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Incident location map. Date: August 17, 2001 bullet DEC Contaminated Sites Red Dog Mine main page
Status: Active  
Location: North of Kotzebue, AK    
DEC Contaminated Sites Contact: Rich Sundet, Project Manager - 907-269-7578

BERRY AND PLANT SAMPLING INVESTIGATION,
VICINITY OF DELONG MOUNTAIN TERMINAL,
CAPE KRUSENSTERN NATIONAL MONUMENT, ALASKA

August 17, 2001

Jeffrey D. Hock
Statewide Database Chief
Air & Water Quality Division
Alaska Department of Environmental Conservation
410 Willoughby Ave., Suite 303
Juneau, AK 99801

RE: Contract No. 18-5006-10; Notice to Proceed No. 185006101A; Final Berry and Plant Sampling, Summer 2001; Vicinity of DeLong Mountain Terminal, Northwest Alaska


Dear Mr. Hock:


Ecology & Environment Inc. (E & E) is pleased to submit this work plan to the Alaska Department of Environmental Conservation's, Air and Water Quality Division (Department). This work plan document discusses planned activities for assessing concentrations of certain metals in berries and plants (subsistence foods) near the DeLong Mountain Terminal (Port Site). The document is a combined sampling and analysis plan (SAP), quality assurance project plan (QAPP), and health and safety plan (HSP).


E & E adopted an abbreviated format for this combined SAP/QAPP/HSP. Given the expediency of the proposed subsistence food sampling, we sought brevity for the document. However, the proposed actions have been thoroughly explained so that the project may be well executed by the Department and residents of villages proximal to the sample areas.


If you, or Ron Klein, have questions or comments on the work plan document, please contact me at 257-5000. E & E thanks the Department for the opportunity to assist with implementing this very interesting project.


Sincerely,

ECOLOGY AND ENVIRONMENT, INC.

Greg J. Horner, R.G.

Manager, Alaska

XC: L. Flynn (E&E)

B. Martich (E&E)

C. Mach (E & E)


WORK PLAN DOCUMENTS FOR BERRY AND PLANT SAMPLING INVESTIGATION,
VICINITY OF DELONG MOUNTAIN TERMINAL,
CAPE KRUSENSTERN NATIONAL MONUMENT, ALASKA

August 2001

Prepared for:

Alaska Department of Environmental Conservation
Division of Air and Water Quality
410 Willoughby Ave., Suite 303
Juneau, AK 99801


SAMPLING AND ANALYSIS PLAN

1.0 Scope and Objectives

In recent years, residents from the coastal village of Kivalina have expressed concern about potential metal contamination in berries and plants (subsistence foods) harvested near the DeLong Mountain Terminal (Port Site). The Port Site is where zinc and lead ores mined at Red Dog Mine are stockpiled as ore concentrates. Periodically, these concentrates are loaded on ocean-going vessels and taken to smelters for incineration.


This investigation will study whether metals, dispersed from the Port Site as dust particles from the ore concentrates, are impacting subsistence foods via airborne transport and/or plant uptake. The study will focus on the target metals that have been identified in the Environmental Protection Agency's (EPA) Toxic Release Inventory (TRI) reports for Red Dog Mine: cadmium, chromium, cobalt, copper, lead, manganese, nickel, and zinc, plus selenium. The metal content results of samples collected near Ipiavik Lagoon (Site A) and the Port Site (Site B) will be compared statistically to results of a subsistence food sample set collected from a control site (Site C) located near Noatak in a historical subsistence harvest area. Figure 1-1 depicts the locations of Kivalina and the Port Site. Site C will be selected by the sample team based on its distance from any known mine impacts, use as a harvest area, and similar geologic features and soil types as the test sample areas.


The objectives of this investigation are:

  • To determine statistically whether dust released by Port Site activities has accumulated on nearby subsistence foods;
  • To determine statistically whether metals, through uptake, have accumulated in nearby subsistence foods;
  • To provide data for health professionals to determine if ingestion of these subsistence foods is a potential exposure pathway.

