United States Office of Research and EPA/540/R-06/004
Environmental Protection Development February 2006
Agency Washington, DC 20460
Innovative Technology
Verification Report
XRF Technologies for Measuring
Trace Elements in
Soil and Sediment
Niton XLt 700 Series
XRF Analyzer
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EPA/540/R-06/004
February 2006
Innovative Technology
Verification Report
Niton XLt 700 Series
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 Niton XLt 700 Series (XLt) XRF Services 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 XLt 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 XLt 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 Niton XLt is a small, field-portable instrument designed for chemical characterization of soils,
sediment, and other thick homogeneous samples (plastics and metals). The analyzer features a
miniaturized x-ray tube for the excitation source and a Peltier-cooled Si-PiN x-ray detector. The
analyzer's standard software is programmed to analyze and automatically report 25 elements. The Niton
XLt analyzer is designed to be used as either a hand-held instrument for in situ analysis or as a bench-top
instrument, in a test stand with a sample drawer below the instrument, for ex situ analysis. The Niton XLt
analyzer can be used to analyze elements under three primary scenarios: (1) bulk sample mode (includes
soils, sediments, and metal alloys); (2) thin film mode (includes dust wipes and filters); and (3) plastics
mode. XRF analyses using the Niton XLt analyzer comply with EPA Method 6200, "Field Portable XRF
Spectrometry for the Determination of Elemental Concentrations in Soil and Sediment."
This report describes the results of the evaluation of the XLt 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 XLt 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 41
6.2.1 Setup and Calibration 41
6.2.2 Demonstration Sample Processing 41
6.3 General Demonstration Results 42
6.4 Contact Information 42
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 52
7.4 Primary Obj ective 4 - Impact of Chemical and Spectral Interferences 53
7.5 Primary Objective 5 - Effects of Soil Characteristics 56
7.6 Primary Objective 6 - Sample Throughput 60
7.7 Primary Objective 7 - Technology Cost 60
7.8 Secondary Objective 1 - Training Requirements 60
7.9 Secondary Objective 2 -Health and Safety 61
7.10 Secondary Objective 3 - Portability 62
7.11 Secondary Objective 4 - Durability 62
7.12 Secondary Objective 5 -Availability 62
8.0 ECONOMIC ANALYSIS 63
8.1 Equipment Costs 63
8.2 Supply Costs 63
8.3 Labor Costs 64
8.4 Comparison of XRF Analysis and Reference Laboratory Costs 65
9.0 SUMMARY OF TECHNOLOGY PERFORMANCE 67
10.0 REFERENCES 73
APPENDICES
Appendix A: Verification Statement
Appendix B: Developer Discussion
Appendix C: Data Validation Summary Report
Appendix D: Developer and Reference Laboratory Data
Appendix E: Statistical Data Summaries
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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 Niton XLtXRF Analyzer Technical Specifications 40
7-1 Evaluation of Sensitivity - Method Detection Limits for Niton XLt 44
7-2 Comparison of XLt MDLs to XLt Instrument LODs and EPA
Method 6200 Data 46
7-3 Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data
for the Niton XLt 48
7-4 Summary of Correlation Evaluation forthe Niton XLt 50
7-5 Evaluation of Precision - Relative Standard Deviations for the Niton XLt 54
7-6 Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory
versus the XLt and All Demonstration Instruments 55
7-7 Effects of Interferent Elements on the RPDs (Accuracy) for Other Target Elements 57
7-8 Effect of Soil Type on the RPDs (Accuracy) for Target Elements 58
7-9 RPDs Calculated for Wickes Smelter Sample Blends for the Niton XLt 60
8-1 Equipment Costs 63
8-2 Time Required to Complete Analytical Activities 64
8-3 Comparison ofXRF Technology and Reference Method Costs 66
9-1 Summary of Niton XLt Performance - Primary Objectives 68
9-2 Summary of Niton XLt Performance - Secondary Objectives 70
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 In-situ Testing with the Niton XLT 700 Series Analyzer 39
6-2 Niton Technician Using a Stainless Steel Scoop to Fill a Sample Cup 41
6-3 Instrument Setup with Samples Awaiting Analysis 42
7-1 Linear Correlation Plot for Niton XLt Showing High Correlation for Selenium 51
7-2 Linear Correlation Plot for Niton XLt Showing Low Correlation and Bias
For Vanadium 52
8-1 Comparison of Activity Times for the XLt versus Other XRF Instruments 65
9-1 Method Detection Limits (sensitivity), Accuracy, and Precision of the Niton XLt
in Comparison to the Average of All Eight XRF Instruments 71
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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; David Mercuro and Laura Stupi of Niton Analyzers, A Division of Thermo
Electron Corporation; 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 Niton
XLt 700 Series 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 introduction (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
evaluation (Chapter 7), a cost analysis (Chapter 8),
and a summary of the demonstration results (Chapter
9).
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 Bruker
AXS, 1 1/2005)
Distributor in the
United States
Xcalibur XRF Services
Innov-X Systems
NITON Analyzers, A
Division of Thermo
Electron Corooration
Oxford Instruments
Analytical, Ltd.
Rigaku, Inc.
RONTEC USA
Developer Short
Name
Xcalibur
Innov-X
Niton
Oxford
Rigaku
Rontec
Instrument Full
Name
ElvaX
XT400 Series
XLi 700 Series
XLt 700 Series
X-Met 3000 TX
ED2000
ZSX Mini II
PicoTAX
Instrument Short
Name
ElvaX
XT400
XLi
XLt
X-Met
ED2000
ZSX Mini II
PicoTAX
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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
(wwuv.cga.goy/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 (www.eBa.govAierlgsd_l/)- 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
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.
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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).
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
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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-shelt electron
Incident
...
"itr -
_
5J
V-, L-sheM electron
'-.fills vacancy
je-ray Emitted
M-shetl 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 become worse 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)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. The
demonstration therefore focused on the analysis of
these 13 elements in evaluating the various XRF
instruments.
