United States
Environmental Protection
Agency
Office of
Research and Development
Washington, DC 20460
EPA/600/R-03/053
April 2003
EPA Field Demonstration Quality
Assurance Project Plan
Field Analysis of Mercury in
Soil and Sediment
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EPA/600/R-03/053
April 2003
Field Demonstration
Quality Assurance
Project Plan
Field Analysis of Mercury in
Soil and Sediment
Prepared by:
Science Applications International Corporation
Idaho Falls, Idaho
Contract No. 68-C-00-179
Prepared for:
Dr. Stephen Billets
Environmental Services Division
National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Las Vegas, Nevada 89193
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Concurrence Signatures
The primary purpose of the Demonstration is to evaluate innovative field technologies for the measurement of mercury in soil and
sediment based on their performance and cost as compared to a conventional, off-site laboratory analytical method. The
Demonstration will take place under the sponsorship of the United States Environmental Protection Agency's (EPA) Superfund
Innovative Technology Evaluation (SITE) Program.
This document is intended to ensure that all aspects of the Demonstration are documented and scientifically sound and that
operational procedures are conducted in accordance with quality assurance and quality control specifications and health and safety
regulations.
The signatures of the individuals specified below indicate their concurrence with and agreement to operate in compliance with the
procedures specified in this document.
Dr. Stephen Billets Date Mikhail Mensh Date
U.S. EPA Task Order Manager Milestone Inc.
George Brilis Date Volker Thomsen Date
U.S. EPA NERL Quality Assurance Manager NITON LLC
John Nicklas Date Joseph Siperstein Date
SAIC Task Order Manager Ohio LumexCo.
Joseph Evans Date Felecia Owen Date
SAIC Quality Assurance Manager MTI, Inc.
Ray Martrano Date John I.H. Patterson Date
Analytical Laboratory Services, Inc.'s Laboratory Manager Metorex
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Demonstration Plan Distribution List
Organization
EPA-NERL/ESD
EPA-NRMRL/LRPCD QA Manager
EPA Office of Solid Waste
DOE-ORNL
UT-Battelle/ORNL
TDEC Department of Energy Oversight
Bechtel Jacobs
Metorex, Inc.
Milestone
NITON LLC
Ohio LumexCo.
MTI, Inc.
Analytical Laboratory Services, Inc.
Science Applications International
Corporation
Science Applications International
Corporation
Mailing Address
944 East Harmon Ave.
Las Vegas, NV89119
26 W. Martin Luther King Drive
Cincinnati, OH 45268
2800 Crystal Drive
Arlington, VA 22202
Oak Ridge Operations Office
Oak Ridge, TN 37831
One Bethel Valley Road
Oak Ridge, TN 37831
761 Emory Valley Road
Oak Ridge, TN 37830
One Bethel Valley Road
Oak Ridge, TN 37831
Princeton Crossroads Corp. Center
250 Phillips Blvd., Suite 250
Ewing, NJ08618
160B Shelton Road
Monroe, CT 06468
900 Middlesex Turnpike, Bldg. 8
Billerica, MA 01 821
9263 Ravenna Road, Unit A-3
Twinsburg, OH 44087
1609 Ebb Drive
Wilmington, NC 28409
34 Dogwood Lane
Middletown, PA 17057
950 Energy Drive
Idaho Falls, ID 83401
11251 Roger Bacon Drive
Reston, VA20190
411 Hackensack Ave.
Hackensack, NJ 07601
2260 Park Ave., Suite 402
Cincinnati, OH 45206
151 Lafayette Drive
Oak Ridge, TN 37831
595 East Brooks Ave, #301
Las Vegas, NV 89030
Recipient
Dr. Steve Billets
George Brilis
Ann Vega
Shen-yi Yang
Elizabeth Phillips
Roger Jenkins
Dale Rector
Janice Hensley
John I.H. Patterson
Mikhail Mensh
Volker Thomsen
Joseph Siperstein
Felecia Owen
Ray Martrano
John Nicklas
Joseph Evans
Maurice Owens
Fernando Padilla
Rita Schmon-Stasik
Mike Bolen
John King
Andy Matuson
Herb Skovronek
Jim Rawe
Joseph Tillman
Allen Motley
W. Kevin Jago
Nancy Patti
Mark Pruitt
No. Of
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2
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Notice
This document was prepared for the EPA SITE Program under Contract No.: 68-C-00-179. It has
been subjected to the Agency's peer and administrative reviews and has been approved for
publication as an EPA document. Mention of corporation names, trade names, or commercial
products does not constitute endorsement or recommendation for use.
IV
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged byCongress with protecting the nation's
natural resources. Under the mandate of national environ mental laws, the agency strives to formulate
and implement actions leading to a compatible balance between human activities and the ability of
natural systems to support and nurture life. To meet this mandate, the EPA's Office of Research and
Development provides data and scientific support thatcan be used to solve environmental problems,
build the scientific knowledge base needed to manage ecological resources wisely, understand how
pollutants affect public health, and prevent or reduce environmental risks.
The National Exposure Research Laboratory is the agency's centerfor investigation of technical and
management approaches for identifying and quantifying risks to human health and the environment.
Goals of the laboratory's research program are to (1) develop and evaluate methods and technologies
for characterizing and monitoring air, soil, and water; (2) support regulatory and policy decisions; and
(3) provide the scientific support needed to ensure effective implementation of environmental
regulations and strategies.
The EPA's Superfund Innovative Technology Evaluation (SITE) Program evaluates technologies
designed for characterization and remediation of contaminated Superfund and Resource
Conservation and Recovery Act sites. The SITE Program was created to provide reliable cost and
performance data in order to speed acceptance and use of innovative remediation, characterization,
and monitoring technologies by the regulatory and user community.
Effective monitoring and measurement technologies are needed to assess the degree of
contamination at a site, provide data that can be used to determine the risk to public health or the
environment, and monitor the success or failure of a remediation process. One component of the
EPA SITE Program, the Monitoring and Measurement Technology Program, demonstrates and
evaluates innovative technologies to meet these needs.
Candidate technologies can originate within the federal government or the private sector. Through
the SITE Program, developers are given the opportunity to conduct a rigorous demonstration of their
technologies under actual field conditions. By completing the demonstration and distributing the
results, the agency establishes a baseline for acceptance and use of these technologies. The
Monitoring and Measurement Technology Program is managed by the Office of Research and
Development's Environmental Sciences Division in Las Vegas, Nevada.
Gary Foley, Ph. D.
Director
National Exposure Research Laboratory
Office of Research and Development
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Abstract
The Demonstration of innovative field devices for the measurement of mercury in soil and sediment
is being conducted under the EPA's SITE Program in February2003 atthe United States Department
of Energy's (DOE) Oak Ridge National Laboratory (ORNL) in Oak Ridge, Tennessee and the
Tennessee Department of Environment and Conservation's Department of Energy Oversight facility
in Oak Ridge, Tennessee. The primary purpose of the Demonstration is to evaluate innovative field
devices for the measurement of mercury in soil and sediment based on their performance and cost as
compared to a conventional, off-site laboratoryanalytical method. The five field measurement devices
listed below will be demonstrated:
• Metorex's X-MET 2000 Metal Master Analyzer, X-Ray Fluorescence Analyzer
• Milestone Inc.'s Direct Mercury Analyzer (DMA-80), Thermal Decomposition Instrument
• NITON's XL-700 Series Multi-Element Analyzer, X-Ray Fluorescence Analyzer
• Ohio Lumex's RA-915+ Portable Mercury Analyzer, Atomic Absorption Spectrometer, Thermal
Decompostion Attachment RP 91C
• MTI, Inc.'s PDV 5000 Hand Held Instrument, Anodic Stripping Voltammeter(1).
This Demonstration Plan describes the procedures that will be used to verify the performance and
cost of each field measurement device. The plan incorporates the quality assurance and quality
control eleme nts needed to generate data of sufficient quality to document each device's performance
and cost. A separate Innovative Technology Verification Report (ITVR) will be prepared for each
device. The ITVRs will present the Demonstration findings associated with the Demonstration
objectives.
MTI, Inc. participated in the Pre-Demonstration under the name Owen Scientific.
VI
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Contents
Concurrence Signatures ii
Demonstration Plan Distribution List iii
Notice iv
Foreword v
Abstract vi
Contents vii
Tables x
Figures xi
Abbreviations, Acronyms, and Symbols xii
Acknowledgments xv
Executive Summary xvi
1 Project Description and Objectives 1
1.1 Purpose of this Study 1
1.1.1 Background 1
1.1.2 SITE Demonstration 2
1.2 Vendor Technology Descriptions 2
1.2.1 Metorex Technology Description 2
1.2.2 Milestone Inc. Technology Description 4
1.2.3 NITON Technology Description 5
1.2.4 Ohio Lumex Co. Technology Description 6
1.2.5 MTI, Inc. Technology Description 6
1.3 Pre-Demonstration Activities 8
1.3.1 Site Descriptions 8
1.3.2 Site Sampling Activities 13
1.3.3 Soil and Sediment Homogenization 15
1.3.4 Pre-Demonstration Results 15
1.4 Project Objectives 17
1.4.1 Primary Objectives 17
1.4.2 Secondary Objectives 18
2 Project Organization 19
2.1 General Responsibilities 19
2.1.1 EPA 19
2.1.2 DOE 19
2.1.3 Tennessee Department of Environmental Conservation 19
2.1.4 SAIC 19
2.1.5 Referee Laboratory 20
VII
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Contents (Continued)
2.1.6 Vendors 20
2.2 Contact Information 20
Experimental Approach 25
3.1 Experimental Design 25
3.1.1 Field (Environmental) Sample Selection and Preparation 25
3.1.2 SRM Sample Selection 26
3.1.3 Spiked Samples 27
3.1.4 Vendor Testing 27
3.1.5 Independent Laboratory Confirmation 27
3.1.6 Schedule 27
3.2 Primary Project Objectives 27
3.2.1 Statement of Primary Objectives 27
3.2.2 Statistical Approach and Evaluation of Primary Objectives 29
3.3 Secondary Objectives 34
3.3.1 Secondary Objective # 1: Ease of Use 35
3.3.2 Secondary Objective # 2: Health and Safety Concerns 35
3.3.3 Secondary Objective # 3: Portability of the Device 36
3.3.4 Secondary Objective # 4: Instrument Durability 36
3.3.5 Secondary Objective # 5: Availability of Vendor Instruments
and Supplies 38
Demonstration Activities 39
4.1 Preparation of Test Material 39
4.1.1 Homogenized Field Samples 39
4.1.2 SRM Samples 44
4.2 Field Analysis by Vendors 46
4.2.1 Distribution of Samples 46
4.2.2 Handling of Waste Material 47
4.3 Field Observations 47
4.3.1 Roles and Responsibilities 47
4.3.2 Records 49
Referee Laboratory Testing and Measurement Protocols 51
5.1 Referee Laboratory Selection 51
5.2 Reference Method 53
5.2.1 Laboratory Protocols 53
5.2.2 Laboratory Calibration Requirements 55
5.3 Additional Analytical Parameters 55
Referee Laboratory QA/QC Checks 56
6.1 QA Objectives 56
6.2 QC Checks 57
Data Reporting, Data Reduction, and Data Validation 59
7.1 Referee Laboratory 59
7.1.1 Data Reduction 59
7.1.2 Data Validation 59
VIM
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Contents (Continued)
7.1.3 Data Storage Requirements 60
7.1.4 Laboratory Reporting 60
7.2 Vendor Reporting 60
7.2.1 Field Reporting 60
7.2.2 Data Reduction/Validation 60
7.3 Final Technical Reports 61
8 QA Assessments 62
8.1 Performance Audits 62
8.2 Systems Audits 62
8.2.1 Systems Audit - SAIC GeoMechanics Laboratory 63
8.2.2 Systems Audit - Referee Laboratory (ALSI) 63
8.2.3 Systems Audit - Vendor Technology Evaluation 63
8.3 Corrective Action 64
8.3.1 Corrective Action for Systems Audits 65
8.3.2 Corrective Action for Data Outside Control Limits 65
9 References 66
Appendix A - Laboratory Homogenization and Subsampling of Field Collected Geo Mate rials
Revision 1
Appendix B - Analytical Laboratory Services, Inc.'s Standard Operating Procedures
IX
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Tables
Table Page
1-1 Summary of Vendor Technologies 3
1-2 Milestone DMA-80 Precision and Accuracy for Various Matrices 5
1-3 Ohio Lumex RA-915+ Detection Limits for Various Matrices 7
1-4 Mercury in Tailings Piles - Six Mile Canyon Area of Carson River Site 10
1-5 Y-12 Mercury Concentration in Surface and Subsurface Soil
at Building 8110 11
1-6 Mercury Concentration in Sediments - Upper East Fork of
Poplar Creek at Y-12 11
1-7 Mercury in Subsurface Soils at the Confidential Manufacturing Site 12
1-8 Mercury in Selected Test Plot Core Locations - Puget Sound 13
1-9 Pre-Demonstration Analytical Results from Candidate Laboratories 16
2-1 Vendors Selected for the Mercury Field Analysis Demonstration 22
2-2 Demonstration Contact List 23
3-1 Test Samples Collected from Each of the Four Field Sites 26
3-2 Field Sample Contaminant Ranges for Vendor Technologies 26
3-3 Projected Field Measurement Demonstration Schedule 28
3-4 Estimated Sensitivities for Each Field Measurement Device 28
3-5 Example Ease of Use Form 35
3-6 Example Health and Safety Concerns Form 36
3-7 Example Portability of the Device Form 37
3-8 Example Instrument Durability Form 38
4-1 Sample Volume, Containers, Preservation, and Holding Time Requirements 43
4-2 Shipping Addresses and Contacts for Demonstration Samples 46
5-1 Methods for Total Mercury Analysis 54
5-2 Analytical Methods for Non-Critical Parameters 54
6-1 QA Objectives for Mercury Measurements by SW-846 Method 7471B 56
6-2 QC Checks for Mercury Measurements by SW-846 Method 7471B 58
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Figures
Figure Page
1-1 Experimental Design Flow Diagram 9
2-1 Organizational Chart 21
4-1 Test Sample Preparation at the SAIC GeoMechanics Laboratory 40
4-2 Example Sample Homogenization Form 42
4-3 Example Sample Label 43
4-4 Example Chain-of-Custody Form 45
XI
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Abbreviations, Acronyms, and Symbols
% Percent
%D Percent difference
°C Degrees Celsius
|jg/kg Microgram per kilogram
|jg/l Microgram per liter
AA Atomic absorption
AAS Atomic absorption spectrometry
AC Alternating current
ALSI Analytical Laboratory Services, Inc.
Ag Silver
Am Americium
As Arsenic
ASV Anodic stripping voltammetry
Au Gold
bis Below land surface
Cd Cadmium
CIH Certified Industrial Hygienist
Cl Chlorine
cm Centimeter
cm3 Cubic centimeter
COC Chain of custody
CSV Cathodic stripping voltammetry
Cu Copper
CVAFS Cold vapor atom ic fluorescence spectrometry
DL Detection limit
DMA-80 Direct Mercury Analyzer
DOE Department of Energy
EPA United States Environmental Protection Agency
EPA-NERL Environmental Protection Agency's National Exposure Research Laboratory
FP Fundamental parameters
FPXRF Field portable x-ray fluorescence
g Gram
g/cm3 Gram per cubic centimeter
gal Gallon
hr Hour
XII
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Abbreviations, Acronyms, and Symbols (Continued)
Hg Mercury
HgCI2 Mercury (II) chloride
ICAL Initial calibration
ICP Inductively coupled plasma
IDL Instrument detection limit
IDW Investigation-derived waste
Inc Incorporated
ITVR Innovative Technology Verification Report
kg Kilogram
L Liter
L/min Liter per minute
LCS Laboratory control sample
LEFPC Lower East Fork Poplar Creek
LLC Limited Liability Company
LRPCD Land Remediation and Pollution Control Division
3
Cubic meter
MDL Method detection limit
mg Milligram
mg/kg Milligram per kilogram
mg/L Milligram per liter
ml Milliliter
mm Millimeter
MMT Measurement and Monitoring Technology
MSDS Material safety data sheet
MS/MSD Matrix spike/matrix spike duplicate
ND Non-detectable, not detected, less than detection limit
NERL National Exposure Research Laboratory
ng/L Nanogram per liter
ng/m3 Nanogram per cubic meter
NIST National Institute of Standards and Technology
nm Nanometer
NRMRL National Risk Management Research Laboratory
ORNL Oak Ridge National Laboratory
Pb Lead
PI Prediction interval
POC Point of contact
PPE Personal protective equipment
PQL Practical quantitation limit
QA Quality assurance
QAPP Quality Assurance Project Plan
QC Quality control
RPD Relative percent difference
RSD Relative standard deviation
XIII
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Abbreviations, Acronyms, and Symbols (Continued)
SAIC Science Applications International Corporation
Se Selenium
Sec Second
SITE Superfund Innovative Technology Evaluation
SOP Standard operating procedure
SOW Statement of work
SRM Standard reference material
SW-846 Test Methods for Evaluating Solid Waste; Physical/Chemical Methods
SWDA Solid Waste Disposal Act
TD/AAS Thermal decomposition / atomic absorption spectrometry
TDEC Tennessee Department of Environment and Conservation
TOC Total organic carbon
TOM Task Order Manager
TP Tailings pile
TSA Technical system audit
UEFPC Upper East Fork of Poplar Creek
VOC Volatile Organic Compound
XRF X-ray fluorescence
Y-12 Y-12 Oak Ridge Security Complex, Oak Ridge, Tennessee
Zn Zinc
XIV
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Acknowledgments
Science Applications International Corporation (SAIC) acknowledges the support of the following
individuals in preparing this document: Dr. Stephen Billets of the EPA National Exposure Research
Laboratory (NERL); Ms. Elizabeth Phillips of the DOE ORNL; Mr. John Patterson of Metorex; Mr.
Mikhail Mensh of Milestone, Inc.; Mr. Volker Thomsen, Ms. Debbie Schatzlein, and Mr. David
Mercuro, of NITON LLC; Mr. Joseph Siperstein of Ohio Lumex; and Ms. Felecia Owen of MTI, Inc.
This document was Q A reviewed by Ms. Ann Vega of the EPA National Risk Management Research
Laboratory's Land Remediation and Pollution Control Division and Mr. George Brillis of NERL.
xv
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Executive Summary
Performance verification of innovative environmental technologies is an integral part of the regulatory and research mission
of the EPA. The SITE Program was established by the EPA Office of Solid Waste and Emergency Response and Office
of Research and Development under the Superfund Amendments and Reauthorization Act of 1986. The program is
designed to meet three primary objectives: (1) identify and remove obstacles to the development and commercial use of
innovative technologies; (2) demonstrate promising innovative technologies and gather reliable performance and cost
information to support site characterization and cleanup activities; and (3) develop procedures and policies that encourage
use of innovative technologies at Superfund sites as well as other waste sites or commercial facilities. The in tent of a SITE
Demonstration is to obtain representative, high-quality performance and cost data on innovative technologies so that
potential users can assess a given technology's suitability for a specific application.
The Demonstration of innovative field devices for the measurement of mercury in soil and sediment is to be conducted
under the SITE Program in February 2003 at DOE ORNL in Oak Ridge, Tennessee and the Tennessee Department of
Environment and Conservation's Department of Energy Oversight facility in Oak Ridge, Tennessee. The Demonstration
is being conducted under the Monitoring and Measurement Technology Program, which is administered by the
Environmental Sciences Division of the EPA NERL in Las Vegas, Nevada. The primary purpose of the Demonstration is
to evaluate innovative field measurement devices for mercury in soil and sediment based on comparison of their
performance and cost to those of a conventional, off-site laboratory analytical method. Laboratory and method selection
followed a carefully documented procedure to ensure the best data quality possible for the collected samples.
The following five field measurement devices will be demonstrated and evaluated:
Metorex's X-MET 2000 Metal Master Analyzer, X-Ray Fluorescence Analyzer
Milestone Inc.'s Direct Mercury Analyzer (DMA-80), Thermal Decomposition Instrument
NITON LLC's XL-700 Series Multi-Element Analyzer, X-Ray Fluorescence Analyzer
Ohio Lumex's RA-915+ Portable Mercury Analyzer, Atomic Absorption Spectrometer, Thermal Decompostion
Attachment RP 91C
MTI, Inc.'s PDV 5000 Hand Held Instrument, Anodic Stripping Voltammeter.
The mission of this program is to obtain high quality performance data. The performance and cost of each device will be
compared to those of a conventional, off-site laboratory analytical method -that is, a reference method. The performance
and cost of one device will not be compared to those of another device. The reference method that will be used for the
Demonstration is EPA's "Test Methods for Evaluating Solid Waste; Physical/Chemical Methods" (SW-846) Method 7471B.
SW-846 methods are intended as performance-based methods and, therefore, specified objectives have been designated
in this Demonstration Plan. A separate ITVR will be prepared for each device. The Demonstration has both primary and
secondary objectives. The primary objectives are critical to the technology evaluations and require use of quantitative
results to draw conclusions regarding technology performance. The secondary objectives pertain to information that is
useful but do not necessarily require use of quantitative results to draw conclusions regarding technology performance.
The primary objectives for the Demonstration of the individual field measurement devices are as follows:
Primary Objective # 1. Determine the sensitivity of each field instrument with respect to the Method Detection
Limit and Practical Quantitation Limit generated by each vendor.
XVI
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Primary Objective # 2. Determine the potential analytical accuracy associated with the field measurement
technologies.
Primary Objective # 3. Evaluate the precision of the field measurement technologies.
Primary Objective # 4. Measure the amount of time required for performing five functions related to mercury
measurements: 1) mobilization and setup; 2) initial calibration; 3) daily calibration, 4)
demobilization; and 5) sample analysis.
Primary Objective # 5. Estimate the costs associated with mercury measurements for the following four
categories: 1) capital; 2) labor; 3) supplies; and 4) investigation-derived waste.
The secondary objectives for the Demonstration of the individual field measurement devices are as follows:
Secondary Objective # 1. Document the ease of use, as well as the skills and training required to properly operate
the device.
Secondary Objective # 2. Document potential health and safety concerns associated with operating the device.
Secondary Objective # 3. Document the portability of the device.
Secondary Objective # 4. Evaluate the durability of the device based on its materials of construction and
engineering design.
Secondary Objective # 5. Document the availability of the device and spare parts.
It is not an objective of the Demonstration to characterize the concentration of mercury in soil at specific sampling sites.
It is, however, necessary to ensure comparability between vendor results and the referee laboratory results by utilizing a
homogenous matrix, such that, all sub-samples have consistent mercury concentrations. For this reason some conditions
of field samples have been sacrificed to obtain sub-samples with a consistent mercury concentration.
To address the Demonstration objectives, both environmental and standard reference material (SRM) samples will be
analyzed during the Demonstration. The environmental samples were collected from four sites contaminated with mercury.
The SRMs will be obtained from commercial providers. Collectively, the environmental and SRM samples will have the
range of physical (sand, silt, and clay) and chemical (mercury concentration) characteristics necessary to properly evaluate
the field measurement devices. In addition to SRMs and environmental samples, environmental spike samples using a
known concentration of mercury (II) chloride will be prepared in an environmental matrix. This will be done as an additional
test of each technology.
Upon completion of the Demonstration, field measurement device and reference method results will be compared to
evaluate the performance and associated cost of each device. The ITVRs for the five devices are scheduled for completion
in October 2003.
XVII
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Chapter 1
Project Description and Objectives
1.1 Purpose of this Study
This Demonstration project is being performed to evaluate vendor field analytical equipment for the measurement of
mercury (Hg) concentrations in soil and sediment. The Hg concentration results from the field analytical equipment of five
vendors will be compared to results from a selected referee laboratory. In addition, factors such as the ease of use, cost,
safety, portability, and durability of the vendor equipment will be evaluated.
1.1.1 Background
Performance evaluation of innovative environmental technologies is an integral part of the regulatory and research mission
of the United States Environmental Protection Agency (EPA). The Superfund Innovative Technology Evaluation (SITE)
Program was established by EPA's Office of Solid Waste and Emergency Response and Office of Research and
Development under the Superfund Amendments and Reauthorization Act of 1986.
The overall goal of the SITE Program is to conduct performance evaluation studies and to promote the acceptance of
innovative technologies that may be used to achieve long-term protection of human health and the environment. The SITE
Program includes the following elements:
Measurement and Monitoring Technology (MMT) Program - evaluates innovative technologies that sample, detect,
monitor, or measure hazardous and toxic substances. These technologies are expected to provide better, faster, or
more cost-effective methods for producing real-time data during site characterization and remediation studies than
do conventional technologies.
Remediation Technology Program - conducts demonstrations of innovative treatment technologies to provide reliable
performance, cost, and applicability data for site cleanups.
Technology Transfer Program - provides and disseminates technical information in the form of updates, brochures,
and other publications that promote the SITE Program and participating technologies. The Technology Transfer
Program also offers technical assistance, training, and workshops to support the technologies. A significant number
of these activities are performed by EPA's Technology Innovation Office.
This Demonstration is being performed under the MMT Program. The primary objectives of the MMT Program are as
follows:
Test and verify the performance of innovative field sampling and analytical technologies that enhance sampling,
monitoring, and site characterization capabilities.
Identify performance attributes of innovative technologies thataddressfield sampling, monitoring, and characterization
problems in a more cost-effective and efficient manner.
Prepare protocols, guidelines, methods, and other technical publications that enhance acceptance of these
technologies for routine use.
The MMT Program is administered by the Environmental Sciences Division of the EPA National Exposure Research
Laboratory (NERL), in Las Vegas, Nevada. Science Applications International Corporation (SAIC) has prepared this
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Quality Assurance Project Plan (QAPP) under the MMT Program to evaluate field analytical techniques for detecting Hg
in soil and sediment. The EPA Task Order Manager (TOM) is Dr. Stephen Billets.
1.1.2 SITE Demonstration
This SITE Demonstration is divided into two phases: 1) Pre-demonstration and 2) Demonstration. The Pre-demonstration
activities were completed in the Fall of 2002 and are described in Subchapter 1.3. Planned Demonstration activities are
summarized in this subchapter and presented in detail throughout the remainder of this document.
The Demonstration will involve evaluating the capabilities of five vendors to measure mercury concentrations in soil and
sediment. During the Demonstration, each vendor will receive field samples for analysis. Each sample will be analyzed
in replicate. The samples were obtained during the Pre-demonstration phase from the following locations:
Carson River Mercury Site (soil and sediment)
Oak Ridge Y-12 National Security Complex (Y-12) (soil and sediment)
A Confidential Manufacturing Facility (soil)
Puget Sound (sediment).
In addition, each vendor will analyze certified standard reference material (SRM) samples and spikes prepared using
environmental samples spiked with mercury (II) chloride (HgCI2). Together, the field samples, SRMs, and spikes will be
called "Demonstration samples" for the purpose of this Demonstration. Each vendor will receive between 150 and 200
Demonstration samples. All Demonstration samples will be independently analyzed by a carefully selected referee
laboratory. It is the intention of this program to compare results to a suitable analytical method. Samples will be in
replicates of up to seven. The experimental design is fully described in Chapter 3.
1.2 Vendor Technology Descriptions
The following paragraphs provide details on each of the field technologies to be evaluated during this Demonstration.
Information was provided by the vendors via responses to questionnaires, instrument manuals, brochures, and/orvendor
web sites. This information has not been independently verified by SAIC; however, vendor claims (e.g., accuracy,
precision, and sensitivity) will be evaluated as part of this Demonstration. Table 1-1 summarizes much of this information.
Actual vendor operating conditions will be observed and recorded by SAIC during the Demonstration.
1.2.1 Metorex Technology Description
The Metorex X-2000 Metal Master analyzer is based on x-ray fluorescence (XRF) technology (Metorex, 2002). The
sample to be measured is irradiated with a radioactive isotope. The isotopes most commonly used in soil analysis are
cadmium (109Cd) and americium (241Am). If the energy of radiation from the source is higher than the absorption energy
of a target element, the atoms of that element will be excited, and fluorescent x-ray radiation from that element can be
detected with the instrument. The x-ray energies for specific elements are well defined. The instrument's detector
converts the energies of x-ray quanta to electrical pulses. The pulses are then measured and counted. The intensity
(counts in a certain time) from the measured element is proportional to the concentration of the element in the sample.
The measurement technique is fast and nondestructive, and multiple elements can be measured simultaneously. The
chemical or physical form of the atom does not affect the x-ray energy, because the electrons producing x-rays are not
valence (outer) shell electrons. Both identification and quantitation can be accomplished from a single measurement. The
high-resolution silicon-PIN (as in diode which is positive, intrinsic, negative) detectoris stable and accurate, and continuous
self-testing and automatic source decay correction insure the reliability and accuracy of the measurement results.
Application and Specifications - The Metorex analyzer can reportedly perform analysis on solids, powders, waste water,
solutions, slurries, sludge, air particulate matter collected on filter, coating materials, and paste samples. The main unit
weighs 5.67 kilograms (kg) and has dimensions of 44.96 centimeters (cm) by 33.53 cm by 10.16 cm. The probe has a
weightof 1.36 kg and measures 22.35 cm by 24.89 cm by 7.62 cm. Required accessories include battery, battery charger,
and field case for carrying the unit on the shoulder. The battery operates for approximately 4 hours before needing to be
charged. For sample preparation, required accessories include sample cups, film, and a tool for compressing powder
samples (pressing tool).
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Table 1 -1. Summary of Vendor Technologies.
