Sampling Analysis Plan (SAP)
Sampling and Analysis Plan for Survey of Heavy Metal Contamination
of Spring Water and Associated Culturally Significant Plants on Tribal
Jurisdictional Lands
Prepared By: Tribal Environmental Management Services
Prepared For: Cherokee Nation, Eastern Shawnee Tribe, Miami Tribe, Ottawa Tribe, SenecaCayuga Tribe, and Wyandotte Nation
Date: February 15, 2012
Revision: 2
Contents
1) Background ................................................................................................................................ 1
2) General Study Design .................................................................................................................. 2
3) Study Objectives ........................................................................................................................ 2
4) Spring Water and Plant Sample Collection ................................................................................. 3
4.1) Identification of Sampling Locations .................................................................................... 3
4.2) Spring Water Sampling Methods ......................................................................................... 3
4.3) Plant Sampling Methods ...................................................................................................... 3
4.4) Decontamination Procedures .............................................................................................. 4
4.5) QA/QC Samples .................................................................................................................... 4
4.6) Sampling Documentation .................................................................................................... 4
4.6.1) Sampling Log Book ........................................................................................................ 4
4.6.2) Photographic Record .................................................................................................... 5
4.6.3) Chain-of-Custody .......................................................................................................... 5
4.7) Identification of Samples ..................................................................................................... 5
4.8) Analysis................................................................................................................................. 5
4.8.1) Laboratory Analysis....................................................................................................... 5
4.8.2) Shipment of Samples to Analytical Laboratory ............................................................ 6
4.9) Health and Safety ................................................................................................................. 6
5) Injury Benchmark Identification ................................................................................................. 6
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1) Background
For centuries Native Americans have relied upon traditional hunting and gathering for
subsistence. The use of traditional plants, animals, and waters continues today to provide food,
medicine, and clothing for Tribes as well as being important for ceremonial purposes. The
traditional methods used to hunt and gather have and continue to be passed to future
generations through the teachings of elders within the Tribe and are essential for the
preservation of cultural identity.
The Cherokee Nation, Eastern Shawnee Tribe, Miami Tribe, Ottawa Tribe, Seneca-Cayuga Tribe
and Wyandotte Nation have jurisdictional lands located in Northeastern Oklahoma just
downstream of the Tar Creek, Cherokee County, Kansas; Jasper and Newton counties, Missouri
Superfund Site (aka Tri-State Mining District or TSMD). Heavy metals released from mining
activities have been transported through mine shafts within the Boone Formation into the
groundwater, which comprises the Boone aquifer.
The Boone aquifer is located within the Mississippian age Boone Formation, a 50 to 150 footthick layer of strata in which most mining activities occurred. Composed of limestones and
cherts, the Boone aquifer ranges approximately 90 to 400 feet from the ground surface.
Because of its highly fractured nature, the Boone aquifer is considered a karst aquifer. Karst
topography, such as caves, sinkholes, disappearing streams, and springs occur where the Boone
Formation crops out. The water level of the Boone aquifer is generally near the ground surface,
and its regional direction of flow is south west. The Boone aquifer’s recharge rate occurs
relatively fast by the infiltration of precipitation via overlying fractured carbonate strata and
abandoned mine shafts. Surface waters within the area receive substantial base flows from the
Boone aquifer by means of springs and direct discharge to stream channels (Christenson 1995;
ODEQ 2002). Additionally, mineshafts within the area discharge acid mine drainage to local
surface waters.
The 2009 Tribal Cultural Resource Survey indicated the following information about the use of
spring water by tribal members:
Use
Percentage of Tribal Members Surveyed
Subsistence
Ceremonial
Culture/Tradition
Crafts
Medicinal
24.9
7.1
11.0
1.8
8.7
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The Tribal Trustees have determined that it is of high priority to assess heavy metal
concentrations within spring waters and associated culturally significant plants on their
jurisdictional lands given that a large percentage of tribal members make use of these
potentially contaminated resources. The Trustees recognize that springs and plants that uptake
spring water may present a significant pathway in the spread of contaminants emanating from
the TSMD. This Sampling and Analysis Plan (SAP) describes the general study design, sampling
methods, locations, numbers and analytical techniques that will be used by the Tribes for the
assessment of the level of injury to spring water and associated plants on tribal jurisdictional
lands.
