United States
Environmental Protection
Agency
Office of Research and
Development
Washington, DC 20460
EPA/540/R-06/005
February 2006
Innovative Technology
Verification Report
XRF Technologies for Measuring
Trace Elements in
Soil and Sediment
Rontec PicoTAX
XRF Analyzer
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EPA/540/R-06/005
February 2006
Innovative Technology
Verification Report
Rontec PicoTAX
XRF Analyzer
Prepared by
Tetra Tech EM Inc.
Cincinnati, Ohio 45202-1072
Contract No. 68-C-00-181
Task Order No. 42
Dr. Stephen Billets
Characterization and Monitoring Branch
Environmental Sciences Division
Las Vegas, Nevada 89193-3478
National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
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Notice
This document was prepared for the U.S. Environmental Protection Agency (EPA) Superfund Innovative
Technology Evaluation Program under Contract No. 68-C-00-181. The document has been subjected to
the Agency's peer and administrative review 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.
11
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the nation's
natural resources. Under the mandate of national environmental 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, EPA's Office of Research and Development
(ORD) provides data and scientific support that can 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 center for 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.
EPA's Superfund Innovative Technology Evaluation (SITE) Program evaluates technologies designed for
characterization and remediation of contaminated Superfund and Resource Conservation and Recovery
Act (RCRA) sites. The SITE Program was created to provide reliable cost and performance data 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 (MMT) 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 an 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 MMT Program is
managed by ORD's Environmental Sciences Division in Las Vegas, Nevada.
Gary Foley, Ph.D.
Director
National Exposure Research Laboratory
Office of Research and Development
in
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Abstract
The Rontec PicoTAX x-ray fluorescence (XRF) analyzer was demonstrated under the U.S. Environmental
Protection Agency (EPA) Superfund Innovative Technology Evaluation (SITE) Program. The field
portion of the demonstration was conducted in January 2005 at the Kennedy Athletic, Recreational and
Social Park (KARS) at Kennedy Space Center on Merritt Island, Florida. The demonstration was
designed to collect reliable performance and cost data for the PicoTAX analyzer and seven other
commercially available XRF instruments for measuring trace elements in soil and sediment. The
performance and cost data were evaluated to document the relative performance of each XRF instrument.
This innovative technology verification report describes the objectives and the results of that evaluation
and serves to verify the performance and cost of the PicoTAX analyzer. Separate reports have been
prepared for the other XRF instruments that were evaluated as part of the demonstration.
The objectives of the evaluation included determining each XRF instrument's accuracy, precision, sample
throughput, and tendency for matrix effects. To fulfill these objectives, the field demonstration
incorporated the analysis of 326 prepared samples of soil and sediment that contained 13 target elements.
The prepared samples included blends of environmental samples from nine different sample collection
sites as well as spiked samples with certified element concentrations. Accuracy was assessed by
comparing the XRF instrument's results with data generated by a fixed laboratory (the reference
laboratory). The reference laboratory performed element analysis using acid digestion and inductively
coupled plasma - atomic emission spectrometry (ICP-AES), in accordance with EPA Method
3 05 OB/601 OB, and using cold vapor atomic absorption (CVAA) spectroscopy for mercury only, in
accordance with EPA Method 7471 A.
The PicoTAX is a transportable bench-top device that provides quantitative and semi-quantitative multi-
element microanalysis of soils and sediments using total reflection XRF spectroscopy. The spectrometer
includes a 40-watt metal-ceramic x-ray tube excitation source and a thermoelectrically cooled silicon drift
(Si Drift) x-ray detector. The PicoTAX is capable of detecting up to 75 elements from aluminum to
yttrium and from palladium to uranium.
The PicoTAX uses an internal standard for instrument calibration; thus, initial calibration is not required.
A solution of internal standard that contains a project-specific element is added to each sample to
establish response factors (determined by the software). Element quantitation is determined by
comparing the response to the unknown element to the response of the internal standard with a known
concentration.
A laptop computer is used to monitor and control all aspects of PicoTAX system operation. Rontec's
Quantum software, which is loaded into the laptop computer, calibrates the instrument, handles
measurement data and methods, controls all hardware functions, and provides statistical functions,
reporting functions, and data and spectra export.
This report describes the results of the evaluation of the PicoTAX analyzer based on the data obtained
during the demonstration. The method detection limits, accuracy, and precision of the instrument for each
of the 13 target analytes are presented and discussed. The cost of element analysis using the PicoTAX
analyzer is compiled and compared to both fixed laboratory costs and average XRF instrument costs.
IV
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Contents
Chapter Page
Notice ii
Foreword iii
Abstract iv
Acronyms, Abbreviations, and Symbols x
Acknowledgements xiv
1.0 INTRODUCTION 1
1.1 Organization of this Report 1
1.2 Description of the SITE Program 2
1.3 Scope of the Demonstration 2
1.4 General Description of XRF Technology 3
1.5 Properties of the Target Elements 4
1.5.1 Antimony 5
1.5.2 Arsenic 5
1.5.3 Cadmium 5
1.5.4 Chromium 5
1.5.5 Copper 5
1.5.6 Iron 5
1.5.7 Lead 6
1.5.8 Mercury 6
1.5.9 Nickel 6
1.5.10 Selenium 6
1.5.11 Silver 7
1.5.12 Vanadium 7
1.5.13 Zinc 7
2.0 FIELD SAMPLE COLLECTION LOCATIONS 9
2.1 Alton Steel Mill Site 9
2.2 Burlington Northern-ASARCO Smelter Site 11
2.3 Kennedy Athletic, Recreational and Social Park Site 11
2.4 Leviathan Mine Site 12
2.5 Navy Surface Warfare Center, Crane Division Site 12
2.6 Ramsay Flats-Silver Bow Creek Site 13
2.7 Sulphur Bank Mercury Mine Site 13
2.8 Torch Lake Superfund Site 14
2.9 Wickes Smelter Site 14
3.0 FIELD DEMONSTRATION 15
3.1 Bulk Sample Processing 15
3.1.1 Bulk Sample Collection and Shipping 15
3.1.2 Bulk Sample Preparation and Homogenization 15
3.2 Demonstration Samples 17
3.2.1 Environmental Samples 17
3.2.2 Spiked Samples 17
3.2.3 Demonstration Sample Set 17
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Contents (Continued)
Chapter Page
3.3 Demonstration Site and Logistics 20
3.3.1 Demonstration Site Selection 20
3.3.2 Demonstration Site Logistics 20
3.3.3 EPA Demonstration Team and Developer Field Team Responsibilities 21
3.3.4 Sample Management during the Field Demonstration 21
3.3.5 Data Management 22
4.0 EVALUATION DESIGN 23
4.1 Evaluation Objectives 23
4.2 Experimental Design 23
4.2.1 Primary Objective 1 - Method Detection Limits 24
4.2.2 Primary Objective 2 -Accuracy 25
4.2.3 Primary Objective 3 - Precision 26
4.2.4 Primary Objective 4 - Impact of Chemical and Spectral Interferences 27
4.2.5 Primary Objective 5 - Effects of Soil Characteristics 28
4.2.6 Primary Objective 6 - Sample Throughput 28
4.2.7 Primary Objective 7 -Technology Costs 28
4.2.8 Secondary Objective 1 - Training Requirements 28
4.2.9 Secondary Objective 2 - Health and Safety 29
4.2.10 Secondary Objective 3 - Portability 29
4.2.11 Secondary Objective 4 - Durability 29
4.2.12 Secondary Objective 5 -Availability 29
4.3 Deviations from the Demonstration Plan 29
5.0 REFERENCE LABORATORY 31
5.1 Selection of Reference Methods 31
5.2 Selection of Reference Laboratory 32
5.3 QA/QC Results for Reference Laboratory 33
5.3.1 Reference Laboratory Data Validation 33
5.3.2 Reference Laboratory Technical Systems Audit 34
5.3.3 Other Reference Laboratory Data Evaluations 34
5.4 Summary of Data Quality and Usability 36
6.0 TECHNOLOGY DESCRIPTION 39
6.1 General Description 39
6.2 Instrument Operations during the Demonstration 39
6.2.1 Setup and Calibration 39
6.2.2 Demonstration Sample Processing 40
6.3 General Demonstration Results 41
6.4 Contact Information 41
VI
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Contents (Continued)
Chapter Page
7.0 PERFORMANCE EVALUATION 43
7.1 Primary Objective 1 - Method Detection Limits 43
7.2 Primary Objective 2 - Accuracy and Comparability 46
7.3 Primary Objective 3 - Precision 51
7.4 Primary Objective 4 - Impact of Chemical and Spectral Interferences 52
7.5 Primary Objective 5 - Effects of Soil Characteristics 56
7.6 Primary Objective 6 - Sample Throughput 56
7.7 Primary Objective 7 - Technology Cost 59
7.8 Secondary Objective 1 - Training Requirements 59
7.9 Secondary Objective 2 -Health and Safety 59
7.10 Secondary Objective 3 - Portability 60
7.11 Secondary Objective 4 - Durability 60
7.12 Secondary Objective 5 -Availability 60
8.0 ECONOMIC ANALYSIS 61
8.1 Equipment Costs 61
8.2 Supply Costs 61
8.3 Labor Costs 61
8.4 Comparison of XRF Analysis and Reference Laboratory Costs 62
9.0 SUMMARY OF TECHNOLOGY PERFORMANCE 65
10.0 REFERENCES 71
APPENDICES
Appendix A:
Appendix B:
Appendix C:
Appendix D:
Appendix E:
Verification Statement
Developer Discussion
Data Validation Summary Report
Developer and Reference Laboratory Data
Statistical Data Summaries
vn
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Contents (Continued)
TABLES Page
1-1 Participating Technology Developers and Instruments 1
2-1 Nature of Contamination in Soil and Sediment at Sample Collection Sites 10
2-2 Historical Analytical Data, Alton Steel Mill Site 11
2-3 Historical Analytical Data, BN-ASARCO Smelter Site 11
2-4 Historical Analytical Data, KARS Park Site 11
2-5 Historical Analytical Data, Leviathan Mine Site 12
2-6 Historical Analytical Data, NSWC Crane Division-Old Burn Pit 13
2-7 Historical Analytical Data, Ramsay Flats-Silver Bow Creek Site 13
2-8 Historical Analytical Data, Sulphur Bank Mercury Mine Site 14
2-9 Historical Analytical Data, Torch Lake Superfund Site 14
2-10 Historical Analytical Data, Wickes Smelter Site-Roaster Slag Pile 14
3-1 Concentration Levels for Target Elements in Soil and Sediment 18
3-2 Number of Environmental Sample Blends and Demonstration Samples 19
3-3 Number of Spiked Sample Blends and Demonstration Samples 19
4-1 Evaluation Objectives 24
5-1 Number of Validation Qualifiers 35
5-2 Percent Recovery for Reference Laboratory Results in Comparison to ERA Certified Spike
Values for Blends 46 through 70 37
5-3 Precision of Reference Laboratory Results for Blends 1 through 70 38
6-1 Rontec PicoTAXXRF Analyzer Technical Specifications 40
7-1 Evaluation of Sensitivity - Method Detection Limits for Rontec PicoTAX 44
7-2 Comparison of Mean PicoTAX MDLs to All-Instrument Mean MDLs and EPA
Method 6200 Data 46
7-3 Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data
for the Rontec PicoTAX 48
7-4 Summary of Correlation Evaluation forthe PicoTAX 50
7-5 Evaluation of Precision - Relative Standard Deviations for the Rontec PicoTAX 53
7-6 Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory
versus the PicoTAX and All Demonstration Instruments 54
7-7 Effects of Interferent Elements on the RPDs (Accuracy) for Other Target Elements, Rontec
PicoTAX 55
7-8 Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Rontec PicoTAX 57
8-1 Equipment Costs 61
8-2 Time Required to Complete Analytical Activities 62
8-3 Comparison ofXRF Technology and Reference Method Costs 64
9-1 Summary of Rontec PicoTAX Performance - Primary Objectives 66
9-2 Summary of Rontec PicoTAX Performance - Secondary Objectives 68
Vlll
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Contents (Continued)
FIGURES Page
1-1 The XRF Process 4
3-1 Bulk Sample Processing Diagram 16
3-2 KARS Park Recreation Building 20
3-3 Work Areas for the XRF Instruments in the Recreation Building 21
3-4 Visitors Day Presentation 21
3-5 Sample Storage Room 22
6-1 Rontec PicoTAX XRF Analyzer Set Up for Benchtop Analysis 39
6-2 Quart Disks Drying on a Hot Plate 41
6-3 Rontec Technicians Recording Identification Numbers 41
7-1 Linear Correlation Plot for PicoTAX Showing High Correlation for Zinc 49
7-2 Linear Correlation Plot for PicoTAX Showing High Data Variability for Silver 51
8-1 Comparison of Labor Requirements for the PicoTAX versus Other XRF Instruments 63
9-1 Method Detection Limits (sensitivity), Accuracy, and Precision of the Rontec PicoTAX
in Comparison to the Average of All Eight XRF Instruments 69
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Acronyms, Abbreviations, and Symbols
(ig Micrograms
(iA Micro-amps
AC Alternating current
ADC Analog to digital converter
Ag Silver
Am Americium
ARDL Applied Research and Development Laboratory, Inc.
As Arsenic
ASARCO American Smelting and Refining Company
BN Burlington Northern
C Celsius
Cd Cadmium
CFR Code of Federal Regulations
cps Counts per second
CPU Central processing unit
Cr Chromium
CSV Comma-separated value
Cu Copper
CVAA Cold vapor atomic absorption
EDXRF Energy dispersive XRF
EDD Electronic data deliverable
EPA U.S. Environmental Protection Agency
ERA Environmental Research Associates
ESA Environmental site assessment
ESD Environmental Sciences Division
ETV Environmental Technology Verification (Program)
eV Electron volts
Fe Iron
FPT Fundamental Parameters Technique
FWHM Full width of peak at half maximum height
GB Gigabyte
Hg Mercury
Hz Hertz
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Acronyms, Abbreviations, and Symbols (Continued)
ICP-AES Inductively coupled plasma-atomic emission spectrometry
ICP-MS Inductively coupled plasma-mass spectrometry
IR Infrared
ITVR Innovative Technology Verification Report
KARS Kennedy Athletic, Recreational and Social (Park)
keV Kiloelectron volts
kg Kilograms
KSC Kennedy Space Center
kV Kilovolts
LEAP Light Element Analysis Program
LiF Lithium fluoride
LIMS Laboratory information management system
LOD Limit of detection
mA Milli-amps
MB Megabyte
MBq Mega Becquerels
MCA Multi-channel analyzer
mCi Millicuries
MDL Method detection limit
mg/kg Milligrams per kilogram
MHz Megahertz
mm Millimeters
MMT Monitoring and Measurement Technology (Program)
Mo Molybdenum
MS Matrix spike
MSB Matrix spike duplicate
NASA National Aeronautics and Space Administration
NELAC National Environmental Laboratory Accreditation Conference
NERL National Exposure Research Laboratory
Ni Nickel
NIOSH National Institute for Occupational Safety and Health
NIST National Institute for Standards and Technology
NRC Nuclear Regulatory Commission
NSWC Naval Surface Warfare Center
ORD Office of Research and Development
OSWER Office of Solid Waste and Emergency Response
XI
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Acronyms, Abbreviations, and Symbols (Continued)
P Phosphorus
Pb Lead
PC Personal computer
PDA Personal digital assistant
PCB Polychlorinated biphenyls
Pd Palladium
PE Performance evaluation
PeT Pentaerythritol
ppb Parts per billion
ppm Parts per million
Pu Plutonium
QA Quality assurance
QAPP Quality assurance project plan
QC Quality control
r2 Correlation coefficient
RCRA Resource Conservation and Recovery Act
Rh Rhodium
RPD Relative percent difference
RSD Relative standard deviation
%RSD Percent relative standard deviation
SAP Sampling and analysis plan
SBMM Sulphur Bank Mercury Mine
Sb Antimony
Se Selenium
Si Silicon
SITE Superfund Innovative Technology Evaluation
SOP Standard operating procedure
SRM Standard reference material
SVOC Semivolatile organic compound
TAP Thallium acid phthalate
Tetra Tech Tetra Tech EM Inc.
Ti Titanium
TSA Technical systems audit
TSP Total suspended particulates
TXRF Total reflection x-ray fluorescence spectroscopy
U Uranium
USFWS U.S. Fish and Wildlife Service
xn
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Acronyms, Abbreviations, and Symbols (Continued)
V Vanadium
V Volts
VOC Volatile organic compound
W Watts
WDXRF Wavelength-dispersive XRF
WRS Wilcoxon Rank Sum
XRF X-ray fluorescence
Zn Zinc
Xlll
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Acknowledgements
This report was co-authored by Dr. Greg Swanson and Dr. Mark Colsman of Tetra Tech EM Inc. The
authors acknowledge the advice and support of the following individuals in preparing this report: Dr.
Stephen Billets and Mr. George Brilis of the U.S. Environmental Protection Agency's National Exposure
Research Laboratory; Dr. Hagen Stosnach, Dr. Armin Gross and Ulrick Waldschlager of RONTEC AG in
Germany, Paul Smith of RONTEC USA; and Dr. Jackie Quinn of the National Aeronautics and Space
Administration (NASA), Kennedy Space Center (KSC). The demonstration team also acknowledges the
field support of Michael Deliz of NASA KSC and Mark Speranza of Tetra Tech NUS, the consultant
program manager for NASA.
xiv
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Chapter 1
Introduction
The U.S. Environmental Protection Agency (EPA),
Office of Research and Development (ORD)
conducted a demonstration to evaluate the
performance of innovative x-ray fluorescence (XRF)
technologies for measuring trace elements in soil and
sediment. The demonstration was conducted as part
of the EPA Superfund Innovative Technology
Evaluation (SITE) Program.
Eight field-portable XRF instruments, which were
provided and operated by six XRF technology
developers, were evaluated as part of the
demonstration. Each of these technology developers
and their instruments are listed in Table 1-1. The
technology developers brought each of these
instruments to the demonstration site during the field
portion of the demonstration. The instruments were
used to analyze a total of 326 prepared soil and
sediment samples that contained 13 target elements.
The same sample set was analyzed by a fixed
laboratory (the reference laboratory) using
established EPA reference methods. The results
obtained using each XRF instrument in the field were
compared with the results obtained by the reference
laboratory to assess instrument accuracy. The results
of replicate sample analysis were utilized to assess
the precision and the detection limits that each XRF
instrument could achieve. The results of these
evaluations, as well as technical observations and
cost information, were then documented in an
Innovative Technology Verification Report (ITVR)
for each instrument.
This ITVR documents EPA's evaluation of the
Rontec PicoTAX XRF analyzer based on the results
of the demonstration.
1.1 Organization of this Report
This report is organized to first present general
information pertinent to the demonstration. This
information is common to all eight ITVRs that were
developed from the XRF demonstration.
Specifically, this information includes an intro-
duction (Chapter 1), the locations where the field
samples were collected (Chapter 2), the field
demonstration (Chapter 3), the evaluation design
(Chapter 4), and the reference laboratory results
(Chapter 5).
The second part of this report provides information
relevant to the specific instrument that is the subject
of this ITVR. This information includes a description
of the instrument (Chapter 6), a performance
Table 1-1. Participating Technology Developers and Instruments
Developer Full Name
Elvatech, Ltd.
Innov-X Systems
NITON Analyzers, A
Division of Thermo
Electron Corooration
Oxford Instruments
Analytical, Ltd.
Rigaku, Inc.
RONTEC AG
(acquired by Brooker
AXSAXS, 11/2005)
Distributor in the
United States
Xcalibur XRF Services
Innov-X Systems
NITON Analyzers, A
Division of Thermo
Electron Corooration
Oxford Instruments
Analvtcal, Ltd.
Rigaku, Inc.
RONTEC USA
Developer Short
Name
Xcalibur
Innov-X
Niton
Oxford
Rigaku
Rontec
Instrument Full
Name
ElvaX
XT400 Series
XLt 700 Series
XLi 700 Series
X-Met 3000 TX
ED2000
ZSX Mini II
PicoTAX
Instrument Short
Name
ElvaX
XT400
XLt
XLi
X-Met
ED2000
ZSX Mini II
PicoTAX
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evaluation (Chapter 7), a cost analysis (Chapter 8),
and a summary of the demonstration results (Chapter
9). References are provided in Chapter 10.
A verification statement for the instrument is
provided as Appendix A. Comments from the
instrument developer on the demonstration and any
exceptions to EPA's evaluation are presented in
Appendix B. Appendices C, D, and E contain the
data validation summary report for the reference
laboratory data and detailed evaluations of instrument
versus reference laboratory results.
1.2 Description of the SITE Program
Performance verification of innovative environmental
technologies is an integral part of EPA's regulatory
and research mission. The SITE Program was
established by the EPA Office of Solid Waste and
Emergency Response and ORD under the Superfund
Amendments and Reauthorization Act of 1986. The
overall goal of the SITE Program is to conduct
performance verification studies and to promote
acceptance of innovative technologies that may be
used to achieve long-term protection of human health
and the environment. The program is designed to
meet three primary objectives: (1) identify and
remove obstacles to development and commercial
use of innovative technologies (2) demonstrate
promising innovative technologies and gather reliable
information on performance and cost to support site
characterization and cleanup; and (3) maintain an
outreach program to operate existing technologies
and identify new opportunities for their use.
Additional information on the SITE Program is
available on the EPA ORD web site
(www.cpa.gov/ord/SITE).
The intent of a SITE demonstration is to obtain
representative, high-quality data on the performance
and cost of one or more innovative technologies so
that potential users can assess a technology's
suitability for a specific application. The SITE
Program includes the following program elements:
Monitoring and Measurement Technology
(MMT) Program - Evaluates 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 can conventional technologies.
Remediation Technology Program -
Demonstrates innovative treatment technologies
to provide reliable data on performance, cost, and
applicability 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 the participating
technologies.
The demonstration of XRF instruments was
conducted as part of the MMT Program, which is
administered by the Environmental Sciences Division
(ESD) of the National Exposure Research Laboratory
(NERL) in Las Vegas, Nevada. Additional
information on the NERL ESD is available on the
EPA web site (w^vw^^gov/nerlesdl/)- Tetra Tech
EM Inc. (Tetra Tech), an EPA contractor, provided
comprehensive technical support to the
demonstration.
1.3 Scope of the Demonstration
Conventional analytical methods for measuring the
concentrations of inorganic elements in soil and
sediment are time-consuming and costly. For this
reason, field-portable XRF instruments have been
proposed as an alternative approach, particularly
where rapid and cost-effective assessment of a site is
a goal. The use of a field XRF instrument for
elemental analysis allows field personnel to quickly
assess the extent of contamination by target elements
at a site. Furthermore, the near instantaneous data
provided by field-portable XRF instruments can be
used to quickly identify areas where there may be
increased risks and allow development of a more
focused and cost-effective sampling strategy for
conventional laboratory analysis.
EPA-sponsored demonstrations of XRF technologies
have been under way for more than a decade. The
first SITE MMT demonstration of XRF occurred in
1995, when six instruments were evaluated for their
ability to analyze 10 target elements. The results of
this demonstration were published in individual
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reports for each instrument (EPA 1996a, 1996b,
1998a, 1998b, 1998c, and 1998d). In 2003, two XRF
instruments were included in a demonstration of field
methods for analysis of mercury in soil and sediment.
Individual ITVRs were also prepared for each of
these two instruments (EPA 2004a, 2004b).
Although XRF spectrometry is now considered a
mature technology for elemental analysis, field-
portable XRF instruments have evolved considerably
over the past 10 years, and many of the instruments
that were evaluated in the original demonstration are
no longer manufactured. Advances in electronics and
data processing, coupled with new x-ray tube source
technology, have produced substantial improvements
in the precision and speed of XRF analysis. The
current demonstration of XRF instruments was
intended to evaluate these new technologies, with an
expanded set of target elements, to provide
information to potential users on current state-of-the-
art instrumentation and its associated capabilities.
During the demonstration, performance data
regarding each field-portable XRF instrument were
collected through analysis of a sample set that
included a broad range of soil/sediment types and
target element concentrations. To develop this
sample set, soil and sediment samples that contain the
target elements of concern were collected in bulk
quantities at nine sites from across the U.S. These
bulk samples of soil and sediment were
homogenized, characterized, and packaged into
demonstration samples for the evaluation. Some of
the batches of soil and sediment were spiked with
selected target elements to ensure that representative
concentration ranges were included for all target
elements and that the sample design was robust.
Replicate samples of the material in each batch were
included in the final set of demonstration samples to
assess instrument precision and detection limits. The
final demonstration sample set therefore included 326
samples.
Each developer analyzed all 326 samples during the
field demonstration using its XRF instrument and in
accordance with its standard operating procedure.
The field demonstration was conducted during the
week of January 24, 2005, at the Kennedy Athletic,
Recreational and Social (KARS) Park, which is part
of the Kennedy Space Center on Merritt Island,
Florida. Observers were assigned to each XRF
instrument during the field demonstration to collect
detailed information on the instrument and operating
procedures, including sample processing times, for
subsequent evaluation. The reference laboratory also
analyzed a complete set of the demonstration samples
for the target elements using acid digestion and
inductively coupled plasma-atomic emission
spectrometry (ICP-AES), in accordance with EPA
Method 3 05 OB/601 OB, and using cold vapor atomic
absorption (CVAA) spectroscopy (for mercury only)
in accordance with EPA Method 7471 A. By
assuming that the results from the reference
laboratory were essentially "true" values, instrument
accuracy was assessed by comparing the results
obtained using the XRF instrument with the results
from the reference laboratory. The data obtained
using the XRF instrument were also assessed in other
ways, in accordance with the objectives of the
demonstration, to provide information on instrument
precision, detection limits, and interferences.
1.4 General Description of XRF Technology
XRF spectroscopy is an analytical technique that
exposes a solid sample to an x-ray source. The x-
rays from the source have the appropriate excitation
energy that causes elements in the sample to emit
characteristic x-rays. A qualitative elemental
analysis is possible from the characteristic energy, or
wavelength, of the fluorescent x-rays emitted. A
quantitative elemental analysis is possible by
counting the number (intensity) of x-rays at a given
wavelength.
Three electron shells are generally involved in
emissions of x-rays during XRF analysis of samples:
the K, L, and M shells. Multiple-intensity peaks are
generated from the K, L, or M shell electrons in a
typical emission pattern, also called an emission
spectrum, for a given element. Most XRF analysis
focuses on the x-ray emissions from the K and L
shells because they are the most energetic lines. K
lines are typically used for elements with atomic
numbers from 11 to 46 (sodium to palladium), and L
lines are used for elements above atomic number 47
(silver). M-shell emissions are measurable only for
metals with an atomic number greater than 57
(lanthanum).
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As illustrated in Figure 1-1, characteristic radiation
arises when the energy from the x-ray source exceeds
the absorption edge energy of inner-shell electrons,
ejecting one or more electrons. The vacancies are
filled by electrons that cascade in from the outer
shells. The energy states of the electrons in the outer
shells are higher than those of the inner-shell
electrons, and the outer-shell electrons emit energy in
the form of x-rays as they cascade down. The energy
of this x-ray radiation is unique for each element.
An XRF analyzer consists of three major
components: (1) a source that generates x-rays (a
radioisotope or x-ray tube); (2) a detector that
converts x-rays emitted from the sample into
measurable electronic signals; and (3) a data
processing unit that records the emission or
fluorescence energy signals and calculates the
elemental concentrations in the sample.
Ejected K-shell electron,-;'
Shells
Ka x-ray emitted
P
<:, '':-_.. L-shelf electron
5| 'n fills vacancy
M-shel! electron
fills vacancy '" ""
Figure 1-1. The XRF process.
Measurement times vary (typically ranging from 30
to 600 seconds), based primarily on data quality
objectives. Shorter analytical measurement times (30
seconds) are generally used for initial screening,
element identification, and hot-spot delineation,
while longer measurement times (300 seconds or
more) are typically used to meet higher goals for
precision and accuracy. The length of the measuring
time will also affect the detection limit; generally, the
longer the measuring time, the lower the detection
limit. However, detection limits for individual
elements may be increased because of sample
heterogeneity or the presence of other elements in the
sample that fluoresce with similar x-ray energies.
The main variables that affect precision and accuracy
for XRF analysis are:
1. Physical matrix effects (variations in the physical
character of the sample).
2. Chemical matrix effects (absorption and
enhancement phenomena) and Spectral
interferences (peak overlaps).
3. Moisture content above 10 percent, which affects
x-ray transmission.
Because of these variables, it is important that each
field XRF characterization effort be guided by a well-
considered sampling and analysis plan. Sample
preparation and homogenization, instrument
calibration, and laboratory confirmation analysis are
all important aspects of an XRF sampling and
analysis plan. EPA SW-846 Method 6200 provides
additional guidance on sampling and analytical
methodology for XRF analysis.
1.5 Properties of the Target Elements
This section describes the target elements selected for
the technology demonstration and the typical
characteristics of each. Key criteria used in selecting
the target elements included:
The frequency that the element is determined in
environmental applications of XRF instruments.
The extent that the element poses an
environmental consequence, such as a potential
risk to human or environmental receptors.
The ability of XRF technology to achieve
detection limits below typical remediation goals
and risk assessment criteria.
The extent that the element may interfere with
the analysis of other target elements.
In considering these criteria, the critical target
elements selected for this study were antimony,
arsenic, cadmium, chromium, copper, iron, lead,
mercury, nickel, selenium, silver, vanadium, and
zinc. These 13 target elements are of significant
concern for site cleanups and human health risk
assessments because most are highly toxic or
interfere with the analysis of other elements.
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7.5.7 Antimony
Naturally occurring antimony in surface soils is
typically found at less than 1 to 4 milligrams per
kilogram (mg/kg). Concentrations greater than 5
mg/kg are potentially phytotoxic and concentrations
above 31 mg/kg in soil may be hazardous to humans.
Antimony may be found along with arsenic in mine
wastes, at shooting ranges, and at industrial facilities.
Typical detection limits for field-portable XRF
instruments range from 10 to 40 mg/kg. Antimony is
typically analyzed with success by ICP-AES;
however, recovery of antimony in soil matrix spikes is
often below quality control (QC) limits (50 percent or
less) as a result of loss through volatilization during
acid digestion. Therefore, results using ICP-AES may
be lower than are obtained by XRF.
7.5.2 Arsenic
Naturally occurring arsenic in surface soils typically
ranges from 1 to 50 mg/kg; concentrations above 10
mg/kg are potentially phytotoxic. Concentrations of
arsenic greater than 0.39 mg/kg may cause
carcinogenic effects in humans, and concentrations
above 22 mg/kg may result in adverse
noncarcinogenic effects. Typical detection limits for
field-portable XRF instruments range from 10 to 20
mg/kg arsenic. Elevated concentrations of arsenic are
associated with mine wastes and industrial facilities.
Arsenic is successfully analyzed by ICP-AES;
however, spectral interferences between peaks for
arsenic and lead can affect detection limits and
accuracy in XRF analysis when the ratio of lead to
arsenic is 10 to 1 or more. Risk-based screening
levels and soil screening levels for arsenic may be
lower than the detection limits of field-portable XRF
instruments.
7.5.5 Cadmium
Naturally occurring cadmium in surface soils
typically ranges from 0.6 to 1.1 mg/kg;
concentrations greater than 4 mg/kg are potentially
phytotoxic. Concentra-tions of cadmium that exceed
37 mg/kg may result in adverse effects in humans.
Typical detection limits for field-portable XRF
instruments range from 10 to 50 mg/kg. Elevated
concentrations of cadmium are associated with mine
wastes and industrial facilities. Cadmium is
successfully analyzed by both ICP-AES and field-
portable XRF; however, action levels for cadmium
may be lower than the detection limits of field-
portable XRF instruments.
1.5.4 Chromium
Naturally occurring chromium in surface soils
typically ranges from 1 to 1,000 mg/kg;
concentrations greater than 1 mg/kg are potentially
phytotoxic, although specific phytotoxicity levels for
naturally occurring chromium have not been
documented. The variable oxidation states of
chromium affect its behavior and toxicity.
Concentrations of hexavalent chromium above 30
mg/kg and of trivalent chromium above 10,000
mg/kg may cause adverse health effects in humans.
Typical detection limits for field-portable XRF
instruments range from 10 to 50 mg/kg. Hexavalent
chromium is typically associated with metal plating
or other industrial facilities. Trivalent chromium
may be found in mine waste and at industrial
facilities. Neither ICP-AES nor field-portable XRF
can distinguish between oxidation states for
chromium (or any other element).
7.5.5 Copper
Naturally occurring copper in surface soils typically
ranges from 2 to 100 mg/kg; concentrations greater
than 100 mg/kg are potentially phytotoxic.
Concentrations greater than 3,100 mg/kg may result
in adverse health effects in humans. Typical
detection limits for field-portable XRF instruments
range from 10 to 50 mg/kg. Copper is mobile and is
a common contaminant in soil and sediments.
Elevated concentrations of copper are associated with
mine wastes and industrial facilities. Copper is
successfully analyzed by ICP-AES and XRF;
however, spectral interferences between peaks for
copper and zinc may affect the detection limits and
accuracy of the XRF analysis.
7.5.6 Iron
Although iron is not considered an element that poses
a significant environmental consequence, it interferes
with measurement of other elements and was
therefore included in the study. Furthermore, iron is
-------
often used as a target reference element in XRF
analysis.
Naturally occurring iron in surface soils typically
ranges from 7,000 to 550,000 mg/kg, with the iron
content originating primarily from parent rock.
Typical detection limits for field-portable XRF
instruments are in the range of 10 to 60 mg/kg. Iron
is easily analyzed by both ICP-AES and XRF;
however, neither technique can distinguish among
iron species in soil. Although iron in soil may pose
few environmental consequences, high levels of iron
may interfere with analyses of other elements in both
techniques (ICP-AES and XRF). Spectral
interference from iron is mitigated in ICP-AES
analysis by applying inter-element correction factors,
as required by the analytical method. Differences in
analytical results between ICP-AES and XRF for
other target elements are expected when
concentrations of iron are high in the soil matrix.
1.5.7 Lead
Naturally occurring lead in surface soils typically
ranges from 2 to 200 mg/kg; concentrations greater
than 50 mg/kg are potentially phytotoxic.
Concentrations greater than 400 mg/kg may result in
adverse effects in humans. Typical detection limits
for field-portable XRF instruments range from 10 to
20 mg/kg. Lead is a common contaminant at many
sites, and human and environmental exposure can
occur through many routes. Lead is frequently found
in mine waste, at lead-acid battery recycling
facilities, at oil refineries, and in lead-based paint.
Lead is successfully analyzed by ICP-AES and XRF;
however, spectral interferences between peaks for
lead and arsenic in XRF analysis can affect detection
limits and accuracy when the ratio of arsenic to lead
is 10 to 1 or more. Differences between ICP-AES
and XRF results are expected in the presence of high
concentrations of arsenic, especially when the ratio of
lead to arsenic is low.
1.5.8 Mercury
Naturally occurring mercury in surface soils typically
ranges from 0.01 to 0.3 mg/kg; concentrations greater
than 0.3 mg/kg are potentially phytotoxic.
Concentrations of mercury greater than 23 mg/kg and
concentrations of methyl mercury above 6.1 mg/kg
may result in adverse health effects in humans.
Typical detection limits for field-portable XRF
instruments range from 10 to 20 mg/kg. Elevated
concentrations of mercury are associated with
amalgamation of gold and with mine waste and
industrial facilities. Native surface soils are
commonly enriched by anthropogenic sources of
mercury. Anthropogenic sources include coal-fired
power plants and metal smelters. Mercury is too
volatile to withstand both the vigorous digestion and
extreme temperature involved with ICP-AES
analysis; therefore, the EPA-approved technique for
laboratory analysis of mercury is CVAA
spectroscopy. Mercury is successfully measured by
XRF, but differences between results obtained by
CVAA and XRF are expected when mercury levels
are high.
7.5.9 Nickel
Naturally occurring nickel in surface soils typically
ranges from 5 to 500 mg/kg; a concentration of 30
mg/kg is potentially phytotoxic. Concentrations
greater than 1,600 mg/kg may result in adverse health
effects in humans. Typical detection limits for field-
portable XRF instruments range from 10 to 60
mg/kg. Elevated concentrations of nickel are
associated with mine wastes and industrial facilities.
Nickel is a common environmental contaminant at
metal processing sites. It is successfully analyzed by
both ICP-AES and XRF with little interference;
therefore, a strong correlation between the methods is
expected.
1.5.10 Selenium
Naturally occurring selenium in surface soils
typically ranges from 0.1 to 2 mg/kg; concentrations
greater than 1 mg/kg are potentially phytotoxic. Its
toxicities are well documented for plants and
livestock; however, it is also considered a trace
nutrient. Concentrations above 390 mg/kg may result
in adverse health effects in humans. Typical
detection limits for field-portable XRF instruments
range from 10 to 20 mg/kg. Most selenium is
associated with sulfur or sulfide minerals, where
concentrations can exceed 200 mg/kg. Selenium can
be measured by both ICP-AES and XRF; however,
detection limits using XRF usually exceed the
ecological risk-based screening levels for soil.
-------
Analytical results for selenium using ICP-AES and
XRF are expected to be comparable.
7.5.77 Silver
Naturally occurring silver in surface soils typically
ranges from 0.01 to 5 mg/kg; concentrations greater
than 2 mg/kg are potentially phytotoxic. In addition,
concentrations that exceed 390 mg/kg may result in
adverse effects in humans. Typical detection limits
for field-portable XRF instruments range from 10 to
45 mg/kg. Silver is a common contaminant in mine
waste, in photographic film processing wastes, and at
metal processing sites. It is successfully analyzed by
ICP-AES and XRF; however, recovery may be
reduced in ICP-AES analysis because insoluble silver
chloride may form during acid digestion. Detection
limits using XRF may exceed the risk-based
screening levels for silver in soil.
1.5.12 Van adium
Naturally occurring vanadium in surface soils
typically ranges from 20 to 500 mg/kg;
concentrations greater than 2 mg/kg are potentially
phytotoxic, although specific phytotoxicity levels for
naturally occurring vanadium have not been
documented. Concentrations above 550 mg/kg may
result in adverse health effects in humans. Typical
detection limits for field-portable XRF instruments
range from 10 to 50 mg/kg. Vanadium can be
associated with manganese, potassium, and organic
matter and is typically concentrated in organic shales,
coal, and crude oil. It is successfully analyzed by
both ICP-AES and XRF with little interference.
7.5.75 Zinc
Naturally occurring zinc in surface soils typically
ranges from 10 to 300 mg/kg; concentrations greater
than 50 mg/kg are potentially phytotoxic. Zinc at
concentrations above 23,000 mg/kg may result in
adverse health effects in humans. Typical detection
limits for field-portable XRF instruments range from
10 to 30 mg/kg. Zinc is a common contaminant in
mine waste and at metal processing sites. In addition,
it is highly soluble, which is a common concern for
aquatic receptors. Zinc is successfully analyzed by
ICP-AES; however, spectral interferences between
peaks for copper and zinc may influence detection
limits and the accuracy of the XRF analysis.
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Chapter 2
Field Sample Collection Locations
Although the field demonstration took place at KARS
Park on Merritt Island, Florida, environmental
samples were collected at other sites around the
country to develop a demonstration sample that
incorporated a variety of soil/sediment types and
target element concentrations. This chapter describes
these sample collection sites, as well as the rationale
for the selection of each.
Several criteria were used to assess potential sample
collection sites, including:
The ability to provide a variety of target elements
and soil/sediment matrices.
The convenience and accessibility of the location
to the sampling team.
Program support and the cooperation of the site
owner.
Nine sample collection sites were ultimately selected
for the demonstration; one was the KARS Park site
itself. These nine sites were selected to represent
variable soil textures (sand, silt, and clay) and iron
content, two factors that significantly affect
instrument performance.
Historical operations at these sites included mining,
smelting, steel manufacturing, and open burn pits;
one, KARS Park, was a gun range. Thus, these sites
incorporated a wide variety of metal contaminants in
soils and sediments. Both contaminated and
uncontaminated (background) samples were collected
at each site.
A summary of the sample collection sites is presented
in Table 2-1, which describes the types of metal-
contaminated soils or sediments that were found at
each site. This information is based on the historical
data that were provided by the site owners or by the
EPA remedial project managers.
2.1 Alton Steel Mill Site
The Alton Steel Mill site (formerly the Laclede Steel
site) is located at 5 Cut Street in Alton, Illinois. This
400-acre site is located in Alton's industrial corridor.
The Alton site was operated by Laclede Steel
Company from 1911 until it went bankrupt in July
2001. The site was purchased by Alton Steel, Inc.,
from the bankruptcy estate of Laclede Steel in May
2003. The Alton site is heir to numerous
environmental concerns from more than 90 years of
steel production; site contaminants include
polychlorinated biphenyls (PCBs) and heavy metals.
Laclede Steel was cited during its operating years for
improper management and disposal of PCB wastes
and electric arc furnace dust that contained heavy
metals such as lead and cadmium. A Phase I
environmental site assessment (ESA) was conducted at
the Alton site in May 2002, which identified volatile
organic compounds (VOCs), semivolatile organic
compounds (SVOCs), total priority pollutant metals,
and PCBs as potential contaminants of concern at the
site.
Based on the data gathered during the Phase I ESA
and on discussions with Alton personnel, several soil
samples were collected for the demonstration from
two areas at the Alton site, including the Rod
Patenting Building and the Tube Mill Building. The
soil in the areas around these two buildings had not
been remediated and was known to contain elevated
concentrations of arsenic, cadmium, chromium, lead,
nickel, zinc, and iron. The matrix of the contaminated
soil samples was a fine to medium sand; the
background soil sample was a sand loam.
Table 2-2 presents historical analytical data (the
maximum concentrations) for some of the target
elements detected at the Alton site.
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Table 2-1. Nature of Contamination in Soil and Sediment at Sample Collection Sites
Sample Collection Site
Alton Steel, Alton, IL
Burlington Northern-
ASARCO Smelter Site,
East Helena, MT
KARS Park - Kennedy
Space Center, Merritt
Island, FL
Leviathan Mine
Site/ Aspen Creek, Alpine
County, CA
Naval Surface Warfare
Center, Crane Division,
Crane, IN
Ramsay Flats-Silver Bow
Creek, Butte, MT
Sulphur Bank Mercury
Mine
Torch Lake Site (Great
Lakes Area of Concern),
Houghton County, MI
Wickes Smelter Site,
Jefferson City, MT
Source of Contamination
Steel manufacturing facility with metal arc
furnace dust. The site also includes a metal
scrap yard and a slag recovery facility.
Railroad yard staging area for smelter ores.
Contaminated soils resulted from dumping and
spilling concentrated ores.
Impacts to soil from historical facility
operations and a former gun range.
Abandoned open-pit sulfur and copper mine
that has contaminated a 9-mile stretch of
mountain creeks, including Aspen Creek, with
heavy metals.
Open disposal and burning of general refuse
and waste associated with aircraft
maintenance.
Silver Bow Creek was used as a conduit for
mining, smelting, industrial, and municipal
wastes.
Inactive mercury mine. Waste rock, tailings,
and ore are distributed in piles throughout the
property.
Copper mining produced mill tailings that were
dumped directly into Torch Lake,
contaminating the lake sediments and
shoreline.
Abandoned smelter complex with
contaminated soils and mineral-processing
wastes, including remnant ore piles,
decomposed roaster brick, slag piles and fines,
and amalgamation sediments.
Matrix
Soil
Soil
Soil
Soil and
Sediment
Soil
Soil and
Sediment
Soil
Sediment
Soil
Site-Specific Metals of Concern for XRF Demonstration
Sb
X
X
X
X
As
X
X
X
X
X
X
X
X
X
Cd
X
X
X
X
X
X
Cr
X
X
X
X
X
X
Cu
X
X
X
X
X
X
Fe
X
X
X
X
X
Pb
X
X
X
X
X
X
X
X
Hg
X
X
X
Ni
X
X
X
X
Se
X
AŁ
X
X
Zn
X
X
X
X
X
X
Notes (in order of appearance in table):
Sb: Antimony Cr: Chromium Pb: Lead
As: Arsenic Cu: Copper Hg: Mercury
Cd: Cadmium Fe: Iron Ni: Nickel
Note: Vanadium was not a chemical of concern at any of the sites and so does not appear on the table.
Se: Selenium
Ag: Silver
Zn: Zinc
10
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Table 2-2. Historical Analytical Data, Alton
Steel Mill Site
2.3 Kennedy Athletic, Recreational and Social
Park Site
Metal
Arsenic
Cadmium
Chromium
Lead
Maximum Concentration (mg/kg)
80.3
97
1,551
3,556
2.2 Burlington Northern-ASARCO Smelter Site
The Burlington Northern (BN)-ASARCO Smelter
site is located in the southwestern part of East
Helena, Montana. The site was an active smelter for
more than 100 years and closed in 2002. Most of the
ore processed at the smelter was delivered on railroad
cars. An area west of the plant site (the BN property)
was used for temporary staging of ore cars and
consists of numerous side tracks to the primary
railroad line into the smelter. This site was selected
to be included in the demonstration because it had not
been remediated and contained several target
elements in soil.
At the request of EPA, the site owner collected
samples of surface soil in this area in November 1997
and April 1998 and analyzed them for arsenic,
cadmium, and lead; elevated concentrations were
reported for all three metals. The site owner
collected 24 samples of surface soil (16 in November
1997 and 8 in April 1998). The soils were found to
contain up to 2,018 parts per million (ppm) arsenic,
876 ppm cadmium, and 43,907 ppm lead. One
sample of contaminated soil and one sample of
background soil were collected. The contaminated
soil was a light brown sandy loam with low organic
carbon content. The background soil was a medium
brown sandy loam with slightly more organic
material than the contaminated soil sample. Table 2-
3 presents the site owner's data for arsenic, cadmium,
and lead (the maximum concentrations) from the
1997 and 1998 sampling events.
Table 2-3. Historical Analytical Data, BN-
ASARCO Smelter Site
Soil and sediment at the KARS Park site were
contaminated from former gun range operations and
contain several target elements for the demonstration.
The specific elements of concern for the KARS Park
site include antimony, arsenic, chromium, copper,
lead, and zinc.
The KARS Park site is located at the Kennedy Space
Center on Merritt Island, Florida. KARS Park was
purchased in 1962 and has been used by employees
of the National Aeronautics and Space
Administration (NASA), other civil servants, and
guests as a recreational park since 1963. KARS Park
occupies an area of Kennedy Space Center just
outside the Cape Canaveral base. Contaminants in
the park resulted from historical facility operations
and impacts from the former gun range. The land
north of KARS is owned by NASA and is managed
by the U.S. Fish and Wildlife Service (USFWS) as
part of the Merritt Island National Wildlife Refuge.
Two soil and two sediment samples were collected
from various locations at the KARS Park site for the
XRF demonstration. The contaminated soil sample
was collected from an impact berm at the small arms
range. The background soil sample was collected
from a forested area near the gun range. The matrix
of the contaminated and background soil samples
consisted of fine to medium quartz sand. The
sediment samples were collected from intermittently
saturated areas within the skeet range. These samples
were organic rich sandy loams. Table 2-4 presents
historical analytical data (the maximum
concentrations) for soil and sediment at KARS Park.