INSTRUMENT
PARAMETER
Principle of Operation
Analytical Range
MDL2
Potential Interferences
Accuracy1
Precision 1
Required Sample Size
Expected Throughput
Metorex, Inc.
XRF
10 to
1,000 mg/kg
10 mg/kg
High Pb, As, Se,
&Zn
15-20%
5-20%
8g
10/hr
Milestone Inc.
TD/AAS
50 ug/kg-5 mg/kg
(8 ug/kg with
larger sample
aliquot)
50 ug/kg
VOCs,
concentrated
inorganic acids, &
heavy metals
+/- 10%
+/- 5%
0.01 to5g
12/hr
VENDOR NAME
NITON LLC
EDXRF
20 to
1 ,000 mg/kg
20 mg/kg
Pb, As, and Zn >
500 mg/kg
At 1 00 mg/kg
+/- 15%
10% RSD @60
ppm to 20% for
environmental
samples
5 to 10 g
25/hr- direct
analysis; 10/hr
with preparation
Ohio Lumex Co.
AAS
5 ug/kg to
1 00 mg/kg
5 ug/kg
None
Identified
+/- 10%
+/- 10%
0.01 to 0.2 g
10/hr
MTI, Inc.
ASV
1 00 ug/kg to
1 ,000 mg/kg
100 ug/kg
High Ag
+/- 10%
+/- 15%
2to5g
10/hr
1 This information is based solely upon vendor claims. These claims will be evaluated during the Demonstration.
2 MDL for soil and sediment.
3 Sample analyses based upon multiple hours of operation
ug/kg - micrograms per kilogram
mg/kg - milligrams per kilogram
AAS - Atomic Absorption Spectrometry
As, Cu, Hg, Pb, Se, and Zn - Arsenic, Copper, Mercury, Lead, Selenium and Zinc, respectively
ASV - Anodic Stripping Voltammetry
EDXRF - Energy Dispersive X-Ray Fluorescence
g - gram
hr- Hour
LLC - Limited Liability Company
MDL - Method Detection Limit
RSD - Relative Standard Deviation
TD - Thermal Decomposition
VOCs - Volatile Organic Compounds
XRF - X-Ray Fluorescence
-------
Operation - The Metorex X-MET 2000 comes factory calibrated. When measuring with the Metal Master, calibration can
utilize either fundamental parameters (FPs) or empirical calibration. FP calibration is reportedly fast and easy and does
not require user interaction orcalibration standards. The standard version analyzes the 25 most common elements from
titanium to uranium, including, for example, arsenic, selenium, tin, lead, iron, and chromium. The elements analyzed can
be customized according to the user needs. Empirical calibration is used when maximum accuracy is required; for
example, when measuring trace elements. For site-specific ana lysis, the instrument needs to be calibrated either with site-
specific or site-typical samples. The number of samples for calibration should be between 5 to 20, and must be an
accurate analysis available for the elements of interest. The calibration sample must cover the concentration range for
each element the user wants to measure.
The measurement is done either by placing the probe on the sample or placing the sample in a sample cup and placing
the cup on the probe. The trigger is pressed, and the sample is measured for a preset time. One analysis takes from 30
seconds to 10 minutes, depending on the desired accuracy. On completion of the measurement an assay is displayed.
Data collection, analysis, and management are completely automated. Connection to a remote computer allows transfer
of the collected data for further evaluation and report generation.
When measuring soil, oversize materials and plants should be removed. If sample cups are used, it is advantageous to
sieve the sample so that the particle size is homogenous. The water content difference between calibration samples and
samples to be analyzed should be less than 25 percent (%) to minimize error. If the difference is larger than 25%, samples
should be dried for accurate analysis.
Elements with energies close to mercury may interfere with the analysis if they are present in large quantities
(approximately 5 times the mercury concentration). Large quantities of lead, arsenic, selenium, and zinc, for example can
cause interference.
1.2.2 Milestone Inc. Technology Description
The thermal decomposition, atomic absorption (AA) spectrometry technique employed by Milestone Inc.'s Direct Mercury
Analyzer (DMA-80) analyzes samples directly, eliminating digestion, chemical pretreatment, and waste disposal (Milestone,
2002). Samples are introduced to the DMA-80, dried, and then thermally decomposed in a continuous flow of oxygen.
Combustion products are carried off and further decomposed in a hot catalyst bed. Mercury vapors are trapped on a gold
amalgamator and subsequently desorbed forquantitation. The mercury content is determined using AAspectrophotometry
at 254 nanometers (nm). The DMA-80 analyzes liquid and solid samples with no sample preparation and no waste
disposal. The vendor notes that the DMA-80 can automatically process 40 samples in about 4 hours, start to finish. An
intuitive controller uploads sample weights, controls the analysis, and processes data with built-in report generation and
networking capabilities.
As per Milestone, the thermal decomposition technique eliminates the sample digestion step since the sample is thermally
decomposed. In addition, the DMA-80 eliminates a chemical pretreatment step since the mercury is reduced by the
catalysts in the decomposition tube. The use of the DMA-80 eliminates waste disposal because no reagents are required.
Milestone notes that it has validated results for solid and liquid matrices.
Application and Specifications -The DMA-80 permits direct analysis of trace level mercury in several matrices, including
solids (sediment, soil, sludge, food/feed, plant and animal tissues, coal, oil, fish, cement, paints) and liquids (wastewater,
beverages, biological fluids). Milestone indicates that the DMA-80 has application in various industries including
environmental, agriculture, petrochemical, food and feed, power plant, mines, and resources laboratories.
The Milestone system requires bench space measuring 150 cm in length and 80 cm deep. The dimensions of the unit
itself are 80 cm by 42 cm by 30 cm (height) and the terminal measures 33 cm by 27 cm by 26 cm (height). The total
weight is 56 kg. The DMA-80 can interface with any Windows® compatible printer. The unit requires alternating current
(AC) power (110 volts, 60 hertz, 10-15 amperes). Standard grade oxygen is required with a gas regulator having a
capacity of 60 pounds per square inch. The unit exhaust is connected to a fume hood. The DMA-80 is equipped with a
40-position autosampler and can optionally be interfaced to an analytical balance.
Operation - Instrument calibration is achieved using applicable SRMs, as recommended in the Milestone installation guide.
These standards can be soil or other solids, tissue samples, or a certified liquid standard. Calibration is based on a second
order calibration. The DMA-80 has dual measuring cells for an extended analysis range of 0-600 nanograms mercury.
The method analytical range is 50 micrograms per kilogram (ug/kg) to 5 milligrams per kilogram (mg/kg) using a 100
milligram (mg) sample size. Using a 500 mg sample, a quantitation limit of 8 ug/kg is expected with a detection limit of
0.04 ug/kg- Maximum sample size is 500 mg. It is expected that approximately 12 samples per hour can be analyzed
-------
during the Demonstration. Expected variability for the DMA-80 is +/- 5% with expected accuracy 90-110%. Milestone
presents the following information on precision and accuracy in its manual for the DMA-80 (Table 1-2).
Table 1-2. Milestone DMA-80 Precision and Accuracy for Various Matrices.
Matrix (SRM Material)
Rice Flour (NIST 1568a)
Tomato Leaves (NIST 1573a)
Coal (NIST 1630a)
FlyAsh(NIST1633b)
Soil (NIST 2709)
Soil (NIST 2711)
Certified Results
5.8 + 0.5 ug/kg
34 + 4 ug/kg
93.8 + 3.7 ug/kg
141 + 19 ug/kg
1400 + 80 ug/kg
6250+ 190 ug/kg
DMA-80 Results*
5.5 + 0.8 ug/kg
31.7 + 1 .4 ug/kg
93.4 + 2.4 ug/kg
148.6 + 1.8 ug/kg
1460 + 20 ug/kg
6240 + 70 ug/kg
'Source: The DMA-80 Direct Mercury Analyzer Manual (Milestone, 2002)
NIST - National Institute of Standards and Technology
ug/kg - microgram/kilogram
1.2.3 NITON Technology Description
The NITON XL 700 series sample analyzer is an energy dispersive XRF spectrometer that uses either a 109Cd radioactive
isotope (XLi model) or a low-powered miniature x-ray tube with a silver target (XLt model) to excite characteristic x-rays
of a test sample's constituent elements (NITON, 2002). These characteristic x-rays are continuously detected, identified,
and quantified by the spectrometer during sample analysis. Stated simply, the energy of each x-ray detected identifies
a particular element present in the sample, and the rate at which x-rays of a given energy are counted provides a
determination of the quantity of that element that is present in the sample.
Detection of the characteristic mercury x-rays is achieved using a highly-efficient, thermo-electrically cooled, solid-state
detector. Signals from this detector are amplified, digitized, and then quantified via integral multichannel analysis and data
processing units. Sample test results are displayed in parts per million (ppm) of total elemental mercury.
Application and Specifications - The NITON XLt 700 series analyzer with x-ray tube excitation provides the user with
the speed and efficiency of x-ray tube excitation, while reducing the regulatory demands typically encountered with isotope-
based systems. In most cases, the x-ray tube equipped 700 analyzer can be shipped from state to state and country to
country with minimal paperwork and expense. The XLi and XLt 700 Series analyzers offer testing modes for soil and other
bulk samples; filters, wipes, and other thin samples; and lead-based paint. Testing applications include management of
remediation projects, site assessments, and com pliance testing. They provide simultaneous analysis of up to 25 elements,
including all eight of the metals listed under the Resource Conservation and Recovery Act. XRF analysis is non-
destructive, so screened samples can be sent to an accredited laboratory for confirmation of results obtained on-site.
NITON's software corrects automatically for variations in soil matrix and density making it applicable for both in-situ and
ex-situ testing.
Operation - For in-situ analysis, the analyzer is placed directly on the ground or on bagged soil samples. Because
contamination patterns tend to be heterogeneous, a large num ber of data points can be produced using in-situ testing to
delineate contamination patterns. In-situ testing with either the XLi or XLt 700 Series instrument is in full compliance with
EPA Method 6200. In-situ testing allows for testing many locations in a short time and is ideal for rapid site-profiling,
locating sources of contamination, and monitoring and fine-tuning remediation efforts on-the-spot. In-situ analysis is not
appropriate for wet sediment samples. In this case, sediments must be dried and can then be measured either bagged
or in sample cups.
For ex-situ testing, the XL 700 series can test prepared, representative soil samples (dried, ground, sifted, homogenized)
to generate analytical-grade data quality when required. Both the XLi and XLt700 Series soilanalyzers come with sample-
preparation protocols.
The NITON instrument is factory calibrated. NITON's Compton normalization software automatically corrects for any
differences in sample density and matrix so site specific calibration standards are never required. The unit also analyzes
-------
for zinc, arsenic, and lead as these elements may cause interference at certain concentration levels. Total analysis time
does not exceed 120 seconds (after sample preparation).
Sample preparation, for those samples not analyzed directly in-situ, may include the grinding and/or sieving of dried
samples using either mortar and pestle or electric grinder. Wet samples, at a minimum, are filtered to remove standing
waterthen dried. Although EPA Method 6200 specifies thatmercury samples should not beoven-dried due to the potential
volatilization loss of mercury, NITON uses oven-dried sample material without negative impact.
1.2.4 Ohio LumexCo. Technology Description
The RA-915+ Mercury Analyzer is a portable AA spectrometer with a 10-meter (m) multipath optical cell and Zeeman
background correction (Ohio Lumex, 2001). Among its features is the direct detection of mercury without its preliminary
accumulation on a gold trap. The instrument has a wide dynamic quantification measuring range (5 ug/kg to 100 mg/kg).
The RA-915+ includes a built-in test cell for field performance verification. The unit can be used with the optional RP-91
for an ultra low mercury detection limit in water samples using the "cold vapor" technique. For direct mercury determination
in complex matrices without sample pretreatment, including liquids, soils and sediments to be analyzed during this
Demonstration, the instrument will be operated with the optional RP-91 C accessory.
The operating principle of the RA-915+ is based on the effect of differential, Zeeman AAspectrometry combined with high-
frequency modulation of polarized light. This combination eliminates interferences and provides the highest sensitivity.
The RP-91 C attachment is intended to decompose a sample and to reduce the mercury using the pyrolysis technique.
The RP-91C attachment is a furnace heated to 800 degrees Celsius (°C) where mercury is converted from a bound state
to the atomic state by thermal decomposition and reduced in a two-section furnace. In the first section of the furnace the
"light" mercury compounds are preheated and burned. In the second section a catalytic afterburner decomposes "heavy"
compounds. After the atomizer, the gas flow enters the analytical cell of the attachment. Ambient air is used as a carrier
gas; no cylinders with compressed gasses are required. Zeeman correction eliminates interferences, thus, no gold
amalgamation is required. The instrument is controlled and the data is acquired by software based on a Microsoft
Windows® platform.
Application and Specifications - The RA-915+ is a portable spectrometer designed for interference-free
analysis/monitoring of mercury content in ambient air, water, soil, natural and stack gases, chlorine alkali manufacturing,
spill response, hazardous waste, foodstuff, and biological materials. The Ohio Lumex system is fully operational in the
field and could be set up in a van, as well as a helicopter, marine vessel, or hand-carried for continuous measurements.
It is suitable for field operation using a built-in battery for measurements of ambient air and industrial gases. The RP-91
and RP-91 C attachments are used to convert the instrument into a liquid or solid sample analyzer, respectively.
According to the RA-915+ Analyzer manual, the base unit has dimensions of 47 cm by 22 cm by 11 cm and weighs 7.57
kg. The palm unit measures 13.5 cm by 8 cm by 2 cm and weighs 0.32 kg. Power supply can be a built-in 6 volt
rechargeable battery, a power pack adapter, an external electric battery, or an optional rechargeable battery pack. The
RP-91C system includes a pumping unit that has dimensions of 34 cm by 24 cm by 12 cm and a power supply unit
measuring 14.5 cm by 15 cm by 8.5 cm. Site requirements cited in the manual include a temperature range of 5 to 40 °C,
relative humidity of up to 98%, atmospheric pressures of 84 -106.7 kilopascals, along with requirements for sinusoidal
vibration and magnetic field tension. Sensitivity of the instrument is not affected by up to a 95 percent background
absorption caused by interfering components (dust, moisture, organic and inorganic gases).
Operation - The instrument calibration is performed by use of liquid or solid primary National Institute of Standards and
Technology (NIST) traceable standards. The normal dynamic analytical range is from 5 ug/kg to 100 mg/kg of direct
determination without dilution. No sample mineralization is needed, and no waste is generated. Sample throughput is up
to 30 samples per hour without an auto sampler. Table 1-3 presents a summary of the analysis conditions provided by
the vendor.
1.2.5 MTI, Inc. Technology Description
The principle of analysis used by the MTI, Inc. PDV 5000 is anodic stripping voltammetry (ASV) (MTI, Inc., 2002). A
negative potential is applied to the working electrode. When the electrode potential exceeds the ionization potential of the
analyte metal ion in solution (Mn+), it is reduced to the metal which plates onto the working electrode surface as follows:
- M
-------
Table 1-3. Ohio Lumex RA-915+ Detection Limits for Various Matrices.
Sample Matrix
Ambient air
Natural and other gases
Water
Oil, condensate
Solids, sediments
Urine
Tissues
Hair
Blood
Plants
Foodstuff
Detection Limit
2 ng/m3
2 ng/m3
0.5 ng/L
1 ug/kg
5 ug/kg
5 ng/L
1-5 ug/kg
20 ug/kg
0.5 ug/L
2 ug/kg
1-10 ug/kg
Sample vol/weight
20 L/min
5-20 L/min
20 mL
10mg
200 mg
1 mL
20 mg
10mg
0.2mL
50 mg
5-50 mg
Atomization
Techniques
without atomization
without atomization
cold vapor
pyrolysis
pyrolysis
cold vapor
pyrolysis
pyrolysis
cold vapor
pyrolysis
pyrolysis
# of Analyses/hr
real-time, 1/sec
real-time, 1/sec
15
15
30
15
15
15
15
15
15
ug/kg - microgram per kilogram
L/m in - Liters per m inute
mg - Milligram
ml - Milliliter
ng/L - Nanogram per liter
ng/m 3 - nanogram per cubic meter
sec - Second
Where: Mn+= analyte metal ion in solution
ne" = number of electrons
M = metal plated onto the electrode
The longer the potential is applied, the more metal is reduced and plated onto the surface of the electrode (also known
as the "deposition" or "accumulation" step), concentrating the metal. When sufficient metal has been plated onto the
working electrode, the metal is stripped (oxidized) off the electrode by increasing, at a constant rate, a positive potential
applied to the working electrode. Fora given electrolyte solution and electrode, each metal has a specific potential at
which the following oxidation reaction will occur:
M - Mn++ ne'
The electrons released by this process form a current. This is measured and may be plotted as a function of applied
potential to give a "voltammogram". The current at the oxidation or stripping potential for the analyte metal is seen as a
peak. To calculate the sample concentration, the peak height or area is measured and compared to that of a known
standard solution underthe same conditions. As a metal is identified by the potential atwhich oxidation occurs, a number
of metals may often be determined simultaneously, due to their differing oxidation potentials. The plating step makes it
possible to detect very low concentrations of metal in the sam pie. The length of this step can be varied to suit the analyte
concentration of the sample. For example, analysis of a 10 ug/kg solution of Pb may require a 3 to 5 minute accumulation
step, while a solution in the mg/kg range would require less than 1 minute. Laboratory versions of the ASV device can
measure ppt concentrations.
The MTI, Inc. PDV 5000 can be operated as a stand-alone instrument for screening, or attached to a laptop resulting in
better limits of detection.
Applications and Specifications - As noted above, ASV can detect multiple metals in a single scan, but in the majority
of cases, a specific metal is best analyzed using a specific electrolyte and electrode combination. This is essential for
detection limits in the low ug/kg range. Where the detection range is in the mg/kg range, it is possible to analyze a larger
range of metals per scan, but the reproducibility will be around 10% as opposed to the 3% typically seen when optimum
conditions are used. The field conditions that may affect accuracy and precision include sample homogeneity, sample
-------
handling errors, pipetting errors, unpredictable matrix effects, and sample and cell contamination. High silver
concentrations can interfere with mercury determinations.
For solids, test kits can be used that include all required reagents. To "digest" the solids, a slightly modified Method 3050B
is used from EPA's Test Methods for Evaluating Solid Waste; Physical/Chemical Methods (SW-846).
The MTI, Inc. PDV 5000 weighs approximately 700 grams (g) and has dimensions of 10 cm by 18 cm by 4 cm. It can
operate off a 110V AC source or direct current battery.
Operation - According to the vendor, it is realistic to expect the PDV 5000 to obtain data from the field that is within 20%
of the true value. For this reason it is best to use the PDV 5000 to classify samples as "above a threshold concentration"
or "below a threshold concentration." For example, a lead limit of 20 ug/kg is allowed in drinking water. Therefore, the PDV
5000 should be calibrated with a 20 ug/kg lead standard and any result that is above 20 ug/kg, less 20% (i.e., 16 ug/kg),
should be considered as potentially being above the 20 ug/kg limit.
The standard curve method compares the sample response with that of one or more known standards. Volts can allow
calibration curves of between one and ten standards to be constructed and then compared with up to 15 samples.
Generally, calibration is based on a single point comparison whereby the current generated by the standard is compared
to the current generated by the sample. The response for a particular analyte will be proportional to its concentration in
the analytical cell, so dilution by electrolyte or other reagents must be taken into consideration. For best results, the
sample concentration in the cell should be close to the cell concentration of the standard with which it is being compared.
Standard addition calibration involves analyzing a sample and then "spiking "the same sample solution with a small volume
of standard before re-analyzing that solution. The same sample can be spiked and re-analyzed once or several times
depending on the operator's preference. The results from the sample and spiked sample runs are then plotted and a line
of regression is fitted that is used to calculate the sample concentration.
1.3 Pre-Demonstration Activities
Pre-demonstration activities included development of a Pre-demonstration Plan dated September 2002, along with
collection and homogenization of soils and sediments in late September 2002. There were six objectives for the Pre-
demonstration:
Establish concentration ranges for testing vendor analytical equipment during the Demonstration;
Evaluate sample homogenization procedures;
Determine mercury concentrations in homogenized soils and sediments;
Select a reference method and qualify potential referee laboratories for the Demonstration;
Collect and characterize soil and sediment samples which will be used in the Demonstration; and
Provide soil and sediment matrices to the vendors for self-evaluation.
Figure 1-1 presents a flow diagram for the Pre-demonstration experimental design. Pre-demonstration activities and the
results are discussed in the following subchapters. Site descriptions are provided in Subchapter 1.3.1, sampling activities
are summarized in Subchapter 1.3.2, homogenization procedures are described in Subchapter 1.3.3, and Pre-
Demonstration results are presented in Subchapter 1.3.4.
1.3.1 Site Descriptions
Soil and sediment samples were collected from four sites for use during the Demonstration. The following subchapters
provide a brief description of each of those sites, including concentrations of mercury expected based on background data
supplied by the sites.
1.3.1.1 Carson River Mercury Site
The Carson River Mercury site includes mercury-contaminated soil at former gold and silver mining mill sites; mercury
contamination in waterways adjacent to the mill sites; and mercury contamination in sediment, fish, and wildlife over more
than a 50-mile length of the Carson River. Mercury is present at Carson River as either elemental mercury and/or
inorganic mercury sulfides with less than 1 %, if any, methyl mercury. This site provided both soil and sediment samples
across the range of contaminant concentrations desired for the Demonstration. The point of contact (POC) is Wayne
Praskins of EPA Region 9.
-------
1
INITIAL SITE SELECTION
- Carson River
-Oak Ridge Y-12
- Manufacturing Site
- Puget Sound
COLLECT PRE-DEMONSTRATION
SAMPLES
(Volume Collected -1-3 gal/Sample)
SCREENING OF
OVERSIZE IN FIELD
SAMPLE HOMOGENIZATION
at SAIC GEOMECHANICS LAB
(Method dependent on sample consistency,
See Appendix A)
REPLICATE SAMPLES
Note: "Blind" Label ID Used for all
Samples
"REDUCED" SAMPLE VOLUME
SPLIT INTO ALIQUOTS
Figure 1-1. Experimental Design Flow Diagram.
-------
Site Location and History - The site begins near Carson City, Nevada and extends downstream to the Lahontan Valley
and Carson Desert. Contamination at the site is a legacy of the Comstock mining era of the late 1800s, when mercury
was imported to the area for processing gold and silver ore. Ore mined from the Comstock Lode was transported to mill
sites, where it was crushed and mixed with mercury to amalgam ate the precious metals. The mills were located in Virginia
City, Silver City, Gold Hill, Dayton, Six Mile Canyon, Gold Canyon, and adjacentto the Carson River between New Empire
and Dayton. During the mining era, an estimated 7,500 tons of mercury were discharged into the Carson River drainage,
primarily in the form of mercury-contaminated tailings (i.e., waste rock).
Characterization - Today, the mercury is in the sediments and adjacent flood plain of the Carson River and in the
sediments of Lahontan Reservoir, Carson Lake, Stillwater Wildlife Refuge, and Indian Lakes. In addition, tailings with
elevated mercury levels are still present at and around the historic mill sites, particularly in Six Mile Canyon. Historical
mercury contamination data are presented in Table 1-4.
Table 1-4. Mercury in Tailings Piles - Six Mile Canyon Area of Carson River Site1
PARAMETER TAILINGS PILE (TP) AREA
(Mercury) TP003 TP004 TP005 TP006 TP007 TP008 TP009 TP017 TP018
No. of Samples
Maximum Value (mg/kg)
Minimum Value (mg/kg)2
Mean (mg/kg)
6
1,039
4
729
16
904
4
331
6
937
8
269
6
691
4
191
22
4,672
4
916
11
350
4
139
5
700
4
336
10
1,300
4
587
5
1,606
4
478
1 Source: EPA Region 9. Revised Draft - Human Health Risk Assessment and Rl Report, Carson River Mercury Site (1994).
2 The method detection limit (MDL) was 8 mg/kg, therefore levels below the MDL are reported as !4 the MDL (4 mg/kg)
1.3.1.2 Y-12 National Security Complex
The Y-12 National Security Complex site is located at the U.S. Department of Energy's (DOE) Oak Ridge National
Laboratory (ORNL) in Oak Ridge, Tennessee. Mercury contamination is present in the soil at the Y-12 facility in many
areas and also occurs in the sediments of the Upper East Fork of Poplar Creek (UEFPC). Both soil and sediment samples
were collected from this site. The POCs are Elizabeth Phillips of DOE at ORNL and Janice Hensley of Bechtel Jacobs.
Site Location and History-The Y-12 Site is an active manufacturing and developmental engineering facility that occupies
approximately 800 acres on the northeast corner of the DOE Oak Ridge Reservation adjacent to the city of Oak Ridge,
Tennessee. Built in 1943 by the U.S. Army Corps of Engineers as part of the World War II Manhattan Project, the original
mission of the installation was electromagnetic separation of uranium isotopes and weapon components manufacturing
as part of the national effort to produce the atomic bomb. Between 1950 and 1963, large quantities of elemental mercury
were used at Y-12 during lithium isotope separation pilot studies and subsequent production processes in support of
thermonuclear weapons programs.
Characterization - Soils in the Y-12 facility are contaminated with mercury in many areas. One of the areas of known high
levels of mercury in soils is in the vicinity of the "Old Mercury Recovery Building." Atthis location mercury was recovered
by first "roasting" and then vaporizing. Mercury contamination also occurs in the sediments of the UEFPC. Recent
investigations show thatbank soils containing mercury along this reach of stream were eroding and contributing to mercury
loading; stabilization of the bank soils along this reach of the creek was recently completed. Additional information on soil
and sediment mercury concentrations, based upon historical data are presented in Tables 1-5 and 1-6.
1.3.1.3 Confidential Manufacturing Site
A confidential manufacturing site con tains elemental mercury, mercury amalgams, and mercury oxide in shallow sediments
(less than 0.3 meters deep) and deeper soils (3.65 to 9.14 meters below surface). This site provided soil with
concentrations across the desired contaminant range. The POC is Jim Rawe of SAIC.
10
-------
Table 1-5. Y-12 Site Mercury Concentrations in Surface and Subsurface Soil at Building 8110.
Boring/Station ID
Surface interval
Subsurface interval
Surface interval
Subsurface interval
Surface interval
Subsurface interval
Surface interval
Subsurface interval
Surface interval
Subsurface interval
Surface interval
Subsurface interval
Surface interval
Subsurface interval
Surface interval
Subsurface interval
Surface interval
Subsurface interval
Surface interval
Subsurface interval
Depth Interval (feet bis)
0-5
5-10
—
4-6
0-1
1-3
0-0.3
3.0-4.0
0-1.5
10.5-11.0
—
6.0-6.3
—
5.0-6.0
0-2
2.0-4.0
2.0-4.0
5.0-5.8
—
4.0-6.0
Concentration (mg/kg)
144
48
—
303
100
25
30
1,436
21
1,040
—
44
—
135
134
199
39
84
—
20
1 Source: Rothchild et al., 1984. Note: a dashed line indicated no sample collected/no data.
bis - below land surface
Table 1 -6. Mercury Concentrations (mg/kg) in Sediments - Upper East Fork of Poplar Creek at Y-121
STATION ID
LR-1 UEFPC-1 UEFPC-2 UEFPC-3
Parameter
UEFPC-4
UEFPC-5
Elemental Mercury
Methylmercury
Mercuric sulfide
Total mercury
8.32
0.0632
7.82
140
6.37
0.00326
2.45
14.1
5.26
0.0514
6.18
125
30.1
0.0225
1.46
38.7
29.7
0.019
3.41
51
28.5
0.0142
4.08
38.7
1 Source: DOE, 1998
Site Location and History - A confidential east coast manufacturing site was selected for participation in this
Demonstration. The site had three operations that resulted in mercury contamination. The first operation involved
amalgamation of zinc with mercury. The second process was the manufacturing of zinc oxide. The final operation was
the reclamation of silver and gold from mercury-bearing materials in a retort furnace. Operations led to the dispersal of
elemental mercury, mercury compounds such as chlorides and oxides, and zinc-mercury amalgams.
Characterization - Mercury values range from as low as 0.05 mg/kg to over 5,000 mg/kg with average values of
approximately 100 mg/kg. Mercury can be found in soils at depths ranging from surface levels to approximately 9.14 m
11
-------
below ground surface. Additional details about the historical distribution and concentration of mercury at this site are
provided in Table 1-7.
Table 1-7. Mercury in Subsurface Soils at the Confidential Manufacturing Site.1
DEPTH
INTERVAL
(feet bis)
12-13
14-15
16-17
18-19
20-21
22-23
24-25
26-27
28-29
30-31
A
<0.56
<0.56
<0.55
<0.59
<0.53
<0.62
<0.59
<0.66
<0.18
<0.5
B
8.7
43
117
0.16
61.2
0.4
5.4
2.2
1
0.092
SAMPLE LOCATIONS/ (Concentrations in mg/kg)
C D E F G
68.2
7.6
0.8
0.62
0.13
0.34
0.066
< 0.047
0.67
< 0.059
1,910
114
1.5
0.11
116
10.1
3.7
2.6
1.7
0.89
1.3
3
4.9
19.5
28.8
0.66
3.7
0.15
21.4
< 0.059
21.8
339
244
2,260
342
2.1
180
0.091
2.4
43.9
418
557
494
1,549
349
4,060
30.4
7.1
8.5
3.2
H
11.7
8
14.9
9.3
5.3
81.5
3.7
16.3
42.8
42.8
1
<0.06
17.1
1.3
9.9
2,300
580
—
—
—
—
1 Source: From Confidential Monitoring Site, 2000 (Received from on-site representative). A dashed line indicates no result available for that
interval.
