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Douglas Indian Association Tribal Response Program Sandy Beach Sampling Data Report Douglas, AlaskaPrepared for the Douglas Indian Association

JULY 16, 2014

Douglas Indian Association Tribal Response Program

Sandy Beach Sampling Data Report

Douglas, Alaska

Prepared for

Douglas Indian Association

Prepared by

RIDOLFI Inc.

July 2014

Douglas Indian Association Sandy Beach Sampling Data Report

140718_Data Report_R2 July 2014 Page i

EXECUTIVE SUMMARY

The Douglas Indian Association Tribal Response Program performed sampling of Sandy Beach

sediments, clam tissue, and crab tissue over a two-day period from April 29 through April 30,

2014. Sandy Beach abuts the historical Treadwell Mine Site and is known to be contaminated

with metals from waste rock, tailings, and processing chemicals associated with the mine.

Sediment samples were collected from upper and lower beach locations that are used for

subsistence and recreational purposes by Douglas Indian Association tribal members. Clam

tissue samples were collected from one location near Douglas Marina. Crab tissue samples were

collected from two locations in the nearshore waters adjacent to and south of Sandy Beach.

Sample analysis was performed to determine whether methylmercury, inorganic arsenic, and

lead pose a potential risk to tribal members through direct contact with sediments or through

consumption of local seafood. Both sediment and tissue samples were also analyzed for total

mercury and total arsenic to determine the relative contributions of the methylated and

inorganic metal species, respectively.

Total arsenic and inorganic arsenic were detected in most sediment samples at concentrations

that exceed human health screening levels but not ecological screening levels. The results show

that inorganic arsenic accounts for most if not all of the total arsenic content.

Total mercury and methylmercury were detected in most sediment samples at concentrations

that exceeded ecological screening levels but not human health screening levels. The results

show that methylmercury accounts for very little of the total mercury content. Lead was

detected in all sediment samples at concentrations below project screening levels.

Total arsenic and inorganic arsenic were detected above the reporting limit in all tissue samples.

All tissue results exceeded the human health screening level for inorganic arsenic. The analytical

results show that inorganic arsenic accounts for about half of the total arsenic content in

bivalves and a much lower fraction in crab. Mercury and methylmercury were detected above

the reporting limit in all tissue samples. Methylmercury results exceeded the human health

screening level in crab and nearly exceed the human health screening level in clams.


140718_Data Report_R2 July 2014 Page ii

The collective analytical results indicate that Sandy Beach sediments, clam tissue, and crab tissue

pose an exposure risk to humans. Sediments pose a threat to humans through direct exposure

to both inorganic and total arsenic. Clam tissue collected from Sandy Beach and crabs collected

in the nearby offshore waters contain concentrations of inorganic arsenic that exceed USEPA

screening levels for the consumption of fish. Detections of methylmercury in crab tissue

collected near Sandy Beach also exceeded the U.S. Environmental Protection Agency human

health screening level. Both the arsenic and methylmercury concentrations detected in sampled

tissue present an exposure risk based on the U.S. Environmental Protection agency default fish

consumption rate of 54 grams of fish (or shellfish) per day. Higher rates of consumption may

result in an increased potential for adverse health effects to manifest in human consumers.

Additionally, the high concentrations of arsenic in sediment may be contributing to poor crab

catches in the area directly offshore of Sandy Beach and the absence of clams in the southern

half of the lower beach face, although the available data to support this hypothesis is limited at

this time.


140718_Data Report_R2 July 2014 Page iii

TABLE OF CONTENTS

Executive Summary ..................................................................................................................... i

1.0 Introduction ........................................................................................................................ 1

1.1 Scope of Work .......................................................................................................................................... 1

1.2 Contaminants of Potential Concern ................................................................................................. 1

2.0 Site Descriptions and Histories .......................................................................................... 2

2.1 Site Description ........................................................................................................................................ 2

2.2 Site Background ....................................................................................................................................... 2

2.3 Previous Sampling .................................................................................................................................. 3

3.0 Project Screening Levels ................................................................................................... 4

4.0 Sampling Procedures......................................................................................................... 5

4.1 Sediment Sampling and Analysis ...................................................................................................... 5

4.2 Tissue Sampling and Analysis ............................................................................................................. 5

4.3 Collection of Additional Global Positioning System Data ....................................................... 6

4.4 Exceptions to the Field Sampling Plan ............................................................................................ 6

5.0 Analytical Results Summary .............................................................................................. 7

5.1 Data Validation Summary .................................................................................................................... 7

5.2 Sediment .................................................................................................................................................... 7

5.2.1 Arsenic ....................................................................................................................................... 7

5.2.2 Mercury ..................................................................................................................................... 7

5.2.3 Lead ............................................................................................................................................ 8

5.3 Tissue ........................................................................................................................................................... 8

5.3.1 Arsenic ....................................................................................................................................... 8

5.3.2 Mercury ..................................................................................................................................... 8

6.0 Conclusions ..................................................................................................................... 10

6.1 Sediment .................................................................................................................................................. 10

6.2 Tissue ......................................................................................................................................................... 11

6.3 Exposure Risks ........................................................................................................................................ 11

7.0 References ...................................................................................................................... 13


140718_Data Report_R2 July 2014 Page iv

LIST OF FIGURES

Figure 1. Project Area Location Map

Figure 2. Sampling Locations

LIST OF TABLES

Table 1. Sample Identification, Description, Coordinates, and Analyses Performed

Table 2. Sediment Sampling Results Summary

Table 3. Tissue Sampling Results Summary

LIST OF APPENDICES

Appendix A. Data Validation Report


140718_Data Report_R2 July 2014 Page v

LIST OF ABBREVIATIONS AND ACRONYMS

ADEC Alaska Department of Environmental Conservation

DIA Douglas Indian Association

GPS Global Positioning System

Ridolfi RIDOLFI Inc.

TRP Tribal Response Program

USEPA U.S. Environmental Protection Agency

LIST OF UNITS

°C degrees Celsius

mg/kg milligrams per kilogram (parts per million)

mg/L milligrams per liter (parts per million)

ng/g nanograms per gram (parts per billion)


140718_Data Report_R2 July 2014 Page 1

1.0 INTRODUCTION

The Douglas Indian Association (DIA) Tribal Response Program (TRP), with technical assistance

from RIDOLFI Inc. (Ridolfi) is performing assessment of multiple sites that may impact tribal

subsistence and cultural resources. This work is being performed in cooperation with the U.S.

Environmental Protection Agency (USEPA) Tribal Response Program.

As part of this assessment, the Tribe has performed sampling of environmental media that may

pose an exposure risk to Tribal Members. This environmental sampling work has been

performed in accordance with the guidance described by the Douglas Indian Association

Sampling Quality Assurance Project Plan (Ridolfi, 2014). The most recent round of field sampling

performed by the DIA TRP included sampling and analysis of beach sediment, clam tissue, and

crab tissue from Sandy Beach on Douglas Island.

1.1 Scope of Work

Sandy Beach sediment, clam tissue, and crab tissue were sampled over a two-day period from

April 29 through April 30, 2014. Sediment samples were collected from upper and lower beach

locations that are known to be used for subsistence and recreational purposes. Clam tissue was

collected from one location near Douglas Marina. Crab samples were collected from the

subtidal area adjacent to and south of Sandy Beach.

