373 " .,7., 0.306 --..--_._--_._..._--

Pristane/Phytane 0.005 2.259

CPI 0.003 4.765

Note' - Northstar effects and p-values are reported from an ANOVA model that excluded the station effect due to the nesting ofstations

within regions.

Note2 - This result was considered to be not significant when controlling the false discovery rate (Benjamini and Hochberg, 1995).
.,,,,,,,_..

, '!' .'

HI
!!!!!!!!!!!!t\ ;-:~ -- ----.,: !!!!!l!!!!!!!!!;) - ' --~'!!} I!!!!!!!!!!!!!!;I - -~ ---'I '~) !!!!!!!!!!!!!!!' -- -~ -~----!, --I ,-- - -,t " ----~ ,----\

.•~I -, .'"-'; ',!!!!!!!!!!!!!!!\ ~i~ ~-'

_. -' - -, '--~

._liY \~Ii ~._"

Table 3-11. Statistical Model Result Summary with Perylene Covariate

Performed on matching data sets with 35 stations each year (includes N1-N15, six Liberty stations, and all BSMP stations except 50). Model includes

station as an additional factor and LN Perylene as the covariate for the concentration variables.

LN Total PAH less

,'p'~_~,~,':!~,J.I::'~~~f.!J, O.

LN Petrogenic PAH (lJg/Kg) 0.983 0.000 1.979 1.029 0.000 -0.167 0.086 -0..160 0.003 0.136 0.107

LN Pyrogenic PAH (1J9/Kg) 0.986 0.000 0.131 0.902 0.000 -0.082 0.315 -0.Q38 0.362 0.095 0.150

LN TPHC (mg/Kg) 0.902 0.000 -0.478 0.686 0.000 -0.110 0.353 0.101 0.243 0.085 0.532

LN LALK (mg/Kg) 0.957 0.000 -3.287 0.700 0.000 -0.031 0.729 -0.027 0.645 0.025 0.793 ..............._......

-LNTALK(mg/Kg) 0.954 0.000 ~2.504 0.937- , . 0.000 -0:179 0.073' ; -0'.027 ' 0.722 0.166 0.176

LN Isoprenoids (mg/Kg) 0.938 0.882 -0.105 0.027 0.067 0.364

LN TOC(%) 0.739 0.636 0.183 0.366 -0.222 0.496

Notel - Northstar effects and p-values are reported from an ANOVA model that excluded the station effect due to the nesting ofstations

within regions.
IIIIIIII

IIooDoIoUoDaoooIo

,I

:1
. ' , j ,_1 -,

, ,~II =~ "l!!!!1!!!!!!!!n

,~' I!!!!!f!!!!!!!!' _,I ._, !!!!!!!!!!!!!!!l "Ii "l!!!!!!!!!!!!l) _I ~l , '~ """'1

~II

I!!!!!!!!!!!!!!I ,I!!!!!!!!!!!!!! ,-',-' !!!!!!!!!!!!~ _if !!!!!!!!i!!!!!J) -" ,I!!!!!!!!!!!!!!\

~-~~

!!l!!!!!!!!!!!!l -"

Table 3-12. Statistical Model Result Summary with Aluminum Covariate

Performed on matching data sets with 35 stations each year (includes N1-N15, six Liberty stations, and all BSMP stations except 5D). Model includes

station as an additional factor and Aluminum as the covariate.

0.008

0.890

0.857

0.792

0.019 2

-0.986 0.718

-1.907 0.071

-0.038 0.614

0.081

0.842

0.406

0.089

0.391

0.560

0.677

0.880

46.7

1.44

0.180

0.598

0.761

-0.004

-0.085

0.000

0.000

0.000

-2.27 0.112

-45.3 0.024

-0.092 0.722

-0.010 0.520

-1.89 0.209

0.584 0.749

-0.359 0.608

0.004 0.9

0.000 0.001 0.638 -0.001 0.821

0.000

0.000 0.007

0.000 2.553 1.42

0.000 9.14 13.2

0.771

0.945 1·..····

Fe (%)

Cr (lJg/g)

h_ _ _._ ••••••••••••••••••••••_ ••••••• ••••

As (1J9/g)

Ba (1-I9/g)

Be (lJg/g)

Cd (lJg/g)

Co (lJg/g) 0.812

Cu (lJg/g) 0.953 0.000 -5.46 6.04 I 0.000

0.969 0.000 0.388 0.527 I 0.000 0.026

Hg (lJglg) 0.910 0.000 -0.008 -0.013

Unf.."f,,\ nnn" nntln <7') on" nnnn "'),, nOOA ""0 n<;no ..ton nn..t0 2 •

• Ni (lJg/g) 0.956 0.000 -0.910 6.10 0.000 0.117 0.911 0.499 0.501 0.353 0.750

Pb (lJg/g) 0.863 0.000 3.60 2.49 0.000 0.547 0.429 -1.02 0.067 -0.430 0.601

Sb (lJg/g) 0.847 0.000 0.239 0.098 0.000 -0.039 0.213 -0.074 0.003 0.044 0.220

TI (lJg/g) 0.873 0.000 0.056 0.090 0.000 0.008 0.738 0.001 0.957 0.012 0.699

,_V(lJg/gL_ ,._.0.973_ .0.000._ -4.359 24.4 0.000 .5.J9 .0.057__ _.2.23_" ",0.3,19 __ _-}',04, Jl.0_38 2

Zn (1J9/g) 0.944 0.000 6.80 18.5 0.000 -1.00 0.752 0.463 0.849 -3.18!, 0.383

Notel

- Northstar effects and p-values are reported from an ANOVA model that exclude~ the station effect due to the nesting ofstations

within regions.

Note2 - This result was considered to be not significant when controlling the false discovery rate (Benjamini and Hochberg, 1995).
r

, ~.I

Im

I.mmmmoDI

,0I , 00II

I' moI
8.1

3.2

4.1

2.8

2.7

2.5

2.0

2.4

2.0

3.6

4.0

: Total SIT

; (!lg/Kg wet

weight)

12

26

14

15

NO

NO

1.6

NO

NO

4.4

,NO

"''':0

1".1'ola' PHC (mg/Kg wet weight)

23

16

14

12

13

16

7.4

18

20

39

15

Total PAH

blg/Kgwet

weight)

II

Species

Anonyx

Anonyx

Anonyx

Anonyx

Astarte

Astarte

Astarte

Anonyx

Anonyx

Cyrtodaria

Astarte

-. ;10' ~,,,- ,. '5'

;0'

I

Anonyx (an amphipod), Astarte (a clam), Cyrtodaria (a clam).

ND - Not detected.

StatiOh

Summer - 2000

N03

N12

N13

N18

L08

L09

3A

4A

5(0)

5F

5H

Table 3-13. Map of Sampling Stations for Organisms and Table of Concentrations for

Selected Organic Parameters I I

~'---"--~~

- I~---'--~"-}!-~-:-- , r----..- "

: '~,~---_/ Ii! 'C..... }

'~
I

.iI

·1

.-

DoDooIIIIII 

:0o9IDomo
1111

ilfl

'In

il~!

,II!

1111

10

l~~.

III

111

'II

lIt

II

1~1 1>

I~I

lIt

IfI

I~I

,In,

1, Table 3-13 (continued). Map of Sampling Stations for Organisms and T~ble of

Concentrations for Selected Organic Parameters I

Summer - 2002

N03 Anonyx 13 22 3.2

N04 Anonyx 14 18 2.2

N12 Anonyx 11 4.9 15

N13 Anonyx 35 9.3 2.4

N18 Anonyx 14 17 1.6

4A-1 Anonyx 31 52 2.3

4A -2 Anonyx 18 20 2.1

5(0) Anonyx 17 38 2.0

L08 Astarte 10 2.5 1.2

L09 Astarte 9.6 2.6 1.0

3A Astarte 12 2.7 1.1

5H Astarte 14 3.1 2.0

5F Cyrtodaria 35 3.2 3.1

I

Anonyx (an amphipod), Astarte (a clam), Cyrtodaria (a clam).

ND - Not detected. ' I
-

, i

I:

_

I.a.u.~ IIIIIIIIIIIIHoI

I,

•• ' 

0'

,0I
.,.... 

1,

Table 3-14. Map of Sampling Stations for Organisms ~nd Table of Concentrations for

Selected Metals (Cd, Cu, Hg, and Pb) I

J:A '~" , .. .. ',- ., - ',,_. ~ - ': ',' -, '

, ,

';15 ,0 .

,I

Station Organism 'Cd Cu Hg Pb

(pSiS) (P9/S) , (PSiS) (pg/g)

Summer - 2000

N03 Anonyx, small 0.52 1'11 0.036 0.40

N12 Anonyx, small 0.41 104 0.024 0.27

N13 Anonyx:small 0.29 163 0.038 0.23

N18 Anonyx, small 0.31 41 0.022 0.22

4A Anonyx, small 0.59 93 0.034 0.24

5(0) Anonyx, small 0.60 102 0.024 0.26

L08 Astarte 10.2 1~!.1 0.032 0.66

L09 Astarte 10.8 1~.6 0.032 0.69 ,

3A Astarte 10.2 ~.2 0.025 0.40

5H Astarte 10.3 11.2 0.048 0.64

i

Cyrtodaria i

5F 1.3 12.3 0.014 0.48

Anonyx (an amphipod), Astarte (a clam), Cyrtodaria (a clam).

I~l

II

10

1~1

I~l

'10

II

10

I~I

I~J

II

U
... r.· • .......

i

III

.

,'•. "t· •. !.

, I

'!

..1-.

I

,0

'0

:0o

:0I

III

Imi ImaII

,IIm

I,
lIiU. ---------~-----...

II

II

'ID

il

II

il

:···.0···· ';

,

il

:0

'II'I

:1

'·'·0-

"I'

, '

in

t

I

1 ,

Table 3-14 (continued). Map of Sampling Stations for brganisms and Table of

Concentrations for Selected Metals (Cd, Cu, Hg, and Pb)

1

Summer - 2002

N03 Anonyx, small 0.47 h5 0.063! I

N04 Anonyx, sll)all 0.47 h2 0.0411

N12 Anonyx, small 0.51 1'48 0.060i

N13 Anonyx, small 0.42 1129 0.069

I

N18 Anonyx, small 0.51 11

82 0.056' I I Anonyx, small 1 4A -1 0.77 1i32 0.071'

Anonyx, small i

4A-2 0.55 127 0.067

5(0) Anonyx, small 0.58 134 0.058'

I

L08 Astarte 9.6 1- 0.127

L09 Astarte 10.6 18.3 0.069,

3A Astarte 11.6 1b 8 0.074 I'

5H Astarte 13.1 16.1 0.060 i

SF Cyrtodaria 0.17 1,3.9 0.019

Anonyx (an amphipod), Astarte (a clam), Cyrtodaria (a clam).

0.69

0.28

0.25

0.39

0.23

0.70

0.40

0.18

0.76

0.58

0.77
.

!

I.'

i,i

'I

. ,.:

Qo

,I

,O!I

'm

m

I'Imm

m" I
1111

Table 3-15. Map of Sampling Stations for Organisms and Table of Con~elrltrationsfor

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

Station Organism As Sa V Zn

(pg/g) (pg/g) (Hg/g) (pg/g)

Summer· 2000

N03 Anonyx, small 7.4 25 3.4 92

N12 Anonyx, small 6.7 30 3.1 88

N13 Anonyx, small 6.2 48 2.9 81

N18 Anonyx, small 7.0 21 2.7 88

4A Anonyx, small 6.6 25 2.4 94

5(0) Anonyx, small 7.0 40 2.5 91

L08 Astarte 10.8 18 4.1 76

L09 Astarte 12.1 15 3.4 68

3A Astarte 11.5 11 1.9 62

5H Astarte 10.7 25 5.1 74

5F Cyrtodlilria 7.5 12 2.7 67

Anonyx (an amphipod), Astarte (a clam), Cyrtodaria (a clam).

,>l

II

-... n" hI' ',0'

lU

'0I

10

10

11

10

10

o

I

II

10

10

II

II

II

10

II

II

II
I

'

•:-;,.", -~•<

"

.'

,i

"

\'

iDD

,0

:0IoI, 

D

iDD

:1mI

10

,I

0' IU

:9
I,Ll I I

D

I

I

u

n

::11

'I·,"

r;

il

o

iD

iI,

iB,

:,n~- ,

i

:'n, \

o

',0'" :1

:::

II:

':0

1,1"- i!

"! '

','0·"

",

Table 3-15. Map of Sampling Stations for Organisms and Table of Conc:el1trations for

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

Summer - 2002

N03 Anonyx, small 8.5 29 2.1 114

N04 Anonyx, small 7.5 31 1.9 108

N12 Anonyx, small 4.6 25 1.3 102

N13 Anonyx, small 4.0 45 2.2 86

N18 Anonyx, small 6.4 25 1.6 104

4A -1 Anonyx, small 5.8 29 2.8 113

4A -2 Anonyx, small 5.1 36 2.9 103

5(0) Anony'x, small 5.0 33 1.7 54

L08 Astarte '9.0 14 3.1 103

L09 Astarte 8.2 7 2.5 83

3A Astarte 11.5 11 3.6 78

5H Astarte 8.2 26 5.6 89

5F Cyrtodaria 6.2 58 8.6 27

Anonyx (an amphipod), Astarte (a clam), Cyrtodaria (a clam).
.....

"

,f

.'f :.:

I,H

I'

I , I

I':

I

"'

"

.I:i

I

'I,

,

,"

'I

"~:

.i i i I , I

',~i II

, I

.',

'I,:C ,I

I
IRa

-0

I

n

I

o

n

n

o

I

I

I

o

n

n

I

o

I

o

I

Table 3-16. Map of Sampling Stations for SPMDs and Caged Mussels and Table of

Concentrations for Selected Organic Parameters

'I<i7W 1~O'W

Total N To~al PAH Pyrogenic Petrogenic :t'cltal ST Total PHC Station Matrix pAH PAH (lJg/Kg) (lJg/Kg) (lJg/Kg) (lJg/Kg) ,(~lg/Kg) (mg/Kg)

Reference

3M1 Mussel 3.9 13 0.78 11 1.4 2.5

3M2 Mussel 5.0 14 0.76 12 1.3 2.7

3M3 Mussel 3.6 12 0.68 9.4 1.7 2.8

Mean (SO) 4.2 (0.75) 13(1.3) 0.74 (0.05) 11 (1.3) 1.5 (0.19) 2.1(0;15)

Northstar

NM1 Mussel 6.8 17 0.95 13 1.5 2.9

NM2 Mussel 5.4 17 1.2 14 1.7 2.9

NM3 Mussel 5.3 15 1.2 12 1.3 2.3

Mean (SO) 5.8 (0.85) . 16 (1.2) 1.1 (0.15) 13 (0.96) 1.5 (0.19) 2.7 (0.35)

Predeployment

Mussels

PM1 Mussel 2.7 7.8 0.39 6.7 1.0 3.8
,

l

,.,

II,

,

..

I~

10o

0, m

:0i D

'61

:1

:0

I,

:m

,0mmo

iDI

iO
Notel - The concentrations in the SPMD field blank are adjusted by the number offield exposures; the field blank was

opened and exposed at each ofthe six moorings.

Table 3-16 (continued). Map of Sampling Stations for SPMDs ~nd Cage~ N1ussels and

Table of Concentrations for Selected Organic Parameters .

210 470 18 430

260 540 19 470

220 490 20 450

230 (22) 500 (37) 19 (1.0) 450 (20)

250 500 29 460

240 540 25 480

220 470 28 440

240 (18) 510 (34) 28 (2.0) 460 (21)

120 130 1.2 130

Mean (SO)

Field Blank

FB' SPMO

Mean (SO)

Northstar

NM1 SPMO

NM2 SPMO

NM3 SPMO

Reference

3M1 SPMO

3M2 SPMO

3M3 SPMO

ND - Not detected

CON - Naphthalene

CIN - CI-Naphthalenes

C2N - C2-Naphthalenes

C3N - C4-Naphthalenes

I

n

n

I

n

I

II'

I·

·~

, ,

D'

I"

I

I
,.

"1

If:

1·1

Ii

II

I·

'I

III· Im'll

I.' "-

{

Ij IX,,

j, I_:i1

I ,II

1,

I'i

',,0',' ,I

:

! ,:
I

Table 3-18. Organic Quality Control Result Summary - Polynuclear Aromatic Hydrocarbon

Analyses

"0

I

:il

,

',.

i

i '

"!, .

o

II

:D"~~ > ,

"I\, .

Equipment Blank

Field Blank

SPMO Blank

Field Replicate

Initial Calibration

Continuing Calibration

Surrogate Recoveries

Procedural Blank

No compound to exceed 5

times the MOL

No compound to exceed 5

times the MOL

Assess blank data along with

sample data to determine

usability

RSO < 50% for all

compounds >5 times the RL

%RSO <25% for all ,

compounds (up to 10% of

compounds can be >25%,

but <35% '

%0 <25% for·all compounds

(up to 10% of compounds

can be >25%, but <35%)

45 to 125% recovery .

(35 - 125% for

d8-naphthalene)

No compound to exceed 5

times the MOL unless

sample amount is >10 times

blank amount

All criteria were met

All criteria were met

Concentrations of PAH

compounds detected on the

blank SPMO were greater

than the sample

concentrations for CON,

C1 N, and C2Nand of similar

concentrations for the

remaining PAHs

All criteria were met

All criteria were met

All criteria were met'

All criteria were met for the

water and SPMO samples.

All criteria were met, with the

exception of low recoveries

in two procedural blanks, a

blank spike, and two field

sample for the tissue

samples. All criteria were

met, with the exception of

low recoveries in a blank

spike for the sediment

samples.

All criteria were met with two

exceptions, 1)the

napthalene concentration in

a tissue blank exceeded 5

times the MOL and 2) the

naphthalene and biphenyl

concentrations in a SPMO

blank exceeded 5 times the

MOL. A few additional PAHs

were detected in the

sediment, tissue, and SPMO

blanks at trace

concentrations, but were less

than 5 times the MOL

None

I.

None

,Due to background

,concentrations on the

ISPMOs greater than or

:equal to the sample

iconcentrations, the

u~;ability of the sample

!SI:>MO data to assess

bioavailability of organiCS

lis limited.

