Dredged Material Management Program Sediment ...

Final

Dredged Material Management Program

Sediment Characterization Report

Makah Tribe Emergency Spill Dock Extension

Dredged Material Characterization Prepared for

Makah Indian Tribe

Neah Bay, Washington

Prepared by

BergerABAM

A16.0096.00 February 2017

cc w/attach: Norman Down, Makah Indian Tribe

Bob Buckingham, Port of Neah Bay

3 February 2017

Ms. Lauran Cole‐Warner

Dredged Material Management Office

U.S. Army Corps of Engineers, Seattle District

P.O. Box 3755

Seattle, WA 98124

Subject: Dredged Material Characterization

Makah Indian Tribe – Emergency Spill Dock Extension


Dear Ms. Cole‐Warner:

On behalf of the Makah Indian Tribe, BergerABAM is pleased to submit our report “Dredged

Material Characterization, Makah Indian Tribe ‐ Emergency Spill Dock Extension, Neah Bay,

Washington.” The Makah Indian Tribe requests that the attached data be evaluated relative to

Dredged Material Management Program and Washington State Sediment Management

Standards criteria for in‐water placement and beneficial use of dredged materials. This

characterization was conducted to evaluate the potential suitability of dredged material for in‐

water beneficial re‐use and/or open‐water disposal.

We appreciate the guidance and assistance that the Dredged Material Management Office

provided throughout this project. Please contact us if you have questions regarding this report.

Sincerely,

Victoria England, LG Sally Fisher Senior Environmental Scientist Senior Project Manager

Attachment

FINAL

Dredged Material Characterization Report

Makah Indian Tribe - Emergency Spill Dock Extension Neah Bay, Washington

Prepared for

U.S. Army Corps of Engineers, Seattle District Dredged Material Management Office Seattle, Washington

Attention: Lauran Cole-Warner

3 February 2017

Prepared by

BergerABAM 210 East 13th Street, Suite 300

Vancouver, Washington 98660

Victoria R. England, LG Sally L. Fisher Senior Environmental Scientist Senior Project Manager

Job No. A16.0096.00

Makah Indian Tribe – Emergency Spill Dock Extension Dredged Material Characterization


BergerABAM, A16.0096.00 3 February 2017

Page 1 of 3

FINAL DREDGED MATERIAL CHARACTERIZATION REPORT

MAKAH INDIAN TRIBE – EMERGENCY SPILL DOCK EXTENSION


Dredged Material Management Office

Seattle, Washington

TABLE OF CONTENTS

SECTION PAGE

1 . 0 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1 . 1 Project Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 . 0 SAMPLING AND ANALYSIS PROGRAM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 . 1 SAMPLING ACTIVITIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2 . 2 SAP Deviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

3 . 0 PHYSICAL AND CHEMICAL ANALYTICAL PROGRAM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3 . 1 DMMU Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3 . 2 DMMU-7 Subsamples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3 . 3 Quality Assurance and Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

4 . 0 ANALYTICAL RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

4 . 1 Grain Size Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

4 . 2 Chemical Data relative to DMMP and SMS Criteria - DMMUs . . . . . . . . . . . . . . . . . . 4

4 . 3 Chemical Data relative to DMMP and SMS Criteria - DMMU-7 Subsamples . . 5

5.0 SUMMARY.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

6.0 LIMITATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

7.0 BIBLIOGRAPHY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

LIST OF FIGURES Sheet 1 Vicinity Map

Sheet 2 Site Plan Existing Conditions

Sheet 3 Site Plan - DMMUs Sheet 4 Dredging Sections

Sheet 5 Potential Beneficial Use Area

LIST OF TABLES Table 1 Summary of Sample Coordinates, Corrected Mudline Elevations, and

Compositing Scheme

Table 2 Summary of Grain Size Data Table 3 Summary of DMMU Volumes

Table 4 Summary of Chemical Data Compared to DMMP Guidelines Table 5 Summary of Chemical Data Compared to SMS Criteria




Page 2 of 3

LIST OF APPENDICES

Appendix A Sampling and Analysis Plan and DMMO Approval E-mail Appendix B Sample Logs and Photographs

Appendix C Chemical Analytical Data Report

Appendix D Data QA/QC Review Summary




Page 3 of 3

LIST OF ACRONYMS AND ABBREVIATIONS

ARI Analytical Resources Inc.

COCs chemicals of concern

cy cubic yard

DMMO Dredged Material Management Office

DMMP Dredged Material Management Program

DMMU Dredged Material Management Unit

Ecology Department of Ecology

EPA Environmental Protection Agency

GPS global positioning system

MLLW mean lower low water

PAH polycyclic aromatic hydrocarbons

PCB polychlorinated biphenyls

PSEP Puget Sound Estuary Program

QA/QC quality assurance/quality control

SAP Sampling and Analysis Plan

SL screening level

SMS Sediment Management Standards

SVOC semivolatile organic compounds

TBT tributyltin

Tribe Makah Indian Tribe




Page 1 of 6

DREDGE MATERIAL CHARACTERIZATION

MAKAH INDIAN TRIBE – EMERGENCY SPILL DOCK EXTENSION NEAH BAY, WASHINGTON

1 .0 INTRODUCTION

This report presents the results of sediment sampling activities for the characterization

of proposed dredged material at the proposed emergency spill dock extension for the

Makah Indian Tribe (Tribe). The Tribe proposes to construct an extension of the existing

commercial fishing dock to accommodate emergency spill response vessels near the

south shore of Neah Bay in Clallam County, Washington (Sheet 1).

The purpose of this characterization is to evaluate the suitability of dredged material for

in‐water disposal and beneficial use. The characterization activities were completed in

accordance with the Dredged Material Management Program (DMMP) User’s Manual

dated August 2016 and our Revised Sampling and Analysis Plan (SAP) (BergerABAM,

7 November 2016). The SAP was approved by the Dredged Material Management Office

(DMMO) in an e‐mail dated 15 November 2016. The SAP and the DMMO approval

e‐mail are included as Appendix A.

1 .1 Project Description

The Port proposes to dredge approximately 208,000 cubic yards (cy) of sediment to

provide sufficient draft for emergency spill response vessels, to provide access from the

navigation channel, and to accommodate the new dock extension. The proposed

dredging activities will be conducted in the fall/winter of 2018/2019.

The proposed project will require dredging to increase the depths within the new

berthing area to elevations ranging from ‐15 to ‐25 feet mean lower low water (MLLW)

plus a 1‐foot allowable overdredge (‐16 to ‐26 feet MLLW). The berthing area will be

dredged to elevations of ‐25 feet MLLW (plus 1 foot of allowable overdredge) to

accommodate the drafts of the spill response vessels and provide access to the Neah Bay

basin (see Sheets 1 through 4). The portion of the dredge prism to the south and east of

the existing commercial fishing dock (Sheet 3) will be dredged to an elevation of ‐15 feet

MLLW (plus 1 foot of allowable overdredge) to provide access for small boats.

2 .0 SAMPLING AND ANALYSIS PROGRAM

The objectives of this sediment characterization report are to evaluate the following.

• Suitability of the proposed dredge material for disposal at a DMMP unconfined

(dispersive) open‐water disposal site

• Suitability of the proposed dredge material for in‐water beneficial use or upland fill

• Upland disposal options for dredged material that is not suitable for DMMP open‐

water disposal or beneficial use




Page 2 of 6

2 .1 SAMPLING ACTIVITIES

Sampling of the proposed dredged material was completed on 21 November 2016.

Sampling activities were conducted in accordance with the DMMO‐approved SAP with

deviations as described in Section 2.2.

Dredged volume, dredge prism configuration, and sampling frequency are based on an

approved ranking of low‐moderate, typical cross sections and conditions within the

proposed dredging areas as described in the approved SAP (Appendix A).

A total of 28 grab sediment samples were collected within the proposed dredge prism at

the locations shown on Sheet 3. The grab samples were collected using “power grab”

sampling equipment owned and operated by Research Support Services of Bainbridge

Island, Washington. Positioning at each sample location was performed using a global

positioning system (GPS).

A BergerABAM representative monitored sampling activities and processed the

samples. Sediment samples were examined, screened for indications of petroleum‐

related contamination1, and logged immediately after collection. The sample materials

were composited onboard the sampling vessel. The sample logs and photographs of

each sample are presented in Appendix B.

A stainless steel trowel was used to remove sediment sample material from the grab

sampler. Samples were homogenized in a stainless steel bowl prior to placing into

laboratory‐supplied sample containers. Samples were placed into a cooler with ice and

submitted under chain‐of‐custody procedures to Analytical Resources Inc. (Tukwila,

Washington) for chemical analytical testing. Archive samples were collected from each

sampling location for potential follow‐up analysis and/or bioassays.

Sediment was composited from the grab samples to create seven Dredged Material

Management Unit (DMMU) samples. Table 1 includes a summary of the sample

compositing scheme, sample coordinates, real‐time tidal conditions, tidal‐corrected

mudline elevations, and the sample recovery depth. Grain‐size data and approximate

volumes for each DMMU are in Tables 2 and 3, respectively.

2 .2 SAP Deviations

Field activities and the analytical program were conducted in accordance with the

DMMO‐approved SAP, with the exception of the deviations summarized in this section.

• Some sample station locations were moved as described below and as shown on

Sheet 2. The revised sample locations were coordinated with Lauran Cole‐Warner of

the DMMP during field activities prior to sample collection.

1 Field screening included sheen testing and odor observations. The field screening results are included in

the sample logs.




Page 3 of 6

− Sample location S‐3 was moved approximately 320 feet to the south because the

original proposed location’s measured mudline elevation was below the des ign

dredge depth.

− Sample location S‐24 was moved approximately 20 feet to the east because the

planned GPS coordinates described in the SAP did not match the proposed

location as shown in the SAP figures.

• The subsamples (S‐25 through S‐28) were submitted for analysis of total organic

carbon, total solids, mercury, and polycyclic aromatic hydrocarbons (PAHs)/semi‐

volatile organic compounds (SVOCs) based on the chemical analytical results from

the DMMU‐7 composite sample. The analytical results are summarized in

Section 4.0.

− The mercury analysis on the subsamples was completed outside of the holding

time due to the time it took to receive the DMMU results from the analytical

laboratory.

3 .0 PHYSICAL AND CHEMICAL ANALYTICAL PROGRAM

3 .1 DMMU Samples

Seven composite samples (DMMU‐1 through DMMU‐7) were submitted to Analytical

Resources Inc. (ARI) in Tukwila, Washington, for physical and chemical analyses.

The results of the grain size analyses are summarized in Table 2. The chemical analytical

program consists of the DMMP and SMS COCs shown in Tables 4 and 5. The chemical

analytical results are shown relative to DMMP criteria in Table 4 and SMS criteria in

Table 5.

Analyses were performed in accordance with applicable Environmental Protection

Agency (EPA) methodology along with DMMP and Puget Sound Estuary Program

(PSEP) protocols as appropriate, including the following.

• Total organic carbon by SM5310B/EPA Method 9060 (modified for sediments)

• Total solids by PSEP/SM2540G

• Ammonia by Plumb (1981)

• Sulfides by PSEP and Plumb (1981)

• Grain size by PSEP/ASTM D‐422 (modified)

• Total metals and mercury using EPA Methods 6010/6020/7440/7471

• Semivolatile organic compounds (SVOCs) using EPA Method 8270D

• Polycyclic aromatic hydrocarbons (PAHs) using EPA Method 8270D

• Chlorinated hydrocarbons using EPA Method 8260B/8270D/8081

• Phthalates, phenols, and miscellaneous extractables using EPA Method 8270D/8081

• Pesticides using EPA Method 8081

• Polychlorinated biphenyls (PCBs) using EPA Method 8082

• Bulk tributyltin (TBT) using PSEP, Krone (1989), and Unger (1986)




Page 4 of 6

3 .2 DMMU-7 Subsamples

Four subsamples (S‐25 through S‐28) from DMMU‐7 were submitted for follow‐up

analysis based on the chemical analytical results from sample DMMU‐7 exceeding

DMMP and SMS criteria. The follow‐up analyses included mercury, SVOCs/PAHs, total

solids, and total organic carbon.

3 .3 Quality Assurance and Quality Control

The laboratory reports are included as Appendix C. Review of the data quality of the

chemical analytical results indicates that laboratory goals were achieved based on the

results of quality assurance/quality control (QA/QC) parameters, including surrogates,

spikes, replicates, and method blanks The QA/QC review summary is included as

Appendix D.

4 .0 ANALYTICAL RESULTS

4 .1 Grain Size Characteristics

The grain size results from the dredge prism samples are summarized in Table 2. The

proposed dredged material primarily consists of very fine and fine sand with silt and

clay.

4 .2 Chemical Data relative to DMMP and SMS Criteria - DMMUs

The chemical analytical results from the sediment characterization are summarized

relative to DMMP criteria and SMS criteria in Tables 4 and 5, respectively. The chemical

analytical results are as follows.

• Contaminants of concern were either not detected or were detected at concentrations

less than the applicable DMMP and SMS criteria in the DMMU composite sediment

samples collected from DMMU‐1 through DMMU‐6.

• Mercury was detected in sediment sample DMMU‐7 at a concentration (0.46 mg/Kg)

exceeding the DMMP screening level (SL) and SMS Sediment Quality Standard

(SQS) for mercury (0.41 mg/Kg).

• The total organic carbon (TOC) normalized concentrations of several high molecular

weight PAHs (fluoranthene, chrysene, indeno(1,2,3‐c,d)pyrene,

dibenz(a,h)anthracene, and benzo(g,h,i)perylene) were detected in DMMU‐7 at

concentrations exceeding their respective SMS SQS.

• The TOC normalized concentration of di‐n‐octyl phthalate (245.2 mg/kg OC)

detected in DMMU‐7 exceeded the applicable SMS SQS (58 mg/kg OC).

• The TOC normalized concentration of bis(2‐ethylhexyl) phthalate (180.6 mg/kg OC)

exceeded the SMS Cleanup Screening Level (CSL) for that analyte (47 mg/kg OC).




Page 5 of 6

The TOC for DMMU‐7 is very low (0.62 percent) and was considered a potentially

complicating factor for the TOC normalized SMS exceedances until the subsample

analytical results were received, showing the presence of elevated dry weight

concentrations of certain PAHs in some of the subsamples as summarized in Section 4.3.

4 .3 Chemical Data relative to DMMP and SMS Criteria - DMMU-7 Subsamples

The chemical analytical results for the follow‐up PAH/SVOC and mercury analyses of

DMMU‐7 subsamples S‐25 through S‐28 are summarized relative to DMMP and SMS

criteria in Tables 4 and 5, respectively. The results are as follows.

• Contaminants of concern were either not detected or were detected at

concentrations less than the applicable DMMP and SMS criteria in subsample S‐26.

Sample S‐26 has a TOC of 0.41 percent.

• The concentration of dimethyl phthalate (187 μg/kg) in subsample S‐28 is greater

than the applicable DMMP SL of 71 μg/kg. There were no SMS criteria exceedances

in S‐28. Sample S‐28 has a TOC of 0.57 percent.

• Flouranthene was detected in S‐25 at a dry weight concentration (2,090 μg/kg)

exceeding the DMMP SL of 1,700 μg/kg and a TOC normalized concentration (199

mg/kg OC) greater than the SMS SQS of 160 mg/kg OC. Sample S‐25 has a TOC of

1.05 percent.

• The dry weight concentrations of one low molecular weight PAH (phenanthrene)

and several high molecular weight PAHs (fluoranthene, pyrene, chrysene, and total

HPAH) in subsample S‐27 exceeded their respective DMMP SLs. The TOC

normalized concentrations of phenanthrene and all of the HPAHs except pyrene

exceeded their respective SMS SQS levels. The TOC normalized concentration of

benzofluoranthenes (b, j, k) exceeded the SMS CSL in S‐27. Sample S‐27 has a TOC

of 0.55 percent.

There were no mercury screening level exceedances in the subsamples. However, the

subsamples were analyzed for mercury outside the recommended holding time for

mercury analysis. The mercury analysis of the subsamples occurred outside of the

holding time because of the time it took to receive the analytical results for the

DMMUs. The results for these subsamples are, therefore, inconclusive relative to

mercury.

5.0 SUMMARY

Twenty‐eight sediment samples were collected from the proposed dredge prism and

submitted as seven composite DMMU samples (DMMU‐1 through DMMU‐7) for

chemical analysis. The sediment was sampled and analyzed in general accordance with

the DMMP‐approved project SAP except for the minor deviations noted in Section 2.2.




Page 6 of 6

COCs either were not detected or were detected at concentrations less than the DMMP

and SMS screening levels (SLs) in the samples analyzed from DMMU‐1 through

DMMU‐6. The data indicates that dredged material from DMMU‐1 through DMMU‐6

(Sheet 3) is suitable for in‐water placement, upland placement, and/or beneficial use

based on the chemical analytical results summarized in Tables 4 and 5.

DMMP and SMS screening level exceedances for concentrations of mercury, PAHs, and

phthalates in sample DMMU‐7 triggered follow‐up analyses for those constituents in the

archived subsamples (S‐25 through S‐28) that comprise DMMU‐7. There were no DMMP

or SMS screening level exceedances in the results for the follow‐up sample analysis of

subsample S‐26. However, the results of the subsample follow‐up analyses were

inconclusive for mercury because of hold time exceedances. All of DMMU‐7 is assumed

to be unsuitable for in‐water placement/beneficial use at this time, pending additional

analysis. The material from DMMU‐7 will be placed at a suitable upland location

identified by the Tribe, barring additional analytical results showing in‐water placement

suitability.

6.0 LIMITATIONS

This report has been prepared for the Tribe and the U.S. Army Corps of Engineers

DMMO for their use in evaluating and documenting the suitability of the proposed

dredge material for in‐water and upland disposal.

This study is based on sampling and analyses conducted in accordance with the

guidelines of the DMMP at specific sampling locations. It is possible that sediment

quality may vary over time and/or between sampling locations.

Within the limitations of scope, schedule, and budget, our services have been executed

in accordance with the generally accepted environmental science practices for dredged

material characterization in this area at the time this report was prepared. No warranty

or other conditions, express or implied, should be understood.

7.0 BIBLIOGRAPHY

BergerABAM. November 2016. Revised Sampling and Analysis Plan, Makah Indian

Tribe – Emergency Spill Dock Extension.

Dredged Material Management Office, U.S. Army Corps of Engineers, Seattle District.

August 2016. Dredged Material Evaluation and Disposal Procedures (User’s

Manual).

Dredged Material Characterization Report Makah Indian Tribe – Emergency Spill Dock Extension


Tab les

Table 1. Page 1 of 2

TABLE 1. SUMMARY OF SAMPLE COORDINATES, ADJUSTED MUDLINE ELEVATIONS AND SAMPLE DEPTHS

EMERGENCY SPILL DOCK EXTENSION DREDGED MATERIAL SEDIMENT CHARACTERIZATION REPORT

NEAH BAY, WASHINGTON

DMMU ID

Dredge Depth

Elevation + 1 -ft

OD (ft MLLW)

1 Sample ID

Date Sampled

2 Northing

2 Easting

Water Depth

3 (feet)

Real-Time

4 Tidal Stage

Adjusted

Mudline

Elevation 5

(ft MLLW)

Sample Depth

Recovered

(inches)

1

-26

S-1

11/21/2016

522599.41 721118.52 30.6 6.39 24.21 10.5

S-2 522338.53 721278.71 29.5 6.3 23.20 12

S-3 522211.50 721526.42 30.3 5.98 24.32 8.5

S-4 522076.18 721731.22 31 6.07 24.93 12

2

-26

S-5 521868.41 721772.38 30.4 5.89 24.51 8

S-6 521956.54 721571.43 28.6 5.67 22.93 9

S-7 522093.51 721400.31 27.5 5.53 21.97 10.5

S-8 522190.44 721155.75 27.3 5.49 21.81 8.5

3

-26

S-9 522051.21 721116.85 25.4 5.35 20.05 11

S-10 521949.58 721304.46 25.9 5.21 20.69 10.5

S-11 521848.89 721127.36 24.4 5.12 19.28 11

S-12 521753.59 721305.15 24.4 5.03 19.37 10

4

-26

S-13 521783.08 721490.90 25.6 4.9 20.70 10

S-14 521617.10 721476.04 24 4.76 19.24 10

S-15 521651.74 721627.71 25 4.67 20.33 10.5

S-16 521625.40 721772.95 25.8 4.58 21.22 10

5

-26

S-17 521712.24 721107.34 22.9 4.08 18.82 11

S-18 521627.72 721287.53 22.8 3.99 18.81 10.5

S-19 521552.34 721119.78 21.5 3.95 17.55 8.5

S-20 521491.09 721304.29 21.3 3.94 17.36 10

6

-26

S-21 521539.89 721425.13 22.7 4.02 18.68 9

S-22 521476.01 721541.82 22.7 4.13 18.57 8

S-23 521406.57 721450.00 19.8 4.21 15.59 10

S-24 521320.59 721632.41 18.7 4.33 14.37 9.5

7

-26 S-25 521393.89 721712.53 21.5 4.63 16.87 6

S-26 521482.26 721767.89 24.8 4.75 20.05 6

-16 S-27 521237.51 721794.09 15.8 4.86 10.94 6.5

S-28 521273.17 721914.74 17.6 4.94 12.66 8


TABLE 1. SUMMARY OF SAMPLE COORDINATES, ADJUSTED MUDLINE ELEVATIONS AND SAMPLE DEPTHS



Notes:

1 See Sheet 2 for sample locations

2 Northing and easting are based on the North American Datum of 1983 (NAD83) State Plane Coordinate System, Washington North, Survey Feet.

3 Depth finder on vessel was used to measure water depth.

4 Tidal stage was obtained from the TideTrac mobile application which collects data from the tidal station at Neah Bay (Station ID 9443090).

5 Adjusted Mudline Elevation = Water Depth + Tidal Stage


TABLE 2. SUMMARY OF GRAIN SIZE DATA EMERGENCY SPILL DOCK EXTENSION DREDGED MATERIAL

SEDIMENT CHARACTERIZATION REPORT


DMMU-1 DMMU-2 DMMU-3 DMMU-4 DMMU-5 DMMU-6 DMMU-7

Gravel 0.1% 8.3% 0.1% 0.0% 0.0% 0.0% 3.6%

Coarse Sand 0.0% 0.5% 0.1% 0.1% 0.0% 0.1% 3.4%

Medium Sand 0.4% 1.0% 1.1% 0.6% 0.5% 0.6% 4.8%

Fine Sand 18.9% 22.1% 8.3% 21.3% 13.1% 21.0% 42.2%

Very Fine Sand 56.9% 43.4% 39.1% 50.3% 53.2% 58.0% 29.3%

Coarse Silt 5.5% 5.6% 5.8% 1.7% 6.5% 3.9% 2.4%

Medium Silt 1.3% 1.4% 5.4% 1.7% 1.6% 0.8% 1.2%

Fine Silt 6.4% 7.0% 13.4% 9.2% 10.5% 6.5% 4.9%

Very Fine Silt 2.5% 2.8% 7.2% 3.4% 3.2% 2.5% 2.5%

Clay 8.2% 7.7% 19.6% 11.7% 11.3% 6.5% 5.5%

Total Fines 23.9% 24.5% 51.4% 27.7% 33.1% 20.2% 16.5%


TABLE 3. SUMMARY OF DMMU VOLUMES EMERGENCY SPILL DOCK EXTENSION DREDGED MATERIAL

SEDIMENT CHARACTERIZATION REPORT


DMMU ID

sub units

Dredge Depth Elevation + 1' OD (ft

MLLW)

Assumed Elevation

(f t MLLW)

Approximate Total DMMU

Volume (cy)

DMMU 1

S-1

-26

-23

31,787

S-2 -22

S-3 -24

S-4 -23.5

DMMU 2

S-5 -23

31,983

S-6 -21

S-7 -20

S-8 -20.5

DMMU 3

S-9 -19

31,991

S-10 -19

S-11 -18

S-12 -18

DMMU 4

S-13 -19

31,912

S-14 -18

S-15 -19

S-16 -20

DMMU 5

S-17 -17

31,997

S-18 -17.5

S-19 -16

S-20 -16

DMMU 6

S-21 -17

31,791

S-22 -17

S-23 -14

S-24 -13

DMMU 7

S-25

-26 -16 3,288

S-26 -19 4,359

S-27

-16 -7 4,262

S-28 -12 4,661

Total 208,031


TABLE 4. SUMMARY OF CHEMICAL ANALYTICAL RESULTS COMPARED TO DMMP CRITERIA



CHEMICAL

Sample ID

DMMU-1

DMMU-2

DMMU-3

DMMU-4

DMMU-5

DMMU-6

DMMU-7

S-25

S-26

S-27

S-28

DMMP Criteria

(dry weight)

Sample date 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 SL BT ML

CONVENTIONALS (mg/kg dry weight)

Ammonia 24.9 8.86 17.7 4.35 11.8 4.15 4.83 --- --- --- --- --- --- ---

Total sulfides 5.93 133 845 227 564 88.7 638 --- --- --- --- --- --- ---

GENERAL CHEMISTRY (percent)

Total solids 67.33 64.23 47.02 62.52 51.21 71.79 71.13 66.10 77.03 71.37 72.50 --- --- ---

Total volatile solids 2.98 3.56 6.81 3.84 6.31 2.36 2.54 --- --- --- --- --- --- ---

Total organic carbon 0.62 0.88 1.59 0.92 1.74 0.41 0.62 1.05 0.41 0.55 0.57 --- --- ---

METALS (mg/kg dry weight)

Antimony <18.2 1.45 J 1.23 J 1.09 J 1.32 J 1.08 J 1.26 J --- --- --- --- 150 --- 200

Arsenic <18.2 <6.48 <8.83 <7.58 <8.72 <14.1 <6.15 --- --- --- --- 57 507.1 700

Cadmium 0.55 J, D 0.31 0.64 0.42 0.61 0.60 0.55 --- --- --- --- 5.1 --- 14

Chromium 30.1 23.7 41.6 26.8 37.6 24.1 19.1 --- --- --- --- 260 --- ---

Copper 16.6 12.5 32.5 17.0 22.4 16.5 23 --- --- --- --- 390 --- 1,300

Lead 7.36 6.97 15 7.97 12.2 7.93 7.68 --- --- --- --- 450 975 1,200

Mercury 0.064 0.018 J 0.05 0.04 0.09 0.03 0.46 0.07 H 0.05 H 0.01 H,J 0.17 H 0.41 1.5 2.3

Selenium 1.1 1.41 1.82 1.21 1.49 0.79 0.92 --- --- --- --- --- 3 ---

Silver <1.09 <0.39 <0.53 <0.46 <0.52 <0.85 <0.37 --- --- --- --- 6.1 --- 8.4

Zinc 60.8 D 52.2 94.4 62.7 78.1 54.0 63.3 --- --- --- --- 410 --- 3,800

PAHs (µg/kg dry weight)

Naphthalene 8.9 J 9.4 J 17.6 J 9.6 J 10.2 J <18.6 10.1 J 16.8 J 6 J 11.3 J 13.2 J 2,100 --- 2,400

Acenaphthylene <19.2 <19.5 11.2 J 7.2 J 7.9 J 17.1 J 38.6 54.2 4.7 J 227 32.3 560 --- 1,300

Acenaphthene <19.2 <19.5 11.1 J <19.7 <19.4 4.8 J <19.7 18.4 J <19.4 47.8 6.2 J 500 --- 2,000

Fluorene 5.6 J 6.3 J 16.4 J 8.3 J 6.5 J 12 J 31 29.7 <19.4 74.1 21.9 540 --- 3,600

Phenanthrene 32.3 38.5 117 65.1 51.3 108 347 492 31.2 1,550 118 1,500 --- 21,000

Anthracene 7.3 J 15.4 J 57.9 28 28.2 29.5 187 133 14.3 J 339 176 960 --- 13,000

2-Methylnaphthalene1 13 J 14.3 J 24 14.4 J 13 J 11.6 J 11.9 J <19.2 8 J 11.6 J 18 J 670 --- 1,900

Total LPAH 93 109 231 138 124 190 633 744 95 2,249 368 5,200 --- 29,000

Fluoranthene 32.2 56.7 233 124 170 194 1,340 2,090 E 80.1 3,840 E 388 1,700 4,600 30,000

Pyrene 33.4 53.2 202 112 144 193 1,050 1,730 89.7 3,680 E 395 2,600 11,980 16,000

Benzo(a)anthracene 15.8 J 25.8 90.1 47.5 48.4 62.5 442 346 29.6 835 233 1,300 --- 5,100

Chrysene 24.5 43 152 102 96.1 146 1,080 770 65.4 2,400 E 431 1,400 --- 21,000

Benzofluoranthenes (b, j ,k) 39.5 66.3 213 137 139 227 1,330 903 88.8 2,490 580 3,200 --- 9,900

Benzo(a)pyrene 12.9 J 24.6 84.9 54.6 49.8 81.4 507 229 31.8 840 232 1,600 --- 3,600

Indeno(1,2,3-c,d)pyrene 9.4 J 15.9 J 50.2 31.2 30.4 46.4 259 146 18.5 J 370 106 600 --- 4,400

Dibenz(a,h)anthracene 5.6 Q 8.5 Q 19.0 Q 11.5 Q 11.2 Q 16.6 Q 93.3 49.9 7.4 131 44.6 230 --- 1,900

Benzo(g,h,i)perylene 12.0 J 19.1 J 60.3 33.8 33.8 45.8 266 147 19.8 329 102 670 --- 3,200

Total HPAH 186 313 1,105 654 728 1,013 6,367 6,411 431 14,915 2,512 12,000 --- 69,000

CHLORINATED HYDROCARBONS (µg/kg dry weight)

1,4-Dichlorobenzene <4.8 <4.9 <4.9 <4.9 <4.8 <4.7 12.6 --- --- --- --- 110 --- 120

1,2-Dichlorobenzene <4.8 <4.9 <4.9 <4.9 <4.8 <4.7 <4.9 --- --- --- --- 35 --- 110

1,2,4-Trichlorobenzene <4.8 <4.9 <4.9 <4.9 <4.8 <4.7 <4.9 --- --- --- --- 31 --- 64

Hexachlorobenzene (HCB) <0.94 2.1 J 5.8 <0.84 <0.98 <0.97 <0.96 --- --- --- --- 22 168 230




NEAH BAY, WASHINGTON PHTHALATES (µg/kg dry weight)

Dimethyl phthalate <19.2 <19.5 <19.7 <19.7 <19.4 <18.6 <19.7 34.8 <19.4 <19.1 187 71 --- 1,400

Diethyl phthalate <19.2 <19.5 <19.7 <19.7 <19.4 <18.6 <19.7 <19.2 <19.4 <19.1 <19.3 200 --- 1,200

Di-n-butyl phthalate <19.2 <19.5 <19.7 <19.7 <19.4 <18.6 12.3 J 15.4 J <19.4 <19.1 <19.3 1,400 --- 5,100

Butyl benzyl phthalate <4.8 <4.9 <4.9 <4.9 <4.8 <4.7 <4.9 <4.8 <4.8 <4.8 <4.8 63 --- 970

Bis(2-ethylhexyl) phthalate <47.9 <48.7 74.4 <49.1 <48.5 <46.5 1,120 159 <48.5 42.9 J 40 J 1,300 --- 8,300

Di-n-octyl phthalate <19.2 <19.5 <19.7 <19.7 <19.4 <18.6 1,520 <19.2 <19.4 <19.1 <19.3 6,200 --- 6,200

PHENOLS (µg/kg dry weight)

Phenol 240 24.3 27.8 <19.7 <19.4 11.4 J <19.7 --- --- --- --- 420 --- 1,200

2-Methylphenol <19.2 <19.5 <19.7 <19.7 <19.4 <18.6 <19.7 --- --- --- --- 63 --- 77

4-Methylphenol 23.8 <19.5 <19.7 <19.7 <19.4 <18.6 <19.7 --- --- --- --- 670 --- 3,600

2,4-Dimethylphenol <24 <24.3 <24.7 <24.6 <24.2 <23.3 <24.7 --- --- --- --- 29 --- 210

Pentachlorophenol <95.9 <97.4 <98.6 <98.3 <96.9 <93 <98.6 --- --- --- --- 400 504 690

MISCELLANEOUS EXTRACTABLES (µg/kg dry weight)

Benzyl alcohol <19.2 <19.5 <19.7 <19.7 <19.4 <18.6 <19.7 --- --- --- --- 57 --- 870

Benzoic acid <192 <195 <197 <197 <194 <186 <197 --- --- --- --- 650 --- 760

Dibenzofuran <19.2 <19.5 10 J <19.7 <19.4 7.7 J 8.3 J --- --- --- --- 540 --- 1,700

Hexachlorobutadiene <0.94 <0.97 <0.98 <0.84 <0.98 <0.97 <0.96 --- --- --- --- 11 --- 270

N-Nitrosodiphenylamine <19.2 <19.5 <19.7 <19.7 <19.4 <18.6 <19.7 --- --- --- --- 28 --- 130

PESTICIDES & PCBs (µg/kg dry weight)

4,4’-DDD <0.94 <0.97 <0.98 <0.84 <0.98 <0.97 <0.96 --- --- --- --- 16 --- ---

4,4’-DDE <0.94 <0.97 <0.98 <0.84 <0.98 <0.97 <0.96 --- --- --- --- 9 --- ---

4,4’-DDT <0.94 <0.97 <0.98 <0.84 <0.98 <0.97 <2.4 --- --- --- --- 12 --- ---

sum of 4,4’-DDD, 4,4’-DDE and 4,4’-DDT ND ND ND ND ND ND ND --- --- --- --- --- 50 69

Aldrin <0.47 <0.49 <0.49 <0.42 <0.49 <0.48 <0.48 --- --- --- --- 9.5 --- ---

Total Chlordane ND ND ND ND ND ND ND --- --- --- ---

2.8

37

---

cis-chlordane <0.47 <0.49 <0.49 <0.42 <0.49 <0.48 <0.48 --- --- --- ---

trans-chlordane <0.47 <0.49 <0.49 <0.42 <0.49 <0.48 <0.48 --- --- --- ---

cis-nonachlor <0.94 <0.97 <0.98 <0.84 <0.98 <0.97 <0.96 --- --- --- ---

trans-nonachlor <0.94 <0.97 <0.98 <0.84 <0.98 <0.97 <0.96 --- --- --- ---

oxychlordane <0.94 <0.97 <0.98 <0.84 <0.98 <0.97 <0.96 --- --- --- ---

Dieldrin <0.94 <0.97 <0.98 <0.84 <0.98 <0.97 <0.96 --- --- --- --- 1.9 --- 1,700

Heptachlor <0.47 <0.49 <0.49 <0.42 <0.49 <0.48 <0.48 --- --- --- --- 1.5 --- 270

Total PCBs Aroclors (Sum of: 1016, 1221, 1242,

1248, 1254, 1260, 1268)

6.3

10.5 P1

19.2

12.3

29.8

13.1

17.9

---

---

---

---

130

--

3,100

Total PCBs (mg/kg OC) 1 1.2 1.2 1.3 1.7 3.2 2.9 --- --- --- --- -- 382 --





CHEMICAL

Sample ID

DMMU-1

DMMU-2

DMMU-3

DMMU-4

DMMU-5

DMMU-6

DMMU-7

S-25

S-26

S-27

S-28

DMMP Criteria

Sample date 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 SL BT ML

ORGANOMETALLIC COMPOUNDS

Tributyltin ion (bulk, ug/kg) <3.42 <3.75 --- <3.56 --- --- <3.78 --- --- --- --- --- 73 ---

Petrolum Hydrocarbons (mg/kg dry weight)

Gasoline Range Organics (Tol-Nap) --- --- --- --- --- <9.48 <9.01 --- --- --- --- --- --- ---

Diesel Range Organics (C12-C24) --- --- --- --- --- 12.8 17.1 --- --- --- --- --- --- ---

Motor Oil Range Organics (C24-C38) --- --- --- --- --- 16.9 25.3 --- --- --- --- --- --- ---


TABLE 4. SUMMARY OF CHEMICAL ANALYTICAL RESULTS COMPARED TO DMMP CRITERIA EMERGENCY SPILL DOCK EXTENSION DREDGED MATERIAL SEDIMENT CHARACTERIZATION REPORT


Notes:

DMMP = Dredged Material Management Program (August 2016))

Total LPAH = The sum of acenaphthylene, acenaphthene, anthracene, fluorene, naphthalene and phenanthrene.

Total HPAH = The sum of benzo(a)anthracene, benzo(a)pyrene, total benzofluoranthenes, benzo(g,h,i)perylene, chrysene, dibenzo (a,h)anthracene, fluoranthene, indeno(1,2,3,-c,d)pyrene and pyrene.

Total benzofluoranthenes = the sum of the "b," "j" and "k" isomers. The "j" isomer co-elutes with the "k" isomer, thus the concentration of the "j" isomer is included in the "k" isomer concentration. 1 2-Methylnaphthalene is not included in the summation for total LPAH.

2 This value is normalized to total organic carbon, and is expressed in mg/kg organic carbon.

SL = Screening Level

BT = Bioaccumulation Trigger

ML = Maximum Level

LPAH = low molecular weight polynuclear aromatic hydrocarbon compounds

HPAH = high molecular weight polynuclear aromatic hydrocarbon compounds

H = Hold time violation - Hold time was exceeded.

D = The reported value is from a dilution

E = The analyte concentration exceeds the upper limit of the calibration range of the instrument established by the intial calibration (ICAL)

J = Estimated concentration when the value is less than ARI's established reporting limits

LY = A unique "LY" qualifier has been applied to this set of pesticide data. The elevated value associated with a "Y" flag due to positive chromatographic interference has been taken from the lower of the two column

concentrations. Re-evaluation of the raw data has made this possible with a careful examination of the lower column baseline and retention time. The "L" qualifier was manually added to select results to indicate the lower column

value was used for the final concentration.

P1 = The reported value is greater than 40% difference between the concentrations determined on two GC columns where applicab le.

Q = Indicates a detected analyte with an initial or continuing calibration that does not meet established acceptance criteria (<20% RSD, <20% drift or minimum RRF)

--- = not analyzed

Indicates an exceedance of DMMP SL Criteria

<0.94 = the target analyte was not detected at the reported concentration

0.46


TABLE 5. SUMMARY OF CHEMICAL ANALYTICAL RESULTS COMPARED TO SMS CRITERIA



CHEMICAL

Sample ID

DMMU-1

DMMU-2

DMMU-3

DMMU-4

DMMU-5

DMMU-6

DMMU-7

S-25

S-26

S-27

S-28

SMS Criteria

(normalized)

Sample date 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 SQS CSL

CONVENTIONALS (mg/kg dry weight)

Ammonia 24.9 8.86 17.7 4.35 11.8 4.15 4.83 --- --- --- --- --- ---

Total sulfides 5.93 133 845 227 564 88.7 638 --- --- --- --- --- ---

GENERAL CHEMISTRY (percent)

Total solids 67.33 64.23 47.02 62.52 51.21 71.79 71.13 66.10 77.03 71.37 72.50 --- ---

Total volatile solids 2.98 3.56 6.81 3.84 6.31 2.36 2.54 --- --- --- --- --- ---

Total organic carbon 0.62 0.88 1.59 0.92 1.74 0.41 0.62 1.05 0.41 0.55 0.57 --- ---

METALS (mg/kg dry weight)

Antimony <18.2 1.45 J 1.23 J 1.09 J 1.32 J 1.08 J 1.26 J --- --- --- --- --- ---

Arsenic <18.2 <6.48 <8.83 <7.58 <8.72 <14.1 <6.15 --- --- --- --- 57 93

Cadmium 0.55 J, D 0.31 0.64 0.42 0.61 0.6 0.55 --- --- --- --- 5.1 6.7

Chromium 30.1 23.7 41.6 26.8 37.6 24.1 19.1 --- --- --- --- 260 270

Copper 16.6 12.5 32.5 17 22.4 16.5 23 --- --- --- --- 390 390

Lead 7.36 6.97 15 7.97 12.2 7.93 7.68 --- --- --- --- 450 530

Mercury 0.06 0.018 J 0.05 0.04 0.09 0.03 0.46 0.07 H 0.05 H 0.01 H,J 0.17 H 0.41 0.59

Selenium 1.1 1.41 1.82 1.21 1.49 0.79 0.92 --- --- --- --- --- ---

Silver <1.09 <0.39 <0.53 <0.46 <0.52 <0.85 <0.37 --- --- --- --- 6.1 6.1

Zinc 60.8 D 52.2 94.4 62.7 78.1 54 63.3 --- --- --- --- 410 960

PAHs (mg/kg Organic Carbon)

Naphthalene 1.4 1.1 1.1 1 0.6 <4.5 1.6 1.6 1 2.1 2.3 99 170

Acenaphthylene <3.1 <2.2 0.7 0.8 0.5 4.2 6.2 5.2 1.1 41.3 5.7 66 66

Acenaphthene <3.1 <2.2 0.7 <2.1 <1.1 1.2 <3.2 2 <4.7 8.7 1 16 57

Fluorene 0.9 0.7 1 0.9 0.4 2.9 5 3 <4.7 13 4 23 79

Phenanthrene 5.2 4.4 7.4 7.1 2.9 26.3 56 47 8 282 21 100 480

Anthracene 1.2 1.8 3.6 3 1.6 7.2 30.2 12.7 3.5 61.6 30.9 220 1,200

2-Methylnaphthalene1 2.1 1.6 2 1.6 0.7 2.8 1.9 <1.8 2.0 2.1 3.2 38 64

Total LPAH 15 12 15 15 7 46 102 71 23 409 65 370 780

Fluoranthene 5.2 6.4 15 13 10 47 216 199 20 698 68 160 1,200

Pyrene 5.4 6 13 12 8 47 169 165 22 669 69 1,000 1,400

Benzo(a)anthracene 2.5 2.9 5.7 5.2 2.8 15.2 71 33 7 152 41 110 270

Chrysene 4 5 10 11 5.5 36 174 73 16 436 76 110 460

Benzofluoranthenes (b, j ,k) 6.4 7.5 13 15 8 55 215 86 22 453 102 230 450

Benzo(a)pyrene 2.1 2.8 5.3 5.9 2.9 19.9 82 22 8 153 41 99 210

Indeno(1,2,3-c,d)pyrene 1.5 1.8 3.2 3.4 1.7 11.3 42 14 5 67 19 34 88

Dibenz(a,h)anthracene 1 1 1 1.3 0.6 4 15 5 2 24 8 12 33

Benzo(g,h,i)perylene 1.9 2.2 3.8 3.7 1.9 11.2 43 14 5 60 18 31 78

Total HPAH 29.9 35.6 69.5 71 41.5 247.0 1,027 611 106 2,712 441 960 5,300

CHLORINATED HYDROCARBONS (mg/kg Organic Carbon)

1,4-Dichlorobenzene <0.8 <0.6 <0.3 <0.5 <0.3 <1.1 2 --- --- --- --- 3.1 9

1,2-Dichlorobenzene <0.8 <0.6 <0.3 <0.5 <0.3 <1.1 <0.8 --- --- --- --- 2.3 2.3

1,2,4-Trichlorobenzene <0.8 <0.6 <0.3 <0.5 <0.3 <1.1 <0.8 --- --- --- --- 0.81 1.8

Hexachlorobenzene (HCB) <0.2 0.2 0.4 <0.1 <0.1 <0.2 <0.2 --- --- --- --- 0.38 2.3


TABLE 5. SUMMARY OF CHEMICAL ANALYTICAL RESULTS COMPARED TO SMS CRITERIA



CHEMICAL

Sample ID

DMMU-1

DMMU-2

DMMU-3

DMMU-4

DMMU-5

DMMU-6

DMMU-7

S-25

S-26

S-27

S-28

SMS Criteria

Sample date 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 11/21/2016 SQS CSL

PHTHALATES (mg/kg Organic Carbon)

Dimethyl phthalate <3.1 <2.2 <1.2 <2.1 <1.1 <4.5 <3.2 3.3 <4.7 <3.5 32.8 53 53

Diethyl phthalate <3.1 <2.2 <1.2 <2.1 <1.1 <4.5 <3.2 <1.8 <4.7 <3.5 <3.4 61 110

Di-n-butyl phthalate <3.1 <2.2 <1.2 <2.1 <1.1 <4.5 2 1.5 <4.7 <3.5 <3.4 220 1,700

Butyl benzyl phthalate <0.8 <0.6 <0.3 <0.5 <0.3 <1.1 <0.8 <0.5 <1.2 <0.9 <0.8 4.9 64

Bis(2-ethylhexyl) phthalate <7.7 <5.5 4.7 <5.3 <2.8 <11.3 180.6 15.1 <11.8 7.8 7.0 47 78

Di-n-octyl phthalate <3.1 <2.2 <1.2 <2.1 <1.1 <4.5 245.2 <1.8 <4.7 <3.5 <3.4 58 4,500

PHENOLS (µg/kg dry weight)

Phenol 240 24.3 27.8 <8.1 <8 11.4 J <8.1 --- --- --- --- 420 1,200

2-Methylphenol <7.5 <7.6 <7.7 <7.7 <7.6 <7.3 <7.7 --- --- --- --- 63 63

4-Methylphenol 23.8 <14.3 <14.5 <14.4 <14.2 <13.7 <14.5 --- --- --- --- 670 670

2,4-Dimethylphenol <9.8 <9.9 <10.1 <10 <9.9 <9.5 <10.1 --- --- --- --- 29 29

Pentachlorophenol <30 <30.5 <30.9 <30..8 <30.3 <29.1 <30.9 --- --- --- --- 360 690

MISCELLANEOUS EXTRACTABLES (µg/kg dry weight)

Benzyl alcohol <14.3 <14.5 <14.7 <14.6 <14.4 <13.9 <14.7 --- --- --- --- 57 73

Benzoic acid <56.7 <57.6 <58.3 <58.1 <57.3 <55 <58.3 --- --- --- --- 650 650

Dibenzofuran (mg/kg Organic Carbon ) <3.1 <2.22 0.63 <2.14 <1.11 1.88 1.34 --- --- --- --- 152 582

Hexachlorobutadiene (mg/kg Organic Carbon ) <0.15 <0.11 <0.06 <0.09 <0.06 <0.24 <0.15 --- --- --- --- 3.92 6.22

N-Nitrosodiphenylamine (mg/kg Organic Carbon ) <3.1 <2.22 <1.24 <2.14 <1.11 <4.54 <3.18 --- --- --- --- 112 112

PESTICIDES & PCBs (µg/kg dry weight)

4,4’-DDD <0.3 <0.31 <0.31 <0.27 <0.31 <0.31 <0.31 --- --- --- --- --- ---

4,4’-DDE <0.13 <0.13 <0.13 <0.11 <0.13 <0.13 <0.13 --- --- --- --- --- ---

4,4’-DDT <0.31 <0.32 <032 <0.27 <0.32 <0.31 <2.4 Y --- --- --- --- --- ---

sum of 4,4’-DDD, 4,4’-DDE and 4,4’-DDT 0.94 0.97 0.98 0.84 0.98 0.97 2.4 --- --- --- --- --- ---

Aldrin <0.35 <0.36 <0.36 <0.31 <0.36 <0.36 <0.35 --- --- --- --- --- ---

Total Chlordane 0.94 0.97 0.98 0.84 0.98 0.97 0.96 --- --- --- --- --- ---

cis-chlordane <.01 <0.11 <0.11 <0.09 <0.11 <0.11 <0.11 --- --- --- --- --- ---

trans-chlordane <0.31 <0.32 <0.32 <0.27 <0.32 <0.32 <0.31 --- --- --- --- --- ---

cis-nonachlor <0.2 <0.2 <0.2 <0.18 <0.21 <0.2 <0.20 --- --- --- --- --- ---

trans-nonachlor <0.22 <0.22 <0.22 <0.19 <0.98 <0.22 <0.22 --- --- --- --- --- ---

oxychlordane <0.12 <0.12 <0.12 <0.11 <0.13 <0.12 <0.12 --- --- --- --- --- ---

Dieldrin <0.11 <0.11 <0.11 <0.1 <0.11 <0.11 <0.11 --- --- --- --- --- ---

Heptachlor <0.04 <0.05 <0.05 <0.04 <0.05 <0.04 <0.04 --- --- --- --- --- ---

PCBs (mg/kg Organic Carbon)

Total PCBs Aroclors (Sum of: 1016, 1221, 1242, 1248,

1254, 1260, 1268) 1 1.2 1.2 1.3 1.7 3.2 2.9 --- --- --- --- 12 65

Petrolum Hydrocarbons (mg/kg dry weight)

Gasoline Range Organics (Tol-Nap) --- --- --- --- --- <9.48 <9.01 --- --- --- --- --- ---

Diesel Range Organics (C12-C24) --- --- --- --- --- 12.8 17.1 --- --- --- --- --- ---

Motor Oil Range Organics (C24-C38) --- --- --- --- --- 16.9 25.3 --- --- --- --- --- ---


TABLE 5. SUMMARY OF CHEMICAL ANALYTICAL RESULTS COMPARED TO SMS CRITERIA EMERGENCY SPILL DOCK EXTENSION DREDGED MATERIAL SEDIMENT CHARACTERIZATION REPORT


Notes:

SMS = Sediment Management Standards (March 2015)

Total LPAH = The sum of acenaphthylene, acenaphthene, anthracene, fluorene, naphthalene and phenanthrene.