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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). Antimony is mobile in the
environment and is bioavailable for uptake by plants;
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 for XRF analysis when the ratio of lead to
arsenic in 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. Concentrations 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;
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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.
7.5.* 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.
7.5.70 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
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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
Ag
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 Site
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
demonstration 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
15
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Model T 50A Turbula shaker-mixer. This shaker
was 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
steel hammer mill
Samples are
mixed and homogenized
using Model T50A
Turbula shaker-mixer
Samples are
mixed and homogenized
Model T 10B
and Turbula shaker-mixer
Aliquots from each
homogenized soil and sediment
were sampled and analyzed
in triplicate using ICP-AES
and CVAA for the target elements
Was
the percent difference
between the highest and
lowest result greater
than 10%?
Yes
Package samples
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).
Presentations by NASA and EPA representatives
were followed by a tour of the XRF instruments in
the recreation building while demonstration samples
were being analyzed.
^^^BA^::"-^ .-.i-::..™
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
21
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that might provide the developer's field team any
insight as to the nature or content of the sample.
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 Excel® 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 Access® 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
from the corresponding result for all eight
23
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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.
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:
MDL = t(n-U-a=o.99)(s)
where
MDL = method detection limit
t = Student's t value for a 99 percent
confidence level and a standard
deviation estimate with n-1 degrees
of freedom
n = number of samples
s = 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
n
C_k
C
= Standard deviation
= Number of replicate
samples
= Concentration of sample K
= 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, Mylar®, 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
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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.
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
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 1
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.
MSD 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
-------
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
As
Cd
Cr
Cu
Fe
Pb
Hg
Ni
Se
Ag
V
Zn
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
37
-------
Table 5-3. Precision of Reference Laboratory Results for Blends 1 through 70
Statistic
Number of %RSDs
Minimum %RSD
Maximum %RSD
Mean %RSDl
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
As
Cd
Cr
Cu
Fe
Pb
Hg
Ni
Se
Ag
V
Zn
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
38
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Chapter 6
Technology Description
The XLt 700 Series XRF analyzer is manufactured
by NITON Analyzers, a division of Thermo Electron
Corporation (Niton). This chapter provides a
technical description of the XLt based on information
obtained from Niton and observation of this analyzer
during the field demonstration. This section also
identifies a Niton company contact, where additional
technical information may be obtained.
6.1 General Description
The Niton XLt 700 Series XRF analyzer is a small,
field-portable instrument designed for chemical
characterization of soils, sediment, and other thick,
homogeneous samples (plastics and metals). The
analyzer features a miniaturized x-ray tube for the
excitation source and a Peltier-cooled Si-PiN x-ray
detector. The analyzer's standard software is
programmed to analyze and automatically report 25
elements. The optional proprietary software package
called PERFECT (for Programmable Excitation by
Regulation of Filters, Energy, Current, and Time)
provides additional capabilities for analyzing and
reporting light elements (including vanadium and
chromium) and optimizes the detection limits for a
suite of elements specific to an application. Other
features include an integrated touch-screen display;
completely sealed housing to protect the analyzer
from moisture and dust; lithium-ion batteries; an
integrated bar code reader and virtual keypad; remote
operation and custom report generation capability
from a Windows-based PC; a shielded bench-top test
stand; and Bluetooth wireless communication to a
laptop or personal data assistant (PDA).
The XLt is factory calibrated to simultaneously
analyze up to 25 elements, including all eight
Resource Conservation and Recovery Act (RCRA)
metals. The analyzer does not require a site- or
material-specific calibration; however, it is capable of
handling user-generated empirical calibrations, if
required for specific applications.
The XLt is designed to be used either as a hand-held
instrument for in situ analysis (Figure 6-1) or as a
bench-top instrument, in a test stand with a sample
drawer below the instrument, for ex situ analysis. To
analyze soil samples in the in situ mode, the
instrument x-ray window is placed directly on the
ground or on soils in a plastic bag; for ex situ
analysis, samples are prepared in x-ray sample cups
and are placed in the sample drawer at the bottom of
the test stand, directly beneath the instrument x-ray
window. In situ testing with the XLt allows for a
semi-quantitative assessment of element
concentrations at multiple locations or over large
areas in a short time. Quantitative ex situ testing
involves properly preparing the samples, placing the
samples in x-ray sample cups, and analyzing them in
a controlled area, typically free from dust and
weather extremes. Most field applications
incorporate a combination of in situ and ex situ
testing.
Figure 6-1. In situ testing with the Niton XLt 700
Series analyzer.
The XLt can be used to analyze elements under three
primary scenarios: (1) bulk sample mode (includes
soils, sediments, and metal alloys); (2) thin film
mode (includes dust wipes and filters); and (3)
plastics mode. Two standard calibrations are
provided under the bulk sample mode and include
one for standard soils and one for industrial bulk
(metal alloys). Additional user-defined calibrations
can be programmed and used under the bulk sample
39
-------
mode. In the thin film mode, the XLt can be used to
analyze thin samples (dust wipes) and other filter
media used to capture airborne particulate matter.
XRF analysis using the XLt can comply fully with
EPA Method 6200, "Field Portable XRF
Spectrometry for the Determination of Elemental
Concentrations in Soil and Sediment." Since XRF
analysis is nondestructive, samples analyzed by XRF
can be sent to a fixed analytical laboratory for
confirmation of results.
The technical specifications for the XLt are presented
in Table 6-1.
Niton has not published formal standard operating
procedures for the XLt analyzer operations, but
recommends that users follow EPA Method 6200 and
the instrument user's manual to ensure that the
appropriate protocol is followed. The recommended
steps include the following:
(1) Insert the battery, turn on the system, and allow it
to warm up for 15 minutes.
(2) Ensure the date and time is correct.
(3) Analyze the standard check samples (National
Institute of Standards and Technology [NIST]
2709; NIST 2710; and blank) to ensure proper
precision. Repeat this step every 4 to 6 hours, or
after a battery exchange and reboot.