1.3.1.4 Puget Sound
The Puget Sound site consists of offshore sediments contaminated with mercury, polynuclear aromatic hydrocarbons, and
phenolic compounds. The particulararea of the site used for this Pre-demonstration (and Demonstration) activity consists
of the Georgia Pacific, Inc. Log Pond in Bellingham Bay, Washington. SAIC is currently performing a SITE remedial
technology evaluation in the Puget Sound. As part of ongoing work at that site, SAIC collected additional sediment for use
during this M MT project. This site will be used to provide sediment in several concentration ranges. Joe Evans of SAIC
is the primary POC for the Puget Sound site.
Site Location and History - The Georgia Pacific Log Pond is located within the Whatcom Waterway in Bellingham Bay,
a well-established heavy industrial land use area with a maritime shoreline designation. Log Pond sediments measure
approximately 1.52 to 1.82 m thick, and contain various contaminants including mercury, phenols, PAHs, polychlorinated
biphenyls and wood debris. The area was capped in late 2000 and early 2001 with an average of seven feet of clean
capping material as part of a Model Toxics Control Act interim cleanup action. The total thickness ranges from
approximately 0.15 m along the site perimeter to 3 m within the interior of the project area. The restoration project
produced 2.7 acres of shallow sub-tidal and 2.9 acres of low intertidal habitat, all of which had previously exceeded the
Sediment Management Standards cleanup criteria (Anchor, 2001).
Characterization -Total PAHs rangefrom 50 to 1200 mg/kg, and detected phenolic compounds (phenol, 4-methylphenol,
and 2,4-dimethylphenol) range from 350 to 670 ug/kg. Mercury concentrations range from 0.16 to 400 mg/kg (dry wt.).
The majority (98%) of the mercury detected in nearshore ground waters and sediments of the Log Pond is believed to be
comprise of complexed divalent (Hg ++) forms such as mercuricsulfide (Bothner,etal., 1980, ENSR, 1994, cited in Anchor,
2000). Zinc is also present in 18 of 27 samples at concentrations greater than 200 mg/kg. Additional information about
the distribution and concentration of mercury collected as part of a pre-demonstration effort conducted in May, 2002 is
presented in Table 1-8.
12
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Table 1-8. Mercury in Selected Test Plot Core Locations - Puget Sound (Sampled in May 2002).
Horizon Sampled '
Cap Sediments (top)
Cap Sediments (top)
"Contaminated
"Contaminated
"Contaminated
"Contaminated
"Contaminated
"Contaminated
Layer"
Layer"
Layer"
Layer"
Layer"
Layer"
(middle)
(middle)
(middle)
(middle)
(middle)
(middle)
Native Sediments (bottom)
Native Sediments (bottom)
Core Sample ID
PD-T3-00.0-1 .3-S
PD-T5-0-2.3-S
PD-T1-1.
PD-T2-0
PD-T3-1
PD-T4-1.
PD-T5-2
.2-10.0
.8-6.8
.3-7.6
1-6.25-A
.3-6.8
PD-T6B-3. 5-7.0
PD-T3-7.6-9.7-N
PD-T6B-7. 0-9.1
Core Depth Interval
(meters)
0.0-
0 -
0.
0.
0.
0.
0.
1.
2.
2.
,36
,02
,39
,33
,70
,06
,31
13
-0.39
0.70
-3,
-2
- 2
- 1
-2
-2
- 2
- 2
.04
.07
.31
.90
.07
.13
.95
.77
Mercury Level
(mg/kg-dry wt.)
0.28
3.87
192
98.3
112
118
46.4
74.7
0.16
0.46
1 Three horizons were sampled. Cap sediments are 0.8-2.3 feet thick medium sand. "Contaminated layer" sediments are 1.37 -
2.68 meters thick clayey or sandy silt containing wood debris. Bottom native sediments are moderately stiff, silty, medium-to-
fine sands with scattered shell and plant (twig) pieces.
1.3.2 Site Sampling Activities
Sampling activities for each of the four sites are summarized in the following subchapters. At each site, the soil and/or
sediment was collected, homogenized by hand in the field, and sub-sampled forquick-turn around analysis. These sub-
samples were sent to analytical laboratories to determine the general range of mercury concentrations at each of the four
sites. In addition, at each site, soil and/or sediment samples were shipped to SAIC's GeoMechanics Laboratory for
additional sample homogenization (as described in Subchapter 1.3.3 and Appendix A) and sub-sampling for use during
the Pre-demonstration. For each sample point, the geographical positioning system coordinates or the latitude and
longitude position was collected and recorded.
1.3.2.1 Carson River Mercury Site
Sixteen near-surface soil samples were collected between 2.54 cm and 7.62 cm below ground surface. Two sediment
samples were collected at the water-to-sediment interface. All eighteen samples were collected on September 23, 2002
with a hand shovel. Samples were collected in Six Mile Canyon and along the Carson River.
The sampling sites were selected based upon historical data from the site. Specific sampling locations in the Six Mile
Canyon were selected based upon local terrain and visible soil conditions (e.g., color and particle size). The specific sites
were selected to obtain soil samples with as much variety in mercury concentration as possible. These sites included hills,
run-off pathways, and dry riverbed areas. Sampling locations along the Carson River were selected based upon historical
mine locations, local terrain, and river flow.
When collecting the soil samples, approximately 2.54 cm of surface soil was scraped to the side. The sample was then
collected with a shovel, screened through a 6.3 millimeter (mm) (0.25-inch) sieve to remove larger material, and collected
in 4.54 liter (L) scalable bags identified with a permanent marker. The sediment samples were collected with a shovel,
screened through a 6.3 mm sieve to remove larger material, and collected in 4.54 L scalable bags identified with a
permanent marker. Each of the 4.54 L scalable bags was placed into a second 4.54 L scalable bag, and the sample label
was placed onto the outside bag. The sediment samples were then placed into 11.36 L buckets, lidded, and labeled with
a sample label.
1.3.2.2 Y-12 National Security Complex
Two matrices were sampled at Y-12 in Oak Ridge, TN; 1) creek sediment and 2) soil. A total of 10 sediment samples were
collected; one sediment sample was collected from the Lower East Fork of Poplar Creek (LEFPC) and 9 sediment samples
13
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were collected from the UEFPC. A total of 6 soil samples were collected from the Building 8110 area. The sampling
procedures used are summarized below.
Creek Sediments - Creek sediments were collected on September 24-25, 2002 from the East Fork of Poplar Creek.
Sediment samples were collected from various locations in a downstream to upstream sequence (i.e., the downstream
LEFPC sample was collected first and the most upstream point of the UEFPC was sampled last). The sediment samples
from Poplar Creek were collected using the following procedure:
• A commercially available clam-shell sonar dredge attached to a rope was slowly lowered to the creek bottom
surface, where it was pushed into the sediment by foot. Several drops (usually 7 or more) of the sampler were
made to collect enough material for screening. On some occasions, a shovel was used to remove overlying
"hardpan" gravel to expose finer sediments at depth. Also, one sample consisted of creek bank sediments, which
was collected using a stainless steel trowel.
• The collected sediment material was then poured onto a 6.3 mm sieve to remove material larger than 6.3 m m in
diameter. Sieved samples were then placed in 13.63 L scalable plastic buckets. The sediment samples in these
buckets were homogenized as well as possible with a plastic ladle.
Soil - Soil samples were collected from pre-selected boring locations on September 25, 2002 and sent for quick laboratory
analysis in order to verify the presence of mercury prior to homogenization for the demonstration. All samples were
collected in the immediate vicinity of Building 8110 using a commercially available bucket auger. Oversize material was
hand picked from the excavated soil because the soil was too wet to be passed through a sieve. The screened soil was
transferred to an aluminum pan, homogenized by hand, and sub-sampled to a 20 milliliter (ml_) vial. The remaining soil
was transferred to 4.54 L plastic containers.
1.3.2.3 Confidential Manufacturing Facility
Eleven subsurface soils were collected on September 24. All samples were collected with a Geoprobe® unit using plastic
sleeves. Samples were collected in the former Plant # 2 area.
Drilling locations were determined based on historical data provided by the site. The intention was to gather soil samples
across a range of concentrations. Because the surface soils were relatively clean fill, the sampling device was pushed
to a depth of 3.65 m using a blank rod. Samples were then collected at pre-selected depths ranging from 3.65 to 8.53 m
below the surface. Individual cores were 1.21 m long. The plastic sleeve for each 1.21 m core was marked with a
permanent marker; the depth interval and the bottom of each core was marked. The filled plastic tubes were transferred
to a staging table where appropriate depth intervals were selected for mixing. Selected tubes were cut into 0.6 m intervals,
which were emptied into a plastic container for pre-mixing soils. When feasible, soils were initially screened to remove
materials larger than 6.3 mm in diameter. In many cases, soils were too wet and clayey to allow screen ing; in these cases,
the soil was broken into pieces by hand and using a wooden spatula, oversize materials were removed. These soils
(screened or hand-sorted) were then mixed until the soil appeared visually uniform in color and texture. The mixed soil
was then placed into a 4.54 L sample containerforeach chosen sample interval. This process was then repeated for each
subsequent sample interval.
1.3.2.4 Puget Sound
Sediment samples collected on August 20 and 21 from the Georgia-Pacific Log Pond in Puget Sound were obtained
beneath approximately 3.04 to 6.09 m of water using a vibra-coring system capable of capturing cores to one foot below
the proposed dredging prism. The vibra-corer consisted of a core barrel attached to a power head. Aluminum core tubes,
equipped with a stainless steel "eggshell" core catcher to retain material, were inserted in the core barrel. The vibra-core
was lowered into position on the bottom and advanced to the appropriate sampling depth. Once sampling was completed,
the vibra-core was retrieved and the core liner removed from the core barrel. The core sample was examined at each end
to verify that sufficient sediment was retained for the particular sample. The condition and quantity of material within the
core was then inspected to determine acceptability.
To verify whether an acceptable core sample was collected the following criteria had to be met:
target penetration depth (i.e., into native material) was achieved;
sediment recovery of at least 65% of the penetration depth must be achieved to deem the core acceptable; and
sample appears undisturbed and intact without any evidence of obstruction or blocking within the core tube or core
catcher.
14
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The percent sediment recovery was determined by dividing the length of material recovered by the depth of core
penetration below the mud line. If the sample was deemed acceptable, overlying water was siphoned from the top of the
core tube, and each end of the tube capped and sealed with duct tape. Following core collection, representative samples
were collected from each core section representing a different vertical horizon. Sediment was collected from the center
of the core that had not been smeared by, or in contact with, the core tube. The volumes removed were placed in a
decontaminated stainless steel bowl or pan, and mixed until homogenous in texture and color (approximately 2 minutes).
After all sediment for a vertical horizon composite was collected and homogenized, representative aliquots were placed
in the appropriate pre-cleaned sample containers for analysis. Samples of both the sediment and the underlying native
material were collected in a similar manner. Distinct layers of sediment and native mate rial we re easily recognizable within
each core. Once the samples were collected and homogenized in the field, they were sent to the SAIC GeoMechanics
Laboratory for additional homogenization and sub-sampling. At that point, sub-samples were sent from the SAIC
GeoMechanics Laboratory to one of the pre-selected analytical laboratories for a quick-turnaround analysis.
1.3.3 Soil and Sediment Homogenization
One of the objectives of the Pre-demonstration activities was to plan, implement, and evaluate the procedure by which the
samples collected from the various sites and locations were homogenized and prepared for distribution to the parties
involved in the Pre-demonstration. To ensure comparability between vendor results and the referee laboratory results,
it is necessary to have a homogenous matrix, such that, all sub-samples have consistent mercury concentrations. It is
not necessary, however, that the homogenized sample accurately reflects the actual concentration of mercury at a given
location. The Pre-demonstration activities included the analysis of samples selected to adequately test the comparability
of multiple sub-samples.
During the Pre-demonstration, eight homogenized samples were prepared - two from each of the four sites from which
samples were collected. Three of the samples were prepared using the "slurry" homogenization procedure and the other
five were prepared using the "dry" homogenization protocol (see Appendix A). Each homogenized batch had enough
sample material to fill vials for distribution to the vendors (one sample each) and the candidate laboratories (each sample
was sent as blind triplicates to each of the three labs used during the Pre-demonstration). As discussed in the following
subchapter, results from the sample aliquots (sub-samples) collected from each of the homogenized batches indicated
that the dry and slurry protocols were suitable for the purposes of the Demonstration, with an average relative standard
deviation (RSD) of 13% for all 24 triplicates analyzed (8 samples in triplicate by each of the three labs).
1.3.4 Pre-Demonstration Results
As noted earlier, there were six objectives associated with Pre-demonstration activities (SAIC, 2002). The results
supporting the achievement of each of these objectives are discussed below.
Pre-Demonstration Objective No. 1 - Establish Concentration Ranges for Testing Vendor Analytical Equipment
During the Demonstration: Based upon the results of the homogenized soil and sediment samples analyzed by the
candidate laboratories, the following concentration ranges were established for samples to be analyzed during the
Demonstration:
Low Concentration Range = ~ 1 ug/kg to ~ 100 ug/kg
Mid Concentration Range = -100 ug/kg to ~ 10 mg/kg
High Concentration Range = ~ 10 mg/kg to ~ 1,000 mg/kg
These concentration ranges reflect the target ranges of each of the vendor technologies, the concentrations expected
based on the samples collected from each of the site locations, and the need to present samples that will challenge both
the field and laboratory methods on both the high and low end of the method limitations.
Pre-Demonstration Objective No. 2 - Evaluate Sample Homogenization Procedures: Based upon the results of
triplicate analyses performed by the candidate laboratories, it was determined that the homogenization procedure was
effective and adequate for sample preparation during the Demonstration. The average RSD for all field sample triplicates
averaged between 11.8 and 14.9% at each of the three candidate laboratories, thereby meeting established criteria for
the Pre-demonstration Plan. Similarly, SRM samples were analyzed in triplicate at each of the laboratories with average
RSDs for these samples ranging from 6.1 to 1 3.3 percent.
The RSD results were used to further evaluate the homogenization procedure by assessing if each homogenized sample
triplicate set had an RSD of <25%. A single sample set at two of the candidate laboratories had an RSD that slightly
15
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exceeded this value; one sample triplicate at one of the labs had an RSD of 27.4% and one triplicate at another lab had
an RSD of 30.5%. In both cases the remaining two laboratories had RSDs between 12.0% and 17.5%, within acceptable
limits. The individual sample RSDs indicate that additional replicates should be performed during the Demonstration in
orderto reduce average variability in samples thatare more difficultto homogenize. These Pre-demonstration results were
also used to statistically determine the number of replicates needed during the Demonstration as discussed in detail in
Chapter 3.
Pre-Demonstration Objective No.3 - Determine Mercury Concentrations in Homogenized Soils and Sediments:
Based upon the results of the triplicate analyses performed by the candidate laboratories, the mercury concentrations in
the homogenized soils and sediments collected at the fourselected field sites were determined as presented in Table 1-9.
The sample concentrations from all sites ranged from approximately 0.18 to 993 mg/kg mercury.
Table 1-9. Pre-Demonstration Analytical Results from Candidate Laboratories
Field Site/
Sample ID
Puget Sound
MFA-P-P-1-XXX
MFA-P-P-2-XXX
Carson River
MFA-P-C-3-XXX
MFA-P-C-4-XXX
Manufacturing Facility
MFA-P-M-5-XXX
MFA-P-M-6-XXX
Oak Ridge Y-1 2 Plant
MFA-P-Y-7-XXX
MFA-P-Y-8-XXX
SRM
MFA-P-S-9-XXX
MFA-P-S-10-XXX
Mercury Concentrations (mg/kg)
Minimum
0.25
140
120
0.18
26
420
7.7
120
0.056
62
Maximum
0.445
260
180
0.43
50
993
13
210
0.092
99
Average
0.33
220
160
0.31
40
675
9.7
163
0.079
78
Percent Solids
Average
99.1
33.67
97.03
99.17
98.07
99.2
65.97
61.7
97.6
99.1
Pre-Demonstration Objective No. 4 - Select a Reference Method and Qualify Potential Referee Laboratories for
the Demonstration'. Based on the dynamic range of the method, types of mercury included in the analysis, and the fact
that the method was a widely-used protocol, SW-846 Method 7471 B (analysis of mercury in solid samples by cold-vapor,
AA spectrometry) was selected as the reference method. This conclusion was also supported by information obtained
from the technology vendors, as well as the expected contaminant types and soil/sediment mercury concentrations
expected in the test matrices.
Nine laboratories were sent a Statement of Work (SOW) for the analysis of mercury during the Pre-demonstration. Seven
laboratories responded to the SOW with appropriate bids. (Two laboratories chose not to bid.) Three of the seven
laboratories were selected as candidate laboratories based upon technical merit, experience, and pricing. The three
candidate laboratories were sent ten samples in triplicate for a total of 30 analyses. Eight of the samples were the
homogenized field samples and two were SRM samples. (See information presented in the previous subchapter.) Each
of the laboratories reported results that were within the 95 percent Prediction Interval (PI). (Measurements should fall
within the PI range 1 9 of 20 times.)
16
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The referee laboratory, to be used for the Demonstration, was selected from one of the three candidate laboratories based
upon the laboratory's interest in continuing into the Demonstration, the laboratory reported SRM results, the laboratory
method detection and quantitation limit, the precision of the laboratory calibration curve, and cost. The data packages
provided by the laboratories were reviewed and a pre-award audit was performed in order to determine final laboratory
selection. This is explained in detail in Chapter 5.
Pre-Demonstration Objective No. 5 - Collect and Characterize Soil and Sediment Samples That Will be Used in
the Demonstration: Soil and sediment samples were collected from four different sites: Puget Sound, Washington;
Carson River Area, Nevada; Oak Ridge, Tennessee; and a Manufacturing Facility on the East Coast. These samples were
characterized as non-homogenous grab samples to determine mercury concentration ranges for subsequent homogenous
samples to be created and used during the Demonstration.
Pre-Demonstration Objective No. 6 - Provide Soil and Sediment Matrices to the Vendors for Self-Evaluation:
Vendors were sent homogenized field samples and SRMs for purposes of a self evaluation. Eight vendors participated
in the Pre-Demonstration. Each of the vendors was senttwo homogenized samples from each of the foursampling sites.
(Two of the homogenized samples were sent to the vendors in triplicate.) The vendors were also sent the SRM samples;
however, the concentration of one of the SRMs was below the detection limit for several of the vendors. These vendors
were, therefore, sent a duplicate of one of the homogenized samples. This resulted in each of the vendors receiving 14
samples. Laboratory results were then sent to the vendors after analysis in order to enable them to perform a self-
evaluation by comparing their results to the laboratory results. Immediately following the Pre-demonstration, two of the
vendors chose to drop out of the Demonstration. An additional vendor chose to drop out about one month prior to the
demonstration thereby leaving 5 vendors participating.
Lessons Learned: In addition to planned objectives, there were several lessons learned as a result of Pre-Demonstration
activities. These included issues related to the slurry sample preparation and custody seals.
Slurry Samples: Several of the sediment samples had standing water upon collection. These samples were shipped to
theSAICGeoMechanics Laboratory with standing water, and the homogenized sub-samples were sent to the vendors with
standing water. The standing water presented a problem with several of the vendors. First, the bottles were sufficiently
full as to prevent mixing of the samples without causing some spillage. Second, the method of collecting aliquots from
the samples with standing water was not consistent between all vendors and laboratories. Therefore, the slurry samples
prepared for the Demonstration will have the standing water removed by the SAIC GeoMechanics Laboratory.
The procedure used by the referee laboratory to collect aliquots from the sample jars is included as Appendix B of this
QAPP.
Custody Seals: Each sample bottle shipped to the laboratories and vendors had a custody seal on the lid. Some of the
sample codes on the labels were damaged by the custody seals. Therefore, during the Demonstration, a method of
ensuring the custody of samples, without applying seals directly to each bottle, will be employed. The method will likely
require placing the bottles into a secondary container and placing the custody seal onto that container.
1.4 Project Objectives
In accordance with QAPP Requirements for Applied Research Projects (EPA, 1998), the technical project objectives of
this Demonstration are categorized as primary and secondary. Critical data support primary objectives, and non-critical
data support secondary objectives.
1.4.1 Primary Objectives
The primary objectives for the Demonstration of the individual field measurement devices are summarized below and
described in more detail in Subchapter 3.2.1:
Primary Objective # 1. Determine the sensitivity of each field instrument with respect to the Method Detection Limit
(MDL) and Practical Quantitation Limits (PQL) generated by each vendor.
Primary Objective #2. Determine the potential analytical accuracy associated with the field measurement technologies.
Primary Objective # 3. Evaluate the precision of the field measurement technologies.
Primary Objective # 4. Measure the amount of time required for performing five functions related to mercury
measurements: 1) mobilization and setup; 2) initial calibration; 3) daily calibration; 4)
demobilization; and 5) sample analysis.
17
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Primary Objective # 5. Estimate the costs associated with mercury measurements for the following four categories: 1)
capital; 2) labor; 3) supplies; and 4) investigation-derived waste (IDW).
1.4.2 Secondary Objectives
The secondary objectives for the Demonstration of the individual field measurement devices are summarized below and
described in more detail in Subchapter 3.3:
Secondary Objective # 1.
Secondary Objective # 2.
Secondary Objective # 3.
Secondary Objective # 4.
Document the ease of use, as well as the skills and training required to properly operate
the device.
Document potential health and safety concerns associated with operating the device.
Document the portability of the device.
Evaluate the durability of the device based on its materials of construction and
engineering design.
Secondary Objective # 5. Document the availability of the device and spare parts.
18
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Chapter 2
Project Organization
2.1 General Responsibilities
This chapteridentifies the participants in the Field Analysis of Mercury in Soil and Sediment Demonstration and delineates
the responsibilities of each participant. The organizational structure of this project is described below and illustrated in
Figure 2-1.
2.1.1 EPA
The EPA NERLTOM, Dr. Stephen Billets, is responsible for all aspects of the Demonstration, including budget, scheduling,
technical performance, data quality and quality assurance, overall health and safety, hazardous waste disposal, and report
preparation. He is the primary EPA POC with the analytical vendors whose equipment is being evaluated during the
Demonstration. He is also the primary EPA POC with each of the sites from which soils and sediments to be used during
the Demonstration were collected. Finally, he is responsible for managing the efforts of the contractor, SAIC, in this effort.
George Brilis is the EPA NERL Quality Assurance (QA) Manager with responsibility for overseeing project data quality.
He will independently evaluate the quality of all data gathered during this project and review of the Field Demonstration's
QAPP and Innovative Technology Verification Reports (ITVR).
Ann Vega is the EPA National Risk Management Research Laboratory/ Land Remediation and Pollution Control Division
QA Manager responsible for QA oversight of the SITE Program. She will also be responsible for QA review and
endorsement of the Field Demonstration's QAPP and ITVR.
2.1.2 DOE
Elizabeth Phillips is the DOE POC for the Demonstration, which is planned to take place atthe DOE's ORNL in Oak Ridge,
Tennessee. Ms. Phillips is providing assistance to Dr. Billets and Mr. Nicklas on a variety of Demonstration logistical
issues, including site access, site facilities for the Demonstration participants, and hazardous waste staging on site.
2.1.3 Tennessee Department of Environment and Conservation
Dale Rector is the Tennessee Department of Environment and Conservation (TDEC), Department of Energy Oversight
Division POC for the Demonstration. Mr. Rector is providing assistance to Dr. Billets and Mr. Nicklas on a variety of
Demonstration logistical issues, including visitor access to the Demonstration.
2.1.4 SAIC
SAIC is the prime contractor for this Technical Directive and is responsible for implementing the Pre-demonstration and
Demonstration phases of this project. SAIC will provide the necessary staff, equipment, and fixed facilities to perform all
aspects of the Pre-demonstration and Demonstration. John Nicklas is SAIC's TOM; as such, he is responsible for all
facets of this project, including budgeting, scheduling, subcontracting sampling and analytical services, coordinating with
and providing oversight of vendors, coordinating with site contacts to obtain samples, and overseeing staff technical
performance, health and safety, and report preparation. Mr. Nicklas will be supported by the following project staff:
19
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JimRawe, Joe Tillman, John King, Mike Bolen, Allen Motley, and Andy Matuson. They are responsible for overseeing
vendor activities during the MMT Demonstration, collecting and interpreting data, and preparing draft and final reports.
Joe Evans, SAIC's QA Manager for the contract, will oversee overall data quality by reviewing the Demonstration Plan,
overseeing selection of the referee laboratory, performing field and laboratory assessments and audits, and reviewing draft
and final reports. He will establish data quality objectives for the project and review analytical data to evaluate whether
these objectives were met. He will provide project QA oversight and assist in report preparation, including a discussion
of project data quality. He is independent of SAIC "line management," as noted in Figure 2-1.
Fernando Padilla is responsible for the health and safety of SAIC personnel. He will develop a health and safety plan to
ensure personnel safety during all aspects of the Demonstration. He will establish, as necessary, site-specific health and
safety monitoring parameters and appropriate safety limits.
Sara Hartwell, Rita Schmon-Stasik, Maurice Owens, and Herb Skovronek will serve as technical advisors. Ms. Hartwell
will assist in the selection of appropriate analytical methods. Ms. Schmon-Stasik will assist in establishing data quality
objectives, author chapters of the Demonstration Plan, assist with method and laboratory selection, and provide general
technical assistance to the SAIC TOM. Mr. Owens will identify the statistical requirements and perform the statistical
evaluation for the Demonstration. Dr. Skovronek will provide and coordinate peer review for the project.
Nancy Patti and Mark Pruitt will provide the necessary facilities and direct soil and sediment homogenization, along with
sample splitting and aliquoting. Ms. Patti developed the sample preparation (homogenization, splitting, and aliquoting)
procedure included in this plan. She will ultimately prepare and distribute the soil and sediment samples for analyses by
the vendors and the analytical laboratories.
Finally, Mr. W. Kevin Jago of the SAIC, Oak Ridge office will serve as a local liaison between SAIC and DOE and as a
POC for Demonstration sample receipt.
2.1.5 Referee Laboratory
The referee laboratory is Analytical Laboratory Services, Inc. (ALSI). ALSI is responsible for analyzing and reporting data
for all demonstration samples, plus any additional quality control samples required by this plan. Mr. Ray Martrano is the
laboratory manager and is responsible for all phases of ALSI's involvement in this project.
2.1.6 Vendors
A total of five vendors are participating in this Demonstration. Table 2-1 lists these five vendors. The table also identifies
the type of instrument to be utilized, and summarizes the purpose and application of the instruments.
Vendors will be responsible for reviewing and endorsing this plan prior to the Demonstration. They will be responsible for
supplying all necessary information regarding their respective technologies. The vendors will also be responsible for
performing the type and number of analyses specified in this plan, including quality control samples, and promptly reporting
those results to SAIC.
2.2 Contact Information
Table 2-2 lists the Demonstration project participants and corresponding contact information for each.
20
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EPA NERL QA
Manager
George Brilis
EPA NRMRL QA
Manager
Ann Vega
EPA Task Order
Manager
Dr. Stephen Billets
— = Reporting Line
---- = Communication Line
i Demonstration Site
j (ORNL) Contact
Elizabeth Phillips
(DOE Environmental POC)
Dale Rector
(TDEC)
W. Kevin Jago
(SAIC - Oak Ridge)
Field Measurement
Device Vendors
Metorex
John Patterson
Milestone
Mikhail Mensh
NITON Corporation
Volker Thomsen
Ohio Lumex
Joseph Siperstein
MTI, Inc.
Fe/ecia Owen
SAIC QA Manager
Joe Evans
SAIC Task Order
Manager
John Nicklas
ALSI Laboratory
Manager
Ray Martrano
SAIC Technical
Advisors
Sara Hartwell
Rita Schmon-Stasik
Maurice Owens
Herb Skovronek
SAIC Project Health &
Safety Manager
Fernando Padilla, CIH
SAIC Staff
Jim Rawe
Joe Tillman
John King
Mike Bo/en
Andy Matuson
Allen Motley
L
SAIC
GeoMechanics
Laboratory
Nancy Patti
Mark Pruitt
Figure 2-1. Organizational Chart
21
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Table 2-1. Vendors Selected for the Mercury Field Analysis Demonstration.
Company
Technical Name
Principle of Operation
Design Application/
Description
Applicable Media
Metorex
Milestone Inc.
NITON LLC
Ohio LumexCo.
MTI, Inc.
X-Ray Fluorescence
Direct Mercury
Analyzer (DMA-80)
XL-700 Series
Multi-Element
Analyzer
Portable Mercury
Analyzer Lumex RA
915
Portable Digital
Voltammeter 500
Energy Dispersive X-Ray
Fluorescence
Method 7473 - Thermal
Decomposition,
Amalgamation, Atomic
Absorption
X-Ray Fluorescence
Atomic Absorption
Spectrometry, Thermal
Decompostion Attachment
RP91C
Anodic Stripping Voltammetry
Energy Dispersive X-Ray
Fluorescence technology.
Designed for matrix independent
analysis of a broad range of solid
and liquid samples.
Portable, multi-element testing for
on-site metal contamination.
Direct, fast, and precise
measurements of mercury.
Designed for on-site analysis.
Sediment and soil
samples
Solid and liquid
samples (matrix
independent)
Soil, sediment, air
filter, and thin-film
samples
Air, liquid, soil, and
sediment samples
Sediment and soil
samples
22
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Table 2-2. Demonstration Contact List.