Analysis of these samples was performed to determine whether methylmercury, inorganic

arsenic, and lead pose a potential risk to tribal members through direct contact or consumption

of seafood. This sampling work was limited in nature and not intended to determine the full

nature and extent of contamination or exposure risks at Sandy Beach.

1.2 Contaminants of Potential Concern

Contaminants of potential concern in sediment included methylmercury, inorganic arsenic, and

lead. Contaminants of potential concern in tissue included methylmercury and inorganic

arsenic. Both sediment and tissue samples were also analyzed for total mercury and total

arsenic in order to determine the relative contributions of the methylated and inorganic metal

species, respectively.



2.0 SITE DESCRIPTIONS AND HISTORIES

2.1 Site Description

Sandy Beach is located on Douglas Island adjacent to the historic Treadwell Mine immediately

southeast of Douglas, Alaska. The site is located less than a mile to the southwest of downtown

Juneau across Gastineau Channel (Figure 1). The beach is used by DIA tribal members for

collection of traditional subsistence food resources as well as by the general public for

recreational purposes.

Sandy beach is a broad and flat reach of shoreline covered by a mix of sand, coarse gravel, and

various debris associated with the former mine workings. Public facilities at the beach include

picnic shelters, public bathrooms, and an upland trail system with multiple outlets onto the

beach. The largest of the Treadwell Mine shafts is located at the southern extent of Sandy Beach

where it was flooded by Gastineau Channel. This feature is colloquially referred to as the “Glory

Hole.”

2.2 Site Background

Historic disposal practices of waste rock, tailings, and processing chemicals at the Treadwell

Mine have left Sandy Beach and the surrounding environment contaminated with heavy metals.

Two primary sources of contaminants are associated with the Treadwell Mine Complex:

processed ore tailings and chemicals used in ore concentrating activities. Tailings from mine

sites with similar geology in the region have been found to contain elevated concentrations of

arsenic, barium, and lead that are associated with the primary ore minerals (Ecology and

Environment, 1991).

Because early milling and ore concentration practices were relatively inefficient, the mass of

tailings produced by the mine was nearly as large as that of the extracted ore. Over its

operational lifetime, the estimated total mass of tailings produced by the Treadwell complex was

more than 20 million tons. These tailings have been deposited in a variety of locations around

the Treadwell Mine Complex, including directly on and around Sandy Beach. Tailings and waste

rock remain visible across the beach, particularly in the vicinity of the glory hole at the south end

of the beach and near the barge loading station located approximately halfway between the

parking lot and the glory hole.



Processing chemicals used in the ore concentration process included sodium cyanide and

elemental mercury. Although mercury was routinely reclaimed for later use during ore

concentration operations, significant quantities were lost along with tailings during ore

processing and through spills. Between June 1908 and May 1911, approximately seven tons of

mercury went unaccounted for at the Treadwell mills. Assuming this loss rate represented an

average for the operating history of the Treadwell mills, it is possible that up to 70 tons of

mercury may have been released from the mill sites over their operational lives1.

2.3 Previous Sampling

Due to concerns related to the presence of mine contaminants at Sandy Beach, DIA TRP staff

and Alaska Department of Environmental Conservation (ADEC) staff collected sediment and co-

located interstitial water (porewater) samples in July 2011 at five locations in the intertidal zone

at Sandy Beach. The samples were analyzed for total mercury and total arsenic in both media.

Analytical results provided to DIA in a draft report from ADEC showed total mercury

concentrations in porewater ranging from 0.0007 to 0.12 milligrams per liter mg/L.

Concentrations of total mercury in sediment ranged from 0.1 to 1.83 milligrams per kilogram

(mg/kg). Total arsenic results ranged from 0.039 to 1.58 mg/L in porewater, and 2.3 to 16.6

mg/kg in sediment. The draft report released by ADEC concluded that the analytical results from

this sampling event indicated that mercury concentrations posed an exposure risk to human

health, safety, and the environment.

1 70 tons of mercury is approximately equivalent to 220 x 55-gallon drums filled with elemental mercury at standard

temperature and pressure. This is, by every conventional measure, a very large amount of elemental mercury.



3.0 PROJECT SCREENING LEVELS

Sediment analytical results from the Sandy Beach sampling event were compared to ADEC

human health screening levels for soil in an area with more than 40-inches of rain annually

(Table B1; ADEC, 2012), and the USEPA Regional Screening Level for Residential Soil (USEPA,

2013). These screening levels were considered appropriate since they assume direct contact

with the contaminated media, which occurs during harvesting of subsistence resources such as

clams and crab, as well as during recreational use.

Sediment ecological screening levels for sediment include sediment quality guideline threshold

effects level (MacDonald et al., 1996) and USEPA Region 5 Ecological Screening Levels (USEPA,

2003). Both screening levels are applied to marine sediment and are therefore directly

applicable in this investigation.

Tissue analytical results were compared to USEPA Regional Screening Levels for fish ingestion

(USEPA, 2014), since these were the most directly applicable to bivalve and crustacean tissue.



4.0 SAMPLING PROCEDURES

Sediment and tissue samples were collected during a period from April 29 through April 30,

2014. Sampling locations are identified in Figure 2. Sample location coordinates, descriptions,

and analytical methods are identified in Table 1. Sampling methods and handling procedures

followed the guidance provided in the Sampling Quality Assurance Project Plan (Ridolfi, 2014).

Samples were submitted to Brooks Rand Labs in Seattle, Washington. All samples were

submitted under a chain-of-custody as specified in the Sampling Quality Assurance Project Plan

(Ridolfi, 2014).

Analytical parameters detected during this sampling event are presented and compared to

project screening criteria in Tables 2 and 3. All the data presented in this report were validated

in accordance with the requirements of the USEPA Office of Solid Waste and Emergency

Response Stage 4 Full Validation (USEPA, 2010) by EcoChem Inc., a third party validation firm. A

validation report is provided in Appendix A.

4.1 Sediment Sampling and Analysis

Sediment samples were collected from eight locations on Sandy Beach, including one location

where sediment samples were co-located with bivalve tissue samples. Sediment samples were

collected directly from the beach using pre-cleaned, disposable sampling spoons and Teflon

bucket liners for homogenization. New sampling equipment was used at each sampling station.

Composite samples were collected from just below the beach surface to a maximum depth of up

to 6-inches. Sediment collected from the co-located bivalve substations was taken from the

media below each bivalve. The surface of each excavation where bivalves were collected was

scraped clean with a sampling spoon prior to sediment collection. All homogenized sediment

samples were transferred to laboratory-supplied glassware and labeled.

Sediment samples were analyzed for total mercury (Method USEPA 1631E), methylmercury

(Method USEPA 1630 Modified), total arsenic (Method USEPA 1638 Modified), inorganic arsenic

(Method USEPA 1632 Modified), and total lead (Method USEPA 6010C).

4.2 Tissue Sampling and Analysis

Bivalve tissue samples were collected from one location on Sandy Beach. Bivalves were dug up

using a garden shovel, rinsed in ambient seawater, and then individually bagged in freezer



Ziploc® bags. Each composite set of bivalves was then bagged as a group and labeled for the

laboratory. Shucking and tissue preparation was performed by the analytical laboratory.

Crab samples were collected from the locations shown in Figure 2. Crabs were rinsed in ambient

sea water and then placed in a cooler for euthanization. Euthanized crabs were wrapped in

aluminum foil and double bagged using freezer Ziploc® bags. Each composite crab sample was

then bagged as a group, labeled, and frozen for transport to the analytical laboratory. Shucking

and tissue preparation were performed by the analytical laboratory.