Ecology and Environment, Inc. (E & E) was contracted by the Alaska Department of Environmental Conservation (DEC), Air and Water Quality Division (Contract No. 18-5006-10; Notice to Proceed No. 185006101A) to prepare a sampling and analysis plan (SAP), quality assurance project plan (QAPP), and health and safety plan (HSP) for use in conducting this subsistence food sample collection and analysis.


2.0 Sampling Rationale

The subsistence food species selected for analysis were identified by DEC and the Alaska Department of Health and Social Services (DHSS) in consultation with representatives from Kivalina and Noatak, nearby villages that utilize these foods in subsistence activities. The species of interest were selected based on their abundance in the area and use for subsistence activities.


Three species of subsistence foods will be targeted for sampling during this investigation. Table 2-1 presents the target subsistence foods. Other subsistence foods may be sampled depending on current species prevalence.

Table 2-1 Targeted Subsistence Foods
Common Name Scientific Name Inupiat Name
Sour Dock Rumex arcticus Quaguq
Blackberry (commonly called Crowberry) Empetrum nigrum Asiaq
Salmonberry (commonly called Cloudberry) Rubus chamaemorus Aqpik

A DEC field team will lead the sampling efforts defined in this SAP/QAPP. Assisting the DEC team in the identification and collection of subsistence food samples will be residents of the villages of Kivalina and Noatak. In addition, representatives of the Maniilaq Association, from Kotzebue, may participate. Site A and Site B will be sampled together. A helicopter will transport the sample team from Kivalina to Site A and Site B. The helicopter should land sufficiently distant from the sample areas, so that minimal disturbance occurs prior to entry and sampling. Site C will be sampled after sampling at Sites A and B is finished. A boat will be used to transport the sample team from Noatak to Site C.


At each sampling area, the samples should be collected in a pattern that begins most distant from the Port Site. In this way, the sample team will move toward the potential source of airborne metals and toward the biota that may have been more impacted by Port Site activities, thereby reducing the potential for carry over of residue containing metals.


At each sample location within each sample area, two samples will be collected. One sample will contain the subsistence food as it was picked, containing only those parts of the plants that are consumed. The other sample will be washed prior to containerization. The washed sample will indicate whether metals are accumulating within the subsistence food, while the unwashed sample will indicate how airborne deposition may be impacting subsistence foods. Given the nature of the sample collection, these samples are composite samples.


The goal for Site A and Site B is to collect a minimum of ten samples each of washed and unwashed sample material for the subsistence foods that are present at each area. The goal for Site C is to collect a minimum of ten samples each of washed and unwashed sample material for all species collected at Sites A and B. Ten samples will constitute a sufficient data set to adequately fit the statistical model that will be used (see Section 4.0). It should be noted that collecting more than ten samples would increase the power of the statistical analysis and provide more definitive results. E & E recommends as many as 20 samples per sample location, washed and unwashed. The final decision on the number of samples obviously will depend on economics, weather conditions, prevalence of the subsistence foods, and time in the field. It should be noted that the statistical models do not require the same number of samples per food species or the same number of samples between the test sites and the control site.


In addition to the samples of subsistence foods, a single surface water sample will be collected at either Site A or Site B. Subsistence users sometimes use surface water as a drinking water source during subsistence activities. The exact sample location should be chosen based on known historical and/or prospective drinking locations by the residents of Kivalina.


The sample team should also use a portable GPS unit to record all sample locations, so that the investigation may be replicated, if necessary.


 3.0 Sampling Methodology

For Site A and Site B, the sample team should attempt to collect a minimum of ten samples for each species of subsistence food. Each sample should be collected from a distinct area, independent from the other samples collected. This means at a minimum that no two samples will be collected from the same plant. For each sample, the sample material will be placed in one, pre-cleaned wide mouth, 8-ounce glass jar with a teflon-lined lid. Each jar will contain at least 50 grams (wet weight) of sample material. Only the portion of each subsistence food that is consumed should be included for analysis. Extraneous material, such as grass, stems, mosses, and rocks, will be removed from the sample material. If necessary, the sour dock will be folded, not torn, to fit in the sample jar. Samplers will wear a new pair of talc-free latex or nitrile gloves for each sample collected. Care will be taken to ensure that only the same species are grouped together. Project samplers will rely on the expertise of the Kivalina and Noatak residents and any other village residents to catalogue the species appropriately.