(4) Download and delete data after 3,000 readings
have been taken.
Table 6-1. Niton XLt XRF Analyzer Technical Specifications
Weight:
Dimensions:
Excitation Source:
Detector:
Signal Processing:
Element Range:
Batteries:
Display:
Testing Modes:
Standard Accessories:
3.0 pounds (1.4 kg)
Hand-held, approx. 9.75 by 10.5 by 3.75 inches (248 by 273 by 95 millimeter).
Miniature x-ray tube and power supply (40 kilovolts [kV]/50 microamps [|iA]
maximum) with optional PERFECT technology.
High-performance Si-PiN detector, Peltier cooled.
Hitachi SH-4 CPU ASICS high-speed DSP 4096 channel MCA
• Up to 25 standard elements in the range from titanium (atomic number: 22)
to plutonium (atomic number: 94)
• Some nonstandard in-range elements available at additional cost
(2) Rechargeable lithium-ion battery packs with quick-swap capability; 6 to 12
hour life between recharges (maximum depends on platform and duty cycle),
2-hour recharge cycle.
% Backlit VGA touch-screen LCD.
• Bulk sample mode
• Thin sample mode, including dust wipe mode and 37-millimeter filter mode
• Soil Sampling Kit/Thin Sample Kit (varies by model and configuration)
• Lockable, shielded waterproof carrying case
• Shielded belt holster
• Spare lithium-ion battery pack with holster
• 11 0/220 volt AC battery charger/adapter
• PC interface cable
• Niton Data Transfer (NOT) PC software
• Safety lanyard
• Check and verification standards
• Integrated bar code scan engine and virtual keypad for rapid and reliable
entry of sample information
40
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6.2 Instrument Operations during the
Demonstration
The XLt can be shipped or transported as checked or
carry-on baggage. For transport to the field
demonstration, the XLt was packed in a Pelican case
that was 8 inches tall by 20 inches wide and 16
inches deep. The Pelican case was inspected by
airport transportation security staff without concerns
or delays. One additional large box was needed to
hold all the accessories and supplies for routine
analysis. A laptop computer is not required for
analysis, but was used during the field demonstration
for data downloading and to serve as a larger screen
for viewing results and for assigning sample
numbers.
6.2.1 Set up and Calibration
During the field demonstration, the XLt was used in
the ex situ, bulk analysis mode. Instrument set-up
involved placing the unit in the environmental test
stand, connecting the analyzer to the laptop
computer, and powering up both the analyzer and the
computer. As part of the standard set-up routine, the
analyzer was initially calibrated using the silver and
tungsten shielding on the inside of the shutter to fine-
tune the known peaks for these elements. Even
though a warm-up time is not required, about 5
minutes is recommended to allow the analyzer to
equilibrate with ambient conditions.
Niton included five calibration and reference samples
with the analyzer to be used for calibration. Included
were three NIST standards, one RCRA metals
reference sample, and one silica blank. The Niton
field team also used additional standards and samples
with known element concentrations (the pre-
demonstration samples) to further evaluate the
calibration of the XLt analyzer. Individual element
results and the error for each value were evaluated to
verify that the analyzer was calibrated. The pre-set
factory standard calibration for soil was selected for
all routine analysis of soil and sediment and included
the simultaneous analysis of up to 25 elements. The
XLt analyzer software allows for empirical
calibrations and corrections for any of the 25
elements. However, no empirical calibrations or
corrections were used during the field demonstration.
6.2.2 Demonstration Sample Processing
Niton sent a two person team to the demonstration
site to operate the two Niton instruments that were
participating in the demonstration. One field team
member was assigned to each instrument and
completed the sample preparation, analysis, and data
reduction for that instrument. Thus, the XLt had a
dedicated operator for the entire length of the field
demonstration, which showed how a single person
could efficiently prepare and analyze samples in the
field using the XLt.
Before sample processing was initiated, each sample
set was arranged in numerical order. Custody seals
were broken, and the soil samples were placed in
standard 32-millimeter sample cups using a small
stainless steel spatula (Figure 6-2). The sample cups
were filled approximately 1/2 to 2/3 full. Each
sample cup was then fitted with a small paper disc,
polyester batting material behind the soil, and an end
cap. The polyester batting and paper disc were
necessary to hold the soil firmly against the upper
Mylar® film when the sample cup is inverted. A
colored self-adhesive dot was used to label each
sample cup with the proper number and was attached
to the bottom of the prepared sample cups.
Figure 6-2. Niton technician using a stainless steel
scoop to fill a sample cup.
Prepared samples were placed in a queue and
analyzed in order (Figure 6-3). Each sample was
placed in the environmental sample holder and the
drawer closed. The sample analysis was started from
the laptop computer that was directly connected to
41
-------
the XLt instrument. A 120-second analysis run time
was selected as an appropriate length that would
simulate the choice of a typical customer under
normal field conditions. At the end of the 120-
second test, the sample number recording screen was
viewed on the laptop computer, and then the sample
number was entered and the results were saved. The
Niton data transfer (NDT) software has the option to
save the data simultaneously to the laptop computer
and to the XLt. The data were written to the
computer using a comma-separated value (CSV)
format.
Figure 6-3. Instrument set-up with samples
awaiting analysis.
6.3
General Demonstration Results
The Niton operator for the XLt analyzed all 326 soil
and sediment samples in 4 days using the standard
soils calibration in the bulk sample mode. All
analyses were completed in the ex situ mode after the
samples were placed in the sample cups for analysis.
Samples with results for iron above 50,000 ppm (5
percent) and samples with results for lead above
10,000 ppm (1 percent) were set aside for an
additional 30-second analysis using the industrial
bulk calibration in the bulk sample mode.
The industrial bulk calibration is not considered as
accurate as the standard calibration for elements in
soils below approximately 1 percent. However, the
industrial bulk calibration is considered more
accurate than the standard calibration for most
elements in soils at concentrations above 1 percent.