Tissue samples were analyzed for total mercury (Method USEPA 1631E), methylmercury (Method

USEPA 1630 Modified), total arsenic (Method USEPA 1638 Modified), and inorganic arsenic

(Method USEPA 1632 Modified).

4.3 Collection of Additional Global Positioning System Data

In addition to collecting sediment and tissue samples, global positioning (GPS) coordinates of

metal beach debris associated with the former mine workings were also collected. The resulting

data are provided in Figure 2 and show the distribution of metal including former ore carts,

culverts, small gauge rail lines, and other debris along Sandy Beach.

4.4 Exceptions to the Field Sampling Plan

Exceptions to the field sampling plan during this sampling event included the following:

Only one bivalve tissue sampling station was established and sampled (Figure 2). While

other portions of the lower beach were searched for bivalves, none were present.

Two crab sampling locations were moved south of the original target sampling area

since crab pots set immediately offshore of Sandy Beach did not catch any crabs.

The USEPA Regional Screening Level for Fish Ingestion table was updated in May 2014.

The SQAPP specified the August 2013 values. The revised values are used in this report.



5.0 ANALYTICAL RESULTS SUMMARY

Analytical results are presented in this Section by sample matrix. Complete analytical results and

comparison of those results to screening levels are provided in Tables 2 and 3.

5.1 Data Validation Summary

A full data validation was performed by EcoChem Inc. in Seattle, Washington. The data were

reviewed based on the quality control criteria provided in the Sampling Quality Assurance

Project Plan and the USEPA National Functional Guidelines for Inorganic Data Review (USEPA,

2010). EcoChem’s overall assessment found that the laboratory followed all specified analytical

methods and the resulting data were acceptable for use as qualified.

5.2 Sediment

5.2.1 Arsenic

Total arsenic and inorganic arsenic were detected in all sediment samples. Half of the analytical

results for total arsenic exceeded the human health screening level of 3.7 mg/kg2. (ADEC Table

B1). Total arsenic concentrations across Sandy Beach ranged from 2.62 to 5.40 mg/kg, with the

highest values detected at sampling station SBeach-06, in the northern half of the lower beach

sediments (Figure 02). Four of the five samples that exceeded the human health sediment

screening level were collected from upper beach locations (stations SBeach-01, -02, -03, and

including the duplicate at SBeach-01).

All of the inorganic arsenic results exceeded the human health screening level of 0.39 mg/kg

(USEPA Regional Screening Level for Residential Soil). Concentrations of inorganic arsenic

ranged from 0.728 to 4.50 mg/kg. The highest detected value for inorganic arsenic of 4.50

mg/kg was located near the Glory Hole at the south end of the upper beach.

No arsenic results exceeded the ecological screening level (Marine Sediment TEL).

5.2.2 Mercury

Total mercury was detected in all samples at concentrations that exceeded the ecological

threshold effects level for sediment of 130 nanograms per gram (ng/g)3. Concentrations of total

2 Milligrams per kilogram are equivalent to parts per million.

3 Nanograms per gram are equivalent to parts per billion.



mercury in sediment ranged from 181 to as high as 469 ng/g. As was the case with inorganic

arsenic, the highest concentration of total mercury was found on the upper beach near the Glory

Hole. Total mercury results did not exceed the human health screening level of 25,000 ng/g.

Methylmercury results for sediment included six detections above the method reporting limit

and several non-detections. Three of the four non-detects were located at upper beach

sampling stations SBeach-01, -03, and -04. All of the detected concentrations of methylmercury

exceeded the ecological screening level of 0.01 ng/g (USEPA Region 5 Ecological Screening

Level for Sediment). However, four of these exceedances were by less than one-hundredth ng/g.

Methyl mercury results did not exceed the human health screening level of 78,000 ng/g.

5.2.3 Lead

Lead was detected in all sediment samples at concentrations that ranged from 5.4 to 10.2

mg/kg. None of the lead detections exceeded the ecological threshold effects level for sediment

of 30.2 mg/kg. The highest lead concentration was detected at sampling station SBeach-05,

near the Douglas Harbor jetty.

5.3 Tissue

5.3.1 Arsenic

Total arsenic was detected in both clam and crab tissue at concentrations that ranged from 2.85

to 9.07 mg/kg. The highest concentration was found in crab tissue from station SBeach-10

south of the Glory Hole. No screening level is available for total arsenic in tissue. Inorganic

arsenic was detected in all tissue samples at concentrations that exceeded the human health

screening level of 0.0028 mg/kg (USEPA Regional Screening Level for Fish Ingestion).

Concentrations of inorganic arsenic ranged from 0.024 to 1.67 mg/kg. The highest

concentration of arsenic was found in the bivalve tissue duplicate from sampling station SBeach-

05.

5.3.2 Mercury

Total mercury was detected in all tissue samples at concentrations that ranged from 33.7 to 61.7

mg/kg. Methylmercury was also detected in all tissue samples at concentrations that ranged

from 13.1 to 38.5 ng/g. The highest concentrations of both mercury and methylmercury were

found in crab tissue at station SBeach-10. Concentrations of both metal species in crab tissue

from station SBeach-09 were also high when compared to the bivalve results from stations

SBeach-05. Methylmercury concentrations in both crab samples exceeded the human health



screening level of 15 ng/g (USEPA Regional Screening Level for Fish Ingestion). Methylmercury

concentrations in bivalves did not exceed the screening level, but were close to doing so. No

screening level is available for total mercury in tissue.



6.0 CONCLUSIONS

The DIA TRP performed sampling of Sandy Beach sediment, clam, and crab tissue over a two-

day period from April 29 through April 30, 2014. Sandy Beach abuts the historical Treadwell

Mine Site and is known to be contaminated with metals from waste rock, tailings, and

processing chemicals associated with the mine.

Sediment samples were collected from upper and lower beach locations that are used for

subsistence and recreational purposes by DIA tribal members. Clam tissue was collected from

one location near the Douglas Marina. Crab samples were collected from two locations in the

offshore area adjacent to and south of Sandy Beach. Crab sampling stations were moved south

of the originally proposed sampling area due to lack-of-catch in the area directly offshore of

Sandy Beach. Similarly, only one clam tissue sampling station was established due to an

absence of clams on the southern beach. While there is limited evidence available for

interpretation, the crab lack-of-catch off the Sandy Beach shoreline and the absence of clams

near the barge loading facility may be indicative of generally poor ecosystem productivity and

health in this area.

Sediment sample analysis was performed to determine whether methylmercury, inorganic

arsenic, and lead pose a potential risk to tribal members through direct contact with sediment.

Tissue sample analysis was performed to determine whether methylmercury and inorganic

arsenic pose a potential risk to tribal members or through consumption of local seafood. Both

sediment and tissue samples were also analyzed for total mercury and total arsenic in order to

determine the relative contributions of the methylated and inorganic metal species, respectively.

6.1 Sediment

Arsenic, inorganic arsenic, mercury, methylmercury, and lead were all detected in sediment at

concentrations that exceeded at least one screening level. Total arsenic results for sampling

stations SBeach-01, -02, -03 (upper beach), and SBeach-07 (lower beach) exceeded the human

health screening level of 3.7 milligrams per kilogram (ADEC Table B1). All sediment stations

sampled had inorganic arsenic concentrations that exceeded the human health screening level

of 0.39 mg/kg (USEPA Regional Screening Level for Residential Soil). Inorganic arsenic made up

the majority of the arsenic detected in sediment at all of the upper beach samplings stations

(stations SBeach-01, -02, -03, and-04) and near the Douglas Harbor (station SBeach-05) with

concentrations that ranged from 72 to 100-percent of the measured total arsenic. However,



inorganic contributions to the lower beach sediments was much lower, with concentrations

ranging from approximately 20 to 30-percent of the total.