2) General Study Design
The information gathered during the 2009 Tribal Resource Survey indicated that tribal members
are fearful that Tribal trust resources have been injured due to heavy metals released from the
TSMD. The Tribal Trustees have deemed it necessary to quantify injuries to spring water on
jurisdictional lands as part of the Natural Resource Damage Assessment and Restoration
(NRDAR) process. Currently, no published data exist regarding contamination of spring water
downstream of the TSMD.
Spring water is used by tribal members for several purposes including: subsistence, crafts,
medicinal, and ceremonial (Tribal Cultural Resource Survey 2009). Spring water is gathered
from natural outcroppings as well as from well houses. This study will focus on artesian springs
that outcrop naturally from the Boone aquifer. The locations of several springs of this type are
known to the Tribal Trustees, however, it is certain that many more exist on jurisdictional lands.
Water will be collected from the springs using sterile glass bottles with Teflon-lined lids and
stored at 4°C until shipment to an EPA certified laboratory. Additionally, select culturally
significant plants found growing in or in the immediate vicinity of the springs will also be
sampled. Only the organ of the plant that is used in cultural practice will be sampled. Plant
samples will be collected in resealable bags and stored at 4°C before shipment to an EPA
certified laboratory.
3) Study Objectives
1. Measure the concentrations of lead, zinc, and cadmium in artesian spring water on
jurisdictional lands.
2. Measure the concentration of lead, zinc, and cadmium in culturally significant plants
growing in or near the potentially contaminated spring water.
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3. Determine the level of injury to spring water as a result of heavy metals released from
the TSMD.
4) Spring Water and Plant Sample Collection
4.1) Identification of Sampling Locations
Sampling locations will be found by identifying areas where the potentiometric surface of the
Boone aquifer intersects the surface of the land. Samples will be taken as close to the source
rock as possible. Ten such locations will be identified on jurisdictional lands and three will be
identified to the north east of the TSMD (regional groundwater flow is oriented south west) and
act as control locations. Sampling locations will be as evenly spaced as possible across the
extent of the jurisdictional lands of the Six Treaty Tribes.
Personnel from Tribal Environmental Management Services will conduct sampling procedures
and may or may not be accompanied by employees of the Six Treaty Tribe’s environmental
departments. Tribal Environmental Services will process the samples and their associated
Chain-of-Custody as well as coordinate shipping.
4.2) Spring Water Sampling Methods
1. Samplers shall wear disposable clear or white latex gloves at all times during the
collection of spring water samples. Gloves will be changed before the collection of each
new sample.
2. The sampler shall dip the sample container (50ml glass jar with Teflon-lined lid) into the
spring, collect 50ml of spring water, and tightly replace the cap.
3. Samples will be collected in triplicate at each location. A total of 30 samples from
potentially contaminated sampling locations will be collected. A total of 9 samples from
control locations will be collected.
4.3) Plant Sampling Methods
1. Samplers shall wear disposable clear or white latex gloves at all times during sampling.
Gloves will be changed before the collection of each new sample.
2. Depending on the plant organ to be sampled different sampling methods will be
implemented;
a. Roots or rhizome:
i. A stainless steel trowel will be used to dig up the plant,
ii. The organ to be sampled will be removed from the plant using stainless
steel scissors,
iii. The organ will be thoroughly rinsed using de-ionized water,
iv. The organ will be placed in a resealable plastic bag,
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v. The resealable bag will be stored at 4°C until shipment.
b. Leaves, stems, or fruit:
i. The organ to be collected will be removed from the plant using stainless
steel scissors,
ii. The organ will be thoroughly rinsed using de-ionized water,
iii. The organ will be placed in a resealable plastic bag,
iv. The resealable bag will be stored at 4°C until shipment.
The plant organ to be sampled will be dependent on how the plant is utilized in
traditional cultural practice.
3. Three plant samples will be collected from each potentially contaminated sampling
location and each control location. A total of 39 plant samples will be collected during
the course of the study.
4.4) Decontamination Procedures
Sampling equipment will be cleaned after each use by scrubbing with Liquinox® and rinsing with
de-ionized water. All waste generated during the sample collection process will be gathered in
a trash bag and placed in a container where it will be transported to a landfill.