Name
Organization/Role
Address
Phone/Fax
E-mail
EPA
Steve Billets
George Brilis
Ann Vega
EPA-NERL/ESD
TOM
EPA-NERL/
ESD QA Manager
EPA-NRMRL/
LRPCD QA
Manager
P.O. Box 93478
Las Vegas, NV 89193-3478
P.O. Box 93478
Las Vegas, NV 89193-3478
26 W. Martin Luther King Dr.
Cincinnati, OH 45268
P - 702-798-2232
P- 702-798-3 128
P- 51 3-569-7635
billets.stephen@epa.gov
brilis.george@epa.gov
vega.ann@epa.gov
DOE
Elizabeth
Phillips
Roger Jenkins
DOE Environmental
POC
UT-Battelle/ORNL
Oak Ridge Operations Office
Oak Ridge, TN 37831
One Bethel Valley Rd.
Oak Ridge, TN 37831
P- 865-241 -6 172
P - 865-574-4871
phillipsec@oro.doe.gov
jenkinsra@ornl.gov
TDEC
Dale Rector
TDEC POC
761 Emery Valley Road
Oak Ridge, TN 37830
P- 865-481 -0995
dale.rector@state.tn.us
SAIC
John Nicklas
Mike Bolen
Joe Evans
Sara Hartwell
W. Kevin Jago
John King
Andy Matuson
Allen Motley
Maurice Owens
Fernando
Padilla
Nancy Patti
Mark Pruitt
SAIC TOM
SAIC Observer
SAIC QA Manager
SAIC Technical
Advisor
SAIC Oak Ridge
Support
SAIC Observer
SAIC Observer
SAIC ORNL
Support
SAIC Statistician
SAIC Project H&S
Manager
SAIC
GeoMechanics Lab
Manager
SAIC
GeoMechanics Lab
Technician
950 Energy Dr.
Idaho Falls, ID 83401
411 Hackensack Ave., 3rd Floor
Hackensack, NJ 07601
950 Energy Dr.
Idaho Falls, ID 83401
11251 Roger Bacon Dr. MS R-1-7
Reston, VA 20190
151 Lafayette Dr.
Oak Ridge, TN 37831
411 Hackensack Ave., 3rd Floor
Hackensack, NJ 07601
411 Hackensack Ave., 3rd Floor
Hackensack, NJ 07601
151 Lafayette Drive
Oak Ridge, TN 37831
11251 Roger Bacon Dr.
Mail Stop R-2-2
Reston, VA 20190
11251 Roger Bacon Dr. MS R1-5
Reston, VA 20190
595 E. Brooks Ave., Suite 301
North Las Vegas, NV 89030
3960 Howard Hughes Pkwy.
Ste 200, Las Vegas, NV 89109
P- 208-528-21 10
F- 208-528-2 197
P- 20 1-498-7335
F- 20 1-489- 1592
P- 208-528-2 168
F- 208-528-2 197
P - 703-318-4662
F- 703-31 8-4682
P- 61 5-481 -4600
P- 20 1-498-7333
F- 20 1-489- 1592
P- 20 1-498-7343
F- 20 1-489- 1592
P- 865-481 -4607
F- 865-48 1-4757
P- 703-318-4513
F- 703-709- 1041
P - 703-318-4573
F- 703-736-09 15
P - 702-739-7376
F - 702-739-7479
P - 702-739-7376
F - 702-739-7479
john.h.nicklas@saic.com
michael.m.bolen@saic.com
joseph.d.evans@saic.com
sara.w.hartwell@saic.com
jagow@saic.com
john.j.king@saic.com
andrew.f.matuson@saic.com
c.allen.motley@saic.com
maurice.e.owens.iii@saic.com
fernando.d.padilla@saic.com
nancy.c.patti@saic.com
NA
23
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Table 2-2 (Cont'd). Demonstration Contact List.
SAIC (Cont'd)
Rita Schmon -
Stasik
Herb Skovronek
JoeTillman
SAIC Chemist
SAIC Peer Review
Coordinator
SAIC Observer
41 1 Hackensack Ave., 3rd Floor
Hackensack, NJ 07601
41 1 Hackensack Ave., 3rd Floor
Hackensack, NJ 07601
2260 Park Ave., Suite 402
Cincinnati, OH 45206
P- 20 1-498-8426
F- 20 1-489- 1592
P- 20 1-498-7345
F- 20 1-489- 1592
P- 51 3-569-5869
F- 51 3-569-5864
rita.m.schmon-stasik@saic.com
herbert.s.skovronek@saic.com
joseph.w.tillman@saic.com
REFEREE LABORATORY
Ray Martrano
ALSI Manager
34 Dogwood Lane
Middletown, PA 17057
P- 71 7-944-5541
F- 71 7-944-1 430
rmartrano@analyticallab.com
VENDORS
Mikhail Mensh
Felecia Owen
John I.H.
Patterson
Joseph
Siperstein
Volker
Thomsen
Milestone
MTI, Inc.
Metorex, Inc.
Ohio LumexCo.
NITON Corporation
160B Shelton Road
Monroe, CT 06468
1609 Ebb Drive
Wilmington, NC 28409
Princeton Crossroads Corp.
Center
250 Phillips Blvd., Ste. 250
Ewing, NJ 08618
9263 Ravenna Road, Unit A-3
Twinsburg, OH 44087
900 Middlesex Turnpike, Bldg. 8
Billerica, MA01821
P- 203-261 -61 75
F- 203-26 1-6592
P- 91 0-392-57 14
F- 91 0-392-4320
P - 609-406-9000
F - 609-530-9055
C - 330^05-0837
P- 888-8 76-26 11
F - 330-405-0847
P- 800-8 75- 1578
F - 978-670-7430
support@milestonesci.com
fowen@owenscientific.com
john.patterson@metorexusa.com
siperst@yahoo.com
vthomsen@niton.com
24
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Chapter 3
Experimental Approach
This Demonstration consists of the independent evaluation of five different field technologies for the determination of
mercury in soil and sediment. Environmental samples from various locations, comprising different matrices and containing
varying mercury concentrations, will be analyzed by each field technology vendor, as well as a referee laboratory
performing the reference method selected. Specially prepared spiked samples using HgCI2 will be included as an
additional reference material. Spikes will be prepared from environmental matrices and concentrations determined in
replicate by the referee laboratory for comparison to vendor results. Certified SRM swill also be analyzed to further assess
performance. This section describes the experimental approach for evaluating the field mercury measurement
technologies. It details the preparation and selection of the environmental samples and the SRMs, as well as the test
design for the Demonstration(Subchapter3.1). Subchapter 3.2 presents the project objectives along with the methodology
and statistical approach for evaluating each primary objective. Subchapter 3.3 presents the secondary objectives along
with the evaluation mechanism.
3.1 Experimental Design
The evaluation of the five technology vendors will be conducted at the ORNL site over a 4-day period, during which it is
expected that each vendorwill analyze 150 to 200 samples. All technologies will be independently evaluated as per the
technical project objectives discussed in detail below. The mechanism for evaluating the field technologies centers around
obtaining homogeneous environmental, SRM, and spiked samples with challenging levels of mercury concentrations, to
be analyzed by each of the vendors. All samples will be provided to the vendors and the referee laboratory according to
a blind code that provides only basic information as to the matrix of the sample (based on the site from which it was
collected).
It is important to the equitable evaluation of all technologies, that the matrix analyzed be the same for all vendors and the
laboratory; therefore the Pre-demonstration included extensive study to design and confirm the suitability of a procedure
for preparing well-mixed, homogeneous samples from the soils and sediments collected from various locations. The
results of the study were discussed in Subchapter 1.3. This homogenization protocol, presented in detail in Appendix A,
will be implemented for all samples prepared for the Demonstration.
3.1.1 Field (Environmental) Sample Selection and Preparation
Test samples were collected and prepared during the Pre-demonstration with the ultimate goal of producing a set of
consistent test soils and sediments to be equally distributed among all participating vendors and the referee laboratory for
analysis during the Demonstration. Samples were collected from different locations at four sites:
Carson River Mercury Site (near Virginia City, NV)
Y-12 National Security Complex (in Oak Ridge, TN)
Manufacturing Facility (Eastern U.S.)
Puget Sound (Bellingham, WA)
The collected matrices, soils and sediment, varied in 1) soil consistency and soil type and 2) mercury contamination levels.
Table 3-1 shows the number of distinct test samples that were collected from each of the four field sites.
25
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Table 3-1. Test Samples Collected from Each of the Four Field Sites.
No. Of Samples / Matrices
Field Site Collected Areas For Collecting Sample Material
Volume Required
Carson River
18 - Soil or Sediment
Tailings Piles (Six mile Canyon)
River Bank Sediments
> 4.54 L each
Oak Ridge
(Y-12)
Manufacturing Site
Puget Sound
10 Sediment
6 Soil
11 Soil
4 Sediment
Poplar Creek Sediments
Old Mercury Recovery Bldg. Soils
Subsurface Soils
High Level Mercury (below cap)
Low Level Mercury (native
material)
-13.63 L each for sediment;
> 4.54 L each for soil
>4.54 L each
-13.63 Leach
>4.54 L each
From these samples, those with mercury concentrations falling within three broad ranges were selected and will be
prepared for distribution to the vendors. Samples will be homogenized using the same protocol as was used during the
Pre-demonstration, with the removal of standing water from the slurry samples. Based on information provided about the
technologies, the ranges include low-level concentrations (1-100 ug/kg), mid-level (100 ug/kg - 10 mg/kg) and high-level
mercury contamination (10 - 1000 mg/kg). Table 3-2 summarizes the contaminant range each vendor is expected to
analyze and indicates the approximate concentration of mercury in the majority of the samples each vendor will receive.
Table 3-2. Field Sample Contaminant Ranges for Vendor Technologies.
Contaminant Range of the Majority of the Samples to be Analyzed
Vendor Technology Low (1-100 ug/kg) Medium (100 ug/kg-10 mg/kg) High (10-1000 mg/kg)
Metorex X
Milestone X X
NITON X
Ohio Lumex X X
MTI, Inc. X X
Each vendor will receive 150 - 200 samples, in replicates of up to seven. Field samples will be provided to each vendor
from a variety of sites, such that, a majority of the samples have concentrations within the range of the vendor's
technology. Some sam pies will have expected concentrations at or below the estimated level of detection for each of the
vendor instruments. These samples are designed to evaluate the reported MDL and PQL, and also to assess the
prevalence of false positives. Field samples distributed to each vendorwill include sediments and soils prepared by both
the slurry and dry homogenization procedures. Samples will be submitted to the vendorand the referee laboratory using
a "blind code"; the site of collection will be identified but no other information regarding expected concentration or replicate
status will necessarily be provided. This blind code will be known only by the SAIC TOM, SAIC QA Manager, and the SAIC
GeoMechanics Laboratory Manager. Selected field samples will also be spiked with aqueous HgCI2 to generate samples
with additional concentrations.
3.1.2 SRM Sample Selection
Certified SRM swill be analyzed by both the vendors and the referee laboratory. These samples are homogenized matrices
which have a known amount of mercury. Concentrations are certified values, as provided by the supplier, based on
independent confirmation via multiple analysis of multiple lots and/or multiple analyses by different laboratories (i.e., round
robin testing). These analytical results are then used to determine a "true" value, as well as a statistically derived interval
(a 95% confidence interval) that provides a range within which the true value is expected to fall.
The SRMs selected are designed to encompass the same contaminant ranges indicated previously: low-, medium- and
high-level mercury concentrations. In addition, SRMs of varying matrices will be included in the Demonstration to
26
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challenge the vendor technologies as well as the referee laboratory. The referee laboratory will analyze all SRMs. All SRM
samples will be submitted using a "blind code"; the site of collection will be identified but no other information regarding
expected concentration or replicate status will necessarily be provided. SRMs will be intermingled with site location
samples, labeled in the same manner as field samples.
3.1.3 Spiked Samples
Spike samples will be prepared by the SAIC GeoMechanics Laboratory. Aqueous HgCI2 will be used in order to evenly
distribute the contaminant in a slurry matrix. Spikes will be prepared using environmental samples from one or more of
the selected sites. Additional information will be gained by preparing spikes at concentrations not previously obtainable.
Similar to sample results , the laboratory results will be considered the "true" value and vendor results will be compared
to the reference laboratory values. The SAIC GeoMechanics Laboratory ability to prepare spikes will be tested prior to
the demonstration and evaluated in order to determine expected variability and accuracy of the spiked sample. This will
be included in a special report, supplemental to the demonstration.
3.1.4 Vendor Testing
Upon arrival at the ORNL site, vendors will set up their measurement devices, at the direction and oversight of SAIC, and
prepare to begin testing the Demonstration samples. At the start of the Demonstration, vendors will be provided with a
cooler of samples: each sample identified with a blind code. Samples will be identified with respect to the site from which
they were collected, since in any field application the location and general type of the samples would be known. It will not
be obvious what samples are replicates, nor will SRM samples be distinguished from field samples. Each vendor will be
responsible for analyzing all samples provided, performing any dilutions or reanalyses needed, calibrating the instrument
if applicable, performing any maintenance necessary, and reporting all results. Samples will be provided to each vendor
in accordance with procedures outlined in Chapter 4.
3.1.5 Independent Laboratory Confirmation
All samples, field, SRMs, and spikes will be analyzed atthe referee laboratory at the same replicate frequency. Therefore,
the laboratory will analyze significantly more samples than anyone individual vendor. Atthe same time the fie Id analyses
begin, sample coolers will be shipped from the SAIC GeoMechanics Laboratory to the referee laboratory. The samples
will all be identified in the same way, and all samples will be labeled according to the "blind code." All sample analysis
at the referee lab will be in accordance with SW-846 Method 7471B. The referee laboratory's standard operating
procedure (SOP) is included in Appendix B.
3.1.6 Schedule
Table 3-3 presents the tentative schedule for field Demonstration activities.
3.2 Primary Project Objectives
This section details the project objectives and the method of measuring or evaluating each of those objectives. In
accordance with QAPP Requirements for Applied Research Projects (EPA, 1998), the technical project objectives of this
Demonstration are categorized as primary and secondary. Critical data support primary objectives, and non-critical data
support secondary objectives. Section 3.2.1 discusses in detail the five primary objectives that were introduced in Section
1.4.1. Section 3.2.2 describes how these objectives will be evaluated and the statistical approach to be used.
3.2.1 Statement of Primary Objectives
3.2.1.1 Primary Objective #1: Sensitivity
Sensitivity is the ability of a method or instrument to discriminate between small differences in analyte concentration. (EPA,
2002). It can be discussed in terms of M DLs or instrument detection limits as well as PQLs. Detection limit (DL) involves
the ability ofthe instrument and/ormethod to confidently determine the difference between a sample thatdoes contain the
27
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Table 3-3. Projected Field Measurement Demonstration Schedule.
Activity Date
Final Demonstration Plan to EPA December 20, 2002
Comments due from EPA on final Demonstration Plan January 3, 2003
Demonstration Plan approved/endorsed by EPA February 11, 2003
SAIC arrives at ORNL site to prepare sample bottles for distribution May 1, 2003
Vendors arrive on site to begin set-up May 5, 2003
Samples arrive at referee laboratory May 2, 2003
Vendors receive first batch of samples; field measurements begin May 5, 2003
Field testing concludes, vendors demobilize and leave site May 9, 2003
First of five ITVRs submitted to EPA June 30, 2003
Fifth ITVR submitted September 1, 2003
EPA approval of final ITVR September 30, 2003
SAIC submits Demonstration Summary Report October 27, 2003
analyte (mercury) of interest at a low concentration and a sample that does not. The DL is generally considered to be the
minimum true concentration ofan analyte producing a non-zero signal that can bedistinguished from the signals generated
when no concentration of the analyte is present, with an adequate degree of certainty. For this project, a primary project
objective will be to assess the sensitivity of each field technology with respect to the MDL and PQL generated by each
vendor.
Table 3-4 presents the expected MDLs for each measurement device based on data provided by the developers. These
are estimates but will be used to determine the standards needed in order to verify actual MDLs during the demonstration.
The reference method MDL will be verified by the referee laboratory. The PQL of the referee laboratory is the lowest
concentration calibration standard. This low standard is 10 ug/kg based upon Pre-demonstration results. SAIC will
document exactly which calibration options are used by each vendor during the demonstration. The actual concentration
of the lowest calibration standard for any of the vendors is estimated around 10 ug/kg but may be lower. In the event that
the vendor is able to measure lower concentrations for samples or SRMs below 10 ug/kg, the selected referee laboratory
(ALSI) has confirmed that it too can calibrate it's instrument using a lower calibration curve to achieve quantitation limits
that are up to 100 times lower than the 10 ug/kg standard noted above. This was verified as part of the Pre-demonstration
audit. In the eventthatthis becomes necessary, re-analysis of these low concentration samples will be performed byALSI
using it's lower calibration curve.
Table 3-4. Estimated Sensitivities for Each Field Measurement Device.
Vendor / Referee Laboratory Expected , units
Metorex 10 mg/kg
Milestone Inc. 8 ug/kg
NITON Corporation 20 mg/kg
Ohio LumexCo. 10 ug/kg
MTI, Inc. 100 ug/kg
Referee Laboratory (ALSI) Method SW-846 7471B: 10 ug/kg
28
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3.2.1.2 Primary Objective #2: Accuracy
The second primary objective of this Demonstration is to determine the potential analytical accuracy associated with the
field measurement technologies. For the purposes of this project, accuracy will be assessed by field measurements made
by the vendors and compared to the measurements made by the referee laboratory. In addition, accuracy will be assessed
by comparison to the certified result for the SRM and by spike samples prepared by the SAIC GeoMechanics laboratory.
Each of these assessments will be discussed separately in the final report. SRMs provide very tight statistical comparisons
but do not provide all associated matrices nor all ranges of concentrations. The spike samples prepared by the SAIC
GeoMechanics Laboratory, using previously collected environmental samples as well as including these same previously
collected samples without spikes, will ensure a more complete comparison. Concentration ranges for each vendor are
based upon information provided by the vendor and appropriate samples will be included to test different concentrations
(low, medium, and high) within the vendors predicted range of operation.
3.2.1.3 Primary Objective #3: Precision
The experimental design for this Demonstration includes a mechanism to evaluate the precision of the field measurement
technologies. Each homogenized sample prepared from the soils and sediments collected previously will be analyzed as
(blind) replicate samples by each technology vendor as well as the referee laboratory. These replicate sample results will
be used to calculate an RSD for each method, including the reference method. Average field method RSD values will be
compared to the reference method for an assessment of precision.
3.2.1.4 Primary Objective #4: Time per Analysis
The amount of time required for performing the analysis will be measured and reported in five categories: mobilization
and set-up, initial calibration, daily calibration, demobilization, and sample analyses. Mobilization and set-up are the time
it takes to unpack and prepare the instrument for operation. Initial calibration is the time it takes to perform the vendor
recommended on-site calibrations. Daily calibration is the vendor-recommended calibrations performed on subsequent
field days, but this may be the same as the initial calibration, a reduced calibration, or none. Demobilization is the time
it takes to tear down the instrument and package it for shipment. Sample analysis includes the preparation, measurement,
and calculation of demonstration samples and necessary quality control (QC) samples performed by the vendor.
3.2.1.5 Primary Objective #5: Cost
To estimate the cost associated with mercury measurements, the following four cost categories will be considered: 1)
capital; 2) labor; 3) supplies; and 4) IDW. The calculated costs will not be compared among the vendors, nor will they be
compared with the reference laboratory.
3.2.2 Statistical Approach and Evaluation of Primary Objectives
The following paragraphs discuss how each of the primary objectives will be evaluated for this Demonstration. Primary
objectives have been previously stated and are the criteria by which the individual field technologies will be evaluated.
Specifically these include sensitivity, precision, accuracy, time peranalysis, and cost. Sensitivity, precision, and accuracy
all require additional explanation in terms of the experimental design and the descriptive statistics that will be used as the
tools for evaluation. The purpose of this section is to describe the approach and subsequent evaluation of these objectives.
It should be noted, however, that while possible statistical tests that will be used for data interpretation have been
presented, exact statistical tests will be determined at the end of the Demonstration based upon actual results.
3.2.2.1 Sensitivity
Two separate and distinct sensitivity parameters are included for evaluation. MDL is the more common sensitivity
evaluation. The purpose of this measurement is to determine the level at which an individual field instrument will be able
to detect a minimum concentration that is statistically different from instrument background or noise. Guidance for the
definition of the MDL is provided in EPA G-5i (EPA, 2002). The evaluation of MDL requires seven different measurements
of a low concentration standard or sample. Following procedures established in 40 CFR Part 136 for water matrices, the
Demonstration MDL definition will be as follows:
MDL = t(n-1, 0.99)3
29
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where:
t(n-i,o.99) = 99'h percentile of the t-distribution with (-1) degrees of freedom
n = number of measurements
s = standard deviation of replicate measurements
The PQL is another important measure of sensitivity. This is defined in EPA G-5i as the lowest level at which the
instrument is capable of producing a result that has significance in terms of precision and bias. It is usually considered
the lowest standard on the instrument calibration curve. It is often 5 to 10 times higherthan the MDL, depending upon the
analyte, the instrument being used, and the method for analysis. The PQL measurement is often much more meaningful
than the M DL because it defines a specific concentration with an associated level of accuracy.
The PQL will be defined by each vendor calibration curve. Once the vendor has determined the level of it's low calibration
standard (this method will be discussed in the final report), the evaluation will include a determination of the percent
difference (%D) between the calculated value and true value. [The true value in this case is the value defined by the
reference laboratory for samples or spikes, or the certified value provided by the supplier in the case of standard reference
materials (SRMs).] For example, if the low point of the calibration curve (the concentration which defines the PQL) is
thought to be 1 mg/kg, then a %D will be calculated by using the reported value of the low standard versus its true value.
Therefore, if the reported value is 1.15 mg/kg and the true value is 1 mg/kg, then the %D would be 15%. The equation
for the %D calculation is included below:
%D =
C - C
'true "calculated
Ctrue
100
where
Ctme = true concentration as determined from the calibration curve
^calculated = calculated test sample concentration
The % D will be reported for each individual vendor. The associated PQL for the reference method, along with the %D
for the referee laboratory, will be reported for purposes of comparison. There is no statistical comparison between these
two values but only a descriptive comparison for purposes of this evaluation. (The %D requirement for the referee
laboratory has been previously defined as 10% or less. The expected reference method PQL is approximately 10 ug/kg.)
3.2.2.2 Accuracy
Accuracy is the instrument measurement compared to a standard or true value. For purposes of this Demonstration, three
separate standards will be used. The primary standard will be SRMs. These will be obtained from reputable suppliers
with reported concentrations and associated 95% confidence intervals. All SRMs will be analyzed by the referee
laboratory, and selected SRMs will be analyzed by each vendor based upon instrument capabilities and concentrations
of SRMs that can be obtained. Therefore, not all vendors will analyze all SRMs. SRMs will cover an appropriate range
for each vendor. Replicate SRMs will be analyzed by each vendor and by the laboratory.
The second accuracy determination will be a comparison of vendor results for field samples to the referee laboratory
results. These will be used to ensure that "real-world" samples are tested foreach vendor. The referee laboratory result
will be considered the standard for comparison to each vendor.
The third measure of accuracy will be spiked field samples. These will be analyzed by the vendors and the laboratory in
replicate in order to provide additional measurement comparisons to a known or laboratory defined "true" value. Spikes
will be prepared to cover additional concentrations not available from SRMs or environmental samples. The accuracy
comparison is explained in more detail later in this discussion.
The intention of the following discussion is to provide examples of how accuracy evaluations will be performed. There will
likely be several ways to perform accuracy comparisons. Statistical evaluations will be determined once the data has been
reviewed with the project statistician. In consultation with the project manager and QA manager the project statistician
will determine several possible means of evaluation based upon reported data or results.
30
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The purpose for SRM analysis by the referee laboratory is to provide a check on laboratory accuracy. During the
Pre-demonstration, the referee laboratory was chosen, in part, based upon the analysis of SRMs. This was done in order
to assure that a competent laboratory would be used for the Demonstration. Because of the need to provide confidence
in laboratory analysis during the Demonstration, the referee laboratory will analyze SRMs as an on-going check on
laboratory bias.
The Pre-demonstration laboratory evaluation was conducted to help ensure that laboratory SRM data would fall within
expected ranges. It is possible that during the Demonstration the laboratory may fail to fall within the expected
concentration ranges for a particular SRM. In the event that this occurs, laboratory corrective action will include a check
of their calibration and calibration criteria for that particular run. If this is found to fall outside pre-specified ranges then
the laboratory will be asked to recalibrate and rerun the appropriate SRM. The second set of data will then likely confirm
that the laboratory is within compliance.
If, however, this is not the case and laboratory calibration criteria are satisfied, then SAIC will have the laboratory perform
two more sets of analysis for the SRM in question. Therefore there will be a total of three separate sets of data for the
SRM in question. Based upon these three sets of data it will be determined either that the initial SRM set of results is in
error or that perhaps the SRM concentration reported by the respective manufacturer is in error. (This could occur as a
result of the sample preparation process.) With this information SAIC and the EPA Project Manager will make a decision
as to whether this SRM should be used for evaluation or whether the laboratory result should be used instead of the
manufacturer reported result.
Evaluation of vendor and laboratory analysis of SRMs will be performed in several different fashions. Accuracy will be
reported by noting the average concentration of the analyzed sample by the vendor and laboratory compared to the 95%
two-tailed confidence interval for the SRM. (95% confidence intervals around the true value are provided by the SRM
supplier.) This will be reported for individual sample concentrations and average concentrations of replicate
measurements made at the same concentration.
Two-tailed confidence intervals are computed as follows:
Z±t(n-1, 0.975)
where:
f(n-i, 0.975) = 97.5th percentile of the t-distribution with (n-1) degrees of the freedom
n = number of measurements
s = sample standard deviation of replicate measurements
The number of SRM results for the vendor's analytical instrumentation and the referee laboratory that are within the
associated 95% confidence interval will be evaluated. For example, the referee laboratory may be within this confidence
interval 95% of the time (i.e., 5% or more of the time, values may fall outside this interval simply because of statistical
uncertainty). The vendor results may only be within this window 50% of the time, depending upon actual instrument
conditions. If vendor results are outside this window more then 10% of the time, for example, then it might be assumed
that instrument bias for that particular vendor may be an issue, but this is not strong evidence for such a prediction
considering the statistical uncertainty associated with the 95% confidence interval. If a vendor is outside this window 30%
of the time or even 50% of the time as noted above, then this is stronger evidence of vendor bias and therefore the vendor
result may be off-set from the true value and accuracy may be considered as questionable.
Another measure of accuracy that may be determined for SRMs might be a frequency distribution that would show the
percentage of measurements within, for example, a 30% window of a reported concentration, within a 50% window, and
outside a 50% window of a reported concentration. This could be reported as average concentrations of replicate results
from the vendor for a particular concentration and matrix compared to the same collected sample from the laboratory.
These are descriptive statistics and are used to better describe comparisons, but are not intended as inferential tests.
In addition, sample results from environmental and spiked samples for the vendor compared to the referee laboratory will
be used as another accuracy check. Vendor sample results for a given field sample will be compared to the 90%
confidence interval for the replicates analyzed by the laboratory for the same field sample. Average comparisons for a
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specific matrix or concentration will be made in order to provide additional information on that matrix or concentration.
Comparison to laboratory values will be similar to the comparisons noted above for SRMs. Comparisons will be made
using average concentrations in order to eliminate measurement variability.
Accuracy is a combined measure of bias plus precision or variability. Replicate analyses at a specified concentration can
be used to determine average concentrations and a 90% confidence interval. A 90% confidence interval will be used for
replicate measurements made by the referee laboratory on environmental samples compared to vendor results. Using
the Student's t-test, a comparison between vendor results and SRMs can be performed to determine if sample populations
are significantly different. This will also be performed for referee laboratory results for the collected samples compared
to vendor results for these same samples.
If sample populations overlap, then results will not be considered as significantly different. If sample populations do not
overlap, then sample results will be considered as significantly different at a 0.1 level of significance. Because this test
does not separate precision from bias, if a vendor's computed confidence interval was extremely wide due to a highly
variable result (indication of poor precision), the two confidence intervals may overlap and, therefore, there may be no
significant difference between the two results. This test could then give the false impression that vendor results were
"better" because populations would not be significantly different. Therefore, this resultwould need to be reported in such
a fashion stating that vendor results are overlapping the 90% confidence interval because of poor precision. If such a case
were to occur, it may be best not to report the result of this test. For this reason, precise statistical determinations on how
to interpret results cannot be made at this time.
3.2.2.3 Precision
Precision is usually thought of as repeatability of a specific measurement. Precision is often reported as RSD. RSD is
computed from a specified number of replicates. The more re plications of a measurement the more confidence associated
with a reported RSD. Replication of a measurement may be as few as 3 separate measurements to 30 or more
measurements of the same sample, depending upon the degree of confidence desired in the specified result. In addition,
the precision of an analytical instrument may vary depending upon the matrix being measured, the concentration of the
analyte, and whether the measurement is made for an SRM or a field sample. The purpose of this evaluation is to
determine the field instrument's capability to precisely measure analyte concentrations under real-life conditions.
Instrument repeatability will, therefore, be measured using collected samples from each of four different sites.