Total mercury concentrations for all sediment stations exceeded the ecological threshold effects

level for sediment. Methylmercury was not detected above the method reporting limit at some

sediment sampling stations, however detected concentrations at stations SBeach-01, -02, -05, -

07, and -08 all exceeded the ecological screening level for sediment of 0.01 ng/g (USEPA Region

5 Ecological Screening Level). Where methylmercury was detected in sediment, it made up less

than one percent of the total mercury measured.

While lead was detected in all sediment samples, none of the detected concentrations exceeded

project screening levels.

6.2 Tissue

Arsenic, inorganic arsenic, mercury, and methylmercury were detected above the method

reporting limit in all tissue samples that were analyzed. All of the detected concentrations of

inorganic arsenic in both bivalve and crab tissue exceeded the USEPA Regional Screening Level

for Fish Ingestion of 0.0028 mg/kg. Inorganic arsenic contributions to total arsenic in clam

tissue were relatively high in both the primary and duplicate samples from SBeach -05, with

relative contributions ranging from approximately 45 to 57-percent of the total arsenic

measured. Inorganic arsenic in crab tissue made up a relatively low percentage of the total

arsenic measured.

Methylmercury concentrations in both crab samples exceeded the human health screening level

of 15 ng/g (USEPA Regional Screening Level for Fish Ingestion); methylmercury concentrations

in clam tissues did not exceed this screening level but were close to doing so. Methylmercury in

clam tissue ranged from approximately 35 to 38-percent of the total mercury measured.

Methylmercury in crab tissue made up approximately 62 to 65-percent of the total mercury

measured.

6.3 Exposure Risks

Based on these combined analytical results, Sandy Beach sediments, clam tissue, and crab tissue

pose an exposure risk to humans. Sediments pose a threat through direct exposure to inorganic

and total arsenic concentrations in sediments. Clam and crab tissue of from Sandy Beach

sediments or the nearby offshore waters also contain concentrations of inorganic arsenic that



exceed USEPA human health screening levels for the consumption of fish tissue. Additionally

high concentrations of arsenic in sediment may be related to poor crab and clam catches in the

area directly offshore of Sandy Beach and along the lower beach face.

Methylmercury concentrations in crab tissue from stations in the Sandy Beach nearshore exceed

the USEPA human health screening levels for the consumption of fish tissue. This means that

crab tissue with the detected concentrations of methylmercury pose an additional exposure risk

to human consumers on top of the risk associated with inorganic arsenic identified above.

It should be noted that the default fish consumption rate used to set the USEPA Regional

Screening Level for Fish Ingestion is 54 grams of fish (or shellfish) tissue per day. This value is

frequently much lower than the rates of consumption observed among people who rely on

fishing or shellfishing as a means of subsistence4. Because target hazard quotients are set based

on the default fish consumption rate, the risk of adverse health effects manifesting in human

consumers will be higher for individuals who consume more than the default amount the USEPA

has specified.

4 Estimates vary but a typical single restaurant serving of cooked fish ranges from approximately 85 to 175 grams.

Subsistence consumption rates may be considerably higher.



7.0 REFERENCES

Alaska Department of Environmental Conservation (ADEC). 2012. 18 AAC 75 Oil and Other

Hazardous Substances Pollution Control. April.

Ecology and Environment Inc. (E&E). 1991. Site Inspection Report for Treadwell Mine Juneau,

Alaska.

MacDonald, D.D., R.S. Carr, F.D. Calder, E.R. Long, and C.G. Ingersoll. 1996. Development and

evaluation of sediment quality guidelines for Florida coastal waters. Ecotoxicology V.5, p.

253-278.

RIDOLFI Inc. (Ridolfi) 2014. Douglas Indian Association Tribal Response Program Sampling

Quality Assurance Project Plan. February.

U.S. Environmental Protection Agency (USEPA). 2003. Region 5 RCRA Ecological Screening

Levels. August. Available: http://epa.gov/region5/waste/cars/pdfs/ecological-screening-

levels-200308.pdf.

U.S. Environmental Protection Agency (USEPA). 2009. Guidance for Labeling Externally Validated

Laboratory Analytical Data for Superfund Use. EPA 540-R-08-005. January.

U.S. Environmental Protection Agency (USEPA). 2010. USEPA Contract Laboratory Program

National Functional Guidelines for Superfund Inorganic Methods Data Review. USEPA-540-

R-10-011. January.

U.S. Environmental Protection Agency (USEPA). 2013. Regional Screening Levels for Chemical

Contaminants Summary Table. May. Accessed August 2013. Available:

http://www.epa.gov/reg3hwmd/risk/human//rb-

concentration_table/Generic_Tables/docs/ressoil_sl_table_01run_MAY2013.pdf.

U.S. Environmental Protection Agency (USEPA). 2014. Regional Screening Level Fish Ingestion

Table. May. Accessed May 2014. Available:

http://www.epa.gov/reg3hwmd/risk/human/pdf/MAY_2014_FISH_THQ01_watermark.pdf.

Tables

Table 1. Sandy Beach Sample Identification, Description, Coordinates, and Analyses Performed

Station Identification Latitude LongitudeSample

Identification

Sample

MatrixSample Description Comments Date Collected

Time

Collected

58.26820 -134.37500 14042901 Sediment Brown coarse sand. Pore water rust colored. 4/29/2014 16:45 X X X X X X

58.26820 -134.37500 14042902 Sediment Field Duplicate of 14042901 4/29/2014 17:00 X X X X X X

SBeach-02 58.27040 -134.37801 14042903 Sediment Brown coarse sand. 4/29/2014 17:30 X X X X X X

SBeach-03 58.27100 -134.37900 14042904 Sediment Brown coarse sand with slate inclusions. 4/29/2014 17:45 X X X X X X

SBeach-04 58.27290 -134.38499 14042905 Sediment Brown coarse sand with gravel inclusions. 4/29/2014 18:00 X X X X X X

14043001 Bivalve Tissue Composite clam tissue sample. 4/30/2014 7:15 X X X X

14043002 Sediment Black coarse sand. Sulfurous smell. 4/30/2014 7:30 X X X X X X

14043003 Bivalve Tissue Field Duplicate of 14043001 4/30/2014 7:45 X X X X

14043004 Sediment Field Duplicate of 14043002 4/30/2014 8:00 X X X X X X

SBeach-06 58.27300 -134.37900 14043005 Sediment Gray coarse sand. Pore water clear. 4/30/2014 8:30 X X X X X X

SBeach-07 58.27100 -134.37500 14043006 Sediment Red-brown coarse sand. Rust coloring in subsurface. 4/30/2014 9:00 X X X X X X

SBeach-08 58.26950 -134.37300 14043007 Sediment Gray coarse sand. 4/30/2014 9:15 X X X X X X

SBeach-10 58.26620 -134.36600 14043008 Crab Tissue Composite crab sample. 4/30/2014 13:00 X X X X

SBeach-11 58.26900 -134.37000 14043009 Crab Tissue Composite crab sample. 4/30/2014 13:30 X X X X

Notes:1 Coordinates with 5-place precision were determined by global positioning system instrumentation.