INone

iNone

jMinor. The results for

iMsue samples 00-4A-01-

:PHC-T-AN and 02-N03-

01-PHC-T-AN should be

:c6nsidered estimated

:values due to low

!surrogate recoveries. No

ifurther impact was noted

;since surrogate

Irecoveries were

lacceptable in the

jremaining quality control

:s~lmples and associated

ifiE'lld sam les.

:Minor. Results within 5

!tirnes the blank result

iwere qualified "B" and

,m:ay be biased high or

'fa'ise positives.

!
,

:m

II

I

:1

W'

I

I

:1

'w

m

m

m

m

m

m

I,

m' I
Table 3..18 (continued). Organic Quality Control Result Summary - Polynuclear Aromatic

Hydrocarbon Analyses !

'Minor. Results for these

compounds in the

:as;sociated samples may

bEl bias hi h.

Several PAHs were

recovered at >125% in a

tissue BS, in the SPMD BS,

and in three sediment BS.

:,1"·-','

"

Laboratory Duplicate

Instrument SRM (1491)

Sediment SRM (1941a)

Tissue SRM (1974a) for

samples collected in

2000

Tissue SRM (2978) for

samples collected in

2002

RPD <30% for all

compounds >10 times the

MOL; mean RPD <30%

Measured values must be

within 15% of true value for

all certified compounds

Measured values must be

within 30% of the true value

on average for all

compounds, not to exceed

35% of true value for 'more

than 30% of the compounds

Measured values must be

within 30% of the true value

on average for all

compounds, not to exceed

35% of true value for more

than 30% of the com~ounds

Measured values must be

within 30% of the true value

'on average for all

compounds, not to exceed

35% of true value for 'more

than 30% of the compounds

All criteria were.

All criteria were met

All criteria were met for the

sediment SRMs, with the

exception of low responses

for naphthalene and

benzo[k]f1uoranthene in the

2000 sample set and low

responses for naphthalene,

acenaphthene, and biphenyl

and high responses for

chrysene and indeno(1 ,2,3-

cd)pyrenein the 2002

sample set.

All criteria were met for the

tissue SRM, with the

exception of a high response

for naphthalene, anthracene,

and benzo[b]f1uoranthene.

11 of the 19 certified and

reference PAH compounds

were recovered high.

None

;Minor. The naphthalene

iaM benzo[k]f1uoranthene

'results in the sediment

'samples collected in

,2(WO may be biased low.

iThe naphthalene,

:ac;enaphthene, and

:biphenyl results may be

'biased low and the

:chrysene and indeno-

:(1,2,3-cd)pyrene results

imay be biased high in the

IS~lmples collected in

:2002.

'Minor. The certified

lVc;lue for naphthalene

land anthracene in SRM

1

',1 B74a appears to be

incorrect based on

!consistently high

;ar,thracene results in

Irepeated analyses over

~the past four years.

:Benzo[b]f1uoranthene

!results may be bias high

lin samples collected in

2000.

:Minor. The other quality

;c(~ntrol indicators

af;sociated with these

IS~lmples were

~aGceptable. The

:associated results may

'bl~ bias high for tissue

:sclmples collected in

12002.

-,I,I'-~, Oil Reference Standard

(North Slope Crude)

%D <35% for compounds

above the RL

All criteria were met. !None

.il
m

'1.:-,

!, .'

I -.

'm·~I.~· ,I

:

':

I'

iml'

~lliI I

.,'· .;.I

,,

:1HiI ;.~ !, . :'.

;J

,
Table 3-19. Organic Quality Control Result Summary - Saturated Hydrocarbon Analyses

Minor. Results within 5

times the associated

blank result may be

biased high or may be

false ositives.

All criteria were met with the

exception of n-C38 in the 2002,

field blank which was detected'

at a concentration greater than

5 times the MOL.

',QualitY,Confro\ Result .~"i!' ii'h'npact.to.Data Qualjty., S~mmary ··;~it,~:~r~')i"·:f.,· f~nd:(jsability" ·;A'j~.,

+~~~~~...~' ...J,~ '~!,:', :;.;,~':-;~: ."~;:~:,,:~,~;.'~/' ,i~i~>~::.·?f~f~;t:;<r·\~(J;.~<'~; ._.

All criteria were met with the Minor. Results within 5

exception of n-C25 through n- times the associated

C29 in one of the 2002 blank result may be

equipment blanks; these biased high or may be

compounds were detected at false positives.

concentrations greater than 5

times the MOL.

No compound to exceed 5

times the MOL

Field Blank

I.g.'--- 'I

,

,I

"I~ i .

SPMO Blank Assess blank data along

with sample data to

determine usability'

Concentrations of SHC

compounds detected on the

blank SPMO were similar to

the sample concentrations.

Due to background

concentrations on the

SPMOs greater than or

equal to the sample

concentrations, the

sample SPMO data are

not usable to assess

bioavailabilit of or anics.

Field Replicate RSO < 50% for all

compounds >5 times the RL

All criteria were met. None

Initial Calibration %RSO <25% for all

compounds (up to 10% of

compounds can be >25%,

but <35%

All criteria were met. None

I'

l.i'·I-~.'

Continuing Calibration %0 <25% for all

compounds (Up to 10% of

compounds can be >25%,

but <35%

All criteria were met. None

·':1

I

'~I-- i ,

Surrogate Recoveries

Procedural Blank

45 to 125% recovery

No compound to exceed 5

times the MOL unless

sample amount is >10 times

blank amount

All criteria were met, with the

exception of low surrogate

recoveries in one oftM

sediment blank spike samples.'

All criteria were met with the

exception of n-C26 through nC29 in two sediment

procedural blanks; these

compounds were detected at ,

concentrations greater than 5 :

times the MOL. Several SHCs

were detected at trace

concentrations less than the

MRL in all rocedural blanks.

None. Surrogate

recoveries were

acceptable in the

remaining quality control

samples and associated

. field sam les.

Minor. Results within 5

times the associated

blank result were qualified

, with a "B" and may be

biased high or may be

: false positives.

,I

I

Blank Spike Sample

Recoveries

Laboratory Duplicate

35 to 125% recovery for

spiked compounds

RPO <30% for all

compounds >10 times the

MOL; mean RPO <30%

Oecane was recovered at less'

than 35% in two sediment

BSs. Pentacosane and

triacontane were recovered at ,

greater than 125% in one BS.

Oecane and pentadecane

were recovered at less than

35% in one tissue 8S.

All criteria were met.

Minor. The decane and

pentadecane results in

the associated samples

may be biased low and

the pentacosane and

triacontane results may

be biased high.

None

Oil Reference Standard

(North Slope Crude)

%0 <35% for compounds

above the RL

All criteria were met. None
/1 .elQllld,l

'I

il

il

mi m"

I.m

W' mmm

.~mmm

Iim
Table 3-20. Organic Quality Control Result Summary - Sterane and Tri~el"paneAnalyses

$u,¥",,~,;'~~,~~~f]~:ik~ft~·t',$).~~r,~,,:f~\,~~,tJt!.\~\',::/~j~ il"lm ·actt9;.[)~~a QU.al~ty~,;;

la:: d'L!sability '~,f,;kJl, J~:i :>. ''~J~~;:-':'j~~,\~;tf~~('~~~';.,.1\~:&:, "U;~';\;{_

None

"..11t

l

:1

I,

il,L.

i' \

I·

II

Field Blank

SPMD Blank

Field Replicate

Initial Calibration

Continuing Calibration

Surrogate Standards

Laboratory Duplicate

Procedural Blank

Oil Reference Standard

(North Slope Crude)

No compound to exceed 5

times the MOL

Assess blank data along

with sample data to

determine usability

RSD < 50% for all

compounds >5 times the RL

%RSD <25% for all

compounds

%0 <25% for all

compounds

45 to 125% recovery

RPD <30% for all

compounds >10 times the

MOL; mean RPO <30%

No compound to exceed 5

times the MOL unle'ss

sample amount is >:10 times

blank amount

%0 <35% for compounds

above the RL

All criteria were met.

Concentrations of SHC

compounds detected on the

blank SPMD were similar to

the sample concentrations.

All criteria were met with one

exception. The results for

S28-ethylcholestane and ntriacontane exceeded the

precision criterion in one field

replicate set collected in 2000. :

All criteria were met.

All criteria were met.

All criteria were met.

All criteria were met.

All criteria were met.

All criteria were met.

None

Due to background

,concentrations on the

SPMDs greater than or

equal to the sample

concentrations, the

sample SPMD data are

not usable to assess

bioavailabilit of or anics.

Minor. The positive

results for

S28-ethylcholestane and

n-triacontane are

considered estimated

values in the affected

sam les.

None

.None

.None

None

None

None
I.i

i,

;:

.'

IIJ ~,

-oM 

.-.,

,ffiI Illil w····.',·· ' J,,

;!II !m

I

iD

:1

II .1,

'0

III I, III ~.
II,

I

I

II

I

I

'I

II··.· '1

I

I

I

Table 3-21. Inorganic Quality Control Result Summary - Trace-Metal Analyses

No trace-metal

concentration to exceed 5

times the MOL

Field Blanks No trace-metal All criteria were met. None

concentration to exceed 5

times the MOL

Field Replicates RSD <50% for all trace All criteria were met. None;

metal concentrations >5

times the MOL

Initial Calibration Standard Curve All criteria were met. NoM

correlation coefficient r

0.999 for a 3 to5 point

curve for all trace metals

Continuing Calibration %0 <15% for all trace All criteria were met. None

metals or repeat Initial

Calibration and sample

anal ses

Matrix Spike Recoveries 70 to 130% recovery for All criteria were met. None

all trace metals

Procedural Blanks No trace metal All criteria were met. Nohe

concentration to exceed 5 I

times the MOL unless the

sample amount is >10

times the blank

concentration

Laboratory Duplicates RSD <25% for all trace All criteria were met. NO,nei

metal concentratiohs >10

times the MOL; mean

RSD <25%

Sediment SRMs Measured values must be All criteria were met. None

(MESS-2, 2704, 1643d) within 20% of the certified

or reference value~ for

>85% of the SRM

anal ses.

Tissue SRMs Measured values must be All criteria were met. Nope

(DORM-2, 2976, 1643d) within 20% of the certified

or reference values for

>85% of the SRM ;

anal ses.

Dissolved SRMs Measured values must be All criteria were met. No:ne

(CASS-3) within 20% of the certified

or reference values for

>85% of the SRM

anal ses.
/1

I .

Ii,

i.

mi

melII
'.. = s=~ •• =i .. =m. lim lID

- .. - -t .. _

_1 _I IIII!!I' IIIIIIIIII -!'

Table 3-22. SRM Results for Sediment Metal Analyses: MESS-2 and 1643d

0.17 8.59 21.2 1004 2.40 0.25 13.9 105 37.9 4.20

±0.01 ±O.07 ±O.5 ±49 ±0.02 ±0.01 ±O.5 ±2 ±O.5 ±0.04

0.18 8.57 20.7 2.32 0.24 13.8 106 39.3 4.35

±O.02 ±0.26 ±0.8 -- ±O.12 ±O.Ot ±1.4 ±8 ±2.0 ±O.22

509.2 IJg/L

±4.2

506.5 "giL I I I I I I : ±8.9 -- -- -- -- -- -- :1..4-

~4

I I I I I I I I I

. 95.5 104.9 97.4 98.2 99.0 98.9 101.9 108.4 102.0 97.2

±5.5 ±4.4 ±6.6 ±4.8 ±5.8 ±2.7 ±5.3 ±11.1 ±5.9 ±3.2

.

.• ;;.

"j;.

0.091 355 46.7 22.1 1.19 1.01 252 160 1.95

±O.004 ±4 ±1.9 ±O.4 ±O.06 ±O.03 ±5 ±4 ±O.04

. 0.092 365 49.3 21.9 1.09 (0.98) 93.4 119 2.14*

±O.009 ±21 ±1.8 ±1.2 ±0.13 ±4.9 ±12 ±O.03

- - - -

84.4

I

99.3

I

93.7

I

97.2 I 99.4

I

102.5 I 114.7 I 97.4 I NA ±6.2 ±8.5 ±1.0 ±4.5 ±5.1 ±3.6 ±5.8 ±1.5

Notes: Values in parenthesis are for reference only; SRM not certified by the NRC.

Mean results ±standard deviation are presented. *MESS-2 certified TOC value is for total carbon (organic plus inorganic).

SRM MESS-2 - Marine sediment issued by NRC; SRM 1643d - Trace Elements in Water issued by NIST.
r:

I

I

l ... ,.i m.1 I

~'

w:

im

~.mm

'mmmwmmm

illm

mcr
_Ii) .. .' _I _I . .. _I .

'l!IIlIIIIl' '= _Ii) -' lilli, _J

. -~-',

-~-Ir) -' -

Table 3-23. SRM Results for Tissue Metal Analyses: 2976, DORM-2 and 1643d

0.014 148 13.4 0.63 0.006 0.91 0.63 0.53 3.84

(0.011 ) (134) 13.3 0.82 (0.61 ) (0.50) 4.02 -- -- (±D.005) (±34) ±1.8 ±D.16 (±0.02) (±D.16) ±0.33

0.043 12.5 17.4 2.83 0.006 0.048 0.185 37.5 2.26,

0.041 I 10.9 I. 18.0 0.043 0.182 34.7 2.34

±0.013 ±1.7 ±L1. -- -- ~.-- ±D.OOB. ±D.031 ±5.5 ±D.16

514.91Jg/L 12.72lJg/L

506.51J9/L 12.53 IJg/L

±8.9 ±0.28

106.7 96.9 98.7 98.3 102.7

I

99.1

I

128.1

I

93.3

I

102.5

±2.7 ±3.7 ±D.5 ±1.5 ±8.0 ±2.3 ±2.3 ±D.7 ±2.6

Notes: Values in parenthesis are for reference only; SRM not certified by the NIST or NRC. Mean results standard deviation are presented.

SRM 2976 - Mussel tissue issued by NIST; SRM DORM-2 - Dogfish Muscle issued by NRC; SRM 1643d - Trace Elements in Water issued by NIST.
'.

,i'

,;'. ,.. ,

t·;

m-:; i mmm
_J_: _ ,1II!lI:_) .' .... __) .. _) l!!!!!I_o. ---~-- IIIJ' r= GIll) ..

Table 3-23 (continued). SRM Results for Tissue Metal Analyses: 2976, DORM-2 and 1643d

174 0.061 34.6 0.87 I 1.05 I 0.009 I 0.002 I 0.75 I 145 ±O.004

171.0 0.061 (33) (0.93)

I

1.19

I I (0.001 ) I I

137

±4.9 ±O.0036 (±2) (±O.12) ±O.18 -- -- ±13

147 -- 3.48 17.6 0.070 0.023 0.005 0.18 24.4

142 4.64 3.66 19.4 0.065 (0.004) 25.6

±10 ±O2§ ±O.34. ,.. ±3.1 ±O.007 •.. -- -- 0 - . _,. -or.. '~

±2.3 -I _. - , ,.. -..,-.".... '-. -

53.5IJg/L 7.34 IJg/L 36.4IJg/L

--

54.1 IJg/L 7.28IJg/L 35.1 IJg/L

±1.1 ±0.25 ±1.4

106.7 106.7 106.7 106.7 106.7 106.7 106.7 106.7

I

106.7

±2.7 ±2.7 ±2.7 ±2.7 ±2.7 ±2.7 ±2.7 ±2.7 ±2.7

Notes: Values in parenthesis are for reference only; SRM not certified by the NIST or NRC. Mean results ± standard deviation are presented.

SRM 2976 - Mussel tissue issued by NIST; SRM DORM-2 - Dogfish Muscle issued by NRC; SRM 1643d - Trace Elements in Water issued by NIST.

A
illmmwmm

w. mm

1ft.-

'Ill m

I' m

iOIo

01

01o
.

) =,..,l _,)_._11III ..)_ ..~_ __ _i;' 1\_ _) .IIISI

Table 3-24. SRM Results for Particulate and Dissolved Metal Analyses: 2704, MESS-2, CASS-3 and SLRS-3

437

±6

438

±12

159

±6

161

±17

4.15

±O.05

3.45

±0.22

98.3

±2.6

98.6

±5.0

133

±2

135

±5

23.6 424 3.42

±O.4 ±4 ±0.11

6.11 23.4 414 3.45

±0.16 ±0.8 ±12 ±O.22

2.14*

±0.03

I -

1.15 IJg/L 0.027 IJg/L 0.095IJg/L I -- 0.551 I,lg/L -- -- 0.014 IJg/L 1.03 IJg/L

1.09IJg/L -- 0.030 IJg/L 0.092 IJg/L 0.517 IJg/L -- -- 0.012 IJg/L 1.24 IJg/L

±O.07 ±O.005 ±O.006 ±0.062 ±0.004 ±O.25

13.5 IJg/L

-

13.4

±O.6

I I

'-~~'H 94.4 u[ 99.2 1_ -96A_ 1

__9J.~ __ _ 1_ Ut1.7 1__ 97.3_

1 1

101.9 1 - ~~~; - . -I-NA- -,------- ±5.4 ±3.0 ±2.9 -- ±3.2 . +2.8 ±4.2 ±2.2 ±6.1

94.1 MOA** 107.6 98.4 98.7 MOA** 98.2 98.0

±5.2 ±2.1 ±9.1 ±l.5 - ±2.6 ±4.2

Notes: Values in parenthesis are for reference only; SRM not certified by the NIST or NRC. Mean results 2:. standard deviation are presented.

*MESS-2 certified TOC value is for total carbon (organic plus inorganic). ** MOA - Method of Standard Additions analysis.

SRM 2704 - Buffalo River Sediment issued by NIST; SRM MESS-2 - Marine Sediment issued by NRC; SRM CASS-3 - Nearshore Seawater issued by NRC; SRM

SLRS-3 - Riverine Water issued by NRC.
"

mmm

-'::;:-::~ mmmmmm;:cmm

m: mm,

m:

,;mI

.,

,mm
_I) _1 (_ _1 _) _~ _: _ ;;;; _) ,;i;;I"'~ '_ ;iill;c ,_ _I) \(_ _~ !c.I

Table 3-25. SRM Results for Sediment Metal Analyses: MESS-2 and 1643d

0.18 8.59 21.3 1017 2.25 0.24 I 14.1 I 106 I 37.9

I

4.23

±0.01 ±0.08 ±O.1 ±32 ±0.06 ±0.01 ±O.3 ±2 ±0.3 ±O.04

0.18 8.57 20.7 2.32 0.24

I

13.8

I

106

I

39.3 I 4.35

±O.02 ±O.26 ±O.S -- ±O.12 ±0.01 ±1.4 ±8 ±2.0 ±0.22

508 jJg/L

±1

506.5 jJg/L

±8.9

92.9 I 102.0 98.6 102.9 93.5 I 93.3 I 98.5

I

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±2.5 ±2.8 ±5.7 ±4.7 ±1.8 ±1.4 ±5.3 ±4.9 ±2.9 ±4.7

.~ .