Two samples will be collected for each subsistence food at each sample location. The first sample collected will contain sample material that has been washed. The sample material will be placed in a dedicated pre-cleaned plastic bowl and completely rinsed three successive times with deionized, reagent grade - ASTM Type II water. The second sample will contain unwashed sample material as it was collected. After collection of each sample, the containers will be sealed and placed on ice. After rinsing the sample material in the plastic bowl and placing the sample material in the sample jar, the bowl will be rinsed clean with deionized, reagent grade - ASTM Type II water.


For the single surface water sample to be collected, a pre-cleaned polyethylene bottle will be dipped into the surface water source. The water from this polyethylene bottle will then be transferred to one pre-cleaned 1-liter polyethylene bottle and preserved with nitric acid. After collection of the sample, the bottle will be sealed and placed on ice.


All samples will be submitted to Battelle Laboratory in Sequim, Washington. Approximately half of the samples from each sample area will be immediately analyzed for the following metals: cadmium, chromium, cobalt, copper, lead, manganese, nickel, selenium, and zinc. The other half of the samples will be analyzed if the analytical results from the first set do not exhibit normal distributions for the concentrations of the metals. The laboratory will report results on a wet weight (fresh - as received) basis to compare with other food data and on a dry weight basis to allow for a standardized comparison between the test areas and control area samples. The samples selected for immediate analysis will be randomly selected from the collection of samples.


 4.0 Statistical Data Analysis

When analytical data is received, the data will be examined to determine if a significant difference exists between the test sets, Site A and Site B, and the control set, Site C. The examiner must first make a determination regarding the distribution of the data sets. For each metal of each food type, four data sets will exist: washed sample results from one of the test sites, washed samples results from Site C, unwashed sample results from one of the test sites, and unwashed sample results from Site C. The data sets should be paired for comparison this way:

  • results from Site A or Site B and Site C for washed samples; and
  • results from Site A or Site B and Site C for unwashed samples.

For washed samples, the examiner must verify that the data sets are normally distributed for each metal. The recommended test for normality is the Shapiro Wilk W Test. This test is very time consuming and its execution is best performed by computer software. If software is not available, the studentized range test is a possible alternative to the Shapiro Wilk W Test. If the data sets prove to be normally distributed, then the two data sets may be compared using a t-test that assumes unequal variances (also known as Satterthwaite's t-Test). If any of the data sets do not exhibit a normal distribution, then the data should be log transformed (natural logarithm function) and again tested for normality. If the log transformed data passes the test for normality, then the log transformed data sets for the metal in question should be compared using Satterthwaite's t-Test. The same process will apply for the unwashed sample sets. For analytical results detected below the method reporting limit, one-half the reporting limit should be used as the analytical result for the statistical analysis.


In the event that a data set for any metal, washed or unwashed, does not exhibit a normal distribution, then the nonparametric Wilcoxon Rank Sum test (also known as Mann-Whitney U test) will be employed to compare data sets for the metal that failed the normality test.


Regardless of the statistical test employed to compare data sets, the following statistical hypothesis should be tested:

H0: up = uc

H1: up > uc


where up = the average concentration of a metal from a Site A or Site B data set and uc = the average concentration of a metal from a Site C data set. It is recommended that a p-level, or level of significance, of 0.05 be utilized throughout the data analysis.


For the project report, a thorough literature search will be performed to locate data for similar plant species. The findings from the literature search will be compared to the analytical results to assist in the data evaluation.


5.0  Proposed Schedule

Table 5-1 highlights the planned schedule for the project:

Table 5-1 Project Schedule
DATES ACTIVITY
August 15, 2001 Submit Work Plan
Late August Fieldwork
Early October Receipt of Data
November Submit Draft Report

6.0  References

Ford, Jesse, and Linda Hasselbach. May 2001. Heavy Metals in Mosses and Soils on Six Transects Along the Red Dog Mine Haul Road, Alaska. Western Alaska Arctic National Parklands. National Park Service.


Guidance for Data Quality Assessment: Practical Methods for Data Analysis. January 1998. EPA QA/G-9. QA97 Version. United States Environmental Protection Agency: Office of Research and Development. Washington, D.C.