SM = Standard Method

USEPA = U. S. Environmental Protection Agency

Analytical Methods

Coordinates 1

(decimal degrees)

To

tal

Me

rcu

ry

(US

EP

A 1

63

1E

)

Me

thy

lme

rcu

ry

(US

EP

A 1

63

0

Mo

dif

ied

)

To

tal

Ars

en

ic

(US

EP

A 1

63

8

Mo

dif

ied

)

Ino

rga

nic

Ars

en

ic

(US

EP

A 1

63

2

Mo

dif

ied

)

To

tal

Le

ad

(US

EP

A 6

01

0C

)

To

tal

So

lid

s

(SM

25

40

G)

SBeach-05

SBeach-01

58.27540 -134.38400



July 2014 Page 1 of 3140520_DRtables

Table 2. Sediment Analytical Results

Sampling Station: SBeach-02 SBeach-03 SBeach-04 SBeach-06 SBeach-07 SBeach-08

Sample Identification 14042901 14042902 14042903 14042904 14042905 14043002 14043004 14043005 14043006 14043007

Sample Date: 4/29/2014 4/29/2014 4/29/2014 4/29/2014 4/29/2014 4/30/2014 4/30/2014 4/30/2014 4/30/2014 4/30/2014

Laboratory Identification: 1418034-01RE1 1418034-02 1418034-03 1418034-04 1418034-05 1418034-07 1418034-09 1418034-10 1418034-10RE1 1418034-11

Field QC:

Field Duplicate of

14042901

Field Duplicate of

14043002

Metals

Arsenic 3.70 -- 7.24 -- mg/kg 4.09 3.86 3.96 3.71 3.25 2.62 3.04 3.34 5.40 3.35

Inorganic Arsenic -- 0.39 7.24 -- mg/kg 4.38 4.50 3.85 3.70 2.34 2.31 2.76 0.728 1.66 0.698

Lead -- -- 30.2 -- mg/kg 6.56 5.40 8.68 8.49 7.56 10.2 7.91 7.71 9.83 5.58

Mercury 25,000 -- 130 -- ng/g 469 J 262 J 181 J 183 J 202 J 251 J 242 J 339 J 200 J 268 J

Methylmercury -- 780 -- 0.01 ng/g 0.011 UJ 0.013 U 0.013 J 0.010 UJ 0.010 U 0.158 J 0.117 J 0.010 UJ 0.029 J 0.102 J

Total Solids -- -- -- -- % 78.45 78.60 90.97 93.51 81.86 75.76 79.41 79.20 83.61 83.80

Result exceeds the Alaska Department of Environmental Conservation Table B1 Value for Zones with more than 40 inches of rain annually

Result exceeds the U.S. Environmental Protection Agency Regional Screening Level for Residential Soil May 2013

Result exceeds the Marine Sediment Threshold Effects Level (MacDonald et al. 1996)

Result exceeds the U.S. Environmental Protection Agency Region 5 Ecological Screening Level

Notes:

-- = No Screening Level Value

mg/kg = milligrams per kilogram

ng/g = nanograms per gram

Analytical Flags:

U = The analyte was analyzed for, but was not detected above the reported sample quantitation limit.

J = The analyte was positively identified; the associated numberical value is the approximate concentration of the analyte in the sample.

Bold values indicate the analyte was detected above the method reporting limit.

Upper Beach Stations Lower Beach Stations

SBeach-05

ADEC Table

B1 40+

Inches

Reporting

Units

USEPA

Region 5

Ecological

Screening

Level

USEPA RSL for

Residential Soil

Marine

Sediment

TEL

SBeach-01




Table 3. Tissue Analytical Results

Sampling Station: SBeach-10 SBeach-11

Sample Identification 14043001 14043003 14043008 14043009

Sample Date: 4/30/2014 4/30/2014 4/30/2014 4/30/2014

Laboratory Identification: 1418034-06RE1 1418034-08 1418034-13RE1 1418034-14

Field QC:

Field Duplicate of

14043001

Tissue Type: Bivalve Bivalve Crab Crab

Tissue

Arsenic -- mg/kg 2.85 3.65 9.07 3.19

Inorganic Arsenic 0.0028 mg/kg 1.65 1.67 0.040 0.024

Mercury -- ng/g 33.7 J 37.9 J 61.7 J 49.1 J

Methylmercury 15 ng/g 13.1 J 13.5 J 38.5 J 32.2 J

Notes:

-- = No Screening Level Value

mg/kg = milligrams per kilogram

ng/g = nanograms per gram

Analytical Flags:

J = The analyte was positively identified; the associated numberical value is the approximate concentration of the analyte in the sample.

Bold values indicate the analyte was detected above the method reporting limit.

SBeach-05

USEPA RSL Fish

Ingestion

Reporting

Units

Result exceeds the U.S. Environmental Protection Agency Regional Screening Level for Fish Ingestion

using a target hazard quotient of 0.1

Lower Beach Stations Nearshore Stations




Figures

_̂!(

S t a t e o f A l a s k a

S t a t e o f A l a s k a

N a t i o n o f C a n a d a

N a t i o n o f C a n a d a

Juneau

Douglas

Sources: Esri, USGS, NOAA

Prepared for the Douglas Indian Association

Sandy BeachSampling Data Report

Location Map

July 2014 Figure 1

Path: M:\Projects\238_DIA\238D_TRP\Mapfiles\SandyBeach_ARS\Figure01_Location.mxd

_̂

_̂

_̂

Juneau

FairbanksAnchorage

L o c a t i o n M a pL o c a t i o n M a p

¯0 4 8

Scale in Miles

Legend_̂ Major City!( Village

Major RoadAlaska Marine Highway

E

E

E

EEEEEE

EE

E

E

EE

EEEE

!(EEE

!(

!(

!( !(

!(

!(

GF

GF

GF

SBeach-01

SBeach-02

SBeach-03

SBeach-04

SBeach-05

SBeach-06

SBeach-07

SBeach-08

SBeach-09

SBeach-10

SBeach-11(Not Sampled)

G a s t i n e a uC h a n n e l

Douglas Harbor

Barge LoadingStation

Former TreadwellMineshaft

(Glory Hole)

Source: Esri, DigitalGlobe, GeoEye, i-cubed, USDA, USGS, AEX,Getmapping, Aerogrid, IGN, IGP, swisstopo, and the GIS UserCommunity

Prepared for the Douglas Indian Association


Sampling Locations

July 2014 Figure 2

Path: M:\Projects\238_DIA\238D_TRP\Mapfiles\SandyBeach_ARS\Figure02_locations.mxd

¯0 250 500

Scale in Feet

LEGENDGF Crab StationE Metal!( Sediment Station

Co-LocatedSediment-BivalveSample Area(SBeach-05)

Appendix AData Validation Report

ej 7/3/2014 i EcoChem, Inc. L:\Ridolfi 252\25210-1 Douglas IA - Sandy Beach\25210-1CVR.docx

PROJECT NARRATIVE

Basis for the Data Validation

This report summarizes the results of full validation (EPA Stage 4) performed on sediment, tissue and quality control sample data for the Douglas Indian Association – Sandy Beach sampling. A complete list of samples is provided in the Sample Index.