Total HPAH = The sum of benzo(a)anthracene, benzo(a)pyrene, total benzofluoranthenes, benzo(g,h,i)perylene, chrysene, dibenzo (a,h)anthracene, fluoranthene, indeno(1,2,3,-c,d)pyrene and

pyrene.

Total benzofluoranthenes = the sum of the "b," "j" and "k" isomers. The "j" isomer co-elutes with the "k" isomer, thus the concentration of the "j" isomer is included in the "k" isomer concentration. 1 2-Methylnaphthalene is not included in the summation for total LPAH.

2 This value is normalized to total organic carbon, and is expressed in mg/kg organic carbon.

SQS = Sediment Quality Standards

CSL = Cleanup Screening Levels



TOC = Total organic carbon

H = Hold time violation - Hold time was exceeded.

D = The reported value is from a dilution

J = Estimated concentration when the value is less than ARI's established reporting limits

P1 = The reported value is greater than 40% difference between the concentrations determined on two GC columns where applicab le.

Q = Indicates a detected analyte with an initial or continuing calibration that does not meet established acceptance criteria (<20% RSD, <20% drift or minimum RRF)

--- = not analyzed

indicates an exceedance of SMS SQS criteria

indicates an exceedance of SMS CSL criteria

<0.37 = the target analyte was not detected at the reported concentration

180.6

245.2



F ig ures

Neah Bay

Neah Bay

Legend

Proposed Dredge Area

MLLW = 0

MHHW = +7.95

-35 MLLW

MHHW

Medium Lower Low Water

Medium Higher High Water

-30

1020 ft

Note: Outfalls are present at each

street end.

1350 ft

-25

-20

Existing fuel dock

Existing commercial fishing dock & trestle

MLLW = 0

-15

-10

-5

0

+5 MHHW = +7.95

Approximate shoreline

Neah Bay

0 125

F 250 500 750 1,000 1,250

Feet

Source: Esri, DigitalGlobe, GeoEye, Earthstar Geographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN, and the GIS User Community

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-25' EL. = 1' OD. PROPOSED POST-DREDGE MUDLINE ELEVATION IN FEET MLLW + ONE FOOT ALLOWABLE OVERDREDGE

DMMU DREDGED MATERIAL MANAGEMENT UNIT

4

SAMPLE ID

+

SAMPLE LOCATION

YD³ CUBIC YARD

MLLW MEAN LOWER LOW WATER

MHHW MEAN HIGHER HIGH WATER

OD ALLOWABLE OVERDREDGE

AREA WITH POST DREDGE ELEVATION AT -15' EL.+1' OD.

CROSS SECTION LOCATION

4

(-25' EL. + 1'OD.)

(-15' EL. + 1'OD.)

NOTE: 1. THE BATHYMETRY INFORMATION DEPICTED ON THIS CHART REPRESENTS THE RESULTS OF SURVEYS COMPLETED BY WILSON ENGINEERING, LLC BETWEEN THE DATES 16 AUGUST 2016 AND 19 AUGUST 2016. THE DATA REFLECTS THE STATE OF THE SEA FLOOR AT THE TIME THE SUVEY WAS COMPLETED. 2. MLLW = 0.0 and MHHW = +7.95 FEET 3. VOLUME OF THE SIDE SLOPES ARE INCLUDED IN THE TOTAL DREDGE VOLUME 4. ONE FOOT ALLOWBLE OVERDREDGE IS INCLUDED IN TOTAL DREDGE VOLUME

Approximate Drawing Scale: 1"

DREDGE VOLUME 170,400YD³ OVER DREDGE (1 FT) VOLUME 37,600YD³ TOTAL DREDGE VOLUME 208.000YD³

Approximate Horizontal Drawing Scale: 1" = 160'

0 ft. 96 ft. 160 ft. 320 ft.

PURPOSE: Construct an extension to the existing

commercial fishing dock to provide adequate, dedicated

infrastructure to support an enhanced oil spill prevention

and response capacity in Neah Bay. Dredging is required to accommodate vessels.

APPLICANT: Makah Tribe

SITE OWNER: Makah Tribe ADJACENT PROPERTY OWNERS: Department of Natural Resources

MAKAH TRIBE EMERGENCY SPILL DOCK EXTENSION DREDGED MATERIAL CHARACTERIZATION

SHEET 3: Site Plan - DMMUs

WATERWAY: Neah Bay AT: Neah Bay

COUNTY: Clallam

LAT/LONG: 48.36746 N/-124.61416 W S/T/R: S11/T33N/R15W DATUM: MLLW=0.0

DATE: January 2017

Sheet 3 of 5

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Legend

DMMU DREDGED MATERIAL MANAGEMENT UNIT

S-7 SAMPLE ID

SAMPLE LOCATION

MLLW MEAN LOWER LOW WATER

Feet

Exist Mudline

Post Dredge Surface 1' Allowable Overdredge

SCALE: HORIZ: 1" = 100' VERT: 1" = 20'

Feet

Exist Mudline

Post Dredge Surface 1' Allowable Overdredge

SCALE: HORIZ: 1" = 100' VERT: 1" = 20'

HORIZ SCALE: 1" = 100'

PURPOSE: Construct an extension to the existing

commercial fishing dock to provide adequate, dedicated infrastructure to support an enhanced oil spill prevention

and response capacity in Neah Bay. Dredging is required to accommodate vessels.

APPLICANT: Makah Tribe

SITE OWNER: Makah Tribe ADJACENT PROPERTY OWNERS: Department of Natural Resources

MAKAH TRIBE EMERGENCY SPILL DOCK EXTENSION

DREDGED MATERIAL CHARACTERIZATION

SHEET 4: Dredging Sections

WATERWAY: Neah Bay AT: Neah Bay

COUNTY: Clallam

LAT/LONG: 48.36746 N/-124.61416 W

S/T/R: S11/T33N/R15W

DATUM: MLLW=0.0 DATE: January 2017

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PURPOSE: Construct an extension to the existing commercial fishing dock to provide adequate, dedicated infrastructure to support an enhanced oil spill prevention and response capacity in Neah Bay. Dredging is required to accommodate vessels.

APPLICANT: Makah Tribe SITE OWNER: Makah Tribe ADJACENT PROPERTY OWNERS: Department of Natural

Resources

MAKAH TRIBE EMERGENCY SPILL DOCK EXTENSION


SHEET 5: POTENTIAL BENEFICIAL USE AREA

WATERWAY: Neah Bay

F

AT: Neah Bay COUNTY: Clallam

LAT/LONG: 48.36746 N/-124.61416 W S/T/R: S11/T33N/R15W 0 50 100 200 300 400 500

DATUM: MLLW=0.0 Feet

DATE: January 2017 Source: Esri, DigitalGlobe, GeoEye, Earthstar Geographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN, and the GIS User Community

Legend

Beneficial Use Area

Approximate Eelgrass Location



Appendix A Sampling and Analysis Plan and DMMO Approval E-mail

Watanabe, Carissa

From: Warner, Lauran C CIV USARMY CENWS (US) <[email protected]>

Sent: Tuesday, November 15, 2016 11:01 AM

To: Watanabe, Carissa; England, Victoria

Cc: Celia Barton ([email protected]); Laura Inouye ([email protected]); Justine

Barton ([email protected]); Schnell, Kaitlin E CIV USARMY CENWS (US);

Houghton, Juliana CIV USARMY CENWS (US)

Subject: Makah Oil Spill Response Dock - SAP approval (UNCLASSIFIED)

Attachments: sample Signature Page For Subcontractors.docx

CLASSIFICATION: UNCLASSIFIED

Carissa and Victoria: The DMMP has reviewed the “Revised Sampling and Analysis Plan, Makah Tribe Emergency Spill Dock Extension Dredged Material Characterization,” received November 7, 2016. We appreciate your updates based on our previous comments. The DMMP approves this SAP with the following conditions:

Prior to sampling, we need agreement with the following clarifications in writing (a reply to this email is suitable). A fina l SAP that incorporates these modifications should be included as an appendix to the final project report.

1) TPH Analysis. Due to the nearby spill reported earlier this year, and to projected use of this material for either in -

water or upland beneficial uses, the DMMP requests analysis of Total Petroleum Hydrocarbons be added as a special contaminant of concern. Analysis for this chemical could be tiered, with only sediment from DMMUs 6 and 7 (closest to the marina spill area) initially tested. Though the DMMP has no regulatory guidelines for this chemical in marine sediment, we will look to state upland guidelines to evaluate suitability, based on potential upland use.

2) PS-SRM: The DMMP will not be able to approve use of the Puget Sound Sediment Reference Material unless dioxin testing is proposed. Another laboratory standard should be used for PCB Aroclors.

3) Signature Page: sample attached. Please have all subcontractors sign and return to DMMO prior to sampling. 4) Pre-sampling conference call: A brief agency call will be required prior to sampling.

CLASSIFICATION: UNCLASSIFIED

1

mailto:[email protected]

REVISED FINAL


Sampling and Analysis Plan


Dredged Material Characterization

Prepared for

Makah Indian Tribe


Prepared by

BergerABAM

A16.0096.00 January 2017

Revised


Sampling and Analysis Plan

Makah Tribe Emergency Spill Dock Extension Dredged Material Characterization

Prepared for

Makah Indian Tribe

P.O. Box 115


31 January 2017

Prepared by

B e r g e rA B A M 210 East 13th Street, Suite 300 Vancouver, Washington 98660

A16.0096.00

Sally L. Fisher Victoria R. England, LG Senior Project Manager Environmental Scientist

Makah Indian Tribe - Emergency Spill Dock Extension Dredged Material Characterization


BergerABAM, A16.0096.00 31 January 2017

Page ii of v

REVISED

DREDGED MATERIAL MANAGEMENT PROGRAM

SAMPLING AND ANALYSIS PLAN



TABLE OF CONTENTS

SECTION PAGE

1.0 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2.0 PROJECT DESCRIPTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2.1 Proposed Dredging Configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2.1.1 Proposed Dredged Material Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2.2 Project Area Dredging History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3.0 EXISTING SITE CONDITIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3.2 Subsurface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3.3 New Zealand Mud Snail . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

4.0 SITE HISTORY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

5.0 POTENTIAL SOURCES OF CONTAMINATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

5.1 Database Review.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

5.1.1 Regulatory Database Search . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

5.1.2 Ecology Spill Investigation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

6.0 PROGRAM OBJECTIVES AND APPROACH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

6.1 Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

6.2 Approach Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

6.2.1 General Assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

6.2.2 Potential Beneficial Use and Open-Water Disposal . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 6.2.3 Site Ranking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

7.0 SAMPLE COLLECTION AND HANDLING PROCEDURES.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7

7.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

7.2 General Sampling Scheme.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

7.3 Compositing Scheme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

7.3.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 7.3.2 Surface Unit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

7.4 Sample Collection and Handling Procedures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

7.4.1 Sample Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

7.4.2 Sampling Equipment Decontamination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 7.4.3 Sample Handling and Compositing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

7.4.4 Sulfides Sampling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

7.5 Sample Archiving . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

7.6 Field Sampling Schedule. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

7.7 Positioning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

7.8 Sample Transport and Chain-of-Custody Procedures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12




Page ii of v

8.0 LABORATORY PHYSICAL AND CHEMICAL SEDIMENT ANALYSIS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

8.1 Analysis Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

8.2 Laboratory Analyses Protocols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

8.3 Chain-of-Custody . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

8.4 Limits of Detection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

8.5 Quality Assurance/Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

8.6 Laboratory Written Report . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

9.0 REPORTING . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

9.1 Quality Assurance/Quality Control Report. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

9.2 Final Report. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

10.0 STUDY TEAM AND RESPONSIBILITIES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

10.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

10.1.1 Project Planning and Coordination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 10.1.2 Field Sample Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

10.1.3 Laboratory Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 10.1.4 Quality Assurance/Quality Control Management. . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

10.1.5 Final Data Report . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

11.0 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

LIST OF TABLES

Table 1. Compositing Scheme and DMMU Volumes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

Table 2. DMMP and SMS Chemical Evaluation Criteria1................................ ................................ ............... 21 Table 3. Proposed Sample Coordinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

LIST OF SHEETS

Sheet 1. Vicinity Map

Sheet 2. Site Plan – Existing Conditions Sheet 3. Site Plan - DMMUs

Sheet 4. Schematic DMMU Plan Section

Sheet 5. Potential Beneficial Use Area

LIST OF APPENDICES

Appendix A Sample Containers, Holding Times, Volume, and Chemical Analytical Methods and

QA/QC Criteria

Appendix B Analytical Resources, Inc. Sediment Reference Certificates

Appendix C Signature Page for Subcontractors




Page iv of v

Acronyms and Abbreviations

ASTM American Society for Testing and Materials

BT Bioaccumulation Trigger

CERCLA Comprehensive Environmental Response, Compensation, and Liability Act of 1980

CFR Code of Federal Regulations

COCs contaminants of concern

CSL cleanup screening level

cy cubic yard

DMMO Dredged Material Management Office

DMMP Dredged Material Management Program

DMMU Dredged Material Management Unit

Ecology Washington State Department of Ecology

EIM Environmental Information Management

EPA Environmental Protection Agency

ERTV emergency response towing vessel

g grams

GPS Global Positioning System

HPAH high molecular weight polynuclear aromatic hydrocarbon compounds

xxH:xxV Horizontal to Vertical

KG kilograms

mg milligrams

LPAH low molecular weight polynuclear aromatic hydrocarbon compounds

ML maximum level

MLLW mean lower low water

MTCA Model Toxics Control Act

NAD North American Datum

PCB polychlorinated biphenyl

PCDD/F dioxins and furans (?)

PSDDA Puget Sound Dredged Disposal Analysis program

PSEP Puget Sound Estuary Program

QA/QC quality assurance/quality control




Page v of v

SAP Sampling and Analysis Plan

SL screening level

SMS Sediment Management Standards

SQS Sediment Quality Standards

SRM Sediment Reference Material

SVOCs semi-volatile organic compounds

TBT tributyltin

TOC total organic carbon

TPH-Dx diesel-range petroleum hydrocarbons

Tribe Makah Indian Tribe

USACE U.S. Army Corps of Engineers

USCG U.S. Coast Guard

VOCs volatile organic compounds

WAC Washington State Administrative Code

µg micrograms



BergerABAM, A16.0096.00

31 January 2017

Page 1 of 22

REVISED

SAMPLING AND ANALYSIS PLAN MAKAH TRIBE EMERGENCY SPILL DOCK EXTENSION


1.0 INTRODUCTION

The Makah Indian Tribe (Tribe) owns a commercial fishing dock in Neah Bay,

Washington, on the southern shore of the Strait of Juan de Fuca. The Tribe proposes

to construct an extension of the existing commercial fishing dock to accommodate

emergency spill response vessels. The proposed dock extension would provide a

permanent mooring location for the emergency response vessels and allow greater

functionality for vessel loading and unloading operations. The project location is

shown on the Vicinity Map and Site Plan (Sheets 1 and 2).

Approximately 208,000 cubic yards (cy) of dredging is needed to provide sufficient

draft for the emergency response vessels, to provide access from the navigation

channel and accommodate the new dock extension. This Sampling and Analysis Plan

(SAP) provides the methods for characterizing the area to be dredged. This SAP

describes the site history, potential sources of contaminants, existing data, the

proposed project, and associated sampling and analysis of the proposed dredge

material.

The analytical results will be used to evaluate the potential suitability of dredged

material for in-water beneficial use and/or upland reuse in accordance with Dredged

Material Management Program (DMMP) and the Washington State Department of

Ecology (Ecology) Sediment Management Standards (SMS) protocols.

This SAP is provided to the Dredged Material Management Office (DMMO) for the

review and approval of the sampling program and procedures prior to completing

sediment sampling.

2 .0 PROJECT DESCRIPTION

The purpose of the proposed project is to provide adequate, dedicated infrastructure

to support an enhanced oil spill prevention and response capacity in Neah Bay. The

dock extension project is a high priority for both the Tribe and the Port of Neah Bay.

Over 2 million gallons of oil have been spilled in the Makah Treaty Area since the

1970s and the potential exists for future incidences due to shipping vessel traffic in

the Strait of Juan de Fuca.

The project consists of construction of an extension to the existing commercial

fishing dock to accommodate an emergency response towing vessel (ERTV) and

associated spill response vessels that are required to be stationed in Neah Bay. ERTV

and associated vessels have been stationed at Neah Bay since 1999 under contract to




31 January 2017

Page 2 of 22

Ecology. Owners or operators of vessels transiting through the Strait of Juan de Fuca

(except for transits extending no further west than Race Rocks Light, a lighthouse in

Canada) can contract the ERTV for compliance with state Ecology oil spill response

contingency plan regulations and during vessel emergencies. The tugboat Marshall

Foss is stationed at the marina in Neah Bay under charter to the Washington State

Maritime Cooperative as per a service agreement with the ERTV Compliance

Group1. Vessel emergencies include propulsion and steering failures, groundings,

fires, structural failures, and collisions.

In addition to the ERTV standards, both State of Washington (Ecology regulations

[WAC 172-183]) and federal (U.S. Coast Guard [USCG] regulations [33 CFR 155])

regulations require that vessels (tankers carrying oil and non-tank vessels over a

certain size) have adequate resources under contract to respond to a cargo or fuel oil

spill within specified time frames. These requirements – response planning

standards – establish minimum levels of boom, skimmers, and recovered oil storage

equipment that must be able to arrive on the scene at various time intervals to

respond to a potential reasonable worst-case spill. The current moorage and draft

depth at the marina do not accommodate the vessels required to meet the response

planning standards. The proposed project will accommodate an expanded

emergency response fleet that meets Washington and USCG criteria.

The project site was chosen to construct a new spill response facility because of the

opportunities to achieve the project goals while minimizing the amount of new

construction and dredging. The proposed spill dock will extend from the existing

fishing dock trestle, which will eliminate the need for a new trestle that extends to

the shore (i.e., the fishing dock and spill dock extension will share the same trestle

for shore access). The Makah dock trestle was constructed to accommodate semi-

trucks and sharing that trestle provides important unloading/loading capabilities

that will work well for the spill response operations.

The proposed project will be located west of and adjacent to the existing commercial

fishing dock as shown on Sheet 2. The proposed dock will connect to the existing

fishing dock trestle approximately 40 feet south of the fishing dock and will extend

at an angle from the existing commercial fishing dock trestle, extending

approximately 563 feet to the northwest as shown on Sheet 3. Two finger piers will

extend approximately 325 feet and 340 feet to the north from the angled dock

extension. Two floating docks for berthing small crafts will be located on the north

side of the angled dock extension. The floating docks will be approximately 180 feet

long. An area extending to the north of the extension will be dredged to complete a

channel to the Neah Bay basin to allow for passage of vessels.

1 Background information on the ERTV Compliance Group and associated regulations can be found here

http://www.marexps.com/supporting/ertv.

http://www.marexps.com/supporting/ertv

http://www.marexps.com/supporting/ertv




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2 .1 Proposed Dredging Configuration

The proposed project will require dredging to increase the depths within the new

berthing area to elevations ranging from -15 to -25 feet mean lower low water

(MLLW) plus 1-foot allowable overdredge (-16 to -26 feet MLLW). The berthing area

will be dredged to elevations of -25 feet MLLW (plus 1 foot of allowable overdredge)

to accommodate the drafts of the spill response vessels and provide access to the

Neah Bay basin (see Sheet 3). The south-easternmost shoreward area of the dredge

prism will be dredged to an elevation of -15 feet MLLW (plus 1 foot of allowable

overdredge) to provide access to the east side of the existing commercial dock for

small boats.

Approximately 208,000 cubic yards (cy) of material (including 1-foot overdredge

allowance) will be dredged from the project area (see Table 1) and used for in-water

and/or upland beneficial uses in Neah Bay and the adjacent upland.

The proposed placement of the spill dock extending from the existing trestle

approximately 300 feet from shore to approximately 563 feet to the northwest results

in the dredge prism covering an area with an existing mudline elevation ranging

from – 3 feet MLLW to -25 feet as shown on Sheet 3. High-value intertidal habitat

will not be impacted by dredging or construction of the spill dock extension. The

dredge prism cut will range in thickness from 1 foot to 20 feet below mudline

(including overdredge allowance)(see Sheet 4). The number of dredged material

management units (DMMUs) and associated subsamples are based upon the DMMP

ranking of low-moderate as described in Section 6.2.3. The boundaries of each

DMMU were identified based on existing bathymetry, volume, and proposed dredge

depth.

2.1.1 Proposed Dredged Material Use

Placement of the dredged material as in-water beneficial use for restoration/

enhancement of the beach area in the northwest corner of the bay (see Sheet 5) is

proposed if the material is found potentially suitable for beneficial reuse. A portion

of the material may also be stockpiled in the upper zones of the beach and the

adjacent upland for use by the Makah Tribe for various upland projects. The area

and thickness of dredged material placement shown on Sheet 5 is preliminary. A

final placement design will be included with the project permit applications should

this placement option be selected. Alternative beneficial use of the dredged material

may be identified during ongoing coordination with the Tribe, U.S. Army Corps of

Engineers (USACE), DMMO, and the Environmental Protection Agency (EPA).

The dredged material may also be disposed of at the Port Angeles DMMP dispersive

disposal site if it is found suitable for open-water disposal.




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2 .2 Project Area Dredging History

The proposed dredge area has never been dredged according to Port records and

information provided by locals familiar with the site.

3 .0 EXISTING SITE CONDITIONS

3 .1 General

The existing commercial fishing dock is located on the south side of Neah Bay on the

southern shore of the Strait of Juan de Fuca. The dock is bounded by the waters of

Neah Bay on the north, a marina on the west, a fuel dock on the east, and upland

portion of the city of Neah Bay on the south. The adjacent upland properties are

occupied by commercial businesses and a gear storage yard. Underwater debris was

removed from the existing commercial fishing dock site in 2014. Debris likely

remains near the perimeter of the fishing dock and may be encountered during

sampling activities. Any debris recovered during sampling activities will be collected

and disposed of at an appropriate upland disposal facility.

3 .2 Subsurface

A geotechnical investigation was conducted by Landau Associates in 2013 for the

replacement of the commercial fishing dock (see Section 4.0). Four exploratory

borings were advanced to depths ranging from approximately 9 to 68 feet below the

mudline. Boring logs from that investigation show that subsurface conditions are

generally marine deposits of “dense” and “dense to very dense” sand deposits from

the mudline to elevations ranging from approximately -28 to -36 feet MLLW.

3 .3 New Zealand Mud Snail

Neah Bay is not documented as an area known or suspected of harboring the New

Zealand mud snail2.

4.0 SITE HISTORY

The commercial fishing dock was originally constructed in 1948 for ice production,

fish loading and unloading, and processing. The timber dock sustained damage in

2013 rendering it unusable and was replaced with the existing concrete dock in 2014.

5 .0 POTENTIAL SOURCES OF CONTAMINATION

Potential sources of contamination were identified based on a comprehensive review

of various available sources, including reports, data, and information from Ecology’s

Environmental Information Management (EIM) database and Facility/Site database

(accessed 5 August 2016).

2 Per Ecology’s Invasive Species website: http://www.ecy.wa.gov/programs/eap/Invasivespecies/AIS-

publicversion.html, visited on 26 September 2016.

http://www.ecy.wa.gov/programs/eap/Invasivespecies/AIS-publicversion.html

http://www.ecy.wa.gov/programs/eap/Invasivespecies/AIS-publicversion.html




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5 .1 Database Review

5.1.1 Regulatory Database Search

The commercial fishing dock is located on a commercial waterfront that includes

retail shops and restaurants, recreational facilities, storage yards, a fueling facility,

and parking. There are no industrial facilities within Neah Bay. The existing fuel

dock is located to the west of the existing commercial fishing dock and no spills or

releases have been reported. However, there is the potential that historical upland

and/or in-water releases may have impacted the sediment within Neah Bay.

We reviewed data from Ecology’s Facility/Site database (accessed 5 August 2016)

regarding historical investigations within 1/2 mile of the proposed dredge area that

may pose an environmental concern to the proposed dredge area. No sites within

1/2 mile were identified within the database search.

We reviewed Ecology’s EIM database (accessed 5 August 2016) to identify outfalls

and review available sediment data within 1/2 mile of the proposed dredge area. No

outfalls were identified in the EIM database however the Tribe documented the

location of three outfalls discharging to Neah Bay. The outfall locations include west

of the existing commercial fishing dock, the marina, and east of the fuel dock as

shown on Sheet 2. Stormwater is collected from Bay View Avenue and intersecting

cross streets and discharged within Neah Bay. Available sediment data from the

existing commercial fishing dock area (sampled in 1993), the marina located east of

the proposed dredge area (sampled in 1993), and the central waters of Neah Bay

(sampled in 2006) did not have any contaminants of concern exceeding DMMP

screening levels (SLs).

5.1.2 Ecology Spill Investigation

We reviewed an Ecology spill investigation summary (Ecology 2016) that

documented an estimated 500-gallon diesel release to Neah Bay on 6 April 2016. The

release occurred at the marina located to the east of the proposed dredge area.

Booms and sorbent materials were applied to the release, and 206.5 gallons of diesel

fuel were recovered during the cleanup activities. It was noted that some fuel

escaped the boomed containment area and light to heavy streaking was observed in

the waters of Neah Bay up to 0.6 nautical mile west of the marina.

6 .0 PROGRAM OBJECTIVES AND APPROACH

6 .1 Objectives

The objective of this SAP is to characterize the proposed dredge materials within the

project area to evaluate the following.

• Suitability for beneficial use as in-water and/or upland fills.

• Upland placement and/or disposal options (if the dredged material is not

suitable for in-water placement or beneficial use).




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6 .2 Approach Considerations

6.2.1 General Assumptions

The approach is based on the following.

• This SAP was developed using a low-moderate ranking with the associated

sampling frequency and recency guidelines, based on existing site conditions

and historical site use.3

• This SAP is based on using a power grab to sample the upper 10 or 11 inches of

the dredged prism4. This methodology was chosen because previous

geotechnical information from the project area indicates that the material is

generally homogenous native dense sand with a lack of contaminant sources and

that the material is too dense to use typical sediment vibracoring methods.

Additional details regarding subsurface conditions and the sampling approach

are provided in the Makah Emergency Spill Dock Expansion – Proposed

Sampling Approach for Dredged Material Characterization memorandum, dated

1 September 2016.

6.2.2 Potential Beneficial Use and Open-Water Disposal

The purpose of this SAP is to characterize the proposed dredged material relative to

DMMP criteria for suitability for unconfined open-water disposal and relative to

Washington State Sediment Management Standards (SMS) for potential suitability

for beneficial use in-water.

The results of this study may also be used by the applicant to evaluate potential

suitability for upland use of the dredged material relative to Washington State

Model Toxics Control Act (MTCA) criteria.

6.2.3 Site Ranking

The DMMP (DMMO 2015) defines site ranking as follows.

• “Low” ranking where there are “Few or no sources of chemicals of concern. Data

are available to verify low chemical concentrations (below DMMP screening

levels) and no significant response in biological tests.”

• “Low-moderate” ranking is used where “Available data indicates a “low” rank,

but there are insufficient data to confirm the ranking.”

• “Moderate” ranking is used at those sites where “Sources exist in the vicinity of

the project, or there are present or historical uses of the project site, with the

3 Recency guidelines allow characterization data to be valid for low-moderate ranked sites six years. 4 Per e-mail received from Lauran Cole-Warner on 15 September 2016.




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potential for producing chemical concentrations within a range associated

historically with some potential for causing adverse biological impacts.”

• “High” ranking is used at those sites where “Many known chemical sources,

high concentrations of chemicals of concern, and/or biological testing failures in

one or both of the two most recent cycles of testing. Projects located within or

adjacent to MTCA/CERCLA cleanup site may be subject to project-specific

ranking guidelines with higher sampling and testing requirements.”

6.2.3.1 Marina Sediment

Sediment at the proposed dredge area has not been ranked within the DMMP User’s

Manual, and would, therefore, be categorized under “Current general rankings for

Puget Sound”5 as “all other unidentified areas” with a low-moderate ranking. The

DMMO concurred with the proposed low-moderate ranking.6 This SAP has been

completed assuming that the sediment within the dredge area will be identified as

having a low-moderate ranking by the DMMO in agreement with the ranking

identified in the DMMP User’s Manual.

7 .0 SAMPLE COLLECTION AND HANDLING PROCEDURES

7 .1 General

Dredge volume, dredge prism configuration, and sampling frequency are based on

typical cross sections and conditions within the project area. The dredge prism for

the option considered for this SAP is based on the following assumptions.

• The existing top of mudline ranges from approximately Elevation -3 to -25 feet

MLLW (bathymetry survey completed by Wilson Engineering LLC on 16 to

19 August 2016).

• The design dredging depth will be Elevation –15 feet MLLW and -25 feet MLLW

(plus 1 foot of allowable overdredge) depending upon the location in the dredge

area. The total volume of the dredge prism includes overdredge elevations

(-16 feet MLLW and -26 feet MLLW, respectively).

• The boundaries of the dredge prism will have a 4H:1V slope from the top of the

dredge prism to the design depth as shown on Sheet 4. The material to be

dredged from the slopes is included within the overall dredge prism volume.

• The material in the dredge prism is homogenous surface material and will be

ranked low-moderate.

5 “Dredged Material Evaluation and Disposal Procedures (Users’ Manual), Table 5 -2” by DMMO, U.S. Army Corps of

Engineers Seattle District, dated August 2016. 6 Per discussions with Lauran Cole-Warner on 1 July 2016.




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7 .2 General Sampling Scheme

The sampling and analyses frequency for DMMP characterization for this project has

been determined in accordance with the proposed site ranking of “low-moderate” as

discussed above. We expect that this frequency will also be sufficient for evaluating

its suitability for beneficial use, compliance with the SMS (WAC 173-204), and/or

other disposal options. Material considered for upland beneficial use or disposal

may require additional testing appropriate to the proposed scenario based on other

regulatory programs and/or requirements that are outside the scope of the DMMP

review and approval authority.

We have assumed for planning purposes that the dredge prism consists entirely of

native material. The material characteristics will be documented in the sample logs.

The dredge prism depths range from 1 foot to approximately 20 feet (plus 1 foot of

allowable overdredge) depending upon the sample location. The potential dredge

area has been delineated into seven surface DMMUs as shown on Sheet 3.

Sampling and analysis for this project will be performed in accordance with

DMMP/Puget Sound Estuary Program (PSEP) protocols. Samples will be collected

using a vessel-mounted power grab sampler. The samples will be processed and

sampled on the vessel.

Each DMMU sample will be analyzed for DMMP/SMS conventional parameters, the

full suite of DMMP/SMS contaminants of concern (COCs), non-chlorinated volatile

organic compounds (VOCs), semi-volatile organic compounds (SVOCs), PCBs,

pesticides, diesel-range petroleum hydrocarbons (TPH-Dx) by Ecology Method

NWTPH-Dx, and bulk tributyltin (TBT) as shown on Table 2. A laboratory supplied-

Sediment Reference Material (SRM) will also be submitted for analysis of PCBs in

accordance with DMMP guidance. The certificates associated with this material will

be included with the sediment characterization report that will be completed after

the analytical results are received.

Post-dredge surface sediment samples will be collected (if needed) from the newly

exposed sediment surface from any of the 28 locations where COCs (if any) are

detected at concentrations exceeding SMS/Sediment Quality Standards (SQS) or

DMMP SLs in the overlying DMMUs. The post-dredge surface samples will be

collected from the upper 10 centimeters of the sediment surface using sampling

equipment operated from a vessel outfitted for that purpose. The post -dredge

samples will be collected from the newly exposed dredge surface in coordination

with the DMMP agencies.

7 .3 Compositing Scheme

7.3.1 General

Sediment will be collected from each sample location and composited to represent

DMMUs as described above. Details of the compositing scheme, including depth




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and DMMU volumes, are shown on Table 1. The proposed sample coordinates are

provided in Table 3. The anticipated compositing schemes are shown schematically

on Sheet 3. DMMU samples will be collected and archived for bioassays, if needed.

A portion of the individual samples will also be archived for potential future

chemical analysis, if needed.

7.3.2 Surface Unit

DMMP requirements for sampling and analysis of surface sediment for a low-

moderate ranked site consist of one sample per 8,000 cy and one analysis per

32,000 cy.

The volume represented by each grab subsample is estimated to range from 3,892 cy

to 8000 cy. The volume of the DMMUs is estimated to range from 15,570 cy to

approximately 31,997 cy. The samples will be composited to represent DMMU

samples as shown on Sheet 3.

7 .4 Sample Collection and Handling Procedures

DMMP-approved sample requirements, analytical methods, and quality

assurance/quality control (QA/QC) criteria are included in Appendix B. Sample

volumes, holding times, containers, preservatives, and chemical analytical methods

are summarized in Table A-1 in Appendix A. QA/QC criteria are summarized in

Tables A-2 and A-3.

7.4.1 Sample Collection

7.4.1.1 Pre-dredge Characterization

Samples will be collected using a power grab sampler operated from a vessel

outfitted for that purpose. The grab sampler is used to collect large-volume surface

samples over a 0.2-square-meter area and is advanced into the substrate and then

closed with a pneumatic ram. Penetration is adjustable up to 30 centimeters

(11.8 inches) and will be adjusted to the greatest depth. Recovery depth of the

material within the sampler will be recorded. Samples will be collected from the full

depth recovered. Sample material that is, or has been, in direct contact with the grab

sampler will not be included in the sample volume.

The following acceptability criteria for the grab samples will be satisfied.

• The minimum allowable penetration depth will be 15 cm to allow collection of a

sample representing at least the upper 10 cm of the proposed dredged material.

• The sampler will not be overfilled with the sample such that the sediment surface

is pressed against the top of the sampler.

• Overlying water will be present (indicates minimal leakage). Overlying water will

be slowly siphoned off near one side of the sampler with a minimum of sample

disturbance.




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• The overlying water will not be excessively turbid (clear water indicates

minimal sample disturbance).

• The sediment surface will be relatively flat (indicates minimal disturbance or

winnowing).

If a sample does not meet any one of these criteria, it will be rejected and the location

will be resampled.

Sampling will be conducted within 10 feet of the target sample location (see

Section 7.7 for positioning details). If for any reason sampling cannot be conducted

within 10 feet of the target location, the DMMO will be contacted to coordinate an

alternative sample location. Any modification to the sampling locations will be

documented in the field notes and summarized in the Dredged Material

Characterization Report.

The sampling scheme will be adjusted in the field and coordinated with the DMMO,

as needed, and recorded on the field logs. Real-time corrections will be completed

based on depth of water column and National Oceanic and Atmosphere Association

tidal gauge data (Neah Bay, Washington; Station ID 9443090). Tide elevations will be

confirmed during setup at each sampling station as described in Section 7.7 below.

7.4.1.2 Post-dredge Characterization

Post-dredge surface sediment samples will be collected (if needed) from the newly

exposed sediment surface from any of the 28 locations where COCs (if any) are

detected at concentrations exceeding SMS/SQS or DMMP SLs in the overlying

DMMUs. The post-dredge surface samples will be collected from the upper

10 centimeters of the sediment surface using grab sampling methods operated from

a vessel outfitted for that purpose.

7.4.2 Sampling Equipment Decontamination

All samplers and miscellaneous sampling tools will be thoroughly cleaned prior to

use according to the following procedure.

• Remove excess sediment with a brush and in-situ water

• Wash with brush and Alconox detergent

• Rinse equipment thoroughly with clean in-situ water

• Triple rinse with distilled water

All sampling equipment not used immediately after cleaning will be wrapped in

aluminum foil and/or stored in plastic bags. The rule of “potential for contaminants”

will be used such that any sampling equipment suspected of contamination will be

rejected and decontaminated prior to use.




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7.4.3 Sample Handling and Compositing

A BergerABAM field scientist will be sampling and compositing the samples on the

vessel. Material from each power grab will be sampled from the upper 10 to

12 inches of existing surface material. Samples from each power grab will be

composited into DMMUs as shown on Sheet 3 and Table 1. An equal and

representative portion of material will be taken from each power grab sample to be

composited for each sample that will be submitted for analysis.

Logs and field notes of all samples will be maintained during sampling activities. At

a minimum, the following will be included in the log.

• Elevation of each station sampled as measured at each location prior to sampling

and corrected for tidal elevation from MLLW as described in Section 7.7 below.

• Station location determined in latitude and longitude using global position

system (GPS)

• Date and time of collection of each sample

• Names of field person(s) collecting and logging in the sample

• Sample characteristics, including grain size, density, moisture, horizons (native

or otherwise), odor and presence of shells, and/or manmade or woody debris

• Weather conditions

• Tidal conditions and tidal stage

• Sample station number as derived from this sampling plan

• Length and depth intervals of each sample

• Picture of each sample

• Any deviation from the approved sampling plan

The sample material will be composited and thoroughly mixed in stainless steel

bowls. One to 2 liters of homogenized sample will be jarred to provide adequate

volume for physical and chemical analyses. Approximately 4 liters of the

homogenized sample will be jarred (with zero headspace) to provide adequate

volume for bioassay testing. The composited samples will be stored in iced coolers

for transport to the laboratory.

All handwork (extruding, mixing, and compositing) will be performed using

stainless steel spoons. All sampling, mixing, and compositing equipment will be

decontaminated prior to collection at each sampling station. Disposable latex/nitrile




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gloves will be used and disposed of after each subsample is collected to prevent

cross contamination. Gloves will be disposed of between composites to prevent cross

contamination.

7.4.4 Sulfides Sampling

Sulfide samples will be preserved using 5 milliliters of 2 Normal zinc acetate per

30 grams of composited sediment (DMMP 2016). The acetate will be placed in a

4-ounce sampling jar and the sample material will be placed in the jar, covered, and

shaken vigorously to completely expose the material to the zinc acetate.

7 .5 Sample Archiving

A portion of the material collected from each sample will be archived for potential

future individual analysis. A portion of the material collected from each DMMU will

be archived for potential future bioassay analysis. The archived samples will be

refrigerated and stored at the analytical laboratory.

7 .6 Field Sampling Schedule

The sampling will be performed using power grab sampling equipment owned and

operated by Research Support Services of Bainbridge Island, Washington. Sampling

is scheduled for 21 through 22 November.