4.5) QA/QC Samples
1. Duplicates: 1 out of every 10 samples collected will be a duplicate sample for both
spring water and plant media types (3 from potentially contaminated sampling locations
and 1 from control locations).
2. Blind Standards: 4 blind standards will be submitted to the analytical laboratory
consisting of de-ionized water (this applies to spring water samples only)
3. No decontamination blanks or field blanks will be submitted for this particular project.
4.6) Sampling Documentation
1.
2.
3.
4.
5.
6.
4.6.1) Sampling Log Book
A Sampling Log Book shall be maintained.
The Sampling Log Book shall be bound and constructed of waterproof paper.
Entries in the Sampling Log Book shall be made in permanent black ink.
Each page in the Sampling Log Book shall be dated.
The preparer shall initial each page of the Sampling Log Book.
For each location sampled, the following information shall be recorded in the Sampling
Log Book:
a. GPS coordinates,
b. Waypoint number,
c. Frame numbers of all photographs taken at the location,
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d. The unique numeric identifier of each sample taken at the location (see section
4.7),
e. The common name and organ sampled of each culturally significant plant sample
taken at each location. This information shall be noted adjacent to the unique
numeric identifier of the sample.
f. A notation of whether the site is potentially contaminated and located on
jurisdictional lands or located within the control area.
4.6.2) Photographic Record
A photographic record shall be made and maintained for all sampling activities on this project.
All photographs shall be time and date stamped.
4.6.3) Chain-of-Custody
A Chain-of-Custody shall be prepared for each set of samples transferred to the ****. The
Chain-of-Custody shall, at a minimum, contain the following information:
1) The project name, Survey of Heavy Metal Contamination of Spring Water on Tribal
Jurisdictional Lands ,
2) Name of person/entity collecting samples,
3) Signature blocks with dates and times for all persons having custody (sampler, shipper,
processing laboratory, etc),
4) For each sample related to a Chain-of-Custody:
a) The unique numeric identifier on the submitted sample container (see section
4.7),
b) The date and time the sample was collected,
c) The sample matrix (water/plant)
4.7) Identification of Samples
Identifying information to be included on the sample label for all water and plant samples:
1. The site identifier will consist of 1, 2, 3 etc.,
2. The sample media identifier will consist of W (for water) or P (for plant),
3. The number of the sample taken: 1, 2, or 3.
4. Duplicate samples will be identified by assigning a D as additional alphanumeric
information to the end of the sample name (1-W-1D, for example).
5. Blind standards will be labeled: 1-W-4, 5-W-4, 10-W-4, and 13-W-4.
4.8) Analysis
4.8.1) Laboratory Analysis
Laboratory analysis of samples will be conducted by ******. Analytical protocols are provided
in a separate document.
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4.8.2) Shipment of Samples to Analytical Laboratory
1) Shipping coolers will be packed such that samples are stored with dry ice and placed
in double-bagged resealable plastic bags.
2) If possible, samples shall be shipped immediately via overnight shipment to the
analytical laboratory. The laboratory address is:
******
3) Samples shall be sent to the laboratory under a Chain-of-Custody.
4) A custody seal will be placed on the outside of the container across the area
between the lid and the container. The custody seal will be signed.
5) The Chain-of-Custody will be placed in a resealable plastic bag and placed within the
container holding those samples to which it refers.
6) Sample containers will be boldly marked “Refreeze upon Receipt” on the outside of
the container.
4.8.3) Data Reporting
1) Data from the laboratory shall be reported in both electronic and paper reports.
2) Data reports shall include all quality control data generated, including results for
duplicates, blanks, and spikes, as applicable.
3) Data reports shall include a copy of the Chain-of-Custody accompanying each set of
samples submitted.
4.9) Health and Safety
Contaminated particulate matter and water will be frequently encountered during the
course of this project. The Health and Safety Plan (provided as a separate document) for this
project shall be reviewed by all samplers.
5) Injury Benchmark Identification
Injury to spring water on jurisdictional lands will be determined by:
1) Comparing data collected from potentially impacted sampling locations to data
collected from control locations and,
2) Comparing data collected from potentially impacted sampling locations to drinking
water standards set by the EPA.
Additionally, heavy metal concentrations within culturally significant plants gathered from
potentially impacted sampling locations will be compared to those from control locations to
determine potential injury to plants. All data collected during the course of this study will be
documented and made available to facilitate future comparisons.
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