Samples were analyzed by Brooks Rand Labs, Seattle, Washington. The analytical methods and EcoChem project chemists are listed in the following table:

Analysis Method Primary Review Secondary

Review

Methyl Mercury E1630

J. Holder C. Ransom

Total Mercury E1631

Inorganic Arsenic E1632

Total Arsenic and Lead E1638

Total Solids SM 2540G

The data were reviewed using guidance and quality control criteria documented in the analytical methods; Douglas Indian Association Tribal Response Program – Sampling Quality Assurance Project Plan (Ridolfi Inc. February 2014); and National Functional Guidelines for Inorganic Data Review (USEPA 2010).

EcoChem’s goal in assigning data assessment qualifiers is to assist in proper data interpretation. If values are estimated (J or UJ), data may be used for site evaluation and risk assessment purposes but reasons for data qualification should be taken into consideration when interpreting sample concentrations. If values are assigned a do-not-report (DNR) flag, the data should not be used for any site evaluation purposes. If values have no data qualifier assigned, then the data meet the data quality objectives as stated in the documents and methods referenced above.

Data qualifier definitions, reason codes, and validation criteria are included as APPENDIX A. A Qualified Data Summary Table is included in APPENDIX B. Data Validation Worksheets and project associated communications will be kept on file at EcoChem, Inc. A qualified laboratory electronic data deliverable (EDD) is also submitted with this report.

Sample Index

Douglas Indian Association - Sandy Beach

Sample ID Laboratory ID

Total

Arsenic

Inorganic

Arsenic

Total

Lead

Total

Mercury

Methyl

Mercury

14042901 1418034-01 P P P P P

14042902 1418034-02 P P P P P

14042903 1418034-03 P P P P P

14042904 1418034-04 P P P P P

14042905 1418034-05 P P P P P

14043001 1418034-06 P P P P

14043002 1418034-07 P P P P P

14043003 1418034-08 P P P P

14043004 1418034-09 P P P P P

14043005 1418034-10 P P P P P

14043006 1418034-11 P P P P P

14043007 1418034-12 P P P P P

14043008 1418034-13 P P P P

14043009 1418034-14 P P P P

7/3/2014

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DATA VALIDATION REPORT Douglas Indian Association – Sandy Beach

Total Arsenic and Lead by Method 1638, Total Mercury by Method 1631, Methyl Mercury by Method 1630, and Inorganic Arsenic by

Method 1632

This report documents the review of the data from the analysis of tissue and sediment samples and the associated laboratory and field quality control (QC) samples. All data received a full validation. The samples were analyzed by Brooks Rand Labs, Seattle, Washington. Refer to the Sample Index for a complete list of samples.

SDG Number of Samples Validation Level

1418034 4 Tissue

10 Sediment EPA Stage 4

I. DATA PACKAGE COMPLETENESS

The laboratory submitted all required deliverables. The laboratory followed adequate corrective action processes and all anomalies were discussed in the case narrative.

II. EDD TO HARDCOPY VERIFICATION

A complete (100%) verification of the electronic data deliverable (EDD) results was performed by comparison to the hardcopy laboratory data package. Laboratory QC results were also verified (10%). The following errors were found:

The laboratory “M” flag for total mercury and “N” and “U” flags for methyl mercury were not included in the EDD for Sample 14042901. These flags were added to the EDD during data validation.

III. TECHNICAL DATA VALIDATION

The quality control (QC) requirements that were reviewed are listed in the following table:

1 Sample Receipt, Preservation, and Holding Times 2 Laboratory Duplicates Initial Calibration (ICAL) 2 Field Duplicates Calibration Verification (CCAL) 1 Reported Results

1 Laboratory Blanks Reporting Limits Laboratory Control Samples (LCS) Target Analyte List

1 Reference Materials (CRM) 1 Calculation Verification

2 Matrix Spike/Matrix Spike Duplicates (MS/MSD)

Method quality objectives (MQO) and QC criteria have been met. No outliers are noted or discussed.

1 Quality control results are discussed below, but no data were qualified. 2 Quality control outliers that impact the reported data were noted. Data qualifiers were issued as discussed below.


Sample Receipt, Preservation, and Holding Times

As stated in validation guidance documents, the sample shipping coolers should arrive at the laboratory within the advisory temperature range of 2° to 6°C. The coolers were received at temperatures less than the minimum control limit, the lowest at 0.6°C. These temperature outliers did not impact data quality; no action was taken.

Sediment samples were frozen upon receipt at the laboratory. The samples were analyzed for methyl mercury after the 28 day holding time specified in the Work Plan. The 1 year holding time specified for frozen tissues was used to evaluate the sediment holding times. No data were qualified.

Laboratory Blanks

To evaluate the effect on the sample data, action levels of five times (5x) the blank concentrations were established. Methyl mercury was detected in one method blank and mercury was detected in two instrument blanks at concentrations greater than the method detection limits. All associated results for these analytes were greater than the action levels; no data were qualified.

Reference Materials

For the sediment samples, the total lead recovery for NIST 2709a was less than the lower control limit of 75%. A second reference material, NIST 2710a, was analyzed with the samples and the recovery was within the control limits. The laboratory control sample (LCS) and matrix spike/matrix spike duplicate (MS/MSD) recoveries for the batch were also within control limits; therefore no action was taken based on the single outlier.

Matrix Spike/Matrix Spike Duplicates

The MS/MSD recoveries for methyl mercury associate with the sediment analyses were less than the lower control limit of 65%. All methyl mercury results for the sediment samples were estimated (J/UJ-8L) to indicate a potential low bias.

Laboratory Duplicates

The mercury laboratory duplicate analysis was performed utilizing Sample 140429001. The relative percent difference (RPD) for mercury (62%) was greater than the control limit of 30%. All results for this analyte in the associated sediment samples were estimated (J-9).

Field Duplicates

The following acceptance criteria were used to evaluate field precision: the RPD control limit is 50% for results greater than 5x the reporting limit (RL). For results less than 5x the RL, the difference between the sample and duplicate must be less than 2x the RL.

Three sets of field duplicates were submitted:

14042901 & 14042902 14043002 & 14043004 14043001 & 14043003


The RPD value for mercury (56.6%) was greater than the control limit for Samples 14042901 & 14042902. The results for this analyte were estimated (J-9) in both samples.

Reported Results

The inorganic arsenic results for samples 1402901 and 14042902 were greater than the total recoverable arsenic results. A comparison of the inorganic arsenic versus total arsenic values showed that the results fell within normal analytical precision criteria; therefore no action was taken.

All sample results were method blank corrected as per Brooks Rand standard operating procedures.

Calculation Verification

Several results were verified by recalculation from the raw data. No calculation or transcription errors were found.

III. OVERALL ASSESSMENT

As determined by this evaluation, the laboratory followed the specified analytical methods. With the exceptions noted above, accuracy was acceptable as demonstrated by the LCS, CRM, and MS/MSD %R values and precision was acceptable as demonstrated by the laboratory duplicate, MS/MSD, and field duplicate RPD values.

Data were estimated based on matrix spike recovery and laboratory and field duplicate precision outliers.

All data, as qualified, are acceptable for use.

APPENDIX A

DATA QUALIFIER DEFINITIONS REASON CODES

AND CRITERIA TABLES

CJW 06/14/95 10:12 AM I:\APPENDIX.DOC

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DATA VALIDATION QUALIFIER CODES National Functional Guidelines

The following definitions provide brief explanations of the qualifiers assigned to results in the data review process.

U The analyte was analyzed for, but was not detected above the reported sample quantitation limit.