Table 2-4. Historical Analytical Data, KARS Park
Site
Metal
Arsenic
Cadmium
Lead
Maximum Concentration (ppm)
2,018
876
43,907
Metal
Antimony
Arsenic
Chromium
Copper
Lead
Zinc
Maximum Concentration (mg/kg)
8,500
1,600
40.2
290,000
99,000
16,200
11
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2.4 Leviathan Mine Site
The Leviathan Mine site is an abandoned copper and
sulfur mine located high on the eastern slopes of the
Sierra Nevada Mountain range near the California-
Nevada border. Development of the Leviathan Mine
began in 1863, when copper sulfate was mined for
use in the silver refineries of the Comstock Lode.
Later, the underground mine was operated as a
copper mine until a mass of sulfur was encountered.
Mining stopped until about 1935, when sulfur was
extracted for use in refining copper ore. In the 1950s,
the mine was converted to an open-pit sulfur mine.
Placement of excavated overburden and waste rock in
nearby streams created acid mine drainage and
environmental impacts in the 1950s. Environmental
impacts noted at that time included large fish kills.
Historical mining distributed waste rock around the
mine site and created an open pit, adits, and solution
cavities through mineralized rock. Oxygen in contact
with the waste rock and mineralized rock in the adits
oxidizes sulfur and sulfide minerals, generating acid.
Water contacting the waste rock and flowing through
the mineralized rock mobilizes the acid into the
environment. The acid dissolves metals, including
arsenic, copper, iron, and nickel, which creates
conditions toxic to insects and fish in Leviathan,
Aspen, and Bryant Creeks, downstream of the
Leviathan Mine. Table 2-5 presents historical
analytical data (the maximum concentrations) for the
target elements detected at elevated concentrations in
sediment samples collected along the three creeks.
Four sediment and one soil sample were collected.
One of the sediment samples was collected from the
iron precipitate terraces formed from the acid mine
drainage. The matrix of this sample appeared to be
an orange silty clay loam. A second sediment sample
was collected from the settling pond at the
wastewater treatment system. The matrix of this
sample was orange clay. A third sample was
collected from the salt crust at the settling pond. This
sample incorporated white crystalline material. One
background sediment and one background soil
sample were collected upstream of the mine. These
samples consisted of light brown sandy loam.
Table 2-5. Historical Analytical Data,
Leviathan Mine Site
Metal
Arsenic
Cadmium
Chromium
Copper
Nickel
Maximum Concentration (mg/kg)
2,510
25.7
279
837
2,670
2.5 Navy Surface Warfare Center, Crane
Division Site
The Old Burn Pit at the Naval Surface Warfare
Center (NSWC), Crane Division, was selected to be
included in the demonstration because 6 of the 13
target elements were detected at significant
concentration in samples of surface soil previously
collected at the site.
The NSWC, Crane Division, site is located near the
City of Crane in south-central Indiana. The Old Burn
Pit is located in the northwestern portion of NSWC
and was used daily from 1942 to 1971 to burn refuse.
Residue from the pit was buried along with
noncombustible metallic items in a gully north of the
pit. The burn pit was covered with gravel and
currently serves as a parking lot for delivery trailers.
The gully north of the former burn pit has been
revegetated. Several soil samples were collected
from the revegetated area for the demonstration
because the highest concentrations of the target
elements were detected in soil samples collected
previously from this area. The matrix of the
contaminated and background soil samples was a
sandy loam. The maximum concentrations of the
target elements detected in surface soil during
previous investigations are summarized in Table 2-6.
12
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Table 2-6. Historical Analytical Data, NSWC
Crane Division-Old Burn Pit
Metal
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Silver
Zinc
Maximum Concentration (mg/kg)
301
26.8
31.1
112
1,520
105,000
16,900
0.43
62.6
7.5
5,110
2.6 Ramsay Flats-Silver Bow Creek Site
The Ramsay Flats-Silver Bow Creek site was
selected to be included in the demonstration because
6 of the 13 target elements were detected in samples
of surface sediment collected previously at the site.
Silver Bow Creek originates north of Butte, Montana,
and is a tributary to the upper Clark Fork River.
More than 100 years of nearly continuous mining
have altered the natural environment surrounding the
upper Clark Fork River. Early wastes from mining,
milling, and smelting were dumped directly into
Silver Bow Creek and were subsequently transported
downstream. EPA listed Silver Bow Creek and a
contiguous portion of the upper Clark Fork River as a
Superfund site in 1983.
A large volume of tailings was deposited in a low-
gradient reach of Silver Bow Creek in the Ramsay
Flats area. Tailings at Ramsay Flats extend several
hundred feet north of the Silver Bow Creek channel.
About 18 inches of silty tailings overlie texturally
stratified natural sediments that consist of low-
permeability silt, silty clay, organic layers, and
stringers of fine sand.
Two sediment samples were collected from the
Ramsay Flats tailings area and were analyzed for a
suite of metals using a field-portable XRF. The
contaminated sediment sample was collected in
Silver Bow Creek adjacent to the mine tailings. The
matrix of this sediment sample was orange-brown
silty fine sand with interlayered black organic
material. The background sediment sample was
collected upstream of Butte, Montana. The matrix of
this sample was organic rich clayey silt with
approximately 25 percent fine sand. The maximum
concentrations of the target elements in the samples
are summarized in Table 2-7.
Table 2-7. Historical Analytical Data, Ramsay
Flats-Silver Bow Creek Site
Metal
Arsenic
Cadmium
Copper
Iron
Lead
Zinc
Maximum Concentration (mg/kg)
176
141
1,110
20,891
394
1,459
2.7 Sulphur Bank Mercury Mine
The Sulphur Bank Mercury Mine (SBMM) is a 160-
acre inactive mercury mine located on the eastern
shore of the Oaks Arm of Clear Lake in Lake County,
California, 100 miles north of San Francisco.
Between 1864 and 1957, SBMM was the site of
underground and open-pit mining at the hydrothermal
vents and hot springs. Mining disturbed about 160
acres of land at SBMM and generated large quantities
of waste rock (rock that did not contain economic
concentrations of mercury and was removed to gain
access to ore), tailings (the waste material from
processes that removed the mercury from ore), and
ore (rock that contained economic concentrations of
mercury that was mined and stockpiled for mercury
extraction). The waste rock, tailings, and ore are
distributed in piles throughout the property.
Table 2-8 presents historical analytical data (the
maximum concentrations) for the target elements
detected at elevated concentrations in surface
samples collected at SBMM. Two contaminated soil
samples and one background soil sample were
collected at various locations for the demonstration
project. The mercury sample was collected from the
ore stockpile and consisted of medium to coarse sand.
The second contaminated soil sample was collected
from the waste rock pile and consisted of coarse sand
and gravel with trace silt. The matrix of the
background soil sample was brown sandy loam.
13
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Table 2-8. Historical Analytical Data, Sulphur
Bank Mercury Mine Site
Table 2-9. Historical Analytical Data, Torch
Lake Superfund Site
Metal
Antimony
Arsenic
Lead
Mercury
Maximum Concentration
(mg/kg)
3,724
532
900
4,296
2.8 Torch Lake Superfund Site
The Torch Lake Superfund site was selected because
native and contaminated sediment from copper
mining, milling, and smelting contained the elements
targeted for the demonstration. The specific metals
of concern for the Torch Lake Superfund site
included arsenic, chromium, copper, lead, mercury,
selenium, silver, and zinc.
The Torch Lake Superfund site is located on the
Keweenaw Peninsula in Houghton County,
Michigan. Wastes were generated at the site from the
1890s until 1969. The site was included on the
National Priorities List in June 1986. Approximately
200 million tons of mining wastes were dumped into
Torch Lake and reportedly filled about 20 percent of
the lake's original volume. Contaminated sediments
are believed to be up to 70 feet thick in some
locations. Wastes occur both on the uplands and in
the lake and are found in four forms, including poor
rock piles, slag and slag-enriched sediments, stamp
sands, and abandoned settling ponds for mine slurry.
EPA initiated long-term monitoring of Torch Lake in
1999; the first monitoring event (the baseline study)
was completed in August 2001. Table 2-9 presents
analytical data (the maximum concentrations) for
eight target elements in sediment samples collected
from Torch Lake during the baseline study.
Sediment samples were collected from the Torch
Lake site at various locations for the demonstration.
The matrix of the sediment samples was orange silt
and clay.
Metal
Arsenic
Chromium
Copper
Lead
Mercury
Selenium
Silver
Zinc
Maximum Concentration'(mg/kg)
40
90
5,850
325
1.2
0.7
6.2
630
2.9 Wickes Smelter Site
The roaster slag pile at the Wickes Smelter site was
selected to be included in the demonstration because
12 of the 13 target elements were detected in soil
samples collected previously at the site.
The Wickes Smelter site is located in the
unincorporated town of Wickes in Jefferson County,
Montana. Wastes at the Wickes Smelter site include
waste rock, slag, flue bricks, and amalgamation
waste. The wastes are found in discrete piles and are
mixed with soil. The contaminated soil sample was
collected from a pile of roaster slag at the site. The
slag was black, medium to coarse sand and gravel.
The matrix of the background soil sample was a light
brown sandy loam. Table 2-10 presents historical
analytical data (maximum concentrations) for the
roaster slag pile.
Table 2-10. Historical Analytical Data, Wickes
Smelter Site-Roaster Slag Pile
Metal
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Zinc
Maximum Concentration (mg/kg)
79
3,182
70
13
948
24,780
33,500
7.3
83
5,299
14
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Chapter 3
Field Demonstration
The field demonstration required a sample set and a
single location (the demonstration site) where all the
technology developers could assemble to analyze the
sample set under the oversight of the EPA/Tetra Tech
field team. This chapter describes how the sample set
was created, how the demonstration site was selected,
and how the field demonstration was conducted.
Additional detail regarding these topics is available in
the Demonstration and Quality Assurance Project
Plan (Tetra Tech 2005).
3.1 Bulk Sample Processing
A set of samples that incorporated a variety of soil and
sediment types and target element concentrations was
needed to conduct a robust evaluation. The demon-
stration sample set was generated from the bulk soil
and sediment samples that were collected from the
nine sample collection sites described in Chapter 2.
Both contaminated (environmental) and
uncontaminated (background) bulk samples of soil and
sediment were collected at each sample collection site.
The background sample was used as source material
for a spiked sample when the contaminated sample did
not contain the required levels of target elements. By
incorporating a spiked background sample into the
sample set, the general characteristics of the soil and
sediment sample matrix could be maintained. At the
same time, this spiked sample assured that all target
elements were present at the highest concentration
levels needed for a robust evaluation.
3.1.1 Bulk Sample Collection and Shipping
Large quantities of soil and sediment were needed for
processing into well-characterized samples for this
demonstration. As a result, 14 soil samples and 11
sediment samples were collected in bulk quantity from
the nine sample collection sites across the U.S. A total
of approximately 1,500 kilograms of unprocessed soil
and sediment was collected, which yielded more than
1,000 kilograms of soil and sediment after the bulk
samples had been dried.
Each bulk soil sample was excavated using clean
shovels and trowels and then placed into clean, plastic
5-gallon (19-liter) buckets at the sample collection site.
The mass of soil and sediment in each bucket varied,
but averaged about 25 kilograms per bucket. As a
result, multiple buckets were needed to contain the
entire quantity of each bulk sample.
Once it had been filled, a plastic lid was placed on
each bucket, the lid was secured with tape, and the
bucket was labeled with a unique bulk sample number.
Sediment samples were collected in a similar method
at all sites except at Torch Lake, where sediments were
collected using a Vibracore or Ponar sediment sampler
operated from a boat. Each 5-gallon bucket was
overpacked in a plastic cooler and was shipped under
chain of custody via overnight delivery to the
characterization laboratory, Applied Research and
Development Laboratory (ARDL).
3.1.2 Bulk Sample Preparation and Homogenization
Each bulk soil or sediment sample was removed from
the multiple shipping buckets and then mixed and
homogenized to create a uniform batch. Each bulk
sample was then spread on a large tray at ARDL's
laboratory to promote uniform air drying. Some bulk
samples of sediment required more than 2 weeks to dry
because of the high moisture content.
The air-dried bulk samples of soil and sediment were
sieved through a custom-made screen to remove coarse
material larger than about 1 inch. Next, each bulk
sample was mechanically crushed using a hardened
stainless-steel hammer mill until the particle size was
sub-60-mesh sieve (less than 0.2 millimeters). The
particle size of the processed bulk soil and sediment
was measured after each round of crushing using
standard sieve technology, and the particles that were
still larger than 60-mesh were returned to the crushing
process. The duration of the crushing process for each
bulk sample varied based on soil type and volume of
coarse fragments.
After each bulk sample had been sieved and crushed,
the sample was mixed and homogenized using a Model
T 50A Turbula shaker-mixer. This shaker was
15
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capable of handling up to 50 gallons (190 liters) of
sample material; thus, this shaker could handle the
complete volume of each bulk sample. Bulk samples
of smaller volume were mixed and homogenized
using a Model T 10B Turbula shaker-mixer that was
capable of handling up to 10 gallons (38 liters).
Aliquots from each homogenized bulk sample were
then sampled and analyzed in triplicate for the 13
target elements using ICP-AES and CVAA. If the
relative percent difference between the highest and
lowest result exceeded 10 percent for any element,
the entire batch was returned to the shaker-mixer for
additional homogenization. The entire processing
scheme for the bulk samples is shown in Figure 3-1.
Material was sieved
through custom 1" screen
to remove large material,
Was
the material smaller
than ,2mm?
the sample greater
than 10
gallons?
Material crushed using
stainless steel hammer mill
Samples are
and homogenized
Model T 50A
Turbula shaker-mixer
Samples are
mixed and homogenized
using Mod el T 10B
and Turbula shaker-mixer
Aliquots from each
homogenized soil and sediment batch
were sampled and analyzed
in triplicate using ICP-AES
and CVAA for the target elements
Was
the percent difference
beta/sen the highest and
lowest result greater
than 10%?
Package
for distribution
Figure 3-1. Bulk sample processing diagram.
16
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3.2 Demonstration Samples
3.2.2 Spiked Samples
After the bulk soil and sediment sample material had
been processed into homogenized bulk samples for
the demonstration, the next consideration was the
concentrations of target elements. The goal was to
create a demonstration sample set that would cover
the concentration range of each target element that
may be reasonably found in the environment. Three
concentration levels were identified as a basis for
assessing both the coverage of the environmental
samples and the need to generate spiked samples.
These three levels were: (1) near the detection limit,
(2) at intermediate concentrations, and (3) at high
concentrations. A fourth concentration level (very
high) was added for lead, iron, and zinc in soil and
for iron in sediment. Table 3-1 lists the numerical
ranges of the target elements for each of these levels
(1 through 4).
3.2.1 Environmental Samples
A total of 25 separate environmental samples were
collected from the nine sample collection sites
described in Chapter 2. This bulk environmental
sample set included 14 soil and 11 sediment samples.
The concentrations of the target elements in some of
these samples, however, were too high or too low to
be used for the demonstration. Therefore, the initial
analytical results for each bulk sample were used to
establish different sample blends for each sampling
location that would better cover the desired
concentration ranges.
The 14 bulk soil samples were used to create 26
separate sample blends and the 11 bulk sediment
samples were used to create 19 separate sample
blends. Thus, there were 45 environmental sample
blends in the final demonstration sample set. Either
five or seven replicate samples of each sample blend
were included in the sample set for analysis during
the demonstration. Table 3-2 lists the number of
sample blends and the number of demonstration
samples (including replicates) that were derived from
the bulk environmental samples for each sampling
location.
Spiked samples that incorporated a soil and sediment
matrix native to the sampling locations were created
by adding known concentrations of target elements to
the background samples. The spiked concentrations
were selected to ensure that a minimum of three
samples was available for all concentration levels for
each target element.
After initial characterization at ARDL's laboratory,
all bulk background soil and sediment samples were
shipped to Environmental Research Associates
(ERA) to create the spiked samples. The spiked
elements were applied to the bulk sample in an
aqueous solution, and then each bulk spiked sample
was blended for uniformity and dried before it was
repackaged in sample bottles.
Six bulk background soil samples were used at
ERA's laboratory to create 12 separate spiked sample
blends, and four bulk sediment samples were used to
create 13 separate spiked sample blends. Thus, a
total of 10 bulk background samples were used to
create 25 spiked sample blends. Three or seven
replicate samples of each spiked sample blend were
included in the demonstration sample set. Table 3-3
lists the number of sample blends and the number of
demonstration samples (including replicates) that
were derived from the bulk background samples for
each sampling location.
3.2.3 Demonstration Sample Set
In total, 70 separate blends of environmental and
spiked samples were created and a set of 326 samples
was developed for the demonstration by including
three, five, or seven replicates of each blend in the
final demonstration sample set. Thirteen sets of the
demonstration samples, consisting of 326 individual
samples in 250-milliliter clean plastic sample bottles,
were prepared for shipment to the demonstration site
and reference laboratory.
17
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Table 3-1. Concentration Levels for Target Elements in Soil and Sediment
Analyte
Level 1
Target Range
(mg/kg)
Level 2
Target Range
(mg/kg)
Level 3
Target Range
(mg/kg)
Level 4
Target Range
(mg/kg)
SOIL
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
40 - 400
20 - 400
50-500
50-500
50-500
60 - 5,000
20 - 1,000
20 - 200
50-250
20-100
45-90
50-100
30-1,000
400 - 2,000
400 - 2,000
500-2,500
500-2,500
500-2,500
5,000-25,000
1,000-2,000
200-1,000
250- 1,000
100-200
90-180
100-200
1,000-3,500
>2,000
>2,000
>2,500
>2,500
>2,500
25,000 - 40,000
2,000 - 10,000
>1,000
>1,000
>200
>180
>200
3,500-8,000
>40,000
>10,000
>8,000
SEDIMENT
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
40-250
20-250
50-250
50-250
50-500
60 - 5,000
20 - 500
20 - 200
50-200
20-100
45-90
50-100
30-500
250-750
250-750
250-750
250-750
500-1,500
5,000-25,000
500-1,500
200 - 500
200 - 500
100-200
90-180
100-200
500-1,500
>750
>750
>750
>750
>1,500
25,000 - 40,000
>1,500
>500
>500
>200
>180
>200
>1,500
>40,000
18
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Table 3-2. Number of Environmental Sample Blends and Demonstration Samples
Sampling Location
Alton Steel Mill Site
Burlington Northern-ASARCO East
Helena Site
Kennedy Athletic, Recreational and
Social Park Site
Leviathan Mine Site
Naval Surface Warfare Center, Crane
Division Site
Ramsay Flats Silver Bow Creek
Superfund Site
Sulphur Bank Mercury Mine Site
Torch Lake Superfund Site
Wickes Smelter Site
TOTAL *
Number of
Sample Blends
2
5
6
7
1
7
9
3
5
45
Number of
Demonstration Samples
10
29
32
37
5
37
47
19
31
247
* Note: The totals in this table add to those for the spiked blends and replicates as summarized in Table 3-3 to
bring the total number of blends to 70 and the total number of samples to 326 for the demonstration.
Table 3-3. Number of Spiked Sample Blends and Demonstration Samples
Sampling Location
Alton Steel Mill Site
Burlington Northern-ASARCO East
Helena Site
Leviathan Mine Site
Naval Surface Warfare Center, Crane
Division Site
Ramsey Flats Silver Bow Creek
Superfund Site
Sulphur Bank Mercury Mine Site
Torch Lake Superfund Site
Wickes Smelter Site
TOTAL *
Number of
Spiked Sample
Blends
1
2
5
2
6
3
4
2
25
Number of
Demonstration Samples
3
6
15
6
22
9
12
6
79
: Note: The totals in this table add to those for the unspiked blends and replicates as summarized in Table 3-2 to
bring the total number of blends to 70 and the total number of samples to 326 for the demonstration.
19
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3.3 Demonstration Site and Logistics
The field demonstration occurred during the week of
January 24, 2005. This section describes the
selection of the demonstration site and the logistics of
the field demonstration, including sample
management.
3.3.1 Demonstration Site Selection
The demonstration site was selected from among the
list of sample collection sites to simulate a likely field
deployment. The following criteria were used to
assess which of the nine sample collection sites might
best serve as the demonstration site:
Convenience and accessibility to participants in
the demonstration.
Ease of access to the site, with a reasonably sized
airport that can accommodate the travel
schedules for the participants.
Program support and cooperation of the site
owner.
Sufficient space and power to support developer
testing.
Adequate conference room space to support a
visitors day.
A temperate climate so that the demonstration
could occur on schedule in January.
After an extensive search for candidates, the site
selected for the field demonstration was KARS Park,
which is part of the Kennedy Space Center on Merritt
Island, Florida. KARS Park was selected as the
demonstration site for the following reasons:
Access and Site Owner Support
Representatives from NASA were willing to
support the field demonstration by providing
access to the site, assisting in logistical support
during the demonstration, and hosting a visitors
day.
Facilities Requirements and Feasibility The
recreation building was available and was of
sufficient size to accommodate all the
demonstration participants. Furthermore, the
recreation building had adequate power to operate
all the XRF instruments simultaneously and all the
amenities to fully support the demonstration
participants, as well as visitors, in reasonable
comfort.
Ease of Access to the Site The park, located
about 45 minutes away from Orlando
International Airport, was selected because of its
easy accessibility by direct flight from many
airports in the country. In addition, many hotels
are located within 10 minutes of the site along
the coast at Cocoa Beach, in a popular tourist
area. Weather in this area of central Florida in
January is dry and sunny, with pleasant daytime
temperatures into the 70s (F) and cool nights.
3.3.2 Demonstration Site Logistics
The field demonstration was held in the recreation
building, which is just south of the gunnery range at
KARS Park. Photographs of the KARS Park
recreation building, where all the XRF instruments
were set up and operated, are shown in Figures 3-2
and 3-3.
A visitors day was held on January 26, 2005 when
about 25 guests came to the site to hear about the
demonstration and to observe the XRF instruments in
operation. Visitors day presentations were conducted
in a conference building adjacent to the recreation
building at KARS Park (see Figure 3-4). Presenta-
tions by NASA and EPA representatives were
followed by a tour of the XRF instruments in the
recreation building while demonstration samples
were being analyzed.
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Figure 3-2. KARS Park recreation building.
20
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Figure 3-3. Work areas for the XRF instruments
in the recreation building.
Figure 3-4. Visitors day presentation.
3.3.3 EPA Demonstration Team and Developer
Field Team Responsibilities
Each technology developer sent its instrument and a
field team to the demonstration site for the week of
January 24, 2005. The developer's field team was
responsible for unpacking, setting up, calibrating, and
operating the instrument. The developer's field team
was also responsible for any sample preparation for
analysis using the XRF instrument.
The EPA/Tetra Tech demonstration team assigned an
observer to each instrument. The observer sat beside
the developer's field team, or was nearby, throughout
the field demonstration and observed all activities
involved in setup and operation of the instrument.
The observer's specific responsibilities included:
Guiding the developer's field team to the work
area in the recreation building at KARS Park and
assisting with any logistical issues involved in
instrument shipping, unpacking, and setup.
Providing the demonstration sample set to the
developer's field team in accordance with the
sample management plan.
Ensuring that the developer was operating the
instrument in accordance with standard
procedures and questioning any unusual practices
or procedures.
Communications with the developer's field team
regarding schedules and fulfilling the
requirements of the demonstration.
Recording information relating to the secondary
objectives of the evaluation (see Chapter 4) and
for obtaining any cost information that could be
provided by the developer's field team.
Receiving the data reported by the developer's
field team for the demonstration samples, and
loading these data into a temporary database on a
laptop computer.
Overall, the observer was responsible for assisting
the developer's field team throughout the field
demonstration and for recording all pertinent
information and data for the evaluation. However,
the observer was not allowed to advise the
developer's field team on sample processing or to
provide any feedback based on preliminary
inspection of the XRF instrument data set.
3.3.4 Sample Man agement during th e Field
Demonstration
The developer's field team analyzed the
demonstration sample set with its XRF instrument
during the field demonstration. Each demonstration
sample set was shipped to the demonstration site with
only a reference number on each bottle as an
identifier. The reference number was tied to the
source information in the EPA/Tetra Tech database,
but no information was provided on the sample label
that might provide the developer's field team any
insight as to the nature or content of the sample.
21
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Spiked samples were integrated with the
environmental samples in a random manner so that
the spiked samples could not be distinguished.
The demonstration sample set was divided into 13
subsets, or batches, for tracking during the field
demonstration. The samples provided to each
developer's field team were randomly distributed in
two fashions. First, the order of the jars within each
batch was random, so that the sample order for a
batch was different for each developer's field team.
Second, the distribution of sample batches was
random, so that each developer's field team received
the sample batches in a different order.
The observer provided the developer's field team
with one batch of samples at a time. When the
developer's field team reported that analysis of a
batch was complete, the observer would reclaim all
the unused sample material from that batch and then
provide the next batch of samples for analysis.
Chain-of-custody forms were used to document all
sample transfers. When the analysis of all batches
was complete, the observer assisted the developer's
field team in cleanup of the work area and
repackaging the instrument and any associated
equipment. The members of the developer's field
team were not allowed to take any part of the
demonstration samples with them when they left the
demonstration site.
Samples that were not in the possession of the
developer's field team during the demonstration were
held in a secure storage room adjacent to the
demonstration work area (see Figure 3-5). The
storage room was closed and locked except when the
observer retrieved samples from the room. Samples
were stored at room temperature during the
demonstration, in accordance with the quality
assurance/quality control (QA/QC) requirements
established for the project.
Figure 3-5. Sample storage room.
3.3.5 Data Management
Each of the developer's field teams was able to
complete analysis of all 326 samples during the field
demonstration (or during the subsequent week, in one
case when the developer's field team arrived late at
the demonstration site because of delays in
international travel). The data produced by each
developer's field team were submitted during or at
the end of the field demonstration in a standard
Microsoft ExcelŽ spreadsheet. (The EPA/Tetra Tech
field team had provided a template.) Since each
instrument provided data in a different format, the
developer's field team was responsible for reducing
the data before they were submitted and for
transferring the data into the Excel spreadsheet.
The observer reviewed each data submittal for
completeness, and the data were then uploaded into a
master Excel spreadsheet on a laptop computer for
temporary storage. Only the EPA/Tetra Tech field
team had access to the master Excel spreadsheet
during the field demonstration.
Once the EPA/Tetra Tech field team returned to their
offices, the demonstration data were transferred to an
Microsoft AccessŽ database for permanent storage.
Each developer's data, as they existed in the Access
database, were then provided to the developer for
review. Any errors the developers identified were
corrected, and the database was then finalized. All
statistical analysis and data evaluation took place on
this final database.
22
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Chapter 4
Evaluation Design
This chapter presents the approach for evaluating the
performance of the XRF instruments. Specifically,
the sections below describe the objectives of the
evaluation and the experimental design.
The Demonstration and Quality Assurance Project
Plan (Tetra Tech 2005) provides additional details on
the overall demonstration approach. However, some
deviations from the plan, involving data evaluation
and laboratory audits, occurred after the
demonstration plan was written. For completeness,
the primary changes to the written plan are
documented in the final section of this chapter.
4.1 Evaluation Objectives
The overall purpose of the XRF technology
demonstration was to evaluate the performance of
various field XRF instruments in detecting and
quantifying trace elements in soils and sediments
from a variety of sites around the U.S. The
performance of each XRF instrument was evaluated
in accordance with primary and secondary objectives.
Primary objectives are critical to the evaluation and
require the use of quantitative results to draw
conclusions about an instrument's performance.
Secondary objectives pertain to information that is
useful but that will not necessarily require use of
quantitative results to draw conclusions about an
instrument's performance.
The primary and secondary objectives for the
evaluation are listed in Table 4-1. These objectives
were based on:
Input from MMT Program stakeholders,
including developers and EPA staff.
General expectations of users of field
measurement instruments.
The time available to complete the
demonstration.
The capabilities of the instruments that the
developers participating in the demonstration
intended to highlight.
4.2 Experimental Design
To address the first four primary objectives, each
XRF instrument analyzed the demonstration sample
set for the 13 target elements. The demonstration
samples originated from multiple sampling locations
across the country, as described in Chapter 2, to
provide a diverse set of soil and sediment matrices.
The demonstration sample set included both blended
environmental samples and spiked background
samples, as described in Chapter 3, to provide a wide
range of concentrations and combinations of
elements.
When the field demonstration was completed, the
results obtained using the XRF instruments were
compared with data from a reference laboratory to
evaluate the performance of each instrument in terms
of accuracy and comparability (Primary Objective 2).
The results for replicate samples were used to
evaluate precision in various concentration ranges
(Primary Objective 3) and the method detection
limits (MDL) (Primary Objective 1). Each of these
quantitative evaluations of instrument performance
was carried out for each target element. The effect of
chemical and spectral interferences and of soil
characteristics (Primary Objectives 4 and 5) were
evaluated to help explain extreme deviations or
outliers observed in the XRF results when compared
with the reference laboratory results.
A second important comparison involved the average
performance of all eight XRF instruments that
participated in the demonstration. For the first three
primary objectives (MDL, accuracy, precision), the
performance of each individual instrument was
compared to the overall average performance of all
eight instruments. Where the result of the instrument
under consideration was less than 10 percent different
than the average result for all eight instruments, the
result was considered "equivalent." A similar
comparison was conducted with respect to cost
(Primary Objective 7). These comparisons were
intended to illustrate the performance of each XRF
instrument in relation to its peers.
23
-------
The evaluation design for meeting each objective,
including data analysis procedures, is discussed in
more detail in the sections below. Where specific
deviations from these procedures were necessary for
the data set associated with specific instruments,
these deviations are described as part of the
performance evaluation in Chapter 7.
4.2.1 Primary Objective 1 Meth od Detection
Limits
The MDL for each target element was evaluated
based on the analysis of sets of seven replicate
samples that contained the target element at
concentrations near the detection limit. The MDL
was calculated using the procedures found in Title 40
Code of Federal Regulations (CFR) Part 136,
Appendix B, Revision 1.11. The following equation
was used:
where
MDL = t(n-U-a=0.99)(s)
MDL = method detection limit
t
n
s
= Student's t value for a 99
percent confidence level and
a standard deviation estimate
with n-1 degrees of freedom
= number of samples
= standard deviation
Table 4-1. Evaluation Objectives
Objective
Primary Objective 1
Primary Objective 2
Primary Objective 3
Primary Objective 4
Primary Objective 5
Primary Objective 6
Primary Objective 7
Secondary Objective 1
Secondary Objective 2
Secondary Objective 3
Secondary Objective 4
Secondary Objective 5
Description
Determine the MDL for each target element.
Evaluate the accuracy and comparability of the XRF measurement to the results of
laboratory reference methods for a variety of contaminated soil and sediment
samples.
Evaluate the precision of XRF measurements for a variety of contaminated soil and
sediment samples.
Evaluate the effect of chemical and spectral interference on measurement of target
elements.
Evaluate the effect of soil characteristics on measurement of target elements.
Measure sample throughput for the measurement of target elements under field
conditions.
Estimate the costs associated with XRF field measurements.
Document the skills and training required to properly operate the instrument.
Document health and safety concerns associated with operating the instrument.
Document the portability of the instrument.
Evaluate the instrument's durability based on its materials of construction and
engineering design.
Document the availability of the instrument and of associated customer technical
support.
24
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Based on the data provided by the characterization
laboratory before the demonstration, a total of 12
sample blends (seven for soil and five for sediment)
were identified for use in the MDL determination.
The demonstration approach specified the analysis of
seven replicates for each of these sample blends by
both the developer and the reference laboratory. It
was predicted that these blends would allow the
determination of a minimum of one MDL for soil and
one MDL for sediment for each element, with the
exception of iron. This prediction was based on the
number of sample blends that contained
concentrations less than 50 percent lower or higher
than the lower limit of the Level 1 concentration
range (from 20 to 50 ppm, depending on the
element), as presented in Table 3-1.
After the field demonstration, the data sets obtained
by the developers and the reference laboratory for the
MDL sample blends were reviewed to confirm that
they were appropriate to use in calculating MDLs.
The requirements of 40 CFR 136, Appendix B, were
used as the basis for this evaluation. Specifically, the
CFR states that samples to be used for MDL
determinations should contain concentrations in the
range of 1 to 5 times the predicted MDL. On this
basis, and using a nominal predicted reporting limit
of 50 ppm for the target elements based on past XRF
performance and developer information, a
concentration of 250 ppm (5 times the "predicted"
nominal MDL) was used as a threshold in selecting
samples to calculate the MDL. Thus, each of the 12
MDL blends that contained mean reference
laboratory concentrations less than 250 ppm were
used in calculating MDLs for a given target element.
Blends with mean reference laboratory
concentrations greater than 250 ppm were discarded
for evaluating this objective.
For each target element, an MDL was calculated for
each sample blend with a mean concentration within
the prescribed range. If multiple MDLs could be
calculated for an element from different sample
blends, these results were averaged to arrive at an
overall mean MDL for the demonstration. The mean
MDL for each target element was then categorized as
either low (MDL less than 20 ppm), medium (MDL
between 20 and 100 ppm), or high (MDL exceeds
100 ppm). No blends were available to calculate a
detection limit for iron because all the blends
contained substantial native concentrations of iron.
4.2.2 Primary Objective 2 Accuracy
Accuracy was assessed based on a comparison of the
results obtained by the XRF instrument with the
results from the reference laboratory for each of the
70 blends in the demonstration sample set. The
results from the reference laboratory were essentially
used as a benchmark in this comparison, and the
accuracy of the XRF instrument results was judged
against them. The limitations of this approach should
be recognized, however, because the reference
laboratory results were not actually "true values."
Still, there was a high degree of confidence in the
reference laboratory results for most elements, as
described in Chapter 5.
The following data analysis procedure was followed
for each of the 13 target elements to assess the
accuracy of an XRF instrument:
1. The results for replicate samples within a blend
were averaged for both the data from the XRF
instrument and the reference laboratory. Since
there were 70 sample blends, this step created a
maximum of 70 paired results for the assessment.
2. A blend that exhibited one or more non-detect
values in either the XRF instrument or the
reference laboratory analysis was excluded from
the evaluation.
3. A blend was excluded from the evaluation when
the average result from the reference laboratory
was below a minimum concentration. The
minimum concentration for exclusion from the
accuracy assessment was identified as the lower
limit of the lowest concentration range (Level 1
in Table 3-1), which is about 50 ppm for most
elements.
4. The mean result for a blend obtained with the
XRF instrument was compared with the
corresponding mean result from the reference
laboratory by calculating a relative percent
difference (RPD). This comparison was carried
out for each of the paired XRF and reference
laboratory results included in the evaluation (up
to 70 pairs) as follows:
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RPD
where
MR
MD
average (MR, MD)
= the mean reference
laboratory measurement
= the mean XRF instrument
measurement.
5. Steps 1 through 4 provided a set of up to 70
RPDs for each element (70 sample blends minus
the number excluded in steps 1 and 2). The
absolute value of each of the RPDs was taken
and summary statistics (minimum, maximum,
mean and median) were then calculated.
6. The accuracy of the XRF instrument for each
target element was then categorized, based on the
median of the absolute values of the RPDs, as
either excellent (RPD less than 10 percent), good
(RPD between 10 percent and 25 percent), fair
(RPD between 25 percent and 50 percent), or
poor (RPD above 50 percent).
7. The set of absolute values of the RPDs for each
instrument and element was further evaluated to
assess any trends in accuracy versus
concentration. These evaluations involved
grouping the RPDs by concentration range
(Levels 1 through 3 and 4, as presented in Table
3-1), preparing summary statistics for each range,
and assessing differences among the grouped
RPDs.
The absolute value of the RPDs was taken in step 5 to
provide a more sensitive indicator of the extent of
differences between the results from the XRF
instrument and the reference laboratory. However,
the absolute value of the RPDs does not indicate the
direction of the difference and therefore does not
reflect bias.
The populations of mean XRF and mean reference
laboratory results were assessed through linear
correlation plots to evaluate bias. These plots depict
the linear relationships between the results for the
XRF instrument and reference laboratory for each
target element using a linear regression calculation
with an associated correlation coefficient (r2). These
plots were used to evaluate the existence of general
bias between the data sets for the XRF instrument
and the reference laboratory.
4.2.3 Primary Objective 3 Precision
The precision of the XRF instrument analysis for
each target element was evaluated by comparing the
results for the replicate samples in each blend. All 70
blends in the demonstration sample set (including
environmental and spiked samples) were included in
at least triplicate so that precision could be evaluated
across all concentration ranges and across different
matrices.
The precision of the data for a target element was
evaluated for each blend by calculating the mean
relative standard deviation (RSD) with the following
equation:
RSD =
SD
C
100
where
RSD = Relative standard deviation
SD = Standard deviation
C = Mean concentration.
The standard deviation was calculated using the
equation:
SD =
where
SD = Standard deviation
n = Number of replicate
samples
Ck = Concentration of sample K
C = Mean concentration.
The following specific procedure for data analysis
was followed for each of the 13 target elements to
assess XRF instrument precision:
1. The RSD for the replicate samples in a blend was
calculated for both data from the XRF instrument
and the reference laboratory. Since there were 70
sample blends, this step created a maximum of
70 paired RSDs for the assessment.
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2. A blend that exhibited one or more non-detect
values in either the XRF or the reference
laboratory analysis was excluded from the
evaluation.
3. A blend was excluded from the evaluation when
the average result from the reference laboratory
was below a minimum concentration. The
minimum concentration for exclusion from the
precision assessment was identified as the lower
limit of the lowest concentration range (Level 1
in Table 3-1), which was about 50 ppm for most
elements.
4. The RSDs for the various blends for both the
XRF instrument and the reference laboratory
were treated as a statistical population. Summary
statistics (minimum, maximum, mean and
median) were then calculated and compared for
the data set as a whole and for the different
concentration ranges (Levels 1 through 3 or 4).
5. The precision of the XRF instrument for each
target element was then categorized, based on the
median RSDs, as either excellent (RSD less than
5 percent), good (RSD between 5 percent and 10
percent), fair (RSD between 10 percent and 20
percent), or poor (RSD above 20 percent).
One primary evaluation was a comparison of the
mean RSD for each target element between the XRF
instrument and the reference laboratory. Using this
comparison, the precision of the XRF instrument
could be evaluated against the precision of accepted
fixed-laboratory methods. Another primary
evaluation was a comparison of the mean RSD for
each target element between the XRF instrument and
the overall average of all XRF instruments. Using
this comparison, the precision of the XRF instrument
could be evaluated against its peers.
4.2.4 Primary Objective 4 Impact of
Chemical and Spectral Interferences
The potential in the XRF analysis for spectral
interference between adjacent elements on the
periodic table was evaluated for the following
element pairs: lead/arsenic, nickel/copper, and
copper/zinc. The demonstration sample set included
multiple blends where the concentration of one of
these elements was greater than 10 times the
concentration of the other element in the pair to
facilitate this evaluation. Interference effects were
identified through evaluation of the RPDs for these
sample blends, which were calculated according to
the equation in Section 4.2.2, since spectral
interferences would occur only in the XRF data and
not in the reference laboratory data.
Summary statistics for RPDs (mean, median,
minimum, and maximum) were calculated for each
potentially affected element for the sample blends
with high relative concentrations (greater than 10
times) of the potentially interfering element. These
summary statistics were compared with the RPD
statistics for sample blends with lower concentrations
of the interfering element. It was reasoned that
spectral interference should be directly reflected in
increased RPDs for the interference samples when
compared with the rest of the demonstration sample
set.
In addition to spectral interferences (caused by
overlap of neighboring spectral peaks), the data sets
were assessed for indications of chemical
interferences. Chemical interferences occur when
the x-rays characteristic of an element are absorbed
or emitted by another element within the sample,
causing low or high bias. These interferences are
common in samples that contain high levels of iron,
where low biases for copper and high biases for
chromium can result. The evaluations for Primary
Objective 4 therefore included RPD comparisons
between sample blends with high concentrations of
iron (more than 50,000 ppm) and other sample
blends. These RPD comparisons were performed
for the specific target elements of interest (copper,
chromium, and others) to assess chemical
interferences from iron. Outliers and
subpopulations in the RPD data sets for specific
target elements, as identified through graphical
means (probability plots and box plots), were also
examined for potential interference effects.
The software that is included with many XRF
instruments can correct for chemical interferences.
The results of this evaluation were intended to
differentiate the instruments that incorporated
effective software for addressing chemical
interferences.
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4.2.5 Primary Objective 5 Effects of Soil
Characteristics
The demonstration sample set included soil and
sediment samples from nine locations across the U.S.
and a corresponding variety of soil types and
lithologies. The accuracy and precision statistics
(RPD and RSD) were grouped by soil type (sample
location) and the groups were compared to assess the
effects of soil characteristics. Outliers and
subpopulations in the RPD data sets, as identified
through graphical means (correlation plots and box
plots), were also examined for matrix effects.
4.2.6 Primary Objective 6 Sample Throughput
Sample throughput is a calculation of the total
number of samples that can be analyzed in a specified
time. The primary factors that affect sample
throughput are the time required to prepare a sample
for analysis, to conduct the analytical procedure for
each sample, and to process and tabulate the resulting
data. The time required to prepare and to analyze
demonstration samples was recorded each day that
demonstration samples were analyzed.
Sample throughput can also be affected by the time
required to set up and calibrate the instrument as well
as the time required for quality control. The time
required to perform these activities was also recorded
during the field demonstration.
An overall mean processing time per sample and an
overall sample throughput rate was calculated based
on the total time required to complete the analysis of
the demonstration sample set from initial instrument
setup through data reporting. The overall mean
processing time per sample was then used as the
primary basis for comparative evaluations.
4.2.7 Primary Objective 7 Technology Costs
The costs for analysis are an important factor in the
evaluation and include the cost for the instrument,
analytical supplies, and labor. The observer collected
information on each of these costs during the field
demonstration.
Based on input from each technology developer and
from distributors, the instrument cost was established
for purchase of the equipment and for daily, weekly,
and monthly rental. Some of the technologies are not
yet widely available, and the developer has not
established rental options. In these cases, an
estimated weekly rental cost was derived for the
summary cost evaluations based on the purchase
price for the instrument and typical rental to purchase
price ratios for similar instruments. The costs
associated with leasing agreements were also
specified in the report, if available.
Analytical supplies include sample cups, spoons, x-
ray film, MylarŽ, reagents, and personal protective
equipment. The rate that the supplies are consumed
was monitored and recorded during the field
demonstration. The cost of analytical supplies was
estimated per sample from these consumption data
and information on unit costs.
Labor includes the time required to prepare and
analyze the samples and to set up and dismantle the
equipment. The labor hours associated with
preparing and analyzing samples and with setting up
and dismantling the equipment were recorded during
the demonstration. The labor costs were calculated
based on this information and typical labor rates for a
skilled technician or chemist.
In addition to the assessment of the above-described
individual cost components, an overall cost for a field
effort similar to the demonstration was compiled and
compared to the cost of fixed laboratory analysis.
The results of the cost evaluation are presented in
Chapter 8.
4.2.8 Secondary Objective 1 Training
Requirements
Each XRF instrument requires that the operator be
trained to safely set up and operate the instrument.
The relative level of education and experience that is
appropriate to operate the XRF instrument was
assessed during the field demonstration.
The amount of specific training required depends on
the complexity of the instrument and the associated
software. Most developers have established training
programs. The time required to complete the
developer's training program was estimated and the
content of the training was identified.
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4.2.9 Secondary Objective 2 Health and Safety
The health and safety requirements for operation of
the instrument were identified, including any that are
associated with potential exposure from radiation and
to reagents. Not included in the evaluation were
potential risks from exposure to site-specific
hazardous materials or physical safety hazards
associated with the demonstration site.
4.2.10 Secon dary Objective 3 Portability
The portability of the instrument depends on size,
weight, number of components, power requirements,
and reagents required. The size of the instrument,
including physical dimensions and weight, was
recorded (see Chapter 6). The number of
components, power requirements, support structures,
and reagent requirements were also recorded. A
qualitative assessment of portability was conducted
based on this information.
4.2.11 Secon dary Objective 4 Durability
The durability of the instrument was evaluated by
gathering information on the warranty and expected
lifespan of the radioactive source or x-ray tube. The
ability to upgrade software or hardware also was
evaluated. Weather resistance was evaluated if the
instrument is intended for use outdoors by examining
the instrument for exposed electrical connections and
openings that may allow water to penetrate.
4.2.12 Secon dary Objective 5 Availability
The availability of the instrument from the developer,
distributors, and rental agencies was documented.
The availability of replacement parts and instrument-
specific supplies was also noted.
4.3
Deviations from the Demonstration Plan
Although the field demonstration and subsequent
data evaluations generally followed the
Demonstration and Quality Assurance Project Plan
(Tetra Tech 2005), there were some deviations as
new information was uncovered or as the procedures
were reassessed while the plan was executed. These
deviations are documented below for completeness
and as a supplement to the demonstration plan:
1. An in-process audit of the reference laboratory
was originally planned while the laboratory was
analyzing the demonstration samples. However,
the reference laboratory completed all analysis
earlier than expected, during the week of the field
demonstration, and thereby created a schedule
conflict. Furthermore, it was decided that the
original pre-award audit was adequate for
assessing the laboratory's procedures and
competence.
2. The plan suggested that each result for spiked
samples from the reference laboratory would be
replaced by the "certified analysis" result, which
was quantitative based on the amount of each
element spiked, whenever the RPD between
these two results was greater than 10 percent.
The project team agreed that 10 percent was too
stringent for this evaluation, however, and
decided to use 25 percent RPD as the criterion
for assessing reference laboratory accuracy
against the spiked samples. Furthermore, it was
found during the data evaluations that replacing
individual reference laboratory results using this
criterion would result in a mixed data set.
Therefore, the 25 percent criterion was applied to
the overall mean RPD for each element, and the
"certified analysis" data set for a specific target
element was used as a supplement to the
reference laboratory result when this criterion
was exceeded.
3. Instrument accuracy and comparability in
relation to the reference laboratory (Primary
Objective 2) was originally planned to be
assessed based on a combination of percent
recovery (instrument result divided by reference
laboratory result) and RPD. It was decided
during the data analysis, however, that the RPD
was a much better parameter for this assessment.
Specifically, it was found that the mean or
median of the absolute values of the RPD for
each blend was a good discriminator of
instrument performance for this objective.
4. Although this step was not described in the plan,
some quantitative results for each instrument
were compared with the overall average of all
XRF instruments. Since there were eight
instruments, it was believed that a comparison of
29
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this type did not violate EPA's agreement with
the technology developers that one instrument
would not be compared with another.
Furthermore, this comparison provides an easy-
to-understand basis for assessing instrument
performance.
5. The plan proposed statistical testing in support of
Primary Objectives 4 and 5. Specifically, the
Wilcoxon Rank Sum (WRS) test was proposed to
assist in evaluating interference effects, and the
Rosner outlier test was proposed in evaluating
other matrix effects on XRF data quality (EPA
2000; Gilbert 1987). However, these statistical
tests were not able to offer any substantive
performance information over and above the
evaluations based on RPDs and regression plots
because of the limited sample numbers and
scatter in the data. On this basis, the use of these
two statistical tests was not further explored or
presented.