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,

0.091 362 48.5 21.9 1.10 1.00 253 168 2.07

±0.004 ±8 ±O.7 ±1.1 ±O.02 ±0.04 ±4 ±3 ±0.01

0.092 365 49.3 21.9 1.09 (0.98) 93.4 119 2.14*

±O.009 ±21 ±1.8 ±1.2 ±O.13 ±4.9 ±12 ±0.03

I I --- -- - -~ I --- ~------~-

93.2 I ;00;3 I 96.5

I

96.9 I 96.5 I 96.9 I l16.5 I 97.8 I NA ±5.8 ±1.6 ±O.4 ±3.2 ±3.1 ±4.9 ±2.5 ±3.7

Notes: Values in parenthesis are for reference only; SRM not certified by the NRC.

Mean results ± standard deviation are presented. *MESS-2 certified TOC value is for total carbon (organic plus inorganic).

SRM MESS-2 - Marine sediment issued by NRC; SRM 1643d - Trace Elements in Water issued by NIST.
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Table 3-26. SRM Results for Tissue Metal Analyses: 2976, DORM-2 and 1643d

0.009 158 12.6 0.71 0.005 0.77 0.61 0.57 I 4.0

(0.011 ) (134) 13.3 0.82 (0.61 ) (0.50) I

4.02 -- -- (±O.005) (±34) ±1.8 ±O.16 (±0.02) (±0.16) ±0.33

0.039 10.6 17.9 2.5 0.006 0.049 0.172 32.2 I 2.3

0.041 10.9 18.0 0.043 0.182 34.7 2.34

±O.013 ±1.7 ±u -- -- .. ±0.008 . ±0.031 ±5.5 ±O.16

506.3 IJg/L 12.66 IJg/L

506.5 IJg/L 12.53 IJg/L

±8.9 ±0.28

100.3

I

96.9

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96.0 98.1 106.9

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97.9

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104.7

I

95.7

I

101.9

+1.2 +0.3 ±4.1 +3.2 +3.2 +0.8 ±O.3 +1.3 +3.5

Notes: Values in parenthesis are for reference only; SRM not certified by the NIST or NRC. Mean results ±standard deviation are presented.

SRM 2976 - Mussel tissue issued by NIST; SRM DORM-2 - Dogfish Muscle issued by NRC; SRM 1643d - Trace Elements in Water issued by NIST.
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Table 3-26 (continued). SRM Results for Tissue Metal Analyses: 2976, DORM..2and 1643d
00,

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Table 3-27. SRM Results for Particulate and Dissolved Metal Analyses: 2704, MESS-2, CASS-3 and SLRS-3

23.0 417 3.41 135 97.2 4.10 159 434

±O.3 ±8 ±O.08 ±3 ±3.0 ±O.02 -- ±5 ±4

6.11 23.4 414 3.45 135 98.6 3.45 161 438

±O.16 ±O.8 ±12 ±O.22 ±5 ±5.0 ±0.22 -- ±17 ±12

1.05 IJg/L -- 0.0271Jg/L 0.097 1Jg/L 0.534 IJg/L -- -- 0.012 IJg/L 1.17 1J9/L

±O.O3 ±0.001 ±O.001 ±O.011 ±0.001 ±0.04

1.09 1J9/L -- 0.030 IJg/L 0.092 1J9/L 0.517 IJg/L -- -- 0.012 IJg/L 1.24 IJg/L

±O.07 ±0.O05 ±0.006 ±O.062 ±O.004 ±O.25

13.6 IJg/L

13.7 IJg/L

--

13.4

±O.6

97.5 103.2 100.2 99.7 100.0 95.2 97.6 98.0 95.6

±4.1 ±2.8 ±1.8 ±O.6 ±5.5 ±1.7 ±3.2 -- ±1.7 ±2.9

. 95.5 MOA** . . 101.1 95.5 100.7 MOA** 95.7 93.9

±4.0 ±5.3 ±1.0 ±4.0 -- ±1.8 ±2.5

Notes: Values in parenthesis are for reference only; SRM not certified by the NIST or NRC. Mean results ±standard deviation are presented.

*MESS-2certified TGC-value isfor-totalcarbon-(organic plusinorganic}.--*!..MOA- Method-of Standard Additions- analysis•.- -

SRM 2704 ~-8uffaloRiverSediment issued by NIS-T; SRM-MESS-2 - Marine Sediment issued by NRC; SRM GASS-3~' Nearshore Seawater issuedbyNRC; SRM

SLRS-3 - Riverin'e Water issued by NRC.
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Figure 3-1. Map of Northstar 2000 Sampling Stations with Grain-Size Histograms • i

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, Histograms show grain-size distribution as percent gravel (black bar), sand (red bar), silt (green bar) and clay (yellow bar).
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Figure 3-3. Map of Liberty 2000 Sampling Stations and Grain-Size Histograms
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Figure 3-4. Grain-Size Histograms for Liberty Prospect 2002 Sampling, Stations

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AI (%)

BSMP samples (blue triangles), Northstar samples (red triangles) and Liberty samples (green triangles).

The line and correlation coefficient (r) are from linear regression calculations.

Figure 3-5. Concentrations of AI versus (a) Silt + Clay and (b) Clay for SUrficial Sediment

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

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4.0 Discussion

The summer field sampling programs conducted in 1999,2000,2001, and 2002 successfully

obtained data on a number ofindicator measurements related to potential contaminant inputs

from the Northstar development. Against a significant background "signal", temporal changes

and spatial trends in these measures were assessed. Hydrocarbon and/or metal, and supporting

parameters were measured in samples ofsurficial sediments, riverine sediments and peat, biota

(clams and amphipods), SPMDs, caged lpussels, and sediment cores collected in the ANIMIDA

study area. The summer 1999 data represent the pre-construction environment for the Northstar

and Liberty prospects for the ANIMIDA Phase I program, and will be used for comparisons to

measurements collected during the summer 2000 and 2002 samplingsurveys (post-construction

and production measurements at Northstar). The results and discussion associated with the

sediment core program (2001 field program) are contained in a separate MMS'Report (Brown, et

aI., 2003). In this section ofthe report,the results ofthe sediments and biota will be further

evaluated for general trends and relationShips, and statistical comparisons ofthe pre- and postconstruction results will be evaluated for the purpose ofhypothesis testing.

4.1 Surficial Sediments (0-1 cm)

4.1.1 Grain Size

Inter-annual shifts in the texture ofsurficial sediment have been observed throughout the

ANIMIDA study area. The largest changes in grain size distribution observed during this study

occurred between 1999 and 2000. During 1999, surficial sediment at station's NIl, N12, N13

and N14 were essentially all sand and gravel (Figure 4-1). In contrast, the 2000 samples were

dominated by silt and clay (Figure 4-1). Although the exact mechanism for this shift is not

known, the 1999 samples were collected after a 6-day storm with winds in e~cess of 25 knots

that may have eroded away finer-grained material. No such storms preceded collection ofthe

2000 samples that probably contained finer-grained material carried in by the Kuparuk River

during the spring breakup of2000. At stations N06 and N10, both close to Northstar Island, the I

opposite condition was observed with much finer-grained particles in the surface layer of

sediment during 1999 than 2000 (Figure 4-1). This shift may have resulted from inputs of

coarser material at these stations in association with construction ofthe island. Grain size

distribution at the other Northstar stations was similar for 1999 and 2000 (Figure 4-1).

Differences in grain size distribution between the 2000 and 2002 sampling are less than observed

between 1999 and 2000. During 2002, much less sand was found at stations. N06, N07, N08 and

N09 than during 2000 (Figure 4-2); most likely because fine-grained sedimert introduced to that

area during river runoff had not yet moved farther offshore. .In contrast, sand has dominated at

stations N01, 5B and N15 throughout the study.

Shifts in grain size in the Liberty area were noted at station LO1 where finer-grained sediment

was collected during the 2000 period than during 1999 and at stations L08 and L09 where the

opposite trend was found (Figure 4-3). Most ofthe other significant shifts in grain size

throughout the ANIMIDA study area are to finer-grained sediment in the 2000 samples versus

the 1999 samples. These other changes also may be related to the effects ofthe storm activity

that preceded the 1999 sampling period in tandem with the' complex movement ofsediment

throughout the area. During 2002, the sl:\.nd content at stations 4C, 4B, L01, ,L08 and L09 (Figure

3-4, Section 3) was markedly greater than observed during 2000 (Figure 4-3). In contrast with

Imms animidaltask 2 final reportlfinal report fileslfinal section 4 text.doc 4-1
-.

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i

North Slope Crude Oil- composite pipeline sample (Figure 4-4)

Northstar Oil- 2002 (Figure 4-5)

Colville River sediment - 1999 (Figure 4-6)

Station N06 - Northstar sediment - 1999 (Figure 4-7)

Station L06 - Liberty sediment - 1999 (Figure 4-8)

Station 3A BSMP sediment station near Stockton Islands - 1999 (Figure 4-9) !

Stat~on L08 - Liberty s~diment - 999 (Figure 4-10) '.I

StatIOn 5D - BSMP sedIment statIOn near Stump Island/West Dock,. 1999 (FIgure 4-11)

Station N06 Northstar sediment - 2000 (Figure 4~12) jl

Station L08 - Liberty sediment - 2000 (Figure 4-13) ,

Station N06 - Northstar sediment - 2002 (Figure 4-14)

Canning River sediment - 2002 (Figure 4-15)

I

I

the Northstar area, less fine~grained material was'present in the area of Liberty Prospedt during

2002 than during 2000. . I

The most important finding from the grain size data is that sediments in m'any location~

throughout the ANIMIDA study area are regularly shifting and that the sediment grai61sizes

found during one year may shift prior to sampling during a subsequent year. Thus, te!chniques

that normalize sediment chemistry to account for differences in grain size need to be h~ed.

Furthermore, care must be taken in future sampling activities to insure that the sedimbdt

collected during any given year is recent and not relict material. I

4.1.2 Organics (Hydrocarbons)

The hydrocarbon dataset for surficial sediments for 1999,2000, and 2002 is complet<i: and

includes SHC, PAH, and SIT data. For the 1999 dataset only a subset ofsamples weJel analyzed

for SIT. These data were assessed in part by using a suite of key diagnostic paramete~s and .

ratios (Table 3-5), which are useful in describing hydrocarbon trends in the marine erl~ironment

(Boehm et al. 2001a). Some ofthe general trends observed in these data for several a1reas of

interest are evaluated in this section. These areas include: 1) sources ofhydrocarbon~, 12) spatial

variability, or comparisons between stations, 3) temporal variability, or comparisons between

years (before and after Northstar construction including results ofstatistic<1t1 evaluatiohk>, and 4)

comparisons to sediment quality benchmarks or "guidelines."

To facilitate the presentation and discussion ofthe organics data, GC/FID chromatograms from

the SHC analysis, PAH distribution plots, and triterpane extracted ion chromatogram Ip~ofiles for

representative samples throughout the study area were selected and are presented in F.i~ures 4~4

through 4-15. The samples selected ~9r presentation are as follows: .

•

•

•

•

•

•

!

The Northstar Oil sample was collected on May 6,2002 from the separator oil line for Well NS08. The North Slope Crude Oil sample was a Valdez Terminal composite :crude oil c61lected in

March 1989. I

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4.1.2.1 Hydrocarbon Sources

Saturated Hydrocarbons ,

In general, the surficial sediments (GC/FID chromatograms in Figures 4~7 through 4-14) exhibit

a mixture of primarily terrestrial biogenic hydrocarbons and lower levels of petroleum

hydrocarbons (Figure 4-4 shows a NorthSlope Crude Oil reference). This assemblage is clearly

dominated by plant wax normal (Le., strdight-chain) alkanes in the n-'C27 through n-C33 carbon

range. This is further demonstrated by carbon preference index (CPI) value~ that range from two

to seven for most samples, which is characteristic ofsediments influenced by terrigenous plant

inputs (Wakeham and Carpenter, 1976; Boehm, 1984). Eleven samples, out ,of a total of 128

sediment samples, have CPI ratios ofless than two (4C [2002], 5(1) [2002], 58 [1999 and 2000],

5E [1999 and 2002],L06 [2000], NOI [1999 and 2002], and N15 [1999 and 2000]). With the I

exception of 5E [1999], the lower CPI ratios at these stations are due to low SHC concentrations

(i.e., trace levels), combined with corresponding low TOC and high sand corltt::nt, factors which

all contribute to CPI ratio uncertainty and potential inaccuracy. However, th~ CPI ratio of 1.25

at station 5E [1999], with a corresponding TPHC concentration of 11 mg/Kg, is characteristic of

a petroleum component present in this sainple. However, in 2000 the CPI ratio at station 5E is

2~6 with a corresponding decrease in SHC concentration to 3.5 mg/Kg and i~ 2002 the CPI ratio

at this station was 1.5 with a SHC concentration of 3.8,mg/Kg, indic~ting a Highly variable

sediment substrate at this station. - I

Traces oflower-molecular-weight alkanes (LALK - n-C9 through n-C20 alkalies), indicative of

a petroleum source, are visible as more tiIinor components relative to the plaht wax alkanes in

the sediment and river samples (Figures 4-6 through 4-9, 4-14 and 4-15). T~is clearly visible

petroleum alkane signature in the sediments has been well documented by previous studies in the • ' I

region (Boehm, et aI., 1987; Steinhauer and Boehm, 1992; and Boehln et aI.,i 1990). The clear

exception to this trend is station L08'in 1'999 (Figure 4-10), which has a GC/FID chromatogram

with a distinct unresolved complex mixture (UCM) or "hump" in the n-CIO through n-C24 , I

carbon range. The GC/FID pattern observed in this sample is characteristic of a diesel fuel

hydrocarbon source. The diesel fuel pattern is slightly weathered, indicatingl

a recent source of

diesel fuel contamination at this station. ,Triplicate field replicates collected from L08 in 2000

revealed a similar diesel fuel pattern in ohe ofthe three ofthe field replicates (Figure 4-13) and a

less pronounced diesel signature in the other two replicates. The diesel fuel pllittern was not

present in the single sample collected at t08 in 2002. The absence of a similar diesel fuel

signature in adjacent samples and the 2002 sample suggests a very limited or patchy area of

sediment contamination. These results warrant continued evaluation and monitoring in future

field surveys.

\mms animida\task 2 final report\final report files\firial section 4 text.doc 4-3
Polynuclear Aromatic Hydrocarbons

The PAH distributions for most ofthe surficial sediments show that the PA.Hs are primarily of a

combined fossil fuel origin (i.e., petroleum and coal) with a biogenic component (perYlene), and

lesser contributions of pyrogenic or combustion-r!elated compounds (e.g., 4-, 5-, and 6-'nng

PAHs). The petrogenic PAHs account for approximately 90 percent ofthe Total PA, jless

perylene throughout the study area. Perylene was abundant in surficial seqiments, oft:ep the most

abundant single PAH compound in the overall PAH distribution (Figures 4-6 throughI4-15).

Perylene is a naturally occurring PAH formed during early diagenesis in sediments frpfu

biological sou:ce precur~ors (Wakeham and Farri~gton, 1980; Wa~eham, et aI., 1980~.1 It may

also be found In crude 011 at very traceconcentratwns. In past studIes, perylene was fiound at

comparable concentrations in the BSMP sediments (Boehm et aI., 1990). '

The variations in PAH composition ofrepresentative surficial sediments from the region in 1999,

2000, and 2002 are shown in the PAHdistribution plots in Figures 4-6 thr6ugh 4-15'I~or

comparison, the PAH distribution plot of a North Slope Crude oil and Northstar production oil

are shown in Figures 4-4 and 4~5. The PAH distributions are generally sirililar througHout all the

regions ofthe study area and are characterized by the presence of a full suite ofrelati~~ly

"unweathered" petroleum PAHs (i.e., naphthalenes:::: phenanthrenes) similar to the PtH

distribution seen in the North Slope Crude oil. As noted previously, peryl~ne dominatJs the '

overall PAH distribution as one ofthe most abundant individualPAHs in t]he samplesl.!perylene

is found at equal or greater relative abundance in the river sediments and pjeat (Figure~ 1~-6 and 4-

15); which suggests the ~elationship ofthe rivers as a source ofthe hydroc?rbons in tlielnearshore

sedIments, as noted preVlOU~IY for the S~cs. :': f

Low levels of4-, 5-, and 6-nng cOmbustIon PAHs are also present, but are1generally (~q.ly a

secondary component ofthe overall PAHcomposition in the sediments. 11he 4-, 5-, aha 6-ring

combustion PAHs are enriched in the river sediments and peat samples relative to the rlearshor,e

sediments, but are still a minor contributoito the overall PAH compositiort.

The PA:H distribution in sta~ion L08 .s~diment from 1999 and 2000.(Figur~s4~10 and 4

1

13,

respectIvely) shows a clear Increase In the abundance of 2- and 3-nng petr?leum PAHs;,

particularly the naphthalenes, relative to the other sediment samples. Thislfurther sup!pprts the

GC/FID evidence ofdiesel fuel contamination at this station. A slight incr,ease in the lapundance

ofthe 2- and 3-ring petroleum PAHs was also observed in the 2002 sample from L08, however,

it was ~ot as evident as in the previous years~ Two samples that were iden4fied as potb~tially

being enriched in petroleum hydrocarbons based on SHC results in 1999 (5D and 5E)ldo not

show evidence of a corresponding enrichment'in PAH or change in PAH d:istribution iq

subsequent years. In 2000, the PAH concentratiohat 5E was comparable to the levelJ in 1999,

(260 ug/Kg), but the concentration in 2002W,as substantially lower at 46 ujs!,.,Kg, due tria

corresponding decrease in fine-grained sediment. At 5D, the PAHconcentrations were

substantially lower in 2000 and 2002 with no apparent change in overall pAH distrib~tion. These

results indicate a highly variable sediment substrate at stations 5Dand 5E. AdditionaUy, the

source ofhydrocarbon enrichment observed at 5D in 1999 may be depleted in PAH v~rsus SHC,

relative to the regional petroleum hydrocarbon bapkground already present in the sediWents (e.g.,

coal). , ' i

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Triterpanes

In general, the triterpane distributions in the sediment samples are indicative of a petroleum

pattern (Figures 4-6 through 4-15), with varying abundances of a suite ofrecent organic material

triterpane markers. For example, a characteristic petroleum triterpane pattern dominated by

norhopane (TI5) land C30-hopane (TI9) is shown in Figure 4-4 for the North Slope Crude oil.