J The analyte was positively identified; the associated numerical value is the approximate concentration of the analyte in the sample.

N The analysis indicates the presence of an analyte for which there is presumptive evidence to make a “tentative identification”.

NJ The analysis indicates the presence of an analyte that has been “tentatively identified” and the associated numerical value represents the approximate concentration.

UJ The analyte was not detected above the reported sample quantitation limit. However, the reported quantitation limit is approximate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample.

R The sample results are rejected due to serious deficiencies in the ability to analyze the sample and meet quality control criteria. The presence or absence of the analyte cannot be verified.

The following is an EcoChem qualifier that may also be assigned during the data review process:

DNR Do not report; a more appropriate result is reported from another analysis or dilution.

T:\A_EcoChem Controlled Docs\Qualifiers & Reason Codes\Reason Codes-EcoChem rev1.doc EcoChem, Inc.

DATA QUALIFIER REASON CODES

Group Code Reason for Qualification

Sample Handling 1 Improper Sample Handling or Sample Preservation (i.e., headspace, cooler

temperature, pH, summa canister pressure); Exceeded Holding Times

Instrument Performance

24 Instrument Performance (i.e., tune, resolution, retention time window, endrin

breakdown)

5A Initial Calibration (RF, %RSD, r2)

5B Calibration Verification (ICV, CCV, CCAL; RF, %D, %R)

Use bias flags (H,L)1 where appropriate

Blank Contamination

6 Field Blank Contamination (Equipment Rinsate, Trip Blank, etc.)

7 Lab Blank Contamination (i.e., method blank, instrument blank, etc.)

Use low bias flag (L)1 for negative instrument blanks

Precision and Accuracy

8 Matrix Spike (MS &/or MSD) Recoveries


9 Precision (all replicates: LCS/LCSD, MS/MSD, Lab Replicate, Field Replicate)

10 Laboratory Control Sample Recoveries (a.k.a. Blank Spikes)


12 Reference Material


13 Surrogate Spike Recoveries (a.k.a. labeled compounds, recovery standards)


Interferences

16 ICP/ICP-MS Serial Dilution Percent Difference

17 ICP/ICP-MS Interference Check Standard Recovery


19 Internal Standard Performance (i.e., area, retention time, recovery)

22 Elevated Detection Limit due to Interference (i.e., chemical and/or matrix)

23 Bias from Matrix Interference (i.e. diphenyl ether, PCB/pesticides)

Identification and

Quantitation

2 Chromatographic pattern in sample does not match pattern of calibration standard

3 2nd column confirmation (RPD or %D)

4 Tentatively Identified Compound (TIC) (associated with NJ only)

20 Calibration Range or Linear Range Exceeded

25 Compound Identification (i.e., ion ratio, retention time, relative abundance, etc.)

Miscellaneous

11 A more appropriate result is reported (multiple reported analyses i.e., dilutions, re-

extractions, etc. Associated with “R” and “DNR” only)

14 Other (See DV report for details)

26 Method QC information not provided

1 H = high bias indicated

L = low bias indicated

DATA VALIDATION CRITERIA Table No.: NFG-ICPMS

Revision No.: 0

Last Rev. Date: 6/17/2009

Page: 1 of 2

VALIDATION

QC ELEMENTACCEPTANCE CRITERIA ACTION

REASON

CODE

Cooler Temperature

and Preservation

Cooler temperature: 4°C ±2°

Waters: Nitric Acid to pH < 2

For Dissolved Metals: 0.45um filter & preserve after filtration

EcoChem Professional Judgment - no qualification based on

cooler temperature outliers

J(+)/UJ(-) if pH preservation requirements

are not met

1

Holding Time180 days from date sampled

Frozen tissues - HT extended to 2 yearsJ(+)/UJ(-) if holding time exceeded 1

Tune

Prior to ICAL

monitoring compounds analyzed 5 times wih Std Dev. < 5%

mass calibration <0.1 amu from True Value

Resolution < 0.9 AMU @ 10% peak height or

<0.75 amu @ 5% peak height

Use Professional Judgment to evaluate tune

J(+)/UJ(-) if tune criteria not met5A

Initial CalibrationBlank + minimum 1 standard

If more than 1 standard, r>0.995J(+)/UJ(-) if r<0.995 (for multi point cal) 5A

Initial Calibration

Verification (ICV)

Independent source analyzed immediately after calibration

%R within ±10% of true value

J(+)/UJ(-) if %R 75-89%

J(+) if %R = 111-125%

R(+) if %R > 125%

R(+/-) if %R < 75%

5A

Continuing Calibration

Verification (CCV)

Every ten samples, immediately following

ICV/ICB and at end of run

±10% of true value

J(+)/UJ(-) if %R = 75-89%

J(+) if %R 111-125%

R(+) if %R > 125%

R(+/-) if %R < 75%

5B

Initial and Continuing

Calibration Blanks

(ICB/CCB)

After each ICV and CCV

every ten samples and end of run

| blank | < IDL (MDL)

Action level is 5x absolute value of blank conc.

For (+) blanks, U(+) results < action level

For (-) blanks, J(+)/UJ(-) results < action level

refer to TM-02 for additional details

7

Reporting Limit

Standard (CRI)

2x RL analyzed beginning of run

Not required for Al, Ba, Ca, Fe, Mg, Na, K

%R = 70%-130% (50%-150% Co,Mn, Zn)

R(-),(+) < 2x RL if %R < 50% (< 30% Co,Mn, Zn)

J(+) < 2x RL, UJ(-) if %R 50-69% (30%-49% Co,Mn, Zn)

J(+) < 2x RL if %R 130%-180% (150%-200% Co,Mn, Zn)

R(+) < 2x RL if %R > 180% (200% Co, Mn, Zn)

14

Interference Check

Samples

(ICSA/ICSAB)

Required by SW 6020, but not 200.8

ICSAB %R 80% - 120% for all spiked elements

| ICSA | < IDL (MDL) for all unspiked elements

For samples with Al, Ca, Fe, or Mg > ICS levels

R(+/-) if %R < 50%

J(+) if %R >120%

J(+)/UJ(-) if %R = 50% to 79%

Use Professional Judgment for ICSA to determine if

bias is present

see TM-09 for additional details

17

Method Blank

One per matrix per batch

(batch not to exceed 20 samples)

blank < MDL

Action level is 5x blank concentration

U(+) results < action level7

EcoChem Validation Guidelines for Metals Analysis by ICP-MS

(Based on Inorganic NFG 1994 & 2004)

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DATA VALIDATION CRITERIA Table No.: NFG-ICPMS

Revision No.: 0


Page: 2 of 2

VALIDATION

QC ELEMENTACCEPTANCE CRITERIA ACTION

REASON

CODE

EcoChem Validation Guidelines for Metals Analysis by ICP-MS



Blank Spike: %R within 80%-120%

R(+/-) if %R < 50%

J(+)/UJ(-) if %R = 50-79%

J(+) if %R >120%

CRM: Result within manufacturer's certified acceptance range

or project guidelines

J(+)/UJ(-) if < LCL,

J(+) if > UCL

Matrix Spike/

Matrix Spike Duplicate

(MS/MSD)


75-125% for samples where results

do not exceed 4x spike level

J(+) if %R>125%

J(+)/UJ(-) if %R <75%

J(+)/R(-) if %R<30% or

J(+)/UJ(-) if Post Spike %R 75%-125%

Qualify all samples in batch

8

Post-digestion SpikeIf Matrix Spike is outside 75-125%,

Spike parent sample at 2x the sample conc.No qualifiers assigned based on this element

Laboratory Duplicate

(or MS/MSD)


RPD < 20% for samples > 5x RL

Diff ≤ RL for samples >RL and < 5x RL

(Diff ≤ 2x RL for solids)

J(+)/UJ(-) if RPD > 20% or diff > RL

all samples in batch9

Serial Dilution5x dilution one per matrix

%D < 10% for original sample values > 50x MDL

J(+)/UJ(-) if %D >10%

All samples in batch16

Internal Standards

Every sample

SW6020: 60%-125% of cal blank IS

200.8: 30%-120% of cal blank IS

J (+)/UJ (-) all analytes associated with IS outlier 19

Field Blank Blank < MDL

Action level is 5x blank conc.