Walpole, Ronald E., and Raymond H. Myers. 1993. Probability and Statistics for Engineers and Scientists. Fifth Edition. MacMillan Publishing Company. New York, New York.


QUALITY ASSURANCE AND PROJECT PLAN

1.0 Scope and Objectives

The general quality assurance objective for this investigation is to obtain analytical data of sufficient quality and quantity to satisfy the specific objectives and intended data uses outlined in the project objectives. To achieve this general objective, data of known and acceptable precision, accuracy, representativeness, completeness, and comparability must be generated.


2.0  Field Documentation

Logbook

The field log will contain a detailed description of all field activities and samples collected. Sample documentation will include sample identification labels, photographs, laboratory analysis requests, and permanently bound field logs. Pages will not be removed from any data logbook for any reason. Corrections will be made by drawing a single line through the original entry, so that the original entry still can be read, and writing the corrected entry alongside. The correction must be initialed and dated.


Based on how many sampling teams are in the field, more than one field log may be used. Each group should maintain their own log if it is not possible for one individual to record the actions and observations of all the sample groups. However, a field team leader should be responsible for keeping a master log. The master log should reference sample team logs when necessary.


Sample Labeling

Each sample container will be pre-labeled and sealed immediately after collection. Sample labels will be completed using waterproof ink and will be affixed firmly to the sample containers with clear, waterproof tape. A sample code should be assigned to each sample as an identification number to track collected samples. The sample label will provide the following information:

  • Project name;
  • Date of collection;
  • Sample identification number;
  • Analysis required (including EPA or reference method number); and
  • Preservation method used.

After the sample is collected, such pertinent information as sample identification number, date and time of collection, collection method, and sample description will be recorded in the field log.


Photographs

Photographs will be taken as directed by the fieldwork task manager. Documentation of a photograph is crucial to its validity as a representation of an existing situation. The following information concerning photographs will be noted in the task log:

  • Date, time, and location of photograph;
  • Photographer;
  • Direction the photographer was facing;
  • Description of photograph; and
  • Sequential number of the photograph and film roll number.

Global Positioning System

Each sample's location will be documented using a portable GPS unit that contains a datalogger. Base station data may be obtained from the National Geodetic Survey (NGS) of the National Oceanic and Atmospheric Administration. NGS coordinates a network of continuously operating reference stations (CORS) that provide GPS carrier phase and code range measurements in support of 3-dimensional positioning activities throughout the United States. The CORS system enables positioning accuracy that approaches a few meters both vertically and horizontally.


3.0 Sampling Equipment

The following equipment should be included in the mobilization effort.

  • Personal Protective Equipment:
  • Talc-free nitrile or latex gloves
  • Sample Containers and Supplies:
  • At least 125 8-ounce glass jars (biota samples)
  • 1 pre-preserved 1-liter polyethylene bottle (surface water sample)
  • 1 1-liter polyethylene bottle (pouring surface water sample)
  • Deionized, reagent grade - Type II ASTM water for sample washing
  • Portable field scale
  • Pre-cleaned plastic bowl
  • Sample Shipment:
  • Chain of custodies
  • Coolers
  • Zip lock baggies
  • Blue ice or ice
  • Clear tape
  • Strapping tape
  • Trash bags

4.0 Sample Handling and Shipping Requirements

Samples must be packaged carefully to avoid breakage or contamination and must be shipped to the analytical laboratory at proper temperatures. The following sample packaging requirements will be followed:

  • Enclose each glass and plastic sample container individually in a sealed, clear, plastic Ziplock bag;
  • Surround sample containers with bubble wrap to prevent breakage from impact;
  • Line each cooler with a garbage bag, and place a 1-inch layer of absorbent packing material at the bottom of the garbage bag;
  • Place the samples into the coolers, and surround the samples with ice placed into freezer bags;
  • Fill any remaining space in the coolers with inert packing material. Under no circumstances should materials such as sawdust or sand be used; and
  • Tape chain of custody documents in a sealed plastic bag under the cooler lid, seal with custody seals, affix a label containing the laboratory name and address, and ship.