The triterpane distributions for most sediment samples comprise a mixture ofthese characteristic

petroleum triterpanes, along with recent organic or biogenic markers such as'diploptene (the

large peaks on left ofthe T21 and T22 doublet - Figure 4-12) 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 ofT22 at much greater levels than T21 in some

samples provides furth~r evidence ofsubstantial recent organic matter inputs to the surficial

sediments. In general, the 2000 and 2002 sediment samples appear to show a greater abundance

ofthese recent organic material or biogenic biomarkers, suggesting a greaterit{~rrestrial influence

(e.g., river runoff) to the sediments in 2000 and 2002. Many ofthe sediment samples contain

trace levels of oleanane (TI8), indicating the presence of a non-North Slope Crude, post~

Cretaceous/Tertiary petroleum source; i.e., T18 is absent in bulk North Slope Crude oil (Bence et

aI., 1996 and Figure 4-4) and Northstar Oil (Figure 4-5). The origin ofthis petroleum signal is

unknown, but it is likely from regional background inputs. Seep oils from Kavik and Angun

may have trace oleananes, as part oftheir biodegraded biomarker signature. The presence of

oleanane has also been reported in Canadian McKenzie Delta crude oils far to the west ofthe

study area (Banet, 1995).

The triterpane distributions ofthe Colville River sediments and peat (Figure 4··10) have the same

mixture ofrecent organic matter and petroleum hydrocarbon patterns as obsenred in many ofthe

sediment samples (for example, station N06 - Figures 4-7 and 4-12). This siinilarity suggests

that there is a strong link between Colville River hydrocarbon sources mos~ly erosional inputs

of coal shale, peat, etc. (i.e., natural background) and the sediments. However, given the

documented current transport regime ofEast to West in the study area, it is likely that rivers to

the East, as well as the Colville River also influence the surficial sediments. For example, the

triterpane distribution ofthe Canning River sediment collected from the Eas~ ofthe region in

2002 (Figure 4-15) is dominated by a suite ofrecent organic markers with a different distribution I

(specifically the unknown peak at -52 minutes) which are found in greater abundance from some

samples in the eastern study area. ; ,

The Kuparuk and Sagavanirktok River sediments contain many ofthe same recent organic

matter triterpane markers, but generally have different distributions than the,~olville River

sediments. In particular, the ratio ofT21/T22, where T22 is an order' ofmaghitude higher than

T21, is characteristic of an immature or recent hydrocarbon source, possibly indicative of coal.

This predominant T22 pattern is also found in several ofthe surficial sediment samples - 5(5)

[1999 and 2000], and 5(0) [2000] near the Sagavanirktok River delta, and N14 [1999 and 2002],

N20 and N21 [2002], 50 [1999, 2000 and 2002], and 5F [2000 and 2002] near the mouth ofthe

Kuparuk River - indicating the influence ofthese rivers to the deposition ofsurficial sediments

at these stations. The presence ofthe predominant T22 pattern at station 5D (Figure 4-11) is of

particular interest, since the .high SHC arid PAH concentrations indicate fossil fuel hydrocarbon

enrichment at this station. The observedT22 pattern indicates that coal particles, possibly from

the Kuparuk River, may be one ofthe sources ofthe hydrocarbon enrichment. ,

Imms anlmidaltask 2 final reportlfinat report file~lfinal section 4 teXl-doc 4-5
4.1.2.2 Sediment Quality Guidelines

Another technique of evaluating the significance ofthe measured sediment hydrocarbo,ns to

overall ecological risk ofthe region involves comparisons to sediment quality guidelihes.

Sediment quality iguidelines have been developed to assess possible adver~e biologicJl\effects

from metals, polychlorinated biphenyls (PCBs), pesticides, and PAH. Th~ commonl~r utilized

criteria are the Effects Range-Low (ERL) and Effects Range-Median (ERM) presentddlby Long

et a1. (1995). The general applications ofthe guidelines have been to state that adver~d

biological effects are "rarely" observed when PAH levels are less than theERL, "occkJionally"

observed when contaminants are present at levels between the ERL and ERM, and "B:dquentIy"

observed when concentrations exceed the ERM. i

Several surficial sediment samples have distinctly different triterpane distributions. stltions 5E

[1999,2000 and 2002], 5B [2000 and 2002], andL08 [1999 and 2000] (Figure 4-10) hkve

triterpane distributions more characteristic of a petroleum source, i.e., a predominanc~ pf

hopanes (T15 and TI9). In the case of L08, this is not surprising since other organic bata clearly

indicate diesel fuel contamination. However, the abundance of petroleum:triterpanesla[so

indicates a petroleum product "heavier" than diesel, as triterpanes are typically removdd from

diesel-range fuels during the distillation process. This result indicates that'the observbiI

petroleum contamination at L08 is a complex mixture ofhydrocarbons including dies1ei and

I I

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., Tern Island), Jsl the

standard practice at the time allowed disposal of used drill muds on the ice during wi~ter drilling.

This is further supported by the elevated ba.rium levels (when normalized t.'.o AI) obsej:V~led in the

sediment from L08 (1999 only). The petroleum triterpanes in the surficialsediment Jt 5B are at

trace levels (7.8 ug/Kg Total SIT), whereas the triterpane distribution at 5E further cohl rms the I I I

presence oflow levels of a heavy petroleum hydrocarbon source shown by the SHC an(l PAH

results, but the specific origins ofthese "contaminants" are not known.

I

ERL and ERM values have been developed for 13 individual PAH compounds and t}jr~e classes

ofPAH (low- and high-molecular-weight PAH, and Total PAH). A comparison ofth1e!TotaI

PAH from a~l ~N~MIDA s~di~ents from the study region in 1999,2000 apd ~002 tolt~e ~RL .

and ERM cntena IS shown III FIgure 4-24. None ofthe Total PAH concentratIOns detepmned III

this study exceed the ERL. Station 5D in 1999, which had the highest measured Tota:lrAH at

2,700j..lg/Kg, was still well below the ERL value of 4,022 j..lg/Kg. The mean Total PAH values

from each study region were generally an order ofmagnitude lower than the ERL. SAriilarly, the

individual PAH concentrations did not exceed the ERL for the individual 13 PAH, wliith could

be compared directly. The CI-naphthalenes parameter in this study is reported as thell stirn ofthe

two individual naphthalene isomers - I-methylnaphthalene and 2-methylnaphthalene., iThe CInaphthalenes values at station 5D in 1999 and 5A in 2000 (130 j..lg/Kg and' 100 j..lg/Kg, I

respectively) were higher than the ERL value listed for the single 2-methylnaphthaleclelisomer

(70 j..lg/Kg). However, the values at both stations would be less than the ERL using ah:estimate

of 50 percent contribution of2-methylnaphthalene to the CI-naphthalenes;parameter.1 ~n

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 thel ~rea

, I

4-6

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4.1.2.3 Temporal and Spatial Trends

In examining the spatial trends (variability between stations), one useful technique involves

examining the relationship between the organic parameter ofinterest and Tdc content or

alternatively, the percent silt + clay. The natural background concentrations of organics will

often vary as a function offine-grained sediment (silt + clay) and TOC. Thus, samples enriched

in organics from anthropogenic sources can be identified by normalizing theita.rget organic

parameter and generating a linear regression line and prediction interval on a cross-plot.

This regression plot technique was used effectively for the 1999 data to identify sediments

enriched in hydrocarbons and data outliers (Boehm, et aI., 2001b). For 1999 data, good linear

correlation was established between concentrations ofTotal PAH less perylene and TPHC with

silt + clay (R2 = 0.83 and 0.69 respectively - station 5D was determined to be a statistical outlier

and was not included in the regression calculation). The value Total PAH less perylene was used

to reduce variability introduced to the Total PAH data by perylene, which can vary widely in

abundance based on sediment type. Total PAH less perylene has been used in other studies in

evaluating sediment PAH in Cook Inlet and Alaska (Hyland, et aI., 1995; Boehm et aI., 2001 a).

These regressions defined the natural geological/geochemical background. In both PAH and

TPHC plots the data point for station 5Dwas well outside the calculated 99 percent prediction

interval ofthe regression line indicating that 5D sediment was enriched in Total PAH relative to

the expected background for the region. As noted previously, station 5D sediments were

identified as being contaminated with hydrocarbons, although the source ofthis contamination is

still unclear (i.e., coal versus petroleum sources). In the TPHC plot samplesL08 and 5E were

found to fall slightly above the upper 99 percent prediction interval. Based on the analytical

data, these two samples were also previously identified as being enriched in petroleum

hydrocarbons. Diesel contamination with possible crude oil was identified in L08 and a heavy

hydrocarbon product depleted in PAH was identified as a possible source in SIS.

Overall, these regression techniques provided a sensitive baseline process to measure temporal

trends of anthropogenic inputs into the system from Northstar, given radial sampling design . around the prospect and regional BSMP station coverage. As noted earlier, statistical analyses of

the 1999,2000 and 2002 data were performed to determine ifthere were significant differences

in the measured key diagnostic organic parameters due to the development ofNorthstar. The

results ofthe statistical analyses indicated that the key bulk hydrocarbon parameters (i.e., Total

PAH, TPHC, pyrogenic PAH, etc.) increased significantly at Northstar in 2000 and 2002, and

several diagnostic parameters were significantly different (Section 3.1.4). The results ofthe

statistical analyses are probably best summarized in a Total PAH minus perylene versus silt +

clay regression plot for 1999, 2000 and 2002 Northstar stations (Figure 4-16). In this plot the

regression lines and 95% prediction intervals do not overlap, indicating a significant increase in

PAH at Northstar in 2000 and 2002 after adjusting for fines (silt + clay). A simple plot ofthe

Total PAH normalized to fines clearly shows this trend ofincreasing PAH concentrations at the

Northstar stations in 2000 with lower levels in 2002, but still generally higher than 1999 (Figure

4-17). Station N15 in 2002 appears as an outlier on this plot due to avery low %fines result

(4.3%) and a total PAH concentration of200 ~g/Kg.

Imms animidaltask 2 final reportlfinal report fileslfinal section 4 text.doc 4-7
r

However, a closer examination ofthe PAH data show that although Northstar concentrations

increased post-construction (2000 and 2002 combined), the distribution and composi~i6n ofthe

PAH remained relatively unchanged, The composition ofthe sediment hydrocarbodlslat

Northstar is best summarized by a comparison ofthe pyrogenic to petrogenic PAH ratibs in

1999, 2000 and 2002. A comparison for this ratio for all paired Northstar stations (Fil~re 4-18)

reveals no significant difference between years 1999 and 2000 indicating that there w1ete no

incremental additions of anthropogenic hydrocarbons to the Northstar ard as a result df

construction activities in 2000.

The pyrogenic to petrogenic PAH ratios for Northstar stations in 2002 show a slight but

significant ~ncre~se in year 2002 (Figure 4-1 ~), A subsequent ANOVA rerea~ed that Ip~ogenic

to petrogemc ratIOS for Northstar 2002 and Llberty/BSMP 2002 were not significantly tllfferent

from each other, but were significantly greater when compared to the 1999 and 2000 tJgional

data sets. This result suggests a slight overall regional shift in the pyrogenic to petrogdnic I

distribution in the surface sedl'ments. A compan.'s.on to the pyrOg.enic to pe..trogenic PAl'fl. ratios in

the 2001 core data show that 2002 results are within the historical range described by theI

sediment core data. The ANOVA model results presented in Tabl,e 3-11 show a signi:ficant

decrease in petrogenic PAR region-wide for years 2000 and 2002, as compared to ye1ri 1999.

Together these results indicate that the observed shift to a greater relative proportion bf

pyrogenic hydrocarbons in 2002 may bethe result of decreased concentrations in pet~ogenic

PAHs and can likely be attributed to annual variability. Thus, while concentrations of PAH

appear to have increased at Northstar in 2000 and 2002, the source ofthe ihcrease ap~dars to be

the same as found in sediments throughout the region and not from Northstar related i

hydrocarbon contamination (i.e., anthropogenic inputs). i

I

I

Another evaluation ofthe sources ofthe PAH wa~ performed using a dibenzothiophenJ to

phenanthrene source ratio plot, which has been used in similar im~estigations ofPAHlspurces in

the environment (Brown and Boehm 1993; Page et. a11998; Boehm et. a12001a). An I

examination ofthe source plot for all 1999, 2000 and 2002 sediments and source sambles (Figure

4-19) reveals that the source composition ofPAH in the Northstar 2000 and 2002 sedhnents is in

the same range as the 1999,2000 and 2002 BSMP and Liberty stations which are replldsentative

ofthe regional hydrocarbon background. In the source ratio plot several ofthe Northktbr 1999

sediments have ratios substantially higher than the "regional background" ;Which is li~€:(ly due to

two factors: 1) the very low concentrations found at some ofthe 1999 Northstar statidrrs which

introduces variability into the ratio and generally results in a ratio increase; and 2) the! lpcalized

influence ofthe Kuparuk river which has a ratio higher than the "regional packgrounq.y

, . I !

The Northstar production oil, which was first analyzed in 2002, was foundIto be relativ~ly low in

sulfur compounds and had a resulting dibenzothiophene to phenanthrene source ratio Is~milar to

the "regional background" (Figure 4-19). The other North Slope field crude oils have I

dibenzothiophene to phenanthrene source ratios that are substantially higher and are Ja~ily

distinguished from the background hydrocarbons. This finding limits the use ofthis Jvaluation

technique since the potential contribution ofNorthstar crude oil could not be determiJ~din the

case of an accidental.release or incremental ~hronic inputs. However, another sourcelr?tio plot

ofthe 20S to 20R epnners ofsteranes and tnterpanes (Sa,14a,17a-24-methylcho1estan~

[S25/S28] versus 17a,21~(H)-30-homohopane [T21/T22]) shown in Figure 4-20, clea~,y

4-8

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differentiates all ofthe North Slope field crude oils and the Northstar production oil from the

regional background signature in the surface sediments and river source samples. This ratio,

which is a relative measure ofthe petroleum hydrocarbon maturity, relies onthe relative

immaturity ofthe biomarker compounds it the sediments versus the crude oi~s and provides a

promising tool to evaluate potential additions of anthropogenic hydrocarbons to the region in the

future.

The earlier observation that the Northstar 1999 sediments may be depleted in hydrocarbons

relative to the other 1999,2000 and 2002 sediments is further supported by a total PAH less

perylene versus silt + clay regression plot for all the 1999,2000, and 2002 sediment data. In this

plot (Figure 4-21) the regression and 95% prediction intervals are shown for all data. The plot

shows a small cluster Northstar 1999 samples which are below the 95% prediction interval,

indicating that these samples are significantly lower in PAH versus silt + clay than the overall

population of 1999, 2000 and 2002 samples. This result corroborates the observed trend of

lower hydrocarbon levels in Northstar 1999 samples. In addition, as part ofthe statistical

analyses, a regression model comparing Northstar 1999 samples to 1999 BsMr and Liberty

samples for all key parameters (Section 3.1.4), revealed that Northstar 1999 sediments were

significantly lower in all bulk hydrocarbon parameters (e.g., Total PAH, TPHC, Petrogenic PAH,

etc.) than 1999 BSMP and Liberty sediments. A further regression comparison ofthe Northstar

2000 and 2002 samples versus the BSMP and Liberty 2000 and 2002 samples resulted in no

significant difference for all bulk hydrocarbon parameters and most ofthe diagnostic ratios. The

results ofthis analysis are illustrated by a PAH regression plot (Figure 4-22) which shows

complete overlap between the regression lines and 95% prediction intervals (i.e., no significant

difference) for the Northstar, BSMP, and Liberty sediments for 2000 and 2002.

As noted previously the initial statistical comparisons revealed that Northstar 1999 sediments

were significantlylowerin all bulk hydrocarbon parameters (e.g., Total PAH, TPHC, Petrogenic

PAH, etc.) than 1999 BSMP and Liberty sediments (Table 3-10) which resulted in a positive

Northstar and Northstar/Construction effects (i.e., a significant increase in these parameters

associated with Northstar). However, a subsequent statistical model with petylene as a covariate

resulted in no significant increases in any ofthe key diagnostic hydrocarbon parameters due to

Northstar or Northstar/Construction effects. The use ofperylene as a covariat(: of a parameter to

normalize sediment data is particularly effective due to the absence or only trace levels of

perylene in the anthropogenic sources of,hydrocarbons to the region (petroleum and pyrogenic

hydrocarbons), and the relative enrichment ofperylene in the regional background (river and

sediment sources). This relationship is clearly shown in a cross-plot ofperyleIle versus PAH

(Figure 4-23, R2 = 0.94) with 95 % prediction intervals to identify outliers. As was noted in the

statistical analyses using perylene as a covariate, this plot shows no significant increase in PAH

due to Northstar or Northstar/Construction effects, and only three stations fall outside the

prediction intervals (4A, L08, and NIl). Sediments from station NIl appear to be slightly

enriched in perylene, possibly due to the proximity to the Kuparuk River that contains sediments

rich in perylene. Station 4A sediments appear to be somewhat depleted in perylene relative to

PAH, but show no signs of petroleum contamination. Petroleum hydrocarbon contamination was

previously identified in Station L08 using other interpretative techniques. The relationship of

perylene to other hydrocarbons in surface sediments clearly warrants further investigation,

however, these re~ults indicate that nonnalization of PAH and other hydrocatbon parameters to

Imms animidaltask 2 final reportlfinal report fileslfinal section 4 text.doc 4-9
_.

perylene is another valuable tool capable dfidentifying anthropogenic hydrocarbons inputs into

the surface sediments ofthis dynamic coastalregion.' [

Based on the results ofthe data evaluations there are several possible explanations or t eories 'for

the observed absolute increase in sediment hydrocarbon concentrations in :the Northstat area in

2000 (and to a lesser degree in 2002) with rno corresponding change in soJrce or combhsition: 1) , , I

the increase could be related to deposition of very fine-grained material associated with the .

gravel used to construct Northstar Island and distJ,lrbances from the pipeline construeti6n; 2) the

ice roads made during the Northstar construction may have diverted suspepded sedirrlehts from

the Kuparuk river flow during break-up, and enriched the deposition offirie-grained li~drocarbon

bearing s~diments i~ the No~hstar area; and 3) that the ~orthstarsediment~ in 19~9 wII ~re depleted m fine-gramed sedIment and hydrocarbons dunng the 1999 samplIng penod.