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Chapter 5
Reference Laboratory
As described in Chapter 4, a critical part of the
evaluation was the comparison of the results obtained
for the demonstration sample set by the XRF
instrument with the results obtained by a fixed
laboratory (the reference laboratory) using
conventional analytical methods. Therefore, a
significant effort was undertaken to ensure that data
of the highest quality were obtained as the reference
data for this demonstration. This effort included
three main activities:
Selection of the most appropriate methods for
obtaining reference data,
Selection of a high-quality reference laboratory,
and
Validation of reference laboratory data and
evaluation of QA/QC results.
This chapter describes the information that confirms
the validity, reliability, and usability of the reference
laboratory data based on each of the three activities
listed above (Sections 5.1, 5.2, and 5.3). Finally, this
chapter presents conclusions (Section 5.4) on the
level of data quality and the usability of the data
obtained by the reference laboratory.
5.1
Selection of Reference Methods
Methods for analysis of elements in environmental
samples, including soils and sediments, are well
established in the environmental laboratory industry.
Furthermore, analytical methods appropriate for soil
and sediment samples have been promulgated by
EPA in the compendium of methods, Test Methods
for Evaluating Solid Waste, Physical/Chemical
Methods (SW-846) (EPA 1996c). Therefore, the
methods selected as reference methods for the
demonstration were the SW-846 methods most
typically applied by environmental laboratories to
soil and sediment samples, as follows:
Inductively coupled plasma-atomic emission
spectroscopy (ICP-AES), in accordance with
EPA SW-846 Method 3050B/6010B, for all
target elements except mercury.
Cold vapor atomic absorption (CVAA)
spectroscopy, in accordance with EPA SW-846
Method 7471 A, for mercury only.
Selection of these analytical methods for the
demonstration was supported by the following
additional considerations: (1) the methods are widely
available and widely used in current site
characterizations, remedial investigations, risk
assessments, and remedial actions; (2) substantial
historical data are available for these methods to
document that their accuracy and precision are
adequate to meet the objectives of the demonstration;
(3) these methods have been used extensively in
other EPA investigations where confirmatory data
were compared with XRF data; and (4) highly
sensitive alternative methods were less suitable given
the broad range of concentrations that were inherent
in the demonstration sample set. Specific details on
the selection of each method are presented below.
Element Analysis by ICP-AES. Method 601 OB
(ICP-AES) was selected for 12 of the target elements
because its demonstrated accuracy and precision
meet the requirements of the XRF demonstration in
the most cost-effective manner. The ICP-AES
method is available at most environmental
laboratories, and substantial data exist to support the
claim that the method is both accurate and precise
enough to meet the objectives of the demonstration.
Inductively coupled plasma-mass spectrometry (ICP-
MS) was considered as a possible analytical
technique; however, fewer data were available to
support the claims of accuracy and precision.
Furthermore, it was available in less than one-third of
the laboratories solicited for this project. Finally,
ICP-MS is a technique for analysis of trace elements
and often requires serial dilutions to mitigate the
effect of high concentrations of interfering ions or
other matrix interferences. These dilutions can
introduce the possibility of error and contaminants
that might bias the results. Since the matrices (soil
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and sediment) for this demonstration are designed to
contain high concentrations of elements and
interfering ions, ICP-AES was selected over ICP-MS
as the instrumental method best suited to meet the
project objectives. The cost per analysis is also
higher for ICP-MS in most cases than for ICP-AES.
Soil/Sediment Sample Preparation by Acid
Digestion. The elements in soil and sediment
samples must be dissolved from the matrix into an
aqueous solution by acid digestion before analysis by
ICP-AES. Method 3050B was selected as the
preparation method and involves digestion of the
matrix using a combination of nitric and hydrochloric
acids, with the addition of hydrogen peroxide to
assist in degrading organic matter in the samples.
Method 3 05 OB was selected as the reference
preparation method because extensive data are
available that suggest it efficiently dissolves most
elements, as required for good overall recoveries and
method accuracy. Furthermore, this method was
selected over other digestion procedures because it is
the most widely used dissolution method. In
addition, it has been used extensively as the digestion
procedure in EPA investigations where confirmatory
data were compared with XRF data.
The ideal preparation reference method would
completely digest silicaceous minerals. However,
total digestion is difficult and expensive and is
therefore seldom used in environmental analysis.
More common strong acid-based extractions, like that
used by EPA Method 3050B, recover most of the
heavy element content. In addition, stronger and
more vigorous digestions may produce two possible
drawbacks: (1) loss of elements through
volatilization, and (2) increased dissolution of
interfering species, which may result in inaccurate
concentration values.
Method 3052 (microwave-assisted digestion) was
considered as an alternative to Method 3050B, but
was not selected because it is not as readily available
in environmental laboratories.
Soil/Sediment Sample Preparation for Analysis of
Mercury by CVAA. Method 7471A (CVAA) is the
only method approved by EPA and promulgated for
analysis of mercury. Method 7471A includes its own
digestion procedure because more vigorous digestion
of samples, like that incorporated in Method 3050B,
would volatilize mercury and produce inaccurate
results. This technique is widely available, and
extensive data are available that support the ability of
this method to meet the objectives of the
demonstration.
5.2 Selection of Reference Laboratory
The second critical step in ensuring high-quality
reference data was selection of a reference laboratory
with proven credentials and quality systems. The
reference laboratory was procured via a competitive
bid process. The procurement process involved three
stages of selection: (1) a technical proposal, (2) an
analysis of performance audit samples, and (3) an on-
site laboratory technical systems audit (TSA). Each
stage was evaluated by the project chemist and a
procurement specialist.
In Stage 1,12 analytical laboratories from across the
U.S. were invited to bid by submitting extensive
technical proposals. The technical proposals
included:
A current statement of qualifications.
The laboratory quality assurance manual.
Standard operating procedures (SOP) (including
sample receipt, laboratory information
management, sample preparation, and analysis of
elements).
Current instrument lists.
Results of recent analysis of performance
evaluation samples and audits.
Method detection limit studies for the target
elements.
Professional references, laboratory personnel
experience, and unit prices.
Nine of the 12 laboratories submitted formal written
proposals. The proposals were scored based on
technical merit and price, and a short list of five
laboratories was identified. The scoring was weighed
heavier for technical merit than for price. The five
laboratories that received the highest score were
advanced to stage 2.
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In stage 2, each of the laboratories was provided with
a set of six samples to analyze. The samples
consisted of three certified reference materials (one
soil and two sediment samples) at custom spiking
concentrations, as well as three pre-demonstration
soil samples. The results received from each
laboratory were reviewed and assessed. Scoring at
this stage was based on precision (reproducibility of
results for the three pre-demonstration samples),
accuracy (comparison of results to certified values for
the certified reference materials), and completeness
of the data package (including the hard copy and
electronic data deliverables). The two laboratories
that received the highest score were advanced to
stage 3.
In stage 3, the two candidate laboratories were
subjected to a thorough on-site TSA by the project
chemist. The audit consisted of a direct comparison
of the technical proposal to the actual laboratory
procedures and conditions. The audit also tracked the
pre-demonstration samples through the laboratory
processes from sample receipt to results reporting.
When the audit was conducted, the project chemist
verified sample preparation and analysis for the three
pre-demonstration samples. Each laboratory was
scored on identical checklists.
The reference laboratory was selected based on the
highest overall score. The weights of the final
scoring selection were as follows:
Scoring Element
Audits (on site)
Performance evaluation
samples, including data package
and electronic data deliverable
Price
Relative
Importance
40%
50%
10%
Based on the results of the evaluation process, Shealy
Environmental Services, Inc. (Shealy), of Cayce,
South Carolina, received the highest score and was
therefore selected as the reference laboratory. Shealy
is accredited by the National Environmental
Laboratory Accreditation Conference (NELAC).
Once selected, Shealy analyzed all demonstration
samples (both environmental and spiked samples)
concurrently with the developers' analysis during the
field demonstration. Shealy analyzed the samples by
ICP-AES using EPA SW-846 Method 3 05 OB/601 OB
and by CVAA using EPA SW-846 Method 7471 A.
5.3 QA/QC Results for Reference Laboratory
All data and QC results from the reference laboratory
were reviewed in detail to determine that the
reference laboratory data were of sufficiently high
quality for the evaluation. Data validation of all
reference laboratory results was the primary review
tool that established the level of quality for the data
set (Section 5.3.1). Additional reviews included the
on-site TSA (Section 5.3.2) and other evaluations
(Section 5.3.3).
5.3.1 Reference Laboratory Data Validation
After all demonstration samples had been analyzed,
reference data from Shealy were fully validated
according to the EPA validation document, USEPA
Contract Laboratory Program National Functional
Guidelines for Inorganic Data Review (EPA 2004c)
as required by the Demonstration and Quality
Assurance Project Plan (Tetra Tech 2005). The
reference laboratory measured 13 target elements,
including antimony, arsenic, cadmium, chromium,
copper, iron, lead, mercury, nickel, selenium, silver,
vanadium, and zinc. The reference laboratory
reported results for 22 elements at the request of
EPA; however, only the data for the 13 target
elements were validated and included in data
comparisons for meeting project objectives. A
complete summary of the validation findings for the
reference laboratory data is presented in Appendix C.
In the data validation process, results for QC samples
were reviewed for conformance with the acceptance
criteria established in the demonstration plan. Based
on the validation criteria specified in the
demonstration plan, all reference laboratory data
were declared valid (were not rejected). Thus, the
completeness of the data set was 100 percent.
Accuracy and precision goals were met for most of
the QC samples, as were the criteria for
comparability, representativeness, and sensitivity.
Thus, all reference laboratory data were deemed
usable for comparison to the data obtained by the
XRF instruments.
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Only a small percentage of the reference laboratory
data set was qualified as undetected as a result of
blank contamination (3.3 percent) and estimated
because of matrix spike and matrix spike duplicate
(MS/MSD) recoveries (8.7 percent) and serial
dilutions results (2.5 percent). Table 5.1 summarizes
the number of validation qualifiers applied to the
reference laboratory data according to QC type. Of
the three QC types, only the MS/MSD recoveries
warranted additional evaluation. The MS/MSD
recoveries for antimony were marginally low
(average recovery of 70.8 percent) when compared
with the QC criterion of 75 to 125 percent recovery.
It was concluded that low recoveries for antimony are
common in analysis of soil and sediment by the
prescribed methods and likely result from
volatilization during the vigorous acid digestion
process or spectral interferences found in soil and
sediments matrices (or both). In comparison to
antimony, high or low recoveries were observed only
on an isolated basis for the other target metals (for
example, lead and mercury) such that the mean and
median percent recoveries were well within the
required range. Therefore, the project team decided
to evaluate the XRF data against the reference
laboratory data for all 13 target elements and to
evaluate the XRF data a second time against the ERA
certified spike values for antimony only. These
comparisons are discussed in Section 7.1. However,
based on the validation of the complete reference
data set and the low occurrence of qualified data, the
reference laboratory data set as a whole was declared
of high quality and of sufficient quality to make valid
comparisons to XRF data.
5.3.2 Refer en ce Laboratory Techn ical
Systems Audit
The TSA of the Shealy laboratory was conducted by
the project chemist on October 19, 2004, as part of
the selection process for the reference laboratory.
The audit included the review of element analysis
practices (including sample preparation) for 12
elements by EPA Methods 3 05 OB and 601 OB and for
total mercury by EPA Method 7471 A. All decision-
making personnel for Shealy were present during the
TSA, including the laboratory director, QA officer,
director of inorganics analysis, and the inorganics
laboratory supervisor.
Project-specific requirements were reviewed with the
Shealy project team as were all the QA criteria and
reporting requirements in the demonstration plan. It
was specifically noted that the demonstration samples
would be dried, ground, and sieved before they were
submitted to the laboratory, and that the samples
would be received with no preservation required
(specifically, no chemical preservation and no ice).
The results of the performance audit were also
reviewed.
No findings or nonconformances that would
adversely affect data quality were noted. Only two
minor observations were noted; these related to the
revision dates of two SOPs. Both observations were
discussed at the debriefing meeting held at the
laboratory after the TSA. Written responses to each
of the observations were not required; however, the
laboratory resolved these issues before the project
was awarded. The auditor concluded that Shealy
complied with the demonstration plan and its own
SOPs, and that data generated at the laboratory
should be of sufficient and known quality to be used
as a reference for the XRF demonstration.
5.3.3 Other Reference Laboratory Data
Evaluations
The data validation indicated that all results from the
reference laboratory were valid and usable for
comparison to XRF data, and the pre-demonstration
TSA indicated that the laboratory could fully comply
with the requirements of the demonstration plan for
producing data of high quality. However, the
reference laboratory data were evaluated in other
ways to support the claim that reference laboratory
data are of high quality. These evaluations included
the (1) assessment of accuracy based on ERA-
certified spike values, (2) assessment of precision
based on replicate measurements within the same
sample blend, and (3) comparison of reference
laboratory data to the initial characterization data that
was obtained when the blends were prepared. Each
of these evaluations is briefly discussed in the
following paragraphs.
Blends 46 through 70 of the demonstration sample
set consisted of certified spiked samples that were
used to assess the accuracy of the reference
laboratory data. The summary statistics from
34
-------
comparing the "certified values" for the spiked
samples with the reference laboratory results are
shown in Table 5-2. The target for percent recovery
was 75 to 125 percent. The mean percent recoveries
for 12 of the 13 target elements were well within this
accuracy goal. Only the mean recovery for antimony
was outside the goal (26.8 percent). The low mean
percent recovery for antimony supported the
recommendation made by the project team to conduct
a secondary comparison of XRF data to ERA-
certified spike values for antimony. This secondary
evaluation was intended to better understand the
impacts on the evaluation of the low bias for
antimony in the reference laboratory data. All other
recoveries were acceptable. Thus, this evaluation
further supports the conclusion that the reference data
set is of high quality.
Table 5-1. Number of Validation Qualifiers.
Element
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Totals
Number and Percentage of Qualified Results per QC type l
Method Blank
Number
5
12
13
0
1
0
0
68
0
16
22
0
1
138
Percent2
1.5
3.7
4.0
0
0.3
0
0
20.9
0
4.9
6.7
0
0.3
3.3
MS/MSD
Number
199
3
0
0
0
0
34
31
0
0
102
0
0
369
Percent2
61.0
0.9
0
0
0
0
10.5
9.5
0
0
31.3
0
0
8.7
Serial Dilution
Number
8
10
6
10
8
10
11
4
10
3
7
9
10
106
Percent2
2.4
3.1
1.8
3.1
2.4
3.1
3.4
1.2
3.1
0.9
2.1
2.8
3.1
2.5
Notes:
MS Matrix spike.
MSB Matrix spike duplicate.
QC Quality control.
1 This table presents the number of "U" (undetected) and "J" (estimated) qualifiers added to the reference
laboratory data during data validation. Though so qualified, these results are considered usable for the
demonstration. As is apparent in the "Totals" row at the bottom of this table, the amount of data that
required qualifiers for any specific QC type was invariably less than 10 percent. No reference laboratory
data were rejected (that is, qualified "R") during the data validation.
2 Percents for individual elements are calculated based on 326 results per element. Total percents at the
bottom of the table are calculated based on the total number of results for all elements (4,238).
35
-------
All blends (1 through 70) were prepared and delivered
with multiple replicates. To assess precision, percent
RSDs were calculated for the replicate sample results
submitted by the reference laboratory for each of the
70 blends. Table 5-3 presents the summary statistics
for the reference laboratory data for each of the 13
target elements. These summary statistics indicate
good precision in that the median percent RSD was
less than 10 percent for 11 out of 13 target elements
(and the median RSD for the other two elements was
just above 10 percent). Thus, this evaluation further
supports the conclusion that the reference data set is of
high quality.
ARDL, in Mount Vernon, Illinois, was selected as the
characterization laboratory to prepare environmental
samples for the demonstration. As part of its work,
ARDL analyzed several samples of each blend to
evaluate whether the concentrations of the target
elements and the homogeneity of the blends were
suitable for the demonstration. ARDL analyzed the
samples using the same methods as the reference
laboratory; however, the data from the
characterization laboratory were not validated and
were not intended to be equivalent to the reference
laboratory data. Rather, the intent was to use the
results obtained by the characterization laboratory as
an additional quality control check on the results from
the reference laboratory.
A review of the ARDL characterization data in
comparison to the reference laboratory data indicated
that ARDL obtained lower recoveries of several
elements. When expressed as a percent of the average
reference laboratory result (percent recovery), the
median ARDL result was below the lower QC limit of
75 percent recovery for three elements chromium,
nickel, and selenium. This discrepancy between data
from the reference laboratory and ARDL was
determined to have no significant impact on reference
laboratory data quality for three reasons: (1) the
ARDL data were obtained on a rapid turnaround basis
to evaluate homogeneity accuracy was not a
specific goal, (2) the ARDL data were not validated,
and (3) all other quality measurement for the reference
laboratory data indicated a high level of quality.
5.4 Summary of Data Quality and
Usability
A significant effort was undertaken to ensure that data
of high quality were obtained as the reference data for
this demonstration. The reference laboratory data set
was deemed valid, usable, and of high quality based
on the following:
Comprehensive selection process for the reference
laboratory, with multiple levels of evaluation.
No data were rejected during data validation and
few data qualifiers were added.
The observations noted during the reference
laboratory audit were only minor in nature; no
major findings or non-conformances were
documented.
Acceptable accuracy (except for antimony, as
discussed in Section 5.3.3) of reference laboratory
results in comparison to spiked certified values.
Acceptable precision for the replicate samples in
the demonstration sample set.
Based on the quality indications listed above, the
reference laboratory data were used in the evaluation
of XRF demonstration data. A second comparison
was made between XRF data and certified values for
antimony (in Blends 46 through 70) to address the low
bias exhibited for antimony in the reference laboratory
data.
36
-------
Table 5-2. Percent Recovery for Reference Laboratory Results in Comparison to ERA Certified Spike Values for Blends 46 through 70
Statistic
Number of %R values
Minimum %R
Maximum %R
Mean "/oR1
Median "/oR1
Sb
16
12.0
36.1
26.8
28.3
As
14
65.3
113.3
88.7
90.1
Cd
20
78.3
112.8
90.0
87.3
Cr
12
75.3
108.6
94.3
97.3
Cu
20
51.7
134.3
92.1
91.3
Fe
NC
NC
NC
NC
NC
Pb
12
1.4
97.2
81.1
88.0
Hg
15
81.1
243.8
117.3
93.3
Ni
16
77.0
116.2
93.8
91.7
Se
23
2.2
114.2
89.9
93.3
Ag
20
32.4
100.0
78.1
84.4
V
15
58.5
103.7
90.4
95.0
Zn
10
0.0
95.2
90.6
91.3
Notes:
'Values shown in bold fall outside the 75 to 125 percent acceptance criterion for percent recovery.
ERA = Environmental Resource Associates, Inc.
NC = Not calculated.
%R = Percent recovery.
Source of certified values: Environmental Resource Associates, Inc.
Sb Antimony
As Arsenic
Cd Cadmium
Cr Chromium
Cu Copper
Fe Iron
Pb Lead
Hg Mercury
Ni Nickel
Se Selenium
Ag Silver
V Vanadium
Zn Zinc
37
-------
Table 5-3. Precision of Reference Laboratory Results for Blends 1 through 70
Statistic
Number of %RSDs
Minimum %RSD
Maximum %RSD
Mean "/oRSD1
Median "/oRSD1
Sb
43
1.90
78.99
17.29
11.99
As
69
0.00
139.85
13.79
10.01
Cd
43
0.91
40.95
12.13
9.36
Cr
69
1.43
136.99
11.87
8.29
Cu
70
0.00
45.73
10.62
8.66
Fe
70
1.55
46.22
10.56
8.55
Pb
69
0.00
150.03
14.52
9.17
Hg
62
0.00
152.59
16.93
7.74
Ni
68
0.00
44.88
10.28
8.12
Se
35
0.00
37.30
13.24
9.93
Ag
44
1.02
54.21
12.87
8.89
V
69
0.00
43.52
9.80
8.34
Zn
70
0.99
48.68
10.94
7.54
Notes:
1 Values shown in bold fall outside precision criterion of less than or equal to 25 %RSD.
%RSD = Percent relative standard deviation.
Based on the three to seven replicate samples included in Blends 1 through 70.
Sb Antimony
As Arsenic
Cd Cadmium
Cr Chromium
Cu Copper
Fe Iron
Pb Lead
Hg Mercury
Ni Nickel
Se Selenium
Ag Silver
V Vanadium
Zn Zinc
38
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Chapter 6
Technology Description
The PicoTAX XRF analyzer is manufactured by
RONTEC AG, Berlin, Germany and distributed in
the United States by RONTEC USA (Rontec). This
chapter provides a technical description of the
PicoTAX based on information obtained from Rontec
and the observation of this analyzer during the field
demonstration. This chapter also identifies a Rontec
company contact, where additional technical
information may be obtained.
6.1 General Description
The PicoTAX is a portable bench-top device that
provides quantitative and semi-quantitative multi-
element microanalysis of soils and sediments using
total reflection x-ray fluorescence spectroscopy. The
spectrometer includes a 40-watt metal-ceramic x-ray
tube excitation source and a thermoelectrically
cooled silicon drift (Si Drift) x-ray detector. The
PicoTAX is capable of detecting up to 75 elements
from aluminum to yttrium and from palladium to
uranium.
The PicoTAX uses an internal standard for
instrument calibration; thus, initial calibration is not
required. A solution of internal standard that
contains a project-specific element is added to each
sample to establish response factors (determined by
the software). Element quantitation is determined by
comparing the response of the unknown element to
the response of the internal standard with a known
concentration.
A laptop computer is used to monitor and control all
aspects of PicoTAX system operation. Rontec's
Quantum software, which is loaded into the laptop
computer, calibrates the instrument, handles
measurement data and methods, controls all hardware
functions, and provides statistical functions, reporting
functions, and data and spectra export.
Technical specifications for the PicoTAX are
presented in Table 6-1. The PicoTAX is shown in
the standard bench-top configuration in Figure 6-1.
Figure 6-1. Rontec PicoTAX XRF analyzer set up
for bench-top analysis.
6.2 Instrument Operations during the
Demonstration
The PicoTAX spectrometer and accessories were
shipped to the demonstration site from Rontec
headquarters in Berlin, Germany in packaging that
complied with international and customs regulations.
A heavy-duty crate with an inner metal liner
contained the instrument, necessary tools, and an
analytical balance. According to Rontec, a smaller
metal and wood box would typically be used for
shipment within the United States. The tools and
balance would typically be shipped separately. The
total weight of the analyzer and accessories was
approximately 45 kg.
6.2.1 Set up and Calibration
The PicoTAX was set on a vibration free bench and
plugged into a 110-volt (V) electrical outlet. After
connecting the instrument to an accompanying laptop
personal computer (PC), the PicoTAX software was
initialized. The XRF detector was allowed to warm
up for 20 to 25 minutes and the optical path of the
instrument was inspected. Sample preparation
equipment consisted of the analytical balance, a
mortar and pestle for sample grinding, test tube rack
to hold sample tubes, and reagents for preparation
39
-------
Table 6-1. Rontec PicoTAX XRF Analyzer Technical Specifications
Weight:
Dimensions:
Excitation Source:
X-ray Optics:
Detector:
Signal Processing:
Software:
Element Range:
Sample Container:
Variants:
Power:
37kg.
420 x 590 x 300 mm.
40W metal ceramic x-ray tube, Mo-target, air cooled.
Ni/C multilayer, 17.5 keV, 80% reflectivity.
XFlash Detector, 10 mm2, 160 eV FWHM.
Digital signal processing unit, data interchange, and control
interface.
Modular Quantum software package for instrument control,
accumulation, calibration, and quantification.
Elements from aluminum to yttrium and from palladium to
(niobium to rhodium are not detectable).
via RS232
spectra
uranium
30 mm quartz disk.
PicoTAX Basic with single sample changer.
PicoTAX Automatic with automatic changer for 25 sample
disks.
1 10-220 volts, 50 hertz, 180 watts.
and analysis. The total time for setting up the XRF
analyzer and sample preparation equipment was about
30 minutes.
Gallium was selected as the internal standard for this
effort. The gallium internal standard solution was
added to each sample to establish response factors and
quantitatively determine the concentrations of
elements in each sample.
6.2.2 Demonstration Sample Processing
Rontec provided a team of three technical staff
members from their headquarters in Berlin, Germany
to process samples. One staff member prepared
samples for analysis, one operated the PicoTAX
analyzer, and the third assisted with data management
or other tasks.
The typical daily routine for this demonstration
involved analyzing 3 batches of 25 samples daily. Of
the 25 samples in a batch, 22 were actual samples and
the other 3 for QC and performance check samples.
Thus, Rontec was able to analyze 66 samples in a 24-
hour period using an autosampler to assist in the
analysis once operations were standardized. At the
beginning of each day, Rontec reviewed the sample
analysis completed during the previous night's run.
The quartz disks used to contain each sample in the
autosampler were cleaned and reused. All samples
were prepared and analyzed in accordance with the
procedures listed in the PicoTAX instrument manual
and application note that was available during the
demonstration.
The procedure for preparing soil samples for analysis
is described briefly below but is provided in detail in
their instrument manual and application note:
Approximately 150 milligrams (mg) of soil was
finely ground to less than 75 microns.
An amount of approximately 25 mg of the finely
ground soil sample was mixed with 2.5 milliliters
of Triton X solution to form a soil suspension and
then with 40 microliters of gallium standard
solution to incorporate the internal standard.
Cleaned quartz disks were prepared for analytical
use by adding a drop of silicon solution to the
center of each disk and warming on a hot plate to
about 60 °C for about 10 minutes. This
procedural step leaves a surface residue of silicon
that helps contain the soil suspension for XRF
analysis.
Ten microliters of the soil suspension was
dispensed on top of the silicon residue and the
disks returned to the hot plate for an additional 10
minutes to dry (Figure 6-2). The final samples for
analysis contained circular soil residues on the
quartz disks.
40
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Figure 6-2. Quartz disks drying on a hot plate.
Cooled disks were placed into the autosampler
tray, which feeds into the PicoTAX analyzer.
Each disk was marked for identification and
recorded on a log sheet (Figure 6-3).
Figure 6-3. Rontec technicians recording
identification numbers.
An autosampler was used to allow overnight
processing of samples through the PicoTAX
analyzer. The autosampler had 25 slots for samples;
thus, samples were analyzed in a batch of 25 samples
that included 22 demonstration samples and 3 QC
samples. Each sample was analyzed for 10 minutes
for the demonstration, thus requiring over 4 hours to
analyze each batch. After the analysis was complete,
the software automatically calculated the element
concentrations from raw data and provided the results
in tabular format (text files or Microsoft ExcelŽ data
files). The quartz disks were cleaned and reused for
this demonstration; however, disposable acrylic disks
may also be used instead.
6.3 General Demonstration Results
The unique sample preparation required for the
PicoTAX analyzer took about 5 minutes to complete
and occupied one member of the field team
essentially full time at the demonstration site. The
analysis time in the XRF analyzer was set at 10
minutes for the demonstration, although Rontec
indicated that sufficient precision and accuracy could
be obtained for soil and sediment samples using
shorter analysis times. These factors limited the
number of samples that could be processed to three
batches of 22 samples (66 samples) per day once the
instrument had been set up and overall efficiency had
been optimized.
The three-person Rontec field team completed the
analysis of 260 samples during 5 full days at the
demonstration site (Monday through Friday).
Because some supplies did not arrive on Monday,
and the team needed to catch an international flight
on Saturday morning, the Rontec field team was
allowed to take the remaining 66 samples in the
demonstration sample set back to Germany for
analysis. At the rate the Rontec field team was
processing samples during the field demonstration,
these remaining samples would have taken 1 full day
to process.
6.4
Contact Information
In November 2005, Rontec was acquired by Bruker
AXS Inc. Additional information on Rontec's
PicoTAX XRF analyzer is available from the
following source:
BRUKER AXS Inc.
5465 East Cheryl Parkway
Madison, WI 53711-5373, USA
Telephone: (800) 234-XRAY
Telephone: (608) 276-3000
Fax: (608)276-3006
Email: InfoS'jbruker-axs.com
41
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42
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Chapter 7
Performance Evaluation
As discussed in Chapter 6, Rontec analyzed 260 of the
326 demonstration samples of soil and sediment at the
field demonstration site between January 24 and 28,
2005. Weather delayed Rontec's arrival at the field
demonstration on Monday, January 24, and further
delayed the receipt of some supplies until Tuesday,
January 25. In addition, Rontec's detailed sample
preparation process affected sample throughput during
the field demonstration and the field team had to catch
an international plane flight on Saturday morning,
January 29. For these reasons, EPA allowed Rontec to
analyze the remaining 66 samples the following week
at Rontec's Berlin laboratories. A complete set of
electronic data for the PicoTAX in Excel spreadsheet
format was delivered to Tetra Tech on March 3, 2005.
Because data quality for antimony was anticipated to
be poor due to the x-ray tube used in the demonstration
(molybdenum), no data were reported for antimony by
Rontec. Although results were reported for silver and
cadmium, Rontec also anticipated poor accuracy and
precision for these two elements because of the x-ray
tube used. All the data provided by Rontec are
tabulated and compared with the reference laboratory
data and the ERA-certified spike concentrations in
Appendix D.
The PicoTAX data set was reviewed and evaluated in
accordance with the primary and secondary objectives
of the demonstration. The findings of the evaluation
for each objective are presented below.
7.1 Primary Objective 1 Method Detection
Limits
Samples were selected to calculate MDLs for each
target element from the 12 potential MDL sample
blends, as described in Section 4.2.1. The evaluation
and selection of data for the MDL calculation also
addressed results reported as "not detected" by Rontec.
For many of the MDL blend results, element
concentrations were below the statistical lower limits
of detection (LLD) calculated by the PicoTAX's
instrument algorithms. Non-detect values were
reported by Rontec as "
-------
Table 7-1. Evaluation of Sensitivity Method Detection Limits for the Rontec PicoTAX1
Matrix
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Sediment
Sediment
Sediment
Sediment
Sediment
Blend No.
2
5
6
85
105
12
18
29
31
32
39
65
Mean Rontec MDL
Matrix
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Sediment
Sediment
Sediment
Sediment
Sediment
Blend No.
2
5
6
85
105
12
18
29
31
32
39
65
Mean PicoTAX MDL
Antimony
Rontec
MDL2
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NC
Rontec
Cone.3
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Ref. Lab
Cone4
17
ND
8
118
ND
62
ND
ND
ND
ND
ND
11
Copper
Rontec
MDL2
11
21
83
NC
7
NC
40
NC
NC
18
36
20
29
Rontec
Cone.3
46
59
149
1249
33
871
56
1638
683
37
95
73
Ref. Lab
Cone. 4
47
49
160
1,243
31
747
50
1,986
1,514
36
94
69
Arsenic
Rontec
MDL2
NC
38
NC
NC
19
NC
12
15
7
21
22
55
23
Rontec
Cone.3
ND
59
343
3596
43
590
19
12
6
34
18
287
Ref. Lab
Cone.4
1.5
47
477
3,943
39
559
9
10
11
31
14
250
Lead
Rontec
MDL2
NC
502
NC
NC
63
NC
60
31
44
54
49
36
105
Rontec
Cone.3
1342
203
4289
47306
86
5142
19
29
36
41
47
326
Ref. Lab
Cone. 4
1,200
78
3,986
33,429
72
4,214
17
33
51
26
27
25
Cadmium
Rontec
MDL2
NC
NC
NC
939
NC
120
NC
NC
NC
NC
NC
NC
529
Rontec
Cone.3
ND
ND
ND
963
ND
48
ND
ND
ND
ND
ND
ND
Ref. Lab
Cone.4
ND
1.9
12
91
0.96
263
ND
ND
ND
ND
ND
44
Mercury
Rontec
MDL2
NC
NC
NC
NC
NC
NC
153
NC
NC
NC
NC
15
84
Rontec
Cone.3
ND
ND
ND
ND
ND
ND
46
ND
ND
ND
ND
196
Ref. Lab
Cone.4
ND
ND
0.83
15
0.14
1.8
56
0.24
ND
ND
ND
32
Chromium
Rontec
MDL2
113
99
43
153
94
79
262
39
124
120
76
106
109
Rontec
Cone.3
230
145
111
56
129
120
255
46
98
96
97
340
Ref. Lab
Cone.4
167
121
133
55
116
101
150
63
133
75
102
303
Nickel
Rontec
MDL2
48
35
32
51
23
98
134
73
200
66
83
93
78
Rontec
Cone.3
112
47
42
31
51
88
218
59
128
113
139
138
Ref. Lab
Cone.4
83
60
70
57
60
91
213
72
196
174
202
214
44
-------
Table 7-1. Evaluation of Sensitivity Method Detection Limits for the Rontec PicoTAX1 (Continued)
Matrix
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Sediment
Sediment
Sediment
Sediment
Sediment
Blend No.
2
5
6
85
105
12
18
29
31
32
39
65
Mean PicoTAX MDL
Selenium
Rontec
MDL2
NC
NC
NC
18
NC
5
NC
NC
NC
NC
NC
2
9
Rontec
Cone.3
ND
ND
ND
15
ND
4
ND
ND
ND
ND
ND
20
Ref. Lab
Cone.4
ND
ND
ND
ND
ND
15
ND
ND
ND
4.6
ND
22
Silver
Rontec
MDL2
NC
NC
NC
539
NC
NC
NC
NC
NC
NC
NC
NC
539
Rontec
Cone.3
ND
ND
ND
1286
ND
ND
ND
ND
ND
ND
ND
ND
Ref. Lab
Cone. 4
ND
0.93
14
144
ND
38
ND
ND
6.2
ND
ND
41
Vanadium
Rontec
MDL2
NC
42
26
NC
31
33
112
53
37
57
34
15
44
Rontec
Cone.3
ND
63
51
ND
51
42
108
48
32
67
32
18
Ref. Lab
Cone. 4
1.2
55
56
34
51
45
67
96
76
57
38
31
Zinc
Rontec
MDL2
6
130
NC
NC
33
NC
48
151
87
27
101
NC
73
Rontec
Cone.3
19
274
754
5609
113
2681
125
158
83
82
138
1284
Ref. Lab
Cone.4
24
229
886
5,657
92
2,114
90
160
137
69
137
1,843
Notes:
1 Detection limits and concentrations are in milligrams per kilogram (mg/kg), or parts per million (ppm).
2 MDLs calculated from the 12 MDL sample blends for the PicoTAX in this technology demonstration (in bold typeface for emphasis).
3 This column lists the mean concentration reported for this MDL sample blend by the PicoTAX.
4 This column lists the mean concentration reported for this MDL sample blend by the reference laboratory.
5 Only six replicates are included for this blend because one outlier replicate with extreme concentrations for all elements was excluded.
6 To increase the number of calculated MDLs for this metal, this blend was included despite the fact that detections were reported by the
developer for only six of the seven replicates. This mean concentration and the corresponding MDL were calculated using the six replicate
detected concentrations.
Cone. Concentration.
MDL Method detection limit.
NA Results for this element were not provided by Rontec.
NC The MDL was not calculated because reference laboratory concentrations exceeded five times the expected MDL range (approximately
50 ppm, depending on the element) or an insufficient number of detected concentrations were reported.
ND One or more results for this blend were reported as "Not Detected." Excepted as noted, blends with one or more ND result as reported
by the XRF were not used for calculating the MDL for this element.
Ref. Lab. Reference laboratory.
45
-------
in individual MDL sample blends for a number of
other target elements. However, these extreme
MDLs appeared to occur on a random and isolated
basis, and no generalized trends in MDLs relative to
sample medium (soil versus sediment) or blend could
be discerned.
The mean MDLs calculated for the PicoTAX are
compared in Table 7-2 with the mean MDLs for all
XRF instruments that participated in the
demonstration and the mean MDLs derived from
performance data presented in EPA Method 6200
(EPA 1998e). As shown, the mean MDLs for the
PicoTAX were lower than the available mean MDLs
calculated from EPA Method 6200 data for all
elements except lead. However, when compared
with the results for all eight XRF instruments that
participated in the demonstration, the PicoTAX
exhibited high relative mean MDLs for nine of the 11
target elements for which MDLs could be calculated.
The only elements for which the PicoTAX had
equivalent or lower MDLs were arsenic and
selenium.
7.2 Primary Objective 2 Accuracy and
Comparability
The number of demonstration sample blends that
met the criteria for evaluation of accuracy, as
described in Section 4.2.2, was low for silver (9
samples) and cadmium (12 samples), but was
greater than 20 for the remaining target elements.
RPDs between the mean concentrations obtained
from the PicoTAX and the reference laboratory
were calculated for each blend that met the criteria.
Table 7-3 presents the median RPDs for each target
Table 7-2. Comparison of Mean PicoTAX MDLs to All-Instrument Mean MDLs
and EPA Method 6200 Data1
Element
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
PicoTAX
Mean MDLs2
NC
23
529
109
29
105
84
78
9
539
44
73
All XRF
Instrument
Mean MDLs3
61
26
70
83
23
40
23
50
8
42
28
38
EPA Method 6200
Mean Detection Limits4
55 5
92
NR
376
171
78
NR
100 5
NR
NR
NR
89
Notes:
1 Detection limits are in units of milligrams per kilogram (mg/kg), or parts per million (ppm).
2 The mean MDLs calculated for this technology demonstration, as presented in Table 7-1.
3 The mean MDLs calculated for all eight XRF instruments that participated in this EPA technology
demonstration.
4 Mean values calculated from Table 4 of Method 6200 (EPA 1998e, www,epitgov;/sw-846).
5 Only one value reported.
EPA U.S. Environmental Protection Agency.
MDL Method detection limit.
NC Not calculated; no XRF data reported for this metal.
NR Not reported; no MDLs reported for this element.
46
-------
element, along with the number of RPD results used
to calculate the median. These statistics are provided
for all demonstration samples as well as for
subpopulations grouped by medium (soil versus
sediment) and concentration level (Levels 1 through
4, as documented in Table 3-1). Additional summary
statistics for the RPDs (minimum, maximum, and
mean) are provided in Appendix E (Table E-l).
Accuracy was classified as follows for the target
elements based on the overall median RPDs:
Very good (median RPD less than 10 percent):
none.
Good (median RPD between 10 and 25 percent):
arsenic, chromium, copper, iron, lead, nickel,
selenium, silver, vanadium, and zinc.
Fair (median RPD between 25 percent and 50
percent): mercury.
Poor (median RPD greater than 50 percent):
cadmium.
The median RPD was used for this evaluation
because it is less affected by extreme values than is
the mean. (The initial evaluation of the RPD
populations for the demonstration showed that they
were generally right-skewed or lognormal.) Further,
the classification of the elements based on accuracy
generally stayed the same when the mean rather than
the median RPD was used for the evaluation,
although the means were somewhat higher for many
elements (Table E-l). Review of the median RPDs
revealed few trends with respect to media type (soil
versus sediment) or concentration level. The most
notable trends are summarized below:
Higher overall median RPDs were observed in
sediment than in soil for nickel and silver. For
silver, however, the limited number of sample
blends available for evaluation and the high
overall variability of the RPDs produce
uncertainty in the accuracy evaluation.
High median RPDs in the soil matrices were
observed in the Level 1 samples for cadmium
(with concentrations between 50 and 500 ppm).
The median RPDs of 157 percent at this
concentration level (classified in the "poor"
range) was much higher than those for higher
concentration levels, where the median RPDs
were in the "fair" to "good" ranges. Although
the accuracy data set was limited for cadmium,
the Level 1 RPDs appeared to be skewed high by
the results for sample Blends 7 through 9 from
the Wickes Smelter site, which contained high
concentrations of other elements (such as lead,
zinc, and iron). A smaller effect was seen for
selenium, where the Level 1 median RPDs were
elevated for both soil and sediment, but remained
in the "fair" range. Review of individual RPDs
in the selenium data set indicated that this trend
appeared to be generalized rather than caused by
limited data or extreme results from specific
blends.
The best accuracy for mercury was observed in
the Level 1 samples (with concentrations
between 20 and 200 ppm) in both the soil and
sediment matrices, where median RPDs were in
the "good" range (the median RPDs for the other
concentration levels were above 25 percent,
falling in the "fair" range). These samples were
generally characterized by very low
concentrations of other elements, including
elements adjacent to mercury in the periodic
table such as cadmium and lead.
As an additional basis for comparison, Table 7-3
presents the overall average of the median RPDs for
all eight XRF instruments. Complete summary
statistics for the RPDs across all eight XRF
instruments are included in Appendix E (Table E-l).
Table 7-3 indicates that the median RPDs for the
PicoTAX were equivalent to or below the all-
instrument medians for 11 of the 12 elements
compared. For arsenic, mercury, selenium, silver and
zinc, the median RPDs for the PicoTAX were less
than half the all-instrument medians. Only cadmium
displayed a higher median RPD for the PicoTAX
than for all eight instruments that participated in the
demonstration.
In addition to calculating RPDs, the evaluation of
accuracy included preparing linear correlation plots
of PicoTAX concentration values against the
reference laboratory values. These plots are
presented for the individual target elements in
Figures E-l through E-l 2 of Appendix E. The plots
include a 45-degree line showing the "ideal"
relationship between the PicoTAX data and the
reference laboratory data, as well as a "best fit" linear
47
-------
Table 7-3. Evaluation of Accuracy Relative Percent Differences versus Reference Laboratory Data for the Rontec PicoTAX
Sample
Matrix Group Statistic
Soil Level 1 Number
Median
Level 2 Number
Median
Level 3 Number
Median
Level 4 Number
Median
All Soil Number
Median
Sediment Level 1 Number
Median
Level 2 Number
Median
Level 3 Number
Median
Level 4 Number
Median
All Sediment Number
Median
All Samples Rontec Number
PicoTAX Median
All Samples All XRF Number
Instruments Median
Antimony
ERA
RefLab Spike
0
NC
0 0
NC NC
0 0
NC NC
..
..
0 0
NC NC
0 0
NC NC
0 0
NC NC
0 0
NC NC
..
..
0 0
NC NC
0 0
NC NC
206 110
84.3% 70.6%
Arsenic
15
20.7%
4
4.6%
4
8.7%
-
--
23
14.3%
17
12.9%
4
8.6%
2
19.2%
-
--
23
12.9%
46
13.4%
320
26.2%
Cadmium
4
157.0%
6
49.6%
2
10.0%
-
--
12
83.2%
0
NC
0
NC
0
NC
-
--
0
NC
12
83.2%
209
16.7%
Chromium
28
20.7%
4
10.9%
2
14.4%
-
--
34
17.9%
21
20.3%
3
13.4%
3
25.0%
-
--
27
20.3%
61
18.1%
338
26.0%
Copper
16
10.4%
8
10.0%
2
24.9%
-
--
26
11.5%
8
5.6%
4
17.2%
10
18.5%
-
--
22
15.4%
48
12.3%
363
16.2%
Iron
5
20.5%
13
23.2%
13
12.0%
7
2.4%
38
14.9%
3
37.6%
19
27.5%
4
31.1%
6
8.4%
32
21.6%
70
17.3%
558
26.0%
Lead
16
24.9%
4
16.3%
8
20.4%
5
22.9%
33
21.6%
16
30.0%
4
10.9%
3
39.7%
-
--
23
25.5%
56
22.9%
392
21.5%
Mercury
7
19.3%
7
43.3%
2
38.9%
-
--
16
33.0%
2
27.5%
4
40.7%
2
31.7%
-
--
8
37.8%
24
33.0%
192
58.6%
Nickel
22
16.7%
5
21.6%
6
5.6%
-
--
33
12.2%
18
34.9%
6
29.4%
4
13.7%
-
--
28
29.4%
61
21.2%
403
25.4%
Selenium
4
41.5%
5
6.9%
4
11.1%
--
--
13
6.9%
5
17.4%
4
18.9%
3
8.8%
-
--
12
14.1%
25
11.6%
195
16.7%
Silver
0
NC
0
NC
4
10.4%
-
--
4
10.4%
1
8.5%
2
86.9%
2
49.7%
-
--
5
59.1%
9
19.3%
177
28.7%
Vanadium
12
29.2%
4
17.5%
4
15.2%
-
--
21
20.7%
6
45.0%
8
43.8%
3
12.9%
-
--
17
24.3%
38
22.9%
218
38.3%
Zinc
20
21.0%
6
11.3%
9
10.9%
-
--
35
16.0%
19
11.6%
5
19.4%
4
14.0%
-
--
28
16.2%
63
16.0%
471
19.4%
Notes:
All median RPDs presented in this table are based on the population of absolute values of the individual RPDs.
No samples reported by the reference laboratory in this concentration ranges.
ERA Environmental Resource Associates, Inc.
NC Not calculated; no XRF data provided for this element.
Number Number of samples appropriate for accuracy evaluation.
RefLab Reference laboratory (Shealy Environmental Services, Inc.)
RPD Relative percent difference.
48
-------
equation (y = mx + b, where m is the slope of the line
and b is the y-intercept of the line) and correlation
coefficient (r2) to help illustrate the "actual" relation-
ship between the two methods. To be considered
accurate, the correlation coefficient should be greater
than 0.9, the slope (m) should be between 0.75 and
1.25, and the y-intercept (b) should be relatively
close to zero (that is, plus or minus the mean MDL in
Table 7-1). Table 7-4 lists the results for these three
correlation parameters and highlights in bold each
target element that met all three accuracy criteria.
This table shows that the results for chromium, iron,
nickel, and zinc met all three of these criteria. The
correlation plot for zinc is displayed in Figure 7-1 as
an example of the correlations obtained for these
elements.
Figure 7-1. Linear correlation plot for PicoTAX
showing high correlation for zinc.
QOOO
8000
'S1 6000 -
Q.
§ 5000
X
X
H 4000
o
Ł
U -JOOO -
H
Ctf 2000
1 000
0 J
(
1 000
ť RONTEC PicoTAX
45 Degrees
Linear (RONTEC PicoTAX)
-
'^^
S'
+ ^ y = 1 0
^ ' Ť
'
^,'m B
i^'
S>'^m
1000 2000 3000 4000 5000 6000 7000 80
7x-21.19
= 0.97
30
Reference Laboratory (ppm)
49
-------
Table 7-4. Summary of Correlation Evaluation for the PicoTAX
Target Element
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
m
0.90
0.78
1.04
1.03
1.02
1.42
0.73
0.89
1.03
0.94
1.04
1.07
b
56
272
27
-33
4489 2
-98
-39
0.07
14
7.0
-11
-21
r2
0.95
0.62
0.95
0.86
0.95
0.94
0.99
0.96
0.70
0.58
0.89
0.97
Correlation
High
Moderate
High
Moderate
High
High
High
High
Moderate
Moderate
Moderate
High
Bias
High1
High
Low
~
Notes:
i
b
m
o
r
A high bias was indicated for cadmium at low concentrations by the high relative y-intercept.
For iron, no MDL was calculated and the high intercept value was the result of the extreme range of
concentrations in the demonstration samples.
No bias observed.
Y-intercept of correlation line.
Slope of correlation line.
Correlation coefficient of correlation line.