As noted previously, precision - or an instrument's capability to replicate a measurement - may be dependent upon matrix
and concentration. Samples from four different sites have been obtained for evaluating each vendor's instrument. Within
each site there may be two separate matrices, soil and sediment. (Not all sites have both soil and sediment matrices, nor
are there all concentrations for each matrix.) Concentrations for purposes of this demonstration have been determined
only as low, medium, or high. Ranges of test samples (environmental, SRMs, and spikes) have been selected to cover
the appropriate analytical ranges of each vendor's instrumentation. Because the vendors have different working ranges,
not all vendors will analyze the same samples. Specific concentrations of test samples are not included in the QAPP
because of the necessity to ensure that this evaluation remains unbiased and that no vendor has an advantage in
performing the analyses by knowing in advance approximate sample concentrations. Not all vendors are capable of
measuring similar concentrations. Some instruments are better at measuring low concentrations and others are geared
toward higher concentration samples or have other attributes such as cost orease of use that define theirspecialty. Each
vendorwill be tested with samples from different sites, different matrices when possible (as noted above depending upon
available concentrations), and different concentrations (high, medium, and low) using a variety of samples. Sample
concentrations for an individual instrument will be chosen based upon vendor attributes in terms of expected low, medium,
and high concentrations that the particular instrument is capable of measuring.
The referee laboratory will measure replicates of all samples. This will be used for purposes of precision comparisons
to the individual vendor. RSD for the vendor and the laboratory will be calculated individually in the following manner:
S
%RSD = —x 100
C"
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Where:
S = standard deviation of replicate results
x =mean value of replicate results
A descriptive determination for differences between a vendor RSD and referee laboratory RSD will be determined. (Note
that no attempt will be made to com pa re different vendors. The purpose of this Demonstration is to evaluate each vendor's
instrumentation compared to standard laboratory procedures.) In addition, an overall average RSD will be calculated for
all measurements made by the vendor and the laboratory. RSD comparisons are descriptive between the vendor and
laboratory and will be compared accordingly.
Other statistical comparisons may be used depending upon actual Demonstration results. The statistics noted above
assume normality. If results are determined to be log-normal, alternate statistical determinations will be considered. In
addition, replicate measurements for SRMs will also be performed, therefore, RSDs for these measurements may be
useful but will not be the primary measurement for determination of precision.
3.2.2.4 Time Per Analysis
The time per analysis will be determined by dividing the total amount of time required to analyze the 1 50 to 200 samples
by the number of analyses. In the numerator, sample analysis will include preparation, measurement, and calculation of
Demonstration samples and necessary QC samples performed by the vendor. In the denominator, the total number of
analyses will include only Demonstration samples, not QC analyses or re-analyses of samples.
Downtime that is required or occurs between each sample as a part of operation and handling will be considered a part
of the sample analysis time. Downtime that occurs due to instrument breakage or unexpected maintenance will not be
counted in the assessment, but will be noted in the final reportas an additional time. Any downtime caused by instrument
saturation or memory effect will be addressed based upon its frequency and impact on the analysis.
Any unique time measurements will be addressed in the final report. For example, if soil samples are analyzed directly,
and sediment samples require 2 hours of drying time before the analyses starts, then the state men twill be made that soil
samples can be analyzed in X hours, and thatsediment samples require 2 hours of drying before analyses can be started.
Recorded times will be rounded to the nearest 15-minute interval. It should also be noted that the number of developer
personnel used will be noted and factored into the cost calculations in Section 3.2.5. No comparison will be made among
various vendors, or between a vendor and the applicable referee laboratory.
3.2.2.5 Cosf
A summary of the costs that will be estimated for each measurement device is provided below:
The capital cost will be estimated based on published price lists for purchasing, renting, or leasing each field
measurement device. If the device is purchased, the capital cost will include no salvage value for the device after
work is completed.
The labor cost will be estimated for each field measurement device based on the number of people required to
analyze samples during the Demonstration. The laborrate will be based on a standard hourly rate for a technician
or other appropriate operator. During the Demonstration, the skill level required will be confirmed based on input
from each vendor regarding the operation of its device to produce mercury concentration results, and based on
observations made by SAIC. The labor costs will be based on: 1) the actual number of hours required to complete
all analyses, quality assurance, and reporting; and 2) the assumption that a technician who has worked for a
portion of a day would be paid for an entire 8-hour day.
The cost of supplies will be estimated for each device based on any supplies required to analyze the field and
SRM samples during the Demonstration. Supplies will include items not included in the capital category, such as,
a balance, extraction solvent, glassware, pipettes, spatulas, agitators, and similar materials. SAIC will note the
type and quantity of all supplies brought to the field and willdocument allsupplies used during the Demonstration.
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If a vendor typically provides all supplies to a user, the vendor's costs will be used to estimate the cost of supplies.
If the supplies required to analyze field samples are covered by the purchase cost, this cost will not be broken out
separately as part of the cost of supplies. However, the costs of any additional supplies required for analysis of
field and SRM samples will be included in the cost of supplies. If a vendor provides supplies as part of a refill kit,
the cost for the number of kits required to analyze all of the Demonstration samples will be included in the cost
of supplies. If a vendor creates refill kits specific to a user's needs, the associated cost of supplies will be based
on the cost of the refill kits that the developer uses during the Demonstration. Unless a vendor allows a user to
return unused portions of a refill kit, the cost of supplies will be estimated under the assumption that no salvage
value is associated with unused refill kit supplies. If unused supplies can be returned to a vendor, the quantities
of unused supplies will be noted during the Demonstration, and the appropriate credit will be applied to the cost
of supplies minus any restocking charge.
If a vendor typically does not provide all required supplies to a user, SAIC will estimate the cost of supplies using
independent vendor quotes. SAIC will note the identification numbers and manufacturers of supplies used by the
developer during the Demonstration and will attempt to obtain pricing information for these supplies. If the costs
of the supplies are not available, SAIC will use the prices of comparable supplies to estimate the cost of supplies.
If unused supplies can be returned to a vendor or manufacturer, the quantities of unused supplies will be noted
during the Demonstration and the appropriate credit will be applied to the cost of supplies minus any restocking
charge.
All maintenance and repair costs during the demonstration will be documented or provided by each vendor.
Equipment costs will be estimated based on this information and standard cost analysis guidelines for the SITE
Program.
The IDW disposal cost will be estimated for each device. Each vendor will be provided with one or more 90.91
L laboratory pack containers for disposal of hazardous wastes, as required. IDW generated may include
decontamination fluids and equipment, spent solvents and/or acids, unused chemicals that cannot be returned
to the vendor or an independent supplier, mercury-contaminated soil and sediment samples, and soil and
sediment extracts. Contaminated personal protective equipment (PPE) normally used in the laboratory will also
be placed into a separate container. The disposal costs for these laboratory packs will be included in the overall
analytical costs for each vendor.
The cost per analysis will be estimated for the field measurement devices based on the number of analyses
performed. However, as the number of samples analyzed increases, the initial capital costs and certain other
costs would be distributed across a greater number of samples. Therefore, the unit costs would decrease. For
this reason, two costs will be reported. The initial capital costs and the operating costs per analyses will be
reported. A comparison to the referee laboratory's method costs will not be made. A generic cost comparison
to data gathered from several different laboratories will be made to better provide a standard of comparison.
Additional explanation regarding this cost comparison will be made in the final report.
3.3 Secondary Objectives
Secondary objectives will be evaluated based on observations made by SAIC during the Demonstration. Because of the
number of vendors involved, SAIC's three technology observers will be required to make simultaneous observations of
one or two vendors each during the Demonstration. (There will be a total of five vendors therefore one observer will only
oversee one vendor and the other two observers will each oversee two vendors.) Four procedures will be implemented
to ensure that these subjective observations made by the observers are as consistent as possible. First, forms have been
developed for each of the five secondary objectives. These forms will assist in standardizing the observations. Secondly,
the observers will meet each day before the evaluation begins, at significant break periods, and after each day of work to
discuss and compare observations regarding each device. Thirdly, a fourth SAIC observer will be assigned to
independently evaluate only the secondary objectives; this will ensure that a consistent approach is applied in evaluating
these objectives. Finally, the SAIC TOM and QA Manager will circulate among the evaluation staff during the
Demonstration to ensure that a consistent approach is being followed by all personnel. The individual approaches for
addressing these five secondary objectives are discussed in the following subsections. It should be noted that the tables
included in this section are provided to show what observations or measurements will be made for each objective.
However, during the Demonstration, these tables will be combined into a single table to minimize redundancy and to
present observation categories in a sequential fashion, making the job of the observer easier. Therefore the forms
presented in this section are not intended as the final forms to be used but are only examples.
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3.3.1 Secondary Objective #1: Ease of Use
The skills and training required for proper device operation will be noted; these will include any degrees or specialized
training required by the operators. This information will be gathered by interviews of the operators. The number of
operators required will also be noted. The ease of use will also be evaluated by subjective observations on the ease of
use of the equipment and major peripherals required to measure mercury concentrations in soils and sediments. If
available, the operating procedure will be evaluated to determine if itis easy to use and understandable. It should be noted
that if the equipment is only provided with a trained operator, this objective will not apply to that vendor unit. Table 3-5
summarizes the observations that will be made in support of this objective.
Table 3-5. Example Ease of Use Form.
Vendor Name: Date:
Equipment Name/Type: Observer
Signature:
Model No.:
Number of Operators Operator Names
Degrees/Training:
Standard Operating Used?
Procedure Available:
(Yes or no) Easy to Use?
Comments:
3.3.2 Secondary Objective #2: Health and Safety Concerns
Health and safety concerns associated with device operation will be noted during the Demonstration. Criterion will include
hazardous materials used, the frequency and likelihood of potential exposures, and any direct exposures observed during
the Demonstration. In addition, any potential for exposure to mercury during sample digestion and analysis will be
evaluated based upon equipment design. Basic electrical and mechanical hazards will also be noted, as well as any other
health and safety concerns. Equipment certifications, such as Underwriters Laboratory, will be documented. Table 3-6
summarizes the observations that will be made in support of the evaluation of this objective.
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Table 3-6. Example Health and Safety Concerns Form.
Vendor Name: Date:
Equipment Name/ Type: Observer
Signature:
Model No.: Serial No.:
Certifications (e.g., UL):
Chemical Used: Exposure:
Potential Mercury
Exposure:
Mechanical Hazards:
Comments on Health
and Safety Concerns:
3.3.3 Secondary Objective #3: Portability of the Device
The portability of each device will be evaluated by observing transport, measuring setup and teardown time, determining
the size and weight of the unit and peripherals, and evaluating the ease with which the instrument is repackaged for
movement to another location. The use of battery power or the need for an AC outlet will also be noted. Table 3-7 lists
the criteria that will be used to evaluate instrument portability.
3.3.4 Secondary Objective #4: Instrument Durability
The durability of each device will be assessed by noting the materials and quality of construction and major peripherals.
All device failures, routine maintenance, repairs, and downtime will be documented during the Demonstration. No specific
tests will be performed to evaluate durability; rather, subjective observations will be made using Table 3-8 as guidance.
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Table 3-7. Example Portability of the Device Form.
Vendor Name:
Equipment
Name/Type:
Model No.:
Weight:
Time - Setup:
Power Source:
Comments on
Portability:
Date:
Observer
Signature:
Dimensions:
- Tear Down:
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Table 3-8. Example Instrument Durability Form.
Vendor Name: Date:
Equipment Observer
Name/Type: Signature:
Model No.:
Materials of Quality of
Construction: Construction:
Downtime (duration Reason (each
of each event): event):
Maintenance (List Reason:
activity):
Repairs (Identify): Reason:
3.3.5 Secondary Objective #5: Availability of Vendor Instruments and Supplies
The availability of each device will be evaluated by determining whether additional units and spare parts are readily
available from the vendor or retail stores. The developer's office (or a web page) and/or a retail store will be contacted
to identify current supplies of the tested measurement device and spare parts. This portion of the evaluation will be
performed after the field Demonstration, in conjunction with the cost estimate. In addition, if replacement parts or spare
devices are required during the Demonstration, their availability and delivery time will be noted.
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Chapter 4
Demonstration Activities
4.1 Preparation of Test Material
This chapter details the sample preparation, containerization, preservation, custody, shipping, and archiving procedures
that will be used for all samples prepared for the Demonstration. This includes homogenized field samples and spiked
samples prepared atthe SAIC GeoMechanics Laboratory and SRM samples purchased from commercial providers. Each
of the sample types is discussed separately in the following subchapters.
4.1.1 Homogenized Field Samples and Spikes
Homogenized field samples that are to be used for the Demonstration will be prepared at the SAIC GeoMechanics
Laboratory in Las Vegas, Nevada. (This was the same laboratory used during the Pre-Demonstration.) Currently, there
are more than 50 separate field samples being stored in plastic containers at the SAIC GeoMechanics Laboratory. The
field samples were collected from four different field sites during the Pre-demonstration portion of this project (refer to
Subchapter 1.3).
The field samples collected during the Pre-demonstration sampling events comprise a variety of matrices, ranging from
material having a high clay content to material composed mostly of gravelly, coarse sand. The field samples also differ
with respect to moisture content, since several were collected as wet sediments. The specific sample homogenization
procedure to be used by the SAIC GeoMechanics Laboratory will largely depend on the moisture content and physical
consistency of the sample. A sample homogenization procedure has been developed by the SAIC GeoMechanics
Laboratory, which are: 1) non-slurry type sample homogenization and 2) slurry type sample homogenization. This SOP
is detailed in Appendix A. (This homogenization procedure was tested during the Pre-demonstration and found to be
satisfactory based upon the results of replicate samples.)
Figure 4-1 summarizes the homogenization steps, beginning with sample mixing. Itshould be noted that priorto the mixing
process (i.e., Step 1 in Figure 4-1), all field samples being processed will be inspected to ensure that oversized material
has been removed and that there are no clumps that would hinder homogenization. Non-slurry type samples will be
air-dried in accordance with the procedures in Appendix A so that they can be passed multiple times through a riffle splitter.
Due to their high moisture content, they are not easily air-dried and cannot be passed through a riffle splitter while wet.
Slurries will not be air dried and will bypass the riffle splitting step. The homogenization steps for each type of matrix are
briefly summarized as follows.
Preparing Slurry Matrices
If the sample matrix is a slurry (i.e., wet sediments), the mixing steps will be thorough enough that the sample containers
can be filled directly from the mixing vessel. There will be two separate mixing steps of the slurry-type samples. Slurries
will initially be mixed mechanically within the sample container (i.e., bucket) in which the sample was shipped to the SAIC
GeoMechanics Laboratory. A sub-sample of this pre-mixed sample may be transferred to a second mixing vessel. A
mechanical drill equipped with a paint mixing attachment will be used to mix the sub-sample. As shown in Figure 4-1,
slurry type samples will bypass the sample riffle splitting step. To ensure all contain the same material, the entire set of
containers to be filled will be submerged into the slurry as a group (see Appendix A for details). The filled vials will settle
fora minimum of two days and the standing waterwill be removed using a Pasteur pipette oranotherappropriate device.
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Test Material Mixed
Until Visually Uniform
For Non-slurries
mix manually
For Slurries
a) mix mechanically the entire
sample volume
b) subsample slurry, transfer to
mixing vessel, and mix
mechanically
r
Slurries transferred
directly to 20 ml vials
(vials submerged into slurry)
Non-Slurries to
Riffle Splitter
f2
-\
Combined splits
are reintroduced
into splitter (6 X)
r .Clean;
Container
\
Transfer cut
sections to
20 ml_ vials
T\
TEFLON SURFACE
Elongated
Rectangular Pile
/(from 6"'split)
n\,
Sample allquots made
by transverse cuts
across sample piles
SAMPLES SHIPPED @ 4°C TO
REFEREE LAB & OAK RIDGE
(Container numbers will vary)
Figure 4-1. Test Sample Preparation at the SAIC GeoMechanics Laboratory.
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Preparing "Non-Slurry" Matrices
If the sample matrix is a soil, or sediment having no excess moisture content, the material will be subjected to both a
mixing step (Step 1) and the sample riffle splitting step (Step 2). Prior to these steps the material will be air-dried and
sub-sampled to reduce the volume of material to a size that is easier to handle.
As shown in Figure 4-1 (Step 1), the non-slurry sub-sample will be manually hand-stirred with a spoon or similar equipment
until the mate rial is visually uniform. Immediately following manual mixing, the sub-sample will be mixed and split six times
to homogenize it (Step 2). After the 6th and final split, the sample material will be leveled to form a flattened, elongated
rectangle and cut into traversed sections to fill the containers (Steps 3 and 4). After homogenization, the filled 20-ml
sample vials will be prepared for shipment (Step 5). Details of the entire homogenization procedure are presented in
Appendix A.
Preparing "Spiked" Samples
Spiked samples will be prepared in a similar fashion to slurry samples. If soils are used for spike preparation, then water
will be added to make the soil a slurry. If sediment slurries are used forspikes water may or may notbe added depending
on the consistency of the sediment. Based upon pre-demonstration studies (separate spiking report) a desired consistency
similar to cake batter is needed in order to sufficiently mix the aqueous HgCI2 into the sample. Once mixed, the sample
is air dried and then oven dried for 24 hours to ensure a consistent matrix is achieved. These samples are subsequently
aliquoted and shipped to the respective vendors and laboratory for analysis. A separate spiking report is being prepared
as a supplement to the QAPP describing pre-demonstration spiking studies.
4.1.1.1 Sample Volumes, Containers, Preservation, and Holding Time
A subset from the Pre-demonstration field collected samples will be selected for use in the Demonstration based on their
mercury concentration range and sample type (i.e., sediment vs. soil). Several of these samples will also be spiked using
HgCI2 in an aqueous solution with the soil being spiked in the form of a slurry. The SAIC GeoMechanics Laboratory will
prepare individual batches of field sample material to fill sample containers for a participating vendor. Due to the variability
of vendor instrument measurement ranges for mercury detection, not all vendors will receive samples from the same fie Id
material. The majority of the total vials prepared from each field sample will comprise vials for the five vendors to test
during the Demonstration. A set of vials from each field sample will be shipped to the referee laboratory for mercury
analysis. Another set of vials will be archived at the SAIC GeoMechanics Laboratory as reserve samples. To properly
record and track which field samples have been homogenized and aliquoted, how many vials of each field sample have
been prepared, and where each set of vials was shipped (or archived), the SAIC GeoMechanics Laboratory will prepare
a sample homogenization form. An example of this form is shown as Figure 4-2.
Because of the critical nature of providing blind samples for the vendors, the details describing sample concentration and
replicate samples are not included in the QAPP. It should be noted, however, that the EPA Project Manager was the first
to provide information in terms of the number of samples needed, the expectation associated with concentration range,
and the split between standard reference materials (SRMs), field samples, and spikes. With this information the SAIC
Project Manager has prepared a chart that outlines samples and sample concentrations. Because the concentration
ranges for each vendor are different, not all the same samples will be sent to every vendor. The goal in deciding which
samples to prepare was to ensure there would be adequate coverage of the concentration ranges for each of the vendors
and thatthere would be sufficient numbers of samples to ensure a statistical comparison. The project statistician was also
consulted concerning number of replicates needed at respective concentrations and this information was included in the
decision making process for determination of sample concentrations, types of samples used, and number of samples to
be prepared.
This entire process of choosing appropriate samples and concentrations was determined by the SAIC Project Manager,
the QA Manager, and Assistant Project Manager. Final decisions regarding types, numbers, and sample concentrations
will be made by the EPA Project Manger once it was internally decided upon within SAIC by the personnel noted above.
This information will then be communicated to the SAIC GeoMechanics Laboratory Supervisor for preparation of field
samples and spikes. SRMs will also be ordered, and once they arrive will be prepared by the SAIC Project Manager and
QA Manager at the Idaho Falls Laboratory Facility (STAR Center). Preparation will include aliquoting each SRM into
separate sample vials which are identical in size and coloras the samples prepared by the SAIC GeoMechanics laboratory.
This will ensure that SRMs appear no different from other samples and by preparing these SRMS at the STAR Center
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Project: Field Analysis of Mercury in Soils and Sediments
Sample Homogenization Record Sheet
Sample Location (site name):
As-Received Sample Names Used:
Page of
Type of Homogenization Procedure Used:
Date Lot was Made:
Assigned Lot Number:
Number of Vials Prepared:
Name of Technician:
Sample Received By
Sample Numbers Sent
Figure 4-2. Example Sample Homogenization Form.
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SAIC will ensure that there is no cross contamination from actual samples or spikes which are prepared in Las Vegas.
The form in Figure 4-2 will serve as a record of sample preparation and copies will be kept by the SAIC GeoMechanics
Laboratory, the SAIC Project Manager, and SAIC QA Manager, as appropriate.
Once all containers from a field sample are filled, each container will be labeled and cooled to 4°C. The sample labeling
will consist of an internal code developed by SAIC. This "blind" code may be used throughout the entire Demonstration,
or changed if deemed necessary. The only individuals that will need to know the key coding of the homogenized samples
to the specific field collected samples will be the SAIC TOM, the SAIC GeoMechanics Laboratory Manager, and the SAIC
QA Manager. The label used for the 20-ml vials will contain important sample information (i.e., sample analyses will not
be designated on the label, but will be designated on the Chain-of-Custody (COC) form that will accompany samples
shipped to the referee laboratory). An example label is provided as Figure 4-3.
SAIC GeoMechanics Lab
595 East Brooks Ave., Suite 301
North Las Vegas, NV 89030
Phone (702) 739-7376
Project: Mercury in Soil Tech.
Sample I.D.: MFA-P-M-5-61
Date/Preservation: 1/30/03 / 4°C
Figure 4-3. Example Sample Label.
Mercury analyses will be performed both by the vendors in the field and by the referee laboratory. Minimum sample size
requirements vary from 0.1 g orless (Milestone, 2002 & Ohio Lumex, 2002) to 8-1 0 grams (XRF technologies). Only the
referee laboratory will be analyzing separate sample aliquots for the additional parameters of arsenic, lead, selenium,
silver, copper, zinc, oil & grease, and total organic carbon (TOC). Since the mercury method (SW-846 7471B) being used
by the referee laboratory uses 1 g for analysis, the sample size being collected and sent to all participants (20 ml vials)
will be sufficientfor all analyses. Table 4-1 summarizes the minimum sample volume, container type, preservation, and
holding time requirements for the field samples prepared at the SAIC GeoMechanics Laboratory.
Table 4-1. Sample Volume, Containers, Preservation, and Holding Time Requirements
Parameter Minimum Sample
Size1
Mercury
Oil & Grease
TOC
Ag, As, Cu, Pb, Se, Zn
10g
5g
sg
sg
Container
Glass 20-ml vial
Glass 20-ml vial
Glass 20-ml vial
Glass 20-ml vial
Preservation
Cool to 4° C
Cool to 4° C
Cool to 4° C
Cool to 4° C
Holding Time
28 days
28 days
28 days
6 months
1 Minimum sample size required for laboratory is less than 1 gram for mercury; other parameters require separate
aliquot for laboratory analysis only.
Ag, As, Cu, Pb, Se, and Zn - Silver, Arsenic, Copper, Lead, Selenium and Zinc
C - Celsius
g - gram
ml - milliliter
TOC - Total Organic Carbon
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4.1.1.2 Sample Custody, Shipment, and Archiving
Preparation of the 20-ml sample vials for shipment will be performed in the following manner:
Label bottles with prepared blind coded labels,
Log the "blind coded" sample ID with the actual field sample ID,
Secure labels with clear tape,
Place sample containers in foam or othercompartmentalized vial holders. If foam is not available, bubble-wrap
or wrap with other appropriate material to prepare the vials for shipping,
Add other sample protection material, as needed. Place vial holders or bubble-wrapped vials in freezer bags,
Place vials in cooler with bagged wet ice to maintain sample temperature at 4°C during shipment to the referee
laboratory and to the Oak Ridge office, and
Place an original signed COC form inside the cooler (retain a copy) and apply custody seals to cooler. Sample
custody seals will also be wrapped around each plastic bag inside each cooler containing the foam vial holders.
Each custody seal will be attached in such a manner as to be able to detect unauthorized tampering with samples
after preparation and prior to analysis. The SAIC GeoMechanics Laboratory Manager or the designated alternate
will put his/her initials and the date on each seal.
An example COC form is provided as Figure 4-4. All information on the COC form should be filled out.
Prior to the Demonstration, the appropriate number of samples will be shipped to two destinations: 1) Oak Ridge, TN and
2) the referee laboratory (ALSI). The SAIC Oak Ridge office will serve as the designated shipping receipt location for
Demonstration samples. The sample shipment arriving in Oak Ridge will be retained at all times in custody with SAIC at
the Oak Ridge office until arrival of the Demonstration field crew. The coolers will be re-iced at this location, as needed,
and the internal temperature of each cooler monitored and recorded on the appropriate COC form. Once the
Demonstration crew arrives, the coolers will be retrieved from the SAIC office. The custody seals on the plastic bags inside
the coolerwill only be broken by SAIC personnel. Samples designated for analysis at the referee laboratory will be shipped
by an overnight courier from the SAIC GeoMechanics Laboratory. The shipping addresses and contacts for the SAIC Oak
Ridge office and the referee laboratory (ALSI) are provided in Table 4-2.
4.1.2 SRM Samples
SRM samples containing mercury (only critical contaminant) at different concentrations will be purchased for the
Demonstration to supplement the field sample concentration ranges. SRMs will be purchased as solid matrices (e.g., soil
or sediment) that contain mercury and will be accompanied by certificates of analysis. At a minimum, as discussed earlier
in subchapter3.1.2, low level (1-100 ug/kg Hg), mid-level (100 ug/kg -10 mg/kg), and high level (10-1000 mg/kg)SRMs
will be distributed to the vendors in accordance with the concentration ranges suitable to their technologies.
In order to reduce the risk of sample cross-contamination at the SAIC GeoMechanics Laboratory, the SRMs will be shipped
by one or more providers to the SAIC Idaho Falls office. SAIC will transfer the SRM material from the provider containers
to 20-ml glass vials. Temporary labels will be fixed to the vials. Once all SRM vials are labeled, they will be sent to the
SAIC GeoMechanics Laboratory in Las Vegas, where the SRM vials will be re-labeled with a "blind code" that will render
them indistinguishable from each other and from the field samples. The vials will be cooled to 4°C and shipped to the
SAIC Oak Ridge Office and the referee laboratory intermingled with the field samples.
For each separate concentration, replicate SRM vials will be prepared for each of the five vendors to test during the
Demonstration. Replicate vials of each prepared SRM sample will be shipped to the referee laboratory for mercury
analysis, and at leastone replicate vial of each SRM will be archived at the SAIC GeoMechanics Laboratory as a reserve.
To properly record and track which SRMs have been prepared (i.e., aliquoted to 20-ml vials), and where each set of vials
were shipped (or archived), the SAIC GeoMechanics Laboratory will use the same or a similar form as shown in Figure
4-2.
4.1.2.1 Sample Volumes, Containers, Preservation, and Holding Times
The minimum sample volume, container, preservation, and holding time requirements for SRM samples, that will be
shipped from the SAIC GeoMechanics Laboratory to SAIC - Oak Ridge and the referee laboratory, are described in Table
4-1. The sampling date will be identified as the day the first samples are shipped from the SAIC GeoMechanics
Laboratory.
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i i I l
O Ok- UOZH*—ZUJItM
Figure 4-4. Example Chain-of-Custody Form.
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Table 4-2. Shipping Addresses and Contacts for Demonstration Samples.
OAK RIDGE
REFEREE LABORATORY
Science Applications International Corp.
151 Lafayette Drive
Oak Ridge, TN 37831
Attention: Kevin Jago / Allen Motley
Phone: (865) 481-4614 / Fax: (865) 481-4607
Analytical Laboratory Services, Inc.
34 Dogwood Lane
Middletown, PA 17057
Attention: Ray Martrano
Phone: (717) 944-5541 / Fax: (717) 944-1430
4.1.2.2 Sample Custody, Shipment, and Archiving
Handling and shipment of SRM samples will use coded labels that will mask sample sources. The SRM samples will be
shipped directly from one or more commercial suppliers to the SAIC Idaho Falls Office at the following address:
Science Applications International Corp.
950 Energy Drive
Idaho Falls, ID 83401
Attention: John Nicklas/Joe Evans
Phone/ Fax: (208) 528-2110 / (208) 528-2168
All acquired SRMs will be packaged in containers much larger than vials. Therefore, at the SAIC Idaho Falls office, SRM
samples will be aliquoted into 20-ml glass vials that are consistent with homogenized field samples. The prepared vials
will be shipped at 4°C to the SAIC GeoMechanics Laboratory in Las Vegas at the following address:
SAIC GeoMechanics Laboratory
595 East Brooks Ave., Suite 301
North Las Vegas, NV 89030
Attention: Nancy Patti
Phone: (702) 739-7376
At the SAIC GeoMechanics Laboratory, the SRM samples will be incorporated into the same "blind coding" system used
for the homogenized field samples so that they are indistinguishable from field samples. This process may be done
several days prior to the Demonstration; the SRM vials will be kept at 4°C. SRM samples will be shipped directly from
the SAIC GeoMechanics Laboratory per procedures in Subchapter4.1.1.2.
4.2 Field Analysis by Vendors
This chapter defines the procedures that will be applied by the complete Demonstration team during the field analysis of
samples by vendors at the ORNL facility. This chapter details the procedures for distribution of samples to vendors by
SAIC, record keeping by SAIC and the vendor, and EPA's and SAIC's handling of wastes generated during the
Demonstration.
Field analyses will be performed by five vendors at the ORNL facility. Each vendor will receive sediment, soil, and SRM
samples for analysis. Demonstration samples will cover a range of mercury concentrations; this range will vary for each
vendor.