The first two hypotheses would require that the sOurce fine-grained materi~l depositJ in the.

Northstar area after 1999 (e.g., Northstar construction gravel and/or Kupar:uk river setl,ment) was

enriched in PAH and other hydrocarbons relative to the fine-grained mateiial in the ekisting

surface sediment. Analyses ofthe Kuparuk river'sediments reveal that the. river sedirhbnt is not

enriched in hydrocarbons relative to the Northstar area sediments, and is tljms unlikely to account

for the observed increase. It is possible that the very fine~gfained fraction:iofNorthst~rl

construction gravel could be enriched in hydrocatbons due to burial and c6mpaction ~:f the

historic Kuparuk river sediments, which were the source ofthe gravel (thelconstructi~ri gravel

was mined from the Kuparuk river delta). Subsequent analysis of:'source inaterial" ftob the

Kuparuk river gravel mine (borrow pit) revealed results similar to the pre~iously anal1yked

Kuparuk Riversediments.' . I

However, the most likely explanation ofthe thre~ is that the Northstar sed,ments were ~eplete9 in hydrocarbons in 1999. The organic analyses and resulting statistical co~nparisons bfthe 1999,

2000 and 2002 Northstar, BSMP and Libency dat~, support this explanation. In additipP, during

the 1999 sampling survey, nearly all the Northstar stations were sampled within 24 h@urs after a

five-day gale (peak winds in excess of25 knots).' This stonn was observe~ to resusp~rld

substantial amounts ofsurface sediments into the water column (Boehm et aI., 2001 b) knd would

account for the observed depletion ofhydrocarbons in the 1999 Northstar sediments Jrld

corresponding lower abundance offine-grained s¢diment. Regardless ofthe mechan~$m for the

observed increase in hydrocarbon concentrations ,at Northstar, it is critical!to recognde!that the

hydrocarbon assemblage identified at Northstar in 1999,2000 an9 2002 represents th~ hatural

background (both in composition and concentratipns) and are not indicati¥e of anthro~bgenic

inputs. However, equally important is the recognition thatthe monitoring!techniques ahd data

evaluation approaches used in this study ar:e very sensitive and capable ofidentifying 1

incremental anthropogenic inputs to the system.' 'I

In summary, the hydrocarbon measures do'not reveal any detectable contaminant input that can

be attributed to the Northstar operations, when viewed against the pre-construction le~bls in the

sediments and the pre-construction hydroc~rbon composition. .' i

4-10

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4.1.3 Metals

Data for concentrations ofAg, AI, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Mn, ~i, Pb, Sb, Tl, V and

Zn in sediment from the ANIMIDA study are now available for surficial sediments collected

during 1999, 2000 and 2002. Metal data also are available for sediment cores collected during

2001. The patchwork ofmetal concentrations described in the Results section can be normalized

reasonably well by plotting metal values 'versus concentrations ofthe major e}{~ments Al or Fe.

Concentrations oftrace metals generally correlate well with concentrations ofAl and Fe because

concentrations ofmost metals are very low in quartz sand or carbonate shell material and much

higher in fine-grained aluminosilicates. Aluminum and Fe are rarely introduced by

anthropogenic processes and are present at percent levels in most sediment relative to part-permillion (ppm) levels for trace metals. Thus, Al and Fe often provide valuable normalization

tools that can incorporate the metal controlling variables of grain size, organic carbon content

and mineralogy. In the ideal case (e.g., Figure 3-6, Section 3), a good linear correlation was

observed between concentrations of a trace metal and Al and/or Fe. Significant, positive

deviations from this linear trend, as explained in more detail below, usually identify metal

contamination. Plots oftrace metal concentrations versus Fe or Al have been used in various

forms for many years to identify sediment metal contamination (e.g., Trefry and Presley, 1976;

Schropp et al., 1990). The 1999,2000, and 2001 data from the Beaufort Sea are used here to

produce a series oftemplates that can be used to identify possible metal contamination now and

in the future. These templates are furthet tested with the 2002 data.

Concentrations ofV correlate well with Al (r = 0.97, Figure 3-6, Section 3) and Fe (r = 0.96) in

all sediment samples collected during 1999, 2000, 2001 and 2002. The good linear fit for Al

(and Fe) versus V is consistent with the mixing ofrelatively uniform compOSition, metal-rich

aluminosilicate phases with metal-poor sand and shell. Thus, either Al or Fe can be used to

normalize trace metal concentrations in this study. Occasionally, in areas where the Fe/AI

relationship is not as well defined, some trace metals are better correlated with Fe, most likely

due to the presence of an iron oxide phase that is somewhat independent ofAl and enriched with

selected metals. We have chosen Al for normalization in this study because it is the major

element least affected by chemical weathering and diagenesis and because itworks well for these

sediments.

A 99% prediction interval was calculated and plotted around the regression line for Al versus V

to establish a template for future assessments. Three points from 1999-2001' on that graph plot

slightly above the upper prediction interval in Figure 3-6; however, they exceed that limit by

<10% and are consistent with the statistical boundaries of a 99% prediction interval. Any future,

positive deviations in V concentrations above the upper prediction interval most likely will be

related to anthropogenic inputs ofV. Thus, V levels in natural sediment froth the Beaufort Sea

are predicted to follow the trend presented in Figure 3-6. Concentrations ofV in some sediment

samples from the coastal Beaufort Sea are higher than reported in grand avetages for continental

crust or marine sediment (Figure 3-6). However, background levels ofV in sediment from

ShelikofStrait, Alaska, with comparable Al concentrations, are about 140-1~0 f..lg/g (Boehm et

al., 2001 a) and similar to values from the Beaufort Sea. !

Imms animidaltask 2 final reportlfinal report fileslfinal section 4 text.doc 4-11
_

Graphs for Al versus Cu, Cr, Ni and Pb (Figures 4-25 and 4-26) also sho\V; strong (r>0.87) linear

relationships with no points from 1999-2001 that plot at >10% above the tipper predibt~on

interval. Correlation coefficients for Al versus Co (0.85), Sb (0.84) and Ti (0.86) als? hre strong

with no data points that plot at >10% above the upper prediction intervaI.CollectivelYl the . I ,

results support the conclusion that no statistically discernible anthropogenic inputs ofjthese seven

metals dm be identified. Available metal data for suspended sediments from source ri~ers (Fe,

Al in Figure 3-6 and Cr, Cu and Pb; Figures 4~25 and 4~26) show that the Inetal/Al dtips for

river particles fit within, or very close to, the prediction intervals .found fot bottom setliments in

the coastal .Beaufort Sea.. These similarities i~ metal/AI ra~ios for river source materi~ll and .

bottom sedIment, when hnked to data for sedIment cores dIscussed below" are used to evaluate

whether diagenetic impacts distort the historicalliecord for these metals in 'area sedimbiIts.

Concentrations ofmetals in the river suspended matter plotted at the higher end ofth~ ketal/AI

continuum (e.g., Figures 4-25 and 4~26) due to a greater fraction of clay~rich particle~ ~uspended

in the rivers.

Snyder-Conn et aI., (1990) previously not~d that Cr levels were as high as 331 J.lg/g a(ljacent to a . '. I ,

mud discharge area near Cross Island. Crecelius et aI. (1991) noted elevat¢d levels ofCr in

Western Harrison Bay (BSMP stations 7A, 7B and 70) and western Camden Bay (BSMP station

2E). Such levels have not been observed during fhe ANIMIDA program..

In contrast with the metals discussed above, concentrations at one or more)ocations vrere >10%

above the upper prediction interval on the metal versus Al plots for Zn, Hg and Ba (Fi~re 4-27

and 4-28). An anomalous Zn value was observed for site 5H (near Endicott Island), In'd

'. .' I I anomalous values for Hg and Ba were fouad for sediments collected near ~orthstar IsI~md

(Figure 4-27 and 4-28). Considerable industrial activity is common to both areas; h9~ever, the

degree ofmetal enrichment averaged <25% more, than the value at the upper predictiOli limit for

a given concentration of AI. I

.' I . I

Barium has been used historically as a sensitive indicator for the presence pf petroleum drilling

mud in sediment because barite is such a common and distinctive additive:(e.g., Cho~v ~t aI.,

1978). The graph for ~l versus Ba .(Figure4-27) show.s a reason~bly good fi~ for mo~t;ofthe ,

data; however, five pomts were omItted from the basehne regressIOn calculatIOn as dI~cussed

below. The Ba concentration from station N22, Close to Northstar Island on the sout~ ~ide had

an elevated Ba level during 2000. Data from stations N12, N13,N14 andlL08 also pl9t slightly

above the upper 99% prediction interval dtawn Oll Figure 4~27. : 1

Minor anomalies in Ba levels at stations N12, N13 and N14 (all during 1999) may be r~lated to

runoff from adjace'nt land operations via the Kuparuk River, based on data: for suspentl~d

sediment in the river (Figure 4-27). The aij.omaly at station N22 in 2000 may be relat~~ to

activity at Northstar Island. Subtle enhancement in the Ba value at station, L08 (199~)imaybe a

remnant of exploratory drilling in the area in 1982 and 1997 (URSGWC, 2001). Although these

'various anomalies are minor, and are identified only at low levels of AI, th1ey do suppbtt the

sensitivity ofAl versus Ba graphs and serve as indicators oflocatipns whe}e future m6hitoring

efforts can be focused.' I

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Concentrations of an additional eight metals (Ag, As, Be, Cd, Co, Mn, Sb and Tl) were

determined for samples collected during 1999-2002. Concentrations ofAg a;re low and

somewhat variable with most values <0.1 Ilg/g and in close agreement with th(~ value of 0.07

Ilg/g reported by Wedepohl (1995) for average continental crust. Background levels of As in the

study area are high relative to average marine sediment. This point was previously noted

throughout the Beaufort Sea by Valette-Silver et aI. (1999). We'find As levels in suspended

sediment from local rivers to average 15± 5 Ilg/g (n == 17). Concentrations of,Be, Cd; Co, Sb

andTl also correlate relatively well withAl as shown by the example for Cdl(Figure 4-28). ,

~v~n in the surface samples, variability i~ metal levels can occur at a' given site when replicate

samples are collected on the same day or during another year. This observation is consistent

with the overall patchiness, both horizontally ~. -and vertically, in the compositionI ofsediment from

the study area. For example, concentrations, ,of P.9 in. three replicate grab samples from station

5(I)'in 1999 have a coefficient of variance [(standard deviation/mean) x 100%],of 1% relative to

17% for sediment from station Lll in 1999 (Figure 4-29): Furthermore, sedhrlent collected at

station 5(1) in 2000 is finer grained and has higher levels of both Ph and Al relative to the

sample collected in 1999 (Figure 4-29). Also, a dramadc diff~rence was obs~r:Yed in metal levels

at station 5D between 1999 and 2000 (Fi~re 4-29). These patterns and observations are

consistent with the dynamics ofthese shallow-water sediihents. Fortunately: the Al versus plots

normalize and therefore explain most ofthis variability.'] , . f d ; _

4.1.3.1 Sediment Quality Guidelines

Various investigators have developed sediment quality guidelines to assess ~ossible adverse

biological effects from trace metals (e.g., Long et aI., 1995; MacDonald et aI'., 1996; Field et aI., , • . -' _ I . .f

1999). The guidelines introduced by Long et aI. (1995) use an ERL and ERM that are based on

field, laboratory, and modeling studies conducted in North America that coupled concentrations

of contaminants in sediment with adverse biological effects. The ERL is defined as the

concentration of a substance that affects 10 percent ofthe test organisms. The ERM is defined as

the concentration of a substance in the sedimtmt',that results in an adverse biological effect in

about 50 percent ofthe test organisms. .

Nine metals (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb and in) ofthe 16 metals investigated during this

study have been assigned ERL and ERM concentrations by Long et aI. (1995). These guidelines

are evolving as demonstrated by the extensiv~ efforts ofField et aI. (1999) to validate values for

Hg, Pb and Zn. No concentrations of any ofthe nine metals'exceeded their tespective values for

the ERM (Table 4-1). Furthermore, no cbncentrations ofAg, Cd, 'Pb or Zn from this study

exceeded the respective values for the ERL (Table 4-1) and thus adverse biological effects from . t·

these four metals would be rarely expect~d based on Long et aI. (1995). One data point each for

As and Hg, both from station 5D during 1999, exceeds the ERL. No anomalous metal values

were found for sediment from station 5D' during 2009 and 2002. '

Concentrations ofCr in quite a few sediment samples (FigUre 4-25) and continental crust (126

f.lg/g, Wedepohl, 1995) exceed the value for the ERiof82 f.lg/g. Such'observations are

commonly made for Cr, most likely because the database, compiled by Long:et aI. (1995) used Cr

concentrations from an acid leach ofthe sediment rather than a total digestion. Only a small

fraction «25%) ofthe total Cr is removed by a st~ong acid leach (Trefry and Preshiy, 1976;

Sinex et al., 1980). Thus, a leachable Cr value' equ'al to the ERL level of 82 ~g/g is more likely

I Imms animidaltask 2 final reportlfinal report fileslfinal section 4 text.doc 4-13
_

, I

and Trefry 2003). The depositional area for this sediments in the coastal Beaufort Se~ lis at least

1000 km2 to yield an estimated deposition rate of ~0.02 cm/y based on a sediment buV~ density of

1.6 g/cm3([0.3 x 1012g dry sediment/lOOO x 1010cm

2

] x [(1.6 g wet sediment/cm3)/(~¥ g dry

sediment/cm3)]). As previously noted, the coastal Beaufort Sea in this area may be n~tl erosional

at this time (Reimnitz and Wolf, 1998). I I

In the Colville River delt~ at station 6G, the maximum activity ofexcess 210Pb was 0.17b dpm/g to

yield a calculated sedimentation rate of 0.04 ± 0.02 cm/year (Figure 4-30). The I37CS, ~rofile

supports a sediment accumulation rate of40.06 cm/,ye,ar (Figure 4-3Of),. o,nce again, j't1)e record

ofsediment input since the 1950s is seque~tered in the top 4 to 5 cmofsediment. At n~arby

station 6~, detectable levels.of excess 210pp at 0.2,7 dpm/? were obse~ed only in the ~qP 0.5 cm

ofthe sediment column. ThiS latter result IS consistent With thatofNatdu and others (2001) for

the same area.

Concentrations oftrace metals were determined for 104 samples from six cores (PI, Iq, 3A, 6A,

6G a~d N2). Some variability i~ concentr~ho~s ~f m~tals was observed in ~ach cor~ I(Table 3-1

and Figures 4-31 and 4-32), mamly due to lvanatHms m amounts offine-gt;amed sediment.

However, the coefficient of variation (CV) for metal/AI ratios averaged W% in eac~ 6fthe six

cores for Ni, V, Zn, Fe, Cr, Ba, Co, Tl, Be,. Pb, Sb and Cu ('fable 4-2). Su~h uniformlrhetallAl

ratios support long-term deposition ofsediments with,uniformc6mposition and no ideilitifiable

impact from diagenesis for these metals. These conclusions are further supported belbf through

detailed evaluation of cores from stations PI and 6G and from data for river suspenddd:

sediments. i ' I i

II

In Prudhoe Bay (station PI), concentrations ofAl and Fe follow parallel tr¢nds downlcpre

(Figure 4-31). Variations in concentrations ofAl'and Fe in the core result ,from shiftsiir the

fraction ofsand, silt and clay deposited duri~g a given time period." Vertical distributions for Ba,

Pb, Cr, V and Zn (Figure ~-31), as well as Be,Cu, Ni, S~ and Tl,Jollow trends s~mil~rlto those

observed, for Al and Fe with the CVs ~or themetal/AI Tattos all <8,',%' These vertlcall?,rolfiles

support long-term deposition ofsediments with no discernible shifts in metal/AI ratio~ or

anthropogenic inputs. Metal concentrations and the metal/AI ratios for Fei AI, Pb, C~, fln in

suspended sediments from the Sagavanirktok !River are plotted atthe top ofeach vert~c!al profile

in Figure 4-31 and are coincident with values foundin the surficial layers ofthe core·1 ]This

continuity, in conjunction with the vertical profiles, supports no discemibl~ diagenetif impacts in

the vertical distributions for Ag, Ba, Be, Co, Cr, Cu, Hg, Ni, Pb, $b, TI, V ,and Zn. I I

Concentrations ofTOC (and the TOC/AI ratio) are elevated by about 30%:in the top 9.~ cm and

by a factor of~2 at about20 cm relative to:other sections in the cQre (Figure 4-31). qdincident

with elevated levels ofTOC in the surface layer ofsediment are increasedconcentrati9ns of

As/AI and slightly 10werJevels ofMn/Al (FigureA-31). Furthermore, the :MnJAl ratibs are

enriched in the layers at ~20 cm where concentrations ofTOC are high. Diagenetic i~pacts on

Mn in sediments are well studied and can l,ead to a variety ofperturbationS inconcentirftions of

Mn (Trefry and Presley 1982; Gobeil and others 1997). In the top 0.5 cm ofthe corelftom

Prudhoe Bay, concentrations ofMn are about double levels found in subs~quent layetsj to a depth

of 15 cm, yet the Mn and Mn/Al levels in the top 0.5 cm ofsediment are albout 25% lprver than

in river suspended sediment. One possible ,explanation for this observation is that pa~t~cles

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deposited in the sediment lose Mn via reductive dissolution and diffusion ofdissolved Mn2+ from

the sediments to the overlying water column (e.g., Gobeil and others 1997). The onset ofthis I

process in Prudhoe Bay occurs in the top layer ofsediment and reaches completion at depths>1

cm. Such behavior (reducing conditions in the top 1 cm) seems inconsistent.with a

sedimentation rate of 0.1 cm/year and may reflect processes that occUr in a stagnant, thin «1 mthick) layer ofwater trapped under 2 m ofice during 8 months ofthe year. A similar impact on

As levels is observed in this core. The loss ofAs from the sediments is related to release ofAs

from sediments to the overlying water during diagenetic remobilization under reducing

conditions (Farmer and Lovell 1986). Overall, diagenetic effects alter the vertical distributions

ofMn, As and, to some lesser degree, Cd, but none ofthe other metals studied are impacted.