General observations from the correlation plots are as
follows:
Consistent with the RPD evaluation and
developer predictions, the correlation analysis
showed a low degree of accuracy for cadmium
and silver. However, these findings may have
been affected by the limited availability of data in
the various concentration ranges. Removal of the
high outliers associated with complex Blends 8
and 9 (Wickes Smelter slag) from the correlation
analysis for cadmium improved the r2 value to
0.90 and lowered the y-intercept to near 0,
producing a high correlation and eliminating the
apparent positive bias at low concentrations. For
silver, however, the low degree of correlation
appeared to be due to a broader variability in the
data rather than a few outliers. Figure 7-2 shows
the correlation plot for silver.
Removal of a single outlier associated with the
Alton Steel site (Blend 53) improved the
correlation coefficient for selenium from 0.70 to
0.90.
Mercury exhibited a high r2 value (0.99) but a
slightly low bias (m = 0.73). Removing two
extreme Level 4 concentrations (Blends 21 and
22) from the plots produced a much poorer
correlation coefficient (in the range of 0.81) and a
lower bias (m = 0.58).
Overall, the evaluations of accuracy showed an
accept-able overall level of performance by the
PicoTAX for the target elements. Correlations with
the reference laboratory were generally high, and
median RPDs were better for most elements in
comparison to the average of all eight XRF
instruments that participated in the demonstration.
Factors such as Rontec's rigorous sample preparation
protocol and use of internal standards (Chapter 6)
may have contributed to the high relative level of
accuracy attained. However, the use of a
molybdenum x-ray tube precluded the reporting of
antimony results and produced low relative accuracy
in the cadmium and silver results, consistent with
Rontec's predictions.
50
-------
450
400
?
3
^ 250
o
w 900
PH
^ 1 50
O
1 00
50
0
C
Figure 7-2. Linear correlation plot for PicoTAX
showing high data variability for silver.
Ť RONT EC PicoTAX
Linear (RONTEC PicoTAX)
.XX*
X
y-0.94x
R2 = 0
. x*
X
x^
^* *
X
X
50 100 150 200 250 300 350 400
Reference Laboratory (ppm)
+ 6.98
58
450
7.3 Primary Objective 3 Precision
As described in Section 4.2.3, the precision of the
PicoTAX was evaluated by calculating RSDs for the
replicate measurements from each sample blend.
Median RSDs for the various concentration levels
and media (soil and sediment), as well as for the
demonstration sample set as a whole, are presented in
Table 7-5. An expanded set of summary statistics for
the RSDs (including minimum, maximum, and mean)
is provided in Appendix E (Table E-2).
The median RSDs calculated for the target elements
ranged as high as 50.2 percent (silver). The ranges of
median RSDs are further summarized below:
Very low (median RSD between 0 and 5
percent): none.
Low (median RSD between 5 and 10 percent):
selenium.
Moderate (median RSD between 10 and 20
percent): arsenic, copper, iron, lead, nickel,
vanadium, and zinc.
High (median RSD greater than 20 percent):
cadmium, chromium, mercury, and silver.
The median RSDs for sediment were slightly larger
for some target elements (such as arsenic, lead, and
vanadium) than the median RSDs for soil.
The level of precision observed may have been
facilitated by the level of pre-processing
(homogenizing, sieving, crushing, and drying) on the
sample blends before the demonstration (Chapter 3).
This observation is consistent with the previous SITE
MMT program demonstration of XRF technologies
that occurred in 1995 (EPA 1996a, 1996b, 1998a,
1998b, 1998c, and 1998d). The high level of sample
processing applied during both XRF technology
demonstrations was necessary to minimize the effects
of sample heterogeneity on the demonstration results
51
-------
and on comparability with the reference laboratories.
During project design, site investigation teams that
intend to compare XRF and laboratory data should
similarly assess the need for sample processing steps
to manage sample heterogeneity and improve data
comparability.
Over and above the pre-processing prior to the
demonstration, Rontec performed an additional
detailed preparation protocol during the demon-
stration to emulsify the samples, as described in
Section 6.2.2. This level of additional sample
preparation during the demonstration differentiated
the PicoTAX from the other technology developers.
(The other developers generally performed minimal
additional sample preparation, consisting of only of
transferring sample into analysis cups or pressing the
samples into pellets.)
Further review of the median RSDs in Table 7-5
based on concentration range reveals slightly higher
RSDs (in other words, lower precision) for the target
elements in Level 1 samples when compared with the
rest of the data set. This effect was observed for
multiple target elements in both soil and sediment,
with large relative effects for arsenic, chromium,
lead, mercury, and nickel in the sediment samples.
This observation indicates that, to a minor extent,
analytical precision for the PicoTAX may depend on
concentration.
As an additional comparison, Table 7-5 presents the
overall average of the median RSDs for all eight XRF
instruments that participated in the demonstration.
Complete summary statistics for the RSDs across all
eight XRF instruments are included in Table E-2.
Table 7-5 indicates that the median RSDs for the
PicoTAX were above the all-instrument medians for
all 12 of the target elements compared. For
cadmium, iron, mercury, and silver, the median RSDs
for the PicoTAX were more than three times higher
than the all-instrument medians.
Table 7-6 presents median RSD statistics for the
reference laboratory and compares these to the
summary data for the PicoTAX. (Complete summary
statistics are provided in Table E-3 of Appendix E.)
Table 7-6 indicates that the median RSDs for the
PicoTAX were higher than the RSDs for the
reference laboratory for all 12 target elements. For
cadmium, mercury, and silver, the median RSDs for
the PicoTAX were more than three times higher than
the reference laboratory medians. Thus, the
PicoTAX exhibited lower precision overall than
either the reference laboratory or the other XRF
instruments. The reduced precision of the PicoTAX
relative to other XRF technologies may be a function
of Rontec's sample preparation process, in which a
very small subsample (10 (iL of a soil emulsion
prepared using 0.15 grams of soil) is used for
analysis (see Section 6.2.2). Despite the grinding and
homogenizing protocols applied prior to the
demonstration, the use of such a small aliquot of
sample may have diminished the representativeness
of the samples, reducing precision.
7.4 Primary Objective 4 Impact of
Chemical and Spectral Interferences
The RPD data from the accuracy evaluation were
further processed to assess the effects of
interferences. The RPD data for elements considered
susceptible to interferences were grouped and
compared based on the relative concentrations of
potentially interfering elements. Of specific interest
for the comparison were the potential effects of:
High concentrations of lead on the RPDs for
arsenic.
High concentrations of nickel on the RPDs for
copper (and vice versa).
High concentrations of zinc on RPDs for copper
(and vice versa).
The rationale and approach for evaluation of these
interferents are described in Section 4.2.4.
Interferent-to-element ratios were calculated using
the mean concentrations the reference laboratory
reported for each blend, classified as low (less than
5X), moderate (5 to 10X), or high (greater than 10X).
Table 7-7 presents median RPD data for arsenic,
nickel, copper, and zinc that are grouped based on
this classification scheme. Complete summary
statistics are presented in Appendix E (Table E-4).
The tables confirm significant interference effects of
lead on arsenic. Specifically, as lead concentrations
increased to greater than 10 times the arsenic
concentration, the median RPD for arsenic increased
from 12.9 percent (well within the "good" range
defined in Section 7.2) to 43.0 percent (at the upper
end of the "fair" range). Similar effects are observed
for copper as an interferent for nickel; as copper
52
-------
Table 7-5. Evaluation of Precision Relative Standard Deviations for the Rontec PicoTAX
Matrix
Soil
Sediment
All Samples
All Samples
Sample
Group
Level 1
Level 2
Level 3
Level 4
All Soil
Level 1
Level 2
Level 3
Level 4
All Sediment
PicoTAX
A11XRF
Instruments
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Antimony
0
NC
0
NC
0
NC
0
NC
0
NC
0
NC
0
NC
0
NC
0
NC
206
6.1%
Arsenic
15
13.8%
4
15.1%
4
12.7%
23
14.3%
17
28.3%
4
8.1%
2
10.1%
23
18.8%
46
15.1%
320
8.2%
Cadmium
4
27.6%
6
31.5%
2
26.2%
12
30.0%
0
NC
0
NC
0
NC
0
NC
12
30.0%
209
3.6%
Chromium
28
26.3%
4
9.6%
2
3.7%
34
22.1%
21
32.5%
3
9.9%
3
7.2%
27
25.1%
61
24.2%
338
12.1%
Copper
16
11.9%
8
16.7%
2
15.9%
26
13.3%
8
11.1%
4
17.2%
10
22.5%
22
16.2%
48
15.2%
363
5.1%
Iron
5
19.2%
13
13.3%
13
17.9%
7
15.7%
38
16.6%
3
20.3%
19
14.0%
4
16.0%
6
17.5%
32
16.5%
70
16.5%
558
2.2%
Lead
16
20.9%
4
12.6%
8
12.0%
5
9.4%
33
14.4%
16
24.4%
4
8.6%
3
11.9%
23
21.3%
56
14.5%
392
4.9%
Mercury
7
25.2%
7
26.0%
2
33.8%
16
25.6%
2
55.8%
4
29.8%
2
12.9%
8
26.9%
24
26.0%
192
6.8%
Nickel
22
19.5%
5
11.6%
6
19.5%
33
17.3%
18
31.6%
6
17.0%
4
10.9%
28
18.8%
61
18.5%
403
7.0%
Selenium
4
14.9%
5
18.9%
4
6.0%
13
7.0%
5
5.6%
4
15.8%
3
8.2%
12
8.6%
25
8.2%
195
4.5%
Silver
0
NC
0
NC
4
51.4%
4
51.4%
1
46.5%
2
50.2%
2
57.4%
5
50.2%
9
50.2%
177
5.2%
Vanadium
13
27.1%
4
12.9%
4
7.0%
21
18.2%
6
31.0%
8
24.4%
3
9.9%
17
27.0%
38
19.8%
218
8.5%
Zinc
20
15.5%
6
13.8%
9
12.0%
35
14.7%
19
21.7%
5
11.2%
4
16.4%
28
15.5%
63
14.7%
471
5.3%
Notes:
Number
RSD
No samples reported by the reference laboratory in this concentration range.
Number of samples appropriate for precision evaluation.
Relative standard deviation
53
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Table 7-6. Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory versus the PicoTAX and All Demonstration Instruments
Matrix
Soil
Sediment
All
Samples
All
Samples
All
Samples
Sample
Group
Ref. Lab
Ref. Lab
Ref. Lab
PicoTAX
A11XRF
Instruments
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Antimony
17
9.8%
7
9.1%
24
9.5%
0
NC
206
6.1%
Arsenic
23
12.4%
24
9.2%
47
9.5%
46
15.1%
320
8.2%
Cadmium
15
9.0%
10
8.2%
25
9.0%
13
31.0%
209
3.6%
Chromium
34
10.6%
26
7.5%
60
8.4%
61
24.2%
338
12.1%
Copper
26
9.1%
21
8.9%
47
8.9%
48
15.2%
363
5.1%
Iron
38
8.7%
31
8.1%
69
8.5%
70
16.5%
558
2.2%
Lead
33
13.2%
22
7.4%
55
8.6%
56
14.5%
392
4.9%
Mercury
16
6.6%
10
6.9%
26
6.6%
24
26.0%
192
6.8%
Nickel
35
10.0%
27
7.3%
62
8.2%
61
18.5%
403
7.0%
Selenium
13
7.1%
12
7.6%
25
7.4%
25
8.2%
195
4.5%
Silver
13
7.5%
10
6.6%
23
7.1%
9
50.2%
177
5.2%
Vanadium
21
6.6%
17
8.1%
38
7.2%
38
19.8%
218
8.5%
Zinc
35
9.1%
27
6.9%
62
7.4%
63
14.7%
471
5.3%
Notes:
Number
Ref. Lab
Number of samples appropriate for precision evaluation
Reference Laboratory
54
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Table 7-7. Effects of Interferent Elements on the RPDs (Accuracy) for Other Target Elements for the Rontec PicoTAX1
Parameter
Interferent/
Element Ratio
Number of
Samples
Median RPD of
Target Element 2
Median Interferent
Concentration
Median Target
Element
Concentration
Lead Effects on Arsenic
<5 5-10 >10
29 7 10
12.9% 5.5% 43.0%
89 9262 3434
135 1071 56
Copper Effects on Nickel
<5 5-10 >10
42 5 14
13.8% 42.2% 41.6%
123 871 1877
183 100 75
Nickel Effects on Copper
<5 5-10 >10
39 1 8
11.1% 16.1% 14.4%
98 288 1906
786 92 107
Zinc Effects on Copper
<5 5-10 >10
35 2 11
14.1% 6.6% 8.9%
177 4462 3015
829 851 124
Copper Effects on Zinc
<5 5-10 >10
50 3 10
16.8% 11.4% 17.2%
169 938 2221
674 127 145
Notes:
1 Concentrations are reported in units of milligrams per kilogram (mg/kg), or parts per million (ppm).
2 All median RPDs presented in this table are based on the population of absolute values of the individual RPDs.
< Less than.
> Greater than.
RPD Relative percent difference.
55
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concentrations increased to greater than 10 times the
nickel concentration, the median RPD for nickel
increased from 13.8 percent to 41.6 percent.
Evaluation of the effects of nickel on copper, copper
on zinc, and zinc on copper do not appear to show
significant interferences.
In presenting statistics for the raw RPDs as well as
the absolute values of the RPDs, Table E-4 further
shows that the interferences from lead appeared to
produce an increasingly low bias in the arsenic data
(as indicated by more positive raw RPDs). A similar
trend was observed for the effect of copper on nickel.
7.5 Primary Objective 5 Effects of Soil
Characteristics
The population of RPDs between the results obtained
from the PicoTAX and the reference laboratory was
further evaluated against sampling site and soil type.
Separate sets of summary statistics were developed
for the mean RPDs associated with each sampling
site for comparison to the other sites and to the data
set for all samples. The site-specific median RPDs
are presented in Table 7-8, along with descriptions of
soil or sediment type from observations during
sampling at each site. Complete RPD summary
statistics for each soil type (minimum, maximum, and
mean) are presented in Table E-5 of Appendix E.
Another perspective on the effects of soil type was
developed by graphically assessing outliers and
extreme values in the RPD data sets for each target
element. This evaluation focused on correlating
these extreme values with sample types or locations
for multiple elements across the data set. Some
outliers and extreme values are apparent in the
correlation plots (Figures E-l through E-12) and are
further depicted for the various elements on box and
whisker plots in Figure E-13.
Review of Table 7-8 indicates that the median RPDs
were highly variable and that trends or differences
between sample sites were difficult to discern.
Evaluations relative to sampling site were further
complicated by the low numbers of samples for many
target elements. (Table 7-8 indicates that only one to
three samples were available from many sampling
sites for evaluation of specific target elements.) High
relative median RPDs for cadmium and nickel were
observed in blends from the Wickes Smelter site.
The median RPDs in these blends were 165 percent
for cadmium and 50 percent for nickel, which were
significantly higher than blends from other sampling
sites for these two elements. The soil matrix from
this site was described during the demonstration
sample collection program (Chapter 2) as roaster
slag, consisting of a black, fairly coarse sand and
gravel material. This slag is an intermediate product
in processing ore, wherein volatile sulfide materials
are thermally removed, leaving concentrated heavy
elements. Effects of the Wickes Smelter sample
blends on XRF data quality were noted earlier for
cadmium in the accuracy evaluation (Section 7.2).
Review of the box and whiskers plot (Figure E-13)
and the correlation plots from the accuracy evaluation
revealed few other major trends in RPDs relative to
sampling site. The outliers and extreme values
apparent in Figure E-13 were broadly distributed
between eight of the nine sampling sites. The Torch
Lake site represented higher numbers of outliers
relative to the other sampling sites. However, the
evaluation found that sample matrix had a minor
effect on the overall accuracy of the XRF data given
that the ranges of RPDs observed for the target
elements were very broad. The spread in the
accuracy results is illustrated on the box and whiskers
plot in Figure E-13. The plot shows that the broad
overall distributions of RPDs precluded the
identification of statistical outliers and extreme
values for cadmium, mercury, and silver. Further data
review indicated that the large spread in the RPD data
for these metals was affected by high RPD values
from the Wickes Smelter blends for cadmium, the
Sulfur Bank mine blends for mercury, and a Ramsey
Flats blend for silver.
7.6 Primary Objective 6 Sample
Throughput
The Rontec three-person field team was able to
analyze all 326 demonstration samples in 4.5 days at
the demonstration site and an equivalent of 1
additional day in Berlin, Germany. Once the
PicoTax instrument had been set up and operations
had been streamlined, the Rontec field team was able
to analye 66 samples (that is, three batches of 22
samples) during an extended work day. This sample
throughput was achieved by using different members
of the field team to perform sample preparation and
instrumental analysis and by loading one sample
batch into the autosampler to run overnight. Without
an extended work day, it was estimated that the
56
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Table 7-8. Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Rontec PicoTAX
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Soil
Sediment
Soil
Site
AS
BN
CN
KP
LV
RF
SB
TL
WS
All
Matrix
Description
Fine to medium sand (steel
processing)
Sandy loam, low organic (ore
residuals)
Sandy loam (burn pit residue)
Soil: Fine to medium quartz sand.
Sed.: Sandy loam, high organic.
(Gun and skeet ranges)
Clay/clay loam, salt crust (iron
and other precipitates)
Silty fine sand (tailings)
Coarse sand and gravel (ore and
waste rock)
Silt and clay (slag-enriched)
Coarse sand and gravel (roaster
slag)
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Antimony
~
Arsenic
1
181.4%
7
5.5%
1
17.6%
11
9.2%
12
17.7%
5
20.7%
2
42.1%
7
12.2%
46
13.4%
Cadmium
1
0.8%
5
82.5%
1
83.8%
1
6.1%
1
6.3%
3
165.3%
12
83.2%
Chromium
2
10.8%
7
17.9%
2
90.1%
4
16.3%
11
11.7%
12
22.2%
11
39.8%
5
20.3%
7
11.5%
61
18.1%
Copper
o
3
34.8%
6
10.3%
3
20.7%
2
8.0%
4
6.4%
13
15.9%
4
13.6%
7
19.2%
6
4.2%
48
12.3%
Iron
3
18.6%
7
15.8%
3
20.8%
6
30.3%
12
30.7%
13
20.5%
12
12.6%
7
8.9%
7
7.6%
70
17.3%
Lead
o
3
22.9%
7
19.8%
3
27.2%
6
19.9%
6
42.8%
13
23.0%
7
19.5%
4
23.5%
7
25.7%
56
22.9%
57
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Table 7-8. Effect of Soil Type on RPDs (Accuracy) of Target Elements, Rontec PicoTAX (Continued)
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Soil
Sediment
Soil
Site
AS
BN
CN
KP
LV
RF
SB
TL
WS
All
Matrix
Description
Fine to medium sand (steel
processing)
Sandy loam, low organic (ore
residuals)
Sandy loam (burn pit residue)
Soil: Fine to medium quartz
sand.
Sed.: Sandy loam, high organic.
(Gun and skeet ranges)
Clay /clay loam, salt crust (iron
and other precipitates)
Silty fine sand (tailings)
Coarse sand and gravel (ore and
waste rock)
Silt and clay (slag-enriched)
Coarse sand and gravel (roaster
slag)
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Mercury
~
1
110.4%
2
23.4%
4
41.9%
4
11.2%
11
43.3%
2
81.7%
24
33.0%
Nickel
1
74.6%
6
10.6%
o
3
21.6%
o
3
12.2%
11
10.2%
13
36.7%
11
5.7%
6
30.1%
7
50.0%
61
21.2%
Selenium
1
110.7%
4
40.6%
2
6.0%
5
14.7%
5
11.6%
3
9.6%
4
34.4%
1
4.8%
25
11.6%
Silver
1
19.3%
1
5.6%
1
34.5%
2
89.7%
~
2
33.8%
2
10.4%
9
19.3%
Vanadium
1
68.7%
4
13.5%
1
14.5%
9
15.0%
3
17.2%
10
33.7%
7
52.4%
3
8.2%
38
22.9%
Zinc
3
15.4%
7
17.9%
3
17.6%
2
7.0%
10
19.0%
13
11.6%
11
22.9%
7
7.9%
7
9.9%
63
16.0%
Notes: AS Alton Steel Mill
BN Burlington Northern railroad/ASARCO East.
CN Naval Surface Warfare Center, Crane Division.
KP KARS Park - Kennedy Space Center.
LV Leviathan Mine/Aspen Creek.
RF Ramsey Flats - Silver Bow Creek.
SB Sulphur Bank Mercury Mine.
TL Torch Lake Superfund Site.
WS Wickes Smelter Site.
Other Notes:
No samples reported by the reference laboratory in this concentration range.
Number Number of demonstration samples evaluated.
RPD Relative percent difference (absolute value).
58
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Rontec field team could have only processed 44
samples (that is, two batches of 22 samples) per day.
This estimated sample throughput for a normal working
day was lower than that observed for the other
instruments that participated in the demonstration
(average of 66 samples per day). The lower sample
throughput was primarily the result of the long run time
in the XRF spectrometer (10 minutes per sample).
Rontec selected this instrument run time to provide the
maximum analytical precision and accuracy for the
demonstration. Rontec indicated that a reduction in
analysis time of up to 50 percent could still provide data
of sufficient accuracy and precision. If this claim is
valid, then a sample throughput of 66 samples (3
batches of 22 samples) per day could have been
maintained with a normal 8-hour work day.
A detailed discussion of the time required to complete
the various steps of sample analysis using the PicoTAX
is included as part of the labor cost analysis in Section
8.3.
7.7 Primary Objective 7 Technology Costs
The evaluations pertaining to this primary objective are
described in Chapter 8, Economic Analysis.
7.8 Secondary Objective 1 Training
Requirements
Technology users must be suitably trained to set up and
operate the instrument to obtain the level of data quality
required for specific projects. The amount of training
required depends on the configuration and complexity
of the instrument, along with the associated software.
Rontec offers on-site training, on-line support, and
telephone support to instrument users on an informal, as
needed basis. Although Rontec provided three Ph.D.-
level scientists for the demonstration, plus an additional
logistical support person, this level of expertise and
staffing is not needed for analysis of soil and sediment
samples.
Two operating manuals are provided with the
instrument, including an instrument manual and a
software manual. The instrument manual provides the
user with instructions for installing and operating the
instrument, including packaging, transporting, and
setup. The manual provides a descriptive summary of
connections, control, and display elements, as well as
the structural elements of the spectrometer. A section is
also provided that discusses instrument maintenance,
including adjusting the optical path, gain correction, and
change out of the x-ray tube. The observer assessed
that proper instrument setup and operation requires a
chemist or technician with a basic knowledge of
spectroscopy.
The software manual provides a detailed description of
the instrument operating system and Windows-based
data management software. The software is operated
from a notebook computer that is provided with the
spectrometer. The manual includes instructions for
installing software, starting the program, the user
interface, spectral measurement, spectral evaluation,
data export, and crystal orientation. This manual is
detailed and thorough and is readily understandable for
a technician-level analyst with basic computer and
software skills along with an understanding of
spectroscopy and RS-232 communications technology.
On-line help is available to assist the analyst in
operating the instrument and using the software.
Processing soil and sediment samples entailed relatively
simple procedures that could be performed by a field
technician. In addition to the instrument manual, an
application note was provided that listed instructions for
analysis of soil and sediment samples. This document,
although intended as a marketing document on the
performance of XRF against traditional laboratory
methodology, provided an excellent description of the
sample preparation and analysis procedures required by
the PicoTAX. The application note is available from
the developer.
7.9 Secondary Objective 2 Health and Safety
Included in the health and safety evaluation were the
potential risks from: (1) potential radiation hazards
from the instrument itself, and (2) exposure to any
reagents used in preparing and analyzing the samples.
However, the evaluation did not include potential risks
from exposure to site-specific hazardous materials, such
as sample contaminants, or to physical safety hazards.
These factors were excluded because of the wide and
unpredictable range of sites and conditions that could be
encountered in the field during an actual project
application of the instrument.
The PicoTAX spectrometer is enclosed within a
cabinet; the x-ray tube is totally encased within the
cabinet and emits no detectable radiation to the analyst
or surrounding environment. Acetone (reagent grade)
59
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was used to clean the quartz disks between uses.
Acetone is extremely flammable, and the vapor may
cause a flash fire. Inhalation of acetone fumes may
irritate the respiratory tract. High concentrations of
acetone fumes may cause coughing, dizziness, dullness,
and headache. Higher concentrations can produce
central nervous system depression, narcosis, and
unconsciousness. However, the exposure to acetone
during the disk cleaning process should be minimal as
the quantities of acetone used are very small (a few
drops). Further, exposure to acetone can be eliminated
by using disposable acrylic disks that are available from
Rontec.
7.10 Secondary Objective 3 Portability
Portability depends on the size, weight, number of
components, and power requirements of the instrument,
and the reagents required. The size of the instrument,
including physical dimensions and weight, is presented
in Table 6-1. The number of components, power
requirements, support structures, and reagent
requirements are also listed in Table 6-1. Two
distinctions were made during the demonstration
regarding portability:
(1) The instrument was considered fully portable if the
dimensions were such that the instrument could be
easily brought directly to the sample location by
one person.
(2) The instrument was considered transportable if the
dimensions and power requirements were such that
the instrument could be moved to a location near
the sampling location, but required a larger and
more stable environment (for example, a site trailer
with AC power and stable conditions).
Based on its dimensions and power requirements, the
PicoTAX is defined as transportable. The PicoTAX
Spectrometer is a bench-top unit that can be set on a
table or bench in an office or mobile laboratory, or on
the back of a truck bed, for field analysis. It is not
capable of providing in situ analysis of soil. The
instrument consists of a spectrometer, autosampler,
sampler holders, and notebook PC that runs the
operating system of the instrument and provides data
analysis and management. There are two handles on
each side of the instrument for ease in transporting. The
PicoTAX is transported in a wood-lined metal box
provided by the developer to protect the instrument
from damage during shipment. Peripheral supplies for
sample preparation are transported in separate
shipments weighing less than 10 pounds.
The PicoTAX spectrometer operates using a standard
110 V AC power source. The notebook computer for
the spectrometer also uses 110 V AC. Additionally, a
balance was used to weigh sample material, and a hot
plate was used to dry a suspension of each sample into a
residue on a quartz disk. In total, therefore, four
separate devices were required to complete the
PicoTAX system, each needing 110 V AC power.
7.11 Secondary Objective 4 Durability
Durability was evaluated by gathering information on
the instrument's warranty and the expected lifespan of
the radioactive source or x-ray tube. The ability to
upgrade software or hardware was also evaluated.
Weather resistance was evaluated by examining the
instrument for exposed electrical connections and
openings that may allow water to penetrate (for portable
instruments only).
The PicoTAX system is constructed from impact-
resistant coated metal and molded plastic. The
instrument is operational up to a maximum temperature
of 40°C and 80 percent relative humidity (limited by the
air cooling requirements of the detector). Because the
spectrometer is intended for indoor use, it requires a
stable operating environment and must be protected
from weather.
The metal ceramic x-ray tube is warranted for 2,500
hours of operation; typically, Rontec tubes have a
minimum lifespan of 10,000 operating hours. The
entire instrument is warranted for 1 year for full
coverage, and software is upgradeable for up to 2 years
at no additional cost to the owner. Rontec provides
product support as requested throughout the life of the
instrument.
7.12 Secondary Objective 5 Availability
Rontec is headquartered in Berlin, Germany, but also
maintains an office in Carlisle, Massachusetts. The
PicoTAX is available from the manufacturer for
purchase only; no rental or long-term leasing options
are currently available. In addition, no third party
distributors for Rontec instrumentation were identified
at the time of the demonstration. Rontec operates
telephone and on-line support in both the U.S. and
Europe.
60
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Chapter 8
Economic Analysis
This chapter provides cost information for the Rontec
PicoTAX XRF analyzer. Cost elements that were
addressed included instrument purchase or rental,
supplies, labor, and ancillary items. Sources of cost
information included input from the technology
developer and suppliers as well as observations
during the field demonstration. Comparisons are
provided to average costs for other XRF technologies
and for conventional fixed-laboratory analysis to
provide some perspective on the relative cost of using
the PicoTAX.
8.1 Equipment Costs
Capital equipment costs include either purchase or
rental of the PicoTAX and any ancillary equipment
that is generally needed for sample analysis. (See
Chapter 6 for a description of available accessories.)
Information on purchase price and rental cost for the
analyzer and accessories was obtained from Rontec.
The PicoTAX used at the demonstration costs
approximately $99,990 for the complete equipment
package. The package includes a required 2 day
training program for first time users, which
separately costs $4,600. The package includes a
cassette for 25 sample discs and Messjobebitor PC-
controller, which separately costs $15,440.
The standard equipment package includes the metal
ceramic x-ray tube. Purchased models include a 1-
year warranty on the x-ray tube. The x-ray tube is
guaranteed for 2,500 hours. The lifespan of the x-ray
tube is at least 5 years in normal usage.
Rontec indicated that the PicoTAX is not available
for rental. For comparison to the rental cost of other
XRF instruments and for general evaluation
purposes, an estimated rental cost was derived based
on similar XRF technologies where both purchase
and rental prices were available.
The purchase price, rental cost, and shipping cost for
the PicoTAX exceed the average costs for all XRF
instruments that participated in the demonstration, as
shown in Table 8-1.
Table 8-1. Equipment Costs
Cost Element
Shipping
Capital Cost
(Purchase)2
Weekly Rental
Autosampler (for
Overnight Analysis)
PicoTAX
$750
$99,990
$5,2003
Included
XRF
Demonstration
Average 1
$410
$54,300
$2,813
N/A
Notes:
1 Average for all eight instruments in the
demonstration
2 Capital cost includes cost for required instrument
training
3 Estimated rental cost.
N/A Not available or not applicable for this
comparison
8.2 Supply Costs
The supplies that were included in the cost estimate
include sample containers, Mylar film, spatulas or
scoops, wipes, and disposable gloves. The rate of
consumption for these supplies was based on
observations during the field demonstration. Unit
prices for these supplies were based on price quotes
from independent vendors of field equipment.
Additional costs could include purchase of disposable
acrylic discs rather than the quartz discs if the user
wishes to eliminate disc cleaning efforts.
The PicoTAX was operated for five days at the
demonstration site, and two days in Berlin, to
complete the analysis of all 326 samples. The
supplies required to process samples were similar for
all XRF instruments that participated in the
demonstration and were estimated to cost about $245
for 326 samples or $0.75 per sample.
8.3
Labor Costs
Labor costs were estimated based on the total time
required by the field team to complete the analysis of
61
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all 326 samples and the number of people in the field
team, while making allowances for field team
members that had responsibilities other than sample
processing during the demonstration. For example,
some developers sent sales representatives to the
demonstration to communicate with visitors and
provide outreach services; this type of staff time was
not included in the labor cost analysis.
While overall labor costs were based on the total time
required to process samples, the time required to
complete each definable activity was also measured
during the field demonstration. These activities
included:
Initial setup and calibration.
Sample preparation.
Sample analysis.
Daily shutdown and startup.
End of proj ect packing.
The estimated time required to complete each of
these activities using the PicoTAX is listed in Table
8-2. The "total processing time per sample" was
calculated as the sum of all these activities assuming
that the activities were conducted sequentially;
therefore, it represents how much time it would take
a single trained analyst to complete these activities.
However, the "total processing time per sample" does
not include activities that were less definable in terms
of the amount of time taken, such as data
management and procurement of supplies, and is
therefore not a true total.
The time to complete each activity using the
PicoTAX is compared with the average of all XRF
instruments in Table 8-2 and is compared with the
range of all XRF instruments in Figure 8-1. In
comparison to other XRF analyzers, the PicoTAX
exhibited higher-than-average times except for daily
shutdown and startup and end of project packing.
Further, Rontec used a three-person team to operate
the instrument during the field demonstration,
whereas the field teams used by other developers
included only one or two people.
Table 8-2. Time Required to Complete Analytical
Activities1
Activity
Initial Setup and Calibration
Sample Preparation
Sample Analysis
Daily Shutdown/Startup
End of Project Packing
Total Processing Time per
Sample
PicoTAX
90
5.9
12.5
0
20
18.7
Average2
54
3.1
6.7
10
43
10.0
Notes:
1 All estimates are in minutes
2 Average for all eight XRF instruments in the
demonstration
The Rontec field team expended about 138 man-
hours to complete all sample processing activities
during the field demonstration using the PicoTAX.
This was significantly higher than the overall average
of 69 hours for all instruments that participated in the
demonstration. The primary reasons that labor hours
were higher for the PicoTAX include:
The unique sample preparation protocol
employed by Rontec, as described in Section 6.3,
required substantial more time than the sample
preparation procedures employed by other
instruments.
The instrument run time of 10 minutes was
longer than most other instruments.
As noted by Rontec, however, the instrument run
time could be reduced to 5 minutes without
significantly affecting precision and accuracy. This
would directly reduce the time required for sample
analysis and significantly reduce the labor hours.
Use of the autosampler saved significantly on the
time required for sample analysis and the associated
labor hours during the field demonstration.
8.4 Comparison of XRF Analysis and
Reference Laboratory Costs
Two scenarios were evaluated to compare the cost for
XRF analysis using the PicoTAX with the cost of
fixed-laboratory analysis using the reference
methods. Both scenarios assumed that 326 samples
were to be analyzed, as in the field demonstration.
62
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Initial Set up and Calibration
Sample Preparation
Sample Analysis
Total Processing Time
Daily Shut Down/Start Up
End of project packing
20
40
60 80 100 120 140
Minutes
0 PicTAX
I Range for all eight XRF instruments
Figure 8-1. Comparison of activity times for the PicoTAX versus other XRF instruments.
The first scenario assumed that only one element was
to be measured in a metal-specific project or
application (for example, lead in soil, paint, or other
solids) for comparison to laboratory per-metal unit
costs. The second scenario assumed that 13 elements
were to be analyzed, as in the field demonstration, for
comparison to laboratory costs for a full suite of
metals. However, Rontec did not report data for
antimony during the field demonstration; thus, the
second scenario includes only 12 elements for the
PicoTAX.
Typical unit costs for fixed-laboratory analysis using
the reference methods were estimated using average
costs from Tetra Tech's basic ordering agreement
with six national laboratories. These unit costs
assume a standard turnaround time of 21 days and
standard hard copy and electronic data deliverables
that summarize results and raw analytical data. No
costs were included for field labor that would be
specifically associated with off-site fixed laboratory
analysis, such as sample packaging and shipment.
The cost for XRF analysis using the PicoTAX was
based on equipment rental for 1 week, along with
labor and supplies estimates established during the
field demonstration. Sample preparation and sample
analysis labor were estimated based on the observed
division of responsibilities during the field
demonstration, wherein Rontec utilized two people to
prepare samples and one person to monitor the
spectrometer and manage data on the laptop
computer,. Additional sample preparation labor was
added for drying, grinding, and homogenizing the
samples (estimated at 10 minutes per sample) since
these additional steps in sample preparation are
required for XRF analysis but not for analysis in a
fixed laboratory. A typical cost for managing
investigation-derived waste (IDW), including general
trash, personal protective equipment, wipes, and soil,
was also added to the cost of XRF analysis because
IDW costs are included in the unit cost for fixed-
laboratory analysis. Since the cost for XRF analysis
of one element or multiple elements does not vary
significantly (all target elements are determined
63
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simultaneously when a sample is analyzed), the
PicoTAX analysis cost was not adjusted for one
element versus 12 elements.
Table 8-3 summarizes the costs for the PicoTAX
versus the cost for analysis in a fixed laboratory.
This comparison shows that the PicoTAX compares
favorably to a fixed laboratory in terms of overall
cost when a large number of elements are to be
determined. The PicoTAX compares unfavorably to
a fixed laboratory when one element are to be
determined. Use of the PicoTAX will likely produce
additional cost savings, however, because analytical
results will be available within a few hours after
samples are collected, thereby expediting project
decisions and reducing or eliminating the need for
additional mobilizations.
The total cost for the PicoTAX in the example
scenario (326 samples) was estimated at $14,678,
whether one or a number of elements was analyzed.
This estimate compares with the average of $8,932
for all XRF instruments that participated in the
demonstration. However, it should be noted that
bench-top instruments, such as the PicoTax, are
known to cost more than hand-held instruments that
were included in the calculation of the average cost
for all XRF instruments. In comparison to other
bench-top XRF instruments, the PicoTAX cost for
the example scenario only slightly exceeded other
instruments.
Table 8-3. Comparison of XRF Technology and Reference Method Costs
Analytical Approach
PicoTAX (1 to 12 elements)
Shipping
Weekly Rental1
Supplies
Labor
IDW
Total PicoTAX Analysis Cost (1 to 12 elements)
Fixed Laboratory (1 element)
(EPA Method 6010, ICP-AES)
Total Fixed Laboratory Costs (1 element)
Fixed Laboratory (13 elements)
Mercury (EPA Method 7471, CVAA)
All other Elements (EPA Method 6010, ICP-AES)
Total Fixed Laboratory Costs (12 elements)
Quantity
1
1
326
192
N/A
326
326
326
Item
Roundtrip
Week
Sample
Hours
Each
Sample
Sample
Sample
Unit
Rate
$750
$5,200'
$0.75
$43.75
N/A
$21
$36
$160
Total
$750
$5,200
$245
$8,393
$90
$14,678
$6,846
$6,846
$11,736
$52,160
$63,896
Notes:
1 Estimated value as Rontec currently does not have a rental rate for the PicoTAX.
64
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Chapter 9
Summary of Technology Performance
The preceding chapters of this report document that
the evaluation design succeeded in providing detailed
performance data for the Rontec PicoTAX XRF
analyzer. The evaluation design incorporated 13
target elements, 70 distinct sample blends, and a total
of 326 samples. The blends included both soil and
sediment samples from nine sampling locations. A
rigorous program of sample preparation and
characterization, reference laboratory analysis,
QA/QC oversight, and data reduction supported the
evaluation of XRF instrument performance.
One important aspect of the demonstration was the
sample blending and processing procedures
(including drying, sieving, grinding, and
homogenization) performed prior to the demon-
stration that significantly reduced uncertainties
associated with the demonstration sample set. These
procedures minimized the impacts of heterogeneity
on method precision and on the comparability
between XRF data and reference laboratory data. In
like manner, project teams are encouraged to assess
the effects of sampling uncertainty on data quality
and to adopt appropriate sample preparation
protocols before XRF is used for large-scale data
collection, particularly if the project will involve
comparisons to other methods (such as off-site
laboratories). An initial pilot-scale method
evaluation, carried out in cooperation with an
instrument vendor, can yield site-specific standard
operating procedures for sample preparation and
analysis to ensure that the XRF method will meet
data quality needs, such as accuracy and sensitivity
requirements. A pilot study can also help the project
team develop an initial understanding of the degree
of correlation between field and laboratory data. This
type of study is especially appropriate for sampling
programs that will involve complex soil or sediment
matrices with high concentrations of multiple
elements because the demonstration found that XRF
performance was more variable under these
conditions. Initial pilot studies can also be used to
develop site-specific calibrations, in accordance with
EPA Method 6200, that adjust instrument algorithms
to compensate for matrix effects.
The findings of the evaluation of the PicoTAX for
each primary and secondary objective of the
technology demonstration are summarized in Tables
9-1 and 9-2. The PicoTAX and the average
performance of all eight instruments that participated
in the XRF technology demonstration are compared
in Figure 9-1. The comparison in Figure 9-1
indicates that, when compared with the mean
performance of all eight XRF instruments, the
PicoTAX showed:
Equivalent or better MDLs for only two elements
including arsenic and selenium (iron was not
included in the MDL evaluation).
Equivalent or belter accuracy (lower RPDs) for
11 target elements (cadmium was the lone
exception).
Equivalent or better precision (lower RSDs) for
no target elements.
As a transportable bench-top instrument that requires
AC power, the PicoTAX must be operated in a
mobile laboratory or other stable environment, and
cannot be used for in situ soil analysis. Although
good overall performance was observed for this
instrument, the metal-ceramic x-ray tube used in this
instrument produced poor results for cadmium and
silver and precluded the reporting of any results for
antimony (reducing the number of target elements
from 13 to 12 for the PicoTAX). Moreover, a
rigorous sample preparation protocol was applied by
the developer during the demonstration to convert
small aliquots of sample into emulsified residues on
quartz disks for analysis. This on-site preparation
protocol required additional equipment and space,
reduced sample throughput, and may have also
reduced analytical precision.
65
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Table 9-1. Summary of Rontec PicoTAX Performance - Primary Objectives
Objective
Performance Summary
PI: Method
Detection Limits
Low numbers of detections in the MDL blends produced limited data
and therefore, uncertainty in the MDL calculations for cadmium,
mercury, selenium, and silver.
Mean MDLs for the target elements ranged as follows:
o MDLs of 1 to 20 ppm: selenium.
o MDLs of 20 to 50 ppm: arsenic, copper, and vanadium.
o MDLs of 50 to 100 ppm: mercury, nickel, and zinc.
o MDLs of greater than 100 ppm: cadmium, chromium, lead, and
silver. (MDLs were greater than 500 ppm for cadmium and
silver. Iron was not included in the MDL evaluation.)
The MDLs calculated for the PicoTAX were generally lower than
reference MDL data from EPA Method 6200 (higher MDLs were
observed only for lead).
P2: Accuracy and
Comparability
Median RPDs relative to reference laboratory data revealed the
following, with lower RPDs indicating greater accuracy:
o RPDs less than 10 percent: none.
o RPDs of 10 to 25 percent: arsenic, chromium, copper, iron,
lead, nickel, selenium, silver, vanadium, and zinc.
o RPDs of 25 to 50 percent: mercury.
o RPDs of greater than 50 percent: cadmium.
Correlation plots relative to reference laboratory data indicated:
o High correlation coefficients (greater than 0.9) for seven of the
12 target elements evaluated. However, the high correlation
observed for one of these elements, mercury, was artificially
improved by a few extreme concentrations.
o Moderate correlation coefficients for cadmium, copper,
selenium, silver, and vanadium.
o High biases in the XRF data versus the lab data for cadmium
and lead. A low bias was observed for mercury.
Significant uncertainty was introduced into the accuracy assessment for
cadmium and silver because the low sensitivity of the instrument
limited the sample blends available for evaluation.
P3: Precision
Median RSDs for sample replicates were as follows, with lower RSDs
indicating greater precision:
o RSDs below 5 percent: none.
o RSDs between 5 and 10 percent: selenium,
o RSDs between 10 and 20 percent: arsenic, copper, iron, lead,
nickel, vanadium, and zinc.
o RSDs greater than 20 percent: cadmium, chromium, mercury,
and silver.
RSDs were slightly higher (that is, precision was lower) in the lowest
concentration sample blends for many of the target elements, indicating
a slight concentration dependence for precision.
For all 12 of the target elements evaluated, median RSDs for the
PicoTAX were higher than the RSDs for the reference laboratory data,
indicating better precision for the reference laboratory.
66
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Table 9-1. Summary of Rontec PicoTAX Performance - Primary Objectives (continued)
Objective
Performance Summary
P4: Effects of
Sample
Interferences
High relative concentrations (greater than 10X) of lead as an interfering
element reduced accuracy for arsenic from "good" (median RPDs
between 10 percent and 25 percent) to "fair" (median RPDs between 25
and 50 percent). Further, the high concentrations of lead produced an
increasingly low bias in arsenic results.
Similar effects (decreasing accuracy from good to fair, and an
increasing negative bias) were observed for nickel in samples
containing high concentrations of copper as an interferent.
Evaluation of high concentrations of nickel on copper, copper on zinc,
and zinc on copper did not appear to show significant interference
effects.
P5: Effects of Soil
Type
Low relative accuracy was observed for cadmium and nickel in blends
of roaster slag from the Wickes Smelter site, which contained high
overall element concentrations.
Slightly higher numbers of extreme RPDs were observed in blends from
the Torch Lake site (copper, selenium, vanadium, zinc), the Sulfur Bank
mine (mercury), and the Ramsey Flats site (silver). However, the
evaluation found that sample matrix had a minor overall effect on
accuracy for the PicoTAX.
P6: Sample
Throughput
Rontec's rigorous sample preparation of protocol that included grinding
the soil, creating a suspension, spiking internal standard, applying
droplets of the suspension to a quartz disc, and then drying the disc to
produce a thin residue for analysis took an average of 5.9 minutes per
sample.
With an average instrument analysis time of 12.5 minutes per sample,
the total sample processing time was 18.7 minutes per sample.
A maximum sample throughput of 66 samples per day (three batches of
22 samples) was achieved during the demonstration by loading one
sample batch into the autosampler to run overnight after sample
preparation during the day. A more typical sample throughput was
estimated to be 44 samples per day (two batches of 22 samples) for an
8-hour work day.
P7: Costs
Purchase cost is about $99,990 for the instrument as equipped in the
demonstration (with autosampler, sample preparation equipment, and
laptop PC). The purchase cost includes training.
The Rontec field team expended approximately 138 man-hours to
complete the processing of the demonstration sample set (326 samples).
In comparison, the average for all participating XRF instruments was 69
man-hours.
By approximating a 1-week rental cost (based on similar bench-top
instruments) and adding labor and shipping/supplies costs, a total
project cost of $14,678 was estimated for a project the size of the
demonstration. In comparison, the average project cost for all
participating XRF instruments was $8,932 and for fixed-laboratory
analysis of all 13 elements was $63,896.
67
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Table 9-2. Summary of Rontec PicoTAX Performance - Secondary Objectives
Objective
Performance Summary
SI: Training
Requirements
Field or laboratory technicians that have some familiarity with analytical
chemistry and spectroscopy are qualified to operate the PicoTAX.
Rontec offers unlimited product support throughout the lifetime of the
instrument, including on-line support and training as needed. Instrument
purchase costs include a required 2-day training program ($4,600
separately).
Detailed instrument and software manuals, as well as application notes,
assist operators with soil analysis.
S2: Health and
Safety
The PicoTAX's x-ray tube is totally encased and emits no detectable
radiation outside of the instrument cabinet.
Acetone is used in the sample preparation process. This solvent is
flammable and toxic, but exposure can be eliminated by using
disposable acrylic disks.
S3: Portability
Based on dimensions, weight, and power requirements, the PicoTAX is
a transportable instrument and is designed to be used on a table top or
possibly a truck bed. Required accessories for efficient sample
processing include the autosampler, sample holders, a laptop, and
sample preparation equipment.
The instrument and its laptop computer, along with an analytical balance
and hotplate, require 110 volt AC power.
S4: Durability
The PicoTAX's x-ray tube is warranted for 2,500 hours, with an
anticipated lifetime of 10,000 hours.
The instrument is fully warranted for 1 year, and software is upgradeable
for 2 years at no cost.
The instrument is operational up to 40°C and 80 percent humidity. It
requires a stable operating environment and protection from weather.
S5: Availability
In November, 2005, Rontec was acquired by Bruker AXS Inc. with
several world-wide offices, including Berlin, Germany and Madison,
Wisconsin.
The PicoTAX is available for purchase only; no rental or long-term
leasing options are currently available.