Iron is a common element in soils and is typically at
concentrations above 10,000 ppm; therefore, the
standard soil calibration range for iron extends to
50,000 ppm.
6.4
Contact Information
Additional information on Niton's XLt 700 Series
XRF analyzer is available from the following source:
Mr. Dave Mercuro
Niton Analyzers
900 Middlesex Turnpike, Building #8
Billerica, Massachusetts 01821
Telephone: (800) 875-1578, Ext. 333
Fax: 978-670-7430
E-mail: dmcrcurQ^niton.cQin
Internet: www.Niton.com
42
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Chapter 7
Performance Evaluation
As discussed in Chapter 6, Niton analyzed all 326
demonstration samples of soil and sediment at the
field demonstration site between January 25 and 27,
2005. A complete set of electronic data for the XLt
in Microsoft Excel® spreadsheet format was delivered
to the EPA/Tetra Tech field team before Niton
demobilized from the site on January 28, 2005. All
the data provided by Niton at the close of the
demonstration are tabulated and compared with the
reference laboratory data and the ERA-certified spike
concentrations in Appendix D.
The XLt 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 MDL calculation also
addressed results reported as "not detected" by Niton.
For many of the MDL blend results, element
concentrations were below the statistical limits of
detection (LODs) calculated by the XLt's instrument
algorithms. These LODs are sample-specific and are
calculated based on blank measurements, calibration
routines, and relative element concentrations in the
samples analyzed. (Additional information on
calculating LODs is available from the developer,
and a technical bulletin is available at
http://www.NITONiton.com/docs/LODs.pdf.) In
selecting samples from among the 12 blends for the
calculation of MDLs, blends where one or more of
the seven replicates was reported as "
-------
Table 7-1. Evaluation of Sensitivity ~ Method Detection Limits for the Niton XLt1
Matrix
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Sediment
Sediment
Sediment
Sediment
Sediment
Blend
No.
2
5
6
8
10
12
18
29
31
32
39
65
Mean XLt MDL
Matrix
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Sediment
Sediment
Sediment
Sediment
Sediment
Blend
No.
2
5
6
8
10
12
18
29
31
32
39
65
Mean XLt MDL
Antimony
XLt
MDL2
NC
NC
NC
234
NC
198
NC
NC
NC
NC
NC
NC
XLt
Cone.3
ND
ND
ND
646
ND
326
ND
ND
ND
ND
ND
ND
Ref. Lab
Cone.4
17
ND
8
118
ND
62
ND
ND
ND
ND
ND
11
216
Copper
XLt
MDL2
19
NC
67
NC
NC
NC
NC
NC
NC
NC
66
40
XLt
Cone.3
42
ND
143
2,900
ND
845
ND
1,877
1,522
ND
98
80
Ref. Lab
Cone.4
47
49
160
1,243
31
747
50
1,986
1,514
36
94
69
48
Arsenic
XLt
MDL2
NC
15
NC
NC
20
NC
NC
NC
NC
22
11
23
XLt
Cone.3
ND
49
389
12,258
36
680
ND
ND
ND
34
19 5
291
Ref. Lab
Cone.4
1.5
47
477
3,943
39
559
9
10
11
31
14
250
18
Lead
XLt
MDL2
NC
11
NC
NC
13
NC
NC
27
20
23
9
13
XLt
Cone.3
974
70
3,703
46,986
60
4,423
ND
40
55
28
36
35
Ref. Lab
Cone.4
1,200
78
3,986
33,429
72
4,214
17
33
51
26
27
25
17
Cadmium
XLt
MDL2
NC
NC
NC
142
NC
69
NC
NC
NC
NC
NC
NC
XLt
Cone.3
ND
ND
ND
173
ND
301
ND
ND
ND
ND
ND
ND
Ref. Lab
Cone.4
ND
1.9
12
91
0.96
263
ND
ND
ND
ND
ND
44
105
Mercury
XLt
MDL2
NC
NC
NC
NC
NC
NC
7
NC
15
12
10
11
XLt
Cone.3
ND
ND
ND
ND
ND
ND
31
ND
23
17
28
38
Ref. Lab
Cone.4
ND
ND
0.83
15
0.14
1.8
56
0.24
ND
ND
ND
32
11
Chromium
XLt
MDL2
38
48
50
NC
86
26
70
NC
47
55
46
NC
XLt
Cone.3
299
98
101
ND
107
78
182
ND
159
79
93
345
Ref. Lab
Cone.4
167
121
133
55
116
101
150
63
133
75
102
303
52
Nickel
XLt
MDL2
47
50
60
171
65
49
58
28
135
100
76
90
XLt
Cone.3
123
78
101
277
78
137
289
154
377
194
263
325
Ref. Lab
Cone.4
83
60
70
57
60
91
213
72
196
174
202
214
77
44
-------
Table 7-1. Evaluation of Sensitivity ~ Method Detection Limits for the Niton XLt1 (Continued)
Matrix
Soil
Soil
Soil
Soil
Soil
Soil
Soil
Sediment
Sediment
Sediment
Sediment
Sediment
Blend No.
2
5
6
8
10
12
18
29
31
32
39
65
Mean XLt MDL
Selenium
XLt
MDL2
NC
NC
NC
NC
NC
27
NC
NC
NC
7
7
4
XLt
Cone.3
ND
ND
ND
ND
ND
19 5
ND
ND
ND
11
10
27
Ref. Lab
Cone.4
ND
ND
ND
ND
ND
15
ND
ND
ND
4.6
ND
22
11
Silver
XLt
MDL2
NC
NC
NC
35
NC
27
NC
NC
NC
NC
NC
27
XLt
Cone.3
ND
ND
ND
224
ND
46 5
ND
ND
ND
ND
ND
41
Ref. Lab
Cone.4
ND
0.93
14
144
ND
38
ND
ND
6.2
ND
ND
41
30
Vanadium
XLt
MDL2
NC
9
23
17
16
11
13
31
5
17
13
10
XLt
Cone.3
ND
47
47
29
42
40
65
62
50
68
39
36
Ref. Lab
Cone.4
1.2
55
56
34
51
45
67
96
76
57
38
31
15
Zinc
XLt
MDL2
23
25
NC
NC
15
NC
21
45
33
33
61
NC
XLt
Cone.3
24
202
749
13,050
77
2,554
86
152
142
79
158
1,946
Ref. Lab
Cone.4
24
229
886
5,657
92
2,114
90
160
137
69
137
1,843
32
Notes:
1 Detection limits and concentrations are milligrams per kilogram (mg/kg), or parts per million (ppm).
2 MDLs calculated from the 12 MDL sample blends for the Niton XLt in this technology demonstration (in bold typeface for emphasis).