7 .7 Positioning

Station positions will be determined in latitude and longitude using a hand-held

GPS unit (North American Datum [NAD] 83/07) to the nearest 0.1 second. The

accuracy of measured and recorded horizontal coordinates will be within 3 meters.

Sample coordinates are shown on Table 3.

Vertical elevations within each sample location will be measured directly based on

depth sampled compared to mudline. Depths below mudline can typically be

determined within approximately 0.1 foot. Vertical elevations will be referenced to

MLLW-based tidal stage and mudline elevations at the time of sampling. Mudline

elevations will be calculated by measuring the depth of water column at the

sampling location using a depth finder on the vessel and adjusting for the tidal stage

at the time of sampling using the Tide Trac phone application for Neah Bay

(Station ID: 9443090).

7 .8 Sample Transport and Chain-of-Custody Procedures

The samples will be transported to an accredited chemical analytical laboratory

when the sampling and compositing is completed. Chain-of-custody procedures will

be used to track sample handling from field collection through delivery of the

samples to the laboratory. Specific procedures will be as follows.

• Samples will be packaged and shipped in accordance with U.S. Department of

Transportation regulations, as specified in 49 CFR 173.6 and 49 CFR 173.24.




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• Individual sample containers will be packed to prevent breakage and

transported in a sealed ice chest or other suitable container. Ice enclosed in the

sample cooler will be double-bagged and well sealed. A temperature blank will

be included in each sample cooler.

• The coolers will be clearly labeled with sufficient information (name of project,

time and date container was sealed, person sealing the cooler, and

BergerABAM’s office name and address) to enable positive identification.

• A sealed envelope containing chain-of-custody forms will be enclosed in a plastic

bag and taped to the inside lid of the cooler.

• Signed and dated chain-of-custody seals will be placed on all coolers prior to

shipping.

• Sample coolers will be transported by vehicle to an accredited chemical

analytical laboratory within 24 hours of being sealed.

The chain-of-custody form will be signed by the persons transferring custody of the

coolers upon transfer of sample possession to the laboratory. The shipping container

seal will be broken and the condition of the samples will be recorded by the receiver

upon receipt of samples at the laboratory. Chain-of-custody forms should be used

internally in the lab to track sample handling and final disposition.

8 .0 LABORATORY PHYSICAL AND CHEMICAL SEDIMENT ANALYSIS

8 .1 Analysis Program

The analysis program for this project has been developed to evaluate suitability for

open-water disposal in accordance with DMMP and potential suitability for in-water

beneficial use in accordance with SMS. Chemical analysis of the DMMU samples will

consist of sediment conventionals, bulk sediment TBT (DMMUs 1, 2, 4, and 7),

TPH-Dx (DMMUs 6 and 7), and DMMP and SMS COCs, as shown in Table 2. Bulk

sediment TBT analysis is proposed on the DMMUs located on the east side of the

dredge prism (DMMUs 1, 2, 4, and 7), closest to the marina. If TBT exceeds DMMP

SLs in any of the DMMUs screened, the remaining DMMUs (DMMUs 3, 5, and 6)

will be analyzed for bulk sediment TBT. TPH-Dx analysis was requested by the

DMMO for the DMMUs (DMMU 6 and 7) closest to area in the marina where there

was a recent diesel spill. The DMMP will evaluate the TPH-Dx results relative to

MTCA guidelines based on potential upland use because the DMMP does not have

regulatory guidelines for TPH-Dx in marine sediment.

DMMP SLs and SMS/SQS are shown in Table 2. Chemical analysis of material

archived from the individual sampling stations may be performed if DMMP SLs are

exceeded. The decision to test individual subunits will be made in conjunction with

the Tribe and the DMMO.




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Dioxins/furans are not proposed for chemical sediment analysis because there is no

record of past or present dioxin/furan-generating industrial activities in Neah Bay,

the nearest creek confluence is approximately 1/2 mile from the proposed dredge

area, and the proposed dredge material is composed primarily of sand. There are

two stormwater outfalls located at the shoreline adjacent to the dredge prism,

however we do not believe dioxins are likely to be present due to the lack of

industrial activity within the area.

Certified reference material, as identified in documentation provided by Analytical

Resources, Inc. and included as Appendix C, will be used for data evaluation and

validation purposes for the metals, SVOCs, and pesticides analyses. The material

will be handled and analyzed in accordance with DMMP guidance (DMMP 2016b).

The chemical analytical data generated from the chemical analysis will also be used

to evaluate general sediment quality in accordance with the SMS. Information

regarding the chemical characteristics of sediments that will be potentially

suspended and/or dispersed during construction may be required for obtaining the

Tribe’s and/or Ecology’s Short-term Water Quality Modification and Water Quality

Certification permits for the project.

Results of the SMS evaluation will be used to determine the antidegradation status of

the surface material exposed by dredging, potential suitability of the material for

beneficial use and to evaluate potential water quality effects during in-water

activities, such as dredging and pile installation.

The need to submit samples for bioassay testing will be evaluated after the dredge

material characterization data results are reviewed. Bioassay testing will be triggered

by the exceedance of one or more SLs for DMMP or SMS COCs in the samples.

Samples selected for bioassay testing will be submitted for both acute and chronic

tests to characterize toxicity. Bioassay testing will include the following tests.

• 10-day amphipod (Eohaustorius estuarius) mortality testing (acute toxicity)

• 20-day juvenile infaunal (Neanthes arenaceodentata) growth test (chronic

toxicity)

• Sediment larval (Mytilus galloprovincialis or Dendraster excentricus) test (acute

toxicity)

8 .2 Laboratory Analyses Protocols

Analytic protocols, including sample holding times and method detection limits, will

be in accordance with EPA, PSEP, and DMMP’s User Manual protocols and

requirements. Laboratory testing procedures will be conducted in accordance with

the DMMP User’s Manual recommended protocols. Several details of these

procedures are discussed below. Laboratory testing procedures will be conducted in




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accordance with the DMMP recommended protocols. Details of these procedures are

discussed below.

8 .3 Chain-of-Custody

A chain-of-custody record for the samples will be maintained throughout all

sampling activities and will accompany samples during shipment to the laboratory,

as previously described. Information tracked by the chain-of-custody records in the

laboratory include sample identification number, date and time of sample receipt,

analytical parameters required, location and conditions of storage, date and time of

removal from and return to storage, signature of person removing and returning the

sample, reason for removing from storage, and final disposition of the sample.

8 .4 Limits of Detection

The samples will be analyzed for all the parameters listed in Table 2. Detection limits

of all chemicals of concern must be below DMMP SLs. Failure to achieve this may

result in a requirement to reanalyze or to conduct bioassays. All reasonable means,

including additional cleanup steps and method modifications, will be used to bring

all limits of detection below DMMP SLs.

All conventional parameters, including grain size, total organic carbon, total solids,

total volatile solids, ammonia, and sulfides, will be analyzed. Particle grain-size

distribution for each composite sample will be determined in accordance with

American Society for Testing and Materials (ASTM) D 422 (modified). Wet sieve

analysis will be used for the sieve sizes U.S. Nos. 4, 10, 20, 40, 60, 140, 200, and 230.

Hydrogen peroxide will not be used in preparations for grain-size analysis.

Hydrometer analysis will be used for particle sizes finer than the 230 sieve. Water

content will be determined using ASTM D 2216. Sediment classification designation

will be made in accordance with U.S. Soil Classification System, ASTM D 2487.

8 .5 Quality Assurance/Quality Control

The chemistry QA/QC procedures will follow the QA/QC criteria established for the

DMMP. The bioassay procedures will follow PSEP protocols and DMMP SMARM

updates. Bioassay performance standards and evaluation guidelines are included in

Appendix A (Table A-3).

8 .6 Laboratory Written Report

A written report will be prepared by the analytical laboratory documenting all the

activities associated with sample analyses. At a minimum, the following will be

included in the report.

• Results of the laboratory analyses and QA/QC results, including case narrative

• All protocols used during analyses




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• Chain-of-custody procedures, including explanation of any deviation from those

identified herein

• Any protocol deviations from the approved sampling plan

• Location and availability of data

• QA2 data required by Ecology

• Electronic data deliverable in EIM format

As appropriate, this sampling plan may be referenced in describing protocols.

9 .0 REPORTING

9 .1 Quality Assurance/Quality Control Report

The project quality assurance representative will prepare a QA/QC report based

upon activities involved with the field sampling and review of the laboratory

analytical data. The laboratory QA/QC reports will be incorporated by reference.

This report will identify any field and laboratory activities that deviated from the

approved sampling plan and the referenced protocols and will make a statement

regarding the overall validity of the data collected. The laboratory QA/QC report

will be incorporated into the final report.

9 .2 Final Report

A written report shall be prepared by BergerABAM documenting all activities

associated with collection, compositing, transportation of samples, and chemical

analysis. The chemical analytical report will be included as an appendix. The

following will be included in the Dredged Material Characterization Report.

• Type of sampling equipment used.

• Protocols used during sampling and testing and an explanation of any deviations

from the sampling plan protocols.

• Logs of the grab samples showing descriptions of each sample as described in

Section 7.4.3 and indicating any visible horizons.

• Photographs of the grab samples.

• Methods used to locate the sampling positions within an accuracy of 3 meters.

• Locations where the grab samples were collected. Locations will be reported in

latitude and longitude to the nearest tenth of a second.




31 January 2017

Page 17 of 22

• A plan view of the project showing the actual sampling locations and DMMU

boundaries.

• Chain-of-custody procedures used and explanation of any deviations from the

sampling plan procedures.

• Description of sampling and compositing procedures.

• Final QA/QC report and validation report.

• Data results relative to DMMP and SMS criteria in a table.

• Measured water depth and tide information for each sample.

• A table with compositing scheme and depth of each sample in inches and

relative to MLLW.

• Bioassay results, including bioassay laboratory report, if applicable.

• Data in EIM format submitted to DMMO.

• QA2 data required by Ecology for data validation prior to entering data in their

Sediment Quality database. In addition, all field and laboratory analyses results

and associated QA data will be submitted to the USACE in electronic format.

• Project cost data will be forwarded to the DMMO separately.

1 0 .0 STUDY TEAM AND RESPONSIBILITIES

1 0 .1 General

The SAP includes (1) project planning and coordination; (2) field sample collection;

(3) laboratory preparation and analyses; (4) QA/QC management; and (5) final data

report. A short pre-sampling conference call will be scheduled with the DMMP

agencies prior to starting the sampling program. The program will use the following

team members and responsibilities.

10.1.1 Project Planning and Coordination

Ms. Victoria England of BergerABAM is the primary contact for characterization

activities and project permitting coordination.

10.1.2 Field Sample Collection

Ms. England will provide overall direction to the field and laboratory programs and

Ms. Carissa Watanabe will coordinate field activities. Ms. Watanabe will be

responsible for assuring that all the required logistics elements and protocols are

followed, including accurate sample positioning, sample handling and field

decontamination procedures, physical evaluation and logging of samples, and chain




31 January 2017

Page 18 of 22

of custody of the samples until delivered to the analytical laboratory. Samples will

be collected using equipment owned and operated by a subcontractor licensed to

work in the state of Washington. The power grab operator will be provided with this

SAP and will be required to follow the procedures described herein. The power grab

operator will record any deviations from the SAP in their daily logs.

10.1.3 Laboratory Analysis

Analytical Resources, Inc. will perform chemical analysis for this project. Analytical

Resources will be provided with this SAP and will be required to follow the

procedures described herein. The laboratory staff will record any deviations from

the SAP in their analytical data package for the project.

10.1.4 Quality Assurance/Quality Control Management

Ms. Sally Fisher will provide QA/QC oversight and senior review for the field-

sampling and laboratory programs. Ms. England will review laboratory QA/QC data

to assure validity of data and conformance to QA/QC requirements and will provide

a written QA/QC report.

10.1.5 Final Data Report

Ms. England will be responsible for preparation of the final sampling data report

identifying sample locations, field and laboratory methods, QA/QC, lessons learned,

and data results.

11.0 REFERENCES

BergerABAM. Makah Emergency Spill Dock Expansion – Proposed Sampling

Approach for Dredged Material Characterization memorandum. 1 September

2016.

Dredge Material Management Office, 2016a. “Dredged Material Evaluation and

Disposal Procedures (User’s Manual).” August 2016.

Dredge Material Management Program, 2016b. “Puget Sound Sediment Reference

Material: Requesting, Analyzing, Validating, and Reporting Data.” March 16,

2016.

Landau Associates, 2013. Geotechnical Engineering Report, Proposed Commercial

Dock Replacement, Port of Neah Bay, Neah Bay, Washington. 17 October 2013.

PSDDA. 1988. Dredged Material Evaluation and Disposal Procedures. A User’s

Manual for the Puget Sound Dredged Disposal Analysis (PSDDA) Program.

Prepared by U.S. Army Corps of Engineers, Seattle District;

U.S. Environmental Protection Agency, Region 10; Washington Department of

Natural Resources; Washington Department of Ecology.




31 January 2017

Page 19 of 22

PSEP. 1986 as updated in 1989, 1991, 1995, and 1997. Recommended protocols for

measuring conventional sediment variables in Puget Sound. Prepared for the

Puget Sound Estuary Program, U.S. Environmental Protection Agency,

Region 10, Office of Puget Sound, Seattle, WA.

SMARM. 2002. DMMP Clarification Paper—Ammonia and Toxicity Testing.

Prepared by Justine Barton, U.S. Environmental Protection Agency, Region 10,

Seattle, WA. April 29, 2002.

SMARM. 2003. DMMP Issue Paper—Revisions to the bioaccumulative contaminants

of concern (BCOC) list. Prepared by Erica Hoffman, U.S. Environmental

Protection Agency, Region 10, Seattle, WA. April 29, 2002.

USACE. 1989. Puget Sound Dredged Disposal Analysis (PSDDA) management plan

report; unconfined open-water disposal of dredged material phase II (north

and south Puget Sound). U.S. Army Corps of Engineers, Seattle District,

Seattle, WA; U.S. Environmental Protection Agency, Region 10, Seattle, WA;

Washington State Department of Natural Resources, Olympia, WA;

Washington State Department of Ecology, Seattle, WA.

Washington State Department of Ecology, 2016. EIM database Ecology EIM

database. Available at: https://fortress.wa.gov/ecy/eimreporting/. (Accessed

5 August 2016).

Washington State Department of Ecology, 2016. Facility/Site Database. Available at:

https://fortress.wa.gov/ecy/facilitysite/SearchData/ShowSearch.aspx?ModuleT

ype=FacilitySite&RecordSearchMode=New. (Accessed 5 August 2016).

Washington State Department of Ecology, 2016. Level 1 Investigation Summary &

ERTS entry: F/V California Horizon Diesel Spill – Neah Bay 4-6-16. 1 July 2016.

Washington State Department of Ecology, 2015. Sediment Cleanup Users’ Manual II.

Publication No. 12-09-057. March 2015.

https://fortress.wa.gov/ecy/eimreporting/

https://fortress.wa.gov/ecy/facilitysite/SearchData/ShowSearch.aspx?ModuleType=FacilitySite&RecordSearchMode=New

https://fortress.wa.gov/ecy/facilitysite/SearchData/ShowSearch.aspx?ModuleType=FacilitySite&RecordSearchMode=New




31 January 2017

Page 20 of 22

Table 1. Compositing Scheme and DMMU Volumes

DMMU ID

Sample Station ID

Dredge Depth Elevation + 1-ft

OD (ft MLLW)

Assumed Sample Elevation (ft MLLW)

Approximate Total DMMU Volume

(cy)

1

S-1

-26

-23 31,787

S-2 -22

S-3 -24 S-4 -23.5

2

S-5 -23 31,983

S-6 -21

S-7 -20 S-8 -20.5

3

S-9 -19 31,991

S-10 -19

S-11 -18 S-12 -18

4

S-13 -19 31,912

S-14 -18

S-15 -19

S-16 -20

5

S-17 -17 31,997

S-18 -17.5

S-19 -16

S-20 -16

6

S-21 -17

31,791 S-22 -17

S-23 -14

S-24 -13

7

S-25 -26

-16 16,570

S-26 -19

S-27 -16

-7

S-28 -12

Approximate Total Dredge Volume (cy) 208,000




31 January 2017

Page 21 of 22

Table 2. DMMP and SMS Chemical Evaluation Criteria1

Chemical

DMMP Criteria SMS Criteria

SL BT ML SQS CSL

Conventionals

Total Solids (%) -- -- -- -- --

Total Volatile Solids (%) -- -- -- -- --

Total Organic Carbon (%) -- -- -- -- --

Ammonia (mg/kg) -- -- -- -- --

Total Sulfides (mg/kg) -- -- -- -- --

Metals2 mg/kg dry wt.

Antimony 150 --- 200 -- --

Arsenic 57 507.1 700 57 93

Cadmium 5.1 -- 14 5.1 6.7

Chromium 260 -- -- 260 270

Copper 390 -- 1,300 390 390

Lead 450 975 1,200 450 530

Mercury 0.41 1.5 2.3 0.41 0.59

Selenium -- 3 -- -- --

Silver 6.1 -- 8.4 6.1 6.1

Zinc 410 -- 3,800 410 960

Organometallic Compounds

Tributyltin – bulk (ug/kg) -- 73 -- -- --

PAHs

LPAH3 µg/kg dry wt.

Total LPAH4 5,200 -- 29,000 370 780

Acenaphthylene 560 -- 1,300 66 66

Acenaphthene 500 -- 2,000 16 57

Anthracene 960 -- 13,000 220 1,200

Fluorene 540 -- 3,600 23 79

Naphthalene 2,100 -- 2,400 99 170

Phenanthrene 1,500 -- 21,000 100 480

2-Methylnaphthalene 670 -- 1,900 38 64

HPAH3 µg/kg dry wt,

Total HPAH5 12,000 -- 69,000 960 5,300

Benzo(a)anthracene 1,300 -- 5,100 110 270

Benzo(a)pyrene 1,600 -- 3,600 99 210

Total Benzofluoranthenes6 3,200 -- 9,900 230 450

Benzo(g,h,i)perylene 670 -- 3,200 31 78

Chrysene 1,400 -- 21,000 110 460

Dibenzo(a,h)anthracene 230 -- 1,900 12 33

Fluoranthene 1,700 4,600 30,000 160 1,200

Indeno(1,2,3-c,d)pyrene 600 -- 4,400 34 88

Pyrene 2,600 11,980 16,000 1,000 1,400




31 January 2017

Page 22 of 22

Table 2. DMMP and SMS Chemical Evaluation Criteria1 (continued)

Chemical

DMMP Criteria SMS Criteria

SL BT ML SQS CSL

Miscellaneous Extractables3 µg/kg dry wt.

Dibenzofuran 540 -- 1,700 15 58

Hexachlorobutadiene 11 -- 270 3.9 6.2

N-Nitrosodiphenylamine 28 -- 130 11 11

Benzoic Acid 650 -- 760 650 650

Benzyl Alcohol 57 -- 870 57 73

Chlorinated Hydrocarbons3 µg/kg dry wt.

Hexachlorobenzene 22 168 230 0.38 2.3

1,2-Dichlorobenzene 35 -- 110 2.3 2.3

1,4-Dichlorobenzene 110 -- 120 3.1 9

1,2,4-Trichlorobenzene 31 -- 64 0.81 1.8

Phthalates3 µg/kg dry wt.

Bis(2-ethylhexyl)phthalate 1,300 -- 8,300 47 78

Butyl benzyl phthalate 63 -- 970 4.9 64

Diethyl phthalate 200 -- 1,200 61 110

Dimethyl phthalate 71 -- 1,400 53 53

Di-n-butyl phthalate 1,400 -- 5,100 220 1,700

Di-n-octyl phthalate 6,200 -- 6,200 58 4,500

PCBs3 µg/kg dry wt.

Total PCBs 130 387 3,100 12 65

Pesticides3 µg/kg dry wt.

4,4 DDD 16 -- -- -- --

4,4 DDE 9 -- -- -- --

4,4 DDT 12 -- -- -- --

Total DDT -- 50 69 -- --

Aldrin 9.5 -- -- -- --

Dieldrin 1.9 -- 1700 -- --

Total Chlordane8 2.8 37 -- -- --

Heptachlor 1.5 -- 270 -- --

Phenols3 µg/kg dry wt.

Pentachlorophenol 400 504 690 360 690

Phenol 420 -- 1,200 420 1,200

2 Methylphenol 63 -- 77 63 63

4 Methylphenol 670 -- 3,600 670 670

2,4-Dimethylphenol 29 -- 210 29 29

Notes:

1. DMMP = Dredged Material Management Program (August 2016), SMS = Sediment Management Standards

(March 2015).

2. Dry weight results are reported as milligrams per kilogram (mg/kg).

3. Dry weight results are micrograms per kilogram (µg/kg).

4. Total LPAH = The sum of acenaphthylene, acenaphthene, anthracene, fluorene, naphthalene and phenanthrene.




31 January 2017

Page 23 of 22

5. Total HPAH = The sum of benzo(a)anthracene, benzo(a)pyrene, total benzofluoanthenes, benzo(g,h,i)perylene,

chrysene, dibenzo(a,h)anthracene, fluoranthene, indeno(1,2,3,-c,d)pyrene and pyrene.

6. Total benzofluoranthenes = the sum of the "b," "j" and "k" isomers. The "j" isomer co-elutes with the "k" isomer,

thus the concentration of the "j" isomer is included in the "k" isomer concentration.

7. This value is normalized to total organic carbon and is expressed in mg/kg carbon.

8. Total Chlordanes = The sum of cis-chlordane, trans-chlordane, cis-nonachlor, trans-nonachlor, and oxychlordane.

SL = Screening Level

SQS = Sediment Quality Standards

CSL = Cleanup Screening Levels

BT = Bioaccumulation Trigger

ML = Maximum Level



TOC = Total organic carbon

Shading indicates that the criteria and results are TOC normalized. To normalize to total organic carbon, the dry

weight concentration for each parameter is divided by the decimal fraction representing the percent total organic

carbon content of the sediment.




31 January 2017

Page 24 of 22

Table 3. Proposed Sample Coordinates

Sample ID Coordinates Northing Easting

S-1 522597.7083 721118.1330

S-2 522337.0439 721277.7468

S-3 522534.2563 721561.0076

S-4 522076.2358 721731.7250

S-5 521869.9552 721769.0653

S-6 521957.3953 721573.4821

S-7 522093.0567 721399.1288

S-8 522189.6923 721155.7709

S-9 522051.7934 721117.4090

S-10 521947.9876 721305.1588

S-11 521849.9191 721129.6685

S-12 521753.6529 721303.8676

S-13 521783.4189 721492.6444

S-14 521616.1711 721477.6424

S-15 521653.1492 721627.2685

S-16 521625.2679 721775.2010

S-17 521713.6375 721107.1794

S-18 521626.5416 721286.6735

S-19 521551.8885 721119.6311

S-20 521491.7507 721305.3490

S-21 521539.4456 721424.6647

S-22 521475.1609 721541.9065

S-23 521404.6548 721450.6030

S-24 521334.1486 721796.1006

S-25 521391.1762 721717.2488

S-26 521479.3089 721770.1643

S-27 521241.6128 721796.1006

S-28 521273.7557 721916.4553

Coordinate System: NAD_1983_StatePlane_Washington_North

Sampling and Analysis Plan Makah Dock Extension

Dredge Material Characterization

Sheets

Project Site

_̂

Waadah Island

Neah Bay


Existing

fuel dock

Project site

Halfway Creek

Agency

Creek Confluence

Neah Bay

Villiage Creek Confluence

Woodland Ave

Confluence

Makah Tribe Reservation

0 500 1,000 2,000 3,000 4,000 Feet


PURPOSE: Collect sediment samples for chemical analysis to characterize proposed dredge material for the spill dock extension project.

APPLICANT: Makah Tribe SITE OWNER: Makah Tribe

ADJACENT PROPERTY OWNERS: Department of Natural Resources

Reference: NWS-2016-826

MAKAH TRIBE EMERGENCY SPILL

DOCK EXTENSION DREDGED

MATERIAL CHARACTERIZATION

SHEET 1: VICINITY MAP

WATERWAY: Neah Bay AT: Neah Bay COUNTY: Clallam

LAT/LONG: 48.36746 N/-124.61416 W

S/T/R: S11/T33N/R15W DATUM: MLLW=0.0 DATE: 25 October, 2016

Sheet 1 of 3

Q:\

Federa

lWay\2

016\A

16.0

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0\G

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F

-35

-30

-25

-20

Existing fuel dock


MLLW = 0

-15

-10

-5

MHHW = +7.95

0

!( +5

(!

Neah Bay

(!

Approximate shoreline

F 0 125 250 500 750 1,000

Feet


PURPOSE: Collect sediment samples for chemical analysis to characterize proposed dredge material for the spill dock extension project.



Reference: NWS-2016-826


DOCK EXTENSION DREDGED MATERIAL CHARACTERIZATION

SHEET 2: SITE PLAN EXISTING CONDITIONS


LAT/LONG: 48.36746 N/-124.61416 W

S/T/R: S11/T33N/R15W DATUM: MLLW=0.0 DATE: 25 October, 2016

Sheet 2 of 3

Legend


MLLW = 0

MHHW = +7.95

(! Outfalls

Q:\

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PURPOSE: Construct an extension to the existing commercial fishing dock to provide adequate, dedicated infrastructure to support an enhanced oil spill prevention

and response capacity in Neah Bay. APPLICANT: Makah Tribe SITE OWNER: Makah Tribe

SHEET 3: SITE PLAN - DMMUs





LAT/LONG: 48.36746 N/-124.61416 W S/T/R: S11/T33N/R15W DATUM: MLLW=0.0

DATE: June 2016

Q:\

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- ....

LEGEND:

DMMU

CID

MLLW

DREDGED MATERIAL MANAGEME NT UNIT

SAMPLE LOCATION

MEAN LOWER LOW WATER

o MLLW

10 ·10

-20 -20

·30 ·30

-40

2+00 3+00 4+00 5+00 6+00 7+00 8+00 9+00 10+00 11+00 12+00 13+00 14+00 15+00

-40

16+00

o MLLW

· 10

· 20

· 10

· 20

· 30 · 30

50 0 50

1"=50 ' scal e

100

feet

--- -- -

--

,,.

· 40 · 40

30+00 31+00 32+00 33+00 34+00 35+00 36+00 37+00 38+00 39+00 40+00 40+50

Legend

Potential Beneficial Use Site

Proposed Stockpile Area (Potential Future Upland Us)

Eelgrass Observed

Mixed Rock/Clam Beds Observed

I# (!


Creek Confluence Outfalls

Waadah Island

Stockpile Area

~1,050' Beneficial Use Site - Proposed Northwest Beach Enhancement / Dredged Material Benefical Use

Eelgrass Observed 1

Neah Bay

~910'

Mixed Rock/Clam

Beds Observed

Proposed

Dredge Area 2

I# Proposed Dock

Extension

I#

Existing breakwater

Neah Bay

I# (! (!

(!

Makah Tribe Reservation

PURPOSE: Construct an extension to the existing commercial fishing dock to provide adequate, dedicated infrastructure to support an enhanced oil spill prevention and response capacity in Neah Bay.





SHEET 5: POTENTIAL BENEFICIAL USE AREA

WATERWAY: Neah Bay

F

AT: Neah Bay COUNTY: Clallam

LAT/LONG: 48.36746 N/-124.61416 W S/T/R: S11/T33N/R15W 0 250 500 1,000 1,500 2,000 2,500

DATUM: MLLW=0.0 Feet

DATE: June 2016 Source: Esri, DigitalGlobe, GeoEye, Earthstar Geographics, CNES/Airbus DS, USDA, USGS, AeroGRID, IGN, and the GIS User Community

Note: 1. An eelgrass survey will be completed prior to placement of any dredged material.

2. A bathymetry survey will be completed before and after dredging is completed.

~5

00

' ~

77

0'

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Appendix A Sample Containers, Holding Times, Volume, and

Chemical Analytical Methods and QA/QC Criteria




31 January 2017

Page A-1 Appendix A

Table A-1. Sample Analytical Methods and Storage Criteria

Sample Type Analytical Methods Holding Time Sample Size (1) Temperature (2) Container Archive (3)

Particle Size PSEP (1986)/ASTM D-

422 (modified) 6 Months

100-200 g 4 degrees C 16 oz. glass jar

X

(75-150 ml)

Total Solids PSEP (1986) /

SM2540G 14 Days

125 g 4 degrees C

8 oz. glass jar

(100 ml)

Total Volatile Solids PSEP (1986) /

SM2540G 14 Days

125 g 4 degrees C

(100 ml)

Total Organic Carbon

SM 5310B/EPA 9060

(modified for sediments)

14 Days 125 g

4 degrees C (100 ml)

Ammonia

Plumb (1981) 7 Days

25 g 4 degrees C 4 oz. glass jar

(20 ml)

Metals (except Mercury)

6010/6020/ 7000 & 200 Series

6 Months 50 g 4 degrees C

4 oz. glass jar

2 years (40 ml) -18 degrees C

Semi-volatiles, Pesticides and PCBs

8082/8270

14 Days until

150 g (120 ml)

4 degrees C

SVOC: 8 oz. glass jar

Pesticides/PCBs:

8 oz. glass jar

extraction

1 Year until -18 degrees C

extraction

40 Days after 4 degrees C

extraction

Total Sulfides

PSEP (1986) / Plumb

(1981)

7 Days

50 g (40 ml)

4 degrees C (4)

4 oz. glass jar

Mercury 7470/7471 28 Days 50 g (40 ml) -18 degrees C 4 oz. glass jar




31 January 2017

Page A-2 Appendix A

Sample Type

Analytical Methods

Holding Time

Sample Size (1)

Temperature (2)

Container

Archive (3)

Tr ibutyltin (bulk)

Krone (1989) / Unger (1986) / (PSEP 1997)

6 months

50 g (40 ml)

-18 degrees C (5)

4 oz. glass jar

X

Bioassay

10-day amphipod

mortality test (acute toxicity)

20-day juvenile infaunal growth test (chronic

toxicity)

Sediment larval test

(acute toxicity)

8 Weeks

5 liters

4 degrees C (5)

5-1-liter glass or polyethylene

X; bioassay archives are not frozen

Notes:

(1) Recommended minimum field sample sizes for one laboratory analysis. Actual volumes to be collected have been increased to pro vide a margin of error and allow

for retests.

(2) During transport to the lab, samples will be stored on ice. All temperatures are +/- 2 degrees Celsius. The mercury and archived samples will be frozen immediately

upon receipt at the lab.

(3) For every DMMU, a 250-ml container is filled and frozen to run any or all of the analyses indicated.

(4) The sulfides sample will be preserved with 5 ml of 2 Normal zinc acetate for every 30 g of sediment.

(5) Headspace purged with nitrogen.




31 January 2017

Page A-3 Appendix A

Table A-2. Laboratory QA/QC Requirements for Conventionals and COCs

Analysis Type Method Blanks1

Replicates1 Triplicates1 CRM/RM MS/MSD1 Surrogates2

Semivolatiles3,4 X5 X6 X X X

Pesticides3,4 X5 X6 X X X

PCBs3,4 X5 X6 X7 X X

Metals X X X X

Ammonia X X

Total Sulfides X X

Total Organic Carbon

X X X

Total Solids X

Total Volatile Solids X

Grain Size X

Tributyltin X X6 X X

Notes:

CRM = Certified Reference Material; RM = Reference Material; MS/MSD = matrix spike/matrix spike duplicate 1 Frequency of Analysis (FOA) = 5 percent or one per batch, whichever is more frequent. 2 Surrogate spikes required for every sample, including matrix spiked samples, blanks, and reference materials. 3 Initial calibrations required before any samples are analyzed, after each major disruption of equipment, and when ongoing

calibration fails to meet criteria. 4 Ongoing calibration required at the beginning of each work shift, every 10–12 samples or every 12 hours (whichever is more

frequent), and at the end of each shift. 5 FOA = one per extraction batch. 6 Matrix spike duplicates may be used. 7The Puget Sound Sediment Reference Material must be used for projects in Puget Sound.




31 January 2017

Page A-4 Appendix A

Table A-3. Solid Phase Bioassay Performance Standards and Evaluation Guidelines

Bioassay Negative Control Performance Standard

Reference Sediment

Performance Standard

Dispersive Disposal Site Interpretation Guidelines

Nondispersive Disposal Site Interpretation Guidelines

1-hit rule 2-hit rule 1-hit rule 2-hit rule

Amphipod MC ≤10% MR - MC ≤ 20% MT - MC > 20% and

MT vs. MR SS (p=.05) and

MT - MC > 20% and

MT vs. MR SS (p=.05) and

MT - MR > 10% NOCN MT - MR > 30% NOCN

Larval NC÷I ≥0.70 NR÷ NC ≥ 0.65 NT ÷ NC < 0.80 and

NT / NC vs. NR/ NC SS (p=.10) and

NT ÷ NC < 0.80 and

NT / NC vs. NR / NC SS (p=.10) and

NR / NC - NT / NC > 0.15 NOCN NR / NC - NT / NC > 0.30 NOCN

Neanthes growth

MC ≤ 10% and

MIGC > 0.38

MR ≤ 20% and

MIGR÷ MIGC ≥ 0.80

MIGT ÷ MIGC < 0.80 and

MIGT vs. MIGR SS (p=.05) and

MIGT ÷ MIGC < 0.80 and

MIGT vs. MIGR SS (p=.05) and

MIGT / MIGR < 0.70 NOCN MIGT / MIGR < 0.50 MIGT / MIGR < 0.70

M = mortality N = normal larvae I = initial count

MIG = mean individual growth rate (mg/individual/day) SS = statistically significant NOCN = no other conditions necessary N/A = not applicable Subscripts: R = reference sediment, C = negative control, T = test sediment



Appendix B Analytical Resources, Inc. Sediment Reference Certificates

Aluminum 59600 7580 6.41 3640 - 11500 2860 - 12300 ·,.--·-· ···· ··· · .,.·- ..- - - - - - - ·- -"'·--·-·-······,,·.,...... ... . . .., .... .•.. ,..,......,... .. .. . . . . . .. . . . .. .... ... . . ., " "'"""' ··· ·" , , , ,_ . . .. .. ..... ......... . , , . , , . ... . •. , .

;-. . . . .- - - - - -..·- ·· •-•· .. . . .. .. -, . ,,, ..., . . . . . .•..•••.·... s··, ,. , •. , , , , , . , , ----

"Mag_n : : um .,_. ...w..- . •w•• j 4 _8 3_o _ o_ ·...·.4..··.·.·0·,·0···, ······. ···-·'··-····-···~--2 2 6_0_- _ 3_6-_7 0-......,·-. .·... ,. ..., ...........·-.- 1 9-5 0 --_ -3-9 8 0_ _ ......... ,

H J•' ""

Page 1 of 4 Lot: D088- 540

S 1 f< ' - , . . '"1:: ·; •-s--: . c : , 1 , 1 . , f f:-:,.:'l'X• : n ::1

ERA Reference Materials

A Waters Com pany ■ Certificate of Analysis■

Product:

Catalog Number:

Lot No.

Certificate Issue Date:

Expiration Date:

Revision Number:

Revision Date:

CERT!FICATiON

Metals in Soil

540

0088-540

October 02, 2015

September 30 , 2018

1.0

October 02, 2015

Total Certified QC Performance

PT Performance

.Parameter Concentration Value1 Uncertainty2 Acceptance Limits3 , Acceptance Limits4

_ mg/kg mg/kg % mg/kg mg/kg

_ Antimony ; 233 107 2.50 D.L. - 223 23.3 - 273

[ Arsenic - - - - - - -..ij- - 1-25 ·-··.·.·-"""''' "..'1 1"·4- ··-· .8 -1 0- - - , - - 8-.9 -7--- ·-1 39 ·····-...J--. - -7-9. -8-- ·1 -6 -1 - . .. . . . . . . ·- - - - - - - - - - - - - - ·-·-"""·· ···................---·-'---- .·. .

' B i - -- - .,, p _ , · . . t ., !9 . ... . ... .1"8 1 . T"= ..·· :95 . ..... ·-·-" t50 : 2 t2 T 1 3 2_- _ 2- 30 - , ..; .

.!.B eryllium ... - - - - -0-- - 1-00- - -c.....---9- 3.8

- 2- .6-8 - - - .. -7,·.7.-....6.......-.,.,1•- 10- l- - - 69-.8 -- 11-8 - .. .: : Boron 1_27 J ,--._1_0_8 1 5_._36_ _ ......_.... ! -·7- _1_3_6

64.6 - 151

: : : i m · ·.-.- - - ----··- ·· · L 1: : : 0 I :: : : ::: - - - --· •,.y w .w,..- ·-· .. - - - ·,.·. ,· . .·..·,•.·•.• .. ,•. . .., ,,,...., , .. .,. .- - - · · . ,y. . w, ,,_ . ,,. ,._ ..., . . . .,, ,, ., . .y y -,•w .,_ .,.. , . .. , .-.-.w·· w , . . , ,... w ,, . , . .

[C hromium 142 109 5.66 -----· ·-'------................ ._., . .._. , , --- ---······' '" •"'·· •""·'

, ...,.4.. ::: : ;:o . 86.9-131

68.3-118

75.8 -142

[C obalt i 113 108 4.34 90.3 - 125 80.0 - 135 - - - -,• •-,_ ., . , . , . , ,.••••w,. c, .w ;;, . ,w,,•.•.·.•. . . . . . . . ,_., . , . , ,_ ,_ w.,. , . . , . . ,, ,_• .w.•.•.•;.•.w .-.•.w.w, .•.w ·.h <;.-.•.w·. ,;.•;. ._ , , .,, , ,_ , , . ._

_, _ w_ w, .,u, ., •, . •. .•.. .-,,•........ w •. w. •• h . , ,. , ,. ,N,.WV, .

!Copper 136 122 8.30 99.1 - 144 91.1 - 152

29800 : 14600 7.88 6630 - 22700 5300 - 24000 ...... .... ..,.h "h " "'"™ '_ ,.,,,_ .,_ ... . . ,,, , , _,-,· , , _ . --

jl ead 125 102 13.2 82.9-120 72.2 - 131

, _=,,_ - . - ..--..,.......,........

[M anganese 625 407

!Mercury 9.32 9.36

Molybdenum 125 110

,Nickel 91.0 79.7 :. .

Potassium 29800 2910

2.67 331 - 483 310 - 504

10.4 6.74 - 12.0 4.80 - 13.9

3.10 86.5 -133 76.9- 142

5.01 66.1 - 93.4 57.0 - 102

3.64 2060 - 3770 1820 - 4010

ISelenium 205 186 2.58 145 - 227 127 - 245

44.6 41.8 8.45 31.5 - 52.1 27.7 - 56.0

14100 545 4.85 393 - 696 285 - 804 },,.·,~ •·'-'·-.,·,.w·.·,-.-·"··'·~·" -" - ••••• .._,.,...,,.,..,. ....·.,.·.,·· ·..· .......... ,.,.,... ..._·,. . .·..· "·•·•·•w- • •-,• •·...·.·.•,·. ..·. ·, ••· ··· •"·, .. .-.'.·..... .·. •··"'""" · · '· ·,·•,• .,.,.. ·•·... •.,,......."· "'" ....,.,..,..., .,., .,.. .,,,,,.,. ,. -•• ""·'"' "'-" '"" "" '-'• ~• «·,··•,,..,....,._. .·..•·•··,·····.·. ,,, .....................................,w•w~ ,._,. . , ._., , , .

281 99.2 6.04 79.4 - 119 69.8 - 129

16341 Table Mount ain Pkwy• Golden, CO 80403 • T: 800.372.0122 • 303.431.8454 • ww w.eragc.com

_,--., ......-...- - - -··-- -,--- - - ---,-- - , -,···.·-····.·.,.···....··.·.···..·-'·····,·,..··..·.•.,.. .. .,,,....••. . ,· .. - .,_ - - - - ----·•--·•-...-·,,....,•• ..,.. ...·. · . ··········. ·.··.....· ·,·., . ·,. ·.-·-·· ··.; , ..... ........ ......., ...,... .., ....,.. ......, .. .,. . . ., .. .. , .. , , .., ,...., .. ....... ..._,

http://www.eragc.com/

Parameter

Total Certified QC Performance

Concentration Value1 · Uncertainty2 Acceptance Limits3

mg/kg mg/kg % mg/kg

220 200 3.79 159 - 241 - - - - - - ••••"•••••••••••• •- •- - -..•••.• M••• ••-'- '" " " •""" •••••• ••• •• ••••• •• •••••••• • • ••••••• •·-

137 • •••"'' "'' ''' " •• •••• ••••••:-' • • • • • • ••••• •. .,_.-, - - •••• ••••••••••• •- - ' - - ••.. •••• ••.•-.- ,. ,- , _ .,M••..••.•., •«. •- - -

122 ;- -•-•. . . , . , ,v.-,,,-,,,,,,,,._,...,, ....,., ,.,. ., -, . , . , . , . - - -- - ···- •··

2.46 _.,. . . , , ,, , ,,_.. .. .. . ,. .. ,._ . • ,w,.,_ ,,w.,_., . ·..

94.2 - 150 , , . . , . . . . . . . . , , . . . . , ,_ . . , , . , , , . ,. ._., .

PT Performance

Acceptance Limits4

mg/kg

138 - 262 • _,.,,., ,, .•.. ,•. ..·..•.-•• - - - - • ••• •- ·

71.5 - 173 ' ·-·· _ _ _ , . , , .,.,, •.•. ,..,,.,,..,_,

. · i

· v anad i um

: Zinc • ••w •••- -- -

.. --· ,. ·-· 146

266

· - . , . . . . . .,,. .

103 ·.--···-·

7.52

7.50

-·- ····-·-····"-· -- - --·-··· ······ · · ·· · - - - --.. ---·····-·'·"•·,-·· :- ..... 80.3 - 126

186 - 269

,.... .............,. ... ·.. 68.3 - 138

160 - 295

- - - - -· ·'--

- •- •,,•, • .,..,.....,._,.,, •••••• y •• - . . . . . . . , • • . . ,_., , . , ,. . . . .. , . , .•, • •• "' •- w -' . • w •y y •-, , •. , ., w " • "" ' "" ' V" •• , . . .- ' -" ,• ., . , , - •w • .,.•••••=• • .,.,••..• . , ._ <.-•~, y

..

Reference Materials

■ Certificate of Analysis ■

! Tit anium 2380 308

... ,, ,. .

6.87 , · .

; .....

88.0 - 527 67.0 - 548 · - -- ···. .·· "·' ·' ·-· -

: Uran ium 14.9 11.5

3.14 9.43 - 13.6 9.36 - 13.1

A.NALYT!CAL VER!FlCAT!ON

Parameter

Certified

Va lue 1 Proficiency Testing Study NIST Traceability •= • ·· ., ... .., .. .... , . - .. - • ••. . . ,, •••-•- - =••- - - < • • • • • < - -•- •• •• •" • •• ••, .- •• h, - • • • •• - ..,.. •., . -•/ ' "" ., <•

C« '< •- •• - • • ••--••- •·· •• •••• •·•··· - •"•<" • = • • - , - • • • • · • · · • · · , . '= • · V··" ••"" ·•,,, , "'."~- • ••' ,· w, .,_ ean !, e: overy s • b .• =•- - um :r _ -• - '.: '_ ! - mg/kg mg/kg % %

- ..... · · - - ' " ..... ...... · - · --

,

, ., ,L · ·- - --··--···········•·····.········,.·,,, ,·,,..., j

. -- , . ·····-··--

]Boron

108 - - - --······-·-·- -

108 82.2 92 l c dm ium 9.3 2 93. -2 - ··· 92.3 " ,w 1 83, , , .......