68
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Comparison of Mean MDLs:
PicoTAX vs. All XRF Instruments
600
500
~ = 400
? 300
Ł 200
100
Ł o
PicoTAX Mean MDL
DAN Instrument Mean MDL
Target Element
Comparison of Median RPDs:
PicoTAX vs. All XRF Instruments
g
Q- g
Ł g
'§ Ť
100%
80%
60%
40%
20%
PicoTAX Median RPD
D All Instrument Median RPD
Target Element
Comparison of Median RSDs:
PicoTAX vs. All XRF Instruments
i
Ť
'i ~
60%
_ 50%
Ť5 o> °
o Q- 30o/0
20%
. _ 10%
I °%
Ť
PicoTAX Median RSD
O All Instrument Median RSD
g
I I
I I I I
-
Target Element
-------
This page was left blank intentionally.
70
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Chapter 10
References
Gilbert, R.O. 1987. Statistical Methods for
Environmental Pollution Monitoring. Van
Nostrand Reinhold, New York.
Tetra Tech EM Inc. 2005. Demonstration and
Quality Assurance Plan. Prepared for U.S.
Environmental Protection Agency,
Superfund Innovative Technology Evaluation
Program. March.
U.S. Environmental Protection Agency (EPA).
1996a. TN Spectrace TN 9000 and TNPb
Field Portable X-ray Fluorescence
Analyzers. EPA/600/R-97/145. March.
EPA. 1996b. Field Portable X-ray Fluorescence
Analyzer HNU Systems SEFA-P.
EPA/600/R-97/144. March.
EPA. 1996c. Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods (SW-
846). December.
EPA. 1998a. Environmental Technology
Verification Report; Field Portable X-ray
Fluorescence Analyzer, MetorexX-Met 920-
MP. EPA/600/R-97/151. March.
EPA. 1998b. Environmental Technology
Verification Report; Field Portable X-ray
Fluorescence Analyzer, Niton XL Spectrum
Analyzer. EPA/600/R-97/150. March.
EPA. 1998d. Metorex X-MET 920-P and 940 Field
Portable X-ray Fluorescence Analyzers.
EPA/600/R-97/146. March.
EPA. 1998e. EPA Method 6200, from "Test
Methods for Evaluating Solid Waste,
Physical/Chemical Methods (SW-846),
Update IVA. December.
EPA. 2000. Guidance for Data Quality Assessment:
Practical Methods for Data Analysis. EPA
QA/G-9 QAOO Update. EPA/600/R-96/084.
July.
EPA. 2004a. Innovative Technology Verification
Report: Field Measurement Technology for
Mercury in Soil and Sediment - Metorex's X-
METŽ 2000X-Ray Fluorescence
Technology. EPA/600/R-03/149. May.
EPA. 2004b. Innovative Technology Verification
Report: Field Measurement Technology for
Mercury in Soil and Sediment - Niton's
XLi/XLt 700 Series X-Ray Fluorescence
Analyzers. EPA/600/R-03/148. May.
EPA. 2004c. USEPA Contract Laboratory Program
National Functional Guidelines for Inorganic
Data Review. Final. OSWER 9240.1-45.
EPA 540-R-04-004. October.
EPA. 1998c. ScitectMAP Spectrum Analyzer Field
Portable X-Ray Fluorescence Analyzers.
EPA/600/R-97/147. March.
71
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APPENDIX A
VERIFICATION STATEMENT
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
SITE Monitoring and Measurement Technology Program
Verification Statement
TECHNOLOGY TYPE: X-ray Fluorescence (XRF) Analyzer
APPLICATION: MEASUREMENT OF TRACE ELEMENTS IN SOIL AND SEDIMENT
TECHNOLOGY NAME: PicoTAX XRF Analyzer
COMPANY: Rontec
ADDRESS: 90 Martin Street
Carlisle, MA 01741
Telephone: (800) 875-1578
Fax: (978) 266-2900
Email: pimitM|lRQMTECusa,com
Internet: www.RONTEC.com
VERIFICATION PROGRAM DESCRIPTION
The U.S. Environmental Protection Agency (EPA) created the Superfund Innovative Technology Evaluation
(SITE) Monitoring and Measurement Technology (MMT) Program to facilitate deployment of innovative
technologies through performance verification and information dissemination. The goal of this program is to
further environmental protection by substantially accelerating the acceptance and use of improved and cost-
effective technologies. The program assists and informs those involved in designing, distributing, permitting, and
purchasing environmental technologies. This document summarizes the results of a demonstration of the Rontec
PicoTAX hand-held x-ray fluorescence (XRF) analyzer for the analysis of 12 target elements in soil and sediment,
including arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc.
(One other target element for the demonstration, antimony, could not be analyzed by the PicoTAX.)
PROGRAM OPERATION
Under the SITE MMT Program, with the full participation of the technology developers, EPA evaluates and
documents the performance of innovative technologies by developing demonstration plans, conducting field tests,
collecting and analyzing demonstration data, and preparing reports. The technologies are evaluated under rigorous
quality assurance protocols to produce well-documented data of known quality. EPA's National Exposure
Research Laboratory, which demonstrates field sampling, monitoring, and measurement technologies, selected
Tetra Tech EM Inc. as the verification organization to assist in field testing technologies for measuring trace
elements in soil and sediment using XRF technology.
DEMONSTRATION DESCRIPTION
The field demonstration of eight XRF instruments to measure trace elements in soil and sediment was conducted
from January 24 through 28, 2005, at the Kennedy Athletic, Recreational and Social (KARS) Park, which is part of
the Kennedy Space Center on Merritt Island, Florida. A total of 326 samples were analyzed by each XRF
instrument, including the PicoTAX, during the field demonstration. These samples were derived from 70 different
blends and spiked blends of soil and sediment collected from nine sites across the U.S. The sample blends were
thoroughly dried, sieved, crushed, mixed, and characterized before they were used for the demonstration. Some
blends were also spiked to further adjust and refine the concentration ranges of the target elements. Between three
A-l
-------
and seven replicate samples of each blend were included in the demonstration sample set and analyzed by the
technology developers during the field demonstration.
Shealy Environmental Services, Inc. (Shealy), of Cayce, South Carolina, was selected as the reference laboratory to
generate comparative data in evaluation of XRF instrument performance. Shealy analyzed all demonstration
samples (both environmental and spiked) concurrently with the developers during the field demonstration. The
samples were analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) using EPA SW-
846 Method 3 05 OB/601 OB and by cold vapor atomic absorption spectroscopy (CVAA) using EPA SW-846 Method
7471A (mercury only).
This verification statement provides a summary of the evaluation results for the Rontec PicoTAX XRF analyzer.
More detailed discussion can be found in the Innovative Technology Verification Report - XRF Technologies for
Measuring Trace Elements in Soil and Sediment: Rontec PicoTAX XRF Analyzer (EPA/540/R-06/005).
TECHNOLOGY DESCRIPTION
XRF spectroscopy is an analytical technique that exposes a sample (soil, alloy metal, filters, other solids, and thin
samples) to an x-ray source. The x-rays from the source have the appropriate excitation energy that causes
elements in the sample to emit characteristic x-rays. A qualitative elemental analysis is possible from the
characteristic energy, or wavelength, of the fluorescent x-rays emitted. A quantitative elemental analysis is
possible from the number (intensity) of x-rays at a given wavelength.
The PicoTAX is a portable bench-top device that provides quantitative and semi-quantitative multi-element
microanalysis of soils and sediments using total reflection XRF spectroscopy. The spectrometer includes a 40-watt
metal-ceramic tube excitation source and a thermoelectrically cooled, silicon drift detector. The XRF analyzer is
capable of detecting up to 75 elements from aluminum (atomic number [Z] = 13) to yttrium (Z = 39) and from
palladium (Z = 46) to uranium (Z = 92). According to Rontec, the molybdenum tube source used for the
demonstration displays poor performance for antimony, cadmium, and silver. (Although Rontec proceeded to
report data for cadmium and silver, the demonstration confirmed poor overall performance for these metals.)
The PicoTAX uses an internal standard for instrument calibration, thus an initial calibration is not required. A
solution of an internal standard element (gallium was selected for the demonstration) is added to each sample to
establish response factors (determined by the software). Element quantitation is determined by comparing the
response of the unknown elements to the response of the internal standard that has a known concentration. The
PicoTAX analysis method requires a rigorous sample preparation protocol that involves grinding a small soil
aliquot (150 mg), emulsifying it, spiking the internal standard, applying drops of the emulsion to quartz disks, and
drying the disks to create a uniform film. The dried disks are loaded on the instrument's autosampler in batches of
25 samples.
VERIFICATION OF PERFORMANCE
Method Detection Limit (MDL): MDLs were calculated using seven replicate analyses from each of 12 low-
concentration sample blends, according to the procedure described in Title 40 Code of Federal Regulations (CFR)
Part 136, Appendix B, Revision 1.11. A mean MDL was further calculated for each element. The ranges into
which the mean MDLs fell for the PicoTAX are listed below.
Relative Sensitivity
High
Moderate
Low
Very Low
Mean MDL
1-20 ppm
20 - 50 ppm
50 - 100 ppm
> 100 ppm
Target Elements
Selenium.
Arsenic, Copper, and Vanadium.
Mercury, Nickel, and Zinc.
Cadmium, Chromium, Lead, and Silver.
Notes: ppm = Parts per million. Iron was not included in the MDL evaluation.
A-2
-------
Accuracy: Accuracy was evaluated based on the agreement of the PicoTAX results with the reference laboratory
data. Accuracy was assessed by calculating the absolute relative percent difference (RPD) between the mean XRF
and the mean reference laboratory concentration for each blend. Accuracy of the PicoTAX was classified from
high to very low for the various target elements, as indicated in the table below, based on the overall median RPDs
for the demonstration.
Relative Accuracy
High
Moderate
Low
Very Low
Median RPD
0% - 10%
10% - 25%
25% - 50%
> 50%
Target Elements
None.
Arsenic, Chromium, Copper, Iron, Lead, Nickel, Selenium, Silver,
Vanadium, and Zinc.
Mercury.
Cadmium.
Accuracy was also assessed through correlation plots between the mean PicoTAX and mean reference laboratory
concentrations for the various sample blends. Correlation coefficients (r2) for linear regression analysis of the plots
are summarized below, along with any significant biases apparent from the plots in the XRF data versus the
reference laboratory data.
Correlation
Bias
Arsenic
0.95
--
Cadmium
0.62
High
Chromium
0.95
--
^
v
e.
e.
o
O
0.86
--
|
0.95
--
1
0.94
High
Mercury
0.99
Low
Nickel
0.96
--
Selenium
0.70
--
^
QJ
1
0.58
--
Vanadium
0.89
--
CJ
0.97
--
Notes: = No significant bias
Precision: Replicates were analyzed for all sample blends. Precision was evaluated by calculating the standard
deviation of the replicates, dividing by the average concentration of the replicates, and multiplying by 100 percent
to yield the relative standard deviation (RSD) for each blend. Precision of the PicoTAX was classified from high to
very low for each target element, as indicated in the table below, based on the overall median RSDs. These results
indicated a lower level of precision in the PicoTAX data than in the reference laboratory data for all 12 of the target
elements.
Relative Precision
High
Moderate
Low
Very Low
Median RSD
0% - 5%
5% - 10%
10% - 20%
> 20%
Target Elements
None.
Selenium.
Arsenic, Copper, Iron, Lead, Nickel, Vanadium and Zinc.
Cadmium, Chromium, Mercury, and Silver.
Effects of Interferences: The RPDs from the evaluation of accuracy were further grouped and compared for a few
elements of concern (arsenic, nickel, copper, and zinc) based on the relative concentrations of potentially
interfering elements. Accuracy for arsenic was reduced from "moderate" (median RPDs of 10 percent to 25
percent) to "low" (median RPDs between 25 and 50 percent) by high relative concentrations of lead (greater than
10X the arsenic concentration). Similarly, accuracy for nickel was reduced from "moderate" to "low" by high
relative concentrations of copper. Low biases were produced in both the arsenic and nickel results by these
interferences.
Effects of Soil Characteristics: The RPDs from the evaluation of accuracy were also further evaluated in terms of
sampling site and soil type. This evaluation found high outlier RPD values, indicating low relative accuracy, for
cadmium and nickel in blends of roaster slag from the Wickes Smelter site. These blends contained high overall
element concentrations. Extreme RPDs were also observed in other blends of mining wastes from the Sulfur Bank
Mercury Mine (mercury), the Ramsey Flats site (silver), and the Torch Lake site (multiple elements). However, the
evaluation found that sample matrix had a minor overall effect on accuracy for the PicoTAX.
A-3
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Sample Throughput: The total processing time per sample was estimated at 18.7 minutes, which included 5.9
minutes of sample preparation and 12.5 minutes of instrument analysis time. On this basis, a sample throughput of
44 samples per 8-hour work day was estimated with the use of the instrument's autosampler. As noted above,
however, the sample blends had undergone rigorous pre-processing before the demonstration. Sample throughput
would have decreased if these sample preparation steps (grinding, drying, sieving) had been performed during the
demonstration; these steps can add from 10 minutes to 2 hours to the sample processing time.
Costs: A cost assessment identified a purchase cost of $99,990 for the PicoTAX as equipped for the
demonstration. Using a hypothetical rental cost approximated from similar types of instruments, a total cost of
$ 14,678 (with a labor cost of $8,393 at $43.75/hr) was estimated for a project similar to the demonstration (326
samples of soil and sediment). In comparison, the project cost averaged $8,932 for all eight XRF instruments
participating in the demonstration and $63,896 for fixed-laboratory analysis of all 13 target elements.
Skills and Training Required: Field or laboratory technicians that have some familiarity with analytical
chemistry and spectroscopy are qualified to operate the PicoTAX. Rontec offers product support as required
throughout the lifetime of the instrument, including on-line support and training. A mandatory 2-day introductory
training course is included in the instrument purchase cost. Detailed instrument and software manuals, as well as
application notes, assist operators with soil analysis.
Health and Safety Aspects: The PicoTAX's x-ray tube is totally encased and emits no detectable radiation outside
of the instrument cabinet. Acetone is used to clean the quartz disks in the sample preparation process, but use of
acetone can be eliminated by using disposable acrylic disks.
Portability: Based on dimensions (42 X 59 X 30 centimeters) and weight (28 kilograms), the PicoTAX is a
transportable instrument, designed to be used on a table top or possibly a truck bed. Required accessories for
efficient sample processing include the autosampler, sample holders, a laptop, and sample preparation equipment.
The instrument and its laptop computer, along with an analytical balance and hotplate for sample preparation,
require 110 volt AC power.
Durability: The PicoTAX's x-ray tube is warranted for 2,500 hours, with an anticipated lifetime of 10,000 hours.
The instrument is fully warranted for 1 year, and software is upgradeable for 2 years at no cost. The instrument is
operational up to 40°C and 80 percent humidity. It requires a stable operating environment and protection from
weather.
Availability: Rontec maintains offices in Berlin, Germany, and Carlisle, Massachusetts. There are currently no
third-party distributors in the U.S. The PicoTAX is available for purchase only; no rental or long-term leasing
options are currently available.
RELATIVE PERFORMANCE
The performance of the PicoTAX relative to the average of all eight XRF instruments that participated in the
demonstration is shown below:
Sensitivity
Accuracy
Precision
Arsenic
Same
ť
0
Cadmium
0
0
0
Chromium
0
ť
0
Copper
0
0
Iron
0
0
Lead
0
Same
0
Mercury
0
ť
0
Nickel
0
0
Selenium
Same
0
Silver
0
ť
0
Vanadium
0
0
Zinc
0
0
Key:
Better
Worse NC
No MDL Calculated
NOTICE: Verifications are based on an evaluation of technology performance under specific, predetermined criteria
and the appropriate quality assurance procedures. EPA makes no expressed or implied warranties as to the
performance of the technology and does not certify that a technology will always operate as verified. The end user is
solely responsible for complying with any and all applicable federal, state, and local requirements.
A-4
-------
APPENDIX B
DEVELOPER DISCUSSION
-------
DEVELOPER DISCUSSION
1. Recent Technological Improvements
1.1 Introduction
The results of the EPA SITE demonstration measurements have shown several benefits of the PicoTAX
TXPvF spectrometer but also some analytical restrictions which desire technical improvements. The
following sections discuss the objectives of the performance evaluation and how the performance could be
improved.
1.2 Method Detection Limits
In addition to counting statistics and instrument sensitivity, the major limiting factor for MDLs is the
reproducibility of measurement results when analysing elements close to the expected MDL.
In TXRF analysis the small analysed sample amount restricts the reproducibility because small
inhomogeneities of element distribution will have a large influence. In addition, the detector of the
PicoTAX TXRF spectrometer is equipped with an active area of 10 mm2, while the average sample area is
about 30 - 40 mm2. Thus, the complete sample is not taken into account for data acquisition.
Two recent developments have improved the performance of the PicoTAX TXRF spectrometer and
increased the quality of MDLs. First, the line focus X-ray tube was replaced by a micro focus tube. The
improvement of excitation intensity can be estimated to be approximately 60 %. In addition, a 30 mm2
detector was introduced recently. This led to an average increase of signal intensity of 200 %. As a second
positive effect, the new detector influences the overall counting statistics by increasing the actually
analyzed sample area by a factor of three.
To evaluate the benefits of these technical improvements for the MDLs, the reproducibility measurements
of 12 soil and sediment samples were repeated. The sample preparation and measurement conditions were
exactly the same as during the first measurement campaign. A summary of the results is given in Table 1;
the complete data set can be found at the end of this chapter (Table 4). As the quality of measurement
results for the elements antimony, cadmium and silver is poor in general, the MDLs for these elements are
displayed in parentheses and are approximate.
B-l
-------
Table 1. Comparison of Old PicoTAX-, new PicoTAX- and All XRF
Instrument Mean-MDLs. All Values are Given in mg/kg.
Element
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
PicoTAX
Mean MDLs
Old Values
NC
23
529
109
29
105
84
78
9
539
44
73
PicoTAX
Mean MDLs
New Values
(167)
15
(329)
30
9
37
16
28
7
(58)
37
39
All XRF
Instrument
Mean MDLs
61
26
70
83
23
40
23
50
8
42
28
38
It is obvious that the application of the recent technology enhancements lead to a distinct improvement of
the MDLs for some elements up to a factor of 3 to 4.
1.3 Accuracy and comparability
The larger detector area will certainly improve the accuracy of the PicoTAX. For a detailed evaluation of
the improvements, the analysis of the complete set of 326 samples would be necessary. Therefore, only a
qualitative assessment of the improvements can be provided at this point. Since for a detailed evaluation of
accuracy and comparability the complete set of 326 samples would have to be analyzed, only an
assessment of possible improvements by the recent technology enhancements is possible. Due to the larger
detected sample area, samples with inhomogeneous element distribution will deliver more accurate results.
The enhanced MDL will allow the analysis of elements in concentrations which were not detectable with
the original equipment.
The quality of measurement results for the elements antimony, cadmium and silver can not be improved
significantly by the introduction of a micro focus tube and a larger detector. As mentioned in the previous
sections, the detection of these elements is limited to the L-lines when applying a Mo tube. In soil and
sediment samples, these lines are completely overlapped by the K-lines of the matrix elements calcium
and potassium. A technical solution can be an alternative excitation source. Recently, initial measurements
with a W-anode tube have been performed successfully. Figure 1 shows a TXRF spectra of a soil sample,
containing 64 mg/kg of Cd. A commercially available system with W-excitation is planned to be released
mid-2006.
B-2
-------
1.4
Figure 1. TXRF spectra of a soil sample analysed with W-excitation.
Precision
The precision defined by the Relative Standard Deviation (RSD) can be assessed on the RSD values of the
repetitive MDL measurements. A comparison of the ranges of median RSDs according to the
classification described in chapter 7.3 is summarized in Table 2. The corresponding data set is given in
Table 5 at the end of this chapter.
Table 2. Comparison of Old and New RSD Values for the PicoTAX TXRF Spectrometer
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Old values
Moderate
High
High
Moderate
Moderate
Moderate
High
Moderate
Low
High
Moderate
Moderate
New values
Moderate
High
High
Low
Low
Moderate
High
Moderate
Low
High
Moderate
Moderate
B-3
-------
Although numerical enhancements are visible, a step into better classification ranges could just be
achieved for the elements copper and iron.
2. Analysis of Digested Soils and Sediments
In contrast to common XRF systems, the application of TXRF spectroscopy is capable for trace element
analysis in liquids. For an assessment of this laboratory based analysis, two samples from the EPA SITE
program were analysed after microwave digestion. Microwave digestion was performed according to the
EPA Method 3051; 10 (il of Ga solution (Merck, 1 g/L) were added to 1 ml of the digested solution for
internal standardisation. After the resulting solution was thoroughly homogenized, an aliquot of 10 (iL was
transferred onto a quartz glass sample carrier and dried on a heating plate. TXRF analysis was performed
with the same instrument as described in chapter 6.0 by applying measurement times of 600 seconds. The
results of the measurements are summarized in Table 3.
Table 3. Comparison of Reference Laboratory Values and PicoTAX Results of Microwave
Digested Samples. All values in mg/kg.
Sample
Element
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Barium
Bromine
Calcium
Manganese
Potassium
Rubidium
Strontium
Thorium
Titanium
Yttrium
CN-SO-03
EPA values
120
88
18
100
20,000
180
42
110
52
130
36
78
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
PicoTAX values
106
Not detected
17
76
20,611
179
Not detected
74
41
Not detected
27
69
95
1.0
2854
227
1 961
39
65
65
391
22
KP-SO-02
EPA values
1.2
Not detected
350
31
1,400
580
0.91
150
Not detected
0.059
1.7
15
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
Not analysed
PicoTAX values
1.0
Not detected
329
26
1,592
588
Not detected
167
Not detected
Not detected
Not detected
10
Not detected
3.0
217
33
23
3
Not detected
Not detected
20
Not detected
Obviously, all values obtained after analysis of microwave digested samples show accuracies which can
be classified either as "very good" or "good". As digestion of the samples has no influence on the matrix
composition, antimony, cadmium and silver could still not be analysed. The analysis of mercury after
microwave digestion is not possible due to the volatility of this element.
No MDL or RPD evaluation was performed for digested samples. But because one of the major limiting
influences on these factors can be found in the sample inhomogeneity, values with increased quality can
be expected.
B-4
-------
Table 4. Evaluation of Sensitivity - Method Detection Limits for the Rontec PicoTAX (30 mm2 detector)
Matrix
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Sediment
Sediment
Sediment
Sediment
Sample No.
AS-SO-01
BN-SO-01
KP-SO-01
KP-SO-02
SB-SO-02
SB-SO-03
WS-SO-02
CN-SO-01
TL-SE-02
RF-SE-02
LV-SE-01
LV-SE-02
Mean Rontec MDL
Antimony
Rontec
MDL
NC
NC
27
NC
NC
NC
NC
205
NC
NC
NC
NC
167
Rontec
Cone
NA
NA
207
NA
NA
NA
NA
127
NA
NA
NA
NA
Ref.
Lab
Cone
ND
140
270
6
ND
17
110
16
2
2
ND
ND
Arsenic
Rontec
MDL
4
NC
NC
6
9
24
NC
11
5
57
NC
3
15
Rontec
Cone
3
1632
NA
4
22
62
10808
145
18
277
767
59
Ref.
Lab
Cone
24
1900
8
1
10
30
6300
100
10
220
800
31
Cadmium
Rontec
MDL
NC
607
NC
NC
NC
NC
NC
51
NC
NC
NC
NC
329
Rontec
Cone
NA
1399
NA
NA
NA
NA
NA
47
NA
NA
NA
NA
Ref. Lab
Cone
62
1000
0,1
ND
ND
ND
170
72
ND
11
ND
ND
Chromium
Rontec
MDL
NC
29
5
85
NC
11
33
7
25
12
50
40
30
Rontec
Cone
196
74
3
306
205
45
27
3
40
12
71
37
Ref. Lab
Cone
220
91
5
350
170
18
70
15
74
38
56
67
B-5
-------
Table 4. Evaluation of Sensitivity - Method Detection Limits for the Rontec PicoTAX (30 mm2 detector) - continued.
Matrix
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Sediment
Sediment
Sediment
Sediment
Sample No.
AS-SO-01
BN-SO-01
KP-SO-01
KP-SO-02
SB-SO-02
SB-SO-03
WS-SO-02
CN-SO-01
TL-SE-02
RF-SE-02
LV-SE-01
LV-SE-02
Mean Rontec MDL
Copper
Rontec
MDL
12
NC
NC
7
4
4
NC
11
NC
NC
14
13
9
Rontec
Cone
87
2384
516
20
41
8
3101
78
1601
1396
36
20
Ref.
Lab
Cone
180
3000
780
31
52
7
1900
86
2000
1700
46
28
Lead
Rontec
MDL
NC
NC
NC
32
24
42
NC
87
44
NC
23
10
37
Rontec
Cone
1404
12797
18253
615
5
12
105085
126
13
707
9
33
Ref.
Lab
Cone
1900
12000
22000
580
22
35
50000
150
15
700
30
70
Mercury
Rontec
MDL
NC
NC
NC
NC
45
NC
1
10
NC
10
NC
NC
16
Rontec
Cone
NA
NA
NA
NA
25
4843
0,3
15
NA
15
NA
NA
Ref. Lab
Cone
3
6
7
1
66
1900
13
41
1
6
18
22
Nickel
Rontec
MDL
84
46
NC
40
39
3
31
10
13
16
9
15
28
Rontec
Cone
48
99
NA
141
189
15
40
82
89
98
20
92
Ref. Lab
Cone
100
180
3
150
230
23
88
88
120
120
64
130
B-6
-------
Table 4. Evaluation of Sensitivity - Method Detection Limits for the Rontec PicoTAX (30 mm2 detector) - continued.
Matrix
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Sediment
Sediment
Sediment
Sediment
Sample No.
AS-SO-01
BN-SO-01
KP-SO-01
KP-SO-02
SB-SO-02
SB-SO-03
WS-SO-02
CN-SO-01
TL-SE-02
RF-SE-02
LV-SE-01
LV-SE-02
Mean Rontec MDL
Selenium
Rontec
MDL
NC
6
9
NC
NC
NC
17
7
1
NC
NC
4
7
Rontec
Cone
NA
35
14
NA
NA
NA
99
40
1
1
2
2
Ref.
Lab
Cone
3
52
0,2
ND
2
ND
3,6
41
ND
ND
14
4
Silver
Rontec
MDL
NC
NC
NC
NC
NC
NC
NC
58
NC
NC
NC
NC
58
Rontec
Cone
NA
NA
NA
NA
NA
NA
NA
71
NA
NA
NA
NA
Ref.
Lab
Cone
4
150
1
0,1
ND
0,2
230
100
2
11
ND
ND
Vanadium
Rontec
MDL
17
30
NC
6
13
44
NC
42
97
20
67
34
37
Rontec
Cone
59
71
NA
5
140
136
NA
68
30
53
141
171
Ref. Lab
Cone
53
44
0,4
2
66
9
24
30
140
43
150
46
Zinc
Rontec
MDL
NC
NC
13
16
80
NC
NC
63
19
NC
72
13
39
Rontec
Cone
3025
7330
98
8
118
NA
16576
84
226
2070
33
75
Ref. Lab
Cone
4100
7700
94
15
97
14
11000
66
220
2200
16
62
B-7
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Table 5. Evaluation of Precision - Relative Standard Deviations for the Rontec PicoTAX (30 mm2 detector)
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
AS-SO-01
NC
45.6
NC
48.6
4.4
3.4
3.2
NC
55.1
NC
NC
9.4
13.0
BN-SO-
01
NC
3.5
13.8
12.5
3.5
4.1
2.8
NC
14.7
5.2
NC
13.4
2.0
CN-SO-
01
NC
2.4
100.9
80.1
4.5
11.3
21.9
21.3
3.8
5.4
89.8
20.0
24.0
KP-SO-02
NC
50.0
NC
8.8
10.3
13.3
1.7
NC
9.0
NC
NC
(34.3) 2)
65.6
SB-SO-02
NC
13.5
NC
42.2
3.2
2.0
(137.9) 2)
58.0
6.5
NC
NC
2.9
21.6
SB-SO-03
NC
12.4
NC
7.7
14.9
8.1
(111.6)2)
14.3
6.3
NC
NC
10.2
NC
ws-so-
02
8.3 1}
12.5
42.7
38.5
8.4
15.6
8.4
36.9
23.7
20.3
NC
NC
10.1
LV-SE-01
NC
9.4
NC
22.5
12.0
2.7
78.9
NC
13.8
NC
NC
15.2
16.7
LV-SE-02
NC
1.8
NC
35.0
20.3
6.0
9.1
NC
5.3
(63.8) 2)
NC
6.3
5.5
RF-SE-02
NC
6.6
NC
32.3
7.3
5.9
9.7
20.6
5.3
NC
NC
12.2
24.9
TL-SE-02
NC
8.5
NC
20.1
4.8
2.9
(104.3) 2)
NC
4.6
(33.3) ^
NC
(103.6)2)
2.6
Mean
NC
15
52
32
9
7
17
30
13
10
90
11
19
1} Sample with extraordinary element distribution (Sb
2) Element concentration close to or below the MDL.
2000 (ig/kg, K and Ca ~ 3000 resp. 4000 mg/kg)
B-8
-------
APPENDIX C
DATA VALIDATION SUMMARY REPORT
-------
Contents
Chapter Page
Acronyms, Abbreviations, and Symbols iii
1.0 INTRODUCTION C-l
2.0 VALIDATION METHODOLOGY C-l
3.0 DATA VALIDATION RESULTS C-3
3.1 Holding Time C-3
3.2 Calibration C-3
3.3 Laboratory Blanks C-4
3.4 Laboratory Control Samples C-5
3.5 Matrix Spike Samples C-5
3.6 Serial Dilution Results C-5
3.7 ICP Interference Check Samples C-6
3.8 Target Analyte Identification and Quantitation C-6
3.9 Quantitation Limit Verification C-6
4.0 PRECISION, ACCURACY, REPRESENTATIVENESS, COMPLETENESS, AND
COMPARABILITY EVALUATION SUMMARY C-6
4.1 Precision C-7
4.2 Accuracy C-7
4.3 Representativeness C-7
4.4 Completeness C-7
4.5 Comparability C-7
5.0 CONCLUSIONS FOR DATA QUALITY AND DATA USABILITY C-8
6.0 REFERENCES C-8
APPENDIX
DATA VALIDATION REPORTS
-------
ABBREVIATIONS AND ACRONYMS
CCV Continuing calibration verification
CVAA Cold vapor atomic absorption
DVSR Data validation summary report
EPA U.S. Environmental Protection Agency
FAR Federal acquisition regulations
ICP-AES Inductively coupled plasma-atomic emission spectroscopy
ICS Interference check sample
ICV Initial calibration verification
LCS Laboratory control sample
LCSD Laboratory control sample duplicate
MDL Method detection limit
mg/kg Milligram per kilogram
MS Matrix spike
MSD Matrix spike duplicate
PARCC Precision, accuracy, representativeness, completeness, and comparability
PQL Practical quantitation limit
QA/QC Quality assurance and quality control
QAPP Quality assurance project plan
QC Quality control
RSD Relative standard deviation
RPD Relative percent difference
SDG Sample delivery group
Shealy Shealy Environmental Services, Inc.
SITE Superfund Innovative Technology Evaluation
Tetra Tech Tetra Tech EM Inc.
XRF X-ray fluorescence
11
-------
1.0 INTRODUCTION
This data validation summary report (DVSR) summarizes the reference laboratory quality control (QC)
data gathered during the x-ray fluorescence (XRF) technologies demonstration conducted under the U.S.
Environmental Protection Agency (EPA) Superfund Innovative Technology Evaluation (SITE) program.
The reference laboratory was procured following the federal acquisition regulations (FAR) and an
extensive selection process. Shealy Environmental Services, Inc. (Shealy), of Cayce, South Carolina, was
selected as the reference laboratory for this project. Thirteen target analytes were measured in reference
samples and include antimony, arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel,
selenium, silver, vanadium, and zinc. The laboratory reported results for 22 metals at the request of EPA;
however, for the purposes of meeting project objectives, only the data validation for the 13 target analytes
is summarized in this document. The objective of the validation is to determine the validity of the
reference data, as well as its usability in meeting the primary objective of comparing reference data to
XRF data generated during the demonstration. Shealy provided the data to Tetra Tech EM Inc. (Tetra
Tech) in electronic and hardcopy formats; a total of 13 sample delivery groups (SDG) contain all the data
for this project.
The DVSR consists of seven sections, including this introduction. Section 2.0 presents the data validation
methodology. Section 3.0 presents the results of the reference laboratory data validation. Section 4.0
summarizes the precision, accuracy, representativeness, completeness, and comparability (PARCC)
evaluation. Section 5.0 presents conclusions about the overall evaluation of the reference data. Section
6.0 lists the references used to prepare this DVSR. Tables are presented following Section 6.0.
2.0 VALIDATION METHODOLOGY
Data validation is the systematic process for reviewing and qualifying data against a set of criteria to
ensure that the reference data are adequate for the intended use. The data validation process assesses
acceptability of the data by evaluating the critical indicator parameters of PARCC. The laboratory
analytical data were validated according to the procedures outlined in the following documents:
"USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data
Review" (EPA 2004). hereinafter referred to as the "EPA guidance."
"Demonstration and Quality Assurance Project Plan, XRF Technologies for Measuring
Trace Elements in Soil and Sediment" (Tetra Tech 2005). hereinafter referred to as "the
QAPP."
Data validation occurred in the following two stages: (1) a cursory review of analytical reports and
quality assurance and quality control (QA/QC) information for 100 percent of the reference data and
(2) full validation of analytical reports, QA/QC information, and associated raw data for 10 percent of the
reference data as required by the QAPP (Tetra Tech 2005).
QA/QC criteria were reviewed in accordance with EPA guidance (EPA 2004) and the QAPP (Tetra Tech
2005). The cursory review for total metals consisted of evaluating the following requirements, as
applicable:
Holding times
C-l
-------
Initial and continuing calibrations
Laboratory blank results
Laboratory control sample (LCS) and laboratory control sample duplicates (LCSD) results
Matrix spike (MS) and matrix spike duplicate (MSB) results
Serial dilutions results
In addition to QA/QC criteria described above, the following criteria were reviewed during full
validation:
ICP interference check samples (ICS)
Target analyte identification and quantitation
Quantitation limit verification
Section 3.0 presents the results of the both the cursory review and full validation.
During data validation, worksheets were produced for each SDG that identify any QA/QC issues resulting
in data qualification. Data validation findings were written in 13 individual data validation reports (one
for each SDG). Data qualifiers were assigned to the results in the electronic database in accordance with
EPA guidelines (EPA 2004). In addition to data validation qualifiers, comment codes were added to the
database to indicate the primary reason for the validation qualifier. Table 1 defines data validation
qualifiers and comment codes that are applied to the data set. Details about specific QC issues can be
found in the individual SDG data validation reports and accompanying validation worksheets provided in
the Appendix.
The overall objective of data validation is to ensure that the quality of the reference data set is adequate
for the intended use, as defined by the QAPP (Tetra Tech 2005) for the PARCC parameters. Table 2
provides the QC criteria as defined by the QAPP. PARCC parameters were assessed by completing the
following tasks:
Reviewing precision and accuracy of laboratory QC data
Reviewing the overall analytical process, including holding time, calibration, analytical or
matrix performance, and analyte identification and quantitation
Assigning qualifiers to affected data when QA/QC criteria were not achieved
Reviewing and summarizing implications of the frequency and severity of qualifiers in the
validated data
Prior to the XRF demonstration, soil and sediment samples were collected from nine locations across the
U.S. and then blended, dried, sieved, and homogenized in the characterization laboratory to produce a set
of 326 reference samples. Each of these samples were subsequently analyzed by both the reference
C-2
-------
laboratory and all participating technology vendors. As such, 326 prepared soil/sediment samples were
delivered to Shealy for the measurement of total metals. The analytical program included the following
analyses and methods:
Total metal for 22 analytes by inductively coupled plasma atomic emission spectroscopy
(ICP-AES) according to EPA Methods 3050B/6010B (EPA 1996)
Total mercury by cold vapor atomic absorption spectroscopy (CVAA) according to EPA
Method 7471A (EPA 1996)
3.0 DATA VALIDATION RESULTS
The parameters listed in Section 2.0 were evaluated during cursory review and full validation of analytical
reports for all methods, as applicable. Each of the validation components discussed in this section is
summarized as follows:
Acceptable - All criteria were met and no data were qualified on that basis
Acceptable with qualification - Most criteria were met, but at least one data point was
qualified as estimated because of issues related to the review component
Since no data were rejected, all data were determined to be either acceptable or acceptable with
qualification. Sections 3.1 through 3.9 discuss each review component and the results of each. Tables
that summarize the data validation findings follow Section 6.0 of this DVSR. Only qualified data are
included in the tables. No reference laboratory data were rejected during the validation process. As such,
all results are acceptable with the qualification noted in the sections that follow.
3.1 Holding Time
Acceptable. The technical holding times were defined as the maximum time allowable between sample
collection and, as applicable, sample extraction, preparation, or analysis. The holding times used for
validation purposes were recommended in the specific analytical methods (EPA 1996) and were specified
in the QAPP (Tetra Tech 2005).
Because the soil and sediment samples were prepared prior to submission to the reference laboratory, and
because the preparation included drying to remove moisture, no chemical or physical (for example ice)
preservation was required. The holding time for sample digestion was 180 days for the ICP-AES
analyses and 28 days for mercury. All sample digestions and analyses were conducted within the
specified holding times. No data were qualified based on holding time exceedances. This fact contributes
to the high technical quality of the reference data.
3.2 Calibration
Acceptable. Laboratory instrument calibration requirements were established to ensure that analytical
instruments could produce acceptable qualitative and quantitative data for all target analytes. Initial
calibration demonstrates that the instrument is capable of acceptable performance at the beginning of an
analytical run, while producing a linear curve. Continuing calibration demonstrates that the instrument is
capable of repeating the performance established during the initial calibration (EPA 1996).
C-3
-------
For total metal analyses (ICP-AES and CVAA), initial calibration review included evaluating criteria for
the curve's correlation coefficient and initial calibration verification (ICV) percent recoveries. The ICV
percent recoveries verify that the analytical system is operating within the established calibration criteria
at the beginning of an analytical run. The continuing calibration review included evaluation of the criteria
for continuing calibration verification (CCV) percent recoveries. The CCV percent recoveries verify that
the analytical system is operating within the established calibration throughout the analytical run.
All ICV and CCV percent recoveries associated with the reference data were within acceptable limits of
90 to 110 percent. As such, no data were qualified or rejected because of calibration exceedances. This
fact contributes to the high technical quality of the data.
3.3 Laboratory Blanks
Acceptable with qualification. No field blanks were required by the QAPP, since samples were prepared
after collection and before submission to the reference laboratory. However, laboratory blanks were
prepared and analyzed to evaluate the existence and magnitude of contamination resulting from
laboratory activities. Blanks prepared and analyzed in the laboratory consisted of calibration and
preparation blanks. If a problem with any blank existed, all associated data were carefully evaluated to
assess whether the sample data were affected. At a minimum, calibration blanks were analyzed for every
10 analyses conducted on each instrument. Preparation blanks were prepared at a frequency of one per
preparation batch per matrix or every 20 samples, whichever is greater (EPA 1996).
When laboratory blank contamination was identified, sample results were compared to the practical
quantitation limit (PQL) and the maximum blank value as required by the validation guidelines (EPA
2004). Most of the blank detections were positive results (i.e. greater than the method detection limit
[MDL]), but less than the PQL. In these instances, if associated sample results were also less than the
PQL, they were qualified as undetected (U); with the comment code "b." In these same instances, if the
associated sample results were greater than the PQL, the reviewer used professional judgment to
determine if the sample results were adversely affected. If so, then the results were qualified as estimated
with the potential for being biased high (J+). If not, then no qualification was required.
In a few cases, the maximum blank value exceeded the PQL. In these cases, all associated sample results
less than the PQL were qualified as undetected (U) with the comment code "b." In cases where the
associated sample results were greater than the PQL, but less than the blank concentration, the results
were also qualified as undetected (U); with the comment code "b." If the associated sample results were
greater than both the PQL and the blank value, the reviewer used professional judgment to determine if
sample results were adversely affected. If so, then the results were qualified as estimated with the
potential for being biased high (J+); with the comment code "b." Sample results significantly above the
blank were not qualified.
In addition to laboratory blank contamination, negative drift greater than the magnitude of the PQL was
observed in some laboratory blanks. Associated sample data were qualified as undetected (U) if the
results were less than the PQL. Professional judgement was used to determine if the negative drift
adversely affected associated sample results greater than the PQL. If so, then sample results were
qualified as estimated with the potential for being biased low (J-) due to the negative drift of the
instrument baseline; with the comment code "b."
Of all target analyte data, 2.6 percent of the data was qualified as undetected because of laboratory blank
contamination (U, b), and less than 1 percent of the data was qualified as estimated (either J+, b or J-, b).
The low occurrence of results affected by blank contamination indicates that the general quality of the
C-4
-------
analytical data was not significantly compromised by blank contamination. Table 3 provides all results
that were qualified based on laboratory blanks.
3.4 Laboratory Control Samples
Acceptable. LCSs and LCSDs were prepared and analyzed with each batch of 20 or fewer samples of the
same matrix. All percent recoveries were within the QC limits of 80 to 120 percent; all relative percent
differences (RPD) between the LCD and LCSD values were less than the criterion of 20 percent. No data
were qualified or rejected on the basis of LCS/LCSD results. This fact contributes to the high technical
quality of the data.
3.5 Matrix Spike Samples
Acceptable with qualification. MS and MSB samples were prepared and analyzed with each batch of 20
or fewer samples of the same matrix. All percent recoveries were within the QC limits of 75 to 125
percent, and all RPDs between the MS and MSB values were less than the criterion of 25 percent, except
as discussed in the following paragraphs.
Sample results affected by MS and MSB percent recoveries issues were qualified as estimated and either
biased high (J+) if the recoveries were greater than 125 percent; or qualified as estimated and biased low
(J-) if the recoveries were less than 75 percent. In at least one case, the MS was higher than 125 percent
and the MSB was lower than 75 percent; the associated results were qualified as estimated (J) with no
distinction for potential bias. All data qualified on the basis of MS and MSB recovery were also assigned
the comment code "e." Of all target analyte data, less than 1 percent was qualified as estimated and
biased high (J+, e), while about 8 percent of the data were qualified as estimated and biased low (J-, e).
Antimony and silver were the most frequently qualified sample results. Based on experience, antimony
and silver soil recoveries are frequently low using the selected methods. Table 4 provides the results that
were qualified based on MS/MSB results.
The precision between MS and MSB results were generally acceptable. If the RPB between MS and
MSB results were greater than 25 percent, the data were already qualified based on exceedance of the
acceptance window for recovery. Therefore, no additional qualification was required for MS/MSB
precision.
No data were rejected on the basis of MS/MSB results. The relatively low occurrence of data
qualification due to MS/MSB recoveries and RPBs contribute to the high technical quality of the data.
3.6 Serial Dilution Results
Acceptable with qualification. Serial dilutions were conducted and analyzed by Shealy at a frequency of
1 per batch of 20 samples. The serial dilution analysis can evaluate whether matrix interference exists
and whether the accuracy of the analytical data is affected. For all target analyte data, less than 1 percent
of the data was qualified as estimated and biased high (J+, j), while about 2 percent of the data were
qualified as estimated and biased low (J-, j). Serial dilution results are used to determine whether
characteristics of the digest matrix, such as viscosity or the presence of analytes at high concentrations,
may interfere with the detected analytes. Qualifiers were applied to cases where interference was
suspected. However, the low incidence of apparent matrix interference contributes to the high technical
quality of the data. Table 5 provides the results that were qualified based on MS/MSB results.
C-5
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3.7 ICP Interference Check Samples
Acceptable. ICP results for each ICS were evaluated. The ICS verifies the validity of the laboratory's
inter-element and background correction factors. High levels of certain elements (including aluminum,
calcium, iron, and magnesium) can affect sample results if the inter-element and background correction
factors have not been optimized. Incorrect correction factors may result in false positives, false negatives,
or biased results. All ICS recoveries were within QC limits of 80 to 120 percent, and no significant biases
were observed due to potential spectral interference. No data were qualified or rejected because of ICS
criteria violations. This fact contributes to the high technical quality of the data.
3.8 Target Analyte Identification and Quantitation
Acceptable Identification is determined by measuring the characteristic wavelength of energy emitted by
the analyte (ICP) or absorbed by the analyte (CVAA). External calibration standards are used to quantify
the analyte concentration in the sample digest. Sample digest concentrations are converted to soil units
(milligrams per kilogram) and corrected for percent moisture. For 10 percent of the samples, results were
recalculated to verify the accuracy of reporting. All results were correctly calculated by the laboratory,
except for one mercury result, whose miscalculation was the result of an error in entering the dilution
factor. Shealy immediately resolved this error and corrected reports were provided. Since the result was
corrected, no qualification was required. No other reporting errors were observed.
For inorganic analyses, analytical instruments can make reliable qualitative identification of analytes at
concentrations below the PQL. Detected results below the PQL are considered quantitatively uncertain.
Sample results below the PQL were reported by the laboratory with a "J" qualifier. No additional
qualification was required.
3.9 Quantitation Limit Verification
Acceptable. Reference laboratory quantitation limits were specified in the QAPP (Tetra Tech 2005).
Circumstances that affected quantitation were limited and included dilution and percent moisture factors.
Since the samples were prepared prior to submission to the reference laboratory, moisture content was
very low and had little impact on quantitation limits. The laboratory did correct all quantitation limits for
moisture content. Due to the presence of percent-level analytes in some samples, dilutions were required.
However, the required PQLs for the reference laboratory were high enough that even with dilution and
moisture content factors applied, the reporting limits did not exceed those of the XRF instruments. This
allows for effective comparison of results between the reference laboratory and XRF instruments.
4.0 PRECISION, ACCURACY, REPRESENTATIVENESS, COMPLETENESS, AND
COMPARABILITY EVALUATION SUMMARY
All analytical data were reviewed for PARCC parameters to validate reference data. The following
sections discuss the overall data quality, including the PARCC parameters, as determined by the data
validation.
C-6
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4.1 Precision
Precision is a measure of the reproducibility of an experimental value without considering a true or referenced
value. The primary indicators of precision were the MS/MSD RPD and LCS/LCSD RPD between the duplicate
results. Precision criteria of less than 20 percent RPD for LCS/LCSD and 25 percent for MS/MSD were
generally met for all duplicate pairs. No data were qualified based on duplicate precision of MS/MSD or
LCS/LCSD pairs that were not already qualified for other reasons. Such low occurrence of laboratory precision
problems supports the validity, usability, and defensibility of the data.
4.2 Accuracy
Accuracy assesses the proximity of an experimental value to a true or referenced value. The primary accuracy
indicators were the recoveries of MS and LCS spikes. Accuracy is expressed as percent recovery. Overall,
about 8 percent of the data was qualified as estimated and no data were rejected because of accuracy problems.
The low frequency of accuracy problems supports the validity, usability, and defensibility of the data.
4.3 Representativeness
Representativeness refers to how well sample data accurately reflect true environmental conditions. The QAPP
was carefully designed to ensure that actual environmental samples be collected by choosing representative sites
across the US from which sample material was collected. The blending and homogenization was executed
according to the approved QAPP (Tetra Tech 2005).