At station 6G, on the Colville River delta, post-development sediments appears to be restricted to

the top 3 cm ofthe sediment column. No discernible differences in metal/AI ratios are observed

for all metals except Mn (Figure 4-32). Available data for suspended sediments from the

Colville River show that concentrations of Fe, AI, Pb and Cr are higher than observed for

sediments at station 6G; however, the metal/AI ratios are similar (Figure 4-32). Overall, no

indications of anthropogenic inputs ofmetals are found in the core from station 6G and only

concentrations ofMn are impacted by diagenesis.

Metal data from other cores in the area of Pole Island (station 3A) to Northstar Island, including

stations 3A, L2, E1 and N2, show similar trends with uniform metal/AI ratios throughout the

cores (Table 4-2). In some cases, the surficial layer ofsediment could be quite old as

demonstrated by undetectable levels of I37Cs and excess 2loPb. Concentrations ofMn, As and

Cd show varying amounts of distortion due to diagenetic effects. Overall, concentrations ofAg,

Ba, Be, Co, Cr, Cu, Hg, Ni, Pb, Sb, Tl, V and Zn in cores from these five sit~s are unimpacted by

anthropogenic inputs or diagenesis.

4.2 Hydrocarbons and Metals in Organisms

4.2.1 Organics (Hydrocarbons)

Concentrations of PAH in organisms were low and were indicative ofresidues ofsediment in the

tissues. No inputs ofNorthstar related activities were discerned in the hydrocarbon distributions

ofthe bivalves or amphipods. The GC/FID chromatogram, PAH distribution plot, and triterpane

extracted ion chromatogram profile of a representative tissue sample (station 3A bivalve -

Astarte) are shown for 1999, 2000, and 2002 in Figures 4-33, 4-34 and 4-35, respectively.

The GC/FID results show trace levels ofterrigenous 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 PAH (e.g., 2- and 3-ring PAH and alkyl PAH) and

pyrogenic PAH (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 some ofthe higher 'alkylated PAH

compounds are below the detection limit ofthe analytical method. Nonetheless, the pattern of

PAH in the tissues is generally similar to the surficial sediments when the influence of detection

limits is accounted for. The sample with the,highest Tot~l PAH concentratidn (1999 L04-

Anonyx at 80 J..lg/Kg ) evidenced an enrichment ofseveral pyrogenic PAH (i.e., phenanthrene,

fluoranthene, and pyrene) that was not observed in any ofthe other tissue samples.

Imms animidaltask 2 final reportlfinal report fileslfinal section 4 textdoc 4-17
,

The SITs in the tissue samples were near th.e detection levels in most samples, making

interpretation ofthe patterns more difficult~ In some samples, the presence ofinterferbnces from

the natural fats and oils ofthe tissue matrix were also encountered (large peaks in Figu~e 4~33).

Nevertheless, the triterpane distributions i~ the tissue samples generally cqrresponded to the

patterns observed in the sediments, with a predominance ofboth biogenic :and recent btganic

matter triterpane markers. Overall, the or9

anic data ~et. for :the~iss.ue s.amples revea~sl tpe

presence oftrace levels ofhydrocarbons, generally sIml1ar III dlstnbutlOn to the sedIments,

indicating a positive relationship between the background sediment hydro6arbons an~l the body

burdens ofthe clams and amphipods. I '

There was limited overlap for stations'where tiss~e samples werecollecteq in 1999, 2,OeO and,

2002, thus allowing only a precursory evaluation oftemporal data trends. IA compari~~n ofthe

PAH data in the 1999, 2000, and 2002 tissues, where stations and organism type coinbide, shows

similar concentrations ofTotal PAH (Figure 4-36). At the four Northstar stations whbte '

organisms (Anonyx) were collected for at least two years, the Total PAH cpncentratiJn~ were

also similar (Figure 4-36). Additional tissue data: corresporiding to the ANIMIDA sain~ling

locations are clearly necessary to further evaluate the hydrocarbon relatioqships in th~ bivalves

and amphipods, and their possible use as sentinetorganisms for bioaccumulation ofh!ytlrocarbon

contaminants.

Ofthe few stations with suspect sediment hydrocarbon content (i.e., statiorts L08, 5£, and 5D), ',' '., , I I corresponding biota samples were only collected :at station L08. The clam,(Astarte) samples

collected atstation L08 hav.e hydrocarbon concentrations aJ.1d di~tribution~ similar to ~~e Astarte

samples collected from statlOns3A, 5H, and L09. Thus, the sedIment ano~aly observed at

station L08 was not reflected in the associated biota tissue data. '

4.2.2 Metals

Data from 1986, 1989, 1999, 2000 and 2002 are now available for Ba, Cd, Cr, Cu, Fe, Pb, V and

Zn in amphipods (Anonyx) and clams (Astqrte) from sites in the area ofth6 BSMP thJtlis being

studi.ed ?uring the ~NIMIDA program. T~ese results provi.de a tem~oral perspectivel ~or momtonng trends III body burdens ofselected metals over tIme. Dunng 1999, 2000 and 2002;

concentrations of 10 additional metals (Ag, AI, As, Be, Co, Hg, Mn, Ni, S~ and, Tl) WII ~re

detennined in the same two species oforg~nismsto broaden the spectrum :ofanalytes.lone

primary goal ofthe organism component oftl1e study is to observe cumulative contaJlinant

inputs from industrial activity in the coastalBeaufort Sea. Variability in cbncentratio~~ of a

given metal within or among years controls the sensitivity ofthatmetal asia discrimirlator of

contamination. In this regard, the discussion beldw focuses on variability in metal

concentrations for amphipods and clams on a site:'by-site and inter-annual ;basis.

Among the metals for which data are available for all four to five years, cqncentrations ofCu and

Zn in the amphipod Anonyx are highest, yet, relatively unifonn with average coefficib~ts of

variation (CV = [mean/standard deviation] x 100) of about 15% for both metals for thlelfive

different years (Figure 4-37). Levels ofthese two essential'metals are controlled by II

osmoregulation within the organism and al).omaldus body burdens for these metals may imply a

Imms animidaltask 2 final reportlfinal report meslfinal section 4texl.doc 4-18

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physiological imbalance. None is observed at this time. Concentrations of Pb, a non-essential

metal, are low, yet, reasonably uniform with an average CV of ~20% for 1989, 1999 and 2000

(Figure 4-37). Higher variability (CV == 50%) was observed for Pb in 2002 (Figure 4-37). The

importance of a low CV to the ANIMIDA program is that any changes that occur in metal

concentrations in organisms over time must be statistically different from the baseline results.

Thus, direct observation of a difference over time is directly related to the CV for a particular

analyte.

The data for 1999,2000 and 2002 for Ag, AI, As, Be, Co and Fe in Anonyx (Figure 4-38) as well

as Hg, Mn, Sb and TI (Figure 4-39) show marked similarity among years. Ov(:rall, the metal

data for the amphipods provide a useful baseline for monitoring shifts in concentrations over

time.

Mean concentrations ofBa, Cu, Pb, V and Zn in clams (Astarte sp.) sampled during 1986, 1989,

1999,2000 and 2002 are relatively uniform (average CV<15%) during some years as discussed

below (Figure 4-40). Such uniformity is:encouraging with respect to using body burdens for

metals as a long-term indicator ofmetal ~vailability. However, the CV for a,given metal in an

individual year is sometimes large (>50%). Such variability limits statistical discrimination of

changes in metal concentrations. For example, the CV for the six pooled samples ofAstarte for

1989 was ~50% for Ba and Pb and 75% for Cd. In contrast, the CVs for the :four-pooled samples

ofAstarte from 1999 were 15% for Ba, 9% for Pb and 17% for Cd. Some anomalous points that

lead to high values for the CV can be partially explained, whereas others may be due to natural

variability as described below.

Direct comparisons ofmetal levels in the few sediment samples where positiv(~ anomalies in

metal concentrations were observed and inetallevels in the biota are limited.' However, no

indication oflinks between metal levels in sediment and organisms were found. For example, an

elevated Zn level was found in sediment at station 5H and higher Ba was fmind in sediment from

station L08. However, no anomalous values for Zn or Ba were observed in clams (Astarte) from

the respective stations.

One factor that sometimes introduces vanability into concentrations ofsome elements in clams is

the amount ofsediment contained in the gut. Samples from this study were rtot depurated, nor

were the guts removed. Therefore, any sediment that remained in the gut is incorporated into the

value reported for a metal concentration for that organism; this may yield higher values for the

CV. For example, the large CV for Ba in the 1989 data for Astarte (Figure 4-40) is partly due to

a Ba level of40.4 J..lg/g (overall mean was 24 J..lg Ba/g) in one sample from station 6D where the

Fe concentration was 80% higher than the average for the other samples. Ifhalf ofthis Fe in the

Astarte is due to sediment in the gut, then Ba associated with sediment can account for >40% 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 ofsediment 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, Co, Pb, Sb, TI and V. For most ofthe remaining elements (Ag, As, Cd, Cu, Hg, Mn, and

Zn), natural metal levels in the clam are ~igh enough to minimize the influence of excess

amounts ofsediment.

Imms animidaltask 2 final reportlfinal report fileslfinal section 4 texl.doc 4-19
_.

Comparisons among the 1986, 1989, 1999; 2000 and 2002 data for metalslin clams also are

limited by geographical differences in sample location because Astarte we're collecte~ kt only

two commonstations during 1989 and 1999 (stations 3A and 5H). However, four sdti6ns (L08,

L09, 3A and 5H) were sampled during 1999 and 2000.

4.3 Caged Mussels and SPMDs

Transplanted, caged mussels and SPMDs were dl::ployed in three replicate;moorings adjacent to

Northstar Island and three at a reference site to the east ofthe study area, as previousl!yidesCribed

in Section 2. This pilot study, performed during the summer 2002. field sUhrey, reprekented the

first known successful caged bivalve/SPMD deployments in this region.

4.3.1SPMDs

Only hydrocarbon measurements were deterniined for the SPMDs, as metals do not readily

diffuse into the SPMD membranes. The SPMDs from the reference site a*d Northstdr Ishowed

no significant differences in most ofthe key PAH parameters measured. ~he total P4M ,

concentrations in the SPMDs were low (470 540 ng!SPMD). All evaluation ofthe ~AH

distribution in the SPMD samples (Figure 4-43) reveals a composition of primarily pyttoleum

PAH in both the No~hst~r a?d r~fe~en.ce SPMDs; mixed with traye ~evels ?fpyrog~nilclPAH.

The observed PAH dIstnbutIon IS sImIlar to the documented PAH signatufle found m ~lie

sediments ofthe region. There is a slight enrichment ofthe 2-ring naphthalenes versuslthe 3-ring

phenanthrenes and dibenzothiophenes, which indicates that; some ofthe more water-~qluble 2-

ring PAH may have diffused into the SPMP membranes directly from the iwater colu~:tin in the

dissolved phase. Whereas the primary mechanis111 ofPAH assimilation into the lipidlriIatrix of

the device appears to have been direct diffusion from the suspended sedim'ents in the ~ater

column.

The composition of combustion related or pyrogenic PAH from both the reference an(l Northstar

SPMDs appears very similar (Figure 4-43); but it should be noted that there is an appa~ent

significant increase in the pyrogenic PAH in the Northstar samples. However, the pyt<}genic

PAH are found at such trace levels in the SPMDs it is difficult to determine whether this result

represents an actual trend or is simply an artifact Ofthe trace PAH analysi~ in these sJrbples.

4.3.2 Caged Mussels

4.3.2.1 Organics

The caged mussels from the Northstar and 'reference deployments showed ino significa~t . , ,,1

differences in most ofthe key hydrocarbon parameters measured.. The PAjH concent~ations in

the mussels were very low (13 - 17 ng!g total PAH), however, the concentrations were:

substantially higher than the pre-deployment teference levels indicating that the muss1els

bioaccumulated trace levels ofhydrocarbons on a regional basis.

An evaluation ofthe PAH distribution in the mus~el samples (Figure 4-44) reveals a si~ilar

composition ofpetroleum PAH in both the Northstar and reference mussels, mixed w!itp perylene

and lower levels of pyrogenic PAH. The obser:ed PAH .distribu~io~ is ~0t1sistent witp Ithe

known hydrocarbon background pattern found m the sedIments, mdicatmg the PAH wyre

probably accumulated during the active filtering of waterby the organisms. This is fi~*her supported when compared to the pre-deploymentPAH distribution where perylene is absent.

Imms animidaltask ifinal rep~rtlfinal report fiI~slfinal section 4 te>ttdoc 4-20

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The only source of perylene to the mussels is natural background, which is wen documented in

the region. Although only trace levels of combustion related pyrogenic hydroc;arbons were

found in all samples, it should be noted that the Northstar mussels had significantly higher levels

than the reference mussels. This result appears to corroborate a similar trend in the associated

SPMDs. However, whether the origin ofthe subtle change in pyrogenic hydrocarbons is

associated with natural variability, Northstar Island activities, or is a result of a. more widespread

oil field phenomenon remains an area fot future investigation.

4.3.1.2 Metals

No significant differences were observed between concentrations ofmetals in samples from the

reference site in the coastal Beaufort Sea versus Northstar Island (Table 3-1 ~). In fact, the mean

values agreed within 5% for most metals~ Some shifts in concentrations were observed between

the predeployment site and the Beaufort Sea sites. For example, Ba in the mhssels from the predeployment site was 6.5 J.lglg relative to 18 J.lglg in the Beaufort Sea. This difference is probably

related to differences in ambient levels of dissolved Ba in the two systems arid supports the " . I

contention that the organisms were actively filtering water. Similar shifts were observed for Be

and Tl (Table 3-17). i

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Table 4-1. Values for the Effects Range Low (ERL) and Effects Range ~edian (ERM) from

Long et al. (1995) and Study Results :

N13 (99) I

Ag 1,0 3.7 0.44 0.07 N14(9~) none

N22 00

As 8.2 70 28.4 1.7 5D(99)* 5D (99)*

Cd 1,2 9.6 0.82 0.1 5D(99)* none

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N17 0'0

Pb 46.7 218 22.3 14.8 5D (99)* None

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Zn 150 410 131 65 5H (99) None I

*One ofthree samples analyzed from the somewhat heterogeneous sediment from this site near West Dock.

**Wedepohl (1995).
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TIIAI 0.11 ± 0.01 4-11

Be/AI 0.24± 0.3 5-14

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Mn/AI 65 ± 19 8-42

Ag/AI 0.03 ± 0.01 16~39

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Table 4-2. Summary of Results for Met~IIAI Ratios and Related Coeffi\cients of V:ariation

(CV) in Sediment Cores • "., I

The sediment core samples were collected from the following locations: Prudhoe Bay (n =29), qndicott ,

Island (n =13), Pole Island 3A (n =10), Colville Delta (6A, n =23; 6G, n =14), Northstar Islan~j (N2, n =

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percent gravel (black bar); sand (red liar), silt (green bar) and clay (yellow bar) for sediment

samples collected during 1999 and 20~O .

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Liberty Prospect 1999

4km

Liberty Prospect

2000 . ;

''''It : 4B

GSSC

''''I _4B :Urh GSBe

''''I~ 4A

: GGG

,'"

I

Figure 4-3. Map identifies sampling sites and histograms show ,grain s,ize distribution as

percent gravel (black bar), sand (red bar), silt (green bar) and clay (yell~w bar) for sediment

samples collected during 1999 and 2000 "

''''I 4C :lJi GSGe

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2500 ,---------------,--"--~---------------___,

"BQ06: NORTH SLOPE CRUDE OIL"

0.00 10.00 20.00 30.00' 40.00 50.00 60.00 70.00 eO.oo

o

5000

Compounds

60000

55000

50000

45000

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30000

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10000

i 1500

a Ii "Ij 1000

Response..:....

I -~},.tl.t~"~·~2:, 'f_,~ -' _':"'L-I·~'·' ,- i

Figure 4-4. North Slope Crude Oil ;2; GC/FID Chromatogram (top), PAHQistribution

Histogram (middle), Triterpanelon Chromatogram (bottom) ,

u

0

0

n

g.;;,

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Figure 4-5. Northstar Oil - GC/FIO Cliromatogram (top), PAH Dlstrlbutlo,n Histogram

(middle), Triterpane Ion Chromatogram (bottom)

Response_

'10170214.D\FID1A

10.00 20.00 30.00 40.00 50.00 60"00 70.00 80.00

I

I~..

II...

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2000

I

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1000

500

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5000 -;-'-~~--r-'"~~--r-'"~~--r-'"~~-r-c---r-'~T-r~~-,-.-~~-,---r~~-,-.-~~-,---r~~r-;:::,...o;""'-~~"-'C=

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.1S

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I •

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r"" i'; ; , ':. i f ••"

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Figure 4-6. Colville River Sediment, Year , 1999 - GC/FID Chromatogram , I'(toP), PAH

Distribution Histogram (middle), Triterpahe Ion Chrornatogram (bottom) " I I

Response_

q

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II

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200

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10.00 20.00 30.00. 40.00 50.00 60.00 70.00 eo.oo

"99A4758: 99-COL·02-PHC·S SEDIMENT"

I

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I,

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n-C27

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., 0.00 20.00 30.00 40.00 50.00 ao.oo 70.00 ep.,oo

4000

0.00

2000

eooo

aooo

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.,0000

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.,eooo

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I

!

Figure 4-7. Northstar Station 6 Se~Uii~nt; Year 1999 2 GC/FID Chromatoigliam (top), PAH

Distribution Histogram (middle), Triterpane Ion Chromatogram (bottom~

I

II..'

"99A4740: 99·N06.01·PHC·S SEDIMENT"

Irne-->

o~~~~:::::::~~~~~~~~~::;:::;= 39.00 40.00 42.00 44.00 :46.00 49.00 50.00 52.00 54.00 56.00 sa~oo

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Figure 4-8. Liberty Station 6 SedimentltYear 1999 .... GC/FID Chtomatogr~nl(top), PAH

Distribution Histogram (middle), Triterpane Ion Chromatogram (bottom)
",

.