£a 1i - --·---· -·· - - ' s s30- ·r 6si o- -; ·"_asA 126 I •.... = ,,. --•- -

;_.,- ··,···,...····..... ...·...............,,,.,..-.--,- ·- --- ........... , .,. , , , . . . , . , , , ,...,•.. ..., . .,..,..;.,.,-.....,.· .···.. .-,.· ···- ·, ,, . . "' - ,, · .,·.···--· - · ·----· ..., ., , , .. , .

: Ch romium 109 ' 109 89.9 , 181 j

ic-;;b 1t . r .wa 1 os ' 96. o .. 137 i i,---- - ....,_..,.,. .

; _ , - - -, .._ .., . , ..,..., ,,..

'c opper 122 122 88.2 180

, . ,

[Mag n esium,

· 2960 l 2960 ; 90.0 ; 132 •

, . ,_ , . , , , . , ••• . . , . . , , . . , , ._ .. . . . , , ,_ ,, . -. . . , . . . . . . . ,_ ,,_ ,,v ,. ; :

>... . . . . . . , , . . - ·A,.. . . . . .

, . \. . . . . · ····· ·· ·• ··• · ··, ,_ -. . , . . , . . . , , . , . . . ._ ,, , . . . . . . . . . , , . , . ._ •. . .• •• • - · ' . . • • • •• • ,_,. · . , ,_.,w ,w,, . .w , . . , . , -,- ·•·••·· · ·•.•· -r · -,..,,....- ;.,. . . . ,•• ••-.-•• > ,-, .v ,. , , .•.•. . , , , , , , , . -, , . , . , ... . .-, ,

.w, , . .•

w.v ·¾ ! Mang anese 407 · 407 .. 94.0 ; 147. · -

··""' . , ....,-:: .... - , .,. .

9 .36 :, •• . . . , . .._, ,, ., , . ,• • . ,_..,• . . . w ·• ·· •• ••· • ··· ··· - ·• ··· ···· ·.·. •· w.---..,..,,c., , w, _ .,.-. ._ ,. . .... .v •. . . . ,

9.36

• ·· ·. .• . . . . , . . . . , . , . ._ , .· w,.·v · ·•·

; ,j:

, y . . ..· . .. C

100 133 1 . . . . ·. . . ...,..=,...·..

Molybdenum 110 . 110 ··· · · s a5. · '. 1 s 1 : •··········• . . . . , . , , , . , , , . . , , . . , , , ._ .. , , . . · . . , . . . . . . . . . . . , ._ ,, . . , . , . . , . , . . . , , . , . . . . . , . , . , . . . , , . . , . . , .m .h ······················. . , ..

. . w·-, · .·.·· v,_-,. ,..,, ,.,...

•· · .,.,,.,. . . . . . . , ,, . . ,; _. " ·

:Nickel

Potassium

79.7 ·

2910 .79.7 89.9 181 2910 90,8 133

Page 2 of 4 Lot : D088 - 5 40

16341 Table Mountain Pkwy• Golden, CO 80403 • T: 800.372.0122 • 303 .4 3 1. 84 54 • w ww.eraqc . com

IMercury

Aluminum '--·-·,,.,.. .·.·- - -

- - - ·····",..

...•.·,.,.,..,.,,. ,,_c 7580

...,..........,-, ... + - -, ,7580

,.,...,.,.,..,.- - -·,.,. ...... .. . ... . . . ..,. ,- -· ,,·"·7"·"·7··."-1- - ' 140

Ant imony 107 107 46.0

147

i Ar se-n -ci - . ..... ... ........... .... .. ...- -. · 114 .. 1 ··· ······ 114 78.3 180

> ,..,N.·----- - - ,.· • • " ••••' ·' " ••·• •·•· "' " •" - - w·,, ,, ... . ·•-• 7 · ···'" •-· • ~,, .,.·..•"··'

'Barium 181 181 92.3 157

lBeryllium _ _ _ _ .,,,Wll_ ,. , . , , . . . , . , , , . . . . . . . . -. .. , .,. .-.w .,_., .., , . . ,_ ., , . , . , , . , . . . . , . . . . . ... ...

93.8 _ ._

93.8 94.8 148

!Iron ·-- ---·14600 l 1 4-_6-0 0 , ······ · w

89.7 ,-. , . , . . ,., .. ., ,. ,._,

139

, Le ad . , . .,. .. , .•, , - >,''' , " " 0

102 , . .............. . .. " • ·•· ,. •·••••·••'

102 A,..,,.. ... .,.,,,.,,-,.,.•,.,-,·, >"" ·

90.0 . •

191

http://www.eraqc.com/

Guidance for SRM Distribution & Reporting 3-16-16 Page 1 of 11

Puget Sound Sediment Referenee Material:

Requesting, Analyzing, Validating and

Reporting Data

Introduction

The Puget Sound Sediment Reference Material (SRM) has been developed to help

assess/evaluate measurement accuracy and monitor laboratory performance when analyzing

for chlorinated dioxin, furans, and biphenyl compounds in sediment samples collected from

the Puget Sound area. The SRM is currently available free of charge, though recipients must

pay shipping costs. This document provides instructions for obtaining, analyzing, and

reporting on the SRM. The guidance and procedures are intended to ensure that SRM users:

• Report methods used for analysis

• Report QA/QC procedures used to verify and validate results, and

• Report results that can be included in periodic recalculations of acceptance limits

The Puget Sound SRM has been established for chlorinated dibenzo-p-dioxins / chlorinated

dibenzofurans (CDD/CDF) and/or chlorinated biphenyl (CB) congener analysis using high

resolution gas chromatography / high resolution mass spectrometry (HRGC/HRMS)

methods. This SRM is also suitable for Aroclor analysis using gas chromatography/electron

capture detection (GC/ECD) methods.

Request Procedure

The Seattle District Corps of Engineers, Washington Department of Ecology, and US EPA

Region 10 have assigned staff to distribute the Puget Sound SRM in support of agency

missions, including regulatory programs. The request procedure is as follows:

• Obtain the electronic Puget Sound SRM Request Form from the appropriate agency

involved with the project (see agency contact list below), or from the Seattle District

Corps of Engineers Dredged Material Management Office (DMMO) website.

• Return completed form to agency contact.

• Agency contact reviews and certifies/signs the bottom of the form as an "authorized

agency requester", and then forwards the signed form to the EPA Region 10 SRM

Manager (Raymond Wu) for processing.

• Request is processed, typically within a week.


Examples of how the request process works:

1. CWA 404 permit applicants would request from and submit the completed form to

the Corps of Engineers DMMO contact.

2. A CERCLA PRP would submit the request form via EPA.

3. The State of Washington's ambient monitoring program would submit the form via

Ecology.

The authorized agency contacts are available to help with any questions about the Request

Form. Submission of incomplete forms may delay the request processing.

Authorized Agency Contacts:

Seattle District Corps of Engineers - Dredged Material Management Office (DMMO):

David Fox (206) 764-6083, [email protected]

Lauran Warner (206) 764-6550, [email protected]

Kelsey van der Elst (206) 764-6945, [email protected]

Heather Fourie (206) 764-6713, [email protected]

Washington Department of Ecology:

Laura Inouye (306) 407-6165, [email protected]

Tom Gries (360) 407-6327, [email protected]

US Environmental Protection Agency Region 10:

Justine Barton (206) 553-6051, [email protected]

Erika Hoffman (360) 753-9540, [email protected]

Donald Brown (206) 553-0717, [email protected]

Raymond Wu (206) 553-1413, [email protected]

Shipping

The Puget Sound SRM is stored at EPA's national Quality Assurance Technical Services

(QATS) contractor located in Las Vegas, Nevada. Lab contacts listed on the Request Form

should be prepared to confirm shipping details (including UPS or FedEx account number) if












contacted by the EPA QATS contractor. The QATS contractor will generally ship the SRM

within 24 hours of receiving the completed Request Form from the EPA Region 10 SRM

Manager. The SRM will arrive with specific instructions on handling and storage

requirements, data reporting requirements, as well as chain of custody paperwork.

When the SRM has been shipped, the EPA QATS contractor will provide a notification email

to the EPA Region 10 SRM Manager, the authorized agency contact (as indicated on the

Request Form), and the destination laboratory. The email will include the project name as

indicated on the Request Form.

SRM Storage Requirements

Each amber glass bottle contains approximately 30 grams of the Puget Sound SRM.

The SRM contains compounds that are light sensitive and should be protected from light

during storage. Store the SRM at 4°C ± 2°C until SRM preparation and analysis.

SRM Analysis Requirements

The SRM is to be analyzed as described in the appropriate methods employed for the

analysis of CDD/CDF and/or CB congener analytes using HRGC/HRMS instrumentation

and/or Aroclors using GC/ECD instrumentation .

The following analytical methods may be used in the analysis of the SRM:

• SW-846 Method 8082A (or current revision), "Polychlorinated Biphenyls (PCBs) by

Gas Chromatography"

• SW-846 Method 8290A (or current revision)," Polychlorinated Dibenzo-p-Dioxins

(PCDDs) and Polychlorinated Dibenzofurans (PCDFs) by High-Resolution Gas

Chromatography/High-Resolution Mass Spectrometry (HRGC/HRMS)"

• Method 1613B (or current revision), "Tetra- through Octa-Chlorinated Dioxins and

Furans by Isotope Dilution HRGC/HRMS"

• Method 1668C (or current revision), "Chlorinated Biphenyl Congeners in Water,

Soil, Sediment, Biosolids, and Tissue by HRGC/HRMS"

Data Verification/Validation

SRM users may be held to different data validation requirements, depending on their

program and project circumstances. Data must be validated to EPA Stage 2B but it is

strongly recommended that Stage 3 or better validation be conducted. For example, the

interagency Dredged Material Management Program (DMMP) strongly recommends third

party Stage 4 validation for all TCDD/F data. Any validation narrative must indicate the


validation stage used. Data validation stages are described in EPA-540-R-08-005 (see

References).

Data Reporting

Individual laboratories typically provide all project data and validation reports to their

clients. The client/project proponent is responsible for ensuring that all information relative

to the SRM, including associated QA data, is sent to the original agency requester. For

DMMP projects, submittal of the complete validated data package to the DMMO contact

fulfills this requirement.

For SRM data meeting established QA requirements, the agency contact will submit the

validated electronic data deliv erable/data summary sheets (or the equivalent) and validation

reports relevant to the SRM to the EPA Region 10 SRM Manager. Changes made by the

data validator (e.g. modification of data qualifiers) must be clearly indicated on the data

sheets. SRM data not meeting established QA requirements will not be forwarded to EPA's

QATS contractor; however, the QATS contractor will be notified of the QA failure for their

records.

The following are the minimum required deliverables for Puget Sound SRM data

submissions. Also included below are optional deliverables that may or may not be needed

depending on the available deliverables.

Required Deliverables

1. Data Validation Report - report that documents the analytical quality of the data. In

regards to the Puget Sound SRM, this report serves two functions. First, it confirms that

data validation was completed, as the guidance requires data validation to at least EPA

Stage IIB. Second, the report documents the reasons for any failure to meet method,

procedural, or contractual requirements, as well as provides an evaluation of the impact

of such failure on the overall data set.

2. Electronic Data Deliverable (EDD) - an electronic, tabular format for sharing,

manipulating, and using data. EDDs should be submitted in a comma- or tab-delimited

file or as a Microsoft Excel spreadsheet. If in doubt about what to request from the lab,

ask for an EDD in EIM format.

3. SRM Sample Data Summary Report- similar to a Form 1 from the Contract

Laboratory Program, this report should provide a summary of the analytical parameters,

analytical results, reporting limits, and laboratory/validation qualifiers. At a minimum,

the sample data summary report should include the following:


• Identification and quantitation of target analytes including dilution and reanalysis

• CAS numbers

• Laboratory name

• Project number

• Project name

• Sample ID number (SRM bottle bar code)

• Agency sample number (if applicable)

• Laboratory sample number

• Date SRM received by the lab

• Date and time of analysis

• For Aroclor data, laboratory reporting limits and method detection limits

• For Chlorinated Biphenyl Congener and Dioxin/Furan data, reporting limits and

estimated detection limits

• Laboratory qualifiers and definitions

• Validation qualifiers

Optional Deliverables

1. Laboratory Case Narrative - laboratory report that describes the analytical process

used by the lab to analyze the samples and any problems encountered in processing the

samples, along with corrective action taken and problem resolution. The case narrative

should only be submitted with the SRM data if there were significant problems during

sample analysis that affected the SRM or ifthere are other observations relevant to the

SRM.

2. Raw Data - laboratory worksheets, records, notes, or instrument printouts that are the

result of original observations and activities . The chromatograms and integration reports

associated with the SRM should be submitted with the SRM Sample Data Summary

Report, if possible.

3. Data Package - the entire laboratory package including all narratives, sample summary

reports, QC reports, calibrations, and raw data. The full data package should only be

submitted if there were significant QC failures that affect the SRM result or if the data

did not go through the data validation process.

Storage and use of previously opened SRM is not recommended. However, it is requested

that any additional data results derived from use of the SRM be submitted to the EPA Region

10 SRM Manager.


Performance / Acceptance Limits

The acceptance limits presented below are guidance values based on the original laboratory

round-robin associated with the development of the SRM. The implications associated with

not meeting these acceptance limits will be determined by data reviewers on a case-by-case

basis, based on the goals of their program/project. For now, the DMMP will review results on

a case-by-case basis and will consider the values advisory.

PCB Aroclors: A twelve-lab round-robin testing of the SRM (including commercial and

CLP labs) was used to calculate an acceptance limit for Aroclor 1260. The average Aroclor

1260 concentration found during the round robin was 108 ug/kg. The acceptance limit is set

at the 95% confidence interval.

• Aroclor 1260:

Warning low: 41 ug/kg

Warning high: 180 ug/kg

CDD/CDF: A ten-lab round-robin testing of the SRM (including commercial and CLP labs)

was used to calculate an acceptance limit of ±50% action low and action high for each

congener as follows:

Acceptance

Limits Source Analyte CAS No.

Avg. Cone.

(ng/kg)

Action Low

-50%

Action High

+50%

± 50 Percent

2,3,7,8-TCDD 1746-01-6 1.05 0.525 1.57

1,2,3,7,8-PeCDD 40321-76-4 1.08 0.542 1.63

1,2,3,4,7,8-HxCDD 39227-28-6 1.59 0.797 2.39

1,2,3,6,7,8-HxCDD 67653-85-7 3.88 1.94 5.82

1,2,3,7,8,9-HxCDD 19408-74-3 3.04 1.52 4.55

1,2,3,4,6,7,8-HpCDD 35822-46-9 90.6 45.3 136

OCDD 3268-87-9 811 406 1217

2,3,7,8-TCDF 51207-31-9 1.11 0.557 1.67

1,2,3,7,8-PeCDF 57117-41-6 1.23 0.613 1.84

2,3,4,7,8-PeCDF 57117-31-4 1.07 0.533 1.60

1,2,3,4,7,8-HxCDF 70648-26-9 3.02 1.51 4.53

1,2,3,6,7,8-HxCDF 57117-44-9 1.09 0.545 1.64

2,3,4,6,7,8-HxCDF 60851-34-5 1.83 0.917 2.75

1,2,3,7,8,9-HxCDF 72918-21-9 0.511 0.255 0.77

1,2,3,4,6,7,8-HpCDF 67562-39-4 18.7 9.36 28.1

1,2,3,4,7,8,9-HpCDF 55673-89-7 1.63 0.815 2.44

OCDF 39001-02-0 58.4 29.2 87.6


CB Congeners: A ten-lab round-robin testing of the SRM (including commercial and CLP

labs) was used to calculate an acceptance limit of ±50% action low and action high for each

congener as follows:

Individually eluting congeners table

Congener#

Target Analyte

Cl Level*

Avg

SD

Acceptance

(-50%)

Low

Acceptance High

(+150%)

ng/kg dry weight

1 2-Chlorobiphenyl 23 2.6 12 35

3 4-Chlorobiphenyl 25 8.4 13 38

4 2,2'-Dichlorobiphenyl 2 114 16.5 57 171


7 2,4-Dichlorobiphenyl 2 17 3.3 8 25


9 2,5-Dichlorobiphenyl 2 20 4.0 10 29



16 2,2',3-Trichlorobiphenyl 3 212 21.3 106 318



22 2,3,4'-Trichlorobiphenyl 3 385 47.8 192 577






37 3,4,4'-Trichlorobiphenyl 3 355 44.7 178 533

42 2,2',3,4'-Tetrachlorobipheny l 4 413 55.9 206 619


48 2,2',4,5-Tetrachlorobiphenyl 4 246 44.4 123 369

52 2,2',5,5'-Tetrachlorobi phenyl 4 3743 447.6 1871 5614

56 2,3,3',4'-Tetrachlorobipheny l 4 651 139.8 326 977

60 2,3,4,4'-Tetrachlorobiphenyl 4 253 124.4 126 379

63 2,3,4',5-Tetrachlorobiphenyl 4 59 11.4 30 89

64 2,3,4',6-Tetrachlorobiphenyl 4 659 81.3 329 988


67 2,3',4,5-Tetrachlorobiphenyl 4 56 10.2 28 84




82 2,2',3,3',4-Pentachlorobipheny l 5 486 33.3 243 729

84 2 ,2',3,3',6-Pentachlorobiphenyl 5 1327 31.5 664 1991

92 2,2',3,5,5'-Pentachlorobipheny l 5 1180 72.1 590 1770





Individually eluting congeners table, continued

Avg

SD Congener#

Target Analyte

Congener #

Target Analyte

Cl Level* ng/kg dry weight

114 2,3,4,4',5-Pentachlorobiphenyl 5 68 8.2 34 102



122 2,3,3',4',5'-Pentachlorobiphenyl 5 44 10.0 22 66

123 2,3',4,4',5'-Pentachlorobiphenyl 5 54 6.1 27 81

130 2,2',3,3',4,5'-Hexachlorobiphenyl 6 591 50.9 296 887

131 2,2',3,3',4,6-Hexachlorobiphenyl 6 116 14.0 58 174




137 2,2',3,4,4',5-Hex ac hlorobipheny l 6 223 29.6 112 335

141 2,2',3,4,5,5'-Hex ac hlorobipheny l 6 3657 395.7 1829 5486

144 2,2',3,4,5',6-Hexachlorobiphenyl 6 862 57.7 431 1293


158 2,3,3',4,4',6-Hexachlorobiphenyl 6 1257 132.4 628 1885

159 2,3,3',4,5,5'-Hexachlorobiphenyl 6 239 81.5 119 358

164 2,3,3',4',5',6-Hexachlorobiphenyl 6 1068 118.1 534 1602


170 2,2',3,3',4,4',5-Heptachlorobiphenyl 7 5251 715.7 2626 7877

172 2,2',3,3',4,5,5'-Heptachlorobiphenyl 7 903 206.0 452 1355




177 2,2',3,3',4,5',6'-Heptachlorobiphenyl 7 3630 471.6 1815 5445




189 2,3,3',4,4',5,5'-Heptachlorobiphenyl 7 185 11.1 93 278

190 2,3,3',4,4',5,6-H eptac hlorobipheny l 7 1077 200.7 539 1616

191 2,3,3',4,4',5',6-Heptachlorobiphenyl 7 217 40.6 108 325

194 2,2',3,3',4,4',5,5'-Octachlorobiphenyl 8 2624 391.8 1312 3936

195 2,2',3,3',4,4',5,6-Octachlorobiphenyl 8 1169 163.2 585 1754




203 2,2',3,4,4',5,5',6-Octachlorobiphenyl 8 1829 354.3 914 2743

205 2,3,3',4,4',5,5',6-Octachlorobiphenyl 8 143 9.2 71 214

206

2,2',3,3',4,4',5,5',6- Nonachlorobiphenyl

9

575

39.2

288

863

207

2,2',3,3',4,4',5,6,6'- Nonachlorobiphenyl

9

91

18.6

46

137

208

2,2',3,3',4,5,5',6,6'- Nonachlorobiphenyl

9

124

7.5

62

186

209 Decachlorobiphenyl 10 97 4.4 48 145

* number of chlorine substituents


Co-eluting congeners table

Congene r

#

Co-eluting Pairs

Cl

Level*

Avg

SD

Acceptance

Acceptance High Low(-50%) (+150%)

Co-eluting Sets ng/kg dry weight

12 3,4-Dichlorobiphenyl 2

70

9.3

35

105

12 /13 13 3,4'-Dichlorobiphenyl 2

18 2,2',5-Trichlorobiphenyl 3

615

78.3

307

922

18 /30 30 2,4 ,6-Trichlorobiphenyl 3

20 2,3 ,3'-Trichl orobiphenyl 3

1436

149.8

718

2154

2 0/28 28 2,4,4'-Trichlorobiphenyl 3

21 2 ,3,4-Trichl orobiphenyl 3

545

49.8

273

818

21 /23 23 2,3,5-Trichl orobiphenyl 3

26 2,3',5-Trichlorobiphenyl 3

506

47.9

253

759

26 /29 29 2,4 ,5-Trichl orobiphenyl 3

40 2,2' ,3,3'-Tetrachlorobiphenyl 4

717

125.8

359

1076

40/41/71

41 2 ,2', 3,4-Tetrachlorobiphenyl 4

71 2 ,3' ,4',6-Tetrachlorobiphenyl 4

44 2,2',3,5'-Tetrachlorobipheny l 4

2026

194.2

1013

3039

44/47/65


65 2,3,5,6-Tet rachlorobiphenyl 4

45 2,2',3,6-Tetrachlorobiphenyl 4

224

37.0

112

336

4 5/51 51 2 ,2' ,4,6'-Tetrachlorobiphenyl 4


1550

185.4

775

2325

4 9/69 69 2,3' ,4,6-Tetrachlorobiphenyl 4

50 2,2',4,6-Tetrachlorobiphenyl 4

242

35.5

121

363

5 0/53 53 2,2' ,5,6'-Tetrachlorobiphenyl 4

59 2,3 ,3', 6-Tetrachlorobiphenyl 4

142

22.5

71

213

59/62/75

62 2,3,4 ,6-Tet rachlorobiphenyl 4

75 2,4,4',6-Tetrachlorobiphenyl 4

61 2 ,3,4 ,5-Tet rachlorobiphenyl 4

3251

513.3

1626

4877

61 /70/74/76

70 2,3',4',5-Tetrachlorobipheny l 4

74 2,4,4',5-Tetrachlorobiphenyl 4

76 2,3' ,4',5'-Tetrachlorobiphenyl 4

83 2,2',3,3' ,5-Pentachlorobiphenyl 5

2548

373.6

1274

3821

8 3/99 99 2,2' ,4,4',5-Pentachlorobiphenyl 5

85 2,2' ,3,4,4'-Pentachlorobiphenyl 5

737

29.5

368

1105

8 5/116/117

116 2,3,4 ,5,6-Pent achlorobiphenyl 5

117 2 ,3,4', 5,6-Pentachlorobiphenyl 5

86 2,2',3,4,5-Pentachlorobiphenyl 5

3337

142.6

1668

5005

86/87/97/108/119/125

87 2,2' ,3,4,5'-Pentachlorobiphenyl 5

97 2,2' ,3,4',5'-Pentachlorobiphenyl 5

108 2 ,3 ,3' ,4,5'-Pentachlorobiphenyl 5

119 2 ,3' ,4,4',6-Pentachlorobiphenyl 5

125 2 ,3' ,4',5',6-Pentachlorobiphenyl 5

88 2,2', 3,4,6-Pentachlorobiphenyl 5

674

49.9

337

1011

8 8/91 91 2 ,2' ,3,4',6-Pentachlorobiphenyl 5


Co-eluting congeners table, continued

Congene r

#

Co-eluting Pairs

Cl

Level*

Avg

SD

Acceptance

Acceptance High Low(-50%) (+150%)

Co-eluting Sets ng/kg dry weight

90 2,2' ,3,4',5-Pentachlorobiphenyl 5

6957

787.6

3478

10435

90/101/113

101 2 ,2' ,4,5,5'-Pentachlorobiphenyl 5

113 2 ,3 ,3' ,5' ,6-Pentachlorobiphenyl 5

93 2,2',3,5,6-Pentachlorobiphenyl 5

5608

516.7

2804

8412

93/95/98/100/102

95 2,2',3,5' ,6-Pentachlorobiphenyl 5

98 2,2' ,3,4',6'-Pentachlorobiphenyl 5

100 2,2',4,4',6-Pentachlorobipheny l 5

102 2,2',4,5,6'-Pentachlorobipheny l 5

107 2,3,3',4',5-Pentachlorobipheny l 5

249

105.2

124

373

107/124 124 2,3',4',5,5'-Pentachlorobiphenyl 5

110 2 ,3 ,3' ,4',6-Pentachlorobiphenyl 5

6488

384.7

3244

9733

1 10/115 115 2,3,4,4',6-Pentachlorobiphenyl 5

128 2 ,2', 3,3',4,4'-Hexachlorobiphenyl 6

1354

167.1

677

2031

128/166 166 2 ,3,4 ,4',5,6-Hexachlorobiphenyl 6

129 2 ,2', 3,3',4,5-Hexachlorobiphenyl 6

14189

1183.2

7094

21283

12 9/138/160/163

138 2 ,2' ,3,4,4',5'-Hexachlorobiphenyl 6

160 2 ,3 ,3' ,4,5,6-Hexachlorobiphenyl 6

163 2 ,3 ,3' ,4',5,6-Hexachlorobiphenyl 6

134 2,2', 3,3',5,6-Hexachlorobiphenyl 6

657

45.0

329

986

1 34/143 143 2 ,2' ,3,4,5,6'-Hexachlorobiphenyl 6

135 2,2' ,3,3',5,6'-Hexachlorobiphenyl 6

6326

374.1

3163

9488

1 35/151/154

151 2 ,2' ,3,5,5',6-Hexachlorobiphenyl 6

154 2,2' ,4,4',5,6'-Hexachlorobiphenyl 6

139 2 ,2', 3,4,4',6-Hexachlorobiphenyl 6

115

18.7

58

173

139/140 140 2 ,2', 3,4,4',6'-Hexachlorobiphenyl 6

147 2 ,2', 3,4',5,6-Hexachlorobiphenyl 6

14314

1582.6

7157

21471

1 47/149 149 2 ,2', 3,4',5',6-Hexachlorobiphenyl 6

153 2 ,2' ,4,4',5,5'-Hexachlorobiphenyl 6

13913

1343.2

6956

20869

1 53/168 168 2,3' ,4,4',5',6-Hexachlorobiphenyl 6

156 2,3 ,3' ,4,4',5-Hexachlorobiphenyl 6

891

52.1

446

1337

156/157 157 2,3,3',4,4',5'-Hexachlorobiphenyl 6

171 2,2',3,3',4,4',6-Heptachlorobiphenyl 7

1794

202.8

897

2691

1 71/173 173 2 ,2', 3,3',4,5,6-Heptachlorobiphenyl 7

180 2 ,2', 3,4,4',5,5'-Heptachlorobiphenyl 7

12396

1530.7

6198

18594

180/193 193 2 ,3 ,3' ,4',5,5',6-Heptachlorobiphenyl 7

183 2 ,2' ,3,4,4',5',6-Heptachlorobiphenyl 7

4184

665.7

2092

6277

183 /185 185 2,2',3,4,5,5',6-Heptachlorobipheny l 7

197 2 ,2' ,3,3',4,4',6,6'-Octachlorobiphenyl 8

496

106.0

248

744

197 /200 200 2,2', 3,3',4,5,6,6'-Octachlorobiphenyl 8

198 2,2', 3,3',4,5,5',6-Octachlorobiphenyl 8

3260

626.4

1630

4890

1 98/199 199 I 2 , 2', 3,3',4,5,5',6'-Octachlorobiphenyl 8

* number of chlorine substituents


Recalculation of Acceptance Limits

The national EPA QATS contractor will store the SRM, conduct stability testing, and

maintain the SRM database used to recalculate acceptance limits. Timing for any acceptance

limit recalculations will depend on the quantity of high quality data received. It is anticipated

that the next recalculation will occur after 30 new data points have been received.

References

Revised Supplemental Information on Polychlorinated Dioxins and Furans (PCDD/F) for

Use in Preparing a Quality Assurance Project Plan (QAPP), dated November 8, 2010.

Guidance for Labeling Externally Validated Laboratory Analytical Data for Superfund Use,

dated January 13, 2009 (EPA-540-R-08-005).

SRM 1944 Page 1 of 5

Date of Issue:

07 April 2014

SAFETY DATA SHEET

1. SUBSTANCE AND SOURCE IDENTIFICATION

Product Identifier

SRM Number: 1944 SRM Name: New York/New Jersey Waterway Sediment

Other Means of Identification: Not applicable.

Recommended Use of This Material and Restrictions of Use

Standard Reference Material (SRMJ 1944 1s a mixture of marine sediment collected near urban areas in New York

and New Jersey. SRM 1944 is intended for use in evaluatmg analytical methods for the determination of selected

polycycllc aromatic hydrocarbom (PAHs). polychlorinated biphenyl (PCB) congeners, chlorinated pesticides. and

trace elements in marine sediment and s1m1lar matrices. All of the constituents for which certified. reference. and

informal!on values are provided m SRM 1944 were naturally present m the sediment before processing. A unit of SRM 1944 consists of a bottle containing 50 g ofradiation-sterilized, freeze-dried sediment.

Company Information

National Institute of Standards and Technology

Standard Reference Materials Program 100 Bureau Drive. Stop 2300 Gaithersburg, Maryland 20899-2300

Telephone: 301-975-2200

FAX. 301-948-3730

E-mail. [email protected] Website: http://www.rnst.gov/srm

2. HAZARDS IDENTIFICATIO:K

Classification

Physical Hazard: Not classified.

Health Hazard: Not class1ficd.

Emergency Telephone ChemTrec- 1-800-424-9300 (North Amenca)

+1-703-527-3887 (International)

Label Elements

Symbol

No Symbol/Pictogram

Signal Word

Not applicable.

Hazard Statement(s): Not applicable.

Precautionary Statement(s): Not applicable.

Hazards Not Otherwise Classified: Not applicable.

lngredients(s) with Unknown Acute Toxicity: Not applicable.

3. COMPOSITIO N AND INFORMATIO N ON HAZARDOUS INGREDIENTS

Substance: Waterway sediment

Other Designations: Sediment.

Thii> material is naturally occurring marine sediment collected near urban areas. The matenal contams trace

amounts of polycychc aromatic hydrocarbons (PJ\Hs), polychlonnated biphenyl (PCB) congeners, chlorinated

pestmdes. and trace clements. Components aic listed rn compliance with OSHA's 29 CFR 1910.1200; for the

actual values see the Certificate of Analysis.

NISI


http://www.rnst.gov/srm


,.

Hazardous Componcnt(s)

Waterway Sediment

CASNumber

Not available

EC Number

(EINECS)

Not available

Nominal Mass Concentration

(%)

100

4. FIRST Arn MEASURES

Description of First Aid Measures:

Inhalation: If adverse effects occur, remove to uncontaminated area. If not breathing. give artificial respiration or oxygen hy qualified personnel. Seek 1mmed1ate medical attention.

Skin Contact: Wash skin with soap and water.

Eye Contact: Flush eyes with water for at least 15 minutes. If necessary, seek medical attention.

Ingestion: If adverse effects occur after ingestion, seek medical treatment.

Most Important Symptoms/Effects, Acute and Delayed: May cause irritation

Indication of any immediate medical attention and special treatment needed, if necessary: If any of the above

symptoms are pre ent, seek medical allention if needed.

5. FIRE FIGHTING MEASURES

Fire and Explosion Hazards: Negligible fire hazard. Avoid generating dust. See Section 9. '"Physical and

Chemical Properties"' for flammability properties.

Extinguishing Media:

Suitable· Use extrnguishing media appropnate for surrounding fire.

Unsuitable: None hsted.

Specific Hazards Arising from the Chemical: None listed.

Special Protective Equipment and Precautions for Fire-Fighters: Avoid inhalation of material or combustion

byproducts. Wear full protective clothing and NIOSH approved self-contained hreathmg apparatus (SCBA).

NFPA Ratings (0 = Mmimal: 1 = Slight; 2 = Moderate; 3 = Serious; 4 = Severe)

Health= I Fire= 0 Reactivity = 0

6. ACCIDENTAL RELEASE MEASLIRES

Personal Precautions, Protective Equipment and Emergency Procedures: Any accumulated matenal on

urfaces should be removed and properly disposed of Use suitable protective equipment; see Section 8, '"Exposure

Controls and Personal Protect10n'"

Methods and Materials for Containment and Clean up: Collect spilled material m appropriate contamer for

disposal. Keep out of water supplies and sewers. Keep unnecessary people away, isolate hazard area and deny

entry.

7. HANDLING AND STORAGE

Safe Handling Precautions: Minimize dust generation and accumulat10n on surfaces Routine housekeeping

should be instituted to ensure that dusts do not accumulate on surfaces. See Section 8, "Exposure Controls and

Personal Protection".

Storage: Store and handling in accordance with all current regulallons and standards

8. EXPOSURE CONTROLS AND PERSONAL PROTECTIO N

Exposure Limits: No occupational exposure hmits have been cs tabhshcd for waterway sedunent. This material is

a particulate matter and adequate inhalation/respiratory protection should he used to mmim1ze exposure. The

exposure limits for Paruculatcs Not Otherwise Regulated (PNOR) are applicable.

OSHA (PEL): 15 mg/m3 (TWA. total particulates not otherwise regulated)

OSHA (PEL) 5 mg/m 3 (TWA, re pirable particulate nol otherwise regulated)

NTOSH (REL)· 10 mg/m 3 (TWA, total particulates not otherwise regulated, 8 h)

NIOSH (REL): 5 mg/m3 (TWA, respirable particulates not otherwise regulated)

..

Engineering Controls: Provide local e:-h aus t or prm:c:,1 -. em.:h,ure vent ilatio n sys te m. E ns ure compliance with

appllcahle exposure lu rnt

Personal Protection: In acc ordance with OSHA 29 CFR I 9 10 .132, suh parl I, wear approprn1tt: Personal P rotecti ve

Equi pment (PPE1 lti nnni rmze exposure lCl this mate11al

Respiratory Protection: If workplace co nd i tion s warra n t a respirator, a re<.piratory protect10n program that meets

OSHA 29CFR 1910.13 4 mus t bt: followed Rder to NIOSH 42 CFR 84 for applicable certified respirators

Eye/Face Protection: Wear splash resistant safoty gL1 ggle s with a face shield. An eye wash station should be

readily available near areas of us e.

Skin and Body Protection: Personal protec tive equipm ent for the body should he selected based on the task

being performed and the n sks involved and shou ld h e appro ved by a specialist before handling thi s produ c t.

C he m1c al-res1stant glove s should be worn at all tim es when hand lin g chemical s .

9. PHYSICAL AND CHEMICAL PROPERTIES

Descriptive Properties:

Appearance

(physical state, color, etc. ):

Molecular Formula:

Molar Mass (g/mol):

Odor:

Odor threshold:

pH:

Evaporation rate:

Melting point/freezing point (°C):

Specific Gravity (water=l)

Vapor Pressure (mmHg):

Vapor Density (air:; 1):

Viscosity (cP):

Solubility(ies):

Partition coefficient (n-octanoVwater):

Particle Size:

Thermal Stability Properties:

Autoignition Temperature (0 C):

Thermal Decomposition (uC):

Initial boiling point and boiling range (°C):

Explosive Limits, LEL (Vol ume %):

Explosive Limits, UEL (Volu me %):

Flash Point ( 0 C):

Flammability (solid, gas):

10. STABILITY AND R EACTIV ITY

Reactivity: Stahle at no rmal te mp e ratures and pressure.

Stability: X Stable Un stable

Possible Hazardous Reacti ons: None listed.

Conditions to Avoid: Avoi d generat in g dust.

Incompatible Materials: None lis ted.

Fire/Explosion Information: See Sectton 5. "F i re Fi ghti ng Meas ure s" .

amorphou powder

not applic a ble

not applicable

not avatl able

not av ailable

not ava 1l a blc

not applicable

not available

not available

not appl1ca blc

not app licable

not app ltc a ble

not ava ilable

not available

not available

not available

not availab le

not ava ilabl e

not avail able

not avail able

not availab le

not availab le

SRM 1944 Pagt' 3 of 5


..

Hazardous Decomposition: Thermal decompo.sit10n will produce oxides of carbon.

Hazardous Polymerization: Will Occur X Will Not Occur

11. TOXICOLOGICAL INFORMATION

Route of Exposure: X Inhalation X Skin Ingestion

Symptoms Related to the Physical, Chemical and Toxicological Characteristics: Generated dust may cause

irntation 1f inhaled.

Potential Health Effects (Acute, Chronic and Delayed):

Inhalation: Generated dust may cause irritation.

Skin Contact: May cause mechanical irritation.

Eye Contact: No data available.

Ingestion: No data availahle.

Numerical Measures of Toxicity:

Acute Toxicity: Not classified. no data available.

Skin Corrosion/Irritation: Not classified; no data available.

Serious Eye damage/ Eye irritation: Not classified, no data available.

Respiratory Sensitization: Not classified; no data available

Skin Sensitization: Not class1foxl; no data available.

Germ Cell Mutagenicity: Not classified; no data availahle.

Carcinogenicity: Nol das ified.

Listed as a Carcinogen/Potential Carcinogen Yes

Sediment is not listed by NTP. IARC or OSHA as a carcinogen.

Reproductive Toxicity: Not classified; no data available

Specific Target Organ Toxicity, Single Exposure: Not classified: no data available.

X No

Specific Target Organ Toxicity, Repeated Exposure: Not classified; no data available.

Aspiration Hazard: Not classified; no data availahle.

12. ECOLOGICAL INFORMATION

Ecotoxicity Data: No data avmlahle.

Persistence and Degradability: No data available.

Bioaccumulative Potential: No data available.

Mobility in Soil: No data available.

Other Adverse effects: No data available

13. DISPOSAL CONSIDERATIONS

Waste Disposal: Di:,po:,c of waste m acc;ordam;c with all applicahle federal, :state, and local regulations

14. TRANSPORTATION INFORMATIO N

U.S. DOT and IATA: Not regulated hy DOT or IATA

15. REGULATO RYINFO RMATIO N

U.S. Regulations:

CERCLA Sec.:tiom, 102a/103 (40 CFR 302.4)· Not regulated

SARA Title III Sect10n 302 (40 CFR 355 30)· Not regulated

SRM 1944 Page 5 ot 5

SARA Title III Section 304 (40 CFR 355 40): Not regulat ed

SARA Title lll Section 3 l3 (40 CFR 372.65): Not regulated.

OSHA Process Safety (29 CFR 1910 119): Nol regulated

SARA Title Ill Sectio ns 311/3l 2 Hazardous Categorie s (40 CFR 370.21 )·

ACUTE HEALTH· No.

CHRONIC HEALTH No.

FIRE· No.

REACTIVE: No.

PRESS URE. No

State Regulations:

California Proposition 65: Not ltsted.

U.S. TSCA Inventory: Not listed.

TSCA 12(b), Export Notification: Not lu,ted.

Canadian Regulations:

WHMIS Information. Not provided for thi material

16. OTHER INFORMATION

Issue Date: 03 April 2014

Sources: 29 CFR Occupational Health and Safety Office (OSHA) 19I0.1000. Limits for Air Contaminant.\,

Table Z-1; available at

http://w ww.osha .gov/pls/os haweb/owadisp.shl 1w_doc ument?p_lable=STAND ARDS&p_ id=9992

(accessed April 2014).

Center for Disease Control (CDC) NIOSH Po1;kel Guide lo Chemical Hazards, Particulates not

otherwise re f?ulared: ava1lable at http://www cdc gov/niosh/npg/n p gd04 80.html (accessed Apnl 2014).

Key of Acronyms:

AC'GIH Amencan Conference of Govt:num:nlal lmlu5lnal

Hygienists NRC Nuclear Regulatory Commissio n

ALI Annual L1m11 o n Int ake NTP National Toxicology Program

CAS Chemical Ah tracl ScrVILC OSHA Occupational Safety and Health Adnum5trat1on

CERCLA Comprehensive Environmental Response. PEL Permiss1ble Exposure Limit

CFR Compensation. and Liability Act

Code of Federal Rcgulalmns

RCRA

Resomce Conservatio n and Recovery Act DOT Department of T1ansponation REL Recommended Exposure L1mu

EC50 Effective Concent ration. 50 o/, RM Reference Malena)

EINECS European Inventor y of E istmg Commercial RQ Reportable Quantity Chemical Substan ces

EPCRA e mergency l'lannmg and Commu nuy R1ght-ro-Know RTF.CS Reg1stry of Tnx,c Effet:t, nf Cherrnral Sub,tancn Ad

IARC Intemational Agency for Research on Cancer SARA Superfund Amendments and Rea urhon zat1on Act

IATA lnlernauonal Atr Transpona11on Agency SCBA Sclf-Conlamctl Breathing Appaiatus

IDLH Immcchatcly Dangerous to Life and Health SRM Standard Reference Malena! LC50 Lethal Concentration. 50 % S1EL Short Term Exposure Lurut

LOSO Lethal Dose, 50 'Ji, TLV Threshold Lmul Value

LEL Lower Explo,ivc Lmut TPQ Threshold Planning Quantity

MSDS Material Safety Dat a She et TSCA Toxic Substances Control Act

NFPA National Fire Protecnon Assoctatmn TWA Time Weighted Avcrdgc

NIOSH Natmnal Im,l1tutc for Occupat10nal Safety and Health UEL Upper E,plosive Limit NIST National Inst11ute of Standard, and Technology WHMIS Workplace Hazard ous Matenal Information Sy5rem

Disclaimer: Physical and chcnucal data contained in this SOS are provided only for u e in as:-.essing the

hazardous nature of the matenal. The SOS was prepared carefully, using current referem :e1;; ho we ver . NIST does

nol <.:ert1fy the data in the SOS. The certified values for this material are given rn the NIST Certificate of Analysis.

U&ers of this SRM shou ld ensu re that the SOS in th eir possession is curr ent. Th is can be acco mpli hed by

contactin g the SRM Pro gram. tt:lepho ne (301) 9 75-220 0: fax (301) 9 48-373 0: e-m ail srmmsds @rnst.gov, or via th e

Inte rne t at http://wwv,. nist gov/srm.

http://w/

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SRM 1944 Page 1 of22

Standard Reference Material® 1944

New York/New Jersey Waterway Sediment

Stand ard Reference Mater ia l (SRM) 1944 is a m ixture of m arin e sed im ent collected near urb an areas in New York and

New Jers ey. SRM 1944 is intended for use in ev aluatin g analytical m ethods for th e d etermin ation o f selected poly cy clic

arom atic h ydro carb ons (PAHs), po lychlor in ated b1ph eny l (PCB) con geners, ch lorinated pes ticid es, an d tr ace elemen ts in

mar ine sedimen t and similar matrices. Reference values ar e a lso provided for selected polybro min ated diphen yl

eth er {PBDE) con geners, s elected d ib enzo -p-dioxin and diben zofuran con gen ers, to tal organic carbon, total ex tr actab le

mater ia l, an d particle size characteristics. Information values are prov ided for se] ected poly chlorin ated

naphthalen es (PCNs ) and h exab rom ocy clo dodecanes (HBCDs). All of th e co nstituents for which cer tified, r eference,

and informatio n v alu es are prov ided in SRM 1944 were n atu rally pres ent in th e s edimen t b efore p rocessin g. A un it of

SRM 1944 consists of a bottle containing 50 g of radiation-sterilized, frceze-dned sediment.