4.4 Completeness
Completeness is defined as the percentage of measurements that are considered to be valid. The validity of
sample results is evaluated through the data validation process. Sample results that are rejected and any missing
analyses are considered incomplete. Data that are qualified as estimated (J) or undetected estimated (UJ) are
considered valid and usable. Data qualified as rejected (R) are considered unusable for all purposes. Since no
data were rejected in this data set, a completeness of 100 percent was achieved. A total of 4,238 target analyte
results were evaluated. The completeness goal stated in the QAPP (Tetra Tech 2005) was 90 percent.
4.5 Comparability
Comparability is a qualitative parameter that expresses the confidence with which one data set may be compared
to another. Widely-accepted SW-846 methods were used for this project. It is recognized that direct
comparison of the reference laboratory data (using ICP-AES and CVAA techniques) to the XRF measurements
may result in discrepancies due to differences in the preparation and measurement techniques; however, the
reference laboratory data is expected to provide an acceptable basis for comparison to XRF measurement results
in accordance with the project objectives.
Comparability of the data was also achieved by producing full data packages, by using a homogenous matrix,
standard quantitation limits, standardized data validation procedures, and by evaluating the PARCC parameters
uniformly. In addition, the use of specified and well-documented analyses, approved laboratories, and the
standardized process of data review and validation have resulted in a high degree of comparability for the data.
C-7
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5.0 CONCLUSIONS FOR DATA QUALITY AND DATA USABILITY
Although some qualifiers were added to the data, a final review of the data set with respect to the data quality
parameters discussed in Section 4.0 indicates that the data are of overall good quality. No analytical data were
rejected. The data quality is generally consistent with project objectives for producing data of suitable quality
for comparison to XRF data. All supporting documentation and data are available upon request, including
cursory review and full validation reports as well as the electronic database that contains sample results.
6.0 REFERENCES
Tetra Tech EM, Inc. (Tetra Tech). 2005. "Demonstration and Quality Assurance Project Plan, XRF
Technologies for Measuring Trace Elements in Soil and Sediment." March.
U.S. Environmental Protection Agency (EPA). 1996. "Test Methods for Evaluating Solid Waste", Third
Edition (SW-846). With promulgated revisions. December.
EPA. 2004. "USEPA Contract Laboratory Program National Functional Guidelines For Inorganic Data
Review". October.
C-8
-------
TABLES
-------
TABLE 1: DATA VALIDATION QUALIFIERS AND COMMENT CODES
Qualifier
No Qualifier
U
J
J+
J-
UJ
R
Comment Code
a
b
c
d
e
f
g
h
i
J
Definition
Indicates that the data are acceptable both qualitatively and quantitatively.
Indicates compound was analyzed for but not detected above the concentration listed.
The value listed is the sample quantitation limit.
Indicates an estimated concentration value. The result is considered qualitatively
acceptable, but quantitatively unreliable.
The result is an estimated quantity, but the result may be biased high.
The result is an estimated quantity, but the result may be biased low.
Indicates an estimated quantitation limit. The compound was analyzed for,
considered non-detected.
The data are unusable (compound may or may not be present). Resampling
reanalysis is necessary for verification.
but was
and
Definition
Surrogate recovery exceeded (not applicable to this data set)
Laboratory method blank and common blank contamination
Calibration criteria exceeded
Duplicate precision criteria exceeded
Matrix spike or laboratory control sample recovery exceeded
Field blank contamination (not applicable to this data set)
Quantification below reporting limit
Holding time exceeded
Internal standard criteria exceeded (not applicable to this data set)
Other qualification (will be specified in report)
C-9
-------
TABLE 2: QC CRITERIA
Parameter
Method
QC Check
Frequency
Criterion
Corrective Action
Reference Method
Target Metals
( 12 ICP metals
andHg)
Percent moisture
3 05 OB/601 OB
and 7471 A
Method and
instrument blanks
MS/MSD
LCS/LCSD
Performance
audit samples
Laboratory
duplicates
One per
analytical batch
of 20 or less
One per
analytical batch
of 20 or less
One per
analytical batch
of 20 or less
One per
analytical batch
of 20 or less
One per
analytical batch
of 20 or less
Less than the
reporting limit
75 to 125 percent
recovery
RPD<25
80 to 120 percent
recovery
RPD<20
Within acceptance
limits
RPD<20
1 . Check calculations
2. Assess and eliminate source of
contamination
3 . Reanalyze blank
4. Inform Tetra Tech project manager
5. Flag affected results
1 . Check calculations
2. Check LCS/LCSD and digest
duplicate results to determine whether
they meet criterion
3 . Inform Tetra Tech project manager
4. Flag affected results
1 . Check calculations
2. Check instrument operating conditions
and adjust as necessary
3 . Check MS/MSD and digest duplicate
results to determine whether they meet
criterion
4. Inform Tetra Tech project manager
5 . Redigest and reanalyze the entire batch
of samples
6. Flag affected results
1 . Evaluated by Tetra Tech QA chemist
2. Inform laboratory and recommend
changes
3 . Flag affected results
1 . Check calculations
2. Reanalyze sample batch
3 . Inform Tetra Tech project manager
4. Flag affected results
C-10
-------
TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION
Sample ID
AS-SO-04-XX
AS-SO-06-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-13-XX
BN-SO-18-XX
BN-SO-28-XX
BN-SO-31-XX
BN-SO-35-XX
KP-SE-01-XX
KP-SE-11-XX
KP-SE-12-XX
KP-SE-14-XX
KP-SE-17-XX
KP-SE-19-XX
KP-SE-25-XX
KP-SE-25-XX
KP-SE-28-XX
KP-SE-30-XX
KP-SE-30-XX
KP-SO-02-XX
KP-SO-02-XX
KP-SO-03-XX
KP-SO-03-XX
KP-SO-04-XX
KP-SO-04-XX
KP-SO-04-XX
KP-SO-05-XX
KP-SO-05-XX
KP-SO-05-XX
KP-SO-06-XX
KP-SO-06-XX
KP-SO-07-XX
KP-SO-07-XX
KP-SO-07-XX
KP-SO-09-XX
KP-SO-09-XX
Analyte
Selenium
Antimony
Selenium
Selenium
Antimony
Silver
Silver
Silver
Silver
Mercury
Mercury
Mercury
Mercury
Mercury
Mercury
Mercury
Selenium
Mercury
Mercury
Selenium
Mercury
Selenium
Cadmium
Mercury
Cadmium
Mercury
Selenium
Cadmium
Mercury
Selenium
Arsenic
Mercury
Arsenic
Mercury
Selenium
Cadmium
Mercury
Result
6.2
2.4
1.1
1.1
2.4
0.94
0.77
0.97
0.85
0.053
0.079
0.06
0.065
0.082
0.044
0.096
0.26
0.056
0.1
0.24
0.043
0.42
0.074
0.044
0.046
0.018
0.28
0.13
0.044
0.24
0.73
0.059
2
0.027
0.21
0.094
0.046
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
U
UJ
U
U
UJ
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
J-
u
J-
u
U
U
U
Comment
Code
b
b,e
b
b
b,e
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
C-ll
-------
TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION
(Continued)
Sample ID
KP-SO-10-XX
KP-SO-10-XX
KP-SO-10-XX
KP-SO-13-XX
KP-SO-13-XX
KP-SO-13-XX
KP-SO-15-XX
KP-SO-15-XX
KP-SO-16-XX
KP-SO-16-XX
KP-SO-18-XX
KP-SO-18-XX
KP-SO-20-XX
KP-SO-20-XX
KP-SO-21-XX
KP-SO-21-XX
KP-SO-22-XX
KP-SO-22-XX
KP-SO-23-XX
KP-SO-23-XX
KP-SO-24-XX
KP-SO-24-XX
KP-SO-26-XX
KP-SO-26-XX
KP-SO-26-XX
KP-SO-27-XX
KP-SO-27-XX
KP-SO-27-XX
KP-SO-29-XX
KP-SO-29-XX
KP-SO-31-XX
KP-SO-32-XX
KP-SO-32-XX
KP-SO-32-XX
LV-SE-02-XX
LV-SE-10-XX
LV-SE-11-XX
Analyte
Arsenic
Mercury
Selenium
Arsenic
Cadmium
Mercury
Arsenic
Mercury
Cadmium
Mercury
Arsenic
Mercury
Arsenic
Mercury
Cadmium
Mercury
Arsenic
Mercury
Cadmium
Mercury
Arsenic
Mercury
Cadmium
Mercury
Selenium
Arsenic
Cadmium
Mercury
Arsenic
Mercury
Mercury
Arsenic
Cadmium
Mercury
Mercury
Mercury
Selenium
Result
0.7
0.028
0.22
1.4
0.045
0.037
0.76
0.029
0.063
0.016
0.56
0.016
1.5
0.03
0.098
0.042
0.7
0.027
0.048
0.017
1.4
0.017
0.061
0.013
0.22
1.3
0.05
0.021
1.5
0.013
0.017
1.6
0.045
0.014
0.02
0.023
1.3
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
U
U
J-
u
U
J-
u
U
U
J-
u
J-
u
U
U
J-
u
U
U
J-
u
U
U
U
J-
u
U
J-
u
U
J-
u
U
U
U
U
Comment
Code
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
C-12
-------
TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION
(Continued)
Sample ID
LV-SE-14-XX
LV-SE-21-XX
LV-SE-24-XX
LV-SE-29-XX
LV-SE-32-XX
RF-SE-07-XX
RF-SE-08-XX
RF-SE-10-XX
RF-SE-12-XX
RF-SE-23-XX
RF-SE-23-XX
RF-SE-33-XX
RF-SE-36-XX
RF-SE-36-XX
RF-SE-45-XX
RF-SE-53-XX
SB-SO-03-XX
SB-SO-12-XX
SB-SO-13-XX
SB-SO-15-XX
SB-SO-17-XX
SB-SO-18-XX
SB-SO-30-XX
SB-SO-32-XX
SB-SO-37-XX
SB-SO-46-XX
SB-SO-48-XX
SB-SO-53-XX
TL-SE-01-XX
TL-SE-03-XX
TL-SE-03-XX
TL-SE-04-XX
TL-SE-10-XX
TL-SE-11-XX
TL-SE-12-XX
TL-SE-14-XX
TL-SE-15-XX
Analyte
Mercury
Mercury
Mercury
Selenium
Mercury
Mercury
Silver
Silver
Mercury
Copper
Zinc
Silver
Mercury
Selenium
Cadmium
Cadmium
Antimony
Silver
Silver
Silver
Silver
Antimony
Selenium
Silver
Silver
Silver
Silver
Antimony
Mercury
Mercury
Silver
Mercury
Mercury
Mercury
Mercury
Mercury
Mercury
Result
0.056
0.048
0.053
1.2
0.052
0.091
0.39
0.34
0.099
0.2
0.6
0.33
0.081
1
0.52
0.57
1.2
2.1
2.2
1.6
2.3
1.2
1.3
0.1
2
2.2
0.1
1.2
0.074
0.32
0.94
0.26
0.19
0.021
0.22
0.08
0.28
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
U
UJ
UJ
UJ
UJ
UJ
UJ
J+
UJ
UJ
UJ
UJ
UJ
U
J-
u
J-
J-
u
J-
u
J-
Comment
Code
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b,e
b
b
b
b,e
b,e
b
b,e
b
b,e
b,e
b,e
b
b
b
b
b
b
b
b
b
C-13
-------
TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION
(Continued)
Sample ID
TL-SE-15-XX
TL-SE-18-XX
TL-SE-19-XX
TL-SE-19-XX
TL-SE-20-XX
TL-SE-22-XX
TL-SE-23-XX
TL-SE-23-XX
TL-SE-24-XX
TL-SE-24-XX
TL-SE-25-XX
TL-SE-25-XX
TL-SE-26-XX
TL-SE-27-XX
TL-SE-29-XX
TL-SE-31-XX
TL-SE-31-XX
WS-SO-06-XX
WS-SO-08-XX
WS-SO-10-XX
WS-SO-12-XX
WS-SO-17-XX
WS-SO-20-XX
WS-SO-23-XX
WS-SO-30-XX
WS-SO-31-XX
WS-SO-35-XX
Analyte
Silver
Mercury
Mercury
Silver
Mercury
Mercury
Mercury
Silver
Mercury
Silver
Mercury
Silver
Mercury
Mercury
Mercury
Mercury
Silver
Mercury
Mercury
Mercury
Mercury
Mercury
Mercury
Mercury
Mercury
Selenium
Mercury
Result
1
0.025
0.32
1.1
0.26
0.082
0.41
1.3
0.26
1.3
0.44
0.94
0.24
0.02
0.076
0.57
1.2
0.07
0.063
0.058
0.068
0.069
0.06
0.05
0.069
1.2
0.071
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
U
U
J-
u
J-
u
J-
u
J-
u
J-
u
J-
u
U
J-
u
U
U
U
UJ
UJ
U
U
UJ
U
UJ
Comment
Code
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b,e
b,e
b
b
b,e
b
b,e
Notes:
mg/kg
b
e
J+
J-
UJ
Milligrams per kilogram
Data were qualified based on blank contamination
Data were additionally qualified based on matrix spike/matrix spike duplicate exceedances
Result is estimated and potentially biased high
Result is estimated and potentially biased low
Result is undetected at estimated quantitation limits
C-14
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
Sample ID
AS-SO-01-XX
AS-SO-02-XX
AS-SO-03-XX
AS-SO-03-XX
AS-SO-04-XX
AS-SO-05-XX
AS-SO-05-XX
AS-SO-06-XX
AS-SO-07-XX
AS-SO-08-XX
AS-SO-08-XX
AS-SO-09-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-12-XX
AS-SO-13-XX
BN-SO-01-XX
BN-SO-01-XX
BN-SO-05-XX
BN-SO-07-XX
BN-SO-07-XX
BN-SO-09-XX
BN-SO-09-XX
BN-SO-10-XX
BN-SO-10-XX
BN-SO-11-XX
BN-SO-11-XX
BN-SO-12-XX
BN-SO-12-XX
BN-SO-14-XX
BN-SO-14-XX
BN-SO-15-XX
BN-SO-15-XX
BN-SO-16-XX
BN-SO-16-XX
BN-SO-19-XX
BN-SO-21-XX
Analyte
Antimony
Antimony
Mercury
Silver
Antimony
Mercury
Silver
Antimony
Antimony
Mercury
Silver
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Silver
Antimony
Silver
Antimony
Silver
Antimony
Silver
Antimony
Silver
Antimony
Silver
Antimony
Silver
Antimony
Arsenic
Antimony
Antimony
Result
3.8
<2.6
3.7
480
<6.4
2.5
330
2.4
3.6
2.5
280
<2.6
1.9
3.7
<2.6
2.4
<1.3
<1.3
160
110
990
750
100
<1.3
<1.3
4
140
750
210
3.5
140
<1.3
<1.3
120
1100
150
150
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
UJ
J-
J-
UJ
J-
J-
UJ
J-
J-
J-
UJ
J-
J-
UJ
UJ
UJ
UJ
J-
J-
J+
J-
J-
UJ
UJ
J-
J-
J-
J-
J-
J-
UJ
UJ
J-
J+
J-
J-
Validation
Code
e
e
e
e
e
e
e
b,e
e
e
e
e
e
e
e
b,e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
C-15
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Sample ID
BN-SO-21-XX
BN-SO-23-XX
BN-SO-23-XX
BN-SO-24-XX
BN-SO-24-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-26-XX
BN-SO-29-XX
BN-SO-32-XX
BN-SO-33-XX
CN-SO-01-XX
CN-SO-02-XX
CN-SO-03-XX
CN-SO-04-XX
CN-SO-05-XX
CN-SO-06-XX
CN-SO-07-XX
CN-SO-08-XX
CN-SO-09-XX
CN-SO-10-XX
CN-SO-11-XX
KP-SE-01-XX
KP-SE-01-XX
KP-SE-08-XX
KP-SE-08-XX
KP-SE-11-XX
KP-SE-11-XX
KP-SE-12-XX
KP-SE-12-XX
KP-SE-14-XX
KP-SE-14-XX
KP-SE-17-XX
KP-SE-17-XX
KP-SE-25-XX
KP-SE-25-XX
KP-SE-30-XX
Analyte
Arsenic
Antimony
Silver
Antimony
Silver
Antimony
Arsenic
Antimony
Antimony
Antimony
Antimony
Antimony
Mercury
Mercury
Antimony
Mercury
Mercury
Mercury
Antimony
Mercury
Antimony
Antimony
Lead
Silver
Lead
Silver
Lead
Silver
Lead
Silver
Lead
Silver
Lead
Silver
Lead
Silver
Lead
Result
1300
<1.2
130
810
140
82
700
150
150
160
100
13
270
34
13
280
40
36
15
260
13
17
310
<0.26
300
<0.27
310
<0.27
320
<0.26
680
<0.26
300
<0.27
310
<0.27
300
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J+
UJ
J-
J-
J-
J-
J
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
UJ
J-
UJ
J-
UJ
J-
UJ
J-
UJ
J-
UJ
J-
UJ
J-
Validation
Code
e
e
e
e
e
e,j
e,j
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e,j
e
e
e
e
e
e
C-16
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Sample ID
KP-SE-30-XX
KP-SO-04-XX
KP-SO-06-XX
KP-SO-07-XX
KP-SO-10-XX
KP-SO-13-XX
KP-SO-15-XX
KP-SO-16-XX
KP-SO-18-XX
KP-SO-20-XX
KP-SO-22-XX
KP-SO-23-XX
KP-SO-24-XX
KP-SO-26-XX
KP-SO-27-XX
KP-SO-29-XX
KP-SO-32-XX
LV-SE-01-XX
LV-SE-02-XX
LV-SE-02-XX
LV-SE-02-XX
LV-SE-05-XX
LV-SE-06-XX
LV-SE-07-XX
LV-SE-08-XX
LV-SE-09-XX
LV-SE-10-XX
LV-SE-10-XX
LV-SE-10-XX
LV-SE-11-XX
LV-SE-12-XX
LV-SE-13-XX
LV-SE-14-XX
LV-SE-15-XX
LV-SE-15-XX
LV-SE-16-XX
LV-SE-17-XX
Analyte
Silver
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Lead
Silver
Mercury
Mercury
Antimony
Antimony
Lead
Antimony
Lead
Silver
Antimony
Lead
Mercury
Antimony
Antimony
Silver
Antimony
Antimony
Result
<0.27
94
8.1
17
6.1
16
6.3
93
6.7
19
8.3
86
17
90
15
18
16
<1.5
<1.3
20
<1.3
2.6
610
<6.7
<1.3
14
<1.3
25
<1.3
<1.4
19
640
<1.5
290
300
<1.3
280
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
UJ
J+
J+
J+
J+
J+
J+
J+
J+
J+
J+
J+
J+
J+
J+
J+
J+
UJ
UJ
J-
UJ
J-
J-
UJ
UJ
J-
UJ
J-
UJ
UJ
J-
J-
UJ
J+
J-
UJ
J+
Validation
Code
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
C-17
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Sample ID
LV-SE-17-XX
LV-SE-17-XX
LV-SE-18-XX
LV-SE-19-XX
LV-SE-20-XX
LV-SE-20-XX
LV-SE-21-XX
LV-SE-22-XX
LV-SE-22-XX
LV-SE-22-XX
LV-SE-23-XX
LV-SE-24-XX
LV-SE-25-XX
LV-SE-25-XX
LV-SE-25-XX
LV-SE-26-XX
LV-SE-27-XX
LV-SE-28-XX
LV-SE-29-XX
LV-SE-30-XX
LV-SE-31-XX
LV-SE-31-XX
LV-SE-31-XX
LV-SE-32-XX
LV-SE-33-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-36-XX
LV-SE-38-XX
LV-SE-39-XX
LV-SE-41-XX
LV-SE-42-XX
LV-SE-43-XX
LV-SE-43-XX
LV-SE-45-XX
LV-SE-47-XX
Analyte
Lead
Silver
Antimony
Lead
Antimony
Silver
Antimony
Antimony
Lead
Silver
Antimony
Antimony
Antimony
Lead
Silver
Lead
Lead
Antimony
Antimony
Antimony
Antimony
Lead
Silver
Antimony
Lead
Antimony
Lead
Silver
Lead
Lead
Lead
Mercury
Lead
Antimony
Silver
Antimony
Antimony
Result
17
200
<6.7
17
140
75
<1.5
<1.3
22
<1.3
<6.6
<1.5
<1.3
23
<1.3
25
16
<1.3
<1.4
<1.3
<1.3
49
<1.3
<1.4
21
<1.3
22
<1.3
21
15
22
610
22
160
60
<6.7
<1.3
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J-
UJ
J-
J+
J-
UJ
UJ
J-
UJ
UJ
UJ
UJ
J-
UJ
J-
J-
UJ
UJ
UJ
UJ
J-
UJ
UJ
J-
UJ
J-
UJ
J-
J-
J-
J-
J-
J+
J-
UJ
UJ
Validation
Code
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
C-18
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Sample ID
LV-SE-48-XX
LV-SE-50-XX
LV-SE-51-XX
LV-SE-51-XX
LV-SO-03-XX
LV-SO-03-XX
LV-SO-04-XX
LV-SO-04-XX
LV-SO-34-XX
LV-SO-34-XX
LV-SO-37-XX
LV-SO-40-XX
LV-SO-40-XX
LV-SO-49-XX
LV-SO-49-XX
RF-SE-02-XX
RF-SE-03-XX
RF-SE-04-XX
RF-SE-04-XX
RF-SE-05-XX
RF-SE-05-XX
RF-SE-06-XX
RF-SE-13-XX
RF-SE-14-XX
RF-SE-14-XX
RF-SE-15-XX
RF-SE-19-XX
RF-SE-19-XX
RF-SE-22-XX
RF-SE-24-XX
RF-SE-25-XX
RF-SE-26-XX
RF-SE-26-XX
RF-SE-27-XX
RF-SE-28-XX
RF-SE-30-XX
RF-SE-31-XX
Analyte
Antimony
Lead
Antimony
Silver
Mercury
Silver
Mercury
Silver
Mercury
Silver
Mercury
Mercury
Silver
Mercury
Silver
Antimony
Antimony
Antimony
Silver
Antimony
Silver
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Antimony
Result
<6.6
24
210
250
48
210
130
<1.2
130
<1.2
130
46
210
52
220
<1.3
<1.2
3.2
12
4.1
7.4
<1.3
<1.3
4.4
13
<1.3
3.7
14
<1.3
<1.3
<1.3
2.2
7.2
<1.3
<1.2
<1.3
<1.3
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
UJ
J-
J+
J-
J-
J-
J-
UJ
J-
UJ
J-
J-
J-
J-
J-
UJ
UJ
J+
J-
J+
J-
UJ
UJ
J+
J-
UJ
J+
J-
UJ
UJ
UJ
J+
J-
UJ
UJ
UJ
UJ
Validation
Code
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
C-19
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Sample ID
RF-SE-32-XX
RF-SE-34-XX
RF-SE-34-XX
RF-SE-38-XX
RF-SE-39-XX
RF-SE-39-XX
RF-SE-42-XX
RF-SE-43-XX
RF-SE-44-XX
RF-SE-44-XX
RF-SE-45-XX
RF-SE-49-XX
RF-SE-52-XX
RF-SE-52-XX
RF-SE-53-XX
RF-SE-55-XX
RF-SE-56-XX
RF-SE-56-XX
RF-SE-57-XX
RF-SE-58-XX
RF-SE-59-XX
SB-SO-01-XX
SB-SO-02-XX
SB-SO-02-XX
SB-SO-03-XX
SB-SO-04-XX
SB-SO-05-XX
SB-SO-06-XX
SB-SO-07-XX
SB-SO-08-XX
SB-SO-09-XX
SB-SO-09-XX
SB-SO-10-XX
SB-SO-11-XX
SB-SO-12-XX
SB-SO-13-XX
SB-SO-14-XX
Analyte
Antimony
Antimony
Silver
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Antimony
Antimony
Silver
Antimony
Silver
Antimony
Antimony
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Antimony
Antimony
Result
<1.3
2.9
10
<1.2
2.9
8.2
<1.3
<1.3
2.7
7.2
<1.3
<1.2
3.4
11
<1.3
<1.2
3.5
8.3
<1.3
<1.3
<1.3
180
44
<1.2
1.2
<1.3
1.6
1.7
45
5.4
<1.3
160
62
5.7
620
430
4.1
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
UJ
J+
J-
UJ
J+
J-
UJ
UJ
J+
J-
UJ
UJ
J+
J-
UJ
UJ
J+
J-
UJ
UJ
UJ
J
J-
UJ
UJ
UJ
J-
J-
J
J-
UJ
J-
J
J-
J
J
J-
Validation
Code
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e,j
e
b, e
e
e
e
e
e
e
e
e
e
e
e
e
C-20
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Sample ID
SB-SO-15-XX
SB-SO-16-XX
SB-SO-17-XX
SB-SO-17-XX
SB-SO-18-XX
SB-SO-19-XX
SB-SO-20-XX
SB-SO-20-XX
SB-SO-21-XX
SB-SO-22-XX
SB-SO-23-XX
SB-SO-23-XX
SB-SO-24-XX
SB-SO-25-XX
SB-SO-26-XX
SB-SO-27-XX
SB-SO-28-XX
SB-SO-28-XX
SB-SO-29-XX
SB-SO-30-XX
SB-SO-31-XX
SB-SO-31-XX
SB-SO-32-XX
SB-SO-32-XX
SB-SO-33-XX
SB-SO-33-XX
SB-SO-34-XX
SB-SO-35-XX
SB-SO-36-XX
SB-SO-37-XX
SB-SO-38-XX
SB-SO-39-XX
SB-SO-40-XX
SB-SO-41-XX
SB-SO-42-XX
SB-SO-43-XX
SB-SO-43-XX
Analyte
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Silver
Antimony
Antimony
Antimony
Antimony
Antimony
Silver
Silver
Antimony
Antimony
Silver
Antimony
Silver
Antimony
Silver
Silver
Antimony
Silver
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Antimony
Silver
Result
600
170
800
2.3
1.2
310
<1.3
140
4.9
10
48
<0.26
180
6.8
61
6.7
42
<0.26
<1.2
3.2
<1.3
160
46
0.1
350
2
<1.3
6
<1.2
340
<1.3
4.7
2.2
<1.3
4.6
40
<0.26
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J
J+
UJ
UJ
J
UJ
J-
J
J
J-
UJ
J
J+
J
J+
J-
UJ
UJ
J-
UJ
J-
J-
UJ
J
J
UJ
J+
UJ
J
UJ
J-
J-
UJ
J-
J-
UJ
Validation
Code
i,e
e
e
b,e
b, e
e
e
e
e
ej
e
e
e
e
e
e
e
e
e
e
e
ej
e
b,e
e
e
e
e
e
e
e
e
e
e
e
e
e
C-21
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Sample ID
SB-SO-44-XX
SB-SO-45-XX
SB-SO-45-XX
SB-SO-46-XX
SB-SO-46-XX
SB-SO-47-XX
SB-SO-48-XX
SB-SO-48-XX
SB-SO-49-XX
SB-SO-50-XX
SB-SO-51-XX
SB-SO-52-XX
SB-SO-53-XX
SB-SO-54-XX
SB-SO-54-XX
SB-SO-55-XX
SB-SO-55-XX
SB-SO-56-XX
TL-SE-01-XX
TL-SE-01-XX
TL-SE-01-XX
TL-SE-05-XX
TL-SE-05-XX
TL-SE-09-XX
TL-SE-09-XX
TL-SE-11-XX
TL-SE-11-XX
TL-SE-11-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-14-XX
TL-SE-14-XX
TL-SE-14-XX
TL-SE-18-XX
TL-SE-18-XX
TL-SE-18-XX
TL-SE-22-XX
Analyte
Antimony
Antimony
Silver
Antimony
Silver
Antimony
Antimony
Silver
Silver
Antimony
Antimony
Antimony
Antimony
Lead
Silver
Antimony
Silver
Silver
Antimony
Lead
Silver
Antimony
Silver
Antimony
Silver
Antimony
Lead
Silver
Antimony
Silver
Antimony
Lead
Silver
Antimony
Lead
Silver
Antimony
Result
6.8
180
2.1
740
2.2
<1.3
39
0.1
<1.2
57
<1.3
150
1.2
5.2
<0.5
340
2.2
<1.2
<1.2
48
5.7
100
180
100
170
<1.2
54
5.5
95
160
<1.2
50
5.7
<1.2
46
6.3
<1.2
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J+
J
J-
J+
UJ
UJ
J-
UJ
UJ
J
UJ
J
UJ
J-
UJ
J
J
UJ
UJ
J-
J-
J+
J-
J+
J-
UJ
J-
J-
J+
J
UJ
J-
J-
UJ
J-
J-
UJ
Validation
Code
e
e
e
e
b, e
e
e
b, e
e
e
e
e
b,e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
j,e
j,e
e
e
e
e
e
e
e
C-22
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Sample ID
TL-SE-22-XX
TL-SE-22-XX
TL-SE-27-XX
TL-SE-27-XX
TL-SE-27-XX
TL-SE-29-XX
TL-SE-29-XX
TL-SE-29-XX
WS-SO-01-XX
WS-SO-01-XX
WS-SO-01-XX
WS-SO-02-XX
WS-SO-02-XX
WS-SO-03-XX
WS-SO-03-XX
WS-SO-04-XX
WS-SO-04-XX
WS-SO-05-XX
WS-SO-05-XX
WS-SO-07-XX
WS-SO-09-XX
WS-SO-09-XX
WS-SO-10-XX
WS-SO-11-XX
WS-SO-12-XX
WS-SO-12-XX
WS-SO-13-XX
WS-SO-13-XX
WS-SO-14-XX
WS-SO-14-XX
WS-SO-15-XX
WS-SO-15-XX
WS-SO-16-XX
WS-SO-16-XX
WS-SO-17-XX
WS-SO-17-XX
WS-SO-18-XX
Analyte
Lead
Silver
Antimony
Lead
Silver
Antimony
Lead
Silver
Antimony
Mercury
Silver
Antimony
Silver
Antimony
Mercury
Antimony
Silver
Antimony
Silver
Silver
Antimony
Mercury
Silver
Silver
Antimony
Mercury
Antimony
Silver
Antimony
Mercury
Antimony
Silver
Antimony
Silver
Antimony
Mercury
Antimony
Result
54
6.5
<1.2
51
7.8
<1.2
51
5.9
41
5.8
69
130
150
8.9
0.86
45
76
8.6
0.76
400
7.1
0.89
<1.3
340
<1.3
0.068
200
170
8.4
0.74
48
90
110
150
<1.3
0.069
130
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J-
UJ
J-
J-
UJ
J-
J-
J-
J
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
UJ
J-
UJ
UJ
J-
J-
J-
J-
J-
J-
J-
J-
UJ
UJ
J-
Validation
Code
e
e
e
e
e
e
e
e
e
ej
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
b, e
e
e
e
e
e
e
e
e
e
b, e
e
C-23
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Sample ID
WS-SO-18-XX
WS-SO-19-XX
WS-SO-19-XX
WS-SO-20-XX
WS-SO-21-XX
WS-SO-21-XX
WS-SO-22-XX
WS-SO-22-XX
WS-SO-23-XX
WS-SO-24-XX
WS-SO-24-XX
WS-SO-25-XX
WS-SO-26-XX
WS-SO-26-XX
WS-SO-27-XX
WS-SO-27-XX
WS-SO-28-XX
WS-SO-28-XX
WS-SO-29-XX
WS-SO-29-XX
WS-SO-30-XX
WS-SO-30-XX
WS-SO-31-XX
WS-SO-31-XX
WS-SO-32-XX
WS-SO-32-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-34-XX
WS-SO-34-XX
WS-SO-35-XX
WS-SO-35-XX
WS-SO-36-XX
WS-SO-36-XX
WS-SO-37-XX
WS-SO-37-XX
Analyte
Silver
Antimony
Silver
Silver
Antimony
Silver
Antimony
Silver
Silver
Antimony
Silver
Silver
Antimony
Mercury
Antimony
Mercury
Antimony
Silver
Antimony
Silver
Antimony
Mercury
Antimony
Mercury
Antimony
Silver
Antimony
Mercury
Antimony
Silver
Antimony
Mercury
Antimony
Silver
Antimony
Silver
Result
140
150
160
<1.3
120
150
41
72
<1.3
97
140
450
7.6
0.83
<1.3
0.11
120
130
120
140
1.2
0.069
7.2
0.85
190
190
6.9
0.87
45
78
<1.3
0.071
120
120
120
140
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J-
J-
UJ
J-
J-
J-
J-
UJ
J-
J-
J-
J-
J-
UJ
J-
J-
J-
J-
J-
J-
UJ
J-
J-
J-
J-
J-
J-
J-
J-
UJ
UJ
J-
J-
J-
J-
Validation
Code
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
e
b, e
e
e
e
e
e
e
e
e
e
b, e
e
e
e
e
C-24
-------
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES
(Continued)
Notes:
< = Less than
mg/kg = Milligram per kilogram
b = Data were qualified based on blank contamination
e = Data were additionally qualified based on matrix spike/matrix spike duplicate exceedances
j = Data were additionally qualified based on serial dilution exceedances
J = Result is estimated and biased could not be determined
J+ = Result is estimated and potentially biased high
J- = Result is estimated and potentially biased low
UJ = Result is undetected at estimated quantitation limit
C-25
-------
TABLE 5: DATA QUALIFICATION: SERIAL DILUTION EXCEEDANCES
Sample ID
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
BN-SO-11-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
KP-SE-14-XX
KP-SE-14-XX
KP-SE-14-XX
KP-SE-14-XX
KP-SE-14-XX
KP-SE-14-XX
LV-SE-29-XX
LV-SE-29-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-35-XX
Analyte
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Vanadium
Zinc
Mercury
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Selenium
Silver
Vanadium
Zinc
Antimony
Chromium
Copper
Iron
Lead
Nickel
Lead
Mercury
Arsenic
Chromium
Iron
Nickel
Vanadium
Zinc
Result
25
100
390
250
94000
3200
170
9.6
65
6800
24
82
700
370
64
930
16000
5400
88
19
48
28
2900
11
46
2.7
520
680
23
7.2
1.5
31
74
24000
170
55
67
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J+
J-
J-
J-
J+
J-
J-
J-
J-
J-
J-
J-
Comment
Code
j
j
j
j
j
j
i
j
j
j
j
e,i
ej
j
j
j
j
j
i
j
j
j
j
i
j
j
j
ej
j
j
i
j
j
j
j
i
j
C-26
-------
TABLE 5: DATA QUALIFICATIONS: SERIAL DILUTION EXCEEDANCES (Continued)
Sample ID
LV-SO-34-XX
LV-SO-34-XX
LV-SO-34-XX
LV-SO-34-XX
LV-SO-34-XX
LV-SO-34-XX
LV-SO-34-XX
LV-SO-34-XX
LV-SO-34-XX
LV-SO-34-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
SB-SO-02-XX
SB-SO-02-XX
SB-SO-02-XX
SB-SO-02-XX
SB-SO-15-XX
SB-SO-15-XX
SB-SO-15-XX
SB-SO-15-XX
Analyte
Antimony
Arsenic
Cadmium
Chromium
Iron
Lead
Nickel
Selenium
Vanadium
Zinc
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Vanadium
Zinc
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Vanadium
Zinc
Antimony
Arsenic
Lead
Mercury
Antimony
Arsenic
Chromium
Copper
Result
870
110
2300
2200
20000
3700
1900
220
230
48
85
72
310
820
73
16000
24
1700
130
32
760
130
6.5
74
860
24000
410
170
3.8
46
1400
44
23
22
130
600
170
91
30
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J+
J+
J+
J+
J+
J+
J+
J+
J+
J-
J-
J-
J-
J+
J-
J-
J-
J-
Comment
Code
j
j
j
j
j
i
j
j
j
j
i
j
j
j
j
j
j
i
j
j
j
j
i
j
j
j
j
j
j
i
j
ej
j
j
i
j,e
j
j
j
C-27
-------
TABLE 5: DATA QUALIFICATIONS: SERIAL DILUTION EXCEEDANCES (Continued)
Sample ID
SB-SO-15-XX
SB-SO-15-XX
SB-SO-15-XX
SB-SO-15-XX
SB-SO-15-XX
SB-SO-22-XX
SB-SO-22-XX
SB-SO-31-XX
SB-SO-31-XX
SB-SO-31-XX
SB-SO-31-XX
SB-SO-31-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
WS-SO-01-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
Analyte
Iron
Lead
Nickel
Vanadium
Zinc
Antimony
Zinc
Arsenic
Nickel
Selenium
Silver
Zinc
Antimony
Chromium
Copper
Iron
Lead
Silver
Vanadium
Mercury
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Vanadium
Zinc
Result
51000
40
100
52
36
10
64
8
3200
28
160
3900
95
36
4400
22000
1100
160
59
5.8
450
11
120
150
28000
3700
65
13
53
830
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J-
J-
J-
J-
J
J-
J-
J-
J-
J-
J-
J+
J+
J+
J+
J+
J
J+
J
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
Comment
Code
J
J
J
J
J
e,i
J
J
J
J
e,i
J
j,e
J
J
J
J
i,e
J
e,j
J
J
i
J
J
J
J
J
J
J
Notes:
mg/kg
e
j
J
J+
J-
Milligram per kilogram
Data were additionally qualified based on matrix spike/matrix spike duplicate exceedances
Data were qualified based on serial dilution exceedances
Result is estimated and biased could not be determined
Result is estimated and potentially biased high
Result is estimated and potentially biased low
C-28
-------
APPENDIX D
DEVELOPER AND REFERENCE LABORATORY DATA
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory
Blend
No.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
Sample ID
KP-SO-06-XX
KP-SO-10-XX
KP-SO-15-XX
KP-SO-18-XX
KP-SO-22-XX
KP-SO-06-RU
KP-SO-10-RU
KP-SO-15-RU
KP-SO-18-RU
KP-SO-22-RU
KP-SO-07-XX
KP-SO-13-XX
KP-SO-20-XX
KP-SO-24-XX
KP-SO-27-XX
KP-SO-29-XX
KP-SO-32-XX
KP-SO-07-RU
KP-SO-13-RU
KP-SO-20-RU
KP-SO-24-RU
KP-SO-27-RU
KP-SO-29-RU
KP-SO-32-RU
KP-SO-04-XX
KP-SO-16-XX
KP-SO-23-XX
KP-SO-26-XX
KP-SO-31-XX
KP-SO-04-RU
KP-SO-16-RU
KP-SO-23-RU
KP-SO-26-RU
KP-SO-31-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
8.1 J+
6.1 J+
6.3 J+
6.7 J+
8.3 J+
n.d.
n.d.
n.d.
n.d.
n.d.
17 J+
16 J+
19 J+
17 J+
15 J+
18 J+
16 J+
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
94 J+
93 J+
86 J+
90 J+
88
n.d.
n.d.
n.d.
n.d.
n.d.
As
1 J-
1 J-
1 J-
1 J-
1 J-
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
Sample ID
KP-SO-06-XX
KP-SO-10-XX
KP-SO-15-XX
KP-SO-18-XX
KP-SO-22-XX
KP-SO-06-RU
KP-SO-10-RU
KP-SO-15-RU
KP-SO-18-RU
KP-SO-22-RU
KP-SO-07-XX
KP-SO-13-XX
KP-SO-20-XX
KP-SO-24-XX
KP-SO-27-XX
KP-SO-29-XX
KP-SO-32-XX
KP-SO-07-RU
KP-SO-13-RU
KP-SO-20-RU
KP-SO-24-RU
KP-SO-27-RU
KP-SO-29-RU
KP-SO-32-RU
KP-SO-04-XX
KP-SO-16-XX
KP-SO-23-XX
KP-SO-26-XX
KP-SO-31-XX
KP-SO-04-RU
KP-SO-16-RU
KP-SO-23-RU
KP-SO-26-RU
KP-SO-31-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
140
150
170
120
130
160
180
174
133
139
87
90
79
78
87
73
88
104
91
126
98
129
105
127
93
100
91
110
68
77
89
77
71
97
Se
0.25 U
0.22 U
0.25 U
0.25 U
0.25 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Sample ID
KP-SO-02-XX
KP-SO-03-XX
KP-SO-05-XX
KP-SO-09-XX
KP-SO-21-XX
KP-SO-02-RU
KP-SO-03-RU
KP-SO-05-RU
KP-SO-09-RU
KP-SO-21-RU
WS-SO-06-XX
WS-SO-08-XX
WS-SO-12-XX
WS-SO-17-XX
WS-SO-27-XX
WS-SO-30-XX
WS-SO-35-XX
WS-SO-06-RU
WS-SO-08-RU
WS-SO-12-RU
WS-SO-17-RU
WS-SO-27-RU
WS-SO-30-RU
WS-SO-35-RU
WS-SO-03-XX
WS-SO-05-XX
WS-SO-09-XX
WS-SO-14-XX
WS-SO-26-XX
WS-SO-31-XX
WS-SO-33-XX
WS-SO-03-RU
WS-SO-05-RU
WS-SO-09-RU
WS-SO-14-RU
WS-SO-26-RU
WS-SO-31-RU
WS-SO-33-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
410
360
410
420
370
n.d.
n.d.
n.d.
n.d.
n.d.
1.3 U
1.3
1.3 UJ
1.3 UJ
1.3 UJ
1.2 J-
1.3 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
8.9 J-
8.6 J-
7.1 J-
8.4 J-
7.6 J-
7.2 J-
6.9 J-
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
As
10
9
12
11
10
28
32
35
20
29
48
45
43
47
49
51
49
50
49
48
62
52
73
78
500
440
480
430
520
520
450 J-
402
418
281
282
334
336
351
Cd
0.1
0.074 U
0.13 U
0.094 U
0.098 U
149
91
205
901
885
1.9
2
1.8
1.9
2
2
2
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Sample ID
KP-SO-02-XX
KP-SO-03-XX
KP-SO-05-XX
KP-SO-09-XX
KP-SO-21-XX
KP-SO-02-RU
KP-SO-03-RU
KP-SO-05-RU
KP-SO-09-RU
KP-SO-21-RU
WS-SO-06-XX
WS-SO-08-XX
WS-SO-12-XX
WS-SO-17-XX
WS-SO-27-XX
WS-SO-30-XX
WS-SO-35-XX
WS-SO-06-RU
WS-SO-08-RU
WS-SO-12-RU
WS-SO-17-RU
WS-SO-27-RU
WS-SO-30-RU
WS-SO-35-RU
WS-SO-03-XX
WS-SO-05-XX
WS-SO-09-XX
WS-SO-14-XX
WS-SO-26-XX
WS-SO-31-XX
WS-SO-33-XX
WS-SO-03-RU
WS-SO-05-RU
WS-SO-09-RU
WS-SO-14-RU
WS-SO-26-RU
WS-SO-31-RU
WS-SO-33-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
4
3
4
3
4
2
3
5
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
Sample ID
WS-SO-01-XX
WS-SO-04-XX
WS-SO-15-XX
WS-SO-22-XX
WS-SO-34-XX
WS-SO-01-RU
WS-SO-04-RU
WS-SO-15-RU
WS-SO-22-RU
WS-SO-34-RU
WS-SO-02-XX
WS-SO-16-XX
WS-SO-18-XX
WS-SO-21-XX
WS-SO-24-XX
WS-SO-29-XX
WS-SO-37-XX
WS-SO-02-RU
WS-SO-16-RU
WS-SO-18-RU
WS-SO-21-RU
WS-SO-24-RU
WS-SO-29-RU
WS-SO-37-RU
WS-SO-13-XX
WS-SO-19-XX
WS-SO-28-XX
WS-SO-32-XX
WS-SO-36-XX
WS-SO-13-RU
WS-SO-19-RU
WS-SO-28-RU
WS-SO-32-RU
WS-SO-36-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
41 J-
45 J-
48 J-
41 J-
45 J-
n.d.
n.d.
n.d.
n.d.
n.d.
130 J-
110 J-
130 J-
120 J-
97 J-
120 J-
120 J-
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
200 J-
150 J-
120 J-
190 J-
120 J-
n.d.
n.d.
n.d.
n.d.
n.d.
As
1900
2000
2300
1900
2000
1,907
1,890
1,496
1,553
2,095
4200
3900
4100
3900
3600
3800
4100
3,327
3,670
3,343
76
3,722
3,884
3,633
5800
5000
4200
5500
3800
5,274
4,034
6,204
4,168
5,987
Cd
47
50
56
47
50
346
432
161
399
365
98
91
95
90
81
90
95
803
827
998
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
Sample ID
WS-SO-01-XX
WS-SO-04-XX
WS-SO-15-XX
WS-SO-22-XX
WS-SO-34-XX
WS-SO-01-RU
WS-SO-04-RU
WS-SO-15-RU
WS-SO-22-RU
WS-SO-34-RU
WS-SO-02-XX
WS-SO-16-XX
WS-SO-18-XX
WS-SO-21-XX
WS-SO-24-XX
WS-SO-29-XX
WS-SO-37-XX
WS-SO-02-RU
WS-SO-16-RU
WS-SO-18-RU
WS-SO-21-RU
WS-SO-24-RU
WS-SO-29-RU
WS-SO-37-RU
WS-SO-13-XX
WS-SO-19-XX
WS-SO-28-XX
WS-SO-32-XX
WS-SO-36-XX
WS-SO-13-RU
WS-SO-19-RU
WS-SO-28-RU
WS-SO-32-RU
WS-SO-36-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
66
62
58
57
60
33
40
22
35
28
57
60
62
51
54
55
63
15
32
20
298
35
58
25
75
74
59
73
55
40
29
35
30
65
Se
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
10
10
10
10
10
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
12
12
12
12
12
Sample ID
BN-SO-01-XX
BN-SO-10-XX
BN-SO-15-XX
BN-SO-18-XX
BN-SO-28-XX
BN-SO-31-XX
BN-SO-35-XX
BN-SO-01-RU
BN-SO-10-RU
BN-SO-15-RU
BN-SO-18-RU
BN-SO-28-RU
BN-SO-31-RU
BN-SO-35-RU
BN-SO-02-XX
BN-SO-04-XX
BN-SO-17-XX
BN-SO-22-XX
BN-SO-27-XX
BN-SO-02-RU
BN-SO-04-RU
BN-SO-17-RU
BN-SO-22-RU
BN-SO-27-RU
BN-SO-03-XX
BN-SO-06-XX
BN-SO-08-XX
BN-SO-13-XX
BN-SO-20-XX
BN-SO-30-XX
BN-SO-34-XX
BN-SO-03-RU
BN-SO-06-RU
BN-SO-08-RU
BN-SO-13-RU
BN-SO-20-RU
BN-SO-30-RU
BN-SO-34-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 U
1.5
1.3
1.4
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
11
9.1
9.3
7.3
9.6
n.d.
n.d.
n.d.
n.d.
n.d.