\ I:.

:,.1

1

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.·'·m·······~ Ii

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Figure 4-9. Station 3A Sediment, Year~~99 - GC/FID Chrornatogram (top), PAH Distribution

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

11000

RasponsEII......

n-C27

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5000

4000

3000

2000

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bunclanoe

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Figure 4-10. Station LOS Sediment, Ye~r 1999 - GC/FID Chromatogram (top), PAH

Distribution Histogram (middle), friterpane Ion Chromatogram' (bottom)

.~ __ ~c:> ..... _

n-C17

n..C27

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eO.loo

I

45 -,------------~------------___+_-~--__,

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Distribution Histogram (middle), Triterparie Ion Chromatogram (bottom)

,~rI' 1:llJ

t~

,':'~~

60000

55000

50000

45000

40000-

35000

30000

25000

20000

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350

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Figure 4-12. Northstar Station N06Seclirtlent, Year 2000 7"'" GC/FID Chromatogram (top), PAH . '.. .. Distribution Histogram (middle), Triterpane Ion Chromatogram (bottom)

fI!I.~ .. '

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PAH Distribution Histogram (middle), friterpane . lonChrotnatogram(b~ttom) .

ResponsEI_

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Figure 4-14. Northstar Station N06 ~edirtlent, Year 2002· GC/FID Chro~atogram (top), PAH

Distribution Histogram (middle), Triterpane Ion Chromatogram (bottom) • I

I

8

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25000

30000

40000

80000

100000

120000

libundance

Time

Response_

!

Figure 4-15. Canning River Sediment, Year 2002 - GC/FID Chromatogram (top), PAH

Distribution Histogram (middle), Tri~erpane Ion Chromatogram (bottom)

20000

Il~~

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o

o

a

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la

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The lines, Rsq, and 95% mean prediction intervals are from linear regression and related statistical calculations for

Northstar stations by year.

• 1999

Rsq =0.8134

• 2000

Rsq = 0.6074

II 2002

Rsq = 0.7915

Year

1001 60 80

7

...-

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Silt+Clay(% )

I

Figure 4-16. Scatterplot of Silt + Clay Results versus Total Polynuclear ~Iromatic

Hydrocarbons Less Perylene for Northstar Surficial Sediment Samplesiin 1999. 2000, and

2002 .

1..I1~ ... ~' 'IIII

(I,

'0

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40.00

35.00

30.00

25.00

20.00

15.00

10.00

5.00

0.00

ClTotal PAH less

Perylene / Fines

1999

- ClTotal PAH less

Perylene / Fines

2000

Cl Total PAH less - - Perylene / Fines

, 2002

- f---- ,.-- - ~" - r-- f----

f-- - f--- - f---- - f-- f---- - - - , - a

- "- , , ,

SA NOl N02 N03 N04 NOS N06 N07 N08 N09 NlO NIl Nl2 N13 N14 Nl5 N16 N17 N18 N19 N20 N21 N23

Figure 4-17. Total Polynuclear Aromatic Hydrocarbon less Perylene Concentrations normalized to Fines for all 1999, 2000,. and

2002 Northstar stations

..
~"" .

-.

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~.,"'~.. ,

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i

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,-

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I

SA NOI N02 N03 N04 NOS N06 N07 N08 N09 NIO Nll N12 N13 N14 NIS N16 N17 N18 N19 N20 N21 N23

I0 Pyrogenic/Petrogenic 1999 0 Pyrogenic/Petrogenic 2000 0 Pyrogenic/Petrogenic 2002 I

Figure 4-18. Pyrogenic:Petrogenic Ratios of Northstar Surficial Sediment Samples for 1999t 2000t and 2002
,"

"

f···

,

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.1

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- I

,

,

i l

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y

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1.80 I I

x

1.60 I A I

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• Northstar 1999

• Liberty 1999

.. SSMP 1999

• Northstar 2000

• Liberty 2000

.. SSMP 2000

• Northstar 2002

• Liberty 2002

.. SSMP2002

., xNorth Slope Crude Oils·

o Northstar Oil

- Canning Sediment

- Colville Sediment

+ Colville Peat

- Kuparuk Sediment

+ Kuparuk Peat

- Sag. Sediment

+Sag. Peat

X

•

Kuparuk River Sediments and Peat

Northstar Oil

Canning River.Sediments

•

x X

Xx XX

North Slope Crude Oils

• • - +

.60 •• _ Sag. River Sediments and Peat .- - - - .. .. A

.40 I ........~.~

.20 , '" - .............. I

1.40 I I

1:20 I /' I

1.00 I X I CO') Kuparuk River Sediments

-0

c

G

[ .00 , • ,! I .00 .20 .40 .60 .80 1.00 1.20 1.40.

C2D/C2P .

Figure 4-19. Double Ratio Source Plot of C2D/C2P vs C3D/C3P for BSMP, Liberty, Northstar, and River Sediment Samples for

1999, 2000, and 2002
'.-.1

. ..

.. , <

',.

I'

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._" .... ~·.'.·i .. ~.-. - .=) .~.~==' =ml._ ._1._ ~' (==~.== == - _.

r=l .&iii:

1.600 T'-------------------------------,

Northstar Oil

• Northstar 1999

• Liberty 1999

~BSMP 1999

• Northstar 2000

• Liberty 2000

~BSMP2000

• Northstar 2002

• Liberty 2002

~.BSMP.2002 .

X North Slope Crude Oils

o Northstar Oil

- Canning Sediment

- Colville Sediment

+ Colville Peat

- Kuparuk Sediment

+ Kuparuk Peat

- Sag. Sediment

+Sag. Peat

XX

o

Kuparuk River Sediments and Peat

II

Canning River Sediments

1.200 II

1.400 I North Slope Crude Oils ,.." f .. X

1.000 I • ...

0.400

0.200 I 0:.. ,/_ '\

0.600 I ./.. • Colville River Sediments and Peats

...

N

~. 0.800-1I__'_:::::;[_'_ L __'__'__'__'__'__'__~~--'--'--'---'--'--'--'--'---=-.--'--'---'-'-'------

0.600 0:800 1.000 1.200 1.400

825/828

0.200 0.400

0.000 !. I ,!

0.000

Figure 4-20. Double Ratio Source Plot of S251S28 vs T211T22 for BSMP, Liberty, Northstar, and River Sediment Samples for 1999,

2000, and 2002
:l.

"1

, ",

. j.

m: mmmmIm

~im

00mmm
, i

The lines, Rsq, and 95% individual prediction intervals are from linear regre$sion.

Figure 4-21. Regression Plot of Total PAH less Perylene versus Silt + qlay for all 1999,

2000, and 2002 Northstar, Uberty and ,BSMP Sediments

o

I

,I

I

I

o

~-';;..,-

I

o

o

o

R

D

o

I

D

~I

o

,I

9

8

- 7

-C>

:::J 6

-Q)

c

Q) 5

Q)

a.

(/) 4

(/)

Q)

I

« 3

0-

ca

+"'

0 2

IZ

.....J 1

-20 0

Silt+Glay(%>)

Region by Year

I

• Lib/BSMP 2000+2002

• Northstar , 2000+2002

I

.to Lib'tBSMP 1999

• Northstar 1999

-_. ,

Total Population

Rs6 =0.6341
.i

•

• <.

i 'I,'

"

•.ll'

i·

i'

'iI,' t""

.'

, .. "

I
8

•

7

-

-0> 6 :::J

...........

Q)

c

Q)

5

Q)

c.

en

en

Q) 4 Regio<n-Year

:r: _.- i

« • Lib/SSMP 2000+2002 a. I

CO 3 • Rsq :: 0.5502 .....

0

I-- • Northstar 2000+2002

Z •

2 I

..J Rsq :: 0.6305

-20 '0 20 40 60 80 100

Silt+Clay(% )

Figure 4-22. RegtessionPlot of LN Total PAH less Perylene versus Silt: + Clay for all 2000

and 2002 Northstar, Liberty and BSMP Sediments

The lines, Rsq, and 95% prediction intervals are from linear regression and related statistical . I calculations .
"

, ..

mmm

00

00wmmmmmImm'i

01

WI mm
8-r-------'----------:----:---,-----,

Figure 4-23. Regression Plot of Total PAH less Perylene versus,Perylehefoi' all 1999, 2000,

and 2002 Northstar, Liberty and BSMP Sediments ;

The lines, Rsq, and 95% individual predibtion intervals are from linear regre~sion.

I

Total Population I

Rsq:= 0.9397

,

• Northstar , 1999

.. Lib/sSMP 1999

• Lib/BSMP 2000+2002

I • Nohhstar 2000+2002

Region by Year

1 2 3 4 5 6 7

7

LN Perylene + 1 (uglKg)

5

Q)

4

C/)

C/)

I 3

<{

0-

S 2

o

I3 1 +--........,..---r-----r---r---......--...,--~

o
c

.,

1'1

I'" I

i'

Ii

,'

,I

mm
_II _i·_

_1 _I _I ::'::·'::-1 - . i

- _i iIiii' _: _I _1

.- .............. _i, ..iiiI'

_i _ii

100000 -,-,-------------------------'------------------,

ERM 44,000 ug/Kg

10000 +1----------------------------------------------1

ERL 4,022 ug/Kg

10

1000 I I I I I I I

/1

-

~I I • II I

100 .• I

I Drnax

I

•.•. Elm~an 1 I ,' •.* .....

Omm

1 1.._.' I'I'I' I.I I' ,n I I I I _I I !

BSMP (1999) BSMP (2000) BSMP (2002) Liberty (1999) Liberty (2000) Liberty (2002) Northstar (1999) Northstar (2000) Northstar (2002)

Figure 4-24. Comparison of Regional Mean 1999, 2000, and 2002 Total Polynuclear Aromatic Hydrocarbon Concentrations to

Sediment Quality Criteria Effects Range-Low and Effects Range-Medium Values (Long et al., 1995) Note: y-axis is presented on a

logarithmic scale.
'. ..

' ..'

I'

"

,

I:

mm

m· mmmmmmmm

m' m

mi,

m', ml

mi

,m, ., Utl;f m
Figure 4-25. Concentrations of aluminum versus (a) chromium and (b) 'copper for

sediment from the ANIMIDA study are~ ,

Equations are from linear regression calculations and ris the correlation coefficierilt. Dashed lines

show the 99% prediction interval. Points, marked with large letters are for suspended sediment

from the Sagavanirktok (S), Kuparuk (K)and Colville (C) rivers. Data for sites.identified on the I " graphs were not included in the regression calculations. ' .

Y = 5.8X -4.6

r =0.94, n = 96

246 8 to

AI (%)

o 2002 0 2001

20

60

+ 2000 6. 1999

150 .-------.----r----.--r--....------,--O---,-r------.--:.'-..,

'/

100 C // .-

.e>

C)

::J.

........

....

U

50 /

/

Y .6./

/

/

/ Y =12.4X + 8.1

/

/ r =0.91, n =1 $1

0

0 2 4 6 8 10

AI (%)

(b) 0 2002 0 2001 .+ 2000 b. 1999 80

(a)

I

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-

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,"

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.;,

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,

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.., ,. ,

, ,:"" '.J.

. I'

I'

.·1

'. i'I

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:<

,

,.

mmmmmmmmmmmmmmmmmmm
'I

30

(a)

Y = 2.4X - 0.3

r= 0.87, n = 196 :

OL...<::::.~---"~---'---'--~_...l...-_~----'_----"----.l--.J

o 2 4 6 8 i 10

i AI (%)

10

0 2002 0 2001 + 2000 I). 1999 i

60

'/'

/"

/'

/'

-.!2> 40 C>

::l.

--z

20

Y =6.4x +'0.991

r=0.91, n=19~

0

0 2 4 6 8 10

AI (%)

(b)

0 2002 0 2001 + 2000 I). 1999 40

,

Figure 4-26. Concentrations of aluminum versus (a) nickel and (b) lead, for sediment from

the ANIMIDA study area 1

Equations are from linear regression calculations and ris the correlation coefficient. Dashed lines

show the 99% prediction interval. Points marked with-large letters are for su~pended sediment

from the Sagavanirktok (S), Kuparuk (K):and Colville (C) rivers. Data for sit~s identified on the

graphs were not included in the regression calculations.

I

I

I

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I

·~I

~I

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I

I

I

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, ~-

"•- -, 0..-.'

.I

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I.

I

$ ., ,

i .

, '.r"11

j

I.

I •

..L

.i!

I 'Immmmmmmm

m: m

m' mI m

ml

I mmmm' m
I Figure 4-27. Concentrations of aluminum versus (a) barium and (b) chromium for

sediment from the ANIMIDA study area .

Equations are from linear regression calculations and r is the correlation coefficient. Dashed lines

show the 99% prediction interval. Points marked with large letters are for sU$pended sediment

from the Sagavanirktok (S), Kuparuk (K)and Colville (C) rivers. Data for sites identified on the

graphs were not included in the regression calculations. i

10

10

/'

'/

/'

8

8

Y:: 20.5X • 5.5,

r:: 0.92, n = 19'5

+ 2000

4 6

AI (%)

D 2001

2

+ N22

246

AI (%»

o 2002

o L...L--,-_.LL-_~_-'----'-_-'-_~_-'----'-~_---.J

o

o 2002 q 2001 + 2000 IJ. 1999 200 r------r-----.----;-~__,_-~_____,c--~-~".___,_;__,~

150

50

-

Q>

C>

:::1. 100 --c

N

(b)

900

-

Q>

C>

::J.. 600 --co

CO

300

(a)

~I

I

I

-I

I

-~I

I

I

fl

I

I

I

I

I

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I

I

~I
,.

.

:"!

. 'i

;.'

!

.~.

j .;

.j .1...

:'" i

'

.~. mmm
(b)

Figure 4-28. Concentrations of alumin'um versus (a) mercury and (b) c~dmiUlm for

sediment from the ANIMIDA study area I

10

10

i'

8

8

!

:

,

Y =0.013X- 0.012

r= 0.88, n = 1~3

I __

D Ie...--- .&J ----, *

+ _".--"- <f---

Y = 0.052X + 0.01

r =0.75, n =191

4 6

AI (%)

4 6

AI (%)

OKBP

o 2001 + 2000 b. 1999

2

o 2002

o.00 '---~~::l-"""-<:'-------'--_L..-.......--'-_-'------'-_......L-.!,-_----J

o

0.2

0.8

C3 0.4

-.!2l 0.6

C)

:::L

--

o 2002 0 2001 + 2000 l:;. 1999 1.0 ,-----r"~--r-'--..,.---__.~~-_,__~,--..__"_r-.,..,_-.....__,

0.05

0.15

-.!2l

C)

C 0.10

C)

J:

(a)

i ,

Equations are from linear regression calculations and r is the correlation coefficient. Dashed lines

show the 99% prediction interval. Data for sites identified on the graphs wer~ not included in the

regression calculations. '

II

I

fl

fl

I

I

~I

~I

I

I

,~I

I

~I

I

I

I

II

~I

I
II!

,,

mi

mmmmmmmmmm

00

m: mmmmm

00
6 8

L11(1999)

4

AI (%)

2

OL.L._~--'----.L..-~""---'-----~--'-----~----.J

o

5D(1999)

_ 20

Q>

C)

::l.

-.0

a.

10

Figure 4-29. Concentrations of alumin~m vs. lead in sediment

Dashed lines show the 99% prediction in~ervals developed for the entire dat~ set.

I

I

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I

I

I

I

I

~I

I

I

~I

I

I

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I

II

,I
t

,tj ,"

1; .'

r,

. .:. "

,'

",' "

mmmmmmmmmmm

00mmmm, mmm
I,,'

,

Figure 4·30. Vertical profiles for activities of excess 210pb, total ~10Pb and 137Cs for

sediment cores from sites in Prudhoe :Bay (P1), near Endicott development ~E1) and on the

Colville River delta (6G) , ,

yolville6G

I

s::: 0.06 cmfy

i 3

a

Q)

0 6

-c:

Q)

E

'5

Q) 9

en

12

Colville6G

Total 210Pb

3 In excess 210Pb s:::.

a.

Q)

0 6

c: S =0.04 cm/y Q)

E r =0.98

'5

Q) 9

en

12

(a) 210Pb Activity (dpm/g) (6) 137Cs Acitivity (dPm/g):

-1 0 1 2 3 4 0.0 0.1 0.2 0.3 :0.4 0.5

0 0

6 A In excess 210Pb 6 6 6

3 A 6 3 6

1:963 I.!:. 6 s:::. a 6

S = 0.11 cm/y J

Total 210Pb

a. ,

Q) Q) 1950 0 6 r = 0.9 0 6

c: - S = 0.10 em/y c: Q) Q)

E E

'5 9 '5 Q) Q) 9

en en

Prudhoe Bay Prudhoe Bay I 12 12

I

I

(C) 210Pb Activity (dpm/g) (d) 137Cs Acitivity (dpm/g)

, -1 0 1 2 3 4 0.0 0.1 0.2 0.3 1 0.4 0.5

0 0 I

6

6

i 6

6 3 1963 6

s:::. :; a Total 210Pb a. Q) Q)

0 6 S = 0.04 cm/y 0 6

c: c: Q) r= 0.9 Q) S =iO.06 Crilly E .E '5 9 '5 Q) Q) 9

en en

Endicott ,Endicott

12 12 I

(e) 210pb Activity (dpm/g) (f) 137Cs Acitivity (dpm/g)

-3 -2 -1 0 1 2 3 0.1 0.2 0.3 i 0.4 0.5 0

~I

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iiIIii

• ,Ii

f"

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, ,,'

6

1950

20 40 60

Zn/AI

Q

8

Q

8

1?