Certified Mass Fraction Values: Cer tif ied v alu es for mass fr actions of PAHs, PCB con gen ers, chlor inated p esticid es,

and trace elem ents ar e prov ided in Tab les 1 throu gh 4. A NIST certified v alue is a v alu e for which NIST h as the h ighes t

confiden ce in its accuracy in th at a ll kno wn or suspected sources of b ias hav e been inv estigated or taken into accou nt [I].

The cer tif ied values for the PAHs, PCB con gen ers, an d ch lor inated pestic id es ar e bas ed on th e agreem ent o f resu lts

obtained at NIST usin g two o r more chemically independ en t an aly tical techn iqu es. Th e certified v alu es for the trace

elem ents are bas ed on NIST m easurem ents by o ne techn ique an d ad dition al resu lts from s everal co llaboratin g

laboratories.

Reference Mass Fraction Values: Reference values are provid ed for mass fractions of additio nal PAHs (so me in

comb in ation) in Tab les 5 and 6, ad dition al PCB con geners an d chlorin ated pestic id es in Tab le 7, PBDE con geners in

Tab le 8, and add itional ino rgan ic constitu ent:; in Tab les 9 an d 1 0. Reference value:; ar e prov ided in Table 11 for th e

2,3,7,8-subs tituted po lychlor inated diben zo-p-d iox in and d1 ben zofuran con geners and to tal tetr a-, p enta-, h exa-, and

hepta-con geners o fpolych lorinated d ib enzo-p-dioxin an d d iben zofu ran. Reference valu es for par ticle size character istics

are pro vid ed in Table 12 an d 13 Referen ce v alues for total organic carbo n an d p ercent extractable m ass are provid ed in

Tab le 1 4. Reference values are non cer tif ied values th at ar e the bes t estim ate of th e true valu e; ho wev er, th e v alu es do no t

meet th e NIST criter ia for cer tif ication and are prov id ed with asso ciated uncertainties that m ay ref lect only m easu remen t

precision, m ay no t in clu de all sources of u ncertain ty, or may ref lect a lack of suff icien t sta tis tical agreement amo n g

multiple analytical methods [ 1].

Information Mass Fraction Values: Information valu es are provided in Table 15 fo rm ass fractions of add itional tr ace

elem ents, in Table 16 for PCN con geners (som e in co mbin ation), an d in Tab le 17 for HBCD iso mers. An inform ation

value is considered to be a value that will be of interest and use to the SRM user, but insufficient information is available

to assess the uncertainty associated with the value or only a limited number of analyses were perfonned l l l-

Expiration of Certification: Th e certification of SRM 1944 is valid, within the m easurement uncertainties specified,

until 31 March 2017, provided the SRM is handled and stored in accordance with the instructions given in this certif icate

(see "Instructions for Handling, Storage, and Use"). The certificat10n i:; nullified if the SRM is damaged, contaminated,

or otherwise modified.

Stephen A. Wise, Chief

Analytical Chemistry Division

Gaithersburg, MD 20899

Certificate Issue Date: 27 September 20 I I Cemfirare Rel'won H1stnrv on Page 20

Robert L. Watters, Jr., Chief

Measurement Services Division

((Lertificat£ of J\nalusis


Maintenance of SRM Certification: NIST will mon ito r this SRM ov er th e per iod of its certificatio n. If substantiv e

technical ch an ges occur that af fect the cer tif ication b efore th e expir ation o f th is certificate. NIST will n otify th e

purchaser. Registration (see attached sheet) will facilitate notification

The coordination of the technical measurements leading to the certification was performed by M.M. Schantz and

S.A. Wise of the NIST Analytical Chemistry Division.

Consultation on the statistical design of the experimental work and evaluation of the data were provided by S.D. Leigh,

M.G. Vangel, and M.S. Levenson of the NIST Statistical Engineering Division.

Supp ort asp ects invo lv ed in the issu ance of th is SRM were coord inated throu gh the NIST Measu remen t Serv ices

Division.

The sedimen t was collected with the assistance of th e New York Dis trict of the U.S. Arm y Corp o f

Engineers (ACENYD), who provided the expertise in the site selection, the ship, sampling equipment, and personnel.

L. Rosm an o f ACENYD an d R. Parr is (NIST) coordinated the co llection of th is sed im ent. Collection an d preparation of

SRM 1944 were p erform ed by R. Parr is, M. Cron ise, and C. Fales (NIST), L. Ros man and P. Higgins (ACENYD), an d

the crew of the Gelberman from the ACE Caven Point facility in Caven Point, NJ.

Analytical measurements for the certification of SRM 1944 were performed at NIST by E.S. Beary, D.A. Becker,

R.R. Greenberg, J.M. Keller, J.R. Kucklick, M. Lopez de Alda, K.E. Murphy, R. Olfa z, B.J. Porter, D.L. Poster.

L.C. Sander, P. Sch uber t, M.M. Sch an tz, S.S. Vand er Po l, an d L. Walton of th e An aly tical Ch em istry Divis ion.

Measurements for percent total organic carbon measurements were provided by three commercial laboratories and

T.L Wade ofth e Geo ch em ical and Environm ental Research Group, Tex as A& M Umversity (Co llege Station , TX, USA).

The par ticle-size d istr ibution data were prov ided by Honey well, In c. (Clearwater, FL . USA). Add itional r esults fo r

PBDE co n geners were used from ten laborator ies (s ee Appen dix A) th at par ticip ated in an in ter lab oratory s tud y

specifically for PBDEs in Marine Sediment coordinated by H.M. Stapleton of the NIST Analytical Chemistry Division.

M. LaGu ard1 a of Virginia lnstitu te of Marin e Science (Glou cester Point, VA. USA) provid ed o ne set of measurements

for the HBCDs.

Valu es for th e poly ch lorinated d iben zo-p-diox ins and d iben zofurans were the r esults of an in ter lab oratory com par ison

study am on g four teen lab oratories (s ee App endix B) coord inated by S.A. Wis e of the NIST An aly tical Ch emistry

Divisio n and R. Turle an d C. Ch iu o f Env iron m ent Can ad a Enviro nm ental Tech nolo gy Centre, Analysis and Air Quality

Divisio n (Ottawa, ON, Can ada). Analytical measurem ents fo r s elected trace elem en ts were prov ided by th e Intern ation al

Atom ic Energy Agency (IAEA, Seib ersdor f, Austr ia) by M. Makarewicz and R. Zeisler. Results were also used fro m

seven labo ratories (see Ap pend ix C) that participated in an intercomp ariso n ex ercise coord inated b y S Willie o f th e

Institute for National Measurement Standards, National Research Council Canada (NRCC; Ottawa, ON, Canada).

INSTRUCTIONS FOR HANDLING, STORAGE, AND USE

Handling: Th is mater ia l is n aturally occurr in g m arin e s ediment fro m an u rban area and m ay con tain constitu ents o f

unknown toxicities; therefore, caution and care should be exercised during its handling and use.

Storage: SRM 1944 must be stored in its original bottle at temperatures less than 30 °C away from direct sunlight.

Use: Prior to remov al of test por tions for an alysis, the contents of the bo ttle should be m ix ed Th e con cen trations of

constitu ents in SRM 1944 are rep orted on a d ry -m ass bas is. The SRM, as r eceiv ed, con tains a mass f raction o f

approx im ately 1.3 % mo isture. The sed im ent sample sho uld be dried to a constant mass b efore weigh in g for an alysis or,

if th e cons tituen ts of interest ar e v olatile, a sep arate tes t p ortion of the sed im ent shou ld be remov ed fro m th e bottle at the

time of analysis and dried to determine the mass fraction on a dry-mass basis.


PREPARATIO N AND ANALYSISllJ

Sample Collection and Preparation: The ediment used to prepare this SRM was collected from six sites in the

vicinity ofNew York Bay and Newark Bay in October 1994. S ite selection was based on contaminant levels measured in

previous samples from these sites and was intended to provide relatively high concentrations for a variety of chemical

classes of contaminants. The sediment was collected using an epoxy-coated modified Van Veen-type grab sampler

desigm:d to sample the sediment to a depth of 10 cm. A total of approximately 2100 kg of wet sediment was collected

from the six sites. The sediment was freeze-dried, sieved (nominally 250 µm to 61 tm). homogenized in a cone blender,

radiation sterihzed at an estimated mmimum dose of32 kilograys (6°Co), and then packaged m screw-capped amber glass

bottles.

Convers ion to Dry-Mass Bas is: The results for the constituents in SRM 1944 are reported on a dry-mass basis;

however, the material as received contains residual moisture. The amount of moisture in SRM 1944 was determined by

measuring the mass loss after freeze drying test portions of 1.6 g to 2.5 g for five days at 1 Pa with a -10 °C shelf

temperature and a -50 °C condenser temperature. The mass fraction of moisture in SRM 1944 at the time of the

certification analyses was 1.25 % ± 0.03 % (95 % confidence level).

Polycyclic Aromatic Hydrocarbons: The general approach used for the value assignment of the PAHs in SRM 1944

consis ted of combining results from analyses us ing various combinations of different extraction techniques and solvents,

cleanup/isolation procedures, and chromatographic separation and detection techniques [2]. Technique!:> and solvents

involved were Soxhlet extraction and pressurized fluid extraction (PFE) using dichloromethane (DCM) or a

hexane/acetone mixture, clean up of the extracts using solid-phase extraction (SPE), or normal-phase liquid

chromatography (LC), followed by analysis using the following techniques : ( l) reversed-phase liquid chromatography

with fluorescence detection (LC-FL) analys is of the total PAH fraction. (2) reversed-phase LC-FL analysis of isomeric

PAH fractions isolated by normal-phase LC (i.e., multidimensional LC), (3) gas chromatography/mass spectrometry

(GC/MS) analys is of the PAH fraction on four stationary phases of different selectivity, i.e., a 5 % (mole fraction)

phenyl-subs tituted methylpolys iloxane phase, a 50 % phenyl-substituted methylpolysiloxane phase, a proprietary

non-polar polysiloxane phase, and a smectic liquid crystalline stationary phase.

Seven sets of GC/MS results, designated as GC/MS (I), GC/MS (II), GC/MS (ITI), GC/MS (IV), GC/MS (V),

GC/MS (VI), and GC/MS (Sm), were obtained using four columns with different selectivities for the separation of PAHs.

For GC/MS (I) analyses, duplicate tes t portions of I g from eight bottles ofSRM 1944 were Soxhlet extracted for 24 h

with DCM. Copper powder was added to the extract to remove elemental sulfur. The concentrated extract was passed

through a s ilica SPE cartridge and eluted with 2 % DCM in hexane. (All extraction and LC solvent compositions are

expressed as volume fractions unless otherwise noted.) The processed extract was then analyzed by GC/MS using a

0.25 mm i.d. "60 m fused s ilica capillary column with a 5 % phenyl-subs tituted methylpolysiloxane phase (0.25 µm film

thickness) (DB-5 MS, J&W Scientific, Folsom, CA). The GC/MS (II) analyses were performed using 1 g to 2 g test

portions from three bottles ofSRM 1944 and 2 g to 3 gtes tportions from three bottles ofSRM 1944 that had been mixed

with a similar amount of water (i.e., a wetted sediment). These tes t portions were Soxhlet extracted with DCM and

processed through the silica SPE as described above; however, the extract was further fractionated using normal-phase

LC on a semi-preparative aminopropylsilane column to isolate the PAH fraction. The PAH fraction was then analyzed

using the same column as described above for GC/MS (I); however, the test portions were extracted, processed, and

analyzed as part of three different sample sets at different times us ing different calibrations for each set. For the

GC/MS (Ill). 1 g to 2 g test portions from s ix bottles of SRM 1944 were Soxhlet extracted for 18 h with 250 mL of a

mixture of50 % hexane/50 % acetone. The extracts were then processed and analyzed as described forGC/MS (II). For

GC/MS (TV) analyses, I g to 2 g test portions from s ix bottles ofSRM 1944 were extracted using PFE with a mixture of

50 % hexane/SO % acetone, and the extracts were processed as described above for GC/MS (11). The GC/MS (V) results

were obtained by analyzing three of the same PAH fractions that were analyzed in GC/MS (III) and three of the PAH

fractions that were analyzed in GC/MS (TV) using a 50 % (mole fraction) phenyl-subs tituted methylpolysiloxane

stationary phase (0.25 mm i.d. x 60 m. 0.25 µm film thickness) (DB- I 7MS, J&W Scientific, Folsom, CA). For

GC/MS (VI) analyses, three test portions of 0.7 g from one bottle of SRM 1944 were Soxhlet extracted for 24 h with

DCM. Copper powder was added to the extract to remove elemental sulfur. The concentrated extract was passed

through an aminopropyl SPE cartridge and eluted with 20 % DCM in hexane. The processed extract was then analyzed

by GC/MS using a 0.25 mm i.d. " 60 m fused silica capillary column with a proprietary non-polar polys1loxane phase

(0 25 µm film thickness) (DB-XLB, J&W Scientific). For GC/MS (Sm) l g to 2 g tes t portions from six bottles of

SRM 1944 were Soxhlet extracted for 24 h with 250 mL of DCM. The extracts were processed as described above for

mcertam commercial eqmpment. instruments, or matenals are 1dentiffod 111 this report to adequately specrty the

expenmental procedure Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology, nor doe it imply that the materials or equipment identified are necessarily the best available for the purpose.


GC/MS (I) using an aminopropyis1lane SPE cartridge followed by GC/MS analysis using 0.2 mm i.d. " - 25 m (0.15 µm

film thickness) smectic liquid crystalline phase (SB-Smectic, Dwnex, Lee Scientific Divi5ion, Salt Lake City, UT).

Two sets of LC-FL results, designated as LC-FL (Total) and LC-FL (Fraction), were used in th e certification process

Test portions of approximately I g from six botlle5 ofSRM 1944 were Soxhlet extr acted for 20 h using 200 mL of 50 %

hexane/SO % acetone. The extr acts were concentrated m1d then processed through two aminopropy lsilane SPE cartrid ges

connected in series to obtam the total PAH fraction. A second 1 g test portion from the s ix bottles was Soxhlet extracted

and processed as described above: the PAH fraction was then fractionated further on a semi-preparativ e

aminopropylsilanc column (µBondapak NH , 9 mm id. x 30 cm, Waters Associates, Milford, MA) to isolate isomeric

PAH fractions. The total PAH fract10n and th e isomeric PAH fractions were analy zed using a 5 -µm particle-size

polymeric octadecylsilane (C18) column (4.6 m m i.d. x 25 cm, Hypersil-PAH, Keystone Scientif ic, Inc.. Bellefonte, PA)

with wavelen gth-programmed f luorescence detection. For all of the GC/MS and LC-FL measurements described above,

selected perd euterated PAHs were added to the sedim ent prior to solvent extr action for use as internal standards for

quantification purposes.

Homogeneity Assessment for PAHs: The homogeneity ofSRM 1944 was assessed by analyzing duplicate test portions

of I g from eight bottles selected by stratified random sampling. Test portions were extracted, processed, and analyz ed

as described above for GC/MS (]). No statistically significant differences among bottles were observed for the PAHs at

the I g test portion size.

PAH Isomers of Molecular Mass 300 and 302: For th e determin ation of th e mo lecular mass 300 an d 3 02 PAH

isom ers, thr ee test por tio ns of approximately 5 g each were extr acted us in g PFE with DCM. Th e ex tracts were then

concentrated with a solven t ch an ge to hex an e and p assed throu gh an am inop ropy l SPE cartr id ge an d elu ted with IO %

DCM in h exane. Th e processed extr act was then analyzed by GC/MS usin g a 0.25 m m i.d . ,., 60 m fused silica capillary

colu mn with a 50 % ph eny1-subs titued methy lpolys ilox an e phase (0.25 µm film thickn ess: DB- l 7 MS, J& W Scientific,

Fo lsom, CA) Perd eu terated d iben zo[a,1]py ren e was add ed to th e sed im ent prior to ex traction for use as an intern al

standard.

PCBs and Chlorinated Pesticides: Th e general app roach used for the determination of PCBs and chlo rin ated pestic ides

in SRM 19 44 cons isted of comb min g r esults from analyses us in g v ario us co mbin ations of diff erent extr action techn iqu es

and solven ts, c leanup /iso latio n procedures, and chro mato graphic separation and d etection techn iqu es [2] . Th is approach

consisted of Soxh let extr actio n and PFE usin g DCM or a h exane/acetone m ixture, clean up/isolation us in g SPE or LC,

follo wed by analysis usin g GC/MS and gas chrom ato graphy with electron cap ture d etection (GC-ECD) o n two co lu mns

with different selectivity.

Eigh t sets of r esults were ob tained des ign ated as GC-ECD (I) A and B, GC-ECD (II) A and B, GC/MS (]), GC/MS (II),

GC/MS ([II), and QA Ex ercise. For the GC-ECD (]) analyses, l g tes t por tions fro m fou r bottles of SRM 194 4 were

Soxh lct ex tracted with DCM for 1 8 h. Copp er po wd er was added to the extr act to r emo ve elemental sulfur. The

concentrated extr act was passed throu gh a silica SPE cartr id ge and eluted with 10 % DCM in hex an e. Th e con cen trated

elu ant was then fr action ated on a 5 emi-prep arativ e amin opropy lsilan e colu mn to isolate two fr actio ns co ntain in g: ( I) the

PCBs and lo wer polarity p esticides and, (2 ) th e more polar p esticides. GC-ECD analyses o f th e two fractions were

performed on two co lu mns of d iff eren t selectivities for PCB s eparations : 0.25 mm x 60 m fused sih ca capillary colu mn

with a 5 % phen yl-subs tituted methylpolys ilox an e ph ase (0.25 µm film th ickness) (DB-5, J& W Scientific , Folso m, CA)

and a 0.32 m m x I 0 0 m fus ed silica cap illary column with a 50 % (mole fraction) o ctadecyl (C 18) methylpolys ilox ane

phase (0.1 µm f ilm thickn ess) (CPSil 5 Cl8 CB, Chro mpack In ternation al, Mid delburg, Th e Neth erlands). The resu lts

from the 5 % phenyl phas e are d esignated as GC-ECD (IA) an d th e r esults fro m the C18 p hase are d esign ated as GC-

ECD (IB). A s eco nd set of samples was also analyzed by GC-ECD ( i.e ., GC-ECD IIA and IIB). Test portions of 1 g to 2

g fro m three bottles of SRM 1944 and 2 g to 3 g test por tio ns from three bottles of SRM 1944 that had b een mix ed

with a similar amou nt of water (i. e., a wetted sedim ent) were ex tracted, pro cessed, and an aly zed as descr ib ed abov e fo r

GC-ECD (I); ho wever, the tes t portions were extr acted, processed and analy zed as p ar t of three d ifferen t sample sets at

different times using different calibrations for each set.


Three sets ofresult5 were obtained by GC/MS. For GC/MS (1). 1 g to 2 g test portions from six bottles were Soxhlet

extracted with a m1xtme of 50 % hexane /50 % acetone. Copper powder was added to the extract to remove elemental

sulfur. The concentrated extract was passed through a silica SPE cartridge and eluted with IO% DCM in hexane. The

extract was then analyzed by GC / MS using a 0.25 mm x 60 m fused silica capillary column with a 5 % phenyl-

suh,tituted methy lpolys1loxane phase (0.25 µm film thic kness). The GC/MS (JI) re5u]ts were obtained in the same

manner as the GC/MS (I) analyses except that the six test portions were extracted us ing PFE The GC/MS (lll)

analyses were performed on the same extract fractions analyzed in GC-ECD (II) us ing the 5 % phenyl-substituted

meth)'lpolysiloxane phase describe above for GC/MS (1). For both the GC-ECD and GC/MS analyses, two PCB

congeners that are not significantly present in the sediment extract (PCB 103 and PCB 198 [3]), and 4,4'-DDT-d8 were

added to the sediment prior to extraction for use as internal standards for quantification purposes.

In addition to the analyses performed at NIST, SRM 1944 wa used in an interlaboratory comparison exercise in 1995 as

part of the NIST lntercompanson Exercise Program for Organic Contaminants in the Marine Environment [4]. Results

from nineteen laboratories that participated in this exercise were used as the eighth data set in the determination of the

certified values for PCB congeners and chlorinated pes ticides in SRM 1944. The laboratories partic1patmg in this

exercise used the analytical procedures routinely used in their laboratories to measure PCB congeners and chlorinated

pesticides.

Polybrominated DiphenyJ Ethers: Value assignment of the concentrations of eight PBDE congeners was based on the

means ofresults from two interlaboratory studies [5,6] and two sets of data from NIST. The laboratories participating in

the interlaboratory exercises (see Appendix A) employed the analytical procedures routinely used in their laboratories to

measure PBDEs. For the two methods used at NIST, six test portions (between lg and2 g) were extracted using PFE at

I 00 "C with DCM. The extracts were cleaned up using an alumina column (5 % deactivated) SPE column. Size exclusion

chromatography (SEC) on adivinylbenzene-polystyrenecolumn (IO µm particle size, LO run (100 angstrom) pore size, 7.5 mm

i.d. .,., 300 mm, PL-Gel, Polymer Labs, Inc.) was then used to remove the sulfur. The PBDEs, as well as PCBs and pesticides.

were quantified using GC/MS m the electron impact mode on a 0.18 mm i.d. x 30 m fused silica capillary column with a 5 %

(mole fraction) phenyl methylpo)ysiloxane phase (0.18 µm film thickness; DB-5MS, Agilent Technologies). The PBDEs were

also quantified using GC/MS in the negative chemical ionization mode on a 0.18 mm i.d. x 10 m fused silica capillary column

with a 5 % {mole fraction) phenyl meth)'lpolysiloxane phase (0.18 µm film thickness; DB-5MS, Agilent Technologies).

Selected Carbun-13 labeled PBDE and PCB congeners were added to the sediment prior to extraction for use as internal

standards for quantification purposes.

Polychlorinated Dibenzo-p-dioxins and Dihenzofurans: Value assignment of the concentrations of the

polychlorinated dibenzo-p-dioxin and dibenzofuran congeners and the total tetra- through hepta- substituted

pol)'chlorinated dibenzo-p-dioxins and dibenzofurans was accomplished by combining results from the analysis of

SRM 1944 by fourteen laboratories that participated in an interlaboratory comparison study (see Appendix B). Each

laboratory analyzed three tes t portions (typically I g) of SRM 1944 using their routine analytical procedures and high

resolution gas chromatography with high resolution mass spectrometry detection (GC-HRMS). The analytical

procedures used by all of the laboratories included spiking with 13C-labeled surrogates (internal standards): Soxhlet

extraction with toluene; sample extract cleanup with acid/base silica, alumina. and carbon columns: and finally analysis

of the cleaned up extract with GC-HRMS Most of the laboratories used a 5 % phenyl-subs tituted methylpolys iloxane

phase capillary column (DB-5), and about half of the laboratories confirmed 2,3,7,8-tetrachlorodibenzofuran using a

50 % cyanopropylphenyl-substituted methylpolysiloxane (DB-225, J&W Scientific, Folsom, CA) capillary column.

Analytical Approach for Inorganic Constituents: Value assignment for the concentrations of selected trace elements

was accomplished by combining results ofthe analyses ofSRM 1944 from NIST, NRCC, IAEA, and seven laboratories

that participated in an interlaboratory comparison exercise coordinated by NRCC [7] (see Appendix C). The analytical

methods used for the detennination of each element are summarized in Table 18. For the certified concentration values

listed in Table 4, results were combined from: (1) analyses at NIST using isotope dilution inductively coupled plasma

mass spectrometry (ID-ICPMS) or instrumental neutron activation analysis (INAA), (2) analyses at NRCC using ID-

ICPMS, graphite furnace atomic absorption spectrometry (GFAAS), and/or inductively coupled plasma optical

emission spectroscopy (ICPOES), (3) analyses at IAEA using INAA, and (4) the mean of the results from seven

laboratories that participated in the NRCC interlaboratory comparison exercise. The reference mass fraction values in

Table 9 were determined by combining results from (I) analyses performed at NIST us ing INAA: (2) analyses at NRCC

using lD-ICPMS, GFAAS, ICPOES, and/or cold vapor atomic absorption spectroscopy (CVAAS); (3) analyses at IAEA

using TNAA; and (4) the mean of the results from five to seven laboratories that participated in the NRCC interlaboratory

comparison exercise. The information concentration values m Table 15 were determined by INAA at NIST and IAEA.

NIST Analyses using ID-TCPMS: Lead, cadmiu,m and nickel were determined by ID-lCPMS [8]. Test portions (0.4 g

to 0.5 g) from six bottles of the SRM were spiked with 206Pb, 11 1 Cd, and 62Ni and wet ashed using a combination of nitric,


hyd rochlo ric , hydrofluoric, and perchloric acids. Lead and cadmium were determined in the same test portions, nickel

as determined in a second sample set. A small amount of crystalline material r ema ine d after the acid dissolution.

Lithium metaborate fusion was performed on this res idue to confirm that the residue contained i ns ignificant amounts of

the analytes. Cadmium and nickel were separated from the matrix material to eliminate the possibility of spectral

interferences, and con centratio ns wen; determin ed from the measurement of the 1 12Cd/111 Cd and 62Ni /60Ni ratios,

respectively. The 208

Pb i206

Pb ratios were measured directly because interferences at these masses are negligible.

NIST Analyses using INAA: An alys es were p erfon ned in two steps [9]. E lemen ts with sho rt- liv ed irr ad iation p rodu cts

(Al, Ca, Cl, K, Mg, Mn, Na. Ti, and V) were determ in ed by measurin g duplicate 300 m g test p ortions fro m each of

ten b ottles of SRM 1944. Th e samp les , s tand ards, and con tro ls were pack aged in clean po lyethy len e b ags and were

indiv idu ally irr adiated for 15 s in the NIST Reactor Pneum atic Facility RT-4. Reactor po wer was 20 MW, which

corresp onds to a neu tron fluen ce r ate of abo ut 8 x 10 13

cm·2 s·1. Af ter irr adiation. the sam ples, con tro ls, an d standards

were repackaged in clean polyethylene bags and counted (gamma-ray spectrometry) three times at different decay

intervals. A s am ple-to-detector distan ce ( coun tin g geo metry) of20 cm was used . Elem en ts with lon g-liv ed irrad iatio n

products (Ag, As, Br, Co, Cr, Cs , Fe, Rb, Sb, Sc, Se, Th, and Zn) were d etenn ined by m easu rin g on e 300 m g test portion

from each of n ine bo ttles ofSRM 1944. Th e samples, standards, con trols. and b lank polyethylen e bags were irrad iated

to gether for a total of 1 h at a reactor po wer of 20 MW. Appro ximately four d ays af ter ir rad iation, the polyethylene bags

were remov ed, and each sample, stand ard, co ntro l, and blank was coun ted at 20 cm from th e d etector. The s amp les were

then r eco unted at IO cm fro m an oth er detector. Af ter an add itional decay time of about o ne m onth , the samp les,

standards, controls, and blanks were counted a third time (at 10 cm) from the second detector.

Homogeneity Assessment for Inorganic Constitutents: For so me of th e trace elemen ts, most no tab ly Cd, Fe, Pb, Rb,

Sb , Sc, and Th, the var ia tio ns amon g the test portions measured at NIST (between 0.3 g an d 0.5 g) were larger than

expected fro m the measurement pro cess. Bas ed on exp erience. it was conclud ed th at th ere is som e m aterial

inho mo geneity for trace elements in the tes t pm 1ions us ed . Sample v ariations amon g the NIST measurem ents are used as

slightly conservative estimates of the sample inhomogeneities.

Particle S ize Information: Dry p article-size d istr ibution measurements for SRM 1944 were ob tained as par t of a

collabo rativ e effor t with Honey well's Par tic le and Co mpon ents Measurem en ts Laboratory (Clearwater, FL). A Microtr ac

partic le analy zer, which mak es use of light-scatter in g tech niqu es, was used to measure th e particle-size distr ibu tion of

SRM 1944. Br ief ly, a r ef eren ce beam is used to pen etrate a f ie ld o f p artic les and th e ligh t that scatters in th e forward

direction from th e fie ld is measured and the p article-s iz e as a v olu me dis trib ution is d eriv ed via a comp uter-assis ted

analysis. From th ese d ata. the to tal v olu me, av erage ize, and a ch aracteris tic wid th of the par ticle size distribu tio n are

calculated. The system has a working range from 0.7 µm to 700 µm.

Total Organic Carbon and Percent Extractable Mass: Four laboratories provided results for total organic

carbon (TOC) usin g simila r procedure . Briefly, test portions of approximately 200 m g were reacted with 6 m ol/L

hydrochloric acid and rinsed with deionized water pnor to combustion in a gas fusion furnace. The carbon monoxide and

carbon dioxide produced were measured and compared to a blank for calculation of the percent TOC. Each laboratory

analyzed test portions from six bottles ofSRM 1944. For the determination of percent extracta ble mass, six test portions

of approximately 1 g to 2 g of SRM 1944 were extracted usin g Soxhlet extr action for 18 h with DCM. The extraction

thimbles were allo wed to a ir dry. After reachin g constant mass, the differen ce in the mass before and after extraction

was determined.

Polychlorinated Naphthalenes: Valu e assignment of PCN congener concentrations was accomplished by combining

results from the analysi s of SRM 1944 by six laboratories that participated in an in te rla boratory comparison study (see

Appendix D). Each laboratory analyzed three test portions (typically 1 g to 2 g) of SRM 1944 using their routine

analytical procedures that included high-resolution gas chromato graphy with either high-resolution m ass spectrometry

detection (GC-HRMS) or low-resolution MS in the negative chemical ionization mode . Calibration mixtures included

either Halowax mixtur es with known volume fractions of individual congeners or indi vidual PCN congeners.


HBCDs: Value assignm ent of the concentrations of three HBCO isomers was accomplished by combinin g results from

the analysis ofSRM 1944 in two sets from NIST and one set from Virginia lmtitute of Marine Science. For the two sets

analy zed at NIST , the second fraction from an acid ified silic a SPE clean-up was analyzed by LC/MS/MS for the HBCDs using

both electrospray ionization (ES!) and atmospheric pressurized photoiomzatton (APPi). A Cl 8 column (3.0 mm ,., 150 mm "

3 .5 µm column, Eclip e Plus. Agilent Technolo gies) and YMC Carotenoid S5 C30 column (4.6 mm ,- 250 mm, 5 µm

column) were used with a solvent grad ient usmg2.5 mmo l /L ammomu m acetate in 12.5 % water in methano l and acetonitrile

at a flow rate of 0.3 mL/min. Carhon-13 labeled HBCDs were added to the sediment pnor to solvent extraction for use as

internal standards for quantification purposes.

Table 1 Certified Mass Fraction Values for Selected PAHs in SRM 1944 (Dry-Mass Basis)

Mass Fraction •1- h )

(mg/kg)

Phenant hrene10. · d e . f g l 5.27 ± 0.22

Fluoranthene(c,d,e,f,g) 8.92 ± 0.32

Pyrene(cd , e f , g ) 9.70 ± 0.42

Benzo[c]phenathrene(c.d.c.f,hl 0.76 ± 0.10

Benz[a]anthracene, (c d e,f g,hJ 4.72 ± 0.11

Chrysene·1,h k J 4.86 + 0.10 (!)

T riphenylene r 11 kl 1.04 ± 0.27

Benzo[b]fluorantheneg. ( h, i l 3.87 ± 0.42

BenzoU]fluoranthene<hJJ 2.09 ± 0.44 Benzo[k]tluoranthene <,c.dd. gJ•)J 2.30 ± 0.20

Pery lene( c,d,e,,f,g h,1 ) 1.17 ± 0.24

Benzo[ghi]perylene''·<l.e.f..iJJ 2.84 ± 0.10

lndeno[1,2,3-c d] pyrenec <, . cd ,.tJ k1 2.78 ± 0.10

Dibenz[a.j]anthracene(c.de.f., J. k l 0.500 ± 0.044

Dibenz[a,c] anthracene' l•1 1 0.335 ± 0.013

Dibenz[a,h]anthracenelJ.kl 0.424 ± 0.069

Pentaphenec.4 dc ... f J.k) 0288 ± 0.026

Benzo[b ]c hr yse ne c 1 .d e . f J..k h ) 0.63 ± 0.10

P iecne (c,d,c,fJ,k) 0.518 ± 0.093

1' 1 Mass fractions an: reported on dry-mass basis. matenal as received contams approximately 1.3 % moisture. fbl Each certified value is a mean of the means from two or more amtlyt iw l rm::lhod:,, weighted as described m Pauk and Mandel [10]

Each uncertainty, computed according to the Com1te International de, Po1ds et Mesures (CIPM) approach as described in the ISO

Gmde [ I 1.12], is an expanded uncertamty at the 95 % level of confidence. which includes random sources of uncertainty w1th111

each analytical method as well as uncertamty due to the drymg study The expanded uncertamty defines a range of values w1thm

which the true value is believed to l,ie at a kvel of confidenl'e of approximately 95 %.

r,, Ga<; chromatog raphy/mass spectrometry (GC'/MS) ( I) on 5 % phcny I-substituted methylpolysiloxane phase after Soxhlet extraction

with DCM.

( d l GC/MS (ll) on 5 % pheny l-s ubstituted methylpolysiloxane phase after Soxhlet extraction wnh DCM

!• I GC/MS (III) on 5 % phenyl-substituted methylpolys1loxane phase after Soxhlet extraction with 50 % he--.ane/50 % acetone mi:,ture.

(fl GC/MS (TV) on 5 % pheny l-s ubstituted mcthylpoly iloxane phas after PFE with 50 % he-xane/50 % acetone mixture Csl LC-FL of total PAH fraction after Soxhlet extraction with 50 % hexane/SO% acetone mixture. Chi GC/MS ( Sm) usmg a smectic liquid crystalline phase after Soxhlet ext1action with DCM

,, c The uncertamty interval for chrysene was widened m accordanci;: wtth expert cons1derat1on of the analytical procedure , along with

the analysis of the dala a a whol e, which suggests that the half-widths of the expanded uncertainties should not be less than 2 %. (Jl GC/MS (V) on 50 % phenyl-wbstitulcd mcthylpoly 1loxane phase of extracts from GC/MS (IJI) and GC/MS (IV).

f l ) LC-FL of 1somenc PAH fractions after Soxhlet extractmn with 50 % hexan e/SO% acetone m1xlurc

Benzo[a]fluoranthene1"·d e .f..h J J 0.78 ± 0.12

Benzo[e]pyrene (c.d.e.f hJI 3.28 ± 0.11

Benzo[a]pyrene(c d.dg hJJ 4.30 ± 0.13


Table 2. Certified Mass Fraction Values for Selected PCB Congener :.13 1 in SRM 1944 (Dry-Mass Basis)

Mass Fractiun 1,h c )

(µg/kg)

PCB 8 (2 ,4 '- Dichlorobiphenyli , .d e f. ., h, . , J J 22 3 ± 2.3

PCB 18 (2,2',5-Tr ichlo robipheny Jl 0e·, ·gf, , , h. J ' 1 51.0 ± 2.6

PCB 28 (2,4,4'-Trichlorobipheny lid ·.e .gf J.•) 80.8 ± 2.7

PCB 31 (2,4',5-Trichlo rob iphenyl)l, de , ..gf )J 78.7 ± l.6!H

PCB 44 ( 2,2'3,5'-Tetrachlorob ipheny l)<,d,•f g . h •J k) 60.2 ± 2.0

PCB 49 (2,2'4,5'-Tetrachlo rob ipheny li d .c.g.f.. , h . J k) 53.0 ± 1.7

PCB 52 (2,2',5,5'-Tetrachlorobipheny l).<d d. . h.•J.k l 79.4 ± 2.0

PCB 66 (2,3',4,4'-Tetrachlorobiphenyl)'e,g.h,iJ, 71.9 ± 4.3

PCB 95 (2,2',3,5',6-Pentachlorobiphenyn<.• g. ,h l J ) 65.0 ± 8.9

PCB 87 (2,2'.3,4,5'-Pentach lorobiph enyl)'d ·• f·-·s, , h Jl 29.9 ± 4.3

PCB 99 (2,2',4,4',5-PentachlorobiphenyI)'d,e.f,g.h.,J.J..J 37.5 ± 2.4

PCB 101 (2.2',4,5,5'-Pentach lorob iph enyl i, d e .gf., , , ,h, 1 •J 73 4 ± 2.5

PCB 105 (2,3,3',4,4'-Pentachlorobip hen y])d1, , s h, . ,J k) 24.5 ± LI

PCB I IO (2,3,3',4'.6-Pentachlo robiphenyl )g< ·h· 1

>J 63 . 5 ± 4.7

PCB 118 (2,3',4,4',5-Pentachlo robiphenyl),' d.e . f ,g, .h, J • l 58.0 ± 4.3

PCB 128 (2,2',3.3',4,4'-Hexachlorobiphenyli , ,d ,c f s , h ,,, J J..J 8.47 ± 0.28

PCB 138 (2 ,2 1, 3 ,4,4',51-Hexachlorobipheny J ,)ld,e ., f s h.,1J k ) 62.1 ± 3.0

PCB 149 (2 ,2 1,3,4 'S ,6-Hexachlo robiphen y l Yd·d .g. h.i J.• 1 49.7 ± 1.2

PCB 151 (2.2',3,5,5 1,6-Hexach lorobiphenyl/ <i• .g.f. , h. J.l J 16.93 ± 0.36

PCB 153 (2.2',4,4 1,5,5 1-Hexach lo ro biphenyl/ d ,.c.gf, , , h, J k > 74.0 ± 2.9

PCB 156 (2 ,3 ,3 1,4,4 1 , 5-Hexachlorobipheny J), 'd, ,c,f s,, ,h 1} 6.52 ± 0.66

PCB 170 (2 ,2 ',3 ,3 1.4,4',5-Heptachlo robiphenyli d ·•·f·sh-, , , Jk l 22.6 ± 1.4

PCB 180 (2 .2 ',3 ,4,41,5,5'-Heptachlorobiphen ylt ·•. f. s,. h. J.kl 44.3 ± L2

PCB 183 (2,2'.3,4,4 1,5',6-Heptachlo robiphenyli d·,e ,gf, ,, h J} 12.19 ± 0.57

PCB 187 (2,2',3,4',5,5',6-Heptachlorob ipheny1 ,) 1,d ,eg, f h,, ,J k) 25.I ± LO

PCB 194 ( 2,2',3,3',4,4',5,51-0 ctach lorobip heny l/ d · • ·gf. h ,,, 1) 11.2 ± l 4

PCB 195 (2,2',3,3',4,4',5,6-Octachlorbipheny l)'d ·• f· ·s -h,.,J kJ 3.75 ± 0.39

PCB 206 (2,2'.3,3',4,4',5.5',6-NonachlorobiphenyIi. d e.f g,h tJ.l/ 9.21 ± 0.51

PCB 209 Decachlo rob iphenyl1d e. f,g,h,t J,k J 6.81 ± 0 .33

'" 1 PCB congeners are numbered accordmg to the scheme propo ed by Ballschmiter and Zell [13) and later revised by Schulte and

Malisch [3] to confonn \\>ith IUPAC rule ; for the specific congener5 mentioned in this SRM. the Ballschm1ter-Zell numbers corre;pond to those of Schulte and Mahsch.

\bJ Mass fractions are reported on dry-mass basis: matenal as received contams approximately I 3 % moisture

(cl Each certified value is a mean of the means from two or more analytical methods. weighted a; de;cribcd in Paule and Mandel [10).

Each uncertainty, computed according to the CIPM approach a; de;cribcd in the ISO Guide [11,12), 1s an expanded uncertainty at

the 95 % level of confidence. which includes random sources ofuncertamt)' within each analytical method as well as uncertainty

due to the drying study. The expanded uncertamty defines a range of values w1thm 1,1,h1ch the true value 1s belie"ed to lie, at a level

of confidence of approximately 95 %

( d J GC-ECD (IA) on 5 % phenyl-substituted methylpolys1loxane phase after Soxhlet extrachon with DCM 101

GC-ECD (1B) on the 50 % C-18 dimethylpolys1loxane phase, same extrm.:b analyLcd a:. in GC-ECD (IA ).

( O GC-ECD (IIA) on 5 % phenyl-substituted methylpoly ilo>.anc phase after So-xhlet extraction with DCM (g J GC-ECD (IIB) on the 50 % octadccyl (C-18) rnethy lpolys1l oxane pha. e, same extracts anal yzed as m GC-ECD (IIA).

<hJ GC/MS (I) on 5 % phenyl- subst itu ted methylpolysiloxane phase after Soxhlet extraction \\>!th 50 % hexane/SO% acetone mixture.

(i) GC/MS (11) on 5 % phenyl-substituted methylpolysiloxane phase after PFE extraction with 50 % hexane/50 % acetone mixture

IJJ GC/MS (lJl) on 5 % phenyl-substituted methylpolysiloxane phase: same extra,t analyzed a in GC-ECD (IIAJ

lk) Results from nmeteen laboratories part1cipatmg man interlaborntory comparison exercise

Ill The uncertainty interval for PCB 31 was widened in accordance with e-xpert cons1de1 ation ot the analyhcal procedures, along with

the analy is of the data as a whole. which sugge ts that the half-widths of the expanded uncertainties should not be less than 2 %


Table 3. Certified Mass Fraction Values for Selected Chlorinated Pesticides in SRM 1944 (Dry-Mass Basis)

Mass Fractlon(a.b)

(µg/kg)

Hexachlorobenzene( •r, g,h.i,,J

cis-Chlordane (a-Chlordane)'"·ct.,.f.g h,,,1)

rrans-Nonachlor Cc.ct.c.f.g.h.,Jl

6 03 ±

16 51 ±

8.20 ±

0.35

0 83

0.51

(a) Mass fracllons are reported on dry-mass basis; material as received contains approximately 1.3 % moisture

(t>J Each certified value is a mean of the means from two or more analytical methods, weighted as described m Paule and Mandel [IO].

Each uncertainty. computed according to the CIPM approach as described in the ISO Guide [11.12], 1s an e:'l.panded uncertamty at

thi.: 95 % kvcl ufconfitk:ni.:c, which indudes random sources ofuncertamty w1thm each analytical method as well as uncertainty

due to the dry mg study The expanded uncertainty defines a range ofvalucs within which the true value is believed to lie , at a level

of confidence of approximately 95 %

(c) GC-ECV (lA) on 5 % phenyl-substituted methylpolys1loxane phase after Soxhlet extraction with DCM

(dl GC-ECD (IB) on the 50 % octadecyl (C- I 8) methylpolysiloxane phase, same extracts analyzed as in GC-ECD {IA).

M GC-ECD (!IA) on 5 % phenyl-substituted methylpolysiloxane phase after Soxhlet extraction with DCM.

(ff GC-ECD (UB) on the 50 % octadccyl (C-18) rnethylpoly,iloxane phase, same extracts analyzed as in GC-ECD (IIA). (g) GC/MS (I) on 5 % phenyl-substituted methylpolysiloxane phase after Soxhlct extraction with 50 % hexane/SO% acetone mixture

(hl GC/MS (lll on 5 % phenyl-substituted methylpolysiloxane phase after PFE extraction with 50 % hexane/50 % acetone mixture

(,J GC/MS (III) on 5 % phenyl-substituted meth:,, lpolysiloxane phase, same extracts analyzed as in GC-ECD ( IIA) (JJ Results from nineteen laboratories participating in an interlaboratory comparison exercise.