65
60
57
65
57
64
68
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
As
38
50
34
37
35
41
37
45
3,042
53
41
42
40
38
140
120
110
98
110
112
132
126
99
126
620
600
570
320
540
630
630
642
490
751
506
583
572
586
Cd
0.94
1.2
0.82
0.89
0.87
1
0.98
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
10
10
10
10
10
10
10
10
10
10
10
10
10
10
11
11
11
11
11
11
11
11
11
11
12
12
12
12
12
12
12
12
12
12
12
12
12
12
Sample ID
BN-SO-01-XX
BN-SO-10-XX
BN-SO-15-XX
BN-SO-18-XX
BN-SO-28-XX
BN-SO-31-XX
BN-SO-35-XX
BN-SO-01-RU
BN-SO-10-RU
BN-SO-15-RU
BN-SO-18-RU
BN-SO-28-RU
BN-SO-31-RU
BN-SO-35-RU
BN-SO-02-XX
BN-SO-04-XX
BN-SO-17-XX
BN-SO-22-XX
BN-SO-27-XX
BN-SO-02-RU
BN-SO-04-RU
BN-SO-17-RU
BN-SO-22-RU
BN-SO-27-RU
BN-SO-03-XX
BN-SO-06-XX
BN-SO-08-XX
BN-SO-13-XX
BN-SO-20-XX
BN-SO-30-XX
BN-SO-34-XX
BN-SO-03-RU
BN-SO-06-RU
BN-SO-08-RU
BN-SO-13-RU
BN-SO-20-RU
BN-SO-30-RU
BN-SO-34-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
63
54
58
59
54
71
63
51
2,982
60
59
45
45
46
54
48
47
40
46
43
54
31
26
62
100
92
94
71
84
99
100
134
67
86
127
69
52
78
Se
1.3 U
1.2 J
1.3 U
1.3
1.3 U
1.3 U
1.2 J
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
Sample ID
BN-SO-07-XX
BN-SO-16-XX
BN-SO-21-XX
BN-SO-25-XX
BN-SO-33-XX
BN-SO-07-RU
BN-SO-16-RU
BN-SO-21-RU
BN-SO-25-RU
BN-SO-33-RU
BN-SO-05-XX
BN-SO-19-XX
BN-SO-26-XX
BN-SO-29-XX
BN-SO-32-XX
BN-SO-05-RU
BN-SO-19-RU
BN-SO-26-RU
BN-SO-29-RU
BN-SO-32-RU
CN-SO-01-XX
CN-SO-04-XX
CN-SO-08-XX
CN-SO-10-XX
CN-SO-11-XX
CN-SO-01-RU
CN-SO-04-RU
CN-SO-08-RU
CN-SO-10-RU
CN-SO-11-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
110 J-
120 J-
150 J-
82 J-
100 J-
n.d.
n.d.
n.d.
n.d.
n.d.
160 J-
150 J-
150 J-
150 J-
160 J-
n.d.
n.d.
n.d.
n.d.
n.d.
13 J-
13 J-
15 J-
13 J-
17 J-
n.d.
n.d.
n.d.
n.d.
n.d.
As
990 J+
1,100 J+
1,300 J+
700 J
1,100
978
1,106
1,380
938
952
1,600
1,600
1,700
1,600
1,600
1,700
1,472
1,451
1,593
1,584
13
11
15
13
16
6
9
3
5
6
Cd
520
570
660
370 J-
640
181
254
292
263
158
850
860
900
880
860
615
640
764
1,125
539
21
21
25
22
30
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
Sample ID
BN-SO-07-XX
BN-SO-16-XX
BN-SO-21-XX
BN-SO-25-XX
BN-SO-33-XX
BN-SO-07-RU
BN-SO-16-RU
BN-SO-21-RU
BN-SO-25-RU
BN-SO-33-RU
BN-SO-05-XX
BN-SO-19-XX
BN-SO-26-XX
BN-SO-29-XX
BN-SO-32-XX
BN-SO-05-RU
BN-SO-19-RU
BN-SO-26-RU
BN-SO-29-RU
BN-SO-32-RU
CN-SO-01-XX
CN-SO-04-XX
CN-SO-08-XX
CN-SO-10-XX
CN-SO-11-XX
CN-SO-01-RU
CN-SO-04-RU
CN-SO-08-RU
CN-SO-10-RU
CN-SO-11-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
120
130
160
88 J-
150
87
91
112
98
87
160
160
160
160
160
93
87
66
125
115
240
240
280
240
320
169
192
237
226
230
Se
26
29
35
19 J-
34
12
13
15
9
13
48
48
49
48
48
24
21
18
22
21
2.2
1.5
1.3 U
1.9
1.3 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
16
16
16
16
16
16
16
16
16
16
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
Sample ID
AS-SO-02-XX
AS-SO-06-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-13-XX
AS-SO-02-RU
AS-SO-06-RU
AS-SO-10-RU
AS-SO-11-RU
AS-SO-13-RU
AS-SO-01-XX
AS-SO-04-XX
AS-SO-07-XX
AS-SO-09-XX
AS-SO-12-XX
AS-SO-01-RU
AS-SO-04-RU
AS-SO-07-RU
AS-SO-09-RU
AS-SO-12-RU
SB-SO-03-XX
SB-SO-06-XX
SB-SO-14-XX
SB-SO-38-XX
SB-SO-41-XX
SB-SO-47-XX
SB-SO-51-XX
SB-SO-03-RU
SB-SO-06-RU
SB-SO-14-RU
SB-SO-38-RU
SB-SO-41-RU
SB-SO-47-RU
SB-SO-51-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
2.6 UJ
2.4 UJ
1.9 J-
3.7 J-
2.4 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
3.8 J-
6.4 UJ
3.6 J-
2.6 UJ
2.6 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
1.2 UJ
1.7 J-
4.1 J-
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
As
18
19
18
22
20
6
3
3
4
4
26
22
21
25 J-
29
1
3
1
1
1
9
8
9
10
9
8
9
17
18
18
13
18
25
22
Cd
50
52
48
63
57
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
16
16
16
16
16
16
16
16
16
16
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
Sample ID
AS-SO-02-XX
AS-SO-06-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-13-XX
AS-SO-02-RU
AS-SO-06-RU
AS-SO-10-RU
AS-SO-11-RU
AS-SO-13-RU
AS-SO-01-XX
AS-SO-04-XX
AS-SO-07-XX
AS-SO-09-XX
AS-SO-12-XX
AS-SO-01-RU
AS-SO-04-RU
AS-SO-07-RU
AS-SO-09-RU
AS-SO-12-RU
SB-SO-03-XX
SB-SO-06-XX
SB-SO-14-XX
SB-SO-38-XX
SB-SO-41-XX
SB-SO-47-XX
SB-SO-51-XX
SB-SO-03-RU
SB-SO-06-RU
SB-SO-14-RU
SB-SO-38-RU
SB-SO-41-RU
SB-SO-47-RU
SB-SO-51-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
91
93
84
120
100
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
19
19
19
19
19
19
19
19
19
19
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
Sample ID
SB-SO-05-XX
SB-SO-18-XX
SB-SO-30-XX
SB-SO-40-XX
SB-SO-53-XX
SB-SO-05-RU
SB-SO-18-RU
SB-SO-30-RU
SB-SO-40-RU
SB-SO-53-RU
SB-SO-08-XX
SB-SO-11-XX
SB-SO-21-XX
SB-SO-39-XX
SB-SO-42-XX
SB-SO-08-RU
SB-SO-11-RU
SB-SO-21-RU
SB-SO-39-RU
SB-SO-42-RU
SB-SO-22-XX
SB-SO-25-XX
SB-SO-27-XX
SB-SO-35-XX
SB-SO-44-XX
SB-SO-22-RU
SB-SO-25-RU
SB-SO-27-RU
SB-SO-35-RU
SB-SO-44-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
1.6 J-
1.2 UJ
3.2 J-
2.2 J-
1.2 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
5.4 J-
5.7 J-
4.9 J
4.7 J-
4.6 J-
n.d.
n.d.
n.d.
n.d.
n.d.
10 J
6.8 J+
6.7 J+
6 J+
6.8 J+
n.d.
n.d.
n.d.
n.d.
n.d.
As
9
10
7
9
10
22
19
13
21
14
13
13
13
13
13
27
24
19
25
29
18
18
18
17
18
29
24
21
27
31
Cd
0.51 U
0.51 U
0.51 U
0.51 U
0.51 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
19
19
19
19
19
19
19
19
19
19
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
Sample ID
SB-SO-05-XX
SB-SO-18-XX
SB-SO-30-XX
SB-SO-40-XX
SB-SO-53-XX
SB-SO-05-RU
SB-SO-18-RU
SB-SO-30-RU
SB-SO-40-RU
SB-SO-53-RU
SB-SO-08-XX
SB-SO-11-XX
SB-SO-21-XX
SB-SO-39-XX
SB-SO-42-XX
SB-SO-08-RU
SB-SO-11-RU
SB-SO-21-RU
SB-SO-39-RU
SB-SO-42-RU
SB-SO-22-XX
SB-SO-25-XX
SB-SO-27-XX
SB-SO-35-XX
SB-SO-44-XX
SB-SO-22-RU
SB-SO-25-RU
SB-SO-27-RU
SB-SO-35-RU
SB-SO-44-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
200
210
120
180
200
180
178
141
225
136
180
200
190
200
200
214
208
232
177
226
160
160
170
160
170
146
122
136
216
235
Se
1.3 U
1.3 U
1.3 J+
1.3 U
1.3 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
24
24
24
24
24
24
24
24
24
24
Sample ID
SB-SO-23-XX
SB-SO-28-XX
SB-SO-32-XX
SB-SO-43-XX
SB-SO-48-XX
SB-SO-23-RU
SB-SO-28-RU
SB-SO-32-RU
SB-SO-43-RU
SB-SO-48-RU
SB-SO-02-XX
SB-SO-07-XX
SB-SO-10-XX
SB-SO-26-XX
SB-SO-50-XX
SB-SO-02-RU
SB-SO-07-RU
SB-SO-10-RU
SB-SO-26-RU
SB-SO-50-RU
SB-SO-01-XX
SB-SO-16-XX
SB-SO-24-XX
SB-SO-45-XX
SB-SO-52-XX
SB-SO-01-RU
SB-SO-16-RU
SB-SO-24-RU
SB-SO-45-RU
SB-SO-52-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
48 J-
42 J-
46 J-
40 J-
39 J-
n.d.
n.d.
n.d.
n.d.
n.d.
44 J-
45 J
62 J
61 J
57 J
n.d.
n.d.
n.d.
n.d.
n.d.
180 J
170 J
180 J
180 J
150 J
n.d.
n.d.
n.d.
n.d.
n.d.
As
37
36
40
35
36
72
37
60
52
61
23 J-
22
26
30
27
34
45
33
31
50
65
64
66
63
62
86
71
75
85
77
Cd
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
24
24
24
24
24
24
24
24
24
24
Sample ID
SB-SO-23-XX
SB-SO-28-XX
SB-SO-32-XX
SB-SO-43-XX
SB-SO-48-XX
SB-SO-23-RU
SB-SO-28-RU
SB-SO-32-RU
SB-SO-43-RU
SB-SO-48-RU
SB-SO-02-XX
SB-SO-07-XX
SB-SO-10-XX
SB-SO-26-XX
SB-SO-50-XX
SB-SO-02-RU
SB-SO-07-RU
SB-SO-10-RU
SB-SO-26-RU
SB-SO-50-RU
SB-SO-01-XX
SB-SO-16-XX
SB-SO-24-XX
SB-SO-45-XX
SB-SO-52-XX
SB-SO-01-RU
SB-SO-16-RU
SB-SO-24-RU
SB-SO-45-RU
SB-SO-52-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
26
26
28
24
25
14
14
37
17
16
180
170
200
220
200
182
181
157
153
232
190
190
200
190
190
157
166
143
181
167
Se
0.22 J
0.26 U
0.36
0.26 U
0.26 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
25
25
25
25
25
25
25
25
25
25
26
26
26
26
26
26
26
26
26
26
27
27
27
27
27
27
27
27
27
27
Sample ID
SB-SO-13-XX
SB-SO-19-XX
SB-SO-33-XX
SB-SO-37-XX
SB-SO-55-XX
SB-SO-13-RU
SB-SO-19-RU
SB-SO-33-RU
SB-SO-37-RU
SB-SO-55-RU
SB-SO-12-XX
SB-SO-15-XX
SB-SO-17-XX
SB-SO-46-XX
SB-SO-54-XX
SB-SO-12-RU
SB-SO-15-RU
SB-SO-17-RU
SB-SO-46-RU
SB-SO-54-RU
KP-SE-08-XX
KP-SE-11-XX
KP-SE-17-XX
KP-SE-25-XX
KP-SE-30-XX
KP-SE-08-RU
KP-SE-11-RU
KP-SE-17-RU
KP-SE-25-RU
KP-SE-30-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
430 J
310 J
350 J
340 J
340 J
n.d.
n.d.
n.d.
n.d.
n.d.
620 J
600 J-
800 J+
740 J+
280
n.d.
n.d.
n.d.
n.d.
n.d.
6.2
5.6
4.9
6
5.7
n.d.
n.d.
n.d.
n.d.
n.d.
As
160
100
110
130
120
152
104
140
145
133
190
170 J-
210
190
31
217
174
161
190
210
3
3
3
3
3
1
3
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
25
25
25
25
25
25
25
25
25
25
26
26
26
26
26
26
26
26
26
26
27
27
27
27
27
27
27
27
27
27
Sample ID
SB-SO-13-XX
SB-SO-19-XX
SB-SO-33-XX
SB-SO-37-XX
SB-SO-55-XX
SB-SO-13-RU
SB-SO-19-RU
SB-SO-33-RU
SB-SO-37-RU
SB-SO-55-RU
SB-SO-12-XX
SB-SO-15-XX
SB-SO-17-XX
SB-SO-46-XX
SB-SO-54-XX
SB-SO-12-RU
SB-SO-15-RU
SB-SO-17-RU
SB-SO-46-RU
SB-SO-54-RU
KP-SE-08-XX
KP-SE-11-XX
KP-SE-17-XX
KP-SE-25-XX
KP-SE-30-XX
KP-SE-08-RU
KP-SE-11-RU
KP-SE-17-RU
KP-SE-25-RU
KP-SE-30-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
180
120
130
150
140
138
114
429
152
122
110
100 J-
120
120
20
125
87
81
89
84
42
46
47
47
39
61
47
45
50
63
Se
4.4
2.5
3
2.5 U
2.5
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
28
28
28
28
28
28
28
28
28
28
29
29
29
29
29
29
29
29
29
29
29
29
29
29
30
30
30
30
30
30
30
30
30
30
Sample ID
KP-SE-01-XX
KP-SE-12-XX
KP-SE-14-XX
KP-SE-19-XX
KP-SE-28-XX
KP-SE-01-RU
KP-SE-12-RU
KP-SE-14-RU
KP-SE-19-RU
KP-SE-28-RU
TL-SE-04-XX
TL-SE-10-XX
TL-SE-12-XX
TL-SE-15-XX
TL-SE-20-XX
TL-SE-24-XX
TL-SE-26-XX
TL-SE-04-RU
TL-SE-10-RU
TL-SE-12-RU
TL-SE-15-RU
TL-SE-20-RU
TL-SE-24-RU
TL-SE-26-RU
TL-SE-03-XX
TL-SE-19-XX
TL-SE-23-XX
TL-SE-25-XX
TL-SE-31-XX
TL-SE-03-RU
TL-SE-19-RU
TL-SE-23-RU
TL-SE-25-RU
TL-SE-31-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
3.2
3.1
11 J-
3
3.3
n.d.
n.d.
n.d.
n.d.
n.d.
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
2.5 U
2.5 U
2.5 U
2.5 U
2.5 U
n.d.
n.d.
n.d.
n.d.
n.d.
As
2
2
2
2
2
2
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
28
28
28
28
28
28
28
28
28
28
29
29
29
29
29
29
29
29
29
29
29
29
29
29
30
30
30
30
30
30
30
30
30
30
Sample ID
KP-SE-01-XX
KP-SE-12-XX
KP-SE-14-XX
KP-SE-19-XX
KP-SE-28-XX
KP-SE-01-RU
KP-SE-12-RU
KP-SE-14-RU
KP-SE-19-RU
KP-SE-28-RU
TL-SE-04-XX
TL-SE-10-XX
TL-SE-12-XX
TL-SE-15-XX
TL-SE-20-XX
TL-SE-24-XX
TL-SE-26-XX
TL-SE-04-RU
TL-SE-10-RU
TL-SE-12-RU
TL-SE-15-RU
TL-SE-20-RU
TL-SE-24-RU
TL-SE-26-RU
TL-SE-03-XX
TL-SE-19-XX
TL-SE-23-XX
TL-SE-25-XX
TL-SE-31-XX
TL-SE-03-RU
TL-SE-19-RU
TL-SE-23-RU
TL-SE-25-RU
TL-SE-31-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
16
20
23 J-
22
22
20
22
21
17
23
71
72
75
63
74
77
70
54
33
94
30
82
61
56
110
120
110
110
130
63
93
99
92
101
Se
0.26 U
0.26 U
0.26 U
0.26 U
0.26 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
31
31
31
31
31
31
31
31
31
31
31
31
31
31
32
32
32
32
32
32
32
32
32
32
32
32
32
32
33
33
33
33
33
33
33
33
33
33
Sample ID
TL-SE-01-XX
TL-SE-11-XX
TL-SE-14-XX
TL-SE-18-XX
TL-SE-22-XX
TL-SE-27-XX
TL-SE-29-XX
TL-SE-01-RU
TL-SE-11-RU
TL-SE-14-RU
TL-SE-18-RU
TL-SE-22-RU
TL-SE-27-RU
TL-SE-29-RU
LV-SE-02-XX
LV-SE-10-XX
LV-SE-22-XX
LV-SE-25-XX
LV-SE-31-XX
LV-SE-35-XX
LV-SE-50-XX
LV-SE-02-RU
LV-SE-10-RU
LV-SE-22-RU
LV-SE-25-RU
LV-SE-31-RU
LV-SE-35-RU
LV-SE-50-RU
LV-SE-12-XX
LV-SE-26-XX
LV-SE-33-XX
LV-SE-39-XX
LV-SE-42-XX
LV-SE-12-RU
LV-SE-26-RU
LV-SE-33-RU
LV-SE-39-RU
LV-SE-42-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
2.5 U
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
2.6 U
2.6 U
2.6 U
2.6 U
2.7 U
n.d.
n.d.
n.d.
n.d.
n.d.
As
9
15
10
10
11
10
11
7
5
4
4
11
6
8
28
34
30
31
32
31 J-
29
25
44
30
39
29
38
31
190
220
170
190
170
247
201
185
191
145
Cd
0.5 U
0.5 U
0.27 J
0.5 U
0.5 U
0.28 J
0.22 J
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
31
31
31
31
31
31
31
31
31
31
31
31
31
31
32
32
32
32
32
32
32
32
32
32
32
32
32
32
33
33
33
33
33
33
33
33
33
33
Sample ID
TL-SE-01-XX
TL-SE-11-XX
TL-SE-14-XX
TL-SE-18-XX
TL-SE-22-XX
TL-SE-27-XX
TL-SE-29-XX
TL-SE-01-RU
TL-SE-11-RU
TL-SE-14-RU
TL-SE-18-RU
TL-SE-22-RU
TL-SE-27-RU
TL-SE-29-RU
LV-SE-02-XX
LV-SE-10-XX
LV-SE-22-XX
LV-SE-25-XX
LV-SE-31-XX
LV-SE-35-XX
LV-SE-50-XX
LV-SE-02-RU
LV-SE-10-RU
LV-SE-22-RU
LV-SE-25-RU
LV-SE-31-RU
LV-SE-35-RU
LV-SE-50-RU
LV-SE-12-XX
LV-SE-26-XX
LV-SE-33-XX
LV-SE-39-XX
LV-SE-42-XX
LV-SE-12-RU
LV-SE-26-RU
LV-SE-33-RU
LV-SE-39-RU
LV-SE-42-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
180
210
180
190
210
200
200
113
80
57
92
216
215
121
160
200
170
170
180
170 J-
170
110
129
137
119
123
86
83
71
83
66
74
67
92
67
37
53
74
Se
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
34
34
34
34
34
34
34
34
34
34
35
35
35
35
35
35
35
35
35
35
36
36
36
36
36
36
36
36
36
36
Sample ID
LV-SE-09-XX
LV-SE-19-XX
LV-SE-27-XX
LV-SE-36-XX
LV-SE-38-XX
LV-SE-09-RU
LV-SE-19-RU
LV-SE-27-RU
LV-SE-36-RU
LV-SE-38-RU
LV-SE-07-XX
LV-SE-18-XX
LV-SE-23-XX
LV-SE-45-XX
LV-SE-48-XX
LV-SE-07-RU
LV-SE-18-RU
LV-SE-23-RU
LV-SE-45-RU
LV-SE-48-RU
LV-SE-01-XX
LV-SE-14-XX
LV-SE-21-XX
LV-SE-24-XX
LV-SE-32-XX
LV-SE-01-RU
LV-SE-14-RU
LV-SE-21-RU
LV-SE-24-RU
LV-SE-32-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
6.7 U
6.7 U
6.7 U
6.7 U
6.7 U
n.d.
n.d.
n.d.
n.d.
n.d.
6.7 UJ
6.7 UJ
6.6 UJ
6.7 UJ
6.6 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
1.5 UJ
1.5 UJ
1.5 UJ
1.5 UJ
1.4 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
As
450
500
530
550
480
595
541
424
455
505
780
800
660
650
680
825
775
772
667
653
6
5
7
5
6
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
34
34
34
34
34
34
34
34
34
34
35
35
35
35
35
35
35
35
35
35
36
36
36
36
36
36
36
36
36
36
Sample ID
LV-SE-09-XX
LV-SE-19-XX
LV-SE-27-XX
LV-SE-36-XX
LV-SE-38-XX
LV-SE-09-RU
LV-SE-19-RU
LV-SE-27-RU
LV-SE-36-RU
LV-SE-38-RU
LV-SE-07-XX
LV-SE-18-XX
LV-SE-23-XX
LV-SE-45-XX
LV-SE-48-XX
LV-SE-07-RU
LV-SE-18-RU
LV-SE-23-RU
LV-SE-45-RU
LV-SE-48-RU
LV-SE-01-XX
LV-SE-14-XX
LV-SE-21-XX
LV-SE-24-XX
LV-SE-32-XX
LV-SE-01-RU
LV-SE-14-RU
LV-SE-21-RU
LV-SE-24-RU
LV-SE-32-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
55
65
64
70
75
160
61
54
45
23
58
60
50 J
50 J
50 J
70
46
54
25
19
49
46
49
44
47
44
39
40
38
32
Se
6.7 U
5.9 J
6.7 U
11
6.7 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
37
37
37
37
37
37
37
37
37
37
38
38
38
38
38
38
38
38
38
38
39
39
39
39
39
39
39
39
39
39
39
39
39
39
Sample ID
LV-SE-08-XX
LV-SE-16-XX
LV-SE-28-XX
LV-SE-30-XX
LV-SE-47-XX
LV-SE-08-RU
LV-SE-16-RU
LV-SE-28-RU
LV-SE-30-RU
LV-SE-47-RU
LV-SE-11-XX
LV-SE-29-XX
LV-SE-44-XX
LV-SE-46-XX
LV-SE-52-XX
LV-SE-11-RU
LV-SE-29-RU
LV-SE-44-RU
LV-SE-46-RU
LV-SE-52-RU
RF-SE-07-XX
RF-SE-12-XX
RF-SE-23-XX
RF-SE-36-XX
RF-SE-42-XX
RF-SE-45-XX
RF-SE-53-XX
RF-SE-07-RU
RF-SE-12-RU
RF-SE-23-RU
RF-SE-36-RU
RF-SE-42-RU
RF-SE-45-RU
RF-SE-53-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
1.4 UJ
1.4 UJ
1.4 U
0.88 U
1.4 U
n.d.
n.d.
n.d.
n.d.
n.d.
1.3 U
1.2 U
0.25 U
1.2 U
1.3 UJ
1.3 UJ
1.3 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
As
30
29
31
30
31
42
33
27
39
28
150
150
140
110
160
147
138
151
117
149
12
14
0 U
12
14
15
14
21
27
5
21
16
20
15
Cd
0.52 U
0.52 U
0.52 U
0.52 U
0.52 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
37
37
37
37
37
37
37
37
37
37
38
38
38
38
38
38
38
38
38
38
39
39
39
39
39
39
39
39
39
39
39
39
39
39
Sample ID
LV-SE-08-XX
LV-SE-16-XX
LV-SE-28-XX
LV-SE-30-XX
LV-SE-47-XX
LV-SE-08-RU
LV-SE-16-RU
LV-SE-28-RU
LV-SE-30-RU
LV-SE-47-RU
LV-SE-11-XX
LV-SE-29-XX
LV-SE-44-XX
LV-SE-46-XX
LV-SE-52-XX
LV-SE-11-RU
LV-SE-29-RU
LV-SE-44-RU
LV-SE-46-RU
LV-SE-52-RU
RF-SE-07-XX
RF-SE-12-XX
RF-SE-23-XX
RF-SE-36-XX
RF-SE-42-XX
RF-SE-45-XX
RF-SE-53-XX
RF-SE-07-RU
RF-SE-12-RU
RF-SE-23-RU
RF-SE-36-RU
RF-SE-42-RU
RF-SE-45-RU
RF-SE-53-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
110
110
120
120
120
100
120
104
90
84
870
860
830
660
910
883
821
946
772
952
180
210
2 U
180
210
220
210
137
175
120
170
132
100
140
Se
4.8
5
5.8
5.6
4.2
1
2
1
2
2
1.3 U
1.2 U
1.4 U
0.88 U
1.4 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
40
40
40
40
40
40
40
40
40
40
41
41
41
41
41
41
41
41
41
41
42
42
42
42
42
42
42
42
42
42
Sample ID
RF-SE-03-XX
RF-SE-28-XX
RF-SE-38-XX
RF-SE-49-XX
RF-SE-55-XX
RF-SE-03-RU
RF-SE-28-RU
RF-SE-38-RU
RF-SE-49-RU
RF-SE-55-RU
RF-SE-06-XX
RF-SE-13-XX
RF-SE-27-XX
RF-SE-31-XX
RF-SE-58-XX
RF-SE-06-RU
RF-SE-13-RU
RF-SE-27-RU
RF-SE-31-RU
RF-SE-58-RU
RF-SE-02-XX
RF-SE-22-XX
RF-SE-25-XX
RF-SE-30-XX
RF-SE-57-XX
RF-SE-02-RU
RF-SE-22-RU
RF-SE-25-RU
RF-SE-30-RU
RF-SE-57-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
As
27
31
27
31
24
21
19
44
28
26
70
76
64
39
71
52
93
90
79
50
110
99
88
89
89
75
83
83
68
74
Cd
1.3
1.5
1.2
1.5
1.1
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
40
40
40
40
40
40
40
40
40
40
41
41
41
41
41
41
41
41
41
41
42
42
42
42
42
42
42
42
42
42
Sample ID
RF-SE-03-XX
RF-SE-28-XX
RF-SE-38-XX
RF-SE-49-XX
RF-SE-55-XX
RF-SE-03-RU
RF-SE-28-RU
RF-SE-38-RU
RF-SE-49-RU
RF-SE-55-RU
RF-SE-06-XX
RF-SE-13-XX
RF-SE-27-XX
RF-SE-31-XX
RF-SE-58-XX
RF-SE-06-RU
RF-SE-13-RU
RF-SE-27-RU
RF-SE-31-RU
RF-SE-58-RU
RF-SE-02-XX
RF-SE-22-XX
RF-SE-25-XX
RF-SE-30-XX
RF-SE-57-XX
RF-SE-02-RU
RF-SE-22-RU
RF-SE-25-RU
RF-SE-30-RU
RF-SE-57-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
150
160
140
170
140
108
138
108
115
95
150
160
130
86
150
78
82
150
85
77
180
160
140
150
150
67
70
80
90
71
Se
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
43
43
43
43
43
43
43
43
43
43
44
44
44
44
44
44
44
44
44
44
45
45
45
45
45
45
45
45
45
45
Sample ID
RF-SE-15-XX
RF-SE-24-XX
RF-SE-32-XX
RF-SE-43-XX
RF-SE-59-XX
RF-SE-15-RU
RF-SE-24-RU
RF-SE-32-RU
RF-SE-43-RU
RF-SE-59-RU
RF-SE-05-XX
RF-SE-26-XX
RF-SE-39-XX
RF-SE-44-XX
RF-SE-56-XX
RF-SE-05-RU
RF-SE-26-RU
RF-SE-39-RU
RF-SE-44-RU
RF-SE-56-RU
RF-SE-04-XX
RF-SE-14-XX
RF-SE-19-XX
RF-SE-34-XX
RF-SE-52-XX
RF-SE-04-RU
RF-SE-14-RU
RF-SE-19-RU
RF-SE-34-RU
RF-SE-52-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
n.d.
n.d.
n.d.
n.d.
n.d.
4.1 J+
2.2 J+
2.9 J+
2.7 J+
3.5 J+
n.d.
n.d.
n.d.
n.d.
n.d.
3.2 J+
4.4 J+
3.7 J+
2.9 J+
3.4 J+
n.d.
n.d.
n.d.
n.d.
n.d.
As
120
130 J+
120
130
140
174
122
167
123
140
160
140
160
140
180
163
218
304
180
135
230
260
250
210
220
227
216
265
246
197
Cd
6.2
6.5 J+
5.1
5.7
5.9
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
43
43
43
43
43
43
43
43
43
43
44
44
44
44
44
44
44
44
44
44
45
45
45
45
45
45
45
45
45
45
Sample ID
RF-SE-15-XX
RF-SE-24-XX
RF-SE-32-XX
RF-SE-43-XX
RF-SE-59-XX
RF-SE-15-RU
RF-SE-24-RU
RF-SE-32-RU
RF-SE-43-RU
RF-SE-59-RU
RF-SE-05-XX
RF-SE-26-XX
RF-SE-39-XX
RF-SE-44-XX
RF-SE-56-XX
RF-SE-05-RU
RF-SE-26-RU
RF-SE-39-RU
RF-SE-44-RU
RF-SE-56-RU
RF-SE-04-XX
RF-SE-14-XX
RF-SE-19-XX
RF-SE-34-XX
RF-SE-52-XX
RF-SE-04-RU
RF-SE-14-RU
RF-SE-19-RU
RF-SE-34-RU
RF-SE-52-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
160
170 J+
140
150
160
110
68
171
82
67
150
140
150
140
160
49
158
116
72
100
130
140
140
120
130
61
49
62
77
71
Se
1.4
1.3 U
1.3 U
1.3 U
1.3 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
46
46
46
46
46
46
47
47
47
47
47
47
48
48
48
48
48
48
49
49
49
49
49
49
50
50
50
50
50
50
Sample ID
BN-SO-11-XX
BN-SO-14-XX
BN-SO-23-XX
BN-SO-11-RU
BN-SO-14-RU
BN-SO-23-RU
BN-SO-09-XX
BN-SO-12-XX
BN-SO-24-XX
BN-SO-09-RU
BN-SO-12-RU
BN-SO-24-RU
SB-SO-09-XX
SB-SO-20-XX
SB-SO-31-XX
SB-SO-09-RU
SB-SO-20-RU
SB-SO-31-RU
SB-SO-29-XX
SB-SO-36-XX
SB-SO-56-XX
SB-SO-29-RU
SB-SO-36-RU
SB-SO-56-RU
SB-SO-04-XX
SB-SO-34-XX
SB-SO-49-XX
SB-SO-04-RU
SB-SO-34-RU
SB-SO-49-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
4 J-
3.5 J-
1.2 UJ
n.d.
n.d.
n.d.
750 J-
750 J-
810 J-
n.d.
n.d.
n.d.
1.3 UJ
1.3 UJ
1.3 UJ
n.d.
n.d.
n.d.
1.2 U
1.2 U
1.2 U
n.d.
n.d.
n.d.
940
980
700
n.d.
n.d.
n.d.
As
2,900
2,800
2,800
47
3,318
2,830
97
89
97
54
64
54
9
11
8 J-
19
12
11
9
8
10
14
14
10
13
12
12
15
24
15
Cd
720
690
700
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
46
46
46
46
46
46
47
47
47
47
47
47
48
48
48
48
48
48
49
49
49
49
49
49
50
50
50
50
50
50
Sample ID
BN-SO-11-XX
BN-SO-14-XX
BN-SO-23-XX
BN-SO-11-RU
BN-SO-14-RU
BN-SO-23-RU
BN-SO-09-XX
BN-SO-12-XX
BN-SO-24-XX
BN-SO-09-RU
BN-SO-12-RU
BN-SO-24-RU
SB-SO-09-XX
SB-SO-20-XX
SB-SO-31-XX
SB-SO-09-RU
SB-SO-20-RU
SB-SO-31-RU
SB-SO-29-XX
SB-SO-36-XX
SB-SO-56-XX
SB-SO-29-RU
SB-SO-36-RU
SB-SO-56-RU
SB-SO-04-XX
SB-SO-34-XX
SB-SO-49-XX
SB-SO-04-RU
SB-SO-34-RU
SB-SO-49-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
2,900
2,800
2,800
63
2,924
2,986
1,500
1,400
1,600
1,399
1,594
1,464
2900
3700
3200 J-
2,958
3,188
1,984
200
160
210
195
202
156
3,300
3,000
2,800
2,524
3,632
3,447
Se
140
130
130
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
51
51
51
51
51
51
52
52
52
52
52
52
53
53
53
53
53
53
54
54
54
54
54
54
55
55
55
55
55
55
Sample ID
WS-SO-07-XX
WS-SO-11-XX
WS-SO-25-XX
WS-SO-07-RU
WS-SO-11-RU
WS-SO-25-RU
WS-SO-10-XX
WS-SO-20-XX
WS-SO-23-XX
WS-SO-10-RU
WS-SO-20-RU
WS-SO-23-RU
AS-SO-03-XX
AS-SO-05-XX
AS-SO-08-XX
AS-SO-03-RU
AS-SO-05-RU
AS-SO-08-RU
LV-SO-03-XX
LV-SO-40-XX
LV-SO-49-XX
LV-SO-03-RU
LV-SO-40-RU
LV-SO-49-RU
LV-SO-04-XX
LV-SO-34-XX
LV-SO-37-XX
LV-SO-04-RU
LV-SO-34-RU
LV-SO-37-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
3.8
1.2 U
1.2 U
n.d.
n.d.
n.d.
1.3 U
1.3 U
1.3 U
n.d.
n.d.
n.d.
1.2 U
1.2 U
1.2 U
n.d.
n.d.
n.d.
1.6
2.7
7.4
n.d.
n.d.
n.d.
860
870 J-
590
n.d.
n.d.
n.d.
As
53
46
59
48
47
68
83
100
110
66
2,876
69
14
9
10
10
10
6
42
42
43
41
54
52
120
110 J-
84
174
133
107
Cd
1.9
1.4
3.1
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
51
51
51
51
51
51
52
52
52
52
52
52
53
53
53
53
53
53
54
54
54
54
54
54
55
55
55
55
55
55
Sample ID
WS-SO-07-XX
WS-SO-11-XX
WS-SO-25-XX
WS-SO-07-RU
WS-SO-11-RU
WS-SO-25-RU
WS-SO-10-XX
WS-SO-20-XX
WS-SO-23-XX
WS-SO-10-RU
WS-SO-20-RU
WS-SO-23-RU
AS-SO-03-XX
AS-SO-05-XX
AS-SO-08-XX
AS-SO-03-RU
AS-SO-05-RU
AS-SO-08-RU
LV-SO-03-XX
LV-SO-40-XX
LV-SO-49-XX
LV-SO-03-RU
LV-SO-40-RU
LV-SO-49-RU
LV-SO-04-XX
LV-SO-34-XX
LV-SO-37-XX
LV-SO-04-RU
LV-SO-34-RU
LV-SO-37-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
260
240
300
211
260
281
290
350
380
327
21
296
520
370
380
206
207
168
2,000
1,900
2,000
2,124
2,344
1,100
2,000
1,900 J-
1,400
2,235
2,136
1,496
Se
1.2 U
1.2 U
1.2 U
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
56
56
56
56
56
56
57
57
57
57
57
57
58
58
58
58
58
58
59
59
59
59
59
59
60
60
60
60
60
60
61
61
61
61
61
61
Sample ID
CN-SO-03-XX
CN-SO-06-XX
CN-SO-07-XX
CN-SO-03-RU
CN-SO-06-RU
CN-SO-07-RU
CN-SO-02-XX
CN-SO-05-XX
CN-SO-09-XX
CN-SO-02-RU
CN-SO-05-RU
CN-SO-09-RU
LV-SE-06-XX
LV-SE-13-XX
LV-SE-41-XX
LV-SE-06-RU
LV-SE-13-RU
LV-SE-41-RU
LV-SE-05-XX
LV-SE-20-XX
LV-SE-43-XX
LV-SE-05-RU
LV-SE-20-RU
LV-SE-43-RU
LV-SE-15-XX
LV-SE-17-XX
LV-SE-51-XX
LV-SE-15-RU
LV-SE-17-RU
LV-SE-51-RU
TL-SE-05-XX
TL-SE-09-XX
TL-SE-13-XX
TL-SE-05-RU
TL-SE-09-RU
TL-SE-13-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
22
20
20
n.d.
n.d.
n.d.
230
130
120
n.d.
n.d.
n.d.
30
31
30
n.d.
n.d.
n.d.
92
140 J+
160 J+
n.d.
n.d.
n.d.
290 J+
280 J+
210 J+
n.d.
n.d.
n.d.
100 J+
100 J+
95 J+
n.d.
n.d.
n.d.
As
87
91
90
109
106
105
19
6
6
10
11
11
23
24
21
96
52
40
20
31
24
33
27
14
32
31
26
47
51
27
34
33
31
74
25
30
Cd
63
64
63
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
56
56
56
56
56
56
57
57
57
57
57
57
58
58
58
58
58
58
59
59
59
59
59
59
60
60
60
60
60
60
61
61
61
61
61
61
Sample ID
CN-SO-03-XX
CN-SO-06-XX
CN-SO-07-XX
CN-SO-03-RU
CN-SO-06-RU
CN-SO-07-RU
CN-SO-02-XX
CN-SO-05-XX
CN-SO-09-XX
CN-SO-02-RU
CN-SO-05-RU
CN-SO-09-RU
LV-SE-06-XX
LV-SE-13-XX
LV-SE-41-XX
LV-SE-06-RU
LV-SE-13-RU
LV-SE-41-RU
LV-SE-05-XX
LV-SE-20-XX
LV-SE-43-XX
LV-SE-05-RU
LV-SE-20-RU
LV-SE-43-RU
LV-SE-15-XX
LV-SE-17-XX
LV-SE-51-XX
LV-SE-15-RU
LV-SE-17-RU
LV-SE-51-RU
TL-SE-05-XX
TL-SE-09-XX
TL-SE-13-XX
TL-SE-05-RU
TL-SE-09-RU
TL-SE-13-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
74
76
75
92
100
86
530
360
330
311
344
328
360
360
320
389
369
338
400
660
530
471
537
463
230
220
200
158
190
136
54
53
49
37
13
20
Se
36
38
37
40
38
39
190
190
170
160
180
174
160
160
150
180
189
176
340
500
420
496
466
414
92
89
76
72
76
68
130
130
120
43
59
60
Ag
90
94
91
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
62
62
62
62
62
62
63
63
63
63
63
63
64
64
64
64
64
64
65
65
65
65
65
65
65
65
65
65
65
65
65
65
Sample ID
TL-SE-06-XX
TL-SE-17-XX
TL-SE-28-XX
TL-SE-06-RU
TL-SE-17-RU
TL-SE-28-RU
TL-SE-07-XX
TL-SE-21-XX
TL-SE-30-XX
TL-SE-07-RU
TL-SE-21-RU
TL-SE-30-RU
TL-SE-02-XX
TL-SE-08-XX
TL-SE-16-XX
TL-SE-02-RU
TL-SE-08-RU
TL-SE-16-RU
RF-SE-01-XX
RF-SE-09-XX
RF-SE-11-XX
RF-SE-17-XX
RF-SE-29-XX
RF-SE-37-XX
RF-SE-50-XX
RF-SE-01-RU
RF-SE-09-RU
RF-SE-11-RU
RF-SE-17-RU
RF-SE-29-RU
RF-SE-37-RU
RF-SE-50-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
1.2 U
1.2 U
1.2 U
n.d.
n.d.
n.d.
30
33
31
n.d.
n.d.
n.d.
77
66
73
n.d.
n.d.
n.d.
12
10
11
11
13
11
8.9
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
As
86
85
89
19
46
80
11
13
11
23
17
17
15
10
15
21
24
12
230
260
240
250
280
260
230
304
276
305
274
297
260
296
Cd
350
340
360
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
62
62
62
62
62
62
63
63
63
63
63
63
64
64
64
64
64
64
65
65
65
65
65
65
65
65
65
65
65
65
65
65
Sample ID
TL-SE-06-XX
TL-SE-17-XX
TL-SE-28-XX
TL-SE-06-RU
TL-SE-17-RU
TL-SE-28-RU
TL-SE-07-XX
TL-SE-21-XX
TL-SE-30-XX
TL-SE-07-RU
TL-SE-21-RU
TL-SE-30-RU
TL-SE-02-XX
TL-SE-08-XX
TL-SE-16-XX
TL-SE-02-RU
TL-SE-08-RU
TL-SE-16-RU
RF-SE-01-XX
RF-SE-09-XX
RF-SE-11-XX
RF-SE-17-XX
RF-SE-29-XX
RF-SE-37-XX
RF-SE-50-XX
RF-SE-01-RU
RF-SE-09-RU
RF-SE-11-RU
RF-SE-17-RU
RF-SE-29-RU
RF-SE-37-RU
RF-SE-50-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
44
43
44
77
33
36
94
100
93
82
75
81
99
100
100
77
88
46
200
220
210
210
240
220
200
175
113
140
99
161
115
164
Se
45
44
45
160
24
41
120
140
120
89
152
156
44
39
44
47
77
28
21
23
20
22
26
23
20
20
20
20
18
20
20
20
Ag
56
56
57
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
66
66
66
66
66
66
67
67
67
67
67
67
68
68
68
68
68
68
69
69
69
69
69
69
70
70
70
70
70
70
Sample ID
RF-SE-08-XX
RF-SE-10-XX
RF-SE-33-XX
RF-SE-08-RU
RF-SE-10-RU
RF-SE-33-RU
RF-SE-16-XX
RF-SE-41-XX
RF-SE-48-XX
RF-SE-16-RU
RF-SE-41-RU
RF-SE-48-RU
RF-SE-18-XX
RF-SE-35-XX
RF-SE-54-XX
RF-SE-18-RU
RF-SE-35-RU
RF-SE-54-RU
RF-SE-20-XX
RF-SE-46-XX
RF-SE-51-XX
RF-SE-20-RU
RF-SE-46-RU
RF-SE-51-RU
RF-SE-21-XX
RF-SE-40-XX
RF-SE-47-XX
RF-SE-21-RU
RF-SE-40-RU
RF-SE-47-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Sb
14
12
13
n.d.
n.d.
n.d.
85 J-
100
100
n.d.
n.d.
n.d.
320
300
320
n.d.
n.d.
n.d.
550
270
480
n.d.
n.d.
n.d.
1.3 U
1.3 U
1.3 U
n.d.
n.d.
n.d.
As
460
400
440
601
660
656
72 J-
82
87
112
99
109
810
740
880
1,162
1,239
906
1300
590
1100
876
956
932
62
70
72
45
37
18
Cd
67
58
64
-------
Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued)
Blend
No.
66
66
66
66
66
66
67
67
67
67
67
67
68
68
68
68
68
68
69
69
69
69
69
69
70
70
70
70
70
70
Sample ID
RF-SE-08-XX
RF-SE-10-XX
RF-SE-33-XX
RF-SE-08-RU
RF-SE-10-RU
RF-SE-33-RU
RF-SE-16-XX
RF-SE-41-XX
RF-SE-48-XX
RF-SE-16-RU
RF-SE-41-RU
RF-SE-48-RU
RF-SE-18-XX
RF-SE-35-XX
RF-SE-54-XX
RF-SE-18-RU
RF-SE-35-RU
RF-SE-54-RU
RF-SE-20-XX
RF-SE-46-XX
RF-SE-51-XX
RF-SE-20-RU
RF-SE-46-RU
RF-SE-51-RU
RF-SE-21-XX
RF-SE-40-XX
RF-SE-47-XX
RF-SE-21-RU
RF-SE-40-RU
RF-SE-47-RU
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Reference Laboratory
Reference Laboratory
Reference Laboratory
RONTEC USA Inc.
RONTEC USA Inc.
RONTEC USA Inc.
Ni
250
220
240
113
136
160
1,700 J-
1,900
2,000
1,037
1,768
1,569
390
350
420
263
277
324
1,400
650
1,200
770
999
901
220
250
250
167
179
338
Se
42
39
41
40
44
44
1.2 U
1.2 U
2.2
-------
APPENDIX E
STATISTICAL DATA SUMMARIES
-------
Figure E-l: Linear Correlation Plot for Arsenic
5000
4000
X
X
H 3000
o
2000
O
Pi
1000
RONTECPicoTAX
-45 Degrees
Linear (RONTEC PicoTAX)
y = 0.90x + 56.55
R2 = 0.95
1000
2000 3000 4000
Reference Laboratory (ppni)
5000
6000
Figure E-2: Linear Correlation Plot for Cadmium
3000 --
1 2500
&
* 2000
X
ZS
8
S 1500
O
I
2 1000
500
0 -
RONTECPicoTAX
45 Degrees
Linear (RONTEC PicoTAX)
y = 0.78x +272.24
R2 = 0.62
500
1000 1500 2000
Reference Laboratory (ppm)
2500
3000
E-l
-------
3500
3000
1 2500
p.
X 2000
X
o
Ł 1500
1
§ 1000
500
0
Figure E-3: Linear Correlation Plot for Chromium
RONTEC PicoTAX
Linear (RONTEC PicoTAX) m n S R2 = 0.95
s
S -_ '
s''
* '
S '
m^f
9?
17
0 500 1000 1500 2000 2500 3000 3500
Reference Laboratory (ppm)
Figure E-4: Linear Correlation Plot for Copper
&000 ________________^^
7000
6000 --
I
fe SOOO
X
X
^ 4000
O
u
Ł
rj
g 3000 --
H
0
2000 -
1 000
o i
RONTEC PicoTAX
Linear (RONTEC PicoTAX)
Ť ^ v= 1.03x- 33.94
^^" R2 = 0.86
**
^^* m
-.<-V-rV
i^^1""^ "
0 1000 2000 3000 4000 5000 6000
Reference Laboratory (ppm)
E-2
-------
250000
200000
Q.
g 150000
rs
X
<{
H
o
ij
I
100000
50000
Figure E-5: Linear Correlation Plot for Iron
RONTECPicoTAX
45 Degrees
Linear (RONTECPicoTAX)
y = 1.02x + 4489.75
R2 = 0.95
0 20000 40000 60000 80000 100000 120000 140000 160000 180000 200000
Reference Laboratory (ppni)
Figure E-6: Linear Correlation Plot for Lead
70000 n
60000
50000
X 40000
X
PH 30000
u
H
Q 20000
10000
RONTECPicoTAX
45 Degrees
Linear (RONTEC PicoTAX)
y = 1.42x-98.03
R2 = 0.94
5000 10000 15000 20000 25000
Reference Laboratory (ppni)
30000 35000 40000
E-3
-------
9000 -j
snnn
S 6000 -
'
&
X
$
2 ddod
PH
U
H 3000 -
O
onnn
1000 -
Figure E-7: Linear Correlation Plot for Mercury
Ť RONTEC PicoTAX
Linear (RONTEC PicoTAX)
4
^
.. ' .*
**
y = 0.73x- 39.22
R2=0.99
^*
^
^
^
^'
*r m
^
. ' ' ^
0 1000 2000 3000 4000 5000 6000 7000
Reference Laboratory (ppni)
8000 9000
Figure E-8: Linear Correlation Plot for Nickel
3500 -,
TflOO
2 7SOO -
Q.