8

Pb/Al 8

(:t5.0%)

2 4

Pb/AI'

Zn (1-19/9) ;

50 100 150

30 L-- Prud~oe ----"-__

Bay J

o

I

I

I

I

I

Pb (1-19/9)

, 0 0~_---,C:;~1~O...::--f. 20

10

EO)

c 20

oo ~--r-6--r--06-..,.-.,.....,

----lp

C,l

;

g

J)

q

Zn/AIf}

(:t5.2%)

. Prudhoe Bay 30 '--~ -LI--.J

o

30 L--~ ~_--J

o 50 100 150 200

Sa/AI

V (1-19/9)

o 50 100 O ......,:....,.....,.....,...n~.........."..........,

~~~~ __i _ , ~;

o

J'

(\~

cPq

q

d) J)

8 . ,VIAl 0

(t4.3%)

\ Prudhoe Bay

Sa/AI g

(:t5.4%)

1950

sa (1-19/9)

,/0,: 200 400 600 O,..........~....-.u:,......;-,........,;r.......,

Prudhoe Bay

30

o 20 40

VIAl

10

Cr

10 20 30

erIAl

8

Q

CS

Q

Cr/AI O

(:t5.0%)

Prudhoe Bay 30L---~~_.:.-J

o

10

EO)

c 20

Mn (1-19/9) I

o 300 600 900 o r---=~oGl.;.a.---,

EO)

c 20

"

6

o

'TOC/AI TOC

(:t 29,2%) Prudhoe Bay

TOC(%)

o 1 2 3 4

o r---~~~"ll--~

10

.s::.

a.

0)

c 20

2 3 4

AslAI

Prudhoe Bay

b

¢

C,J

q)

c\

~)

AslAI ()

(:t21.5%)

As (1-19/9)

o 3 6 9 12 15

o r---~--'----4;:;<:J:;il~~

30 L--__ __-J

o

.s::.

a.

0)

0 20
",'<Ii'

· .•,'•. ,.j

II

"I

m ii mmmmmmmwIWm

'';1'

",'

mwm
~I

Colville 6G Colville 6G Colvill~6G 30 30 30 0 10 20 30 0 10.,20 30 40 50 0 2 4 6

CrlAI , VIAl ColAI

Ni (l-Ig/g) Mn (1-I9/g)

0 20 40 60 0 ;200 400 600 TOC (%) 0 0 ---___8__ 1'950 0 1 2 3 4 <) 0 C;'

'?

?

10 ? 10 8 E 10

0 .s:::. .s:::. E0 - - -- Q. Ni/AI Ni Q.

Mn Q) Q) .s:::.

°20 (±2.9%) °20 15.

(±22.5%) Q)

°20

Colville6G Colville6G

i

Colville 6G Colville 6G Colville6G'

30 30 30

0 50 100 150 200 0 2 4 6

Sa/AI Pb/AI

Cr (1-I9/g) V (lJg/g) Co (l-Ig/g) i

0 30 60 90 0 ;50 100 0 5 10 • 15 0 1950 C<

0 , , 1950 q 0 1950 Q -------'t-- ----·--it---- ------0----- " 0 C,> \l

)' 7' 8

? <\ !)

10 ? _10 % _10 ? E 0

<b <,1(} 5 g .s:::. g .s:::. -- <h .s:::. 15. -Q. 0

CrlAI Cr - cb Q) Q) VIAl V Q.

Q) Co/AI °20 (%4.4%) °20 1(%2.8%)

, °20 (±4.3'10)

Fe and AI (%) Pb (l-Ig/g)

0 2 4 6 8 0 b

0 ..,~ 10 20

0 0 'Q Q 1950 ---rf---- __ ja50~ ------~-Q.--- ------f(-- ----~-~

el' 0

if ~) <~

\ 10 1

10 I 10 1 - Q Q

- 8 E e? E p 0 ,J c!) .s:::. -- 'b .s:::. .s:::.

- 15. Sa/AI 15. Pb/AI Pb Q.

Q) Q) Sa Q) Fe AI °20 (%5.2%) °20 (%4.9%) °20

C~~~ o 5 10 15 20 0 20 40 60 80100 30 L-~ --,

NilAI Mn/AI 0.0 0.1 0.2 q.3 0,4

Figure 4-32. Vertical profiles for conce,ntrations and ,ratios to AI i,n sediment core from

Colville River delta (station 6G) for Fe and AI, Ba, Pb, Cr, V, Co, Ni, Mn ,:alTld total organic

carbon (TOC). Points marked with large letters on Pb, cu, Cr, Zn and Sa graphs are for suspended sediment from the

Sagavanirktok (S), Kuparuk (K) and Colville (C) rivers, Graphs with no line identifying a sediment age of 1950 (As, TOC and Mn) lack

geochronological significance due post-depositional diagenesis/diffusion.

i

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"

~:.,~,.t.·#~.\~} ..> ••

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• ",.r

.,

. -:'- 04"';

.,

,.

Immmmm

00,

!

m:

rnmmmm

00I WWmm

,m
I

I Figure 4-33 Station 3A Astarte sp. Tissue, Year 1999 GC/FID Chromatogram (top),PAH

Distribution Histogram (middle), Ti'iterpane Ion Chromatogram (bottom)

Response_

11179ge6.D\FID2B

4500

4000

i I

n-C27

1

n-C17

I I.' i I I Ii"I

1 0.00 20.00 30.00 40.00 50.00 eo.oo 70.00 60.00

1500

f---,-~~-'-~~~--r--"'C"-r~"--'~~C"-r-r---'-"-~-T-r-r~

0.00

2000

2500

3500

3000

lrne II

I

~I 88-3A-Cl1-PHC-T-AS

2 ~-----..,.--------------------------~------,

I 1.8 t-------------------,-------------------'--------;

1.6 +------------I'I~I~-------------------~---_l

i 1.4 ,

1 1.2 r-}; ,~I--------i.·--.="""-"""-----------------------;

f .. &

.! 1 --,----- ~I--------

I

0.8 I--

0.6

0.4

0.2

o

bundance

il 4500

4000

Ian 191.00 190.701:a 191.70): VV1169.D

3500

3000

2500

2000

,II)

....

... 1500

II

I

1000

500

1"""'8-->

i~

I I _ 1- i I _ ~---;-.--r--.-,--.--.---.---r38.0040.0042.0044.0046.0048.00 50.00 52.00 54.00 56.00 !58.00

I
\

',;r.

,,

..

mm
i

n-C2?

04050161.D\FID2B

I

i

;

,

i I

milI !iii '~ml D i [i1r~ i

1600

,22

1200

.2.000

1400

2600

2800

1000

2200

,19

1800

lcan ~e .... oo (190.70,tc» 191.70): VVa007.C>

I I

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80,00

00-3A-G1-PHC-T-AS

2000

1500

1000

3000

2500

3500

o

0.2

1.2

Dunclmneo

,.. C'!)--::-

.~ ;.r,l<l·' '. _ . ?~:~: _ I

Figure 4-34. Station 3A Astarte sp. Tissue, Year 2000 -;- GC/FID Chromatogram (top), PAH

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

1

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f "~' .. -1', , f' ,I .•,

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, I

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II

02-3A..Q1-PHC-T-AS

,22

',12

I'1 5l~e 1 "r21

'11,JWW

Ion 1e1.00,(190.70·to 191.70): Seea8.D

... 0.00 20..00 30.00 40.00 50.00 eo.oo 70.00 eo.oo I

I

Ij

/"421

n-C17

~l IIIL

I .III '-..1 I, I

,

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fi1 :. rIllll I fil fi1

4500

4000

3500

3000

2500

2000

1500

"1000

500 ,4

5500

3000

4500

5000

2500

4000

3500

2000

1500

0.2

0.4

o

1000

500

0.00

1.2

1,4

1.6

bundanCG

Tirne-->

Figure 4-35 Station 3A Astarte sp. Tis~ue, Year 2002 - GC/FIDChromatogram (top), PAH

Distribution Histogram (middle), Triterpane Ion Chtormltogram (bottom)

'I

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I.

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, ~'

;

.-;

~., .... , ..

.

.-. ,.. ..

~'!- f'

·,i

m

m, mm

,mmmm

:mm

, m;

m.

m: mmmmi m
•. -,

- -'-"

..

- ...............

- ...............; -

- .. fiiii ,iiii , iiiI _Ij ;'

90.00

80.00

70.00

60.00

,

J 50.00

i

~. 40.00

!

30.00

20.00

10.00

0.00

,

I

-

I , i

M~ 11'-llr I(-IIII~: ~f' - I-I~ -II~I ~II , ' ...,.. -----,--,

lil1999

82000 I'

02002

'3A-AS SH-AS L08~AS' L09-AS SF::CY - 4A-l-AN '4A~2-AN SB-AN 'S(O)-AN L04-AN"N03-AN N04-AN Nn~AN NI2~AN'N13-ANNI8-AN

i i

Figure 4-36. Total Polynuclear Aromatic Hydrocarbon Less Perylene Concentrations of Bivalves and Amphipods for BSMP, Liberty and

Northstar Stations in 1999,2000, and 2002

Sample suffix definitions - AN - Anonyx (clams), CY - Cyrtodaria (clams), AS - Astarte (amphipods)
•.,r

I." "" .

.,.

" ~,"

.'

..'

. ,

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I,

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80 2.0 Anonyx(amphipods) Anonyx(am phipods)

- -- . I

-,l;P 60 T .~ 1.5 Q)

== == T -c: 40 • T T "0

• 1 ---,- Ci 1.0

Cl 1 • • ..... .....

Cl Cl A 1- ::J. ---.L :20 T - 20 • 1 - --,

"0 0.5 A A A A

() ---'-

0 0.0 1986 1989 1999 2000 2002 1986 1989 1999: 2000 2002

200 0.8 ,

1

- Anonyx(amphipods) T - Anonyx(amphipods)

..c:

- - !

.l;P 150 • ,~0.6

T Q)

T 1- .~== T • == T T

-c: 100 • • • -C:O.4

Cl 1 -'- OJ

•

-l ---r ' •

·1 ..... -'- ..... .' ---,- Cl OJ • ::J. ::J. ---.L' - - ---.L

::::I 50 .c 0.2

() a.

<MOL

0 0.0 A

" 1986 1989 1999 2000 2002 1986 1989 1999 2000 2002 l

"-'!

6 200

Anonyx(amphipods) ,..." Anonyx(amphipoqs)

-- -,l;P 150 T .l;P

T Q)

Q) 4

== T == • 'f 'f T

'''0 T 1 • "0_ 100 -'- 1 'f

Cl ---'- T -l ..... • Cl

~2 ::L

• • - c..L - 50 > c:

1 N

0 0 1986 1989 1999 2000 2002 ' 1986' 1989 199'9 2000 2002

Figure 4-37. Mean concentrations (f standard deviation) ofBa, Cd, CUj Pb, V and Zn in

amphipods (Anonyx) collected from sites in the BSMP during 1'986, 1989 and for

ANIMIDA during 1999, 2000 and 20,02. ' In some cases the standard deviation is smaller than the marker.
:':",

,

',;

,.

,!

.<

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! •

. 1, •..•.

00- mmmmmmmmmmI mmmmmmwm
,f· i'

Figure 4-38. Mean concentrations (:I: standard deviation) of Ag, AI, A,S, Be, Co and Fe in

amphipods (Anonyx) collected for ANIMIDA during 1999,2000 and 20~2,

!

In some cases the standard deviation is smaller than the marker

1000 1

T'

T -.- ... ... .l. -:c 800 -L .Q> T • Q)

600 • T

'0

~400 en

1 .'l 1

:::l.

- 200

2002

Anonyx(amphipods) I ,

, -

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--L

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o L----'-----'---"i-~---L-----'

1999 200d

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'~600

•

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:::l.

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0 , 1999 2000 2002

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en

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--

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en

- 4 en

::1.

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or.

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0.00 0 I

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;: • 3: ,

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Anonyx(amphipods) Anonyx(amphippds)

0.00 0.000

1999 2000 2002 1999 2doO 2002

\

Figure 4-39. Mean concentrations, (± standard 'deviation) of Hg, IMn, Sb and TI in

amphipods (Anonyx) collected for ANIMIDA during 1999. 2000 and 200'2.

I

,

In some cases the standard deviation is smaller than the marker
,.

.

/ ..I .' .•

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In some cases the standard deviation is smaller than the marker

Figure 4-40. Mean concentrations (± standard deviation) of Ba, Cd, €u, Pb, V and Zn in

clams (Astarte) collected from sites in the BSMP during 1986, 1989 and for ANIMIDA

during 1999, 2000 and 2002.' i

40 30

--. Astarte (clams) --. Astarte (clams)

- -. I

.r::.

T

..r::.

.£2> 30 .£2> I Q) Q)

T 3: T 3: 20

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1986 1989 199~ 2000 2002

:

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8 120 : .

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0 1986 1989 2000 2002 1986 1989 1999 2000 2002

f'

30 1.0

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• 0.6

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5 2500 I

.

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0 0 , 1999 2000 2002 1999 2000 2002

Figure 4-41. Mean concentrations (±' standard deviation) of Ag, AI, As, Be, Co and Fe in

clams (Astarlel collected for ANIMIDA during 1999, 2000 and 2002.

In some cases the standard deviation is smaller than the marker
,- .' <. ;, '.1,· 'I

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C)

C)

,. C) 200 .: ... ::J. 1 ::J.

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:::r: :2

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Q)

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'0 T iT ,.

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0.00 0.00 2002 I

1999 2000 1999 2000 2002

Figure 4-42. Mean concentrations (:t standard deviation) of Hg, Mn, Sb and TI in clams

(Astarte) collected for ANIMIDA during 1999 and 2000.

In some cases the standard deviation is smaller than the marker

..
- :~

mmmm

m, mmm

illmo.

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Referenoe SPMD Samples

,

-

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-

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'40.00

45.00

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02-NM3..o2-PHC-FS-8P

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5.00

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Northstar 8PMD Samples

70.00 1--------------------~---___,

1

35.00

30.00

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15.00

150.

00

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I 20.00

150.

00

I

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30.00

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Figure 4-43. SPMD PAH Distribution Histograms, Northstar SPMDs (tOpll Reference

SPMDs (middle), Field Blank SPMDs (bottom)
. , •. F ,.f,· ,

•... r

.:~

.. "t'

,.F'

"

:1'
Reference Mussel Samples

,~ t . ~.'

:

,

,

•

, ,

: I I -, ,

~. 1110 . ...... n mel r-1fillll brll

0.40

1.40

1.60

1.80

Pro-doployment Mussol sample

02-PM1-o1-PHC"T-MU

0.50

2.00~---------------------"-----___j

2.00

Northstar Mussel Samples

; 2.50 -,----- ..,..- --,

2.50 .,------------'-------------'---- ---'--,

0.50

.0.20

. 0.00 § 5 & § 8 B 8 I § 8 Ma 8 .~ ~. s I

I :.: I0.80

0.80

1,.50 I'00

I

I

Figure 4-44. Mussel PAH Distribution''Histograms, Northstar Mussels (to;p), 'Reference

Mussels (middle), Pre-Deployment Blank Mussels (bottom) ,

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5.0 Recommendations

I

Based on the results and interpretations ofthe sediment and biota samples collected under the

ANIMIDA Phase I program and Task 2 ofthe ANIMIDA Phase II program, and with the

potential development ofthe Liberty Prospect and new Beaufort Sea lease ~a]es, there are a

number ofrecommendations for future work in the ANIMIDA study area.

• Perform continued surface sediment and biota monitoring for hydrocarbons ~nd metals in

the Northstar Island area to assess potential impacts from Northstar productions activities.

• Collect and analyze sediments and biota for hydrocarbons and metals [(om new Liberty

sediment stations to augment existing baseline information for Liberty and to assess

potential impacts from Liberty development and production activities. ;This

recommendation is based the assumption that Liberty Prospect will be develQped from an I

alternative location. I

• Perform continued surface sediment monitoring for hydrocarbons and metals at the wider

regional BSMP study area stations (i.e., Cape Halkett to Griffin Point) ~o develop a

comprehensive baseline ofthe area prior to exploration and development activities

associated with new Beaufort Sea lease sales. ;

• Perform additional water column monitoring around Northstar and at r~ference areas with

sensitive indicator organisms (i.e., transplanted caged mussels) and SPMDs.

• Collect and analyze additional offshore sediment cores for hydrocarbons and metals to

further characterize the historical sediment record in the study area.

• Collect and analyze additional riversediment samples (e.g., McKenzie River, Colville

Watershed) for metals and hydrocarbons to evaluate other regional sediment,sources.

• Analyze additional North Slope field oils and seep oils/source rock/coal samples to enhance

the differentiation of hydrocarbon sources.

• Continue use ofthe Double Ratio Plot of S2S/S28 versus T21 /T22 as a hydrocarbon source

discrimination tool for the ANIMIDA study area.

\mms animida\task 2 final report\finalrep6rt files\final section 5.doc 5-1
I

Ii

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;,"1
6.0 References

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Boehm, P.D. 1984. Aspects ofthe saturated hydrocarbon geochemistry ofrec~nt sediments in the

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,Boehm, P.D., L. Le Blanc, J. Trefry, P. Marajh-Whittemore, J. Brown, A Schutzberg, and A

Kick. 1990. Monitoring hydrocarbons a:nd trace metals in Beaufort Sea sediments and

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Kick. 1991. Beaufort Sea Monitoring }>rogram: Analysis ofTrace Metals and Hydrocarbons

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Boehm, P.D., et al. 2001a. Sediment Quality in Depositional Areas of ShelikOf Strait and

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Service, Anchorage, Alaska.: . . ,

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Area - Final Report. OCS Study MMS2001-104, Anchorage, AK: Minerals Management • I

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m

m

m

m

m

m

m
lil~"~

II

III.

~I

:

:I-~~'

~I

-

-

: .'

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11

The Department of the Interior Mission

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As the Nation's principal conservation agency, the Department ofthe Interior has tesponsibility for most of our

nationally owned public lands and niltural resources. This includes fostering sound use of our land and water

resources; protecting our fish, wildlife, and biological diversity; preserving the enVironmental and cultural values of

our national parks and historical places; and providing for the enjoyment of life through outdoor recreation. The

Department assesses our energy and mineral resources and works to ensure that tHeir development is in the best

interests of all Olirpeople by encouraging stewardship and citizen participation in their c;:tre. 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 ofthe Department ofthe Interior, the Minerals Management Service's (MMS) primary responsibilities

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 reven~es.

Moreover, in working to meet its responsibilities, the Offshore Minerals Manag~ment Program administers the

OCS competitive leasing program arid oversees the safe and environmentally sound exploration and production of

our Nation's offshore natural gas, oil and other mineral resources. The MMS Royalty Management Program

meets its responsibilities by ensuring the efficient, timely and accurate collection and disbursement ofrevenue 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: (l) being responsive to the

public's concerns and interests by maintaining a dialogue with all potentially affedted parties and (2) carrying out its

programs with an emphasis on working to enhance the quality of life for all Americans by lending MMS assistance

and expertise to economic development and environmental protection. j

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