3 This column lists the mean concentration reported for this blend by the XLt.
4 This column lists the mean concentration reported for this blend by the reference laboratory.
5 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.
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." Except where otherwise noted, blends with one or more ND result as reported
by the XRF were not used for calculating the MDL.
Ref. Lab.Reference laboratory.
45
-------
Table 7-2. Comparison of XLt MDLs to XLt Instrument LODs and EPA Method 6200 Data1
Element
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
XLt Mean
MDLs2
216
18
105
52
48
17
11
62
11
30
15
32
XLt Mean
LODs3
91
26
36
46
44
11
30
191
37
29
54
NR
All XRF Instrument
Mean MDLs4
61
26
70
83
23
40
23
50
8
42
28
38
EPA Method 6200s
Mean Detection Limits
556
92
NR
376
171
78
NR
1006
NR
NR
NR
89
Notes:
i
EPA
LOD
MDL
NR
Detection limits are in units of milligrams per kilogram (mg/kg), or parts per million (ppm).
The mean MDLs calculated for this technology demonstration, as presented in Table 7-1.
The mean LODs reported by Niton for the 12 MDL blends.
The mean MDLs calculated for all eight XRF instruments that participated in this EPA
technology demonstration.
Mean values calculated from Table 4 of Method 6200 (EPA 1998e, www.epa.gov/sw-846).
Only one value reported.
U.S. Environmental Protection Agency
Limit of detection
Method detection limit
Not reported; no MDLs or LODs reported for this element.
for the MDL blends, the mean MDLs for all
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 XLt are generally
comparable to Niton's LODs and are generally lower
than the mean MDLs calculated from EPA Method
6200 data. Exceptions include antimony and
cadmium where, as noted above, limited data for the
XLt appear to have produced mean MDLs that are
higher than the LODs and available Method 6200
data. When compared with the results for the
demonstration as a whole (encompassing all eight
XRF instruments), the XLt again exhibited high
relative mean MDLs for antimony and cadmium as
well as for copper, nickel, and selenium. Mean
MDLs for the XLt were well below the all-instrument
means for chromium, lead, mercury, and vanadium.
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 generally in the range of 40 to 70
for most elements. However, low relative numbers
of acceptable blends were noted for antimony (24),
cadmium (22), mercury (26), and selenium (25).
RPDs between the mean XLt and mean reference
laboratory concentrations were calculated for each
blend that met the criteria for an element.
Table 7-3 presents the median RPDs, along with the
number or RPD results used to calculate the median,
for each target element. These statistics are provided
for the demonstration as a whole, as well as for
subpopulations grouped by media type (soil versus
46
-------
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):
copper and selenium.
• Good (median RPD between 10 percent and 25
percent): arsenic, cadmium, chromium, iron,
lead, silver, and zinc.
• Fair (median RPD between 25 percent and 50
percent): nickel and vanadium.
• Poor (median RPD greater than 50 percent):
antimony and mercury.
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 showed that they were right-skewed or
lognormal.) However, the classification of the
elements based on accuracy generally stayed the
same when the mean RPD rather than the median
RPD was used for the evaluation (Table E-l).
Moreover, these classifications did not vary with
media type (soil versus sediment) for any of the
elements. Neither did they vary with concentration
range, with the following exceptions:
• High median RPDs were observed in the Level 3
samples for arsenic (with concentrations greater
than 2,000 ppm) and Level 1 samples for
cadmium (with concentrations between 50 and
500 ppm). At 79 percent for arsenic and 38
percent for cadmium, these median RPDs were
much higher than were observed for other
concentration ranges. These RPDs appeared to
be skewed high by the results for sample blends 8
and 9 from the Wickes Smelter site, which
contained high concentrations of other elements
(lead, copper, zinc, and iron).
• 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 of less
than 50 percent were calculated. 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.
• Median RPDs for silver in the Level 3
concentration samples (in the range of 50 percent
for both soil and sediment) were higher than in
the Level 1 and 2 samples (where median RPDs
ranged only as high as 17 percent). This effect
was also observed for vanadium, where accuracy
declined from "good" or "fair" into the "poor"
range as concentrations increased. These trends
appeared to be generalized rather than caused by
limited data or extreme results, and may be
related to the overall increasing complexity of the
sample matrices as concentrations of these
elements increased.
Section 5.3.3 discussed how the reference laboratory
data for antimony were consistently biased low when
compared with the ERA-certified spike
concentrations. This effect may be caused by
volatilization of the antimony compounds used for
spiking, resulting in loss of antimony during the
sample digestion process at the reference laboratory.
Therefore, Table 7-3 includes a second accuracy
evaluation for antimony, comparing the XLt results
to the ERA-certified values. As shown, this
comparison indicates far better performance for
antimony than does the comparison to the reference
laboratory results, with median RPDs in the range of
5 to 15 percent ("very good" to "good") for all media
and concentration levels. Furthermore, these results
suggest that the XLt analyzer may measure some
antimony compounds more accurately in soil and
sediment than the fixed-laboratory reference
methods.
47
-------
Table 7-3. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data for the Niton XLt
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
Niton XLt
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
Ref.