<&
** 7000 -
X 2UUU
$
O
u
?T i son
o
a
z
O 1000
ctf
SOD
0 -
RONTEC PicoTAX
45 Degrees
Linear (RONTEC PicoTAX)
^
^
S
s'' .
. : '^
s
_ " ^ Ť
s
s
^^
y - 0.89x + C
R2 = 0.96
m. s*m
- -s*
*>*
m mS
.07
0 500 1000 1500 2000 2500 3000 3500
Reference Laboratory (ppm)
E-4
-------
1000
900
800
1 700
ft
X
^ 500
o
O 400
H
O 300
200
100
0
Figure E-9: Linear Correlation Plot for Selenium
RONTECPicoTAX
45 Degrees
Linear (RONTEC PicoTAX)
.
m ^^^^
y= 1.0
R2
3x+ 13.73
*,<~ '
. **- -' m
^V"
JSi^^ ' * IB
0 100 200 300 400 500
Reference Laboratory (ppm)
600
450 i
AOO
ft
ft 300 _
* 250 -
X
H
o
S 200 -
H 150
§
100
50
0
C
Figure E-10: Linear Correlation Plot for Silver
RONTECPicoTAX
45 Degrees
Linear (RONTEC PicoTAX)
-
^
y = 0.94x + 6.98
R2 = 0.58
'S
m '
m ^
^
m >ť
^ ""H
>ťH^* m
** m
s
50 100 150 200 250 300 350
Reference Laboratory (ppm)
400 450
E-5
-------
Figure E-ll: Linear Correlation Plot for Vanadium
500
son
I
5 400 -
3
X
X
H 300 -
8
& 200 -
§
100
0
c
m RONTEC PicoTAX
Linear (RONTEC PicoTAX) B
*
.
f
y = 1.0^
R2 =
S
S
* ^X*
^X*^ "
X" "
^;f- *
50 100 150 200 250 300 350 400 450
Reference Laboratory (ppm)
[a- 10.65
= 0.89
500
900
800
700
| 600
3 500
rS
X
H 400
o
U 300
H
O 200
100
-100
Figure E-12: Linear Correlation Plot for Zinc
3
3
3
3
m RONTEC PicoTAX
45 Degrees
Lin ear (RONTEC PicoTAX) ^
y
= 1.07x-21.19
R2 = 0.97
s
^
, " ^'
mm ^<:- m
"^
"
1000 2000 3000 4000 5000 6000 7000
Reference Laboratory (ppm)
80
30
E-6
-------
Box Plot for Relative Percent Difference (RPD)
Rontec PicoTAX
Median; Box: 25%-75%; Whisker: Non-Outlier Range
^.uu /o
180%
X
< 160%
o ^
o r"1
Ł o 140%
Q) CO
5 Ł 120%
S Ť
0) -1
5 g 100%
§ S
5 80%
01 M-
3 0)
Ł a) 60%
Q ^
Ł 1 40%
CO
a) 20%
0%
-9DO/,
! ! !
1 17-AS i
t * !
i t
~1~~T
58jLV
! 70-JRF
! 0
t ;
! [
u
T
i
57-iCN
^
^
23-iSB
I )
fS
r
r
,
1
i i
j '
' '!!!!!'
57JCN
! 48-iSB I
| 0
5-WS
Q
T-Legfft- \
VL ? -
67-lRF
o
T
\ I n
[ ? 1
j
r~
I n
c
c
T \
r ! 53-
| J
i 61
:
[
' *
6?
C
!
AS .
Tl
i
TI r
)
"p
j rn r
rJ B (
G.d.u
c
J
XI
3 26
SB
S
61fFb
^
l-l
] r i
H
i i i i
As Cd Cr Cu Fe Pb Hg Ni Se Ag V Zn
Target Element
n Median
D 25%-75%
I Non-Outlier Range
o Outliers
* Extremes
Notes:
The "box" in each box plot presents the range of RPD values that lie between the 25th and 75th percentiles (that is, the
"quartiles") of the full RPD population for each element. In essence, the box displays the "interquartile range" of RPD
values. The square data point within each box represents the median RPD for the population. The "whiskers" emanating
from the top and bottom of each box represent the largest and smallest data points, respectively, that are within 1.5 times
the interquartile range. Values outside the whiskers are identified as outliers and extremes.
Some of the more significant extremes and outliers are labeled with the associated Blend numbers and sample site
abbreviations (see the footnotes of Table E-5 for definitions). Also refer to Appendix D for the sampling site associated
with each Blend number.
Figure E-13. Box and Whisker Plot for Mean RPD Values Showing Outliers and Extremes for Target
Elements, Rontec PicoTAX Data Set.
E-7
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rontec
PicoTAX
Matrix
Soil
Cone
Range
Level 1
Level 2
Level 3
Level 4
All Soil
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
RefLab
0
NC
NC
NC
NC
0
NC
NC
NC
NC
0
NC
NC
NC
NC
~
~
~
0
NC
NC
NC
NC
ERA Spike
0
NC
NC
NC
NC
0
NC
NC
NC
NC
0
NC
NC
NC
NC
~
~
~
0
NC
NC
NC
NC
Arsenic
15
2.7%
181.4%
32.9%
20.7%
4
3.1%
32.6%
11.2%
4.6%
4
5.5%
12.2%
8.7%
8.7%
~
~
~
23
2.7%
181.4%
25.0%
14.3%
Cadmium
4
138.5%
168.1%
155.2%
157.0%
6
0.8%
84.2%
45.7%
49.6%
2
6.3%
13.7%
10.0%
10.0%
~
~
~
12
0.8%
168.1%
76.2%
83.2%
Chromium
28
2.5%
130.1%
32.0%
20.7%
4
0.5%
29.8%
13.0%
10.9%
2
10.8%
17.9%
14.4%
14.4%
~
~
~
34
0.5%
130.1%
28.8%
17.9%
Copper
16
1.0%
34.8%
11.6%
10.4%
8
0.5%
26.8%
11.0%
10.0%
2
14.1%
35.6%
24.9%
24.9%
~
~
~
26
0.5%
35.6%
12.4%
11.5%
Iron
5
13.6%
48.6%
23.9%
20.5%
13
8.7%
56.5%
26.0%
23.2%
13
3.0%
25.5%
12.0%
12.0%
7
0.0%
18.6%
5.9%
2.4%
38
0.0%
56.5%
17.2%
14.9%
Lead
16
9.1%
122.7%
43.1%
24.9%
4
2.2%
25.7%
15.1%
16.3%
8
7.3%
42.2%
20.2%
20.4%
5
15.3%
55.4%
28.7%
22.9%
16
11.2%
70.9%
33.7%
30.0%
Mercury
7
5.9%
110.4%
41.9%
19.3%
7
4.7%
73.0%
40.6%
43.3%
2
28.7%
49.1%
38.9%
38.9%
~
~
~
16
4.7%
110.4%
40.9%
33.0%
Nickel
22
1.0%
62.8%
22.7%
16.7%
5
6.2%
74.6%
26.7%
21.6%
6
0.9%
18.6%
7.5%
5.6%
~
~
~
33
0.9%
74.6%
20.6%
12.2%
E-8
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rontec
PicoTAX (Continued)
Matrix
Soil
Cone
Range
Level 1
Level 2
Level 3
Level 4
All Soil
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
22
1.0%
62.8%
22.7%
16.7%
5
6.2%
74.6%
26.7%
21.6%
6
0.9%
18.6%
7.5%
5.6%
~
~
~
~
33
0.9%
74.6%
20.6%
12.2%
Selenium
4
5.2%
80.8%
42.3%
41.5%
5
1.3%
110.7%
27.1%
6.9%
4
3.7%
27.7%
13.4%
11.1%
~
~
~
~
13
1.3%
110.7%
27.5%
6.9%
Silver
0
NC
NC
NC
NC
0
NC
NC
NC
NC
4
5.6%
19.3%
11.4%
10.4%
~
~
~
~
4
5.6%
19.3%
11.4%
10.4%
Vanadium
13
0.1%
68.7%
30.0%
29.2%
4
0.2%
20.7%
14.0%
17.5%
4
4.3%
24.7%
14.8%
15.2%
~
~
~
21
0.1%
68.7%
24.0%
20.7%
Zinc
20
0.0%
83.3%
25.4%
21.0%
6
3.4%
23.6%
12.0%
11.3%
9
0.9%
23.4%
10.5%
10.9%
~
~
~
~
35
0.0%
83.3%
19.3%
16.0%
E-9
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rontec
PicoTAX (Continued)
Matrix
Sediment
Cone
Range
Level 1
Level 2
Level 3
Level 4
All Sediment
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
RefLab
0
NC
NC
NC
NC
0
NC
NC
NC
NC
0
NC
NC
NC
NC
~
~
~
0
NC
NC
NC
NC
ERA Spike
0
NC
NC
NC
NC
0
NC
NC
NC
NC
0
NC
NC
NC
NC
~
~
~
0
NC
NC
NC
NC
Arsenic
17
1.2%
93.5%
24.0%
12.9%
4
0.4%
38.4%
14.0%
8.6%
2
7.9%
30.6%
19.2%
19.2%
~
~
~
23
0.4%
93.5%
21.9%
12.9%
Cadmium
0
NC
NC
NC
NC
0
NC
NC
NC
NC
0
NC
NC
NC
NC
~
~
~
0
NC
NC
NC
NC
Chromium
21
3.0%
63.8%
19.8%
20.3%
3
11.6%
31.8%
18.9%
13.4%
3
3.6%
34.7%
21.1%
25.0%
~
~
~
27
3.0%
63.8%
19.9%
20.3%
Copper
8
0.7%
42.5%
11.4%
5.6%
4
6.2%
18.7%
14.8%
17.2%
10
0.4%
75.7%
24.5%
18.5%
~
~
~
22
0.4%
75.7%
18.0%
15.4%
Iron
3
35.8%
62.2%
45.2%
37.6%
19
2.7%
73.5%
28.6%
27.5%
4
6.0%
54.7%
30.7%
31.1%
6
1.5%
10.5%
6.9%
8.4%
32
1.5%
73.5%
26.3%
21.6%
Lead
4
0.1%
18.8%
10.2%
10.9%
4
0.1%
18.8%
10.2%
10.9%
3
21.8%
39.9%
33.8%
39.7%
~
~
~
23
0.1%
70.9%
29.7%
25.5%
Mercury
2
7.4%
47.7%
27.5%
27.5%
4
0.4%
115.8%
49.4%
40.7%
2
15.1%
48.3%
31.7%
31.7%
~
~
~
8
0.4%
115.8%
39.5%
37.8%
E-10
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rontec
PicoTAX (Continued)
Matrix
Sediment
Cone
Range
Level 1
Level 2
Level 3
Level 4
All Sediment
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
18
4.0%
77.2%
35.5%
34.9%
6
5.1%
53.8%
27.7%
29.4%
4
5.7%
24.6%
14.4%
13.7%
~
~
~
28
4.0%
77.2%
30.8%
29.4%
Selenium
5
4.8%
50.7%
20.5%
17.4%
4
4.4%
81.0%
30.8%
18.9%
3
0.2%
13.4%
7.5%
8.8%
~
~
~
12
0.2%
81.0%
20.7%
14.1%
Silver
1
8.5%
8.5%
8.5%
8.5%
2
59.1%
114.6%
86.9%
86.9%
2
34.5%
64.8%
49.7%
49.7%
~
~
~
5
8.5%
114.6%
56.3%
59.1%
Vanadium
6
15.0%
94.3%
49.5%
45.0%
8
11.4%
66.0%
37.7%
43.8%
3
8.4%
24.3%
15.2%
12.9%
~
~
17
8.4%
94.3%
37.9%
24.3%
Zinc
19
1.0%
53.9%
19.2%
11.6%
5
1.3%
25.5%
16.3%
19.4%
4
0.7%
35.7%
16.1%
14.0%
~
~
~
28
0.7%
53.9%
18.2%
16.2%
E-ll
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rontec
PicoTAX (Continued)
Cone
Matrix Range Statistic
All Rontec Number
Samples PicoTAX Minimum
Maximum
Mean
Median
All All Instruments Number
Samples Minimum
Maximum
Mean
Median
Antimony
RefLab ERA Spike
0 0
NC NC
NC NC
NC NC
NC NC
206 110
0.1% 0.1%
181.5% 162.0%
80.6% 62.7%
84.3% 70.6%
Arsenic
46
0.4%
181.4%
23.4%
13.4%
320
0.2%
182.8%
36.6%
26.2%
Cadmium
12
0.8%
168.1%
76.2%
83.2%
209
0.1%
168.1%
29.6%
16.7%
Chromium
61
0.5%
130.1%
24.8%
18.1%
338
0.1%
151.7%
30.8%
26.0%
Copper
48
0.4%
75.7%
15.0%
12.3%
363
0.2%
111.1%
24.6%
16.2%
Iron
70
0.0%
73.5%
21.4%
17.3%
558
0.0%
190.1%
35.4%
26.0%
Lead
56
0.1%
122.7%
31.0%
22.9%
392
0.1%
135.2%
30.9%
21.5%
Mercury
24
0.4%
115.8%
40.5%
33.0%
192
0.0%
158.1%
62.5%
58.6%
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rontec
PicoTAX (Continued)
Cone
Matrix Range Statistic
All Rontec Number
Samples PicoTAX Minimum
Maximum
Mean
Median
All All Instruments Number
Samples Minimum
Maximum
Mean
Median
Nickel
61
0.9%
77.2%
25.3%
21.2%
403
0.3%
146.5%
31.0%
25.4%
Selenium
25
0.2%
110.7%
24.2%
11.6%
195
0.0%
127.1%
32.0%
16.7%
Silver
9
5.6%
114.6%
36.4%
19.3%
177
0.0%
129.7%
36.0%
28.7%
Vanadium
38
0.1%
94.3%
30.2%
22.9%
218
0.1%
129.5%
42.2%
38.3%
Zinc
63
0.0%
83.3%
18.8%
16.0%
471
0.0%
138.0%
26.3%
19.4%
E-12
-------
Notes:
All RPDs presented in this table are absolute values.
No samples reported by the reference laboratory in this concentration range.
Cone Concentration.
ERA Environmental Resouce Associstes, Inc.
NC Not calculated due to lack of XRF data.
Number Number of demonstration samples evaluated.
Ref Lab Reference laboratory (Shealy Environmental Services, Inc.).
RPD Relative percent difference.
SRF X-ray fluorescence.
E-13
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX
Matrix
Soil
Cone
Range
Low
Medium
High
Veiy High
All Soil
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
0
NC
NC
NC
NC
0
NC
NC
NC
NC
0
NC
NC
NC
NC
~
~
~
0
NC
NC
NC
NC
Arsenic
15
2.0%
71.7%
18.2%
13.8%
4
6.5%
17.3%
13.5%
15.1%
4
6.1%
19.6%
12.8%
12.7%
~
~
~
23
2.0%
71.7%
16.5%
14.3%
Cadmium
4
17.4%
31.0%
25.9%
27.6%
6
20.1%
48.5%
33.4%
31.5%
2
18.7%
33.6%
26.2%
26.2%
~
~
~
12
17.4%
48.5%
29.7%
30.0%
Chromium
28
11.8%
89.0%
34.8%
26.3%
4
3.3%
15.1%
9.4%
9.6%
2
3.1%
4.3%
3.7%
3.7%
~
~
~
34
3.1%
89.0%
30.0%
22.1%
Copper
16
0.1%
25.9%
12.1%
11.9%
8
8.9%
28.2%
17.0%
16.7%
2
9.6%
22.1%
15.9%
15.9%
~
~
~
26
0.1%
28.2%
13.9%
13.3%
Iron
5
10.6%
29.4%
19.9%
19.2%
13
4.4%
20.5%
13.2%
13.3%
13
8.5%
29.1%
17.3%
17.9%
7
8.4%
30.9%
18.9%
15.7%
38
4.4%
30.9%
16.5%
16.6%
Lead
16
2.2%
78.7%
24.3%
20.9%
4
11.7%
25.5%
15.6%
12.6%
8
1.7%
23.0%
11.7%
12.0%
5
3.8%
18.6%
10.7%
9.4%
33
1.7%
78.7%
18.1%
14.4%
Mercury
7
1.1%
105.2%
42.7%
25.2%
7
17.7%
88.2%
35.6%
26.0%
2
22.9%
44.7%
33.8%
33.8%
~
~
~
16
1.1%
105.2%
38.5%
25.6%
E-14
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Continued)
Matrix
Soil
Cone
Range
Low
Medium
High
Veiy High
All Soil
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
22
7.8%
70.0%
22.7%
19.5%
5
5.0%
14.4%
10.3%
11.6%
6
1.5%
35.8%
17.8%
19.5%
~
~
~
33
1.5%
70.0%
19.9%
17.3%
Selenium
4
1.4%
27.4%
14.6%
14.9%
5
5.9%
22.3%
15.1%
18.9%
4
3.7%
7.0%
5.6%
6.0%
~
~
~
13
1.4%
27.4%
12.0%
7.0%
Silver
0
NC
NC
NC
NC
0
NC
NC
NC
NC
4
37.6%
125.3%
66.4%
51.4%
~
~
~
4
37.6%
125.3%
66.4%
51.4%
Vanadium
13
14.7%
51.0%
26.9%
27.1%
4
6.0%
35.7%
16.9%
12.9%
4
0.4%
14.5%
7.2%
7.0%
~
~
~
21
0.4%
51.0%
21.3%
18.2%
Zinc
20
2.5%
42.0%
15.7%
15.5%
6
4.3%
20.1%
12.2%
13.8%
9
0.7%
37.4%
15.1%
12.0%
~
~
~
35
0.7%
42.0%
14.9%
14.7%
E-15
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Continued)
Matrix
Sediment
Cone
Range
Low
Medium
High
Veiy High
All Sediment
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
0
NC
NC
NC
NC
0
NC
NC
NC
NC
0
NC
NC
NC
NC
~
~
~
0
NC
NC
NC
NC
Arsenic
17
6.4%
63.1%
28.9%
28.3%
4
5.2%
13.5%
8.7%
8.1%
2
4.5%
15.8%
10.1%
10.1%
~
~
~
23
4.5%
63.1%
23.8%
18.8%
Cadmium
0
NC
NC
NC
NC
0
NC
NC
NC
NC
0
NC
NC
NC
NC
~
~
~
0
NC
NC
NC
NC
Chromium
21
12.2%
116.3%
35.8%
32.5%
o
3
9.9%
17.6%
12.5%
9.9%
o
3
6.9%
20.4%
11.5%
7.2%
~
~
~
27
6.9%
116.3%
30.5%
25.1%
Copper
8
6.1%
58.3%
17.0%
11.1%
4
2.7%
31.3%
17.1%
17.2%
10
4.3%
45.5%
24.6%
22.5%
~
~
~
22
2.7%
58.3%
20.5%
16.2%
Iron
3
9.7%
20.6%
16.9%
20.3%
19
6.4%
61.7%
21.3%
14.0%
4
8.2%
29.9%
17.5%
16.0%
6
11.2%
29.4%
18.0%
17.5%
32
6.4%
61.7%
19.8%
16.5%
Lead
16
4.7%
115.6%
28.0%
24.4%
4
4.8%
75.9%
24.5%
8.6%
o
5
11.5%
93.2%
38.9%
11.9%
~
~
~
23
4.7%
115.6%
28.8%
21.3%
Mercury
2
16.8%
94.7%
55.8%
55.8%
4
26.0%
75.3%
40.2%
29.8%
2
9.0%
16.8%
12.9%
12.9%
~
~
~
8
9.0%
94.7%
37.3%
26.9%
E-16
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Continued)
Matrix
Sediment
Cone
Range
Low
Medium
High
Veiy High
All Sediment
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
18
5.1%
77.6%
31.6%
31.6%
6
7.0%
41.9%
19.2%
17.0%
4
8.2%
25.9%
14.0%
10.9%
~
~
~
28
5.1%
77.6%
26.4%
18.8%
Selenium
5
3.8%
98.8%
32.6%
5.6%
4
3.6%
28.1%
15.8%
15.8%
o
3
2.8%
9.0%
6.7%
8.2%
~
~
~
12
2.8%
98.8%
20.5%
8.6%
Silver
1
46.5%
46.5%
46.5%
46.5%
2
50.2%
50.2%
50.2%
50.2%
2
41.0%
73.9%
57.4%
57.4%
~
~
~
5
41.0%
73.9%
52.4%
50.2%
Vanadium
6
15.3%
86.1%
37.7%
31.0%
8
5.4%
47.6%
24.4%
24.4%
3
5.6%
12.9%
9.5%
9.9%
~
~
~
17
5.4%
86.1%
26.5%
27.0%
Zinc
19
6.2%
38.5%
21.6%
21.7%
5
6.9%
13.1%
10.6%
11.2%
4
8.1%
24.2%
16.3%
16.4%
~
~
~
28
6.2%
38.5%
18.8%
15.5%
E-17
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Continued)
Matrix
All
All Samples
Cone
Range
All
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
0
NC
NC
NC
NC
421
0.5%
23.2%
8.5%
11.0%
Arsenic
46
2.0%
71.7%
20.1%
15.1%
498
1.1%
33.6%
9.1%
11.5%
Cadmium
12
17.4%
48.5%
29.7%
30.0%
440
1.3%
29.5%
7.2%
6.0%
Chromium
61
3.1%
116.3%
30.2%
24.2%
492
1.0%
36.4%
12.1%
15.6%
Copper
48
0.1%
58.3%
16.9%
15.2%
531
0.3%
32.8%
9.6%
7.3%
Iron
70
4.4%
61.7%
18.0%
16.5%
560
0.1%
20.9%
3.5%
2.2%
Lead
56
1.7%
115.6%
22.5%
14.5%
507
0.4%
29.6%
6.9%
7.4%
Mercury
24
1.1%
105.2%
38.1%
26.0%
435
2.0%
24.9%
7.5%
11.3%
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Continued)
Matrix
All
All Samples
Cone
Range
All
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
61
1.5%
77.6%
22.9%
18.5%
509
1.6%
28.1%
10.9%
8.4%
Selenium
25
1.4%
98.8%
16.1%
8.2%
433
0.3%
18.5%
5.9%
10.6%
Silver
9
37.6%
125.3%
58.6%
50.2%
441
1.5%
24.8%
9.0%
12.9%
Vanadium
38
0.4%
86.1%
23.6%
19.8%
462
0.9%
24.3%
8.8%
11.4%
Zinc
63
0.7%
42.0%
16.7%
14.7%
535
0.1%
19.3%
6.6%
5.8%
Notes:
Cone
NC
Number
RSD
XRF
No samples reported by the reference laboratory in this concentration range.
Concentration.
Not calculated due to lack of XRF data.
Number of demonstration samples evaluated.
Relative standard deviation.
X-ray fluorescence.
E-18
-------
Table E-3. Evaluation of Precision - Relative Standard Deviations Calculated for the Reference Laboratory
Matrix
All Soil
All Sediment
All Samples
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
17
3.6%
38.0%
14.3%
9.8%
7
2.9%
33.6%
14.4%
9.1%
24
2.9%
38.0%
14.3%
9.5%
Arsenic
23
1.4%
45.8%
11.7%
12.4%
24
2.4%
36.7%
10.7%
9.2%
47
1.4%
45.8%
11.2%
9.5%
Cadmium
15
0.9%
21.4%
11.1%
9.0%
10
2.9%
37.5%
11.4%
8.2%
25
0.9%
37.5%
11.2%
9.0%
Chromium
34
1.4%
137.0%
14.3%
10.6%
26
4.6%
35.5%
9.8%
7.5%
60
1.4%
137.0%
12.4%
8.4%
Copper
26
0.0%
21.0%
10.1%
9.1%
21
1.8%
38.8%
9.7%
8.9%
47
0.0%
38.8%
9.9%
8.9%
Iron
38
1.6%
46.2%
10.2%
8.7%
31
2.7%
37.5%
9.9%
8.1%
69
1.6%
46.2%
10.1%
8.5%
Lead
33
0.0%
150.0%
17.6%
13.2%
22
0.0%
41.1%
11.6%
7.4%
55
0.0%
150.0%
15.2%
8.6%
Mercury
16
0.0%
50.7%
13.8%
6.6%
10
2.8%
48.0%
14.3%
6.9%
26
0.0%
50.7%
14.0%
6.6%
Table E-3. Evaluation of Precision - Relative Standard Deviations Calculated for the Reference Laboratory (Continued)
Matrix
All Soil
All Sediment
All Samples
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Selenium
13
0.0%
22.7%
8.9%
7.1%
12
1.3%
37.3%
10.0%
7.6%
25
0.0%
37.3%
9.4%
7.4%
Silver
13
2.3%
37.1%
12.4%
7.5%
10
1.0%
21.3%
9.4%
6.6%
23
1.0%
37.1%
11.1%
7.1%
Vanadium
21
0.0%
18.1%
8.4%
6.6%
17
2.2%
21.9%
8.4%
8.1%
38
0.0%
21.9%
8.4%
7.2%
Zinc
35
1.0%
46.5%
10.4%
9.1%
27
1.4%
35.8%
8.9%
6.9%
62
1.0%
46.5%
9.8%
7.4%
E-19
-------
Table E-4. Evaluation of the Effects of Interferent Elements on RPDs (Accuracy) of Other Target Elements 1
Parameter
Interferent/Element Ratio
Number of Samples
RPD of Target Element2
RPD of Target Element
(Absolute Value)2
Interferent
Concentration Range
Target Element
Concentration Range
Statistic
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Lead Effects on Arsenic
<5
29
-41.9%
21.4%
-13.4%
-12.6%
0.4%
41.9%
15.8%
12.9%
ND
1030
221
89
25
2065
302
135
5-10
7
-5.5%
32.6%
4.1%
-2.7%
2.7%
32.6%
8.9%
5.5%
865
61480
19418
9262
119
5133
1701
1071
>10
10
-93.5%
181.4%
25.3%
24.6%
3.5%
181.4%
55.7%
43.0%
1108
23605
6276
3434
1
1788
323
56
Copper Effects on Nickel
<5
42
-29.2%
69.4%
11.2%
8.3%
0.9%
69.4%
17.8%
13.8%
ND
938
216
123
42
3201
526
183
5-10
5
4.4%
53.8%
36.8%
42.2%
4.4%
53.8%
36.8%
42.2%
683
1393
1000
871
88
136
110
100
>10
14
6.2%
77.2%
43.6%
41.6%
6.2%
77.2%
43.6%
41.6%
655
7308
2481
1877
23
251
94
75
Nickel Effects on Copper
<5
39
-35.6%
75.7%
3.2%
-0.5%
0.4%
75.7%
14.8%
11.1%
ND
875
144
98
56
7308
1209
786
5-10
1
-16.1%
-16.1%
-16.1%
-16.1%
16.1%
16.1%
16.1%
16.1%
288
288
288
288
92
92
92
92
>10
8
-42.5%
14.3%
-8.3%
-5.5%
3.5%
42.5%
15.5%
14.4%
890
3201
1943
1906
81
127
105
107
E-20
-------
Table E-4. Evaluation of the Effects of Interferent Elements on RPDs (Accuracy) of Other Target Elements 1 (Continued)
Parameter
Interferent/Element Ratio
Number of Samples
RPD of Target Element2
RPD of Target Element
(Absolute Value)2
Interferent
Concentration Range
Target Element
Concentration Range
Statistic
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Zinc Effects on Copper
<5
35
-35.6%
75.7%
1.5%
-0.5%
0.4%
75.7%
15.9%
14.1%
45
7675
1084
177
56
7308
1280
829
5-10
2
-6.2%
7.1%
0.4%
0.4%
6.2%
7.1%
6.6%
6.6%
754
8170
4462
4462
149
1553
851
851
>10
11
-42.5%
34.8%
-1.1%
-1.0%
1.0%
42.5%
13.6%
8.9%
678
8071
3143
3015
73
382
144
124
Copper Effects on Zinc
<5
50
-83.3%
35.7%
-11.1%
-12.0%
0.0%
83.3%
18.4%
16.8%
ND
2491
468
169
45
8170
1674
674
5-10
3
-14.0%
-7.1%
-10.8%
-11.4%
7.1%
14.0%
10.8%
11.4%
829
1666
1144
938
118
223
156
127
>10
10
-38.6%
53.9%
-2.0%
-8.5%
1.2%
53.9%
23.2%
17.2%
683
7308
2830
2221
57
411
158
145
Notes:
1. Concentrations are reported in units of milligrams per kilogram (mg/kg), or parts per million (ppm).
2. Table presents statistics for raw (unmodified) RPDs as well as absolute value RPDs.
< Less than.
> Greater than.
RPD Relative percent difference.
NC Not calculated due to lack of XRF data.
ND Nondetect.
XRF X-ray fluorescence.
E-21
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Site
AS
BN
CN
KP
LV
RF
Matrix
Description
Fine to medium sand
(steel processing)
Sandy loam, low
organic (ore residuals)
Sandy loam (burn pit
residue)
Soil: Fine to medium
quartz sand.
Sed. : Sandy loam, high
organic.
(Gun and skeet ranges)
Clay /clay loam, salt
crust (iron and other
precipitate)
Silty fine sand (tailings)
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
Reference Laboratory
RPD
~
~
~
~
~
~
~
~
~
-
-
~
~
~
~
~
-
RPD ABS Val
~
~
~
~
-
~
~
~
~
-
-
~
~
~
~
~
-
Certified Value
RPD
~
~
~
~
~
~
~
~
~
-
-
~
~
~
~
~
-
RPD ABS Val
~
~
~
~
~
~
~
~
~
-
-
~
~
~
~
~
-
Arsenic
Reference Laboratory
RPD RPD ABS Val
1 1
181.4% 181.4%
181.4% 181.4%
181.4% 181.4%
181.4% 181.4%
7 7
-10.2% 2.7%
49.0% 49.0%
3.3% 11.8%
-3.1% 5.5%
1 1
-17.6% 17.6%
-17.6% 17.6%
-17.6% 17.6%
-17.6% 17.6%
~
11 11
-93.5% 0.4%
1.6% 93.5%
-17.6% 18.1%
-9.2% 9.2%
12 12
-38.4% 1.4%
68.4% 68.4%
-5.0% 21.8%
-12.7% 17.7%
Cadmium
Reference Laboratory
RPD RPD ABS Val
1 1
-0.8% 0.8%
-0.8% 0.8%
-0.8% 0.8%
-0.8% 0.8%
5 5
-13.7% 13.7%
138.5% 138.5%
61.6% 67.1%
82.5% 82.5%
1 1
83.8% 83.8%
83.8% 83.8%
83.8% 83.8%
83.8% 83.8%
~
1 1
-6.1% 6.1%
-6.1% 6.1%
-6.1% 6.1%
-6.1% 6.1%
..
..
..
~
E-22
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Site
AS
BN
CN
KP
LV
RF
Matrix
Description
Fine to medium sand
(steel processing)
Sandy loam, low
organic (ore residuals)
Sandy loam (burn pit
residue)
Soil: Fine to medium
quartz sand.
Sed. : Sandy loam, high
organic.
(Gun and skeet ranges)
Clay /clay loam, salt
crust (iron and other
precipitate)
Silty fine sand (tailings)
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Chromium
Reference Laboratory
RPD
2
-12.1%
-9.6%
-10.8%
-10.8%
7
-21.8%
28.6%
-1.6%
-10.9%
2
-50.0%
130.1%
40.1%
40.1%
4
-31.5%
7.1%
-14.3%
-16.3%
11
-39.2%
11.4%
-12.6%
-11.7%
12
-63.8%
24.8%
-15.9%
-16.5%
RPD ABS Val
2
9.6%
12.1%
10.8%
10.8%
7
10.2%
28.6%
17.8%
17.9%
2
50.0%
130.1%
90.1%
90.1%
4
7.1%
31.5%
17.8%
16.3%
11
3.0%
39.2%
16.0%
11.7%
12
5.5%
63.8%
22.1%
22.2%
Copper
Reference Laboratory
RPD
o
6
-35.6%
34.8%
2.7%
8.9%
6
-18.1%
3.9%
-7.8%
-10.3%
o
6
-20.7%
26.8%
-2.6%
-14.0%
2
-11.1%
5.0%
-3.1%
-3.1%
4
-23.4%
7.0%
-2.8%
2.5%
13
-42.5%
22.1%
-0.7%
4.6%
RPD ABS Val
o
6
8.9%
35.6%
26.5%
34.8%
6
3.5%
18.1%
10.2%
10.3%
o
6
14.0%
26.8%
20.5%
20.7%
2
5.0%
11.1%
8.0%
8.0%
4
0.7%
23.4%
9.2%
6.4%
13
1.2%
42.5%
14.6%
15.9%
Iron
Reference Laboratory
RPD
3
-56.2%
18.6%
-12.5%
0.0%
7
-25.5%
-8.7%
-16.0%
-15.8%
3
-28.2%
-2.4%
-17.1%
-20.8%
6
-62.2%
-13.6%
-33.2%
-30.3%
12
-57.9%
35.8%
-22.3%
-19.0%
13
-46.7%
6.0%
-22.3%
-20.5%
RPD ABS Val
3
0.0%
56.2%
24.9%
18.6%
7
8.7%
25.5%
16.0%
15.8%
3
2.4%
28.2%
17.1%
20.8%
6
13.6%
62.2%
33.2%
30.3%
12
2.1%
57.9%
28.2%
30.7%
13
3.4%
46.7%
23.2%
20.5%
Lead
Reference Laboratory
RPD
o
5
-61.9%
-21.4%
-35.4%
-22.9%
7
-22.7%
-9.8%
-18.5%
-19.8%
o
5
-27.2%
122.7%
32.6%
2.2%
6
-31.9%
-11.2%
-20.6%
-19.9%
6
-70.9%
-39.9%
-47.6%
-42.8%
13
-56.0%
-0.1%
-25.2%
-23.0%
RPD ABS Val
o
6
21.4%
61.9%
35.4%
22.9%
7
9.8%
22.7%
18.5%
19.8%
o
6
2.2%
122.7%
50.7%
27.2%
6
11.2%
31.9%
20.6%
19.9%
6
39.9%
70.9%
47.6%
42.8%
13
0.1%
56.0%
25.2%
23.0%
E-23
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Site
AS
BN
CN
KP
LV
RF
Matrix
Description
Fine to medium sand
(steel processing)
Sandy loam, low
organic (ore residuals)
Sandy loam (burn pit
residue)
Soil: Fine to medium
quartz sand.
Sed. : Sandy loam, high
organic.
(Gun and skeet ranges)
Clay /clay loam, salt
crust (iron and other
precipitate)
Silty fine sand (tailings)
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Mercury
Reference Laboratory
RPD
~
~
~
1
110.4%
110.4%
110.4%
110.4%
2
16.2%
30.7%
23.4%
23.4%
-
4
11.7%
53.5%
37.3%
41.9%
4
-0.4%
27.9%
12.5%
11.2%
RPD ABS Val
~
~
~
1
110.4%
110.4%
110.4%
110.4%
2
16.2%
30.7%
23.4%
23.4%
-
4
11.7%
53.5%
37.3%
41.9%
4
0.4%
27.9%
12.7%
11.2%
Nickel
Reference Laboratory
RPD
1
74.6%
74.6%
74.6%
74.6%
6
-4.2%
48.9%
16.3%
10.6%
o
3
-21.2%
22.4%
7.6%
21.6%
3
-29.2%
12.2%
-9.0%
-10.1%
11
-10.2%
43.0%
10.0%
7.8%
13
5.1%
69.4%
38.5%
36.7%
RPD ABS Val
1
74.6%
74.6%
74.6%
74.6%
6
0.9%
48.9%
17.7%
10.6%
o
3
21.2%
22.4%
21.7%
21.6%
o
3
10.1%
29.2%
17.1%
12.2%
11
4.0%
43.0%
14.5%
10.2%
13
5.1%
69.4%
38.5%
36.7%
Selenium
Reference Laboratory
RPD
1
-110.7%
-110.7%
-110.7%
-110.7%
4
-1.3%
80.8%
40.2%
40.6%
2
-5.2%
6.7%
0.8%
0.8%
~
5
-27.7%
17.4%
-8.2%
-8.8%
5
-23.1%
11.6%
-6.0%
-4.8%
RPD ABS Val
1
110.7%
110.7%
110.7%
110.7%
4
1.3%
80.8%
40.8%
40.6%
2
5.2%
6.7%
6.0%
6.0%
~
5
6.9%
27.7%
15.1%
14.7%
5
0.2%
23.1%
10.6%
11.6%
Silver
Reference Laboratory
RPD
1
19.3%
19.3%
19.3%
19.3%
1
5.6%
5.6%
5.6%
5.6%
~
~
~
~
1
-34.5%
-34.5%
-34.5%
-34.5%
2
-64.8%
114.6%
24.9%
24.9%
RPD ABS Val
1
19.3%
19.3%
19.3%
19.3%
1
5.6%
5.6%
5.6%
5.6%
~
~
~
~
1
34.5%
34.5%
34.5%
34.5%
2
64.8%
114.6%
89.7%
89.7%
E-24
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Site
AS
BN
CN
KP
LV
RF
Matrix
Description
Fine to medium sand
(steel processing)
Sandy loam, low
organic (ore residuals)
Sandy loam (burn pit
residue)
Soil: Fine to medium
quartz sand.
Sed.: Sandy loam, high
organic.
(Gun and skeet ranges)
Clay /clay loam, salt
crust (iron and other
precipitate)
Silty fine sand (tailings)
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Vanadium
Reference Laboratory
RPD
1
68.7%
68.7%
68.7%
68.7%
4
-6.5%
22.3%
9.1%
10.2%
1
14.5%
14.5%
14.5%
14.5%
-
9
-24.7%
66.0%
8.8%
-0.2%
3
-24.3%
-16.7%
-19.4%
-17.2%
RPD ABS Val
1
68.7%
68.7%
68.7%
68.7%
4
0.1%
22.3%
12.3%
13.5%
1
14.5%
14.5%
14.5%
14.5%
~
9
0.2%
66.0%
22.9%
15.0%
3
16.7%
24.3%
19.4%
17.2%
Zinc
Reference Laboratory
RPD
o
5
-35.7%
-14.5%
-21.9%
-15.4%
7
-23.6%
-10.3%
-17.2%
-17.9%
o
5
-27.3%
-7.3%
-17.4%
-17.6%
2
-14.0%
0.0%
-7.0%
-7.0%
10
-44.0%
0.7%
-20.9%
-19.0%
13
-11.6%
35.7%
9.3%
8.2%
RPD ABS Val
o
5
14.5%
35.7%
21.9%
15.4%
7
10.3%
23.6%
17.2%
17.9%
o
5
7.3%
27.3%
17.4%
17.6%
2
0.0%
14.0%
7.0%
7.0%
10
0.7%
44.0%
21.0%
19.0%
13
1.0%
35.7%
14.3%
11.6%
E-25
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Sediment
Soil
Site
SB
TL
WS
All
Matrix
Description
Coarse sand and gravel
(ore and waste rock)
Silt and clay (slag-
enriched)
Coarse sand and gravel
(roaster slag)
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
Reference Laboratory
RPD
~
~
~
~
~
~
~
~
~
~
~
~
-
RPD ABS Val
~
~
~
~
~
~
~
~
~
~
~
~
-
Certified Value
RPD
~
~
~
~
~
~
~
~
~
~
~
~
-
RPD ABS Val
~
~
~
~
~
~
~
~
~
~
~
~
-
Arsenic
Referen
RPD
5
-41.9%
-8.4%
-26.0%
-20.7%
2
-27.4%
56.8%
14.7%
14.7%
7
-21.3%
37.0%
8.7%
9.2%
46
-93.5%
181.4%
-2.3%
-6.8%
ce Laboratory
RPD ABS Val
5
8.4%
41.9%
26.0%
20.7%
2
27.4%
56.8%
42.1%
42.1%
7
3.5%
37.0%
17.3%
12.2%
46
0.4%
181.4%
23.4%
13.4%
Cadmium
Referenc
RPD
1
6.3%
6.3%
6.3%
6.3%
~
~
~
3
-168.1%
-148.8%
-160.7%
-165.3%
12
-168.1%
138.5%
-7.6%
2.7%
e Laboratory
RPD ABS Val
1
6.3%
6.3%
6.3%
6.3%
~
~
~
3
148.8%
168.1%
160.7%
165.3%
12
0.8%
168.1%
76.2%
83.2%
E-26
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Sediment
Soil
Site
SB
TL
WS
All
Matrix
Description
Coarse sand and gravel
(ore and waste rock)
Silt and clay (slag-
enriched)
Coarse sand and gravel
(roaster slag)
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Chromium
Reference Laboratory
RPD
11
-83.8%
-6.9%
-40.8%
-39.8%
5
15.0%
30.4%
22.7%
20.3%
7
-17.8%
51.8%
7.3%
0.5%
61
-83.8%
130.1%
-10.2%
-11.2%
RPD ABS Val
11
6.9%
83.8%
40.8%
39.8%
5
15.0%
30.4%
22.7%
20.3%
7
0.5%
51.8%
16.0%
11.5%
61
0.5%
130.1%
24.8%
18.1%
Copper
Reference Laboratory
RPD
4
-14.5%
14.3%
-3.5%
-7.0%
7
-25.6%
75.7%
21.0%
8.5%
6
-14.1%
7.1%
-2.9%
-1.8%
48
-42.5%
75.7%
0.9%
-0.6%
RPD ABS Val
4
1.0%
14.5%
10.7%
13.6%
7
0.4%
75.7%
28.5%
19.2%
6
0.5%
14.1%
5.2%
4.2%
48
0.4%
75.7%
15.0%
12.3%
Iron
Reference Laboratory
RPD
12
-25.5%
7.9%
-11.1%
-12.6%
7
-73.5%
8.9%
-24.7%
-7.6%
7
-27.3%
1.3%
-10.9%
-7.6%
70
-73.5%
35.8%
-19.1%
-16.4%
RPD ABS Val
12
2.3%
25.5%
12.4%
12.6%
7
1.5%
73.5%
27.7%
8.9%
7
1.3%
27.3%
11.2%
7.6%
70
0.0%
73.5%
21.4%
17.3%
Lead
Reference Laboratory
RPD
7
-13.6%
108.8%
35.1%
19.5%
4
5.1%
39.7%
23.0%
23.5%
7
-89.4%
-7.3%
-35.5%
-25.7%
56
-89.4%
122.7%
-14.0%
-21.2%
RPD ABS Val
7
9.1%
108.8%
39.0%
19.5%
4
5.1%
39.7%
23.0%
23.5%
7
7.3%
89.4%
35.5%
25.7%
56
0.1%
122.7%
31.0%
22.9%
E-27
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Sediment
Soil
Site
SB
TL
WS
All
Matrix
Description
Coarse sand and gravel
(ore and waste rock)
Silt and clay (slag-
enriched)
Coarse sand and gravel
(roaster slag)
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Mercury
Reference Laboratory
RPD
11
-94.0%
73.0%
23.0%
28.7%
2
47.7%
115.8%
81.7%
81.7%
~
~
~
24
-94.0%
115.8%
32.2%
29.7%
RPD ABS Val
11
4.7%
94.0%
41.0%
43.3%
2
47.7%
115.8%
81.7%
81.7%
~
~
~
24
0.4%
115.8%
40.5%
33.0%
Nickel
Reference Laboratory
RPD
11
-28.1%
18.6%
0.3%
1.0%
6
18.8%
77.2%
36.4%
30.1%
7
6.2%
62.8%
37.9%
50.0%
61
-29.2%
77.2%
20.7%
18.8%
RPD ABS Val
11
1.0%
28.1%
9.1%
5.7%
6
18.8%
77.2%
36.4%
30.1%
7
6.2%
62.8%
37.9%
50.0%
61
0.9%
77.2%
25.3%
21.2%
Selenium
Reference Laboratory
RPD
3
-17.4%
5.5%
-7.2%
-9.6%
4
-50.7%
81.0%
1.9%
-11.2%
1
4.8%
4.8%
4.8%
4.8%
25
-110.7%
81.0%
-1.1%
-4.8%
RPD ABS Val
3
5.5%
17.4%
10.8%
9.6%
4
4.4%
81.0%
38.5%
34.4%
1
4.8%
4.8%
4.8%
4.8%
25
0.2%
110.7%
24.2%
11.6%
Silver
Reference Laboratory
RPD
~
~
~
2
8.5%
59.1%
33.8%
33.8%
2
-8.9%
12.0%
1.6%
1.6%
9
-64.8%
114.6%
12.3%
8.5%
RPD ABS Val
~
~
-
2
8.5%
59.1%
33.8%
33.8%
2
8.9%
12.0%
10.4%
10.4%
9
5.6%
114.6%
36.4%
19.3%
E-28
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Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Sediment
Soil
Site
SB
TL
WS
All
Matrix
Description
Coarse sand and gravel
(ore and waste rock)
Silt and clay (slag-
enriched)
Coarse sand and gravel
(roaster slag)
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Vanadium
Reference Laboratory
RPD
10
-50.4%
20.7%
-26.7%
-33.7%
7
23.5%
94.3%
57.8%
52.4%
3
-13.9%
8.2%
0.7%
7.9%
38
-50.4%
94.3%
7.3%
2.1%
RPD ABS Val
10
4.3%
50.4%
31.7%
33.7%
7
23.5%
94.3%
57.8%
52.4%
3
7.9%
13.9%
10.0%
8.2%
38
0.1%
94.3%
30.2%
22.9%
Zinc
Reference Laboratory
RPD
11
-83.3%
11.1%
-25.7%
-22.9%
7
-38.6%
53.9%
7.5%
1.2%
7
-18.0%
16.0%
-5.3%
-4.5%
63
-83.3%
53.9%
-9.7%
-11.5%
RPD ABS Val
11
10.9%
83.3%
27.8%
22.9%
7
1.2%
53.9%
22.8%
7.9%
7
0.9%
18.0%
10.1%
9.9%
63
0.0%
83.3%
18.8%
16.0%
Site Abbreviations:
AS Alton Steel Mill
BN Burlington Northern Railroad/ASARCO East
CN Naval Surface Warfare Center, Crane Division
KP KARS Park - Kennedy Space Center
LV Leviathan Mine/Aspen Creek
RF Ramsey Flats - Silver Bow Creek
SB Sulfur Bank Mercury Mine
TL Torch Lake Superfund Site
WS Wickes Smelter Site
Other Notes:
Number
RPD
No samples reported by the reference laboratory in this
concentration range.
Number of demonstration samples evaluated.
Relative percent difference (unmodified).
RPD Abs Val Relative percent difference (absolute value).
E-29
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