4.2.1 Distribution of Samples
During the Demonstration, all field samples, and SRMs utilized to fill in missing concentration ranges will be collectively
termed "Demonstration samples." All Demonstration samples will be handled as "blind samples." For the Demonstration,
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the only individuals who will know the key coding of the Demonstration samples will be the SAIC TOM, the SAIC
GeoMechanics Laboratory Manager, and the SAIC QA Manager. The samples will be shipped from the SAIC
GeoMechanics Laboratory to the SAIC office in Oak Ridge. Samples will be shipped in containers that will be placed in
a cooler, cooled with ice to 4°C, and shipped to SAIC's Oak Ridge office using a COC form and custody seals.
Once received at the SAIC office, sample vials will be distributed into separate coolers for each vendor. SRM samples
will be intermixed. Separate coolers will be dedicated to each vendor and labeled with the vendor's name. The SAIC TOM
will oversee distribution of samples and placement in vendor coolers (coolers will be provided by SAIC). The coolers will
be iced and maintained at 4°C for the duration of the Demonstration.
An SAIC technology observer (see subchapter 4.3.1.2) will distribute sample sets (by geographic location) to the vendors.
Each observer will be responsible for supplying samples to either one or two vendors. At the beginning of each day of the
Demonstration, each observer will transfer a sample cooler and COC form to each of the two vendors. The vendors will
inspect the samples and sign the applicable COC form documenting the transfer of custody. At the end of the day, all
samples will be returned to SAIC under control of the COC forms. Any samples that are not analyzed during the first day
will be returned to the vendorforanalysis atthe beginning of Day 2. Once analysis of the firstsample location is completed
by the vendor, SAIC will provide a cooler containing samples from the second location. Samples will be provided at the
time they are requested by the vendor. Once again, the sample transfer will be documented using a COC form.
This process will be repeated for each sample location. Until that time, SAIC will maintain custody of all remaining sample
sets. SAIC will maintain custody of samples thathave already been analyzed and will follow the waste handling procedures
in Chapter 4.2.2 to dispose of these wastes.
4.2.2 Handling of Waste Material
SAIC will make every attempt to minimize the volume of IDW generated during the Demonstration. The Demonstration
will take place at DOE-ORNL, a large quantity generator. DOE-ORNL has in place a "Waste Management Plan", and
ORNL personnel will provide a staging area for storage and disposal of Demonstration wastes. EPA will ultimately be
responsible for proper disposal of all wastes generated during the Demonstration, assisted by SAIC. It is anticipated that
the overwhelming majority of IDW generated will consist of PPE, mostly disposable gloves. Other significant solids
generated may include excess sample material, paper towels or wipes, and disposable plastic and glassware. Those items
not com ing into direct contact with contaminated sample material will be discarded into a garbage can ordumpster. Liquid
wastes that may be generated during the Demonstration include spent or excess chemicals (e.g., reagents) from the test
instruments and decontamination water. All IDW generated will be managed and disposed of in accordance with
site-specific IDW management practices defined by DOE-ORNL.
Any decontamination water will be placed in an on-site drum for non-hazardous liquid waste; DOE-ORNL or SAIC will
provide this drum. Spent chemicals from the field instrumentation will be staged in appropriate containers provided by
ORNL. Alternatively, the vendors may retain their spent chemicals. In either case, SAIC will measure the volume of waste
generated for estimating disposal costs. Vendors will be responsible for unused, excess chemicals.
After the Demonstration, any hazardous waste will be staged by ORNL pending actions by EPA to remove the waste to
an off-site, state-approved hazardous waste facility. SAIC will assist EPA in labeling and handling wastes while on the site.
ORNL will "green tag," transport, and stage the waste materials on the site. EPA, with assistance from SAIC, will have
ultimate responsibility for off-site shipment and disposal of all hazardous wastes.
4.3 Field Observations
This chapter details the activities that will be performed during the field Demonstration. It identifies the responsibilities
during the field Demonstration and defines record keeping requirements.
4.3.1 Roles and Responsibilities
Chapter 2 defines overall responsibilities for this Demonstration project. This chapter defines the specific roles and
responsibilities of the vendors and SAIC during the field Demonstration portion of the project.
4.3.1.1 Vendor Responsibilities
The vendors are individually responsible for shipping their respective instruments to the Demonstration location. The
vendors are responsible for tracking and, as necessary, expediting equipment shipments to ensure that there are no
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schedule delays. Equipment set up on the site will occur on Monday of the Demonstration week under the oversight of
SAIC. No equipment set up is to begin until SAIC notifies the vendors. Vendors are responsible for ensuring that
equipment is shipped to the proper location, arrives on time, and is operable.
Vendors are also responsible for operating, maintaining, and repairing their equipment during the Demonstration, as well
as reporting analytical results to SAIC (see section 7.2). Vendors will participate in a kickoff meeting on the morning of
the first day to coordinate all field Demonstration activities. During this meeting, project logistics, scheduling, and
responsibilities will be reviewed. An SAIC observer will be assigned to each vendor; this person will coordinate with the
vendor representative to accomplish project objectives. In addition, the vendor will be responsible for the following
activities (note the referenced chapter for the applicable project objective):
Promptly report analytical results, including replicates and QC, to SAIC (Subchapter 3.2.1.1 to 3.2.1.3)
Supply information to SAIC on the cost of the instrument, supplies, and parts used during the Demonstration
(Subchapter 3.2.1.5)
Estimate before the Demonstration the waste volume that will be generated, and report wastes generated during
the Demonstration (Subchapter 3.2.1.5)
Provide in advance of the Demonstration all SOPs for the instrument (Subchapter 3.3.1)
Provide information on operator qualifications and training (Subchapter 3.1.1.5 and 3.3.1)
Supply in advance of the demonstration a listof all chemicals used and corresponding Material Safety Data Sheets
(MSDSs) (Subchapter 3.3.2)
Provide equipment specifications, including dimensions, weight, electrical requirements, and other information
related to equipment design (Subchapter 3.3.2 through 3.3.4)
Report all downtime during the Demonstration and the reason for the downtime. Report also any repairs along
with parts and supplies used (Subchapter 3.2.1.5, 3.3.4, and 3.3.5)
4.3.1.2 SAIC Responsibilities
SAIC will assign one observer per one or two technologies (i.e., XRF, AA, etc.) (each of three SAIC observers will be
dedicated to two vendors except one observer who will be responsible only for the fifth vendor). A fourth observerwill be
responsible for monitoring all vendor technologies during the Demonstration in order to ensure consistency in the approach
for the secondary objectives, which are subjective.
The dedicated SAIC observers will be responsible forassisting their assigned vendors in finding its Demonstration location
and other logistical issues. However, the vendors will ultimately be responsible for all such logistical issues. The SAIC
observer will be responsible for the following activities (note the referenced chapter for the applicable project objective):
Notify the vendor when timing of sample analysis begins (Subchapter 3.2.1.4)
Time equipment setup, sample analyses, and equipment disassembly (Subchapter 3.2.1.4)
Obtain recorded analytical results (including replicates and QC samples) provided by the vendor (Subchapter
3.2.1.1 through 3.2.1.3)
Record and notify the vendor the number of sample analyses completed (Subchapter 3.2.1.4)
Document the duration of instrument downtime, the reasons for the downtime, and the required instrument repairs
(Sections 3.2.1.4 and 3.3.4)
Document the number of vendor operators, and the quantity of supplies and parts used (Subchapter 3.2.1.5)
Collect information on the cost of the instrument, supplies, parts, and labor, and estimate costs for use of the
instrument (Subchapter 3.2.1.5)
Evaluate the ease of use of the instrument (Subchapter 3.3.1)
Document chemicals used, review MSDSs, and evaluate health and safety concerns of the instrument
(Subchapter 3.3.2)
Evaluate instrument portability (Subchapter 3.3.3)
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Evaluate instrument durability (Subchapter 3.3.4)
Evaluate the availability of the instrument and supplies (Subchapter 3.3.5)
4.3.2 Records
Project records will include:
Analytical results, including replicates and other QC samples provided by the vendor
Calculations and results for MDLs and PQLs (sensitivity), percent difference from standards (accuracy), and RSDs
(precision)
Field logs documenting the time required for instrument setup, calibrations, analysis of samples, and instrument
demobilization
Field logs documenting the evaluation results for ease of use, portability, durability, and other secondary
information
Completed and signed COC forms used for each transfer of samples from one party to another
All instrument evaluation information (including cost data) collected from vendors, vendor web pages, suppliers,
and other sources as part of this Demonstration.
A detailed discussion of the records that will be maintained follows for each project objective.
4.3.2.1 Primary Objectives
Primary Objective # 1: Evaluate Instrument Sensitivity
SAIC observers will obtain PQL values from each vendor and maintain records of the analytical results and calculations
used to determine MDLs and associated calibration curves to determine the PQL. SAIC will document exactly which
calibration options are used by each vendorduring the demonstration. PQL determination will be performed at least once
during the Demonstration and perhaps more than once, depending upon individual vendor calibration requirements. The
MDL analysis will be performed during the Demonstration through the analysis of blind samples; corresponding records
will be maintained.
Primary Objective # 2: Evaluate Instrument Accuracy
SAIC observers will receive records of blind replicate analyses performed by each vendor to calculate instrument accuracy.
Records will include the time of the analysis, the sample number, the numerical result, and the units of measurement.
Calculations of instrument accuracy will be maintained as part of the project record.
Primary Objective # 3: Evaluate Instrument Precision
SAIC observers will receive records of blind replicate analyses performed by each vendorto calculate instrument precision.
Records will include the time of the analysis, the sample number, the numerical result, and the units of measurement.
Precision calculations will also be maintained as part of the project record.
Primary Objective # 4: Evaluate Instrument Throughput
SAIC will maintain the following records to evaluate instrument throughput:
Time required for instrument set up and demobilization.
Calibration time.
Total number and types of samples analyzed by each vendor.
Start and completion time for each set of sample analyses (daily except in the case of significant downtime due
to personnel breaks/lunch).
Duration and reasons for any equipment downtime.
Primary Objective # 5: Estimate Cost to Use Vendor Instruments
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SAIC will maintain records used to estimate the cost of using vendor instruments. Examples will include:
Rental or purchase price of instruments, if applicable.
Vendor quoted price per sample.
Capital cost based on published data.
4.3.2.2 Secondary Objectives
SAIC observers will maintain records on the name, type, model, and serial number of the vendor analytical equipment.
In addition, the observers will document the date of all observations and record their names. The recordkeeping
requirements for each secondary objective are discussed below:
Secondary Objective # 1: Ease of Use
SAIC observers will maintain records of the number of operators and the qualifications and training of each (supplied by
each vendor). A copy of any SOPs will be kept as part of the project record, including observations on the ease of the use
of the SOP and equipment.
Secondary Objective # 2: Health and Safety Concerns
SAIC observers will maintain records of equipment certifications and notes on potential mechanical, electrical, and
chemical hazards based on Demonstration activities.
Secondary Objective # 3: Portability
SAIC observers will keep records of the weight, dimensions, power source requirements, setup and teardown time, any
other observations related to equipment portability.
Secondary Objective # 4: Durability
SAIC observers will maintain information on the materials of construction, quality of construction, downtime during
Demonstration (including duration and reason), routine maintenance performed or required, and any repairs that were
performed during the Demonstration (including parts required and reason for repair).
Secondary Objective # 5: Availability of Vendor Instruments and Supplies
SAIC observers will maintain records used to evaluate the availability of equipment and supplies. Records will include fie Id
notes, results of web searches, phone records, and any other information utilized to evaluate this objective.
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Chapter 5
Referee Laboratory Testing and Measurement Protocols
The referee laboratory will analyze all samples that are analyzed by the vendor technologies in the field under the
conditions prescribed by the reference method selected. The following subchapters provide information on the selection
of the referee laboratory and reference method as well as details on the performance of the reference method in
accordance with EPA protocols. Other parameters to be analyzed by the referee laboratory are also discussed briefly.
5.1 Referee Laboratory Selection
During the planning of the Pre-demonstration phase, nine laboratories were senta statement of work SOW for the analysis
of mercury to be performed as part of the Pre-demonstration. Seven laboratories responded to the SOW with appropriate
bids. (Two laboratories chose not to bid.) Three of the seven laboratories were selected as candidate laboratories based
upon technical merit, experience, and pricing. These laboratories received and analyzed blind samples and SRMs during
Pre-demonstration activities, as discussed in Chapter 1. The referee laboratory to be used for the Demonstration was
selected from these three candidate laboratories. Final selection of the referee laboratory was based upon the laboratory's
interest in continuing into the Demonstration, the laboratory-reported SRM results, the laboratory MDL for the reference
method selected (SW-846 Method 7471B), the precision ofthe laboratory calibration curve, othertechnicalconsiderations,
the laboratory's ability to support the demonstration, and cost.
A preliminary audit was performed at two of the laboratories in order to make a final decision on a referee laboratory for
the Demonstration. (One ofthe three candidate laboratories was eliminated from selection prior to performing a pre-audit.
Upon discussion with this laboratory it was determined thatthey would not be able to meet requirements for the quantitation
limit for the Demonstration. Their lower calibration standard was approximately 50 ug/kg and the vendor comparison
requirements were well below this value.) To ensure a complete and fair comparison the same auditor assessed both
laboratories. Mr. Joe Evans, the SAIC QA Manager, performed these audits.
Results ofthe SRM samples were compared for the two laboratories. Each laboratory analyzed each sample (there were
two SRMs) in triplicate. Both laboratories were within the 95% prediction interval for each SRM. In addition, the average
result from the two SRMs was compared to the 95% confidence interval for the SRM.
Calibration curves from each laboratory were reviewed carefully. This included calibration curves from the analyses
previously performed and calibration curves for other laboratory clients. The QC requirement was that the correlation
coefficient be 0.995 or greater and that the lowest point on the calibration curve be within 10% ofthe predicted value. Both
laboratories were able to achieve these two requirements for all curves reviewed and for a lower standard of 10 ug/kg,
which was the lower standard required forthe Demonstration based upon information received from each of the vendors.
In addition, MDLs based upon an analysis of 7 standards were reviewed. Both laboratories could achieve an MDL that
was below 1 ug/kg.
It should be noted that vendor claims in terms of sensitivity are driving how low this lower quantitation standard should be.
These claims are somewhat vague, and the actual quantitation limit each vendor can achieve is uncertain. Some vendors
claim to be able to go as low as 1 ug/kg, but it is uncertain if this is actually a PQLora DL. Therefore, it may be necessary
that the laboratory actually be able to achieve even a lower POL than 10 ug/kg. This will be discussed in more detail in
the conclusion part of this chapter.
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The analytical method used by both laboratories was based upon SW-846 Method 7471B. SOPs from both laboratories
were reviewed. Each SOP followed the reference method. In addition, interferences were discussed. There was some
concern thatorganic interferences may be presentin the samples previouslyanalyzed by the laboratories. Because these
same matrices were expected to be part of the Demonstration, there was some concern associated with interferences and
how these interferences would be eliminated. This is discussed in the Conclusion portion of this chapter.
Sample throughput was somewhat important in that the laboratories would receive all Demonstration samples at the same
time and it is desirable that these samples be run at the same time as the field samples in order to eliminate any question
or variable associated with loss of contaminant due to holding time. This meant that the laboratory would receive
approximately 300 samples in the period of a few days for analysis. It was also desirable for the laboratory to produce a
data report within a 21 day turnaround time for purposes of the Demonstration. Both laboratories indicated that this was
achievable. Instrumentation was reviewed and examined at both laboratories. Each laboratory was using a Leeman
instrument for analysis. One of the two laboratories had back-up instrumentation in case of problems. Both laboratories
indicated that their Leeman mercury analyzer was relatively new and had not been a problem in the past.
Previous SITE program experience was another factor considered as part of these pre-audits. This is because the SITE
program generally requires a very high level of QC, such thatmost laboratories are notfamiliarwith the QC required unless
having previously participated in the program. The other factor was that the SITE program generally requires analysis of
relatively "dirty" samples and many laboratories are not used to analyzing such "dirty" samples. Both laboratories have
been long-time participants in this program.
Other QC factors, such as analyses on other SRM samples not previously examined, laboratory control charts, and
precision and accuracy results were examined during the audit. Each of these issues was closely examined. In addition,
because of the desire to increase the representativeness of the samples for the Demonstration, each laboratory was asked
if sample aliquots could be increased to 1 g (the method requirement noted 0.2 g). Based upon previous results, it was
noted during the audit that both laboratories routinely increased sample size to 0.5 g. They indicated that increasing the
sample size would not be a problem. Besides these QC factors other, less tangible QA elements were examined. This
included analyst experience, management involvement in the demonstration, and internal laboratory QA Management.
These elements were also factored into the final decision.
Conclusion
There were very few factors that separated the quality of these two laboratories. Both were exemplary in performing
mercury analysis. There were, however, some minor differences based upon this evaluation that were noted by the
auditor. These were as follows:
ALSI had back-up instrumentation available. Even though neither laboratory reported any problems with its
primary instrument (the Leeman mercury analyzer), ALSI did have a back-up instrument in case there were
problems with the primary instrument or in the event that the laboratory needed to perform other mercury analyses
during the Demonstration time.
As noted, the low standard requirement for the calibration curve was one of the QC requirements specified for this
Demonstration in order to ensure that a lower quantitation could be achieved. This low standard was 10 ug/kg
for both laboratories. ALSI, however, was able to show experience in being able to calibrate much lowerthan this,
using a second calibration curve. In the event that vendors a re able to analyze atconcentrations as low as 1 ug/kg
with precise and accurate determinations, ALSI will be able to perform analyses at lower concentrations as part
of the Demonstration.
Management practices and analyst experience were considered similar at both laboratories. ALSI has participated
in a few more SITE demonstrations than the other laboratory, but this difference is not significant because both
laboratories have proven themselves capable of handling the additional QC requirements for the SITE program.
In addition, both laboratories have internal QA management procedures that provide the confidence needed to
achieve SITE requirements.
Interferences for the samples previouslyanalyzed were discussed and data were reviewed. ALSI ran two separate
runs for each sample. This included a run with stannous chloride and a run withoutstannous chloride. (Stannous
chloride is the reagent used to release mercury into the vapor phase for analysis. Sometimes organicscan cause
interferences in the vaporphase. Therefore, a run with no stannous chloride would provide information on organic
interferences.) The other laboratory did not routinely perform this analysis. Some samples were thought to
contain organic interferences, based on previous sample results. The Pre-demonstration results were reviewed
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and it was determined that no organic interferences were present. Therefore, while this was thought to be a
possible discriminator between the two laboratories in terms of analytical method performance, it became moot
for the samples included in this Demonstration.
The factors above were considered in the final evaluation. Because there were only minor differences in the technical
factors, cost of analysis was used as the discriminating factor. (If there had been significant differences in laboratory
quality, cost would not have been a factor). ALSI was significantly lower in cost than the other laboratory. Therefore, ALSI
will be used as the referee laboratory for the Demonstration.
5.2 Reference Method
The selection of the SW-846 Method 7471B as the reference method was based on several factors, predicated on
information obtained from the technology vendors, as well as the expected contaminant types and soil/sediment mercury
concentrations expected in the test matrices. There are several laboratory - based, promulgated methods for the analysis
of total mercury. In addition, there are several performance-based methods for the determination of various mercury
species. Based on the vendor technologies, it was determined that a reference method for total mercury would be needed.
Table 5-1 summarizes the methods evaluated, as identified through a review of the EPA Test Method Index. The
procedure used for the reference method selection is summarized below. In selecting which of the potential methods would
be suitable as a reference method, consideration was given to the following questions:
Is the method widely used and accepted? Is the method an EPA-recommended, or similar regulatory method?
The selected reference method should be in sufficient use that it can be cited as an acceptable method for
monitoring and/or permit compliance among regulatory authorities.
Does the selected reference method provide QA/QC criteria that demonstrate acceptable performance
characteristics over time?
Is the method suitable for the types of mercury expected to be encountered? The reference method must be
capable of determining, as total mercury, all forms of the chemical contaminant known or likely to be, present in
the matrices.
Will the method achieve the necessary detection limits to adequately evaluate the sensitivity of each vendor
technology?
Is the method suitable for the concentration range expected in the test matrices?
Methods evaluated for total mercury analysis included SW-846 Method 7471 B, SW-7473, SW-7474, EPA Method 1631,
EPA 6200, and EPA 245.7. These methods are in Table 5-1. Consideration was given to the dynamic range of the
method, types of mercury included in the analysis, and whether the method was a widely-used protocol. Based on these
considerations, it was determined that SW-846 Method 7471B (analysis of mercury in solid samples by cold-vapor, atomic
absorption spectrometry) would be the best reference method. Method SW-7474, an atomic fluorescence spectrometry
method using SW-3052 for microwave digestion of the solid, was also considered a likely technical candidate; however,
the method is not as widely used or referenced, and it was determined that SW-7471B was the better choice for this
reason. The following subchapters provide details on this method. Analytical methods for non-critical parameters are
presented in Table 5-2.
5.2.1 Laboratory Protocols
The critical parameter for this study is the analysis of mercury in soil and sediment samples. Samples to be analyzed by
the laboratoryincludefield samples, as well as SRM samples. Detailed laboratory proceduresforsubsampling,extraction,
and analysis are provided in the SOPs included as Appendix B and are summarized briefly below.
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Table 5-1 : Methods for Total Mercu ry Analysis
Method
SW-7471B
SW-7473
(Uses Milestones
DMA)
SW-7474
(Solids: prep 3052)
EPA 1631
EPA 245.7
EPA 6200
TARGET RANGES:
Based on vendor info
Analytical
Technology
CVAAS
Thermal
decomposition,
amalgamation and
AAS
AFS
CVAFS
CVAFS
FPXRF
Not Applicable
Mercury type(s)
Analyzed
inorganic mercury and
organo-mercury
inorganic mercury and
organo-mercury
inorganic mercury and
organo-mercury
inorganic mercury and
organo-mercury
inorganic mercury and
organo-mercury
inorganic mercury
inorganic mercury, possibly
trace organo-mercury
Approx. Cone.
Range
10 - 2000 ug/kg
0.2 - 400+ ug/kg
1 ug/kg - mg/kg
0.5 - 100+ ng/L
0.5 -200+ ng/L
30 mg/kg
10 ug/kg-1000+
mg/kg
Comments
Widely used standard for total mercury
determinations
Uses participating vendor's equipment
Allows for total decomposition analysis;
less widely used/referenced
Requires "trace" analysis procedures;
written for waters; Appendix A of EPA
1631 written for sediment/soil samples
Requires "trace" analysis procedures;
written for waters will require dilutions of
high-level mercury samples
Considered only a screening protocol
ng/L - Nanograms per liter
AAS = Atomic Absorption Spectrometry
AFS = Atomic Fluorescence Spectrometry
CVAAS = Cold Vapor Atomic Absorption Spectrometry
CVAFS = Cold Vapor Atomic Fluorescence Spectrometry
FPXRF = Field Portable X-Ray Fluorescence
Table 5-2. Analytical Methods for Non-Critical Param eters
Parameter Method Reference
Method Type
Arsenic
Lead
Selenium
Silver
Copper
Zinc
Oil and Grease
TOC
SW-846 3050/6010
SW-846 3050/6010
SW-846 3050/6010
SW-846 3050/6010
SW-846 3050/6010
SW-846 3050/6010
EPA 1664
SW-846 9060
Acid digestion, ICP
Acid digestion, ICP
Acid digestion, ICP
Acid digestion, ICP
Acid digestion, ICP
Acid digestion, ICP
n-Hexane extraction, Gravimetric analysis
Carbonaceous analyzer
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Samples will be analyzed for mercury using Method 7471B, a cold-vapor atomic absorption method, based on the
absorption of radiation at the 253.7-nm wavelength by mercury vapor. The mercury is reduced to the elemental state and
aerated from solution in a closed system. The mercury vapor passes through a cell positioned in the light path of an atomic
absorption spectra photometer. Absorbance (peak height) is measured as a function of mercury concentration. Potassium
permanganate is added to eliminate possible interference from sulfide. As per the method, concentrations as high as 20
mg/kg of sulfide, as sodium sulfide, do not interfere with the recovery of added inorganic mercury in reagent water. Copper
has also been reported to interfere; however, the method states that copper concentrations as high as 10 mg/kg had no
effect on recovery of mercury from spiked samples. Samples high in chlorides require additional permanganate (as much
as 25 ml) because, during the oxidation step, chlorides are converted to free chlorine, which also absorbs radiation of 253
nm. Therefore, free chlorine is removed by using an excess of hydroxylamine sulfate reagent (25 ml_). Certain volatile
organic materials that absorb at this wavelength may also cause interference. A preliminary run without reagents should
determine if this type of interference is present.
Prior to analysis, the contents of the sample container will be stirred and the sample mixed prior to removing an aliquot
for the mercury analysis. An aliquot of soil/sediment (1 g) is placed in the bottom of a biological oxygen demand bottle,
with reagent water and aqua regia added. The mixture is heated in a water bath at 95°C for 2 minutes. The solution is
cooled and reagent water and potassium permanganate solution are added to the sam pie bottle. The bottle contents are
thoroughly mixed and the bottle is placed in the water bath for 30 minutes at 95°C. After cooling, sodium chloride-
hydroxylamine sulfate is added to reduce the excess permanganate. Stannous chloride is then added and the bottle
attached to the analyzer; the sample is aerated and the absorbance recorded. A non-stannous chloride run is also included
as an interference check when organic contamination is suspected. In the event of positive results of the non-stannous
chloride run, the laboratory will report these results to SAIC so that a determination of organic interferences can be made.
5.2.2 Laboratory Calibration Requirements
The instrument will be calibrated for mercury detection in accordance with the method requirements using a five-point
calibration curve that will include a standard concentration at the reporting detection limit. Standards are prepared in the
same manner as the samples. Calibration curve requirements will be r2 > 0.995, with continuing calibration verification
standards run every 10 samples (using a mid-level calibration standard) and meeting a criterion of 90-110% recovery.
In addition, a low standard check will be run after the five-point calibration curve to verify that the calculated concentration
of the low standard is within 10% of the actual concentration. This will serve as a verification of the reported PQL. The
calibration curve will be verified daily by the analysis of a second-source initial calibration verification standard, which will
also meet criteria of 90-110% recovery. These calibration criteria are summarized in tabular form in Chapter 6.
5.3 Additional Analytical Parameters
In addition to the critical parameter of mercury, the referee laboratory will also analyze arsenic, lead, selenium, silver
copper, zinc, oil and grease, total solids, and total organic carbon (TOC) on selected samples according to the methods
listed above.
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ChapterG
Referee Laboratory QA/QC Checks
For this SITE project, QA objectives associated with the reference method have been established to ensure that data
generated by the laboratory are of adequate quality to achieve the project's technical objectives. It is critical for this
Demonstration that the mercury values obtained by the referee laboratory, using the reference method, be accurate and
precise. Concentrations for the certified SRM samples will be generated by both the laboratory and by each of the
individual technology vendors, and will be compared to pre-established concentration ranges provided by the SRM
supplier. The laboratory concentrations of mercury for the fie Id soil and sediment samples will be the basis of comparison
for the vendor results. Therefore, the following section discusses the QA/QC checks to be performed by the referee lab
in compliance with SW-846 protocols for Method 7471B. Acceptance criteria for accuracy, precision, and completeness
objectives are given, along with the expected detection limit of the critical measurements. Specific QC check procedures
for critical measurements are discussed in Subchapter6.2, including corrective actions to betaken in the event these QC
checks do not meet criteria.
6.1 QA Objectives
The critical measurement for this project is mercury in soil and sediment samples collected from the test locations, as well
as in SRM samples. Table 6-1 summarizes QA objectives for this parameter, with the achievement of these objectives
discussed below.
Table 6-1: QA Objectives for Mercury Measurements by SW-846 Method 7471 B
Objective Criteria
Accuracy (1) 80-120% recovery
Precision (1) RPD < 20%
Practical Quantitation Limit 0.01 mg/kg
Completeness 95%
Representativeness (2) RSD < 20%
Comparability EPA-approved method
(1) Accuracy and precision assessed by the analysis of duplicate spikes
(2) Representativeness based on the results of multiple replicates of field samples
Precision for mercury will be assessed by the analysis of duplicate matrix spikes (MS/MSDs) performed on select project
samples to determine thereproducibilityof the measurements. The relative percent difference (RPD) between the spiked
samples will be compared to the objectives given in Table 6-1.
Samples prepared as multiple replicates, as per Chapter 4, will be used to evaluate overall precision of the combined
sampling, homogenization and analysis procedures. Precision will be assessed by calculating the RSD for the
measurements. The analytical QA objectives will be applied to these samples as a guideline only; if the field replicates
meet these objectives, then the combined precision is within the analytical expectations. If these guidelines are exceeded,
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the nature of and reasons for any exceedance will be discussed in the final QA review of the data. Corrective action will
not necessarily be possible or required.
Accuracy objectives for mercury are evaluated by the percent recovery of the MS/MSDs performed using project samples.
In addition, accuracy of the analytical system will be verified by the analysis of second source standards. Laboratory
control spikes (LCSs) will be analyzed with each batch of samples as a further assessment of analytical accuracy in the
absence of matrix effects. These analyses are discussed further in Subchapter6.2 and requirements for LCS results are
specified in Table 6-2.
The SRM samples analyzed by the laboratory (as well as by the field measurement devices) will also provide an
assessment of accuracy for each analytical technique (field and reference method) as discussed previously in Chapter 3.
Results for these samples analyzed during the Demonstration will be compared to the concentration limits provided in the
certification associated with the SRM.