Table 4. Certified Mass Fraction Values for Selected Elements in SRM 1944 (Dry-Mass Basis)

Aluminu m ( c,d ,c )

Jronlc.d,<)

Degrees of

Freedom

4

6

Mass Fractionsca,bJ

(%)

5.33 ± 0.49

3.53 ± 0.16

Arsenic(c,d,e.f.g) 10

Cadmiu m(c,f, h,,) 6

Chro m iu m''· d .f,g. I 9

Lead(c.h.o 5

Manganesecc.d,c) 8 NickeiCc,g .h ,,) 6

Zmc(c O e,g,,J 9

Mass Fract10nsl••hl

(mg/kg)

18.9 ± 2.8

8.8 ± 1.4

266 ± 24

330 ± 48

505 ± 25

76.1 ± 5.6

656 ± 75

(•> The certified value is the mean of four results: ( I) the mean of NIST INM or ID-ICPMS analyses. (2) the mean of two methods

performed at NRCC, and (3) the mean of results from seven selected laboratories partic1patmg m the NRCC intercomparison e"\.erci e. and (4) the mean results from lNAA analyses at IAEA The expanded uncertainty in the certified value 1s equal to

U = k11, where u, 1s the combined tandard uncertainty and k is the coverage factor, both calculated according to the ISO

Guide [I l, 12], The value of lie is mtended to represent at the level of one standard deviation the comhmed effect of all the

uncertainties in the certified value Here lie accounts for both possible method biases. w1thm-method variation. and material

inhomogeneity The coverage factor. k, 1s the Student's t-value for a 95 % confidence interval with the correspondmg degrees of

freedom Because of the material inhomogeneity, the variability among the measurements of multiple samples can be expected to

be greater than that due to measurement vanab1lity alone

lb> Mass fract10ns are reported on dry-mass basis; material as received contain approximately 1.3 % moisture.

(,J Results from five to seven laboratories partic1patmg in the NRCC mterlaboratory comparison exercise (dJ Measured at NIST usmg INAA.

<el Mca:,urc<l at NRCC u:,ing ICPOES.

(fl Mea5ured at NRCC using GFAAS (gl Measured at lAEA usmg lNAA.

lhl Measured at NIST usmg ID-ICPMS.

l•J Measured at NRCC using ID-ICPMS


Table 5 Reference Mass Fraction Values for Selected PAHs in SRM l 944

Mass Fract1ons•1l

(mg/kg)

d J

0.02(h,1)

0.03(h.,)

d J

1-Methy lpyrene1d1 1.29 ± 0.Q3Ch)

Anthanthrenelll 0.9 ± 0.1(h)

• 1

J Mass fractions are reported on dry-mass basis: material as recen,ed contains approximately 1.3 % moisture

(bJ GC/MS ( VI) on proprietary non-polar methy lpolysi]o,.ane phase after Sol\.hlct exlraction wilh DCM

\cl Reference values are the means of results obtained by NIST using one analytical technique The expanded uncertainty, U. 1s

calculated a, lJ = ku,, where u0 1s one standard deviation of the analyte mean, and the coverage factor. k. 1s determmed from the Student's r-distribut10n corresponding to the associated degrees of freedom (df= 2) and 95 % confidence level for each analyte

td) GC/MS (]) on 5 % phenyl-substituted methylpolysiloxane phase after Soxhlet extraction with DCM. re, GC/MS (II) on 5 % phenyl-substituted methylpolys1loxane phase after Soxhlet extraction with DCM

if) GC/MS (III) on 5 % phenyl-substituted methylpolys1loxane phase after Soxhlet extraction with 50 % hexane/SO% acetone

mixture.

s1 > GC/MS (lV) on 5 % phenyl-sub,t1tuted methylpolysiloxane phase after PFE with 50 % hexane/SO% acetone mb.ture.

ih\ J'he reference value for each analyte is the equally-weighted mean of the means from two or more analytical methods or the mean

from one analytical technique The uncertainty in the reference value defines a range ofvaluc that i, intended to function as an

interval that contain the true value al a level of confidence of95 % This uncertainty includes sources of uncertainty within each

analytical method. among methods. and from the drying study (1 )The uncertainty mten,al for this compound was widened m accordance with expert consideration of the analytical procedures,

along with the analysis of the data as a whole. which suggests that the half-widths of the expanded uncertainties should not be less

than 2 % 10 LC-FL of isomeric PAII fractions after Soxhlet e"-tract1on with 50 % hexane/SO% acetone mi"turc.

Naphthalene(bl 1.28 ± 0.04'''

I - Methylnaph thalcnc(b l 0.47 ± o.oic)

2-Methylnaphthalene(h) 0.74 ± 0.06/c)

Biphenyl<bJ 0.25 ± o.oic)

Acenaphthene(b> 0.39 ± 0.03(c)

Fluorene(bJ 0.48 ± 0.04(C)

Dibenzothiophene(hl 0.50 ± 0.03(C)

Anthracene<hJ l.13 ± 0.07(c)

1-Methy lphenanthrene(<l.c.f.gi l.7 ± 0.] Ch)

2- Methy lp henanthrence. d e, .fg )

3- Methy lphenanthreneld,e,f,gJ

l.90

2.1

± ±

0.06Ch)

0.1 (h)

4-Methylphenanthrene and 9-Methylphenanthrene(tl,e,f J

1.6

±

0.ihJ

2-Methylanthracene(<l.e.f.gJ 0.58 ± 0.04ChJ

3,5-Dimethylphen anthrene1 ctJ 1.31 ± 0.04/hl

2,6-Dimethylphenanthrene'ctJ 0.79 ± 0.02(h.1)

2,7-Dimethy lphen anthrene1 0.67 ± o.02'h.,1

3,9-Dimethy lphenanthrene(<lJ 2.42 ± o.05<h.,,

1,6-, 2,9-, and 2,5-Dimethylphenanthrene<ctJ 1.67 ± 0.03(h.,J

1,8-Dimethy lphenanthrene(<lJ 0.24 ± 0.01ch,,)

1, 2-Dimethylphen anthrene1 0.28 ± 0.01(h.,J

8-Methy ltluoranthene(ct) 0.86 ± 0.02(h,1)

7-Methylfluoranthene(rll 0.69 ± o.oihl

l-Me thyl fluoranthene 1h1 0.39 ± 0.01Cc)

3-Methy lfluoranthene<bl 0.56 ± 0.02(c)

2-Methy lpyrene(dJ l.81 ± 0.04Ch,l)

4-Methylpyrener d' 1.44 ± 0.Q3ch,,)

1,7-Dimethy lphen anthrene d1 J 0.62 ±

1,9- and 4,9-Dimethylphenanthrene\d) 1.20 ±


Table 6. Reference Mass Fractions for Selected PAHs of Relative Molecular Ma5, 300 and 302 in SRM 1944 ( Dry-Mass Basis)

Mass Fract10n 1 " b c l

(mg/kg)

Coroncne 0.53 ± 0.04

Dibenzo[b,e]fluoranthene 0.076 ± 0.008

Naphtha[1,2-h]fluoranthene 0.70 ± 0.06

Naphtho[l ,2-k]fluoranthene

and Naphtho[2.3-J ]fluoranthene 0.66 ± 0.05

Naphtho[2,3-h ]fluoranthene 0.21 ± 0.01

Dibenzo[ b,k]fluoranthene 0.75 ± 0.06

Dibenzo[a,k]fluoranthene 0.22 ± 0.02

DibenzoU, l]fluoranthene 0.56 ± 0.03

Dibenzo[a,l]pyrene 0.12 ± 0.02

Naphtho[2,3-!..]fluoranthene 0.11 ± 0.01

Naphtho[2,3-e]pyrene 0.33 ± 0.02

Dibenzo[a,e]pyrene 0.67 ± 0.05

Naphtho[2, 1-a]pyrene 0 76 ± 0,05

Dibenzo[e,l]pyrene 0.28 ± 0.02

Naphtho[2,3-a ]pyrene 0.23 ± o.oi Benzo[b]perylene 0.43 ± 0.04

Dibenzo[a,i]pyrene 0.30 ± 0.03

Dibenzo[a,h]pyrene 0.11 ± 0.01

(al Mass fractions are reported on dry-mass basis, material as received contains approximately 13 % moisture.

(bl Reference values are the means of results obtained by NIST usmg one analytical techmque. The expanded uncertainty. U. is calculated as U == ku,, where u0 1s one standard deviation of the analyte mean, and the coverage factor, k, is determined from the Student's I-

distribution currc,pumling lo the a,,ociatcd degrees of freedom (df= 2) and 95 % confidence level for each analyte (,, GC/MS on 50 % phenvl-suh tituted methylpolysiloxane phase after PFE \\-ith DCM.


a ) Table 7 Reference Mass Fractions for Selected PCB Congeners1

and Chlorinated Pesticides in SRM 1944 (Dry-Mass Basis)

Mass Fraction

1

u-HCH{f,g,h.,i

trans-Chlordane (y-ChlordaneY°l cis-NonachlorCg.h.,,1,rnJ

, 2 4 '- DD E (f,g h,IJ k,I rn)

2,4' -DDD(hJ,k,l,m)

{ tg/kg)

J.4Cd)

1 .9(d)

2 .Q(dl

0 ,6(d)

0.3(e)

1.id)

o.ie) 3le)

g(e)

4 ,4 '-D D E (f g,h 1hJ k,l,mJ tt•l

4,4 '-DDD (f,g,h .lJ.k . l.m ) 108 ± 16'e)

4,4'-DDT'C) 170 ± Jid)

l•J PCB congeners are numbered according to the scheme proposed by Ballschmiter and Zell [13] and later revised by Schulte and

Mahsch [3] to conform with JUPAC rules: for the ,pecific congeners mentioned in this SRM, the Ballschmiter -Zell numhers

wrrcspond to those of Schulte and Malisch

' Mass fract10ns are reported on dry-mass has1s, material as received contams approximately 1.3 % m01sture.

le, NIST participation in the 2007 mterlaboratory study usmg GC/MS.

' Reference values are the means of results obtained by NIST usmg one analytical technique The expanded uncertainty, U, is calculated as U = ku,, where u0 is one standard deviation of the analytr mean, and the coverage factor, k, is determined fro m the Student's t-distribution correspondmg to the as ocmted degree, offieedom (df= 2) and 95 % confidence level for each analyte.

le/ The reference value for each analyte is the equally-weighted mean of the means from two or more analytical methods or he mean

from one analytical technique. The uncertainty in the reference value defines a range of values that is intended to function as an

mtel"\'al that contains the true value at a level of confidence of95 %. This uncertainty mcludes sources of uncertainty within each

analytical method, among methods. am.I from the drying study

!fl GC-ECD (IA) on 5 % phenyl-substituted methylpolysiloxane phase after Soxhlet extraction with DCM.

(sl GC-ECD (IB) on the 50 % octadecyl ( C-18) rnethylpolysiloxane phase; same extracts analyzed as 111 GC-ECD (IA).

' GC-ECD (IIA) on 5 % phenyl-substituted methylpolys1loxane phase after Soxhlet extraction with DCM.

(,, GC-ECD (IIB) on the 50 '}o octadecyl (C-18) methylpolys1loxane phase: same extracts analyzed as in GC-ECD (IIA),

(JI GC/MS (I) on 5 % phenyl-substituted methylpolysiloxane phase after Soxhlet extraction with 50 % hexane/50 % a1.:ctonc mixture

(I.JGC/MS (II) on 5 % phenyl-sub,titutcd rndhylpolysilm,ane phase after PFE extraction with 50 % he-...ane/50 % acetone mixture

(II GC/MS (III) on 5 % phenyl-substituted methylpoly,iloxane phase: same extracts anlayzed as 111 GC-ECD (IIA). 1"'lRe, ult, from nineteen laboratories participating in an mterlaboratory comparison exercise.

h )

th

1d

1h

PCB 45 (2,2',3,6-Tetr achloro biph eny l/°) 10.8 ±

PCB 146 (2,2',3,4',5,5'-Hex achloro biph en yIi '; 10.1 ±

PCB 163 (2,3,3',4',5,6-Hexachloro bip heny Jyc1 14.4 ±

PCB 174 {2,2',3,3' ,4,5,6'-Heptachloro bip h eny ll°J 16.0 ±

2.0 ±

19.0 ±

3.7 ±

19 ±

38 ±

86 ±


Table 8. Reference Mass Fraction Values for Selected PBDF:s in SRM 1944 (Dry -Mass Basis)

Mas5 Fractions<•)

(µg/kg)

PBDE 47 (2.2',4,4'-Tetrabromodiphenyl etherY"d' fl 1.72 i. 0.28(bl

PBDE 99 (2,2',4,4'.5-Pentabromodiphenyl ether)'"·d.fl 1.98 ± 0.26(b)

PBDE I 00 (2,2',4,4• ,6-Pentabromodiph enyl cthcr/c,d) 0.447 ± 0.02ib)

PBDE 153 (2,2',4,4' ,5,5'-Hex abro mod iph eny l ethedc, ,d e, fJ 6.44 ± O.JibJ

PBDE 154 (2.2'.4,4',5,6'-Hexabromodiphenyl ethert·d.n 1.06 ± 0.08(bl

PBDE 183 (2,2',3,4,4',5'.6-Heptabromodtphenyl ether/"·d,e,fl 31.8 ± 0.1 f b ►

PBDE 206 (2,2',3,3· ,4,4',5,5',6-Nonabrom odip hen yl ethedd e) 6.2 ± J_Q(b/

PBDE 209 (Decabromodipheny l ether)\c , ,d e, f) 93.5 ± 4.4(h/

<•► Mass fractions are reported on dry-mass basis. material as received contaim approximately 1 3 % moistun: /bl Reference values are v.eighted means of the results from two to four analytical method5 [14]. The uncertamty listed with each

,alue is an expanded uncertainty about the mean. with coverage factor 2 (approximately 95 % confidence). calculated by

combining a between-method variance incorporatmg inter-method bias with a pooled within-source variance followmg the

JSO/NJST Guide to the Expression ofUncertamty m Measurements [I 1.12]. (c) Results from ten laboratories participating in an inll;rlaboralory ,tudy fo r PBDEs in sediment [12]

(di Results from four laborntones part1c1pating m the 2007 mterlahoratory study [13] cei NIST partic1pat1on m the 2007 mterlaboratory study using GC/MS.

co Data set from NIST for PBDEs usmg GC/MS following PrE with alumina SPE and SEC clean-up.

Table 9. Reference Mass Fraction Values for Selected Elements in SRM 1944 (Dry-Mass Basis)

Degrees of

Freedom

81

Antimony(c.e,f.gi

Beryllium(c,h)

Copper(" a.n

Mercury<c,,J

Selenium<c.e ,I )

Silveic,d,e,g)

Thallium(" fJ

Tin re.fl

Mass Fractionra,bi

(%)

31 ± 3

Mass Fractionr•-b J

(mg/kg)

(al The reference value 1s the equally weighted mean of available results from: ( 1) NIS 'I INAA analyses. (2) two methods performed at NRCC, (3) results from seven selected laboratones participating m the NRCC mtercomparison exercise, and (4) results from

INAA analyses at IAEA. The C'\panded unn:rtainty in the reference value is equal to U = ku, where u, is the combined standard uncertamty and k 1s the coverage factor, both calculated according lo the ISO Guide (I 1.12] The value of u0 is intended to

represent at the level of one standard devmt10n the uncertamty m the value Here 11, account for possible method differences,

w1thm-method ,anation. and material inhomogeneity. ·1 he coverage factor. k. is the Student's t-,alue for a 95 % confidence interval with the corresponding degrees of freedom Because of material mhomogene1ty. the variability among the measurements

of multiple test portions can be e-xpected to be greater than that due to measurement variability alone. (b) Mass fractions are reported on dry-mass basis. material as received contain appro;,,.imately I 3 % mublure

(c) Results from five to seven laboratone parucipatmg m the NRCC mterlaboratory comparison exercise

(dJ Measured at NRCC using GFAAS,

(el Measured at NIST using INAA, (f1 Mea,un:d at NRCC usmg ID-ICPMS.

lil Measured at IAEA using JNAA.

lhJ Measured at NRCC usmg ICPOES.

r,i Measured at NRCC usmg cold vapor atomic absorption spectroscopy (CVMS),

18 46 ± 0.9

17 1.6 ± 0.3

IOI 380 ± 40

18 34 ± 0.5

24 1.4 ± 0.2

8 6.4 ± 1.7

12 0.59 ± 0.1

22 42 ± 6


Table JO. Reference Mass Fract10n Values for Elements m SRM 1944

as Determined by INAA (Dry-Mass Basis)

Effective Degree:, Mass Fract io n13 bl

of Freedom (%)

Calcium 21 1.0 ± 0.1

Chlorine 21 1.4 ± 0.2

Potassium 21 1.6 ± 0.2

Sodium 25 1.9 ± 0.1

Mass Fraction(•.hl

(mg/kg)

Bromine 10 86 ± 10

Cesium 11 3.0 ± 0.3

Cobalt JO 14 ± 2

Rubidium 14 75 ± 2

Scandium 37 10.2 ± 0.2

Titanium 21 4300 ± 300

Vanadium 21 100 ± 9

1"

1 The reference value is based on the results from an INAA study The associated uncertamty accounts for both random and systematic effects. but because only one method was used. the re3ult hould be uso;:d with caution Thi; expanded un1;crtain1y in

the rcfcrcn1;c value is equal to U = kuc where Uc is the combined standard uncertarnty and k i, the coverage factor, both calculated

according to the ISO Guide [11.12]. The value ofuc 1s intended to represent at the level of one standard deviation the uncertainty m the value. Here uc accounts for possible method differences. within-method vanation, and matenal inhomogeneity. The

coverage factor, k, 1s the Student's t-value for a 95 % confidence interval with the corresponding degrees of freedom. Because of

material mhomogeneity. the vanab1lity among the measuremt'nt of multiple te t portion can be C'<pecled lo be greater than tha t

due to mi;asurcmenl variability alone

cb/ Mass fractions are reported on dry-mass basis; material a received contmm approximately 1 3 % moisture.


Table 11. Reference Mass Fraction Values for

Selected D1benzo-p-Dioxm and Dibenzofuran Congeners in SRM 1944 (Dry-Ma s Basis)

Mass fraction'",1,)

( Lg/kg)

2,3,7,8-Tetrachlorodibenzo-p-dioxm 0.133 ± 0.009

1,2.3.7,8-Pentachlorodibenzo-p-dioxin 0.019 ± 0.002

1,2,3,4.7,8-Hexachlorod1benzo-p-dioxin 0.026 ± 0.003

1.2,3,6.7,8-Hexachlorodibenzo-p-dioxin 0.056 ± 0.006

1.2,3,7,8,9-Hexachlorodibenzo-p-dioxin 0.053 ± 0.007

1,2,3,4,6,7,8-Heptachlorodibenzo-p-dioxin 0.80 ± 0 07

Octachlorod1benzo-p-dioxin 5.8 ± 0.7

2,3,7,8-Tetrachlorodibenzofuran1'l 0.039 ± 0.015(dJ

1,2,3,7,8-Pentachlorodibenzofuran 0.045 ± 0.007

2,3,4,7,8-Pentachlorodibenzofuran 0.045 ± 0.004

1,2,3,4,7,8-Hexachlorodibenzofuran 0.22 ± 0 03

1,2,3,6,7,8-Hexachlorodibenzofuran 0.09 ± 0.01

2,3,4,6,7,8-Hexachlorodibenzofuran 0.054 ± 0.006\e)

1,2,3,4,6,7,8-Heptach lorodibenzofuran 1.0 ± 0.1

1,2,3,4,7,8,9-Heptachlorodibenzofuran 0.040 ± 0.0061 ) '

Octachlorodibenzofuran 1.0 ± 0.1

Total Toxic Equivalents (TEQ/ 0 0.25 ± 0.01

Total Tetrachlorodibenzo-p-dioxins 0.25 ± 0.05(e)

Total Pentachlorodibenzo-p-dioxins 0.19 ± 0.06

Total Hexachlorodibenzo-p-dioxins 0.63 ± 0.09

Total Heptachlorodibenzo-p-dioxins l.8 ± 0.2

Total Tetrachlorodibenzofurans 0.7 ± 02

Total Pentachlorodibenzofurans 0.74 ± 0.07

Total Hexachlorodibenzofurans 1.0 ± 0.1

Total Heptachlorodibenzofurans 1.5 ± 0.1

Total Dibenzo-p-dioxins(g) 8.7 ± 0.9

Total Dibenzofurans'g) 5.0 ± 0.5

rai Each reference value i the mean of the results from up to fourteen laboratories participating in an mterlaboratory exercise. The

expanded uncertainty in the reference value is equal t1J U = kuc wher;; u, is the combined standard uncertainty calculated accordmg

to the JSO Uuide 111.12J and k is the coverage factor. The value of u, 1s intended to represent at the level of on.: tandard d.:viation

the combined effect of all the uncertamties in the reference value. Here u, is the uncertarnty in the mean arismg from the variation

among the laboratory results. The degrees of freedom is equal to the number of available results minus one (13 unless noted

otherwise) The coverage factor. k, 1s the value from a Student's t-distnbut1on for a 95 % confidence mterval. ibJ Ma55 fractJOns are reported on dry-mass basis; material a:, n:ceived contains approximately I 3 ¾ moisture

(cJ Confirn1ation results using a 50 % cyanopropyl phenyl polysiloxane or 90 % bis -cyanopropyl IO% cyanopropylphenyl

polysiloxane phase columns. idi Degrees of freedom= 7 for this compound.

◄e J Degrees of freedom= 12 for this compound.

ifl TEQ 1s the sum of the products of each of the 23.7.8-substituted congeners mult1phed by their mdiv1dual toxic equivalency

factors (TEFs) recommended by the North Atlantic Treaty OrganiLalion (NATO) [15]. With regard to 2,3,7.8-

tetrachlorod1benzofuran, the results of the confirmation column were used when available to calculate the TEQ

M Total of tetra- through octachlormated congeners.


Table 12. Reference Values for Particle Size Characteristics for SRM 1944

Particle Measurement

Mean diameter (volume distribution. MV, µm)l b J

Mean diameter (area distribution, µmr 1

Mean diameter (number tlistnbution. 1m)(d)

Surface Area (m2/cm3/el

151.2 ±

120.4 ±

75.7 ±

0.050 ±

0.4

0.1

0.3

0.013

(a ) The reference value 1s the mean "value of measurements from the analysb of tes t portions fro m four bottles Each uncertainty. computed according to the CIPM approach as described in the ISO Guide [1 U2]. is an expanded uncertainty at the 95 % le"vel nf

confidence, which includes random :;ources of un certain ty. The expanded uncertainty defines a range of"values for the reference

value within whic:h the true value is heheved to lie , at a level of confidence of95 %.

( h i The mean diameter of the volume distnbution represents the center of gravity of the distribution and compensates for scattering efficiency and refractive index This parameter is strongly mfluenced by coarse particles

(c ) The mean diameter of the area distribution. calculated from the volume d1stnbullon with less weighting by the presence of coarse

particles than MV

(d)The mean diameter of the number distnbut10n, calculated using tht: volume di tribution weighted to small particles

(el Calculat,;;d pccific surface area assuming solid, spherical particles This 1s a computation and should not be interchanged with an

adsorptton method of urfacc area determination as this value does not reflect porosity or topographical characteristics.

Table 13 . Percentage of the Volume That is Smaller Than the Indicated Size

Percentile Particle Diametet1"'

(µm)

9S 296 ± s 90 247 ± 2

80 201 ± 1

70 174 ± 1

60 152 ± I 50 1b) 135 ± 1

40 120 ± 1

30 106 ± 1

20 91 ± 1

10 74 ± 1

<•J The reference value for particle diameter 1 the mean value of measurements from the analysis oftest portions from four bottles.

Each uncertainty, computed according to the CIPM approach as descnbed in the ISO Guide [11,12), 1s an expanded uncertamty at

the 95 % level of confidence, which includes random sources of uncertainty. The expanded uncertainty defines a range of values for the reference value withm which the true value is believed to lie, at a level of confidence of 95 %

( b l Median diameter (50 % of the volumt: is less than 135 µm).


Table 14. Reference Values for Total Organic Carbon and Percent Extractable Mass in SRM 1944

Mass Fraction

(%)

Total Organic Carbon (TOC)f,.bi

Extractable Mass<c a, 4.4 ±

1.15 ±

03

0.04

(a) Mass fraction is reported on a dry-mass basis: material as received wntain approximately l 3 % moisture

ibi The reference value for total organ 1c carbon is an equally weighted mean value from routine measurements, made by three

laboratories. Each uncertainty. computed according to the CIPM approach as described in the ISO Guide [11,12], 1s an e;1.panded

uncertainty at the 95 % level of confidence, which includes random sources of uncertainty. The expanded uncertainty defines a

range of values for the reference value within which the true value 1s believed to lie, at a level of confidence of95 %

(cJ E'.trnctable mass as determined from Soxhlct extraction using DCM.

(di The reference value for extractable mas5 1s the mean value of six measurements. Each uncertamty. computed accotdmg tn the

CIPM approach as described in the ISO Gmde [11.12], is an expanded uncertainty at the 95 % level of confidence. which includes

random sources ofuncertamty. The expanded uncertamty defines a range of values for the reference value within which the true

value is believed to lie, at a level of confidence of 95 %.

Table 15. Information Mass Fraction Values for Selected Elements in SRM 1944

as Determined by INAA (Dry-Mass Basis)

Mass Fraction'•)

(%)

Magnesium<hJ 1.0

Ceriu m1

b J

Europium Cb)

Gold(bJ

Lanthanum h1 1

Thorium(bl

Uranium(hl

Mass Fract10n'" 1

(mg/kg)

65

I 3

0.10

39

13

3.1

(a) Mas fraction i reported on a dry-mass basis; material a r.:-ccived contain approximately 1.3 % mob tun;.

lb) Measured at IAEA usmg INAA


Table 16 Information Ma,s Fraction Values for

Selected Polychlorinated Naphthalenes m SRM 1944 (Dry-Mass Basis)

Mass Fraction(aJ

(µg/kg)

PCN 19 (1,3,5-Trichloronaphth alene) 1.4

PCN 23 (1,4,5-Trichloronaphth alene) 2.4

PCN 42 (1,3,5,7-Tetrachloron aphthalen e) 2.7

PCN 47 (1,4,6,7-Tetrachloron aphthalen e) 3.5

PCN 52 (1,2,3,5.7-Pentachloronaphth alene) 2.5 60 (1,2,4,6,7-Pentachloronaphth alene)

PCN 50 (1,2,3,4,6-Pentachloronaphth alene) 1.0

PCN 66 (1,2,3,4.6,7-Hexachloronap hth alene) 0.63

67 (1,2,3,5,6,7-Hexachloronap hth alene)

PCN 69 ( 1,2,3,5,7,8-Hexachloronaphth alene) 1.6

PCN 73 ( 1.2,3,4.5,6,7-Heptachloronaphthalene) 0.51

PCN 75 (Octachloronaph thalen e) 0.20

la) Mass fractions reported on dry-mass basis: matenal as received contains approximately 1.3 % moisture. Information values are the

median of the results from six laboratories participating in an interlaboratory compari on exerci e (Appendix D).

Table 17. Information Mass Fraction Values for Three HBCD Isomers in SRM 1944 (Dry -Mass Basis)

alpha- H BC D(l,1 beta-HBCDchl

gamma-HBCD(b)

Mass Fraction(a,b)

(µg/kg)

2.2

1.0

18

(al The information value is the median of the results from three analvt1cal methods.

lbl Mass fractions are reported on dry-mass basis; material as received contams approximately 1.3 % m01sture.


Table 18. Analytical Methods Used for the Mea urement or Element5 m SRM 1944

Elements Analytical Methods

Aluminum

Antimony

Arsenic

Beryllium

Bromine

Cadmium

Calcium

Cerium

Cesium

Chlorine

Chromium

Cobalt

Copper

Europium

Gold Iron

Lanthanum

Lead

Magnesium

Manganese

Mercury

Nickel

Potassium

Rubidmm

Scandium

Selenium

Silicon

Silver

Sodium

Thallium

Thorium

Tin

Titanium

Uranium

Vanadium

Zinc

FAAS, ICPOES. INAA, XRF

GFAAS, HGAAS, fCP-MS, ID-ICPMS, TNAA

GFAAS, HGAAS, ICPMS, INAA, XRF

GFAAS, ICP-AES. JCPMS INAA

FAAS, GFAAS, ICPMS, ID-ICPMS

INAA

INAA

INAA

fNAA

FAAS, GFAAS, ICPMS, ID-ICPMS, INAA, XRF

INAA

FAAS, GFAAS, ICPOES, lCPMS, ID-ICPMS, XRF

INAA INAA

FAAS, ICPOES, JCPMS, ID-TCPMS, INAA, XRF

INAA

FAAS. GFAAS. ICPMS, ID-ICPMS, XRF INAA

FAAS. ICPOES, ICPMS, INAA, XRF

CVAAS, ICPMS

GFAAS, ICPOES, ICPMS, ID-ICPMS, INAA, XRF

INAA

JNAA

INAA

GFAAS. HGAAS, ICPMS, INAA

FAAS, ICPOES, XRF

FAAS. GFAAS. ICPMS, INAA

INAA

GFAAS, JCPOES. JCPMS. ID-ICPMS,

INAA

GFAAS, JCPMS, ID-JCPMS

INAA

INAA INAA

FAAS, ICPOES, ICPMS, TD-TCPMS, XRF, TNAA

Methods

CVAAS

FAAS

GFAAS

HGAAS

ICPOES

ICPMS

10-ICPMS

INAA

XRF

Cold vapor atomic absorption spectrometry

Flame atomic absorption spectrometry

Graphite furnace atomic absorption spectrometry

Hydride generation atomic absorption spectrometry

Inductively coupled plasma optical emission spectrometry

Inductively coupled plasma mass spectrometry

Isotope dilution inductively coupled plasma mass spectrometry

Tnstrumental neutron activation analysis

X-ray fluorescence spectrometry


REFERENCES

[1] May, W.: Parris, R.; Beck, C.; Fassett. L Greenberg, R; Guenther, F; Kramer. G.; W1:c,e, S.: Gills, T; Colbert, J.;

Gettings, R.; MacDonald, B.; Definirions of Terms and Modes Used ar NJST for Va/11e-AHtRIIH1€ llf of Reference

Matenals for Chemical Measuremen ts; NIST Special Publication 260-136, U.S. Government Printing Office:

Gaithersburg. MD (:2000), available at

http://ts.nist.gov /Measurem entServices /ReferenceMater ia ls/PUBLlCATIONS.cf in (accessed Sep 2011)

[2] Wise, S.A. ; Poster, D.L.; Schan tz, M.M.; Ku cklick , J.R.; Sand er, L.C.: Lo pez de Ald a. M.: Schu ber t, P. ;

Pams, R.M. ; Porter, B. J. ; Two New Ma rine S ediment S tand ard Referen ce Materia ls (S RM:.,) jo r th e Determina tio n of

Organic Contaminants; Anal. Bioanal. Chem., Vol. 378, pp. 1251-1264 (2004)

[3] Schulte E.: Malisch, R. ; Calcula tion of the Rea l PCB Content m Environmenta l Samples. l. Investigation of th e

Composition of Two Technical PCB Mixtures; Fresenius Z. Anal. Chem., Vol 314, pp. 545-551 (1983).

[4] Parns, R.M.; Sch antz, MM.; Wise, S.A. ; NIS T/NOAA NS & TIEPA EMAP Interco mpa rison Exemse Prog ra mfo r

Organ ic Con ta minants in the Ma nne Envrron ment. Description and Resu lts of 1995 Organ ic ln terco mpan so n

Exercises; NOAA Technical Memorandum NOS ORCA 104, Silver Spring, MD (1996).

[5] Stapleton, H.M. ; Keller, J.M.; Schan tz. M.M.; Kucklick, J.R. ; Wise, S.A. ; NIS T In ter-Co mpa rison Exercise

Prog ra m fo r Polyb ro minated Diphen yl Eth ers (PBDEs) in Ma rine S ed imen t: Descrip tion and Results of the 20 04

Inter-Compa rison Exercise; NISTIR 7278 (2005).

[6] Schan tz, M.M.; Parris, R.M.; Wis e, S.A.; NIS T Interco mpa rison Exercise Prog ra m for Orga mc Con ta minants in the

Ma nne Environ ment. Descrip tio n and Results of the 20 07 Organic Interco mpa rison Exercises; NISTIR 7 501

(2008).

(7] Willie, S; Berman, S.; NOAA Nationa l Statu s and Trend s Prog ra m Ten th Ro und lntercmnpa risrm Exercise Results

for Trace Metals in Ma rin e S ediments and B iolo gical Tissue: NOAA Technical Memorandu m NOS ORCA 106,

Silver Spring, MD (1996).

[8] Beary, E.S. ; Pau lson, P. J.; S elective App lication o f Ch emical Sep aratwn s to I sotope Dilu tio n Ind uctively Co upled

Plasma Mass Spectrometric Analysis of Standard Reference Materials: Anal. Chem.• Vol. 65, pp. 1602-1608 (1993).

[9] Greenb erg, R.R.; Flem min g, R.F. ; Zeisler, R. ; High Sen sitivity Neutron Activation Ana lysi.5 of En viron mental and

Biological Standard Reference Materials; Environ. Intern., Vol. l 0, pp 129-136 ( 1984)

[10] Paule , R.C.; Man del. J.; Co nsen su s Va lues and Weigh ting Facto rs: J. Res. Nat. Bur. Stand , Vo l. 8 7 pp . 37 7-385

(1982).

[11] JCGM 1 00:2 008; Evaluation o f Mea su rement Data -Guid e tothe Exp re.1 swn o f Uncerta inty in Mea su rement(IS O

GUM 1 995 with Mino r Cor rections); Join t Co m mittee for Gu ides m Metrolo gy (2 008); available a t

http ://www.bip m.org/u tils /co m mon/docu m ents/jcgm /JCGM_l0 0_200 8_E p df (accessed Sep 20 11); see also

Tay lor, B.N. ; Kuy att, C.E.; Gu idelin es fo r El'aluating an d Exp ressmg th e Un certa mty of NIST Mea su remen t

Results; NIST Technical Note 1297 ; U.S. Gover nm ent Pr intin g Ot1ice: Wash in gton, DC (1 994); available a t

http://www.nist.gov/physlab/pubs/index.cfm (accessed Sep 2011).

[12] JCGM 101 :200 8; Eva luation o f mea su remen t data - Supp lement 1 to th e Guid e to Expresswn o f Uncerta rnty in

Mea su rement; Prop agatio n of Distr ibutions Us in g a Mon te Carlo Method; Jo in t Co mm ittee for Gu id es in Metro lo gy

(BJPM, IEC, IFCC, ILAC, ISO, IUPAC, IUPAP and OIML), In tern ation al Bureau of Weigh ts and Measures (BJPM),

Sevres, Fran ce (200 8); av ailab le a t h ttp://www.bipm.o rg/u tils/com mon /do cum ents /jcgm /JCGM_ l0l_ 2008_ E.pdf

(accessed Sep 2011).

[13] Ballsch miter, K. ;Zell, M.; An alysis of Polych lo rina ted Bip hen yls (PCB) by Glas Ca pilla ry Ga s Ch ro ma tog rap hy -

Co mpo sition of Tech nical Aro clo r- and Cloph en-PCB Mixtu res; Fresen ius Z. An al. Chem,.Vo l 302 , pp. 20-31

(1980).

[14] Ru hkin , A.L;Van gel, M.G. Estimatwn o f a Co mmon Mea n and Weigh ted Mean s Sta tistics; J. Am. Statist. Assoc.,

Vol. 93, pp. 303-308 (1998).

[15] Interna tio nal Toxicity Equ ivalency Fa cto r ( 1-TEF) Method of Ri k A sessmen t ja r Co mplex Mixtu re5 of Dio xin s and

Related Co mpound s, Nor th Atlantic Treaty Organ ization Co mm ittee on Ch allen ges in th e Mo dem Society, Repo rt

No. 176. North Atlantic Treaty Organization (NATO), Brussels, Belgium ( 1988).

Certifi cate R evision History : 27 Septem ber 2011 (Add11ton of mass frnct1on values for PBDE and PCN con geners; chan ge of mass fraction

refrrcncc value,, ed1tonal change,), 22 December 2008 (Exten,1110 of cert1ficatmn penod). 14 May 1999 (0rigma1 cert1ficate date)

Users of this SRM should ensure that the Certificate of Analysis in their possesszon is current. Thzs can be accompl rshed

by contacting the SRM Program at. telephone ( 301) 975-2200; fax ( 301) 926-4751: e-mail srminfo@nist gov; or via the

Internet at http://w1,1,w.nist.gov/srm.

http://ts.nist.gov/MeasurementServices/ReferenceMaterials/PUBLlCATIONS.cfin

http://www.bipm.org/utils/common/documents/jcgm/JCGM_l00_2008_E

http://www.nist.gov/physlab/pubs/index.cfm

http://www.nist.gov/physlab/pubs/index.cfm

http://www.bipm.org/utils/common/documents/jcgm/JCGM_l0l_2008_E.pdf


APPENDIX A

The analysts and laboratories listed below participated m the mterlaboratory companson o.crcise for the

determination of PBDEs in SRM 1944 [4].

D. Hoover and C Hamilton, AXYS Analytical, Sidney, BC, Canada

S Klosterhaus and J. Baker, Chesapeake Biolog1cal Laboratory, olomons, MD, USA

S Backus, Em,ironment Canada, Ecosystem Health Diviswn, Burlmgton, ON, Canada

E Sverko, Environment Canada, Canada Centre for Inland Waters, Burlington, ON, Canada

P. Lepom, Federal Environmental Agency, Berlm, Germany

R. Hites and L. Zhu, Indiana University, Bloomington, IN, USA

G. Jiang, Research Center for Eco-Environmental Sciences, Beijing, China

H. Takada, Tokyo University of Agriculture and Technology. Tokyo, Japan

A. Covaci and S. Vorspoels, University of Antwerp, Antwerp, Belgium

A. Li, Universtiy of Illinois at Chicago, Chicago, IL, USA

APPENDIX B

The analysts and laboratories listed below participated in the interlaboratory comparison exercise for the

determination of poly chlorinated dibenzo-p-dioxim and dibenzofurans in SRM 1944.

W.J. Luksemburg, Alta Analytical Laboratory, Inc., El Dorado Hills , CA. USA

L. Phillips, AXYS Analytical Services Ltd., Sidney, British Columbia, Canada

M.J. Armbruster, Battelle Columbus Laboratories, Columbus, OR USA

G. Reuel, Canviro Analytical Laboratories Ltd., Waterloo, Ontario. Canada

C. Brochu, Environment Quebec, Laval, Quebec, Canada

G. Poole. Environment Canada Environmental Technology Centre, Ottawa, Ontario, Canada

B. Henkelmann, GSF National Research Center for Environment and Health, Neuherberg, Germany

R. Anderson. Institute of Environmental Chemistry. Umea University, Umea, Sweden

C. Lastoria, Maxxam Analytics Inc., Mississauga, Ontario, Canada

E. Reiner, Ontario Ministry of Environment and Energy, Etobicoke, Ontario, Canada

J Macaulay, Research and Productivity Council. Fredericton, New Brunswick. Canada

T.L Wade, Texas A&M University, College Station, TX, USA

C. Tashiro, Wellington Laboratories , Guelph. Ontario, Canada

TO Tiernan, Wright State University, Dayton, OH, USA

APPENDIX C

The analysts and laboratories listed below parlic1paled in the interlaboratory comparison exercise for the

determination of trace elements tn SRM 1944.

A. Abbgy, Applied Marine Research Laboratory, Old Dominion University, Norfolk, YA, USA

A Scott, Australian Government Analytical Laboratories, Pymble, Australia

H. Mawhinney. Animal Research Institute, Queensland Department of Primary Industries, Queensland, Austra lia

E. Crecelius, Battelle Pacific Northwest, Sequim, WA, USA

M. Stephenson. California Department of Fish and Game, Moss Landing. CA, USA

B. Presley. Department of Oceanography, Texas A&M University, College Station, TX. USA

K. Elrick, U.S. Geological Survey. Atlanta, GA, USA


APPENDIX D

The analysts and laboratories listed below participated in the interlaboratory comparison exercise for the

determmation of poly chlorinated naphthalenes in SRM 1944.

J. Kucklick, National Jnstitute of Standards and Technology, Charleston, SC, USA

E. Sverko, Environment Canada, Canada Centre for Inland Waters, Burlington, ON, Canada

P Helm, Ontario Ministry of the Environment, Etobicoke, ON, Canada

N. Yamashita, National Jnstitute of Advanced Industrial Science and Technology (AJST), Tsukuba, Japan

T. Harner, Environment Canada, Meteorological Service of Canada, Toronto, ON, Canada

R. Lega, Ontario Mirnstry of the Environment, Etobicoke, ON, Canada

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of4

Certificate of Analysis Certified Reference Material

BNAs - Sandy Loam Number CRM143-50G

Lot LRAA1235

Solvent (Matrix) Sandy Loam Soil

Hazard Irritant

Storage &Handling Store at 4°C.

Expiration Date See Sample Label

Certification Date: April 02, 2013

Certified By: Christopher Rucinski - QA Director

Analyte

Certified Standard Confidence Prediction Units

Value k

Deviation Interval Interval

1,2-Dichlorobenzene µg/Kg 5,410 ± 578 1.96 1,570 4,810 - 6,010 2,270 - 8,550

1,4-Dichlorobenzene

Hexachlorobutadiene

Naphthalene

Acenaphthene

Acenaphthylene

Anthracene

Benzo(a)anthracene

Benzo(a)pyrene

Benzo(b)fluoranthene

506 - 2,410

3,680 - 13,000

1,410-5,080

3,060 - 7,650

1,930 - 5,640

2,000 - 4,310

729 - 1,650

1,880 - 4,020

3,310 - 7,890

Benzo(g,h,i)perylene µg/Kg 994 ± 97.9 1.96 272 900 - 1,090 453 - 1,530

Benzo(k)fluoranthene µg/Kg 4,400 ± 347 1.96 991 4,050 - 4,740 2,430 - 6,370

Benzoic acid µg/Kg 2,230 ± 1160 2.18 1,500 1,150 - 3,300 0.00 - 5,670

4-Bromophenyl phenyl ether µg/Kg 5,840 ± 456 1.96 1,220 5,410 - 6,280 3,420 - 8,270

Butyl benzyl phthalate µg/Kg 8,370 ± 577 1.96 1,540 7,800 - 8,930 5,300 - 11,400

4-Chloro-3-methylphenol µg/Kg 5,920 ± 491 1.96 1,360 5,440 - 6,400 3,210 - 8,630

bis(2-Chloroisopropyl) ether µg/Kg 1,800 ± 221 1.96 561 1,580 - 2,020 674-2,920

2-Chlorophenol µg/Kg 5,960 ± 590 1.96 1,640 5,390 - 6,520 2,700 - 9,210

4-Chlorophenyl phenylether µg/Kg 3,940 ± 321 1.96 857 3,620 - 4,250 2,230 - 5,640

Chrysene µg/Kg 6,730 ± 448 1.96 1,270 6,300 - 7,170 4,200 - 9,270

Dibenzo(a,h)anthracene µg/Kg 1,350 ± 112 1.96 305 1,230 - 1,460 738 - 1,950

Dibenzofuran µg/Kg 7,610 ± 535 1.96 1,440 7,060-8,160 4,730 - 10,500

2,4-Dichlorophenol µg/Kg 9,210 ± 821 1.96 2,270 8,390 - 10,000 4,680 - 13,700

bis(2-Ethylhexyl) phthalate (DEHP) µg/Kg 7,650 ± 500 1.96 1,380 7,160- 8,140 4,910 - 10,400

µg/Kg 1,460 ± 181 1.96 477 1,280 - 1,640

µg/Kg 8,340 ± 833 1.96 2,340 7,570- 9,110

µg/Kg 3,250 ± 327 1.96 922 2,930 - 3,560

µg/Kg 5,360 ± 404 1.96 1,150 4,980 - 5,740

µg/Kg 3,790 ± 326 1.96 932 3,470 - 4,110

µg/Kg 3,160 ± 205 1.96 579 2,950 - 3,370

µg/Kg 1,190±82.6 1.96 231 1,110 - 1,270

µg/Kg 2,950 ± 190 1.96 538 2,770 - 3,130

µg/Kg 5,600±410 1.96 1,150 5,200 - 6,010

of4


Analyte Units

Certified Standard Confidence Prediction k

Additional Information

Sample Description

The sample size provided as a pack of 5 x 1Og units of soil.