U(+) sample values < AL

in associated field samples only

6

Field Duplicate

For results > 5x RL:

Water: RPD < 35% Solid: RPD < 50%

For results < 5 x RL:

Water: Diff < RL Solid: Diff < 2x RL

J(+)/UJ(-) in parent samples only 9

Linear Range Sample concentrations must fall within range J values over range 20

10Laboratory Control

Sample (LCS)

T:\A_EcoChem Controlled Docs\Criteria Tables\EcoChem Default\EcoChem NFG Metals_CNNFG-ICPMS Copyright 2006 EcoChem, Inc.

DATA VALIDATION CRITERIA Table No.: NFG-HG

Revision No.: 0


Page: 1 of 2

VALIDATION

QC ELEMENTACCEPTANCE CRITERIA ACTION REASON CODE

Cooler Temperature

and Preservation

Cooler temperature: 4°C ±2°

Waters: Nitric Acid to pH < 2

For Dissolved Metals: 0.45um filter & preserve after

filtration

EcoChem Professional Judgment - no qualification

based on cooler temperature outliers

J(+)/UJ(-) if pH preservation requirements

are not met

1

Holding Time28 days from date sampled

Frozen tissues: HT extended to 6 monthsJ(+)/UJ(-) if holding time exceeded 1

Initial CalibrationBlank + 4 standards, one at RL

r > 0.995J(+)/UJ(-) if r<0.995 5A

Initial Calibration

Verification (ICV)

Independent source analyzed immediately after

calibration


J(+)/UJ(-) if %R = 65%-79%

J(+) if %R = 121-135%

R(+/-) if %R < 65% R(+) if %R > 135%

5A

Continuing Calibration

Verification (CCV)

Every ten samples, immediately following

ICV/ICB and at end of run


J(+)/UJ(-) if %R = 65%-79%

J(+) if %R = 121-135%

R(+/-) if %R < 65% R(+) if %R > 135%

5B

Initial and Continuing

Calibration Blanks

(ICB/CCB)

after each ICV and CCV

every ten samples and end of run

| blank | < IDL (MDL)

Action level is 5x absolute value of blank conc.

For (+) blanks, U(+) results < action level

For (-) blanks, J(+)/UJ(-) results < action level

refer to TM-02 for additional details

7

Reporting Limit

Standard

(CRA)

conc at RL - analyzed beginning of run

%R = 70-130%

R(-),(+)<2xRL if %R <50%

J(+)<2x RL, UJ(-) if %R 50-69%

J(+) <2x RL if %R 130-180%

R(+)<2x RL if %R>180%

14

Method Blank


(batch not to exceed 20 samples)

blank < MDL

Action level is 5x blank concentration

U(+) results < action level7


Blank Spike: %R within 80-120%

R(+/-) if %R < 50%

J(+)/UJ(-) if %R = 50-79%

J(+) if %R >120%

CRM: Result within manufacturer's certified

acceptance range or project guidelines

J(+)/UJ(-) if < LCL,

J(+) if > UCL

Matrix Spike/Matrix

Spike Duplicate

(MS/MSD)


5% frequency

75-125% for samples less than

4x spike level

J(+) if %R>125%

J(+)/UJ(-) if %R <75%

J(+)/R(-) if %R<30%

all samples in batch

8

Laboratory Duplicate

(or MS/MSD)


RPD < 20% for samples > 5x RL

Diff ≤ RL for samples >RL and < 5x RL

(Diff ≤ 2x RL for solids)

J(+)/UJ(-) if RPD > 20% or diff > RL

all samples in batch9

EcoChem Validation Guidelines for Mercury Analysis by CVAA


Laboratory Control

Sample (LCS)10

T:\A_EcoChem Controlled Docs\Criteria Tables\EcoChem Default\EcoChem NFG Metals_CNNFG-HG Copyright 2006 EcoChem, Inc.

DATA VALIDATION CRITERIA Table No.: NFG-HG

Revision No.: 0


Page: 2 of 2

VALIDATION

QC ELEMENTACCEPTANCE CRITERIA ACTION REASON CODE

EcoChem Validation Guidelines for Mercury Analysis by CVAA


Field Blank Blank < MDL

Action level is 5x blank conc.

U(+) sample values < action level

in associated field samples only

6

Field Duplicate

For results > 5x RL:

Water: RPD < 35% Solid: RPD < 50%

For results < 5x RL:

Water: Diff<RL Solid: Diff < 2x RL

J(+)/UJ(-) in parent samples only 9

Linear Range Sample concentrations must be less than 110% of

high standardJ values over range 20

T:\A_EcoChem Controlled Docs\Criteria Tables\EcoChem Default\EcoChem NFG Metals_CNNFG-HG Copyright 2006 EcoChem, Inc.

W:\APPENDICES\APPENDIX B QDST.docx

APPENDIX B

QUALIFIED DATA SUMMARY TABLE

Qualified Data Summary Table

Douglas Indian Association - Sandy Beach

Sample ID Laboratory ID Method Analyte Result Units

Laboratory

Qualifier

Validation

Qualifier

Validation

Reason

14042901 1418034-01 E1630 Methylmercury 0.011 ng/g N,U UJ 8L

14042901 1418034-01RE1 E1631 Mercury 469 ng/g M J 9

14042902 1418034-02 E1630 Methylmercury 0.013 ng/g U UJ 8L

14042902 1418034-02 E1631 Mercury 262 ng/g J 9

14042903 1418034-03 E1630 Methylmercury 0.013 ng/g B J 8L

14042903 1418034-03 E1631 Mercury 181 ng/g J 9


14042904 1418034-04 E1631 Mercury 183 ng/g J 9


14042905 1418034-05 E1631 Mercury 202 ng/g J 9

14043001 1418034-06 E1631 Mercury 33.7 ng/g J 9

14043002 1418034-07 E1630 Methylmercury 0.158 ng/g J 8L

14043002 1418034-07 E1631 Mercury 251 ng/g J 9

14043003 1418034-08 E1631 Mercury 37.9 ng/g J 9


14043004 1418034-09 E1631 Mercury 242 ng/g J 9


14043005 1418034-10 E1631 Mercury 339 ng/g J 9

14043006 1418034-11 E1630 Methylmercury 0.029 ng/g B J 8L

14043006 1418034-11 E1631 Mercury 200 ng/g J 9


14043007 1418034-12 E1631 Mercury 268 ng/g J 9

14043008 1418034-13 E1631 Mercury 61.7 ng/g J 9

14043009 1418034-14 E1631 Mercury 49.1 ng/g J 9

7/3/2014

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