Lab
6
133.3%
5
129.5%
4
113.8%
-
15
125.9%
2
144.4%
4
138.5%
3
107.7%
-
9
122.3%
24
125.5%
206
84.3%
ERA
Spike
-
1
7.1%
3
8.9%
-
4
8.7%
2
6.7%
4
15.5%
3
13.5%
-
9
13.5%
13
11.0%
110
70.6%
Arsenic
12
19.0%
4
22 5%
4
79.4%
-
20
24.5%
14
9.1%
4
12.6%
2
20.5%
-
20
12.7%
40
18.1%
320
26.2%
Cadmium
4
37.6%
7
10.7%
2
10.3%
-
13
11.0%
2
10.2%
4
14.9%
3
9.4%
-
9
9.8%
22
10.8%
209
16.7%
Chromium
23
20.4%
4
13.2%
2
17.1%
-
29
19.2%
10
15.4%
3
12.9%
3
9.0%
-
16
12.3%
45
16.4%
338
26.0%
Copper
14
10.3%
8
27.6%
2
13.9%
-
24
12.8%
9
8.9%
4
1.2%
10
5.8%
-
23
5.6%
47
9.3%
363
16.2%
Iron
5
16.3%
13
16.1%
12
5.7%
8
15.0%
38
13.5%
3
5.2%
19
12.5%
5
8.5%
5
26.0%
32
13.5%
70
13.5%
558
26.0%
Lead
14
19.1%
4
17.5%
8
9 2%
5
12.4%
31
17.1%
16
12.4%
4
3.3%
3
8.2%
-
23
8.0%
54
12.0%
392
21.5%
Mercury
7
47.6%
7
116.4%
2
126.3%
-
16
92.0%
3
44.7%
4
80.4%
3
91.6%
-
10
81.6%
26
88.8%
192
58.6%
Nickel
23
38.7%
5
39.0%
6
29.4%
-
34
37.0%
18
52.6%
6
37.8%
4
27.5%
-
28
40.1%
62
38.9%
403
25.4%
Selenium
4
15.2%
5
5.4%
4
3.9%
-
13
5.4%
5
9.1%
4
9.7%
3
5.4%
-
12
9.1%
25
6.8%
195
16.7%
Silver
2
17.0%
3
17.4%
7
43.4%
-
12
24.8%
5
12.7%
4
12.4%
3
53.2%
-
12
15.1%
24
19.0%
177
28.7%
Vanadium
13
8.3%
4
73.5%
4
103.7%
-
21
19.3%
6
40.5%
8
53.2%
3
104.0%
-
17
44.5%
38
40.5%
218
38.3%
Zinc
19
4.5%
6
11.8%
9
18.2%
-
34
8.3%
17
16.8%
5
3.3%
4
8.5%
-
26
12.9%
60
11.5%
471
19.4%
Notes:
All RPDs presented in this table are absolute values.
No samples reported by the reference laboratory in this concentration range.
Environmental Resource Associates, Inc.
ERA
NC
Number
Ref. Lab
RPD
Not calculated.
Number of samples meeting criteria for accuracy evaluation (Section (4.2.2).
Reference laboratory (Shealy Environmental Services, Inc.).
Relative percent difference.
48
-------
As an additional comparison, Table 7-3 also presents
the median XRF instrument RPDs for the
demonstration as a whole (across all eight
instruments). Complete summary statistics for the
RPDs across the eight XRF instruments are included
in Appendix E. Table 7-3 indicates that the median
RPDs for the XLt were higher than the all-instrument
medians for antimony, mercury, and nickel, but were
equivalent to or below them for the remaining 10
target elements.
In addition to calculating RPDs, the evaluation of
accuracy included preparing linear correlation plots of
XLt concentration values against the reference
laboratory values. These plots are presented for the
individual target elements in Figures E-l through E-13
of Appendix E. The plots include a 45-degree line
showing the "ideal" relationship between the XLt data
and the reference laboratory data, as well as a "best
fit" linear 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" relationship 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 calculated 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 antimony (correlated with the ERA-
certified values only), cadmium, chromium, iron, and
selenium met all three of these criteria. The
correlation plot for selenium is displayed in Figure 7-1
as an example of the high correlations obtained for
these elements.
49
-------
Table 7-4. Summary of Correlation Evaluation for the Niton XLt
Notes:
Target Element
Antimony (Ref. Lab) :
Antimony (Cert. Val.) 1
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
m
3.40
1.12
1.34
1.20
1.00
1.09
1.23
1.45
0.24
1.31
0.98
1.24
0.22
1.77
b
129
18
12
28
26
55
403 2
509 2
25
56
7
18
40
456
2
r
0.88
0.99
0.95
0.98
0.95
0.87
0.94
0.95
0.98
0.98
0.99
0.71
0.51
0.76
Correlation
Moderate
High
High
High
High
Moderate
High
High
High
High
High
Moderate
Moderate
Moderate
Bias
High
—
High
—
—
—
~
High
Low
High
—
—
Low
High
b
m
9
r
For antimony, correlation was assessed for the Niton XLt versus the reference laboratory data ("Ref. Lab") as
well as versus the ERA-certified spike values ("Cert. Val.") for the spiked sample blends.
For iron, no MDL was calculated and the high intercept value was the result of the extreme range of
concentrations in the demonstration samples. The broad range of concentrations in the demonstration samples
also produced a high intercept for lead.
No bias observed.
Y-intercept of correlation line.
Slope of correlation line.
Correlation coefficient of correlation line.