The soil has been sterilized to minimize degradation of the sample.

The sample has been sized to 100 mesh.

The sample has been intentionally prepared with an apparent headspace.

USEPA Method 8270C was the primary method for certification (GC-MS). Contact RTC for further method details.

Storage

Value Deviation Interval Interval

Diethyl phthalate µg/Kg 8,010 ± 569 1.96 1,540 7,410 - 8,610 4,940 - 11,100

2,4-Dimethylphenol µg/Kg 5,800 ± 459 1.96 1,240 5,340 - 6,260 3,330 - 8,270

2,4-Dinitrophenol µg/Kg 6,180 ± 1520 2.05 3,550 4,630 - 7,730 0.00 - 13,600

2,6-Dinitrotoluene (2,6-DNT) µg/Kg 4,400 ± 376 1.96 986 4,020 - 4,780 2,430 - 6,370

Di-n-octyl phthalate µg/Kg 7,910 ± 673 1.96 1,830 7,250 - 8,570 4,260 - 11,600

Fluoranthene µg/Kg 4,990 ± 338 1.96 949 4,660 - 5,320 3,100 - 6,880

Fluorene µg/Kg 4,610 ± 344 1.96 981 4,270 - 4,950 2,660 - 6,570

lndeno(1,2,3-cd) pyrene µg/Kg 4,600 ± 357 1.96 1,010 4,260 - 4,950 2,590 - 6,620

lsophorone µg/Kg 9,870 ± 993 1.96 2,710 8,880 - 10,900 4,470 - 15,300

2-Methyl-4,6-dinitrophenol µg/Kg 8,340 ± 1210 1.96 3,080 7,180-9,500 2,190 - 14,500

2-Methylnaphthalene µg/Kg 2,320 ± 221 1.96 632 2,110-2,540 1,060 - 3,580

4-Methylphenol (p-Cresol) µg/Kg 5,150 ± 580 2.09 2,010 4,060 - 6,230 815 - 9,480

3+4-Methylphenol (m+p-Cresol) µg/Kg 5,030 ± 579 2.07 1,140 4,470 - 5,600 2,590 - 7,480

2-Nitrophenol µg/Kg 6,860 ± 618 1.96 1,680 6,260 - 7,450 3,510 - 10,200

4-Nitrophenol µg/Kg 6,800 ± 889 1.96 2,390 5,930 - 7,660 2,030 - 11,600

n-Nitrosodiphenylamine µg/Kg 6,420 ± 885 2.05 2,060 5,630 - 7,210 2,120 - 10,700

Pentachlorophenol µg/Kg 4,210 ± 372 1.96 995 3,840 - 4,570 2,220 - 6,190

Phenanthrene µg/Kg 1,910 ± 140 1.96 400 1,780 - 2,050 1,120-2,710

Phenol µg/Kg 4,230 ± 385 1.96 1,100 3,850 - 4,610 2,040 - 6,420

Pyrene µg/Kg 8,360 ± 543 1.96 1,540 7,820 - 8,890 5,290 - 11,400

2,4,5-Trichlorophenol µg/Kg 7,430 ± 591 1.96 1,610 6,890 - 7,960 4,230 - 10,600

2,4,6-Trichlorophenol µg/Kg 9,010 ± 628 1.96 1,730 8,400- 9,620 5,570 - 12,400

of4


BNAs - Sandy Loam Number CRM143-50G

Lot LRAA1235

Solvent (Matrix) Sandy Loam Soil

Hazard Irritant

Storage &Handling Store at 4°C.

Expiration Date See Sample Label

Certification Date: April 02, 2013

Certified By: Christopher Rucinski - QA Director

Storage The sample should be stored at 4°C. It has been determined to be stable for the duration of the expiration date.

After sub-sampling replace cap securely and store remaining sample at 4°C.

The shelf life of the product was determined by historic stability of similar CRM's. The expiration date may be extended based on stock and

popularity upon successful stability testing by a 17025 accredited laboratory.

Stability and shelf life after opening must be determined by the user, taking into account sampling frequency/volume and all local conditions.

Recommended Preparation

Extract an accurately weighed portion (recommended minimum sample is 10 grams) using SW846 Method 3540C, Soxhlet Extraction; 3541,

Automated Soxhlet Extraction; 3550, Ultrasonic Extraction or other technique identified by the method to be acceptable for the analytes of interest.

In addition to the solvent systems listed in Method 3540C,the methylene chloride/acetone (1:1 v/v) system is acceptable.

Note: Sample extracts and calibration solutions should be in the same solvent.

Transfer the entire amount of one vial to your extraction system. Rinse the vial with a 2-5 ml your extraction solvent. Assume 10g for the sampling

size. Smaller amounts may be sampled but RTC does not maintain homogeneity for sample sizes less than 10g.

Results based on as provided basis assume each vial contains 10g of dry soil.

Scope and Application

The Base Neutral Acid (BNA) Compounds in Soil Certified Reference Material (CRM) consists of four amber glass sample jar, wit h a Teflon lined

closure containing approximately 10 grams of soil, fortified with 49 semi-volatile organics. Being a natural matrix waste sample the analyst is

challenged by the same preparation problems, analytical interferences, etc. as is typical for similar matrices received by the laboratory for analysis.

Rigorous analysis identified, quantified, and certified various aliphatic and aromatic banding which are listed on the enclosed Cer tificate of Analysis.

The sample has been analyzed by 41 independent laboratories in a round-robin to meet the requirements specif ied by the ISO Guides 34 and 35,

and ISO 17025.

Evaluation of Results

The Reference Value, 95% confidence interval(C.I.) for the Reference Value and 95% Prediction Interval (P.I.) around the Refe rence Value were

obtained by the methods identified in the 'Scope and Application' section of this Certificate of Analysis. Samples were selected in a random fashion

from the beginning to the end of the bottling sequence and sent for analysis by an independent laboratory round-robin. The data produced in the

round-robin was used to calculate reference values by the USEPA EMSL-CINN's computer program "BIWEIGHT".

The generated BIWEIGHT mean, BIWEIGHT standard deviation and BIWEIGHT standard deviation of the mean are used to calculate the 95%

Confidence Interval (Cl) for the mean and the 95% Prediction Interval (Pl). For normally distributed data, the BIWEIGHT 95% Cl compares well to

the classical calculation method used to generate a 95% Cl. For non-Gaussian data sets, the BIWEIGHT method is more robust in data treatment.

BIWEIGHT data are also used to calculate a 95% Pl. The 95% Pl compares well to a 95% tolerance limit calculated using classic al methods. For

normally distributed data, the BIWEIGHT 95% Pl typically represents approximately a ±2 BIWEIGHT standard deviation window around the

BIWEIGHT mean. Again, the BIWEIGHT method is more robust than classical methods when handling non-Gaussian data sets.

Laboratories performing the same analytical procedures on a sample whose values have been determined by the BIWEIGHT met hod can assume

that the true mean, as determined by the method, is within the 95% Cl window. Laboratories analyzing the sample should have results within the

95% Pl window 19 out of 20 analyses. Laboratories should use the Pl as guidance for laboratory performance.

Additional information on the program may be obtained by referring to the reference or by downloading the program from the EM SL-CINN web site.

Additionally contact RTC for additional guidance - 1(307)742-5452 - [email protected] - www.rt-corp.com

Health and Safety Information

All RTC Certified Reference Mater ials are intended only for prof essional use by properly trained laboratory personnel. This C RM has been reviewed

for both health and safety and shipping risks. It is classified as non hazardous and is not classified as hazardous goods for shipping by road, sea or

air transport.


http://www.rt-corp.com/

of4


Health and Safety Information

A full international MSDS as a downloadable pdf file is available at www.rt-corp.com

1 Certified values are the robust statisitical mean when prepared according to instructions from an lnterlaboratory Study and internal rigorous testing.

2 The standard deviation is the robust statistical standard deviation from the round robin interlaboratory study.

4 Expanded Uncertainty (Ucrm) - All uncertainty values in this document expressed as ± value are expanded uncertainties.

5 k: Coverage factor derived from at-distribution table, based on the degrees of freedom of the data set. Confidence interval = 95%

TRAC EABILITY: The standard was manufactured under an ISO 17025 certified quality system. The balanc e used to weigh raw materials is accurat e to+/ -

0.00019 and calibrat ed regularly using mass standards traceable to NIST. All di lutions were preform ed gravim etric ally. Additional ly, individual analytes are

traceable to NIST SRMs where available and specified above.

HOMOGENEITY ASSESSMENT: Between-bottle homogeneity was assessed in accordance with ISO Guide 35. Completed units were sampled over the

course of the bottling operation. Samples were taken in the following manner: the units produced in the bottling operation were divided into three

chronological groups, those from the Early third, the Middle third, and the Late third (Groups). A pre-determined number of sample units were then randomly

selected from each group. A subset of each group was then randomly selected for chemical analysis. The results of the chemica l analysis were then

compared by Single Factor Analysis of Variance (ANOVA).

UNCERTAINTY STATEMENT: Uncertainty values in this document are expressed as Expanded Uncertainty (Ucrm) corresponding to the 95% confidence

interval. Ucrm is derived from the combined standard uncertainty multiplied by the coverage factor k, which is obtained from a I-distribution and degrees of

freedom. The components of combined standard uncertainty include the uncertainties due to characterization, homogeneity, long term stability, and short

term stability (transport). The components due to stability are generally considered to be negligible unless otherwise indicated by stability studies.

THIS PRODUCT WAS DESIGN ED , PRODUCED AND VERIFIED FOR ACCURACY AND STABILITY IN ACCORDANC E WITH ISO 17025 (AClass Cert AT-1467) and ISO

GUIDE 34 (AClass CertAR-1470).

MSDS reports for components comprising greater than 1.0% of the solution or 0.1% for components known to be carcinogens are available upon request.

Manufactured and certified by Sigma-Aldric h RTC, Inc.

http://www.rt-corp.com/

5410 2270 8550 1,2-Dichlorobenzene 42.0% 158.0%

1460 506 2410 1,4-Dichlorobenzene 34.7% 165.1%

8340 3680 13000 Hexachlorobutadiene 44.1% 155.9%

3250 1410 5080 Naphthalene 43.4% 156.3%

5360 3060 7650 Acenaphthene 57.1% 142.7%

3790 1930 5640 Acenaphthylene 50.9% 148.8%

3160 2000 4310 Anthracene 63.3% 136.4%

1190 729 1650 Benzo(a)anthracene 61.3% 138.7%

2950 1880 4020 Benzo(a)pyrene 63.7% 136.3%

5900 3310 7890 Benzo(b)fluoranthene 56.1% 133.7%

994 453 1530 Benzo(g,h,i)perylene 45.6% 153.9%

4400 2430 6370 Benzo(k)fluoranthene 55.2% 144.8%

2230 0 5670 Benzoic acid 0.0% 254.3%

5840 3420 8270 4-Bromophenyl phenyl ether 58.6% 141.6%

8370 5300 11400 Butyl benzyl phthalate 63.3% 136.2%

5920 3210 8630 4-Chloro-3-methylphenol 54.2% 145.8%

1800 674 2920 bis(2-Chloroisopropyl) ether 37.4% 162.2%

5960 2700 9210 2-Chlorophenol 45.3% 154.5%

3940 2230 5640 4-Chlorophenyl phenylether 56.6% 143.1%

6730 4200 9270 Chrysene 62.4% 137.7%

1350 738 1950 Dibenzo(a,h)anthracene 54.7% 144.4%

7610 4730 10500 Dibenzofuran 62.2% 138.0%

9210 4680 13700 2,4-Dichlorophenol 50.8% 148.8%

7650 4910 10400 bis(2-Ethylhexyl) phthalate (DEHP) 64.2% 135.9%

8010 4940 11100 Diethyl phthalate 61.7% 138.6%

5800 3330 8270 2,4-Dimethylphenol 57.4% 142.6%

6180 0 13600 2,4-Dinitrophenol 0.0% 220.1%

4400 2430 6370 2,6-Dinitrotoluene (2,6-DNT) 55.2% 144.8%

7910 4260 11600 Di-n-octyl phthalate 53.9% 146.6%

4990 3100 6880 Fluoranthene 62.1% 137.9%

4610 2660 6570 Fluorene 57.7% 142.5%

4600 2590 6620 lndeno(1,2,3-cd) pyrene 56.3% 143.9%

9870 4470 15300 lsophorone 45.3% 155.0%

8340 2190 14500 2-Methyl-4, 6-dinitrophenol 26.3% 173.9%

2320 1060 3580 2-Methylnaphthalene 45.7% 154.3%

5150 815 9480 4-Methylphenol (p-Cresol) 15.8% 184.1%

5030 2590 7480 3+4-Methylphenol (m+p-Cresol) 51.5% 148.7%

6860 3510 10200 2-Nitrophenol 51.2% 148.7%

6800 2030 11600 4-Nitrophenol 29.9% 170.6%

6420 2120 10700 n-Nitrosodiphenylamine 33.0% 166.7%

4210 2220 6190 Pentachlorophenol 52.7% 147.0%

1910 1120 2710 Phenanthrene 58.6% 141.9%

4230 2040 6420 Phenol 48.2% 151.8%

8360 5290 11400 Pyrene 63.3% 136.4%

7430 4230 10600 2,4,5-Trichlorophenol 56.9% 142.7%

9010 5570 12400 2,4,6-Trichlorophenol 61.8% 137.6%

SRM 1941b Page I of 15

QI.ertificat.e of nalusis

Standard Reference Material® 1941b

Organics in Marine Sediment

This Standard Reference Material (SRM) is marine sediment collected at the mouth of the Baltimore (MD) Harbor.

SRM 1941b is intended for use in evaluating analytical methods for the determination of selected polycyclic aromatic

hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, and chlorinated pes ticides in marine sediment and

similar matrices. Information values are also provided for total organic carbon (TOC), total carbon, hydrogen, and

nitrogen. All of the constituents for which certified, reference, and information values are provided in SRM 1941b were

naturally present in the sediment before processing. A unit of SRM 1941 b cons ists of a bottle containing 50 g of

radiation-sterilized, freeze-dried sediment.

Certified Mass Fraction Values: Certified mass fraction values for 24 PAHs, 29 PCB congeners, and 7 chlorinated

pesticides are provided in Tables I through 3. The certified values for the PAHs, PCB congeners, and chlorinated

pesticides are based on the agreement of results obtained at NIST from two or more chemically independent analytical

techniques along with results from an interlaboratory comparison study [1]. A NIST certified value is a value for which

NIST has the highest confidence in its accuracy in that all known or suspected sources of bias have been investigated or

taken into account [1].

Reference Mass Fraction Values: Reference mass fraction values for 44 additional PAHs (some in combination),

13 additional PCB congeners, and 2 additional chlorinated pesticides are provided in Tables 4 to 7. Reference values for

27 alkylated PAH groups are provided in Table 8 and for selected hopanes and steranes in Table 9. A reference value for

total organic carbon is provided in Table 10. Reference values are noncertified values that are the bes t estimate of the

true value; however, the values do not meet the NIST criteria for certification and are provided with associated

uncertainties that may reflect only measurement precision, may not include all sources of uncertainty, or may reflect a

lack of sufficient statistical agreement among multiple analytical methods [1].

Information Mass Fraction Values: Information mass fraction values are provided in Table 11 for carbon, hydrogen;

and nitrogen. An information value is considered to be a value that will be of use to the SRM user, but insufficient

information is available to assess the uncertainty associated with the value [1].

Expiration of Certification: The certification ofSRM 1941b is valid. within the measurement uncertainty specified,

until 01 October 2020, provided the SRM is handled and stored in accordance with the instructions given in this

certificate (see "Instructions for Handling, Storage, and Use"'). This certification is nullified if the SRM is damaged,

contaminated, or otherwise modified.

Maintenance of SRM Certification: NIST will monitor this SRM over the period of its certification. If substantive

technical changes occur that affect the certification before the expiration of this certificate, NIST will notify the

purchaser. Registration (see attached sheet) will facilitate notification.

The coordination of the technical measurements leading to the certification of this material was under the leadership of

M.M. Schantz and S.A. Wise of the NIST Analytical Chemistry Division.

Analytical measurements for the certification of SRM 1941 b were performed at NIST by J.R. Kucklick, B.J. P01ier,

D.L. Poster, M.M. Schantz. P. Schubert. S. Tutschku, and L.L. Yu of the NIST Analytical Chemistry Division.

Stephen A. Wise, Chief

Analytical Chemistry Division

Gaithersburg, MD 20899

Certificate Issue Date: IO April 2012 Certificate Re,·111011 Hi,wr_,. 011 Page /3

Robert L. Watters. Jr., Chief

Measurement Services Division

SRM 1941b Page 2 of 15

Measurements for TOC were provided by a commercial laboratory and T.L. Wade of the Geochemical and

Environmental Research Group, Texas A&M Univers ity (College Station, TX). The carbon, hydrogen, and nitrogen data

were provided by a commercial laboratory. Results for the PAHs, PCBs, and chlorinated pesticides from 38 laboratories

(see Appendix A) that participated in an interlaboratory comparison exercise coordinated by NIST were used. Results

for the alkylated PAH groups, hopanes. and steranes from 33 laboratories (see Appendix B) that participated in another

interlaboratory comparison exercise coordinated by NIST were also used.

Collection and preparation of SRM 1941 b were performed by M.P. Cronise and C.N. Fales of the NIST Measurement

Services Divis ion and B.J. Porter and M.M. Schantz of the NIST Analytical Chemis try Divis ion. The sediment material

was collected with the assistance of G.G. Lauenstein, J. Collier, and J. Lewis (National Oceanic and Atmospheric

Administration, Silver Spring, MD).

Consultation on the s tatistical des ign of the experimental work and evaluation of the data were provided by S.D. Leigh

and J.H. Yen of the NIST Statistical Engineering Division.

Support aspects involved in the issuance of this SRM were coordinated through the NIST Measurement Services

Division.

INSTRUCTIONS FOR HANDLING, STORAGE, AND USE

Handling: This material is naturally occurring marine sediment from an urban area and may contain cons tituents of

unknown toxicities; therefore, caution and care should be exercised during its handling and use.

Storage: SRM 1941b must be stored in its original bottle at temperatures less than 30 °C and away from direct sunlight.

Use: Prior to removal of subsamples for analysis, the contents of the bottle should be mixed. The mass fractions of

constituents in SRM 1941 b are reported on a dry-mass basis. The SRM, as received, contains a mass fraction of

approximately 2.4 % moisture (see ·'Conversion to Dry-Mass Basis""). The sediment sample should be dried to a constant

mass before weighing for analysis ; or a separate subsample of the sediment should be removed from the bottle at the time

of analysis and dried to determine the mass fraction on a dry -mass basis. If the constituents of interest are volatile, then

the moisture must be determined with a separate subsample.

PREPARATION AND ANALYSISm

Sample Collection and Preparation: The sediment used to prepare this SRM was collected from the Chesapeake Bay

at the mouth of the Baltimore (MD) Harbor near the Francis Scott Key Bridge (39°12.3'N and 76°3 l .4'W). This location

is very near the site where SRM 1941 and SRM 1941a were collected. The sediment was collected us ing a Kynar-coated

modified Van Veen-type grab sampler. A total of approximately 3300 kg of wet sediment was collected from the s ite.

The sediment was freeze-dried, s ieved at 150 µm (100 % passing), homogenized in a cone blender, radiation

sterilized (6°Co), and then packaged in screw-capped amber glass bottles each containing approximately 50 g.

Convers ion to Dry-Mass Basis: The results for the constituents in SRM 1941 b are report ed on a dry-mass basis;

however, the material ""as received" contains residual mois ture. The amount of mois ture in SRM 1941 b was determined

by measuring the mass loss after freeze-drying subsamples of 1.1 g to 1.3 g for four days at 1 Pa with a -10 °C shelf

temperature and a -50 °C condenser temperature. The moisture content in SRM 1941bat the time ofthc certification

analyses was 2.39 % ± 0.08 % (95 % confidence level). Analytical results for the organic cons tituents were determined

on an as-received basis and then converted to a dry-mass basis by dividing by the convers ion factor of

0.9761 (gram dry mass per gram as-received mass).

Polycyclic Aromatic Hydrocarbons: The general approach used for the value assignment of the PAHs in SRM 1941 b

was similar to that reported in detail elsewhere [2). The approach cons isted of combining results from analyses using

various combinations of different extraction techniques and solvents. clean-up/isolation procedures, and chromatographic

separation and detection techniques: Soxhlet extraction and pressurized-fluid extraction (PFE) using

dichloromethane (DCM) or a hexane/acetone mixture. cleanup of the extracts using solid -phase extraction (SPE) or

normal-phase liquid chromatography (LC). followed by analysis us ing the following techniques: ( 1) reversed-phase

liquid chromatography with fluorescence detection (LC-FL) analysis of the total PAH fraction, (2) reversed-phase LC-FL

analysis of isomeric PAH fractions isolated by normal-phase LC (i.e.. multidimens ional LC). (3) gas

chromatography/mass spectrometry (GCiMS) analysis of the PAH fraction on three stationary phases of different

(I) Certain commercial equipment. instruments or material are identified in this certificate to adequately specify the

experimental procedure. Such identification does not imply recommendation or endorsement by the National Institute of Standar ds

and Technology. nor does it imply that the materials or equipment identified are necessarily the bes t available for the purpose.


selectivity. i.e., a 5 % (all column compositions are given as mole fractions in%) phenyl-substituted methylpolys iloxane

phase, a 50 % phenyl-substituted methylpolysiloxane phase, and a relatively non-polar proprietary phase.

Three sets ofGC/MS results, des ignated as GC/MS (I), GC/MS (II). and GC/MS (Ill). were obtained using three columns

with different selectivities for the separation of PAHs. For GC/MS (I) analyses, duplicate subsamples of approximately

1 g from ten bottles of SRM 1941b were extracted using PFE with DCM. Copper powder was added to the extract to

remove elemental sulfur. The concentrated extract was passed through an aminopropyl SPE cartridge and eluted with

2 % DCM in hexane (all solvent concentrations are given as volume fractions in%). The processed extract was then

analyzed by GC/MS using a 0.25 mm i.d. x 60 m fused silica capillary column with a 5 % phenyl-substituted

methylpolysiloxane phase (0.25 µm film thickness; DB -5 MS, J&W Scientific, Folsom, CA). The GC/MS (II) analyses

were performed using 5 g subsamples from s ix bottles of SRM 1941b. These samples were extracted us ing PFE with

DCM. The high molecular mass compounds were removed from the extracts using size exclusion chromatography (SEC)

with a preparative-scale divinylbenzene-polystyrene column (IO µm particle size with IO nm diameter pores), and the

sulfur was removed from the extracts by adding copper powder. The concentrated extract was passed through an

aminopropyl SPE cartridge and eluted with 10 % DCM in hexane. The analysis was by GC/MS using a

0.25 mm i.d. x 60 m fused silica capillary column with a 50 % phenyl-subs tituted methylpolys iloxane phase (0.25 µm

film thickness; DB-17 MS. J&W Scientific, Folsom. CA). For the GC/MS (III), 9 g subsamples from six bottles of

SRM 1941b were Soxhlet-extracted for 18 h with 250 mL of a mixture of 50 % hexane/SO % acetone. Copper powder

was added to the extract to remove elemental sulfur, and the concentrated extract was passed through a silica SPE

cartridge and eluted with 10 % DCM in hexane. The processed extract was then analyzed by GC/MS using a

0.25 mm i.d. x 60 m fused silica capillary column with a relatively non-polar proprietary phase (0.25 µm film thickness;

DB-XLB, J&W Scientific, Folsom, CA).

Two sets of LC-FL results. designated as LC-FL (total) and LC-FL (isomer), were used in the certification process. For

the LC-FL (total), subsamples of approximately I g from s ix bottles ofSRM 1941b were extracted using PFE with a

mixture of50 % hexane/SO% acetone. The extracts were concentrated and then processed through an aminopropylsilane

SPE cartridge us ing 2 % DCM in hexane to obtain the total PAH fraction. For the LC-FL (isomer). a 5 g subsample from

the s ix bottles was extracted using PFE with DCM and processed through an aminopropylsilane SPE cartridge using

10 % DCM in hexane; the PAH fraction was then fractionated further on a semi-preparative aminopropylsilane column

(µBondapak NH . 9 mm i.d. x 30 cm, Waters Associates, Milford, MA) to isolate isomeric PAH fractions as described

previously [3-6). The total PAH fraction and the isomeric PAH fractions were analyzed using a 5 µm particle-size

polymeric octadecyls ilane (C 18) column (4.6 mm i.d. x 25 cm. Hypersil-PAH, Keystone Scientific. Inc., Bellefonte, PA)

with wavelength-programmed fluorescence detection [4.5).

For the GC/MS and LC-FL measurements described above, selected perdeuterated PAHs were added to the sediment

prior to solvent extraction for use as internal standards for quantification purposes.

In addition to the analyses performed at NIST, SRM 1941b was used in ari1nterlaboratory comparison exercise in }'+9'+9-+9

aspart of the NIST Intercomparison Exercise Program for Organic Contaminants in the Marine Environment [7]. Results

from 38 laboratories that participated in this exercise were used as the sixth data set in the determination of the certified

values for PAHs in SRM 1941 b. The laboratories participating in this exercise used the analytical procedures routinely

used in their laboratories to measure the analytes of interest.

Homogeneity Assessment for PAHs: The homogeneity of SRM 1941b was assessed by analyzing duplicate samples of

approximately I g from ten bottles selected by stratified random sampling. Samples were extracted. processed, and

analyzed as described above for GC/MS (I). No statistically significant differences among bottles were observed for the

PAI-Is at this sample size.

PAH Isomers of Molecular Mass 300 and 302: For the detennination of the molecular mass 300 and 302 isomers,

three subsamples of approximately 5 g each were extracted using PFE with DCM. The extrac ts were then concentrated

with a solvent change to hexane and passed through an aminopropyl SPE cartridge and eluted with IO% DCM in hexane.

The processed extract was then analyzed by GC/MS us ing a 0.25 mm i.d. x 60 m fused silica capillary column with a

50 % phenyl-substituted methylpolysiloxane phase (0.25 µm film thickness ; DB-l 7MS. J&W Scientific, Folsom, CA).

Perdeuterated dibenzo[a,ilpyrene was added to the sediment prior to extraction for use as an internal standard [8].

PCBs and Chlorinated Pesticides: The general approach used for the determination of PCBs and chlorinated pes ticides

in SRM 1941 b consis ted of combining results from analyses using various combinations of different extraction

techniques and solvents, cleanup/isolation procedures. and chromatographic separation and detection techniques.

Techniques and solvents included Soxhlet extraction and PFE us ing DCM or a hexane/acetone mixture, clean -

up/isolation us ing SPE or LC, followed by analys is using GC/MS and gas chromatography with electron capture

detection (GC-ECD) on two columns with different selectivity for the separation of PCBs and chlorinated pesticides.

The analytical methods are described in detail elsewhere [2].


Six sets of results were obtained and designated as GC-ECD ( I) A and B, GC/MS (I) A and B, GC/MS (II), and

Interlaboratory Comparison Exercise. For the GC-ECD (I) analyses, approximately IO g subsamples from six bottles of

SRM 1941b were extracted using PFE with DCM. Copper powder was added to the extract to remove elemental sulfur,

and SEC, as described above, was used to remove the high molecular mass compounds. The concentrated extract was

then fractionated on a semi-preparative aminopropy lsilane column to isolate two fractions containing: (I) the PCBs and

lower-polarity pesticides and (2) the more polar pes ticides. GC-ECD analyses of the two fractions were performed on

two columns of different selectivities for PCB separations : 0.25 mm x 60 m fused silica capillary column with a 5 %

phenyl-substituted methylpolysiloxane phase (0.25 µm film thickness; DB-5, J&W Scientific, Folsom, CA), and a

0.25 mm x 60 m fused silica capillary column with a non-polar proprietary phase (0.25 µm film thickness; DB-XLB,

.J& W Scientific, Folsom. CA). The results from the 5 % phenyl phase are des ignated as GC-ECD (IA) and the results

from the proprietary phase are designated as GC-ECD (IB). For the GC-ECD analyses, two PCB congeners that are not

significantly present in the sediment extract (PCB 103 and PCB 198 [9.10]) and endosulfan I-d,4 4,4' -DDE-d8,

4,4'-DD-d8, and 4,4'-DDT-d 8 were added to the sediment prior to extraction for use as internal standards for

quantification purposes.

Two sets of results were obtained by GC/MS. For GC/MS (1), approximately 9 g subsamples from s ix bottles were

Soxhlet- extracted with a mixture of 50 % hexane/SO% acetone for approximately 18 h. Copper powder was added to

the extract to remove elemental sulfur, and the concentrated extract was passed through a silica SPE cartridge and eluted

with IO% DCM in hexane. The processed extract was then analyzed by GC/MS with two ionization modes, electron

impact (EI) and negative ion chemical ionization (NICI). The GC/MS EI method, GC/MS (IA), used a

0.25 mm i.d. x 60 m fused s ilica capillary column with a relatively non-polar proprietary phase (0.25 µm film thickness;

DB-XLB, J& W Scientific, Folsom, CA). The GC/MS NICI method, GC/MS (IB). used a 0.25 mm i.d. x 60 m fused

silica capillary column with a 5 % phenyl-substituted methylpolys iloxane phase (0.25 µm film thickness: DB-SMS, J& W

Scientific. Folsom, CA). The GC/MS (II) results were obtained in the same manner as the GC/MS (IA) analyses except

that three subsamples were Soxhlet-extracted with DCM for approximately 18 h. For the GC/MS analyses. selected

carbon-13 labeled PCB congeners and chlorinated pesticides were added to the sediment prior to extraction for use as

internal standards for quantification purposes.

In addition to the analyses performed at NIST. SRM 1941 b was used in an interlaboratory comparison exercise in 1999

as part of the NIST Intercomparison Exercise Program for Organic Contaminants in the Marine Environment [7]. Results

from 38 laboratories that participated in this exercise were used as the s ixth data set in the determination of the certified

values for PCB congeners and chlorinated pesticides in SRM 1941b. The laboratories participating in this exercise used

the analytical procedures routinely used in their laboratories to measure the analytes of interest.

The reference value for PCB 77 was determined from a separate fraction. The samples were extracted and processed as

for GC-ECD (I) above. The firs t (PCB and lower-polarity pesticide) fraction from the semi-preparative

aminopropylsilane column was further fractionated using a Cosmosil PYE (pyrenylethy I group bonded) column (5 1111

particle s ize. 4.6 1m11 i.d.x 25 cm : Phenomenex. Torrance, CA) [11]. Three fractions were collected: the first fraction

contained the pesticides and multi-or tho PCBs, the second fraction contained the polychlorinated naphthalenes, non-

ortho PCB congeners, and some mono-ortlw PCB congeners, and the third fraction removed the res idual planar

compounds from the column. The second fraction was analyzed by GC/MS NICI using the same column as GC/MS (IB)

above. Carbon-13 labeled PCB 77 was used as an internal standard for quantification purposes.

Alkylated PAH Groups, Hopanes, and Steranes: SRNI 1941 b was used in an interlaboratory comparison exercise in

2011 [12]. Results from 33 laboratories that participated in this exercise were used in the determination of the reference

values for alky lated PAH groups. hopanes. and steranes in SRM 1941 b. Note that not all laboratories returned data for

each analyte. The laboratories participating in this exercise used the analytical procedures routinely used in their

laboratories to measure the analytes of interest. For the alkylated PAHs, the majority of the laboratories (>90 %) used

the parent PAH for determination of the response factor for the corresponding alkylated group.

Total Organic Carbon: Two laboratories provided results for TOC using similar procedures. Briefly, subsamples of

approximately 200 mg were reacted with 6 mol/L hydrochloric acid and rinsed with deionized water prior to combustion

in a gas fusion furnace. The carbon monoxide and carbon dioxide produced were measured and compared to a blank for

calculation of the percent TOC. Each laboratory analyzed subsamples from three bottles of SRM 1941 b. One of the

laboratories also analyzed three subsamples from three bottles of SRM 1941 b for carbon, hydrogen, and nitrogen.


Table 1. Certified Mass Fraction Values for Selected PAHs in SRM 1941b

PAHs

i Naphthalene(b .c d.c.f.g)

; Fluorene(b .c.< l.d .g l

°) Phenanthrene(h .c.d .c.f.g)

4 Anthracene(b.,.<l,e.f.g)

C, 3-Methy lphenan th rene< b .c.d )

(,, 2-Methy lphenathrenett,.c.< l) 1 1-Methylphenanthrene1h.c.dg . )

q,Fluoran thene(b .,,< l.e.f,g l

0\ Pyrene(h.c.d .c,f.g)

IO Benz[a]an th racene(h .c.< l.e.f.g)

11 Chrysene<ct.t)

1 ).Triph enylene 1<l.f)

o,Benzo[b ]fluoran thene(c.ci

1U Benzo[k]tl uoranthene(b., J.e)

IS Benzo[e]py rcne(b,c.d .g )

fl, Benzo[a]pyrene 16·'-<l f.g)

\ 1 Perylen e< h. c.d .t. g )

i4,Benzo [gh i]pery lene< b .c.< l.f.g )

( lndeno[1,2.3-cd]pyrene'b.c.d.t.g)

'J..oDibenz[a.j]an th racene(b .c.J .fJ

'}-\ Dibenz[a ,c]an th racene< c.t)

iJ,Dibenz[a,h]anth racene 1'n-

r Benzo[b]chrysene(h.c.d t)

'lA.Picene(b., <lJ

Mass Fractions<•)

µg/kg

95(h)

] 5(h)

44(h)

]8(h)

J3(h)

J4(h)

5.9(h)

50(hl

39(h)

25(h) 31(h)

5(1)

21(h)

I 8(h)

25(h)

17'h)

45(h)

45(h)

57'")

4.6(h)

5.i"> ]0(h)

Ji") 4_7'h)

(al Mass fractions reported on dry-mass basis: material as received contains approximately 2.4 % moisture.

<h> GC/MS (I) on 5 % phenyl-substituted methylpolysiloxane phase after PFE with DCM.

re) GC/MS (II) on 50 % phenyl-substituted methylpolysiloxane pha e after PFE with DCM.

iJJ GCIMS (IIJ) on a relatively non-polar proprietary phase after Soxhlet extraction with 50 % hexane/50 % acetone mixture.

lcl LC-FL (total) of total PAH fraction after PFE with DCM.

It) LC-FL (isomer) isomecicPAH fractions after PFE with DCM.

<gl I 999 lnterlaboratory Comparison Study [7] with 21 to 29 laboratories submitting data for each PAI I.

lh> Certified values are weighted means of the results from two to six analytical methods [13). The uncertainty listed with each value

is an expanded uncertainty about the mean. with coverage factor 2 (approximately 95 % confidence), calculated by combining a

between-method variance incorporating inter-method bias with a pooled within-method variance following the ISO Guide [14,15).

> The certified value is an unweighted mean of the results from two analytical methods. The uncertainty listed with the value is an

expanded uncertainty about the mean. with coverage factor 2. calculated by combinin g a between-method variance [16) with a

pooled. within-method variance following the ISO Guide [14,15].

11

848 ±

85 ±

406 ±

184 ±

105 ±

128 ±

73.2 ±

651 ±

581 ±

335 ±

291 ±

108 ±

453 ±

225 ±

325 ±

358 ±

397 ±

307 ±

341 ±

48.9 ±

36.7 ±

53 ±

53 ±

46.6 ±


1

Table 2. Certified Mass Fraction Values for Selected PCB Congeners<•) in SRM 1941b

PCB Congeners Mass Fractions(bJ

µg/kg

PCB 8 (2,4'-Dichlorobiphenylic.d.c.f.g) 1.65 ± 0.J 9(h)

PCB 18 (2,2',5-TrichlorobiphenyJ)'"·d.e.f.gl 2.39 ± 0.29(h)

PCB 28 (2,4.4'-TrichlorobiphenyIl".d.c,f.g) 4.52 ± 0.57'h)

PCB 31 (2,4',5-Trichlorob ip heny 1t·eJ) 3.18 ± 0.41(h)

PCB 44 (2,2'3,5'-Tetrachlorobiphenyorc,d,c.f.g) 3.85 ± 0.20 < 1 )

PCB 49 (2,2'4,5'-Tetrachlorobiphenyl)(c.d.e.J) 4.34 ± 0.28(i)

PCB 52 (2,2',5,5'-Tetrachlorobiphenyl)rc.d.e.t.gJ 5.24 ± 0.28(I)

PCB 66 (2,3',4,4'-Tetrachloro biph eny Jt·eJ.gJJ 4.96 ± 0_53(i)

PCB 87 (2,2',3,4,5 '-P en tach lo rob ip h en y lt·d t,i) 1.14 ± 0.16('1)

PCB 95 (2,2',3,5',6-PentachlorobiphenylY"·e·r,g) 3.93 ± 0.62'1 )

PCB 99 (2,2',4,4',5-Pentachlorobiphenyl)(c.d,c,t.g) 2.90 ± 0.36(i)

PCB 101 (2.2',4,5,5'-Pentachlorobiphenyli'·e.f,g.JJ 5.11 ± 0_34(i)

PCB 105 (2,3,3',4,4'-Pentachlorobiphenylt ct.c.t.g.J) 1.43 ± 0.l0(I)

PCB 110 (2,3,3'.4',6-Pentach lorob iph enylic.e.f. il 4.62 ± 0.36(I)

PCB 118 (2,3',4,4',5-Pentachlorobiphenylt ct.c.f.g.J) 4.23 ± 0.19(I)

PCB 128 (2,2',3,3',4.4'-Hexachlorobiphenyl)(c.d.e.f,gJJ 0.696 ± 0.044'1

)

PCB 138 (2,2',3,4,4',5'-Hexachlorobiphenyl)(c.c.f.i) 3.60 ± 0.28(I)

PCB 149 (2.2',3.4',5',6-Hexachlorobiphenyl)(c.d.e.JJ 4.35 ± 0.26ih)

PCB 153 (2,2'.4.4',5,5'-1-Iexachlorobiphenyl)(c.d.e.f.g.J) 5.47 ± 0.32' 1

PCB 156 (2,3.3',4.4'.5-HexachlorobiphenyI)(c.d.e.f.J) 0.507 ± 0.090(h)

PCB 170 (2,2',3.3'.4.4'.5-Heptachlorobiphenyl)'c.d.c.f,gJI 1.35 ± 0.09(I)

PCB 180 (2.2',3.4.4'.5 ,5 '-Heptachlorobiphenyl)rc.d,e.LgJJ 3.24 ± 0.5l(I)

PCB 183 (2.2',3.4,4',5'.6-Heptachlorobiphenyl)'°·'Lc.il 0.979 ± 0.087'")

PCB 187 (2,2',3.4',5.5',6-HeptachlorobiphenyI)rc.d,e.f.gJJ 2.17 ± 0.22(I)

PCB 194 (2.2',3.3',4,4'.5.5'-Octach lorob iph enyIt.d .C.Jl 1.04 ± 0.06(h)

PCB 195 (2.2 ',3,3'.4.4'.5.6-Octach lo rbiphenyl )"'•0

·g. J l 0.645 ± 0.060'1

PCB 201 (2.2',3.3',4,5',6,6'-Octachlorobiphenyl}'°·c il 0.777 ± 0.034'")

PCB 206 (2,2',3.3',4.4',5.5'.6-Nonachlorobiphenyl)"'·e.f.gJ) 2.42 ± 0.19(I)

PCB 209 Decachlo ro biphenyl 1c.d.eg.f. JJ 4.86 ± o.45(i)

" ) PCB congeners are numbered according to the scheme proposed by Ballschmiter and Zell [9] and later revised by Schulte and

Malisch [101 to conform with IUPAC rules; for the specific congeners mentioned in this SRM. only PCB 201 and PCB 107 (see

Table 5) are different in the numbering systems. Under the Ballschmiter and Zell numbering system. the lUPAC PCB 201 is listed

as PCB 200 and the IUPAC PCB 107 is listed as PCB 108. 101

Mass fractions reported on dry-mass basis: material as received contains approximately 2.4 % moisture.

\cl GC!MS (IA) on a relatively non-polar proprietary phase after Soxhlet extraction with 50 % hexane/SO% acetone mixture.

<JJ GC-ECD (IA) on 5 % phenyl-substituted methylpolysiloxane phase after PFE extraction with DCM. 101 GC-ECD (IB) on a relatively non-polar proprietary phase; same extracts analyzed as in GC-ECD (IA).

ui GC!MS (II) on a relati,-ely non-polar proprietary phase after Soxhlet extraction with DCM.

igJ 1999 Interlaboratory Comparison Study [7] with 13 to 31 laboratories submitting data for each PCB congener. 1 1

" Ce11ified values are unweighted means of the results from three to five analytical methods. The uncertainty listed with each value 1s an expanded uncertainty about the mean, with coverage factor 2.calculated by combining a between-method variance [l 6] with a

pooled. within method variance follov,ing the ISO Guide l14,15]. 111

Certified values are weighted means of the results from three to six analytical methods [13]. The unce11ainty listed ,vith each value

is an expanded uncertainty about the mean. with coverage factor 2 (approximately 95 % confidence). calculated by combining a

between-method variance incorporating inter-method bias with a pooled within-method variance following the ISO Guide [14.I 5]. 111

GC!MS (IB) on 5 % phenyl-substituted methylpolysiloxane phase; same extracts analyl'.ed as in GC!MS (IA).

)

)


Table 3. Certified Mass Fraction Values for Selected Chlorinated Pesticides in SRM 1941b

Chlorinated Pesticides Mass Fractions(al

µg/kg

Hexach lo robenzene(h .c.d .e> 5.83 ± 0.38(!)

cis-Ch lo rd aneth · c.Je. g) 0.85 ± 0.1) th)

tra ns-Chlo rdane th·c.c ) 0.566 ± 0.093(!)

cis-Nonach lo r th·ge. ) 0.378 ± 0.053(h )

trans-N onachlo /h.c.ct.c.g> 0.438 ± 0.073(!) 4,4'-DDE(b ,d ,e,g ) 3.22 ± 0.28(h)

4,4'-DDD(b.d .c.g ) 4.66 ± 0.46(h)

(d) Mass fractions reported on dry-mass basis: material as received contains approximately 2.4 % moisture.

(h> GC/MS (IA) on a relatively non-polar propnetary phase after Soxhlet extraction with 50 % hexane/SO % acetone mixture.

(cl GC/MS (IB) on 5 % phenyl-substituted methylpolysiloxane phase: same extracts analyzed as in GC/MS (IA).

idi GC/MS (II) on a relatively non-polar proprietary phase after Soxhlet extraction with DCM.

le) 1999 Jnterlaboratory Comparison Study [7] with 13 to 31 laboratories submitting d ata for each pesticide.

(I) Certified values are unweighted means of the results from three to five analytical methods. The uncertainty listed with each value

is an expanded uncertainty about the mean, with coverage factor 2. calculated by combining a between-method variance [16] with a

pooled. within-method variance following the ISO Guide [14.15].

(g/ GC-ECD (IA) on 5 % phenyl-substituted methylpolysiloxane phase after PFE extraction with DCM.

(h> Certified values are weighted means of the results from three to five analytical methods [13]. The uncertainty listed with each

value is an expanded uncertainty about the mean. with coverage factor 2 (approximately 95 % confidence). calculated by

combining a between-method variance incorporating inter-method bias with a pooled within-method variance following the ISO

Guide [14.15].