Method detection limit for the reference method is determined in accordance with EPA 40 CFR Part 136, as a statistical
calculation based on the analysis of 7 replicate low-level standards. Quantitation limit is defined as the PQL, determined
by the lowest concentration standard meeting the specified calibration criteria (+/- 10 %D).
Comparability is based on the use of established EPA-approved methods for the analysis of the critical parameter. The
determination of mercury is based on published methods, supplemented with well-documented procedures used in the
laboratory to ensure reproducibility of the data. The selection of SW-846 Method 7471B as the reference method was
discussed previously (See chapter 5)
Representativeness is achieved by collecting samples considered representative of the matrix at the time of collection.
For the soil and sediment samples to be analyzed during the field Demonstration, this is achieved by the homogenization
and sub-sampling procedures summarized in Chapter 4 and presented in detail in Appendix A.
Completeness refers to the amount of measurement data collected relative to that needed to assess the project's technical
objectives. For this project, completeness objectives have been established at 95%, acknowledging the potential for loss
of sample. Sample re-analysis is not expected to be a problem given the 28-day hold time for mercury.
6.2 QC Checks
General QA objectives have been discussed in the preceding paragraphs. The following QC check procedures will be
used to assess the critical parameters. These QC checks are summarized in Table 6-2, and discussed further below.
Calibration criteria were described in Subchapter 5.2.2. In addition to these requirements, mercury analysis will include
the analysis of MS/MSD samples prepared using project samples. MS/MSD samples will be designated on the COC or
will be performed at a frequency of 5% of the samples, whichever is more frequent. Samples will be spiked by the addition
of approximately 5 times the native sample concentration, as estimated based on historical data or after screening of the
primary sample. The sample, MS, and MSD will all be analyzed in the same batch, even if this requires re-analysis of the
primary sample. If the initial spike preparation results in spiking levels that are inappropriately low relative to the native
sample concentration and the MS/MSD do not meet criteria, the three samples (primary, MS, and MSD) will be re-digested
and re-analyzed using an appropriate spike concentration. An LCS will be prepared and analyzed with each batch of
samples prepared. If the results of both the LCS and the MS/MSD do not meet criteria, the entire analytical batch will be
re-digested and re-analyzed. If one or the other fail, but not both, the laboratory QA Coordinator will contact the SAIC QA
Manager to discuss and implement the appropriate corrective action.
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Table 6-2. QC Checks for Mercury Measurements by SW-846 Method 7471 B
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Chapter 7
Data Reporting, Data Reduction, and Data Validation
For data to be scientifically valid, legally defensible, and comparable, valid equations and procedures must be used to
prepare those data. Evaluation of measurements is a systematic process of reviewing a bodyof data to provide assurance
that the quality of the data is adequate for its intended use. The following subchapters describe the data reporting, data
reduction, and data validation procedures to be used for laboratory data, for data generated by the vendors, and reports
to be generated to discuss Demonstration evaluation results.
7.1 Referee Laboratory
7.1.1 Data Reduction
All data reduction will be completed as specified in SW-846 Method 7471 B. Where data reduction is not computerized,
calculation results will be recorded on the raw data printouts, on pre-printed bench sheets, or in permanently bound
notebooks. The data reduction for some analyses may include analysts' interpretations of the raw data and manual
calculations. When this is required, the analysts' observations and/or summary will be written in ink on the raw data
sheets. Any corrections to data sheets will be made by lining out inaccurate information, initialing the line-out, and adding
the revised information next to the line-out.
All mercury data will be reported on an as-received basis.
7.1.2 Data Validation
Data generated shall be reviewed by the Analytical Task Leader on a daily basis for completeness. Data will be reported
in standard units, as described above. Data validation begins with the analyst and continues until the data are reported.
The analyst will verify and sign the appropriate forms to verify the completeness and correctness of data acquisition and
reduction. An independent reviewer will review this information to ensure close adherence to the specified analytical
method protocols. All instrument systems must be in control, and QA objectives for precision, accuracy, completeness,
and method detection limit must be met. In the event that data do not meet the project objectives, the sample shall be re-
analyzed or re-extracted. If the sample still does not meet project requirements, the SAIC TOM and QA manager shall
be notified immediately. The problems will be discussed and appropriate corrective actions shall immediately be
implemented. If project objectives have been impacted, or changes were required in analytical procedures, these
modifications will be clearly noted in the ITVR.
The principal criteria that will be used to validate the integrity of data during collection and reporting are as follows:
Verification by the project analyst that all raw data generated for the project have been documented and stored.
Storage locations must also be documented in the laboratory records
Examination of the data by the laboratory manager or his or her designee to verify adequacy of documentation
and agreement with method protocols
Reporting of all associated blank, standard, and QC data, along with results for analysis of each batch of samples
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Auditing by the analytical laboratory QA/QC manager of ten percent of the data generated.
Analytical outlier data are defined as those QC data lying outside of a specific QC objective window for precision or
accuracyfora given analytical method. Should QC data be outside of such limits, the laboratory supervisor will investigate
the potential causes of the problem. Corrective action (as discussed in Chapter 6) will be initiated as necessary and
documented. Any outlier data will be flagged with a data qualifier in the laboratory report.
7.1.3 Data Storage Requirements
The subcontracted referee laboratory (ALSI) will be responsible for storing on disc all raw data for 5 years. SAIC and/or
its subcontractors will retain all hard copies of the analytical data for a period of 5 years. At the end of this 5 year period
EPA will be contacted concerning the final fate of the above data.
7.1.4 Laboratory Reporting
Laboratory reports will include tabulated results of all samples, along with a cross-reference of laboratory identification and
field sample identification. The final report will also include method summaries, detailing any deviations from, or
modifications to, the proposed methods. Data will be submitted in a report with sufficient detail such that independent
validation of the data can occur. Raw data will include any calibration information, instrument printouts, lab bench sheets,
sample preparation information, and other appropriate information. The completed report will be reviewed by the ALSI
laboratory Q A managerand be approved by the laboratory project man age r (or their design ees) prior to submittal to SAIC.
7.2 Vendor Reporting
7.2.1 Field Reporting
The format of the data record submitted to SAIC at the conclusion of the Demonstration is the choice of each vendor (i.e.,
table, text, etc.) but must include at a minimum the following information:
SAIC sample identification code of each sample analyzed.
Number of field analyses recorded for each sample.
Sample volume (or mass) used for each analysis.
Concentration of each sample analysis result.
Statement as to whether the result is "as received" or dry weight.
Manner in which the result was obtained (e.g., read digitally, print out, etc.).
Any additional sample preparation conducted for any sample (e.g., dilutions, digestion procedures, etc.).
Any QC samples and results that are required/recommended by the vendor and should be reported in the ITVR.
In addition, vendors are also expected to include "raw" data sufficient to validate the data provided. As applicable, this may
include:
Instrument calibration procedures (including calibration standards used).
Instrument calibration records (i.e., calibration curves).
Any suspected sample interferences (matrix or chemical).
Any other observations/concerns regarding sample composition.
Chain of custody records.
Any general comments about the samples, containers, or information provided.
7.2.2 Data Reduction/Validation
The steps taken to reduce data will be well-documented and provided in the report submitted by the vendors. The
validation steps taken by the vendors are left to their discretion; data will need to be submitted at the conclusion of the
Demonstration as "final" results. To the extent possible, SAIC will perform a validation of Vendor Data. Because it is
primarily the Vendor's responsibility to provide data of adequate quality and because the exact process for Vend or analysis
is "unknown," there are no formal validation processes for vendor data as there are for laboratory data. Obvious errors,
however, will be pointed out to the Vendor and it will be left to the Vendor to re-verify or change any data supplied to SAIC.
The final report will document validation steps taken by the vendor.
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7.3 Final Technical Reports
SAIC will use the vendor field results and reference method data to prepare the ITVR for each vendor. These reports will
present the results and evaluation of each vendor technology separately in separate documents. Results for the analysis
of field samples and SRMs will be compared to the referee laboratory results and SRM certified limits. The vendors will
not be compared to one another.
The ITVR will include a QA review and discussion as a separate and identifiable chapter. This review will include, at a
minimum, the following information:
A thorough discussion of the procedures used to define data quality and usability, and the results of these procedures.
The discussion will focus on the data quality indicators such as precision, accuracy, completeness, comparability, and
representativeness, and will include summary tables of the QC data obtained during the Demonstration. Results will
be compared to the data quality objectives set forth in the Demonstration Plan to provide an assessment of the factors
that contributed to the overall quality of the data.
The results of any technical systems audits performed during the course of the project will be documented, including
corrective actions initiated as a result of these audits and any possible impact on the associated data. If any internal
audits were performed, these, too, will be reviewed.
All changes to the original Demonstration Plan will be documented regardless of when they were made. The rationale
for the changes will be discussed, along with any consequences of these changes.
The identification and resolution of significant QA/QC problems will be discussed. Where it was possible to take
corrective action, the action taken, and the result of that action will be documented. If it was not possible to take
corrective action (for example, a sample bottle was broken in transit), this too, will be documented.
A discussion of any special studies initiated as a result of QA/QC issues and/or corrective actions, including why the
studies were undertaken, how they were performed, and how the results impacted the project data.
A summary of any limitations on the use of the data will be provided including conclusions on how these constraints
affect project objectives.
The QA chapter will provide validation of the measurements to be used in the evaluation of the technology. This section
(and the final report) will be subject to review by the QA manager. All ITVRs will be reviewed by SAIC, EPA, and an
Independent Peer Reviewer. This review will assess the assumptions made in evaluating the data and the conclusions
drawn. The EPA TOM must approve the reports prior to release.
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Chapter 8
QA Assessments
A quality assurance audit is an independent assessment of a measurement system. QA audits may be internal or external
audits and performance or system audits. Internal laboratory audits are conducted by the project laboratory's QA/QC
coordinator and may be functionally independent of the sampling and analytical teams. External audits are those
conducted by an independent organization, such as EPA. For this SITE evaluation there will be a field internal systems
audit conducted by the SAIC SITE QA manager during the field Demonstration event. In addition, the SAIC SITE QA
Manager or h is designee will perform a technical systems audit of the laboratory perform ing the homogenization procedure
and the referee laboratory performing the mercury analysis. Performance and system audits are described below.
8.1 Performance Audits
Performance audits are intended to quantify performance of the total measurement system. These types of audits often
include performance evaluation samples supplied by an independent regulatory agency. This type of audit is not
envisioned for this project but as previously stated, SRMs are used for vendor and laboratory evaluation.
8.2 Systems Audits
In general, systems audits may be conducted on sampling, analytical, and other measurement and evaluation activities.
These systems audits are performed by the SAIC SITE QA manager or his designee. These audits are designed to ensure
systems are in place for satisfactory sampling, analysis, measurement, and evaluation of vendor technologies as
designated in the Demonstration Plan. As appropriate, these audits will consist of any or all of the following items:
Review of the organization and responsibilities to determine the functional operation of the quality assurance
program
Check on whether SOPs are available and implemented as written or as specified in the Demonstration Plan
Assessment of traceability of samples and data including COC forms and custody seals
Determination thatthe appropriate QC checks are being made and that appropriate documentation is maintained
Determination of whether the specified equipment is available, calibrated, and in proper working condition
Assurance that records, including notebooks, log sheets, bench sheets, and tracking forms are properly
maintained
Verification that the appropriate chain of command is followed in responding to variances and implementing
corrective action.
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8.2.1 Systems Audit - SAIC GeoMechanics Laboratory
During this Demonstration, the SAIC GeoMechanics Laboratory will be responsible for the homogenization and distribution
of sample vials to be used during the field evaluation. The procedures to be used in performing these activities are
presented in Chapter 4 and Appendix A. The SAIC QA manager will be on site during these activities to ensure that all
protocols are being followed and proper documentation is maintained. The focus of the Technical Systems Audit (TSA)
at the SAIC GeoMechanics Laboratory will include, but not be limited to, issues such as:
Are homogenization procedures being accurately and consistently followed, including the selection of the
procedure (slurry or non-slurry)?
Are all sample preparation steps documented and recorded?
Can all prepared sample vials be traced to their original sample identification?
Is the "blind code" being used for sample identification?
Can SRMs be traced to their original identification?
Can the samples being sent to each vendor be accurately identified for comparison to laboratory results?
The results of this TSA will be reported to the EPA TOM by the SAIC QA manager.
8.2.2 Systems Audit - Referee Laboratory (ALSI)
The referee laboratory will be performing mercury analysis as the critical parameter for the Demonstration. The analyses
will follow SW-846 Method 7471B (see Laboratory SOP, Appendix B) as discussed previously (Chapter 5 presented
analytical requirements and Chapter 6 summarized QC checks). A pre-audit of the laboratory was performed as a
condition of selection as the referee lab. The TSA for the Demonstration phase of the project will be conducted after
samples have been received at the laboratory and shortly after analysis begins. The focus of the TSA at the referee
laboratory will include, but not be limited to, issues such as:
Are all preparation steps documented for all samples?
Is standard preparation documented and are standards traceable?
Are SOPs available for analytical, QA, and are reporting protocols being used?
Is sample custody maintained and documented?
Are sample analysis records kept and can sample results be traced back to the raw data?
Are QC checks performed at the required frequency and are control limits met?
Are analytical instrumentation calibration records evident (including spectrophotometers, balances, etc.)?
Do the analysts appear familiar with the requirements of the Demonstration Plan?
Are sample results correctly calculated and recorded?
8.2.3 Systems Audit - Vendor Technology Evaluation
The SAIC SITE Program QA manager will be present during the MMT Demonstration. He will conduct systems audits to
ensure that the procedures defined in the Demonstration Plan are being properly implemented. Because each of three
SAIC technology observers will simultaneously conduct measurements and evaluations of one or two vendors, and
because some of these evaluations (especially the secondary objectives) will be subjective, it is critical that these
measurements and evaluations be performed in a consistent fashion. Therefore, the SAIC QA manager will audit for
consistency among these observers. These audits will be performed as early as possible in the Demonstration to ensure
that all data are collected in the same fash ion. In addition to the three technology observers, there will be a fourth observer
whose role will be to evaluate the secondary objectives for all five vendors. His role will be to ensure consistency in these
evaluations. He will work closely with the other three observers; their joint observations will be the basis for the evaluation
of secondary objectives. The QA manager will audit to assure that the following procedures defined in this plan are
followed:
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Analytical results are promptly and consistently reported
MDLs and PQLs, along with applicable RPDs, are properly calculated and recorded
Replicate measurements are properly performed and recorded, and accuracy calculated based on the results from
the referee laboratory
Replicate measurements are properly performed and recorded, and RSDs are properly calculated and recorded
to document precision
The amount of time required for performing the analysis is consistently and properly measured and reported for
five categories: mobilization and set-up, initial calibration, daily calibration, demobilization, and sample analyses
Information necessary to estimate the cost associated with mercury measurements is collected for the following
four cost categories: 1) capital; 2) labor; 3) supplies; and 4) IDW. (Note: much of the information collection and
all of the cost calculations will be performed subsequent to the field evaluation)
The skills and training required forproperdevice operation, including any degrees orspecialized training received
by the operators, are fully documented. The number of operators required and the evaluation of ease of use is
also consistently performed and fully documented
Health and safety concerns associated with device operation, including hazardous materials used, the frequency
and likelihood of potential exposures, and any direct exposures or hazards observed during the Demonstration
are properly recorded
Information to evaluate the portability of each device, including ease of transport, setup and tear down time, size
and weight of the unit and peripherals, need for a power source, and ease with which the instrument is re-
packaged for movement to another location are noted in a consistent manner
Observation regarding the durability of each device, such as the materials and quality of construction and major
peripherals, all device failures, routine maintenance, repairs, and downtime are documented according to
procedures
The use of replacement parts or spare devices during the Demonstration, along with their availability and delivery
time, are fully documented. After the field Demonstration, the developer's office (or web page) and/or re tail store
will be contacted to identify current supplies of the tested measurement device and spare parts.
8.3 Corrective Action
This subchapter defines the nature and timing of corrective actions that will be implemented in response to any findings
during the systems audits (no performance audits are planned) performed for this project (Subchapter 8.3.1). In addition,
Subchapter 8.3.2 describes corrective actions for data outside of control limits.
Corrective actions will be initiated immediately upon identification of any problems with the project that affect product
quality. The initial responsibility for identifying the causes of laboratory problems lies with the analyst, who along with the
laboratory QA manager or laboratory technical manager will work towards developing a solution. Field personnel who
identify a problem with data collection activities will report the difficulty to the SAIC TOM or SAIC SITE QA manager. The
root cause(s) of the problem will be determined, and its effect on the program will be identified. The SAIC TOM and QA
manager, and appropriate laboratory personnel (e.g., laboratory QA manager) will develop a plausible corrective action.
If necessary, the SAIC TOM will assist in developing corrective actions.
As data problems arise, the contractorteam will investigate the problems and perform one or more of the following actions:
If the problem occurs in the field, the SAIC observers will attempt to correct the problem. If the observers cannot
correct the problem without loss of field data or samples, he/she will immediately contact the SAIC TOM or SAIC
QA manager for additional instructions
If the problem occurs in the laboratory, the laboratory supervisor will try to correct the problem. If the laboratory
supervisor cannot correct the problem without loss of analytical data of known quality, he or she will immediately
contact the laboratory project manager and/or their respective QA coordinator for additional instructions.
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A corrective action memorandum will be prepared that documents the problem and then describes the proposed corrective
action that will be implemented. All corrective actions will first be approved by SAIC in conjunction with the EPA. A copy
of the memorandum will be sent to the SAIC SITE QA manager and the SAIC TOM. As required, a copy will be sent to
the EPA TOM and to any other personnel who would be affected by the corrective action. The appropriate project manager
or their designees will be responsible for implementing the corrective actions and for assessing the effectiveness in
correcting the problem.
8.3.1 Corrective Action for Systems Audits
As noted above, field and laboratory activities will be audited to ensure that required field and laboratory procedures are
being followed. If deficiencies or problems are discovered during the audit, the SAIC QA manager or designee will prepare
a corrective action memorandum to document the procedures to be implemented to correct the deficiency.
8.3.2 Corrective Action for Data Outside Control Limits
If at any time the data fall outside previously designated limits, the following actions will be taken:
If a laboratory person observes that instruments are not within calibration limits, the instruments will be
immediately re-calibrated; samples will be re-analyzed once an acceptable calibration has been obtained
If afield/laboratory person or engineering staff member observes data problems (for exam pie, if results for specific
QC analyses are outside the QC limits), he or she will immediately notify the appropriate QA manager or SAIC
TOM. A determination will be made on the impact of the problem on the data quality and whether any corrective
action should be taken
If a field/laboratory person observes procedures not being done in accordance with the QAPP he or she will
immediately notify the appropriate QA manager or SAIC TOM.
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Chapter 9
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U.S. Environmental Protection Agency. 1994. Region 9. December 1 994. Human Health Risk Assessment and Remedial
Investigation Report - Carson River Mercury Site (Revised Draft).
U.S. Environmental Protection Agency 1998. Unpublished. Quality Assurance Project Plan Requirements for Applied
Research Projects, August 1998.
U.S. Environmental Protection Agency. 2002. Region 9 Internet Web Site, www.epa.gov/region9/index.html.
U.S. Environmental Protection Agency. 2002. Guidance on Data Quality Indicators. EPA G5i Washington D.C. July 2002.
Wilcox, J.W, Chairman. 1983. Mercury at Y-12: A Summary of the 1983 UCC-ND Task Force Study. Report Y/EX-23,
November 1983.
67
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Appendix A
LABORATORY HOMOGENIZATION AND SUBSAMPLING OF
FIELD COLLECTED GEOMATERIALS
REVISION 1
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APPENDIX A
LABORATORY HOMOGENIZATION AND SUBSAMPLING OF
FIELD COLLECTED GEOMATERIALS
REVISION 1
1. SCOPE AND APPLICATION
The purpose of this laboratory procedure document is to describe the technique for the homogenization and
splitting of geomaterials collected in the field and is intended for further distribution. Geomaterials received
from field sites will be homogenized and aliquoted as described in this procedure.
2. DISCUSSION AND CONSIDERATIONS
Sampling, as discussed herein, is the process of collecting portions of a medium as something that is
representative of a whole part. It is the intention that field-collected geomaterial from one source is to be
homogenized and the subsequently aliquoted samples distributed. The final distributed samples will be
representative of each other and the homogenized material from which they were cut — not necessarily
representative of the original field material. The inherent non-homogeneous nature of a field collected
geomaterial dictates that any subsamples (aliquot) from this material must first be homogenized in a clearly
defined way so thatall produced subsamples (aliquots) represent each other and are interchangeable. Afield
geomaterial sample to subsample (aliquot) producing protocol is outlined in this procedure to obtain reliable,
homogenized common samples for further intra laboratory/vendor investigation.
The goal of this procedure is to produce subsampled materials that meet these criteria.
The end resulting subsampled material may not (and need not be for this demonstration) necessarily be
representative of the field site from which it came. It is clearly important to this project that the final distributed
aliquoted subsamples are equal in their makeup (both texturally and chemically) and are produced from a
common mother material. The common mother material may be initially handled in the field collection process
and/or the processing laboratory prior to homogenization for ease in the homogenization and distribution
process itself. For instance, large bits of debris may be removed from the arriving field geomaterial and not
be included in any of the subsamples (aliquots) subsequently produced. Further, included vegetative cover,
excess water, foreign inclusive materials, and overabundant biomass materials are all sometimes present in
field-collected samples. This procedure allows for their removal prior to the final homogenization process.
This makes the subsamples (aliquot) different from the original collection site, but allows them to be alike
when further homogenized and prepared for distribution.
Prior to the actual field sampling, the true nature of the material will be unknown. As such, the reader will find
two distinct preparation procedures that are presented to accommodate both "dry" and "wet" sample
homogenization and aliquoting. It is left to the SAIC GeoMechanics Laboratory to evaluate the arriving field
sample and discuss with the SAIC TOM the choice of preparation methods to use.
Instruction is offered on appropriate decontamination procedures for the general laboratory sampling and
homogenizing equipmentand is intended to preventcross-contamination. To minimize the potentialforcross
contamination, the laboratory will use disposable equipment when practical. Sampling equipment such as
scoops, bowls, spoons, etc. may be purchased, used, and readily disposed of, alleviating the need for
decontamination.
3. EQUIPMENT
Geomaterial preparation equipment may include the following. The equipment described represents a general
A-1
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guide to acceptable items that may be used while conducting this procedure. Useful items may be:
• Clean, contaminant free tarps, dropcloths, polyethylene sheeting, canvas.
• Various apparatus for grinding geomaterials such as mortar and pestle, motorized or manual
grinders, blenders, stirring devices.
• Contaminant free pails, containers, storage boxes.
• Commercially available coolers.
• Stainless steel, plastic, or other appropriate homogenization buckets, tubs, bowls or pans
• Refrigerator.
• Scoops, spoons, spatulas, shoveling devices.
Ice, blue ice.
Labels.
• Chain of custody records and custody seals.
• Decontamination supplies/equipment.
Personal protection equipment which may include latex (or other protective) gloves, respirators,
safety glasses, aprons, steel toed boots.
• Riffle splitter.
• Teflon sheeting.
Rectangular scoop.
4. DECONTAMINATION
The following steps will be followed to decontaminate any general laboratory equipment that has been in
contact with a potentially contaminated media.
1. Scrub equipment with a non-phosphate detergent.
2. Rinse with tap water.
3. If the presence of oil and grease was observed and is present on the equipment, rinse with ethanol
then rinse with tap water.
4. Rinse with a 1% HCI solution.
5. Rinse with deionized water.
6. Air dry when practical or use clean, disposable toweling to dry.
5A. DRY PREPARATION PROCEDURE (NON-SLURRY MATRIX)
1. Decontaminate any general laboratory equipment that has been in contact with a potentially
contaminated media. Refer to Section 4 for instruction.
2. Lay out clean plastic sheeting (or any other appropriate dropcloth) over a surface large enough to
allow the field sampled geomaterial to lay undisturbed while being air dried — approximately one to
two days. A large open container/tub is also acceptable to use.
3. Allow the field sampled geomaterial shipment container to equilibrate to room temperature and open
the container.
4. Gather a representative field geosample by first emptying the entire representative field sample onto
a large clean tarp or into a large open container/tub. Quarter the sample by making two roughly
perpendiculartop to bottom cuts through the sample forming fourgenerally equal quarters. Take one
or more quarters, depending upon the number of quarters required to obtain a portion that visually
approximates >3 liters of material. Spread the material over the prepared dropcloth (container)
allowing it to air dry.
5. Return the unused quarters to the shipment container, reseal, and store it.
6. Visually inspectthe exposed field geosample forforeign and/ormanmade materials and inconsistent
natural fractions such as large cobbles, sticks, leaves, shells, etc., and dispose of these.
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7. Allow the exposed geosample to air dry undisturbed for a period of approximately 2 days.
8. Break up the entire air-dried field geosample using any various convenient methods including hand
crumbling, use of a mortar and pestle, roller, etc. which will help to facilitate eventual screen ing of the
material.
9. Pass the entire fraction of the now air-dried laboratory sample through a No. 10 mesh screen (2 mm
opening) onto a clean smooth surface.
10. Discard any portion of the air-dried laboratory sample not passing the No. 10 screen, setting aside
that portion passing the No. 10 screen for further handling.
11. To reduce the sample size for ease of further handling, proceed by emptying the air-dried laboratory
sieved sample out onto a clean, smooth surface and pile it into roughly a cone shape. Two
top-to-bottom cuts will be made through the cone at roughly perpendicular angles to form four
generally equal portions (quarters). Remove one quarterfrom the pile using a clean scoop and put
into a clean container.
12. Visually ensure that there is sufficient mate rial to fill the required amount of containers (approximately
>0.75 liters). If there is insufficient sample amount, manually mix the remaining material left from the
quartering procedure. Use the spatula and mix for 2 to 3 minutes until the sample appears to be
uniform and repeat step 11. Add this additionally produced quarter to that originally prepared.
13. The representative laboratory sample should now be homogenized by using a variation of the riffle
splitting method and begins by manually mixing the representative laboratory sample in the container
with a spatula or spoon for 2 to 3 minutes or until the sample appears to be uniform.
14. Pour the representative laboratory sample from the mixing container through a riffle splitter.
15. Combine the resultant split halves back in the container.
16. Combine the halves and reintroduce them through the riffle splitter.
17. Repeat mixing and riffle splitting for a total of five times using the same container and spoon each
time the resultant halves are combined (abridged from ASTM D6323-98 section 6.1.14.2).
18. Again, recombine the two halves taken from the riffle splitter in the container and pour through the
riffle splitter a final sixth time. Keep both halves as produced in the two riffle pans.
19. Pour out one of the half portions of the riffled laboratory sample onto a clean smooth surface such
as a Teflon sheet and shape into an elongated rectangular pile with a flattened top surface using a
clean instrument such as a spatula or knife.
20. Visually ensure that the pile is wide enough to allow sampling which will produce one half the total
samples required. The transverse cuts will be produced with a rectangular scoop; each pass should
allow for enough volume to fill a 20 milliliter container at least 3/4 full.
21. Subsampling of the representative laboratory sample now commences. One complete top-to-bottom
transverse cut is made across the pile and the scooped material is transferred into a clean,
20-milliliter container. Ensure that the container is filled approximately to at least 3/4 full by visual
inspection. Cap the container and set aside.
22. Repeat transverse cuts until one half of the total amount of samples needed are produced (abridged
from ASTM D6323-98 section 6.1.9.1).
23. Transfer the remaining material in the pile, after filling one half of the total amount of samples
required, into a 4 oz (or other appropriately sized) jar. This same jar can be used for both halves.
This jar will be held at the SAIC Geo Mechanics laboratory until the SAIC TOM determines the sample
no longer has value.
24. Repeat steps 19 through 23 using the remaining riffle split half.
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25. Gather all containers of the capped and containerized subsplit samples and apply the appropriate
unique premarked blind-coded labels.
26. Place in a refrigerator with temperature of approximately 4 degrees C to await shipment.
27. Forward the homogenized and subsampled material to the appropriate vendors and/or laboratories
according to the Demonstration plan.
5B. WET PREPARATION PROCEDURE (SLURRY MATRIX)
1. Decontaminate any general laboratory equipment that has been in contact with a potentially
contaminated media. Refer to Section 4 for instruction.
2. Allow the field sampled geomaterial shipment container to equilibrate to room temperature and open
the container.
3. Visually inspectthe exposed field geosample forforeign and/ormanmade materials and inconsistent
natural fractions such as large cobbles, sticks, leaves, shells, etc., and dispose of these.
4. Using a suitable hand-held drill motor with an attached clean paint stirring mixing rod, mix the entire
shipment (in its original shipping container) at constant speed for a period of 2-4 minutes. Care
should be taken to mix the entire fie Id sample by moving the mixing rod throughout the whole volume
of material during the entire mixing time. Do not allow the mixing to be stationary.
5. At the end of the preliminary mixing, gather a representative field geosample by immediately
transferring approximately 2 liters of material to a clean container.
6. Reseal the shipment container containing the remaining original field geosample and store.
7. Using a constant speed, mix the 2 liters of slurry with a commercially available mixer, a handheld
electric drill, or other appropriate instrument equipped with a stirring/mixing rod (e.g., paint stirring
rod). Mix the slurry for approximately 3 minutes to homogenize it.
8. To subsample, use tongs or other convenient instrument to submerse the required number of
20-milliliter containers into the slurry at one time. (This may be accomplished by grouping the
containers together and wrapping them with a rubberband to hold them as one unit and submerging
the unit at one time into the slurry.)
9. Allow the containers to fill, pull the unit of bottles out of the slurry, wipe the sides of each vial, and
immediately cap.
