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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.
Douglas Indian Association Sandy Beach Sampling Data Report
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.
Douglas Indian Association Sandy Beach Sampling Data Report
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
Douglas Indian Association Sandy Beach Sampling Data Report
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
Douglas Indian Association Sandy Beach Sampling Data 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)
Douglas Indian Association Sandy Beach Sampling Data Report
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.
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 2
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.
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 3
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.
Douglas Indian Association Sandy Beach Sampling Data Report
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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.
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 5
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
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 6
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.
Douglas Indian Association Sandy Beach Sampling Data Report
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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.
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 8
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
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 9
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.
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 10
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,
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 11
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
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 12
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.
Douglas Indian Association Sandy Beach Sampling Data Report
140718_Data Report_R2 July 2014 Page 13
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
Douglas Indian Association
Sandy Beach Sampling Data Report
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
Douglas Indian Association
Sandy Beach Sampling Data Report
July 2014 Page 2 of 3140520_DRtables
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
Douglas Indian Association
Sandy Beach Sampling Data Report
July 2014 Page 3 of 3140520_DRtables
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
Sandy Beach Sampling Data Report
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.
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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
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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
9/29/04 PM EcoChem, Inc. T:\Controlled Docs\Qualifiers & Reason Codes\NFG Qual Defs.doc
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
Use bias flags (H,L)1 where appropriate
9 Precision (all replicates: LCS/LCSD, MS/MSD, Lab Replicate, Field Replicate)
10 Laboratory Control Sample Recoveries (a.k.a. Blank Spikes)
Use bias flags (H,L)1 where appropriate
12 Reference Material
Use bias flags (H,L)1 where appropriate
13 Surrogate Spike Recoveries (a.k.a. labeled compounds, recovery standards)
Use bias flags (H,L)1 where appropriate
Interferences
16 ICP/ICP-MS Serial Dilution Percent Difference
17 ICP/ICP-MS Interference Check Standard Recovery
Use bias flags (H,L)1 where appropriate
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)
T:\A_EcoChem Controlled Docs\Criteria Tables\EcoChem Default\EcoChem NFG Metals_CNNFG-ICPMS Copyright 2006 EcoChem, Inc.
DATA VALIDATION CRITERIA Table No.: NFG-ICPMS
Revision No.: 0
Last Rev. Date: 6/17/2009
Page: 2 of 2
VALIDATION
QC ELEMENTACCEPTANCE CRITERIA ACTION
REASON
CODE
EcoChem Validation Guidelines for Metals Analysis by ICP-MS
(Based on Inorganic NFG 1994 & 2004)
One per matrix per batch
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)
One per matrix per batch
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)
One per matrix per batch
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
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 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
%R within ±20% of true value
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
%R within ±20% of true value
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
One per matrix per batch
(batch not to exceed 20 samples)
blank < MDL
Action level is 5x blank concentration
U(+) results < action level7
One per matrix per batch
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)
One per matrix per batch
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)
One per matrix per batch
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
(Based on Inorganic NFG 1994 & 2004)
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
Last Rev. Date: 6/17/2009
Page: 2 of 2
VALIDATION
QC ELEMENTACCEPTANCE CRITERIA ACTION REASON CODE
EcoChem Validation Guidelines for Mercury Analysis by CVAA
(Based on Inorganic NFG 1994 & 2004)
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 E1630 Methylmercury 0.010 ng/g U UJ 8L
14042904 1418034-04 E1631 Mercury 183 ng/g J 9
14042905 1418034-05 E1630 Methylmercury 0.010 ng/g U UJ 8L
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 E1630 Methylmercury 0.117 ng/g J 8L
14043004 1418034-09 E1631 Mercury 242 ng/g J 9
14043005 1418034-10 E1630 Methylmercury 0.010 ng/g U UJ 8L
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 E1630 Methylmercury 0.102 ng/g J 8L
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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