50
-------
Figure 7-1. Linear correlation plot for Niton XLt
showing high correlation for selenium
350
& 300
X 250
3
d 700 -
150 -
100 -
50 -
0 i
C
A Niton XLt
45 Degrees
— — Linear (Niton XLt)
Xs
s
^
= S%:
s'i!"
y = 0.98x + 6.92|
s'
. tS' A
XJT
XA
50 100 150 200 250 300 350 400 450 500
Reference Laboratory (ppm)
The elements with a high relative degree of
correlation between the XLt and reference laboratory
were generally the same elements for which accuracy
was rated "Very Good" or "Good" through the
evaluation of RPDs. Specifically, the elements with
high correlation coefficients (in the range of 0.94 to
0.99) included arsenic, cadmium, chromium, iron,
lead, nickel, selenium, and zinc. Mercury, which was
rated "poor" by the RPD evaluation, also exhibited a
high r2 value. However, this correlation was affected
by two extreme Level 4 concentrations (blends 21
and 22) that were more than three times higher than
the next-highest concentrations in the mercury data
set (see Figure E-8). Removing these extreme
concentrations from the plots produced a much
poorer correlation coefficient, in the range of 0.84,
for the rest of the data set, consistent with the
findings of the RPD evaluation. Other observations
from the correlation plots are as follows:
• Slopes significantly greater than 1 in conjunction
with moderately high correlation coefficients
indicated a high bias in the XLt data for arsenic,
lead, and zinc. However, further review of the
data indicated that removal of high outliers from
complex blends 7, 8, and 9 (Wickes Smelter slag)
improved the r2 values and reduced or eliminated
the positive bias for these elements. Though no
bias was observed for copper, removal of a blend
7 outlier also improved r2 for this element from
0.87 ("Moderate") to 0.95 ("High").
• Large deviations from zero were noted in the y-
intercepts for lead and iron. Examination of the
plots for these elements (Figures E-6 and E-7)
reveals that these deviations were small relative
to the extreme range of concentrations in the
demonstration samples.
• For antimony, the high bias in relation to the
reference laboratory results was eliminated when
the XLt results were compared to the ERA-
certified values. Comparison to the ERA-
certified values also produced a very high r2 of
0.99. These findings agree with the RPD
evaluation above in showing better performance
for antimony by the XLt when ERA-certified
spike values are used to assess accuracy.
51
-------
• Low biases were observed for mercury and
vanadium. Vanadium also had the lowest r2 of
all the target elements (0.51). These
observations are consistent with the RPD
evaluation, which found higher RPDs (lower
accuracy) for these elements in the higher-
concentration samples. The plot for vanadium
is shown Figure 7-2. In the case of mercury,
the low bias may reflect loss of mercury
through volatilization during the high level of
sample processing that preceded the
demonstration.
In conclusion, the evaluations of accuracy showed
an acceptable overall level of performance by the
XLt for the target elements. Correlations with the
reference laboratory were generally high, and
median RPDs were better for most elements in
comparison to all eight XRF instruments as a
whole. Niton's proven calibration and
quantification algorithms for environmental media
may have contributed to the high relative level of
accuracy attained. However, the XLt demonstrated
somewhat low relative performance for mercury
and vanadium in the accuracy evaluation.
7.3 Primary Objective 3 — Precision
As outlined in Section 4.2.3, precision of the XLt
data set 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) are presented in
Table 7-5. The table also presents the median
RSDs for the demonstration data set as a whole for
the XLt. Additional summary statistics for the
RSDs (including minimum, maximum, and mean)
are provided in Appendix E (Table E-2).
The RSD calculation revealed a high level of
precision for the XLt in that the overall median
RSDs were 10 percent or less for all target elements
in both matrices. The ranges into which the median
RSDs fell are further summarized below:
• RSD of 1 percent to 5 percent: cadmium, iron,
lead, selenium, and zinc.
Figure 7-2. Linear correlation plot for Niton XLt
showing low correlation and bias for vanadium
500
450
400
350
& 300
250
e 200
o
2 150
100
50
0
Niton XLt
45 Degrees
Linear (Niton XLt)
y = 0.22x + 39.60
R2 = 0.51
50 100 150 200 250 300 350
Reference Laboratory (ppin)
400
450
500
52
-------
• RSD of 5 percent to 10 percent: antimony,
arsenic, chromium, copper, mercury, nickel,
silver, and vanadium.RSD of greater than 10
percent: none.
No differences were observed between the RSDs for
soil and sediment. Use of the mean RSDs (Appendix
E) as opposed to the median RSDs indicated a
similarly high level of precision in the XLt results.
The high overall level of precision may have been
facilitated by the high level of processing
(homogenizing, sieving, crushing, and drying)
performed 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 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.
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 observation indicates that
analytical precision for the XRF results is somewhat
concentration-dependent. Even for the Level 1
samples, however, the mean RSDs were relatively
good, with the highest RSD being 26 percent (for
cadmium in soil).
As an additional comparison, Table 7-5 also presents
the median RSDs calculated for all XRF instruments
that participated in the demonstration. Complete
summary statistics for the RSDs across all XRF
instruments are included in Appendix E. Table 7-5
indicates that the median RSDs for the XLt were
equivalent to or below the all-instrument medians for
all elements with the exception of antimony, copper,
nickel, and silver, where slightly higher median
RSDs were observed.
Table 7-6 presents median RSD statistics for the
reference laboratory for comparison to the XLt data.
These median RSD statistics were calculated using
the same blends as those used to calculate the XLt
RSD statistics. (Complete summary statistics are
provided in Table E-3 of Appendix E.) Table 7-6
indicates that the XLt median RSDs were equivalent
to or lower than the reference laboratory RSDs for 11
out of 13 target elements (only the chromium and
nickel RSDs were slightly higher). Thus, the XLt
exhibited slightly better precision overall than the
reference laboratory. In comparison, the median
RSDs for all XRF instruments were equivalent to or
lower than the reference laboratory RSDs also for 11
of the 13 target elements (the exceptions were
chromium and vanadium).
7.4 Primary Objective 4 — Impact of
Chemical and Spectral Interferences
The mean RPD data from the accuracy evaluation
were further processed to assess the effects of
interferences. The RPD data for elements 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), and
• 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.