10. Gather all containers of the capped and containerized subsplit samples, remove excess slurry from
the outside of the containers, and apply the appropriate unique pre-marked blind-coded labels.
11. Place in a refrigerator with temperature of approximately 4 degrees C and allow to settle for a
minimum of 48 hours.
12. After settling, remove the containers from the refrigerator. Using a disposable, needle-nose Pasteur
pipette or other appropriate device, remove the standing water from each container.
13. Return the containers to the refrigerator with temperature of approximately 4 degrees C to await
shipping.
14. Forward the homogenized and subsampled material to the appropriate vendors and/or laboratories
according to the governing plan.
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6. REFERENCES
American Society for Testing and Materials. 1998. "Standard Practice for Laboratory Subsampling of Media
Related to Waste Management Activities", ASTM Designation: ASTM D6323-98.
Hawaii UST Technical Guidance Manual, Appendix 7-E , "Recommended Sampling and Analysis Procedures,
Soil Sampling", 2000.
US EPA Environmental Response Team Standard Operating Procedures, SOP 2012, Soil Sampling, 2000.
American Society for Testing and Materials. 1987. "Standard Practice for Sampling Aggregates, ASTM
Designation: D75-87.
"Sample Handling Strategies for Accurate Lead-in-Soil Measurements in the Field and Laboratory", Stephen
Shefsky, NITON LLC, Billerica, MA, 1997.
A-5
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Appendix B
Analytical Laboratory Services, Inc.'s
Standard Operating Procedures
Mercury by Cold-Vapor Atomic Absorption Using
an Automated Continuous-Flow Vapor Generator
Subsampling Procedure for Nonvolatile Analysis or
Preparation
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Document Title:
Mercury by Cold-Vapor Atomic Absorption Using
an Automated Continuous-Flow Vapor Generator
Document Control Number:
Organization Title: ANALYTICAL LABORATORY SERVICES, INC.
(ALSI)
Address:
34 Dogwood Lane
Middletown, PA 17057
Phone:
(717)944-5541
Approved by:
Helen MacMinn,
Quality Assurance Manager
Date
Ray Martrano,
Laboratory Manager
Date
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not intended to
constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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Method: 03-Hg
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TABLE OF CONTENTS
1 Scope and Application 3
2 Summary of Method 3
3 Interferences 4
4 Safety 4
5 Apparatus and Materials 5
6 Reagents 5
7 Instrument Calibration 6
8 Quality Control 7
9 Sample Collection, Preservation and Handling 9
10 Procedure 10
11 Calculations 11
12 Reporting Results 12
13 Waste Disposal 13
14 Pollution Prevention 13
APPENDIX A 14
SOP Concurrence Form 19
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not intended to
constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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Scope and Application
1.1 This document states the policies and procedures established in order to meet
requirements of all certifications/accreditations currently held by the laboratory,
including the most current NELAC standards.
1.2 This method is adapted from EPA Method 245.1, revision 3.0, May 1994; EPA
Method 245.5, Mercury in Sediment, March 1983; SW-846 Method 7470B, Mercury
in Liquid Waste, January 1998; and, Method 747IB, Mercury in Solid or Semisolid
Waste, January 1998.
1.3 This method is restricted to use by or under the supervision of analysts experienced in
the use of cold vapor analysis. Each analyst must also be skilled in the interpretation
of raw data, including quality control data.
1.4 This method measures total mercury (organic-inorganic) in drinking, surface, saline,
and ground waters, domestic and industrial wastes, and mobility-procedure extracts.
It also applies to soils, sediments, bottom deposits, and sludge-type materials.
1.5 In addition to inorganic forms of Mercury, organic materials may also be present.
These organo-mercury compounds will not respond to the cold vapor atomic
absorption technique unless they are first broken down and converted to mercuric
ions. Potassium permanganate oxidizes many of these compounds, but recent studies
have shown that a number of organic mercurials, including phenyl mercuric acetate
and methyl mercuric chloride, are only partially oxidized by this reagent. Potassium
persulfate has been found to give approximately 100% recovery when used as the
oxidant with these compounds. Therefore, a persulfate oxidation step following the
addition of the permanganate has been included to insure that organo-mercury
compounds, if present, will be oxidized to the mercuric ion before measurement. A
heat step is required for methyl mercuric chloride when present in or spiked to a
natural system.
1.6 All samples must be digested prior to analysis.
1.7 Method Detection Limits can be found in the metals department method detection
limit book. The detection limits for a specific sample may differ from those listed due
to the nature of interferences in a particular sample matrix.
2 Summary of Method
2.1 The flameless AA procedure is a physical method based on the absorption of radiation
at 253.7 nm by mercury vapor. The samples/standards and reagents are pumped into
the analyzer and mixed. Argon gas is introduced into the solution stream, which flows
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not intended to
constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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to a mixing coil where the samples and reagents are thoroughly combined in the
mixing coil. The gas and liquid stream is transferred to the gas/liquid separator where
the gas and liquid phases are separated. The liquid waste is drained off and the gas is
pumped to the absorption cell. The absorption cell is positioned in the light path of
the mercury lamp. Absorbance (peak height) is measured as a function of mercury
concentration and recorded as ppb of mercury.
Interferences
3.1 Possible interference from sulfide is eliminated by the addition of potassium
permanganate. Concentrations as high as 20 mg/L of sulfide as sodium sulfide do not
interfere with the recovery of added inorganic mercury from distilled water.
3.2 Copper has also been reported to interfere; however, copper concentrations as high as
10 mg/L had no effect on recovery of mercury from spiked samples.
3.3 Sea waters, brines, and industrial effluents high in chlorides require additional
permanganate (as much as 25 ml). During the oxidation step, chlorides are converted
to free chlorine which will also absorb radiation of 253 nm. Care must be taken to
assure that free chlorine is absent before the mercury is reduced and swept into the
cell. This may be accomplished by using an excess of hydroxylamine hydrochloride
reagent (25 ml). Both inorganic and organic mercury spikes have been quantitatively
recovered from seawater using this technique.
3.4 Interference from certain volatile organic materials which will absorb at this
wavelength is also possible. All positive samples must be checked for false increases
due to organics by analysis without the addition of stannous chloride.
4 Safety
4.1 Operation of an atomic absorption spectrophotometer involves the use of argon gas
and hazardous materials including corrosive fluids. Unskilled, improper, and careless
use of equipment can create explosion hazards, fire hazards or other hazards, which
can cause death, serious injury to personnel, or severe damage to equipment or
property.
4.2 Caution shall be taken when handling all samples, standards, and QC material because
of the acidic nature of the prepared samples as well as the possible mercury content in
the samples.
4.3 Proper personal protective equipment must be used, including gloves, safety glasses,
and lab coat.
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not intended to
constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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4.4 The fume hood must be turned on during the analysis of mercury to vent the waste
vapor.
5 Apparatus and Materials
5.1 Leeman Labs PS200 Automated Mercury Analyzer - instrument with a double beam
optical arrangement.
5.2 Blue sample pump tubing. Leeman Labs, cat. #309-00104-2.
5.3 Red reductant pump tubing. Leeman Labs, cat. #309-00033.
5.4 Yellow, blue, yellow pump tubing - used as drain tubing.
5.5 Mercury Hollow cathode lamp.
5.6 Finnpipette with disposable tips. Baxter #P5055-51
5.7 Various Class A volumetric glassware
5.8 Various calibrated dispensers
5.9 40 ml VGA vials
5.10 25 ml graduated cylinder
5.11 Water Bath maintained at 95°C
5.12 8 ml polystyrene tubes, purchased from CPI.
6 Reagents
6.1 Reagent water is water in which an interferant is not observed at the analyte of
interest. For this purpose, ALSI uses a Filson Water Purification System, which
provides analyte-free DI water greater than 16.0 megohm on demand. This water is
used for preparation of all reagents, calibration standards, and as dilution water.
6.2 Liquid Argon - high purity grade, MG Industries or equivalent.
6.3 Stannous Chloride. Prepare by adding 100 g of stannous chloride crystal (VWR, cat.
#JT3980-11 or equivalent) to a 1000 ml volumetric flask. Add 14.0 ml cone. H2SO4
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and stir until dissolved. Bring up to volume with reagent water.
6.4 Sulfuric Acid, cone. Baker Instra-analyzed grade or equivalent.
6.5 Sodium Chloride (NaCl.) Baker instra-analyzed grade. VWR, cat. #JT3625-15 or
equivalent.
6.6 Hydroxylamine hydrochloride decolorizing reagent. To prepare, dissolve 120 g
Hydroxylamine hydrochloride crystals (VWR, cat. #JT2196-1 or equivalent) and 120
g NaCl in reagent water in a 1000 ml volumetric flask. Bring up to volume using
reagent water.
Instrument Calibration
7.1 The instrument plots a standard calibration curve using five standards and a blank.
The calibration standards, Blank, 0.2 [ig/L, 1.0 |ig/L, 2.0 [ig/L, 4.0 [ig/L, and 10.0
Hg/L, are prepared. Starting with the blank and working toward the high standard, the
standards are introduced into the mercury analyzer by the autosampler. Absorbance
readings are recorded by the data system.
7.2 A calibration curve is drawn by plotting the absorbance readings on the y-axis and
concentration readings on the x-axis. The software of the data system plots the curve.
The calibration curve is used to calculate the concentration for the samples. The
correlation coefficient must be 0.995 or greater.
7.3 A set of calibration standards is prepared along with every batch of mercury samples
digested. It is these standards, which must be used to prepare the calibration curve for
that batch of samples.
7.3.1 This is especially important because Method 245.1 and Method 7470/7471
batches are prepared differently. Drinkingwater batch and groundwater/soil
batch standards shall never be interchanged.
7.4 An Initial Calibration Verification (ICV) must be analyzed after every calibration to
verify the instrument performance during analysis. The ICV is prepared from the
second source standard. Analysis of the ICV immediately following calibration must
verify that the instrument is within +/- 5% of calibration. Subsequent analysis of this
standard is called the continuing calibration verification standard (CCV) and must be
within ±10% of calibration. If outside of this range, determine and correct the
problem. If necessary, recalibrate. Samples may not be analyzed until an acceptable
ICV/CCV is analyzed.
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not intended to
constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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7.5 Laboratory Control Sample (LCS). A same source standard as the calibration
standards must be analyzed with each batch and after every calibration. It is prepared
at 2.0 ppb from the same source as that of the calibration standards. The recovery
must be within +/- 15% of the true value for the calibration. If outside of this range,
determine and correct the problem and re-analyze. If necessary, recalibrate. Samples
may not be analyzed until an acceptable LCS is analyzed.
8 Quality Control
All policies and procedures in the most current revision of the ALSI QA Plan shall be
followed when performing this procedure.
Quality Control Requirements
(Specific Project Requirements may override these requirements)
Parameter
Calibration Blank
(ICB/CCB)
Method Blank
Laboratory Control
Sample (LCS) or
Laboratory Fortified
Blank (LFB)
Concentration
NA
NA
Water: 2.0 ug/L
Soil: 100 ug/kg
Frequency
Prepared with each batch of samples.
Analyzed after every ICV/CCV, at a
minimum frequency of 10% and after
calibration.
One digested with each batch of 20
or less samples. They are analyzed
with that batch of samples.
One digested with each batch of 20
or less samples. They are analyzed
with that batch of samples.
Acceptance
Criteria
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Matrix Spike (MS)*
Matrix Spike
Duplicate (MSD) or
Duplicate (Dup)*
Initial/Continuing
Calibration
Verification
Standard
(ICV/CCV)
(Second Source)
IPC/QCS
Water: 5.0 ug/L
Soil: 250 ug/kg
Water: 5.0 ug/L
Soil: 250 ug/kg
4.0 ug/L
Frequency of 10% per matrix per
batch
Frequency of 10% (USAGE samples
- 100% frequency)
Immediately after calibration, after
every ten samples, and after the last
sample.
80- 120% R
<20%RPD
Immediately
after
calibration
+/-5%R.
Thereafter it
must be
within +/-
10% R.
problem cannot be identified,
the samples in that batch
must be re-digested. If re-
digestion is not possible,
report with a qualifying
comment.
Re-analyze the MS. If still
out of range analyze a post
digestion spike (85-115%). If
still out of range, a qualifying
comment on the final lab
report.
Re-analyze the duplicate. If
the sample is outside the
range, redigest the sample. I
still outside of acceptable
limits, report with a comment
on the lab report.
Re-analyze the ICV. If still
out of range, the problem
must be identified and
corrected before analyzing
any samples. Any samples
analyzed after the last
acceptable ICV/CCV must be
re-analyzed.
* Samples selected for duplicate and matrix spike analysis shall be rotated among client
samples so that various matrix problems may be noted and/or addressed. Poor
performance in a duplicate or spike may indicate a problem with the sample
composition and shall be reported to the client whose sample produced the poor
recovery.
8.2 Sample concentrations must fall within the linear dynamic range to be reported. Any
result greater than the calculated linear dynamic range must be diluted to fall within
the calibration range. For drinking water, any sample with results greater than the
highest standard will be diluted and reanalyzed until the concentrations are within the
calibration range.
8.2.1 Linear Dynamic Range (LDR) - The upper limit of linearity must be
determined. Analyze succeeding higher concentrations of the analyte until the
percent recovery falls under 90%. The last concentration maintaining greater or
equal to 90% recovery is considered the upper limit of linearity. Samples
containing analytes greater than 90% of the upper limit of linearity must be
diluted and reanalyzed for those analytes. The LDRs are verified annually or
any time a change in operating conditions occurs that may change the LDR.
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not intended to
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8.3 Method detection limits are determined annually using the procedure outlined in the
ALSI Quality Assurance Plan. NOTE: If USAGE samples are to be analyzed, an
MDL check sample will be used to verify the MDL. The MDL check sample is at a
concentration equal to 2 x the MDL. If a positive response is detected from the MDL
check sample, another MDL study is not needed for that calendar year.
8.3.1 Practical Quantitation Limits (PQL) or reporting limits are determined by
multiplying the MDL by 3-5 times, and adding an appropriate safely factor.
8.4 If the matrix spike fails criteria, a post digestion spike is performed. If the
recovery of the post digestion spike is within 85-115%, the results will be
reported. If outside of this range, comment on the final report.
9 Sample Collection, Preservation and Handling
9.1 Sample Collection:
9.1.1 Samples can be collected in plastic or glass bottles.
9.1.2 Aqueous samples requiring dissolved metals shall be filtered immediately on
site before adding preservation for dissolved metals.
9.2 Sample Preservation:
9.2.1 Preserve aqueous samples using HNOs to a pH <2. Sample preservation shall
be performed immediately upon sample collection. If this is not possible, then
samples would be preserved as soon as possible when received at the
laboratory.
9.3 Sample Handling:
9.3.1 All samples must be analyzed within 28 days of collection. All samples not
analyzed within this time frame must be discarded and resampled for analysis.
9.3.2 All samples require digestion. Refer to the Sample Preparation SOP for
procedures.
10 Procedure
10.1 Turn on the fume hood and computer data system. Make sure that the Argon gas is at
50 psi.
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constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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Method: 03-Hg
Revision: 9
Date: November 5, 2002
Page: 10 of 19
10.2 If the computer program fails to load and the C prompt appears, type PS to load the
software.
10.3 Type P for protocol and G to open a folder. Type in either 'waters' or 'soils'
depending on the matrix being analyzed.
10.3.1 Name the folder by typing the date and 'W for water or 'S' for soil. Press
enter.
10.3.2 Press Fl to get back to the main menu.
10.4 Press F2 to open the macro. Type COLDSTRT and press enter. This will initiate
heating of the lamp and will condition the pump tubing.
10.5 Change the pump tubing if there is evidence of wear such as flattening with
red/red/red tubing. Remove and replace if needed. Securely clamp down the tubing.
10.5.1 Clean the drying cell with reagent water and dry. Fill the drying cell with
Magnesium Perchlorate.
10.5.2 Fill the rinse bath with 10% HC1 and place both probes into the rinse bath. Fill
the Stannous Chloride bottle.
10.6 After approximately 2.5 hours, a flag will appear saying 'operation complete'. Place
the Stannous Chloride probe into the stannous chloride bottle which is placed on a
magnetic stirrer.
10.6.1 Press Fl to bring up the main menu. Press 'U' for utility and 'G' for
Diagnostics. Use the arrow keys to move down to test optics. Press Enter.
(The values need to be within 5% of each other.)
10.6.2 Press Fl, for main menu. Press F2, for macro. Type APERTEST and Enter
(to test aperture). The aperture shall be +/- 50 (~0). If not, adjust by slightly
turning the lower screw with an alien wrench found inside the instrument.
10.7 Go back to the main menu. Add 1.5 mL of NaCl hydroxylamine hydrochloride to
each vial and shake. Place calibration standards and QC's into appropriate positions
in the tray.
10.7.1 Press F2 (macro) and type Cal 245/enter. The instrument will begin to
automatically calibrate for approximately one hour. Once a flag appears
saying Idle, hit F10 (stop) and Fl (main menu).
10.8 Type 'C' for calibration and 'L' for line calibration (The R factors need to be at least
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constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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Method: 03-Hg
Revision: 9
Date: November 5, 2002
Page: 11 of 19
0.995). Press 'A' for accept. Print screen by pressing F3. Go to the main menu.
10.9 Analyze check standard 1 (blank) by pressing F7 and then number 1. The blank shall
be within +/- (MDL).
10.9.1 Check standard 2 (ICV) by pressing F7 and the #2. The initial QC shall be
within 5% of the true value. The continuing CCV has to be within 10%.
10.10 Load the autosampler trays with the samples, while recording the sample ID in the
logbook.
10.10.1 Go to the main menu and press 'A' for autosampler, 'R' for rack entry
and make sure the instrument is programmed to check QC (4.0) every
10 samples (by typing C31 after every 10th sample) with a 10%
acceptability.
10.10.2 Go back to the main menu and press 'S' for setup under Autosampler.
Go under Station Rack 1 and type the first sample being analyzed and
the last sample being analyzed.
10.11 Go to the main menu, hit F2, type autosaml. This will begin the analysis.
10.12 After analysis, any sample that has a result above the reporting limit (0.0005 mg/L for
TWHG or 0.001 mg/L for SPLP's and SHG or 0.006 mg/L for TCLP's or 0.0002
mg/L for Hglow) must be rerun without stannous chloride to determine if an organic
interference is present.
10.12.1 If the stannous chloride result is greater than the reporting limit,
subtract the non-stannous chloride result to get the final mercury
concentration.
11 Calculations
11.1 Samples results are documented directly form the readout of the instrument in ppb
(from the calibration curve).
11.2 The results are converted to ppm and input into the LIM system.
11.3 Samples requiring dilution at the time of analysis to bring the result into calibration
range are multiplied by the dilution factor used before inputting into the LIM system
using the following equation:
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constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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Method: 03-Hg
Revision: 9
Date: November 5, 2002
Page: 12 of 19
where:
A= Concentration of mercury in the sample
B= Final volume of the dilution (ml)
Z= Concentration of mercury in the dilution
C= Volume of sample aliquot used in the
dilution
12 Reporting Results
12.1 Report water results in the computer as mg/L and soil results as mg/kg using three
significant figures in the AMS LIMS. In the Horizon LEVIS, do not round results.
The LIMS will round off to 3 significant figures after all internal calculations have
been completed.
12.2 All data produced will be reviewed and initialed by the supervisor or his designee to
insure that data reported meets the required quality assurance and regulatory criteria.
12.3 Report results in the LIM system: All results are reported to three significant
figures but limited to the number of decimal places in the reporting limit for the
individual compound or analyte. For rounding off numbers to the
appropriate level of precision, the laboratory will follow the following rules
12.3.1 If the figure following those to be retained is less than 5, the figure is dropped,
and the retained figures are kept unchanged. As an example, 1.443 is rounded
off to 1.44.
12.3.2 If the figure following those to be retained is greater than 5, the figure is
dropped, and the last retained figure is raised by 1. As an example, 1.446 is
rounded off to 1.45.
12.3.3 If the figure following those to be retained is 5, and if there are no figures other
than zeros beyond the five, the figure 5 is dropped, and the last-place figure
retained is increased by one if it is an odd number or it is kept unchanged if an
even number. As an example, 1.435 is rounded off to 1.44, while 1.425 is
rounded off to 1.42.
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not intended to
constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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Method: 03-Hg
Revision: 9
Date: November 5, 2002
Page: 13 of 19
12.4 When entering data into the Horizon LEVIS, do not round off results. The LIMS will
automatically round results off to 3 significant figures after all internal calculations are
completed.
12.5 Any sample with a result less than the reporting limit is reported as ND (non-
detectable) with the appropriate detection limit in the AMS LIMS. Report the actual
result in the Horizon LIMS.
13 Waste Disposal
Refer to ALSI SOP 19-Waste Disposal.
14 Pollution Prevention
Pollution prevention encompasses any technique that reduces or eliminates the quantity or
toxicity of waste at the point of generation. Numerous opportunities for pollution prevention
exist in laboratory operations. Management shall consider pollution prevention a high
priority. Extended storage of unused chemicals increases the risk of accidents. The
laboratory shall consider smaller quantity purchases which will result in fewer unused
chemicals being stored and reduce the potential for exposure by employees. ALSI tracks
chemicals when received by recording their receipt in a traceable logbook. Each chemical is
then labeled according to required procedures and stored in assigned locations for proper
laboratory use.
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not intended to
constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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Method:
Revision:
Date:
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03-Hg
9
November 5, 2002
14 of 19
APPENDIX A
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Method:
Revision:
Date:
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03-Hg
9
November 5, 2002
15 of 19
APPENDIX A
Protocol: waters
RSY: 2.308 Tii*: 12:23:^1
Fgtder: B81398* S»q: 79
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standards
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Method:
Revision:
Date:
Page:
03-Hg
9
November 5, 2002
16 of 19
APPENDIX A
Protocol: waters
Rev: 2,868 tine: 12:33:% 14 Auj 1998
Folde?: B81396M Set' 79 Print: On
User; Bite*: H: Cup: &*: LW
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Method:
Revision:
Date:
Page:
03-Hg
9
November 5, 2002
17 of 19
APPENDIX A
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Method:
Revision:
Date:
Page:
03-Hg
9
November 5, 2002
18 of 19
APPENDIX A
Protocol: SYSTEST
Rtv: 2.S
Balder: SvSTSST Seas 3
User; Batchi
State; Non»
Ti«»; I2;3&l33 14 Sug
Print; On
Id: Cup! Gil: |_P«
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pu»p Bit* S iL/lin (2 - IS) Off
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- uf Aaalftii-al
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ewi/in i.i-fam & nw >r w*
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Method: 03-Hg
Revision: 9
Date: November 5, 2002
Page: 19 of 19
SOP Concurrence Form
for the Distribution and Revision of Standard Operating Procedures
I have read, understood, and concurred with the Standard Operating Procedure (SOP) described
above and will perform this procedure as it is written in the SOP.
Print Name Signature Date
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not intended to
constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
-------
Method: 19-Subsampling
Revision: 0
Date: July 26,1999
Page: 1 of 7
Document Title: Subsampling Procedure for Nonvolatile Analysis or
Preparation
Document Control Number:
Organization Name: ANALYTICAL LABORATORY SERVICES,
INC. (ALSI)
Address: 34 Dogwood Lane
Middletown, PA 17057
Phone: (717)944-5541
Approved by:
Susan Magness,
Quality Assurance Manager
Ray Martrano,
Laboratory Manager
TABLE OF CONTENTS
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intended to constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
-------
Method: 19-Subsampling
Revision: 0
Date: July 26,1999
Page: 2 of 7
1 Scope and Application 2
2 Summary of Method 3
3 Interferences 3
4 Safety 3
5 Apparatus and Materials 3
6 Reagents 3
7 Glassware Cleaning 4
8 Quality Control 4
9 Sample Collection, Preservation and Handling 4
10 Procedure 4
11 Calculations 6
12 Reporting Results 6
SOP Concurrence Form 6
Scope and Application
1.1 This standard operating procedure addresses the removal of solid, soil and water
samples from sampling containers to ensure representativeness and homogeneity in
the aliquot submitted for testing.
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not
intended to constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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Method: 19-Subsampling
Revision: 0
Date: July 26,1999
Page: 3 of 7
1.2 Subsamples removal for volatile organic analysis are addressed in the individual
analytical SOP's and are not discussed here.
2 Summary of Method
2.1 Aliquot removal procedures are described for water, soil and solids.
3 Interferences
3.1 The appropriate sampling, preparation or analytical SOP's address the appropriate
materials of construction for sampling, measuring or transferring samples.
3.2 In general soils should be removed using stainless steel spatulas.
3.3 Soil samples should be placed in polypropylene weigh boats for mixing.
3.4 Subsampling of liquids for organic analysis should incorporate glass apparatus (i.e.
pipets, graduated cylinder) only.
3.5 Soils samples are NOT to enter the organic extraction laboratory.
4 Safety
4.1 Vinyl or latex gloves must be worn when handling sample containers. All samples
should be handled as a potential health hazard.
4.2 Samples known or found to contain irritating volatile constituents should be handled
in a fume hood.
5 Apparatus and Materials
5.1 Weighboats - polypropylene, appropriate sizes.
5.2 Spatula - stainless steel.
5.3 Pipets - polypropylene transfer or glass Pasteur.
5.4 Gloves - latex or vinyl.
6 Reagents
6.1 Not applicable.
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Method: 19-Subsampling
Revision: 0
Date: July 26,1999
Page: 4 of 7
Glassware Cleaning
7.1 Spatulas are cleaned as described in the glassware washing SOP and "general use"
glassware. All other items are single use and disposable.
8 Quality Control
8.1 Not applicable.
9 Sample Collection, Preservation and Handling
9.1 Consult the individual sampling SOP.
10 Procedure
10.1 Aqueous or free flowing samples.
10.1.1 Allow the sample to reach room temperature before aliquoting.
10.1.2 Check that the appropriate preservative has been added by checking the
container label. Consult the specific analytical SOP if preservative as
presented on the labeling or the pH contradicts that required by the
procedure.
10.1.3 Invert the container five times to allow for mixing.
10.1.4 If immiscible layers form that can not be aliquoted proportionally, contact
the appropriate customer service representative. The client should decide if
each layer is to be analyzed individually.
10.1.5 Transfer the sample into an appropriate container within 10 seconds of
inverting.
10.1.6 Return the sample container to the appropriate storage area as soon as
possible.
10.1.7 Consult the specific analytical procedure for guidance on the appropriate
materials of construction for transferring and holding sample.
10.1.8 Make any necessary comments regarding the sample and the aliquot in the
appropriate prep notebook. Be sure to record the actual weight/volume of
the final aliquot used for analysis.
10.2 Soil and solid samples.
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Method: 19-Subsampling
Revision: 0
Date: July 26,1999
Page: 5 of 7
10.2.1 Industrial wastes.
10.2.1.1 Industrial wastes (non-soils) may require crushing cutting or
shredding before use. Employ whatever means possible to
reduce these types of samples to a particle size no greater than
3/8 inch unless some other particle size is defined in the
individual analytical SOP. Comment in the analytical or
extraction logbook if a method defined particular size can not be
achieved.
10.2.1.2 Equipment rinsate blanks must be assessed if any mechanical
device (i.e., Jaw crusher) is used to crush a sample. These blanks
must be analyzed for the same parameters as the sample.
10.2.2 Soil samples.
10.2.2.1 Allow the sample to reach room temperature before aliquoting.
10.2.2.2 Refer to Section 10.1.4 if immiscible layers are observed.
10.2.2.3 Visually inspect the sample in the container. If any stratification
of sample is observed by color, particle size or apparent texture,
every effort should be made to obtain representative proportions
of the sample.
10.2.2.4 If the aliquot needed for the specific procedure is 10 grams or
less, remove a minimum of 50 grams of the sample from the
container using a stainless steel spatula and place in a
polypropylene weighboat. If the aliquot needed for the specific
procedure is greater than 10 grams, remove a minimum of 100
grams using a stainless steel spatula and place in polypropylene
weighboat.
10.2.2.5 Mix the sample with the spatula. Break any clumped soil. Mix
the soil with the spatula to homogenize any particles that may
seem unique in color, particle size or apparent texture.
10.2.2.6 Remove an homogenized representative portion of the subsample
in the weighboat into the appropriate container as described in
the analytical SOP.
10.2.2.7 Transfer the remaining subsample from the weighboat back into
the sample container.
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intended to constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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Method: 19-Subsampling
Revision: 0
Date: July 26,1999
Page: 6 of 7
10.2.2.8 Subsample placed in prerinsed glassware is NOT to be returned
to the sample container for any reason.
10.2.2.9 Cap the sample container immediately and return to storage as
soon as possible.
10.2.2.10 Make any necessary comment regarding the sample and the
aliquot in the appropriate prep notebook. Be sure to record the
actual weight/volume of the final aliquot used for analysis.
11 Calculations
11.1 Not applicable.
12 Reporting Results
12.1 Not applicable.
SOP Concurrence Form
for the Distribution and Revision of Standard Operating Procedures
I have read, understood, and concurred with the Standard Operating Procedure (SOP) described
above and will perform this procedure as it is written in the SOP.
Print Name Signature Date
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not
intended to constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
-------
Method: 19-Subsampling
Revision: 0
Date: July 26,1999
Page: 7 of 7
This document is the property of Analytical Laboratory Services, Inc. It may be used by the recipient only for the purpose for which it was transmitted. It is submitted in confidence and its disclosure to you is not
intended to constitute public disclosure or authorization for disclosure to other parties. It may not be copied or communicated without the written consent of Analytical Laboratory Services, Inc.
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