Shipping containers will be labeled clearly and custody-sealed for shipment. The container custody seal will consist of filament tape wrapped around the package at least twice and two custody seals affixed in such a way that access to the container can be gained only by cutting the filament tape and breaking the seal. When custody is relinquished to a shipper, field team personnel will telephone the analytical laboratory to inform them of the expected arrival of the sample shipment and to advise of any time constraints on sample analysis. All samples will be delivered to the following address for analyses:


Battelle Laboratory
1529 West Sequim Bay Rd.
Sequim, WA 98382
360-681-3604
Attention: Eric Crecelius


E & E recommends holding all samples until the field effort is complete. This will simplify the shipping process and reduce costs. The samples do not have holding times, and the only stipulation is that the samples should be kept on ice. The sample team should bring the samples to Anchorage when they return, and then ship them for overnight delivery to Battelle Laboratory. If for any reason this does not work out is not possible, the sample team will have to arrange for charter delivery of the sample coolers from Kivalina (or from wherever the sample team ships will ship).


5.0 Investigation-Derived Waste

Disposable sampling and personal protective equipment will be used during the field event. All used equipment will be double bagged and the DEC team members will be responsible for transporting all solid (IDW) investigation-derived waste to a State-approved landfill.


Aqueous IDW will consist of the wash liquids used to rinse samples. The field team should dispose of this IDW on the ground directly where the sample was collected.


6.0 Quality Control

Quality control samples will be collected to assess potential errors introduced during sample collection, handling, and analysis. One in twenty samples of the subsistent food samples should contain double volume (100 grams), so that the analytical laboratory can run matrix pike and duplicate samples. No field quality control sample will be collected for the single water sample because laboratory/method quality control data will be used to support the result. In addition, a single water sample of the rinse water will be collected to verify the purity of the rinse water.


Table 6-1 presents the project sample requirements, and Table 6-2 contains laboratory quality assurance requirements.


The analytical laboratory will provide a hard copy and electronic copy of its report. All laboratory data will need to be validated by a chemist prior to using it for reporting purposes.


HEALTH AND SAFETY PLAN

A health and safety plan has been prepared and is provided. Prior to each day's activities, the field team should conduct a health and safety meeting, discussing the chemical and physical hazards present and safety measures to prevent injuries and exposures. The actions to be followed in case of an emergency should also be reviewed.

Table 2-2

SAMPLE AND ANALYSIS PLAN REQUIREMENTS
BERRY AND PLANT SAMPLING
DELONG MOUNTAIN TERMINAL, ALASKA

Matrix No. Samples Analytical Parameter Analytical Method Bottle Type Preservative Total Containers
Washed Samples
Sour Dock 20 Metals EPA Method 6020 - ICPMS (1) 8-ounce glass jar Ice 20
Blackberry 20 Metals EPA Method 6020 - ICPMS (1) 8-ounce glass jar Ice 20
Salmonberry 20 Metals EPA Method 6020 - ICPMS (1) 8-ounce glass jar Ice 20

Unwashed Samples
Sour Dock 20 Metals EPA Method 6020 - ICPMS (1) 8-ounce glass jar Ice 20
Blackberry 20 Metals EPA Method 6020 - ICPMS (1) 8-ounce glass jar Ice 20
Salmonberry 20 Metals EPA Method 6020 - ICPMS (1) 8-ounce glass jar Ice 20
Water Samples
Surface water 1 Metals EPA Method 6020 - ICPMS (1) 1-liter poly bottle Ice; Nitric acid to pH < 2 1

Rinse water

1

Metals

EPA Method 6020 - ICPMS (1) 1-liter poly bottle Ice; Nitric acid to pH < 2 1

Key:

EPA = United States Environmental Protection Agency Test Methods for Evaluating Solid Waste, SW-846, through Update III, 1986.

ICPMS = Inductively coupled plasma/matrix spike.