SRM 1941h Page 8 of 15

1 1

Table 4. Reference Mass Fraction Values for Selected PAHs in SRM 1941b

PAHs Mass Fractions < aJ

µg/kg

14<f)

53(f)

4_5(f)

5.l(f)

Bipheny l(b.c.d.e) 74.0 ± 8.o<0

Acenaph thy lene(b .c.d .c) 53.3 ± 6.4(f)

Acenaph thene(b .c d.eJ 38.4 ± 5.i 0

9-Methy I phenanthrene<cJ 63.5 ± 2_5(g)

4-Mcthylphenanthrene and 80.1 ± 4. 8'0

9-Methy lphenanthrene b1.d J

2-Methy lanthracene Ic.d J 36 ± 1511)

8-Methy!fluoranthene<bJ 49.5 ± 2.ig)

7-Methylfluo rantheneb1 J 45.4 ± 1 _5<g)

1- Methyl fluo ranthene10 ) 42.4 ± 2.1(g)

3 -Methylfluoranthene b1 > 28.8 ± l .3<gl

2- Methy lpyren e b1 > 78.7 ± 4.0(g)

4-Methylpyrene<bJ 66.4 ± 2.6(g)

l -Methylpyreneb1 J 52.5 ± 2.3(g)

Acephenanthrene(dl 30.5 ± l.9(gl

Benzo[c]phenanthrene(b.c.d) 58 ± 15(/)

Benzo[a]fluoranthene(b.c.dl 73 ± 18(1)

Benzo U]f1uoranthenec1 J 217 ± 5(g)

lndeno[ l,,2 3-cd]fluoranthene 1dl 9.63 ± 0.34(g)

Pentaphened1 J 25.3 ± 1.0(g)

• > Mass fractions reported on <lry-mass basis: material as received contains approximately 2.4 % moisture. lh> GC/MS (I) on 5 % pheny I-substituted methylpolysiloxane phase after PFE with DCM. 1 1

' GC!MS (II) on 50 % phenyl-substituted methylpolysiloxane phase after PFE with DCM.

IJ> GC!MS (III) on a relatively non-polar proprietary phase after Soxhlet extraction with 50 % hexane/SO% acetone mixture.

" ' 1999 lnterlaboratory Comparison Study [7] with 14 to 26 laboratories submitting data for each PAI I.

in Reference values are weighted means of the results from two to four analytical methods [13]. The uncertainty listed with each

value is an expanded uncertainty about the mean. with coverage factor 2 (approximately 95 % confidence). calculated by

combining a between-method variance incorporating inter-method bias with a pooled v,ithin-method variance following the ISO

Guide [14.15].

lg> Reference values are the means of results obtained by NIST using one analytical technique. The expanded uncertainty. V. is

calculated as V = 1'11 '" where 11, is one standard deviation of the analyle mean. and the coverage factor." - is determined from

the Student's I-distribution for the associated degrees of freedom (19 for footnote band 5 for footnotes c and d) and 95 %

confidence level for each analyte.

1

1-Methylnaphthalene<b.c.d.e) 127 ± 2-Methylnaphthalene<b.c.d.c) 276 ± 2,6-Dimethylnaphthalene<b.c.d.e) 75.9 ± 2,3,5-Trimethylnaphthalene(b.c.d.c) 25.5 ±


Table 5. Reference Mass Fraction Values for Selected PAHs of Molecular Mass 300 and 302 in SRM 1941b

PAHs Mass Fractions (a.h.c)

µ g/kg

Coronene 72.6 ± 4.7

Dibenzo[b,e]fluoranthene 10.3 ± 0.3

Naphtho[1,2-b]fluoranthene

Naphtho[l ,2-k]fluoranthene

91.0 ± 3.1

and Naphtho[23-j]fluoranthene 79.8 ± 2.5

Naphtho[2,3-h ]fluoranthene 23.5 ± 0.3

Dibenzo[b,k]fluoranthene 95.6 ± 3.1

Dibenzo[a ,k] fluoranthene 26.6 ± 0.4

Dibenzo[j, /]fluoranthene 63.8 ± 1.8

Dibenzo[a,/]pyrene 11.1 ± 1.0

Naphtho[2.3-k]fluoranthene 10.7 ± 0.6

Naphtho[l ,2-a]pyrene 16.7 ± 1.4

Naphtho[2,3-e]pyrene 33.2 ± 2.3

Dibenzo[a,e]pyrene 76.1 ± 3.6

Naphtho[2. l -a]pyrene 59.2 ± 1.8

Dibenzo[e,i]pyrene 35.0 ± 2.4

Naphtho[2.3-a ]pyrene 16.5 ± 0.6

Benzo[h]perylene 38.2 ± 1.2

Dibenzo[a,i]pyrene 25.5 ± 1.0

Dibenzo[a ,h]pyrene 6.94 ± 0.29

· 1" Mass fractions reported on dry-mass basis: material as received contains approximately 2.4 % mo is tur e.

lh) Reference values are the means of results obtained by NlST using one analytical technique. The expanded uncertainty. U, is

calc ulat ed as U = kuc. where Uc is one standard deviation of the analyte mean. and the cove rage factor. k. is determined from

the Student" s r-distribution for two degrees of freedom and 95 % confidence level for each analyte.

'' ' GCiMS on 50 % phenyl-substituted methylpolysiloxane phase after PFE v,ith DCM [8].

SRM 1941b Page 10 of

15

Table 6. Reference Mass Fraction Values for Selected PCB Congeners(aJ in SRM 1941 b

PCB Congeners Mass Fractions<b.cJ

µg/kg

l

PCB 163 (2.3.3',4',5.6-HexachlorobiphenyI le.fg 1

1.28 ± 0.06

PCB 174 (2,2',3,3',4,5,6'-Heptachlorobiphenylrc.t.gi 1.51 ± 0.39

PCB 193 (2,3.3',4',5.5',6-HeptachlorobiphenyI )1J. e . f.g) 0.292 ± 0.075

(,,) PCB congeners are numbered according to the scheme proposed by Ballschmiter and Zell [9) and later revised by Schulte and

Malisch [I OJ to confonn with IUPAC rules: for the specific congeners mentioned in this SRM, only PCB 201 (see Table 2) and

PCB I 07 are different in the numbering systems. Under the Ballschmiter and Zell numbering system. the IUPAC PCB 201 is listed

as PCB 200 and the IUPAC PCB I 07 is listed as PCB I 08. (bl Mass fractions reported on dry-mass basis: material as received contains approximately 2.4 % moisture.

(c) for these PCB congeners except PCB 77. the reference values are unweighted means of the results from two to four analytical

methods. The uncertainty listed with each value is an expanded uncertainty about the mean. with coverage factor 2. calculated by

combining a between-method variance [16) with a pooled within-method variance following the ISO Guide [14,15). For PCB 77,

the reference value is the mean of results obtained by NIST using one analytical technique. The e"panded uncertainty. U. is

calculated as U = kuc• where lie is one standard deviation of the analyte mean. and the coverage factor. k. is detennined from the

Student's I-distribution corresponding to two degrees of freedom and 95 % confidence level for PCB 77.

(dJ GC-ECD (IA) on 5 % phenyl-substituted methylpolysiloxane phase after PFE extraction with DCM.

le) GC-ECD (IB) on a relatively non-polar proprietary phase: same extracts analyzed as in GC-ECD (IA).

(I) GCIMS (IA) on a relatively non-polar proprietary phase after Soxhlet extraction with 50 % hexane/SO% acetone mixture.

lg) GC/MS (IB) on 5 % phenyl-substituted methylpoly iloxane phase: same extracts analyLed a in GC/MS (IA).

lhl GC/MS NICI on a 5 % pheny I-substituted methylpolysiloxane phase: same extracts analyzed as in GC-ECD (I) fractionated using a

PYE column.

PCB 45 (2,2',3.6-Tetrachlorobiphenylid.el 0.73 ± 0.12

PCB 56 (2.3.3',4-Tetrachlorobiphenyl)(ct.f.gJ 1.21 ± 0.11

PCB 63 (2,3.4' ,5 -Tetrach lo rob ipheny I ye-r gJ 0.213 ± 0.040

PCB 70 (2.3',4',5-Tetrachlorobiphenyl)'°"r gJ 4.99 ± 0.29

PCB 74 (2,4,4',5-Tetrachlorobiphenylle.f.gl 2.04 ± 0.15

PCB 77 (3.3',4,4'-Tetrachlorobipheny1y11 0.31 ± 0.03

PCB 107 (2,3,3',4 ,5' -P en tach lo rob ipheny Iti.e f.gJ 0.628 ± 0.028

PCB 132 (2,2',3,3',4,6'-Hexachlorobiphenyl).d1 gf. J 1.28 ± 0.27

PCB 146 (2,2'.3.4',5.5'-Hexachlorobiphenylid.gl 1.22 ± 0.12

PCB 158 (2,3.3',4,4'.6-Hexachlorobiphenyll·c.fg\ 0.65 ± 0.15

SRM 1941b Page 11 of I 5

Table 7. Reference Mass Fraction Values for Selected Chlorinated Pesticides in SRM 1941 b

Chlorinated Pesticides

2,4'-DDE(c.d)

4,4'-DDT10·fl

Mass Fractionsl•.b>

µg /k g

0.38 ± 0.12

1.12 ± 0.42

·1

'1 Mass Fractions reported on dry-m ass basis; material as received contains approximately 2.4 % moistu re.

lhl The reference values are unweighted means of the results from two analy tical methods. The uncertainty li sted with each value is an

expanded uncertainty about the mean. with coverage factor 2. calculated by combining a betwee n-method variance [16] with a

pooled. within-method variance following the ISO Guide (14.15].

(cl GC!MS(]B) on 5 % phenyl-s u bstitut ed meth ylpolysilox ane phase; same extracts analyze d as in GC/MS (]A).

ldi GC-ECD (IB) on a rela tiv e ly non- pola r proprietary phase; same extracts analyzed as in GC-ECD (IA). 101

GCIMS (II) on a relativ e ly non-p olar proprietary phase after Soxhlet extraction with DCM.

(f) 1999 Interlaboratory Comparison Stud)' [7] with IO labo ratories s u bmit ting data for 4.4'-DDT.

Table 8. Reference Mass Fraction Values for Selected Alkylated PAH Groups in SRM 1941b

Alkylated PAH Group Mass Fraction<a.bi

mg/kg

C2-decalins 18 ± 5

C4-decalins 41 ± 4

C2-naphthalenes 187 ± 53

C3-naphth ale nes 158 ± 42

Cl -benzothiophenes 25 ± 14

C2-benzoth iophen es 20 ± 11

C3-benzoth iophene s 22 ± 1 3

C4-benzoth iophencs 18 ± 5

Cl-fluorenes 57 ± 18

C2-tluorenes 122 ± 43

C3-fluorenes 1 28 ± 31

C1-p hen anthrene s/anth racenes 3 1 3 ± 99

C2-phenanthre nes/anthracenes 247 ± 62

C3-phenanthn ;Tl_e_ /antl)racenes 165 ± 46

C4-phenant hrenes/anthracenes 87 ± 36

C1- dibenzothiophene s 54 ± 13

C2-dibenzothioph enes 91 ± 18

C3-dibenzothiophe nes 84 ± 15

C4-dibenzothiophenes 57 ± 1 3

Cl -tluoranthenes /pyrenes 252 ± 48

C2-fluoranthenes / pyren es 205 ± 38

C3-fluoran th encs/py renes 1 02 ± 22

C4-fluoranthene s/pyrenes 121 ± 59

C1 -benzanth races/ch ryse nes /tripheny lenes 208 ± 43

C2-benzanthrace s/chrys enes /triphenylenes 120 ± 24

C3-benzanthraces /ch ryse nes /triphenylenes 73 ± 31

C4-benzanthraces /chrysenes /tri pheny lenes 41 ± 11

(al The reference mass frac ti on va lu e reported on a dry-ma ss basis is the median of results usi ng one anal ytical techniqu e. The

expanded uncertainty. U. is calculated as U = kuc. where li e is one standard deviation of the median . a nd the coverage factor. k = 2.

(hJ Data from the inter lahorato ry s tu dy [1 2].


''

Table 9. Reference Mass Fraction Values for Selected Hopanes and Steranes in SRM 1941 b

Hopane or Sterane Mass Fraction<" h>

mg/kg

I 7a(H)-22,29,30-Trisnorhopane 54 ± 18

l 7a(H)-2 I P(H)-30-Norhopane 137 ± 21

l 7a(H)-2 I (H)-30-Hopane 215 ± 44

l 7a(H)-2 I P(H)-22R-Homohopane 44 ± IO

l 7a(H)-2 l P(H)-22S-Ho mohop an e 48 ± 13

5a(H)-14a(H), l 7a(H)-Cho lestan e 20R 41 ± 11

5a(H)-l 4P(H) , l 7 (H)-Cho les tan e 20R 27 ± 6

5a(H)- I 4P(H), I 7P(H)-24-Methylcholestane 20R 21 ± 8

5a(H)- I 4a(H).l 7a(H)-24-Ethylcho lestan e 20R 19 ± 5

5a(H)-l 4P(H) , I 7P(H)-24-Ethylcholestane 20R 41 ± 9

(a) The reference ma ss fract ion value reported on a dry-ma ss basis is the median of results usi ng one analytical techn iqu e. The

expanded uncertainty. U. is calculated as U = kuv where 11, is one standard deviation of the median. and the coverage factor, k = 1 .

(bJ Data from the inte rlaboratory stu dy [I 2].

Table I 0 . Reference Mass Fraction Value for Total Organic Carbon in SRM 1941 b

Total Organic Carbon (TOC) 2.99 o/o ± 0.24 o/o(a.h)

1 1 Mass fraction is reported on a dr y -mass basis ; material as received contains approximately 2.4 % moi s tu re.

(hJ The reference value for total organ ic carbon is a weighted me an value from routine measurement s made by two laborator ies [21].

The uncertainty lis ted is an expanded uncertainty about the mean. with coverage factor 1 (approximately 95 % confid ence) .

calculated by combining a between-method variance incorporating inter-method bias with a pooled within-method var ianc e. The

reporting follows the ISO Guides [2].

Table 11 . In formatio n Mass Fraction Va lue s for Carbon. Hydrogen, and Nitrogen in SRM 1941 b Ele

ment s Mass Fraction s( J)

%

Carbon

Hydrogen

Nitroge n

3.3

1.2

<0.5

(.,, Mass fraction is reported on a dry-mass basis; material as received contains approxima tely 2.4 % moisture.


Certificate Revision History: IO April 2012 ( rh1, revision adds reference values l<-ir alky lated PAH groups. hopam:,. and ,teranes: extens10n of

certification penod ; editorial changes/. 1 6 August 2004 (Thi s rev 1s 1o n rem o\ eS the re ference values for th e butyl tin s and make s editorial changes).

1 5 July 2002 (Original ce111ticate date)

REFERENCES

[!) May, W.E.; Parris, R.M.: Beck II, C.M.: Fassett. J.D.; Greenberg, R.R.; Guenther, F.R.; Kramer, G.W.; Wise, S.A.;

Gills, T.E.: Colbert. J.C.; Gettings, R.J.: MacDonald, B.R.; Definition ofTerms and Modes Used at NIST for Value

Assignment of Reference Mater ials for Chemical Measurements: NIST Special Publication 260-136 (2000);

available at http://www.nist.gov/sn n/ publications .cfm (accessed Apr 2012).

[2) Wise, S.A.; Poster, D.L.: Schantz, M.M.; Kucklick, J.R.; Sander, L.C.; Lopez de Alda, M.; Schubert, P .;

Parris, R.M.: Porter. B.J.: Two New Marine Sedimelll Standard Reference Materials ( SRMs)for the Determination

of Organic Comaminants; Anal. Bioanal. Chem., Vol. 378, pp. 1251-1264 (2004).

[3) Wise, S.A.; Ches ler. S.N. ; Hertz. H.S.; Hilpert, L.R.: May, W.E.; Chemically-Bonded Aminosilane Stationary

Phase for the High Per formance Liquid Chromatographic Separation of Polynuclear Aromatic Hydrocar bons;

Anal. Chem., Vol. 49. pp. 2306-2310 (1977).

[4) May, W.E.: Wise , S .A.: Liquid Chromatographic Determinatton of Polycyclic Aromatic Hydrocarbons in Air

Particulate Extra cts: Anal. Chem., Vol. 56, pp. 225-232 (1984).

[5) Wise, S.A.; Benner. B.A.: Byrd, G.D.: Chesler, S.N.; Rebbert, R.E.; Schantz, M.M.: Determination of Polycyclic Aromatic Hydrocarbons in a Coal Tar Standard Reference Material: Anal. Chem., Vol. 60, pp. 887-894 (1988).

[6] Wise, S.A.; Deissler. A.: Sander, LC.: Liquid Chromatographic Determination of Polycyclic Aromatic

Hydrocarbon Isomers of Molecular Weight 278 and 302 in Environmental Standard Reference Materials;

Polycyclic Aromat. Compd., Vol. 3, pp. 169-184 (1993 ).

[7) Schantz. M.M.; Parris, R.M .: Wise, S.A.: NIST/NOAA Intercmnpari.1·011 Exercise Program for Organic

Contaminants in the Marine Em'ironment: Description and Results of /999 Organic lnter comparison Exercises;

NOAA Technical Memorandum NOS NCCOS CCMA 146, Silver Sprin g, MD (2000) .

[8) Schubert, P.: Schantz, M.M.: Sander, L.C.: Wise, S.A.; Determination of Polycyclic Aromatic Hydrocarbons with

Molecular Mass 300 and 302 in Environmental-Matr ix Standard Reference Mlllerials by Gas

Chromato g raphy-Mas .1· Spectromet1y; Anal. Chem., Vol. 75, pp. 234-246 (2003).

[9] Ballschmiter, K.: Zell. M.: Analysis of Polychlorinated Biphenyls (PCB) by Glass Capillary Gas Chromatography

Composlfion of Teclmical Aroclor- and Clophen-PCB Mixtures: Fresenius ' Z. Anal. Chem., Vol. 302, pp. 20-31

(1980).

fl0l Schulte, E.: Malisch, R.: Calculation of'the Real PCB Content in Environmental Samples. I. Investigation of'the Composition of Two Technical PCB Mixtures: Fresenius' Z. Anal. Chem.. Vol. 3 I 4, pp. 545- 551 (1983).

[I l] Brubaker. W.W., Jr.; Schantz. M.M.: Wise, S.A.; Determination of Non-ortho Polychlorinated Biphenyls in

Environmental Standard Reference M aterials ; Fresenius· J. Anal. Chem, . Vol. 367, pp. 401-406 (2000).

[12) Schantz. M.M .; Kucklick, J.R..; NIST lnterlaborntory Analytical Comparison Studv to Support Deepwater Horizon

Natural Resource Damage Asses .1111e 11t: Description and Results.for Crude Oil QA JOO/LO I: NTSTIR 7793(2011 ).

[13] Ruhkin, A.L.: Vange l, M.G.; Esti111atio11of a Common Mean and Weighted Means Statistics; J. Am. Statist. Assoc.,

Vol. 93, pp. 303-308" (1-<ns).

[14] JCGM I 00:2008; El'afuation of Measurement Data - Guide to the Expression of Uncertainty in Measurement

(ISO GUM 1995 with Minor Corrections): Joint Committee for Guides in Metrology (2008): available at

http: //www.bipm.org /utils /co mmo n/documents /jcgm/JCGM_l 00_2008_E.pdf (accessed Apr 2012); see also

Taylor, B.N.: Kuyatt, C.E.: Guidelines for E\'(/ltwtint; and Expressing the Uncer tainty of NIST Measurement

Results; NIST Technical Note 1297; U.S. Government Printing Office: Washington. DC (1994); available at

h ttp://www.ni t.gov/pml /pub s/tn 1 297/in dex.cfin (accessed Apr 2012).

[15] JCGM IO I : 2008 : Emluation of measurement data - Supplement I to the "Guide to the expression of uncertainty in

measurement" - Propagarion of' distributions using a Monte Carlo method ; JCGM (2008): available at

http: //www.b ipm.org/ut il s /common/documen ts /jcgm/JCGM_ I 01 _2008_E.pdf (accessed Apr 2012).

[16] Levenson. M.S.: Banks, D.L.: Eberhardt, K.R.: Gill. L.M.: Guthrie, W.F.: Liu. H .-K.: Vangel, M.G.: Yen, J.H.:

Zhang, N.F .: An Approach to Combining Resulrsfrom Multiple Methods Moti1'ated by the ISO GUM: J. Res. Natl.

Inst. Stand. Technol.. Vol. 105. pp. 571-579 (2000).

Users of this SRM .1'1011/d l'llsure that the Certificate of Analysis in their possession is current. This can be accomplished

hy contacting the SRM Prog ram : telephone ( 301) 975-2200; fax ( 30/) 9415-3730; e-mail [email protected]; or via the

/memet at http://w1n l'. nist.go l'!sr111.

http://www.nist.gov/sn

http://www.bipm.org/

http://w1n/


APPENDIX A

The laboratories listed below performed measurements that contributed to the certification of PAHs, PCBs, and

chlorinated pesticides in SRM 1941b Organics in Marine Sediment.

Arthur D. Little, Inc; Cambridge, MA, USA

Axys Analytical Services; Sidney, BC, Canada

B & B Laboratories; College Station, TX, USA

Battelle Ocean Sciences; Duxbury, MA, USA

Bedford Institute of Oceanography; Dartmouth, NS, Canada

California Department of Fish and Game; Rancho Cordova, CA, USA

Central Contra Costa Sanitary District; Martinez, CA, USA

Chesapeake Biological Laboratory; Solomons, MD, USA

Centro de Investigacionies Energeticas Medioambientales y Tecnologicas; Madrid, Spain

City of Los Angeles Environmental Monitoring Division; Playa de] Rey, CA, USA

City of San Jose Environmental Services Department; San Jose, CA, USA

Columbia Analytical Services; Kelso, WA, USA

East Bay Municipal Utility District; Oakland, CA. USA

Florida Department of Environmental Protection; Tallahassee, FL, USA

Manchester Environmental Laboratory; Port Orchard, WA, USA

Murray State University; Murray, KY. USA

Massachusetts Water Resources Authority Central Lab; Winthrop, MA, USA

National Research Council of Canada; Ottawa, Ontario, Canada

National Oceanic and Atmospheric Association (NOAA), National Marine Fisheries Service (NMFS), Auke Bay

Laboratory; Juneau. AK, USA

NOAA, National Ocean Service/Center for Coastal Environmental Health and Biomolecular Research;

Charleston, SC, USA

NOAA, NMFS. Sandy Hook Marine Laboratory; Highlands, NJ. USA

NOAA. NMFS. Northwest Fisheries Science Center; Seattle. WA, USA

Orange County Sanitation District; Fountain Valley. CA, USA

Philip Analytical Services; Burlington. Ontario, Canada

Serv de Hidrografia Naval: Buenos Aires, Argentina

Skidaway Institute of Technology; Savannah. GA, USA

Southwest Laboratory of Oklahoma; Broken Arrow, OK, USA

Severn Trent Knoxville Laboratory; Knoxville, TN, USA

Texas A&M University, Geochemical and Environmental Research Group; College Station. TX. USA

Texas Parks and Wildlife Department: San Marcos, TX. USA

University of California at Los Angeles, Institute of Geophysics and Planetary Physics; Los Angeles. CA. USA

University of Connecticut. Environmental Research Institute; Storrs, CT. USA

University of Rhode Island. Graduate School of Oceanography; Narragansett, RI, USA

US Department of Agriculture. Environmental Chemistry Laboratory; Beltsville, MD, USA

US Environmental Protection Agency, Atlantic Ecology Division; Narragansett. RI. USA

US Geological Survey. National Water Quality Laboratory: Denver, CO. USA

Woods Hole Group Environmental Lab: Raynham. MA, USA

Wright State University: Dayton. OH, USA

of 15 SRM 1941b

APPENDIX B

The laboratories listed below performed measurements that contributed to the certification of alkylated PAH groups,

hopanes, and steranes in SRM 1941b Organics in Marine Sediment.

Alpha Analytical, Inc.; Mansfield, MA, USA

Analytical Resources, Inc.; Tukwila, WA, USA

Axys Analytical Services; Sydney, BC, Canada

Battelle Analytical & Environmental Chemistry Laboratory; Duxbury, MA, USA

Center for Laboratory Sciences; Pasco, WA, USA

Columbia Analytical Services; Jacksonville, FL, USA

Columbia Analytical Services; Rochester , NY, USA

Columbia Analytical Services, Kelso, WA, USA

Florida Department of Environmental Protection; Tallahassee, FL. USA

Florida International University; North Miami, FL, USA

Michigan Department of Natural Resources and Environment; Lansing, MI. USA

Mississippi State Chemical Laboratory; Mississippi State, MS. USA

NIST; Charleston, SC. USA

NIST; Gaithersburg, MD, USA

NOAA/NCCOS/NOS; Charleston, SC, USA

NOAA /NMFS /Alaska Fisheries Science Center; Juneau . AK, USA

NY State Department of Hea lth; Albany, NY, USA

Pace Analytical Services. Inc. Minneapolis: Minneapolis , MN. USA

RJ Lee Group, Inc: Monroeville, PA. USA

TDI/B&B Laboratories. Inc.; College Station, TX

TestAmerica Laboratories; Mobile, AL, USA

TestAmerica Laboratories; West Sacramento, CA, USA

TestAmerica Laboratories; University Park, IL. USA

TestAmerica Laboratories; Schriever. LA, USA

TestAmerica Laboratories; Edison. NJ. USA

TestAmerica Laboratories; Knoxville, TN. USA

TestAmerica Laboratories; Pittsburgh, PA, USA

TestAmerica Laboratories; South Burlington. VT, USA

TestAmerica Labo ratories ; Tacoma, WA, USA

US Army Engineer Research and Development Center; Vicksburg, MS, USA

USGS Columbia Environmental Research Center; Columbia, MO. USA

University oflowa tat Hygienic Laboratory; Iowa City, IO. USA

Washington State Public Health Laboratories ; Shoreline, WA. U-SA



Appendix C Signature Page for Subcontractors

Makah Dock Extension Dredged Material Characterization

Signature Page for Subcontractors

Approval signatures indicate that subcontractors have reviewed this Sampling and Analysis

Plan (SAP) and agree to follow the methods and QA procedures contained herein.

Date: ---- "'-10=/=0=6/-=2=01"""6'--_

Cheronne Oreiro

Chemist

Analytical Resources, Inc.

Date: _

Eric Parker

Research Support Services

Makah Dock Extension Dredged Material Characterization

Signature Page for Subcontractors

Approval signatures indicate that subcontractors have reviewed this Sampling and Analysis

Plan (SAP) and agree to follow the methods and QA procedures contained herein.

Date: _

Cheronne Oreiro

Chemist

Analytical Resources, Inc.

Date: October 6, 2016

Eric Parker

Research Support Services



Appendix B Sample Logs and Photographs





3 February 2017

Page 1 of 18 Appendix B

Photograph 1. Makah Commercial Fishing Dock

Photograph 2. Power grab sampling activities





3 February 2017


Photograph 3. Sample S-1






3 February 2017








3 February 2017



Photograph 28. Sample S-25 First Attempt





3 February 2017


Photograph 29. Sample S-25 Second Attempt






3 February 2017








3 February 2017


Photograph 35. Sample S-

Makah Indian Tribe Dredge Material Characterization


Grab Sample: S-1 Northing 522599.410

Date: 11/21/2016 Easting 721118.523

Time: 8:20 AM Water depth (feet, depth to mudline): 30.6

Weather: Overcast, 46 F Tide stage (feet relative to CRD): 6.39

Field Personnel: Carissa Watanabe & Joe Gallagher Calculated mudline elevation (feet CRD): 24.21

Vessel Operator: Research Support Services Sampling method: Power Grab

Material Description

color, soil type (density, odor/no odor),

additional features, sheen/no sheen

Remarks

SM/ML - grey, loose, fine sandy silt with organic material (sculpin).

No odor or sheen were observed.

10.5" of sediment was recovered.

Notes:




Date: 11/21/2016 Easting 721278.711








Remarks

SM/ML - grey, loose, fine sandy silt with organic material (seaweed).


12" of sediment was recovered.

Notes:




Date: 11/21/2016 Easting 721526.415








Remarks

SM - grey, medium dense, silty fine sand with organic material (roots and

worms).



Notes:

At 8:40am 33.7 at -21, too deep to collect sample (Northing:522534.336 Easting: 721562.603). Contacted Lauran at DMMO moved location and sampled

after S-4.




Date: 11/21/2016 Easting 721731.224

Time: 8:55 AM Water depth (feet, depth to mudline): 31







Remarks

SM - grey, medium dense, silty fine sand with organic material (roots and

worms).



Notes:




Date: 11/21/2016 Easting 721772.381








Remarks

SM - grey, medium dense, fine sand with silt, non-sediment material (2inch

rock, roots, and shells).



Notes:




Date: 11/21/2016 Easting 721571.430


Weather: Sunny, 46 F Tide stage (feet relative to CRD): 5.67






Remarks

SM - grey, medium dense, silty fine sand with organic material (worms).



Notes:




Date: 11/21/2016 Easting 721400.309








Remarks

ML - grey, soft, silt with fine sand, non-sediment material (roots).



Notes:




Date: 11/21/2016 Easting 721155.746


Weather: 46 F Tide stage (feet relative to CRD): 5.49






Remarks

SM - grey, loose, silty fine sand with organic material (worms and shells).



Notes:




Date: 11/21/2016 Easting 721116.846








Remarks

ML - grey, loose, silt with fine sand, organic material (roots).



Notes:




Date: 11/21/2016 Easting 721304.456


Weather: Overcast Tide stage (feet relative to CRD): 5.21






Remarks

ML - grey brown, loose, silt with fine sand, non-sediment material (roots,

and shells).



Notes:




Date: 11/21/2016 Easting 721127.357








Remarks

ML - grey black, loose, silt with trace fine sand, organic material (roots).



Notes:




Date: 11/21/2016 Easting 721305.151








Remarks

ML - brown, loose, silt with trace fine sand, organic material (roots).



Notes:




Date: 11/21/2016 Easting 721490.903


Weather: Cloudy, 47 F Tide stage (feet relative to CRD): 4.9






Remarks

ML - grey, loose, silt with trace fine sand, organic material (roots).



Notes:




Date: 11/21/2016 Easting 721476.039








Remarks

SM - grey, loose, silty fine sand with organic material (roots and worms).



Notes:




Date: 11/21/2016 Easting 721627.708








Remarks

SM/ML - grey, loose, fine sandy silt with organic material (roots).



Notes:




Date: 11/21/2016 Easting 721772.951








Remarks

SM - grey, medium dense, silty fine sand with organic material (shells and

roots).



Notes:




Date: 11/21/2016 Easting 721107.335

Time: 12:35 PM Water depth (feet, depth to mudline): 22.9







Remarks

ML - black, loose, silt with fine sand, organic material (roots and worms).



Notes:




Date: 11/21/2016 Easting 721287.531








Remarks

ML - black, loose, silt with trace fine sand, non-sediment material (roots and

kelp).

Odor present

(faint rotten egg like odor).

No sheen observed.


Notes:




Date: 11/21/2016 Easting 721119.778








Remarks

SM - black, medium dense, silty fine sand with clam shell fragments.



Notes:




Date: 11/21/2016 Easting 721304.289








Remarks

SM - dark grey, medium dense, silty fine sand with organic material (worms

and shells).



Notes:




Date: 11/21/2016 Easting 721425.126








Remarks

ML - black, loose, silt with fine sand, non-sediment material (roots).

Odor present

(rotten egg like odor).

No sheen observed.


Notes:




Date: 11/21/2016 Easting 721541.824








Remarks

SM - dark grey, medium dense, silty fine sand, non-sediment material

(aluminum can and roots).



Notes:




Date: 11/21/2016 Easting 721449.996








Remarks

SM - dark grey, medium dense, silty medium sand, organic material (roots

and shell fragments).



Notes:




Date: 11/21/2016 Easting 721632.410








Remarks

SM - black, medium dense, silty fine sand, non-sediment material shells).



Notes:

Coordiantes incorrect, created new approximate point after calling and getting okay from Lauran at DMMO



Grab Sample: S-25 (1sr attempt) Northing 521390.452

Date: 11/21/2016 Easting 721717.037








Remarks

SM/ML - black, soft, fine sandy silt, non-sediment material (roofing shingle

and shells).



Notes:

1st attempt did not have enough sedmet, asphalt shingles, shells, seacucumbers primarilly.



Grab Sample: S-25 (2nd attempt) Northing 521393.889

Date: 11/21/2016 Easting 721712.531








Remarks

SM - black, medium dense, silty medium sand, non-sediment material

(bottles, shells, metal debris, D battery, sculpins, eels).

Odor present


No sheen observed.


Notes:



Grab Sample: S-26 (1st attempt) Northing 521479.802

Date: 11/21/2016 Easting 721770.364








Remarks

Clam shells and metal



Notes:

1st attempt did not have enough sediment, shells and metal.




Date: 11/21/2016 Easting 721767.887








Remarks

SM - black, medium dense, silty fine sand, non-sediment material (bottles,

barnacle, rock, shell fragmetns, and broken glass).



Notes:



Grab Sample: S-27 (1st attempt) Northing 521242.355

Date: 11/21/2016 Easting 721795.415








Remarks

Kelp and shells


Notes:

1st attempt did not have enough sedmet, kelp and shells.




Date: 11/21/2016 Easting 721794.086








Remarks

ML - black, loose, fine sandy silt with shell fragments, non-sediment

material (kelp and shells).

Odor present


No sheen observed.


Notes:



Grab Sample: S-28 Latitude 521273.168

Date: 11/21/2016 Longitude 721914.744








Remarks

SM - black, loose, silty fine to medium sand, non-sediment material (tire

fragment, rubber glove, shell fragments, and worms).



Notes:



Appendix C Chemical Analytical Data Report

Please see enclosed CD for Appendix C



Appendix D Data QA/QC Review Summary




Page D‐1 of 6

Appendix D

Neah Bay, Washington Data QA/QC Review Summary

APPENDIX D

QUALITY ASSURANCE REVIEW

This appendix summarizes the results of a Level 1 quality assurance (QA1) review of the

analytical data for sediment samples collected November 2016 from the proposed dredged

material associated with the Makah Indian Tribe Emergency Spill Dock Extension dredging

project. Field procedures used for sample collection are discussed in our Sampling and Analysis

Plan (BergerABAM, 2016). BergerABAM submitted sediment samples to Analytical Resources

Inc. (ARI), of Tukwila, Washington, for chemical analysis. A copy of the analytical laboratory

reports are included in Appendix C. Based on our review, the analytical data are valid with

minor qualifications for their intended use. A data completeness checklist is included in Table

D‐1 of this appendix.

The quality assurance review included examination and validation of the following information

from the laboratory’s summary reports (ARI Report 16K0314, 16L0320 [subsample results]).

• Holding times

• Method blanks

• Surrogate recoveries

• Laboratory control sample/laboratory control sample duplicate (LCS/LCSD) recoveries

• Standard reference material (SRM) recoveries

• Calibration criteria

• Internal standard (IS) recoveries

• Laboratory duplicate relative percent difference (RPD)

• Laboratory replicate relative standard deviation (RSD)

ANALYTICAL METHODS AND DETECTION LIMITS

Chemical Analysis

Twenty‐eight subsamples were collected during the sediment characterization activities. The

subsamples were composited into seven Dredged Material Management Unit (DMMU) samples

and were analyzed for the following.

• Total organic carbon by SM5310B/EPA Method 9060/Plumb 1981 (modified for sediments)

• Total solids/Total volatile solids by PSEP/SM2540G‐97

• Ammonia by SM 4500‐NH3 H‐97/Plumb (1981)

• Sulfides by SM 4500‐S2 D‐00/PSEP and Plumb (1981)

• Grain size by PSEP/ASTM D‐422 (modified)

• Total metals and mercury using EPA Methods SW 6010C/6020/7440/7471B

• Semivolatile organic compounds (SVOCs) using EPA Method SW8270D and 8270D‐SIM




Page D‐2 of 6

Appendix D


• Polycyclic aromatic hydrocarbons (PAHs) using EPA Method 8270D and 8270D‐SIM

• Chlorinated hydrocarbons using EPA Method 8260B/8270D/8081

• Phthalates, phenols, and miscellaneous extractables using EPA Method 8270D/8081

• Pesticides using EPA Method SW8081A

• Polychlorinated biphenyls (PCBs) using EPA Method SW8082A

• Diesel‐range petroleum hydrocarbons (TPHD) using Ecology Method NW‐TPHD

• Gasoline‐range petroleum hydrocarbons (TPHG) using Ecology Method NW‐TPHG

• Bulk tributyltin (TBT) using EPA Method SW8270D‐SIM/ PSEP, Krone (1989), and Unger

(1986)

Follow up analysis was completed on subsamples S‐25, S‐26, S‐27, and S‐28 for mercury,

SVOCs/PAHs, total solids, and total organic carbon.

Detection and Reporting Limits

Method detection limits (MDLs) are the minimum concentration of a chemical compound that

can be measured and reported. The MDL is based on instrumentation abilities and the sample

matrix. Method reporting limits (MRL) represent the concentration that can be accurately

quantified. MRLs are set by the laboratory and are based on the low standard of the initial

calibration curve or low‐level calibration check standard.

In some cases, the MRL is raised because of high concentrations of analytes in the samples or

matrix interferences. MRLs were consistent with industry standards. Tables 4 and 5 of this

report list the MDLs for undetected samples. The MDLs are sufficient in achieving the

DMMP/SMS criteria. Analytes that were detected between the MDL and MRL are qualified as

estimated (J qualifier).

QA REVIEW RESULTS

The laboratory provided QC sample results that underwent a QA review. Laboratory QC

samples were consistent with those specified in the SAP to evaluate precision, accuracy,

representativeness, comparability, and completeness. The sample data and laboratory QC data

are suitable for their intended use with minor qualifications. The following summary lists the

results of the QA review by analyte or test.

General Chemistry Parameters (total organic carbon, total solids, sulfide, and ammonia)

All hold times were met. The method blanks were clean at the reporting limits. The LCS percent

recoveries were within control limits.

The matrix spike percent recovery of total organic carbon fell outside the control limits low for

sample DMMU‐1. The SRM percent recovery of total organic carbon for the subsamples (S‐25

through S‐28) was outside the control limits high. All other quality control parameters were met

for this analysis. No corrective action was taken.




Page D‐3 of 6

Appendix D


The duplicate RPD of sulfide was outside the control limit for sample DMMU‐1. All other

quality control parameters were met for this analysis. No corrective action was taken.

Total Metals

All required holding times were met. The method blanks were clean at the reporting limits. The

LCS percent recoveries were within control limits. ERA D088‐540 was analyzed as a reference

material. The duplicate RPDs were within control limits.

The matrix spike percent recovery of antimony fell outside the control limits low for sample

DMMU‐1. A post‐digestion spike was performed, and the recovery was within the control

limits. The lab did not take any further corrective action.

Mercury

All required holding times were met for the DMMU samples. The subsamples (S‐25 through

S‐28) were analyzed outside the recommended holding time.

The method blank was clean at the reporting limit. The LCS percent recovery was within

control limits. ERA D088‐540 was analyzed as a reference material. The matrix spike percent

recovery and duplicate RPD were within control limits.

Tributyltin

The samples and associated laboratory QC were extracted and analyzed within the method

recommended holding times.

Initial and continuing calibrations were within method requirements. Internal standard areas

were within limits. Surrogate percent recoveries were within control limits.

The method blanks were clean at the reporting limit. The LCS and LCSD percent recoveries

were within control limits.

PAHs


holding times. Initial calibrations were within method requirements. Internal standard areas

were within limits. The surrogate percent recoveries were within control limits.

The method blank was clean at the reporting limits. The LCS percent recoveries were within

control limits.

The initial calibration verification (ICV) on 9 December 2016 was outside the 20 percent control

limit high for Dibenzo(a,h)anthracene. All detected results associated with this ICV have been

flagged with a Q qualifier. No further corrective action was taken.

The LCS percent recovery of Dibenzo(a,h)anthracene was outside the control limits high for

BEK0736‐BS1. All other percent recoveries were within control limits. No corrective action was

taken.




Page D‐4 of 6

Appendix D


CRM 143‐50G was analyzed as a reference material.

The matrix spike and matrix spike duplicate percent recoveries were within control limits.

Values on the final data results tables were revised from the draft data results submittal to the

DMMP to show the most conservative analytical result from the EPA Method 8270D and 8270‐

SIM analyses. The following protocols were used to determine the most conservative value.

• If the results for the same COC from both analyses are flagged as estimated concentrations,

the larger concentration is used in the table.

• If the results for the same COC from both analyses are unflagged results, the larger

concentration is used in the table.

• If one result is flagged as an estimated concentration, and one result is not flagged for the

same COC, the unflagged result is used in the table since the laboratory has a greater level

of confidence in the unflagged result.

SVOCs by 8270

The samples and associated laboratory QC were extracted and analyzed within the holding

times. Internal standard areas were within limits. The surrogate percent recoveries were within

control limits. The method blank was clean at the reporting limits. The LCS percent recoveries

were within control limits. Initial calibrations were within method requirements.

The initial calibration verification fell outside the 20 percent control limit low for Benzyl Alcohol

and Benzoic Acid. Associated sample results were undetected for these compounds. No

corrective action was taken.


The matrix spike and matrix spike duplicate percent recoveries of Benzyl Alcohol fell outside

the control limits low for sample DMMU‐2. Several matrix spike and matrix spike duplicate

percent recoveries fell outside the control limits low for sample S‐25. No corrective action is

required for matrix QC. No corrective action is required for matrix QC.

SVOCs by 8270-SIM

The samples and associated laboratory QC were extracted and analyzed within the holding

times. Internal standard areas were within limits. The surrogate percent recoveries were within

control limits. The method blank was clean at the reporting limits.

The initial calibration verification (ICV) on 9 December 2016 was outside the 20 percent control

limit high for Dibenzo(a,h)anthracene. All detected results associated with this ICV have been

flagged with a Q qualifier. No further corrective action was taken.

The initial calibration verification (ICV) on 3 January 2017 fell outside the 20 percent control

limit low for Butylbenzylphthalate and the surrogate p‐Terphenyl‐d14. Associated sample




Page D‐5 of 6

Appendix D


results were undetected for Butylbenzylphthalate. All samples were re‐analyzed on 13 January

2017, and the ICV recoveries were within control limits. Both sets of data have been reported.

No further corrective action was taken.

The LCS percent recovery of Dibenzo(a,h)anthracene was outside the control limits high for

BEK0736‐BS1. All other percent recoveries were within control limits. No corrective action was

taken.



Pesticides





control limits. NIST 1944 was analyzed as a reference material.

The continuing calibration verification on 9 December 2016 at 19:29 fell outside the 20 percent

control limit low for the surrogate Decachlorobiphenyl on the second column, but was within

the control limits on the first column. No corrective action was taken.


PCBs




The initial calibration verification on 9 December 2016 at 16:26 was outside the 20 percent

control limit high for Aroclor 1260 on the first column but was within the control limit on the

second column. The continuing calibration verifications on 9 December 2016 at 20:22 and 22:40

were outside the control limit high for Aroclor 1260 on the first column but were both within

the control limit on the second column. No corrective action was taken.


control limits.


CRM 911‐50g was analyzed as a reference material.

Grain Size

All required holding times were met.




Page D‐6 of 6

Appendix D


Because of the sandy nature of the samples, there was not fine material to acquire accurate

hydrometer readings. Samples 16K0314‐10, 16K0314‐15, 16K0314‐25, 16K0314‐30 and

16K0314‐35 required curve fitting between the sand and silt fractions.

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