Table 6-1

SAMPLE AND ANALYSIS PLAN REQUIREMENTS

BERRY AND PLANT SAMPLING

DELONG MOUNTAIN TERMINAL, ALASKA
Matrix No. Samples Analytical Parameter Analytical Method Bottle Type Preservative Total Containers
Washed Samples
Sour Dock 20 Metals EPA Method 6020

ICPMS

(1) 8-ounce glass jar Ice 22
Blackberry 20 Metals EPA Method 6020

ICPMS

(1) 8-ounce glass jar Ice 22
Salmonberry 20 Metals EPA Method 6020

ICPMS

(1) 8-ounce glass jar Ice 22

Unwashed Samples
Sour Dock 20 Metals EPA Method 6020

ICPMS

(1) 8-ounce glass jar Ice 22
Blackberry 20 Metals EPA Method 6020

ICPMS

(1) 8-ounce glass jar Ice 22
Salmonberry 20 Metals EPA Method 6020

ICPMS

(1) 8-ounce glass jar Ice 22
Water Samples
Surface water 1 Metals EPA Method 6020 ICPMS (1) 1-liter poly bottle Ice; Nitric acid to pH < 2 1
Rinse water 1 Metals EPA Method 6020 ICPMS (1) 1-liter poly bottle Ice; Nitric acid to pH < 2 1

Key:

EPA = United States Environmental Protection Agency Test Methods for Evaluating Solid Waste, SW-846, through Update III, 1986.

ICPMS = Inductively coupled plasma/matrix spike.

Table 6-2

SUMMARY OF LABORATORY QUALITY ASSURANCE OBJECTIVES
BERRY AND PLANT SAMPLING
DELONG MOUNTAIN TERMINAL, ALASKA

Matrix Analysis EPA Analytical Method Quantitation Limits Method Accuracy
(%R)
Method Precision
(%RPD)
Completeness Goal
(%)
Sour Dock Metals EPA SW-846 Method 6020 Cd = 0.05 mg/kg; Cr = 0.5 mg/kg; Co = 0.5 mg/kg; Cu = 0.2 mg/kg;

Pb = 0.05 mg/kg; Mn = 0.1 mg/kg;

Ni = 0.5 mg/kg; Zn = 1.0 mg/kg;

Se = 1.0 mg/kg

75-125 +35 90
Blackberry Metals EPA SW-846 Method 6020 Cd = 0.05 mg/kg; Cr = 0.5 mg/kg; Co = 0.5 mg/kg; Cu = 0.2 mg/kg;

Pb = 0.05 mg/kg; Mn = 0.1 mg/kg;

Ni = 0.5 mg/kg; Zn = 1.0 mg/kg;

Se = 1.0 mg/kg

75-125 +35 90
Salmonberry Metals EPA SW-846 Method 6020 Cd = 0.05 mg/kg; Cr = 0.5 mg/kg; Co = 0.5 mg/kg; Cu = 0.2 mg/kg;

Pb = 0.05 mg/kg; Mn = 0.1 mg/kg;

Ni = 0.5 mg/kg; Zn = 1.0 mg/kg;

Se = 1.0 mg/kg

75-125 +35 90
Surface water Metals EPA SW-846 Method 6020 Cd = 0.05 mg/kg; Cr = 0.5 mg/kg; Co = 0.5 mg/kg; Cu = 0.2 mg/kg;

Pb = 0.05 mg/kg; Mn = 0.1 mg/kg;

Ni = 0.5 mg/kg; Zn = 1.0 mg/kg;

Se = 1.0 mg/kg

75-125 +/- 35 100
Rinse water Metals EPA SW-846 Method 6020 Cd = 0.05 mg/kg; Cr = 0.5 mg/kg; Co = 0.5 mg/kg; Cu = 0.2 mg/kg;

Pb = 0.05 mg/kg; Mn = 0.1 mg/kg;

Ni = 0.5 mg/kg; Zn = 1.0 mg/kg;

Se = 1.0 mg/kg

75-125 +/- 35 100

Key:

  • Cd = Cadmium.
  • Cr = Chromium.
  • Co = Cobalt.
  • Cu = Copper.
  • EPA = United States Environmental Protection Agency.
  • Pb = Lead.
  • mg/kg =Milligrams per kilogram.
  • mg/L =Milligrams per liter.
  • Mn = Manganese.
  • Ni = Nickel.
  • R = Recovery.
  • RPD =Relative percent difference.
  • Se = Selenium.
  • Zn = Zinc