53
-------
Table 7-5. Evaluation of Precision - Relative Standard Deviations for the Niton XLt
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
Niton XLt
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
6
12.8%
5
6.9%
4
3.1%
—
—
15
6.9%
2
19.6%
4
4.9%
3
6.1%
—
—
9
6.1%
24
6.7%
206
6.1%
Arsenic
12
10.8%
4
5.5%
4
3.9%
—
-
20
7.3%
14
10.4%
4
3.3%
2
5.1%
—
—
20
8.2%
40
7.9%
320
8.2%
Cadmium
4
26.4%
7
2.6%
2
2.2%
—
—
13
2.8%
2
10.6%
4
3.0%
3
3.2%
-
—
9
3.2%
22
3.0%
209
3.6%
Chromium
23
10.4%
4
3.9%
2
1.7%
—
-
29
9.9%
10
20.2%
3
2.6%
3
1.8%
-
—
16
9.9%
45
9.9%
338
12.1%
Copper
14
17.1%
8
4.2%
2
1.5%
—
—
24
11.1%
9
16.0%
4
3.7%
10
2.2%
—
—
23
3.5%
47
5.7%
363
5.1%
Iron
5
5.5%
13
2.9%
13
1.8%
7
2.5%
38
2.4%
3
4.4%
19
1.8%
5
2.0%
5
2.1%
32
2.0%
70
2.2%
558
2.2%
Lead
14
8.7%
4
2.6%
8
2.0%
5
3.9%
31
3.7%
16
7.7%
4
2.9%
3
2.5%
-
—
23
4.9%
54
4.1%
392
4.9%
Mercury
7
13.2%
7
6.9%
2
3.1%
—
-
16
7.3%
3
8.6%
4
4.8%
3
3.2%
-
—
10
3.8%
26
5.7%
192
6.8%
Nickel
23
12.8%
5
8.1%
6
1.8%
—
-
34
10.6%
18
12.5%
6
7.9%
4
4.4%
—
—
28
9.2%
62
10.0%
403
7.0%
Selenium
4
9.3%
5
4.4%
4
3.9%
—
-
13
4.4%
5
6.9%
4
4.3%
3
4.7%
—
—
12
5.1%
25
4.7%
195
4.5%
Silver
2
19.8%
3
6.6%
7
3.9%
—
-
12
5.7%
5
19.5%
4
2.6%
3
5.3%
-
—
12
5.9%
24
5.9%
177
5.2%
Vanadium
13
10.0%
4
6.8%
4
6.5%
—
—
21
8.5%
6
15.0%
8
4.0%
3
4.5%
—
—
17
5.8%
38
7.0%
218
8.5%
Zinc
19
6.3%
6
2.4%
9
2.8%
—
-
34
3.9%
17
9.5%
5
2.6%
4
2.8%
-
—
26
7.1%
60
4.8%
471
5.3%
Notes:
Number
RSD
No samples reported by the reference laboratory in this concentration range.
Number of samples meeting criteria for precision evaluation (Section (4.2.3).
Relative standard deviation.
54
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Table 7-6. Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory versus the Niton XLt and All Demonstration
Instruments
Matrix
Soil
Sediment
All
Samples
All
Samples
All
Samples
Sample
Group
Ref. Lab
Ref. Lab
Ref. Lab
Niton
XLt
A11XRF
Instruments
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Antimony
17
9.8%
7
9.1%
24
9.5%
24
6.7%
206
6.1%
Arsenic
23
12.4%
24
9.2%
47
9.5%
40
7.9%
320
8.2%
Cadmium
15
9.0%
10
8.2%
25
9.0%
22
3.0%
209
3.6%
Chromium
34
10.6%
26
7.5%
60
8.4%
45
9.9%
338
12.1%
Copper
26
9.1%
21
8.9%
47
8.9%
47
5.7%
363
5.1%
Iron
38
8.7%
31
8.1%
69
8.5%
70
2.2%
558
2.2%
Lead
33
13.2%
22
7.4%
55
8.6%
54
4.1%
392
4.9%
Mercury
16
6.6%
10
6.9%
26
6.6%
26
5.7%
192
6.8%
Nickel
35
10.0%
27
7.3%
62
8.2%
62
10.0%
403
7.0%
Selenium
13
7.1%
12
7.6%
25
7.4%
25
4.7%
195
4.5%
Silver
13
7.5%
10
6.6%
23
7.1%
24
5.9%
177
5.2%
Vanadium
21
6.6%
17
8.1%
38
7.2%
38
7.0%
218
8.5%
Zinc
35
9.1%
27
6.9%
62
7.4%
60
4.8%
471
5.3%
Notes:
Number
Ref. Lab
RSD
XRF
Number of samples meeting criteria for precision evaluation (Section (4.2.3).
Reference Laboratory.
Relative standard deviation.
X-ray fluorescence.
55
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Interferent-to-element ratios were calculated using
the mean concentrations reported for each blend by
the reference laboratory, are classified as low (less
than 5X), moderate (5 to 10X), or high (10X). Table
7-7 presents median RPD data for arsenic, nickel,
copper, and zinc that are grouped based this
classification scheme. Additional summary statistics
are presented in Appendix E (Table E-4). The table
indicates a clear increase in the median RPD for
arsenic at the higher lead-to-arsenic ratios.
Specifically, a median RPD of 13 percent at low
interferent ratios increases to near 50 percent in the
high interferent ratios. Using the criteria applied in
Section 7.2, high concentrations of lead diminish the
accuracy of the XLt from "good" to "fair" for
arsenic. Similarly, Table 7-7 indicates that high
concentrations of copper reduce instrument accuracy
from "fair" to "poor" for nickel. In presenting
statistics for unmodified RPDs as well as the absolute
values of the RPDs, Table E-4 further shows that the
interferences by lead and copper tend to increase the
positive bias of the results for arsenic and nickel (as
indicated by more negative unmodified RPDs).
Interestingly, Table 7-7 reveals no other trends in
RPDs that would indicate significant potential
interferences of nickel, copper, or zinc with each
other. The only other significant difference in RPDs
apparent in Table 7-7 is in the data for zinc and
copper, where RPDs for blends with moderate zinc-
to-copper ratios are much higher than for blends with
either lower or higher ratios. This effect on RPDs for
copper may be related to matrix effects other than
zinc interference. The four samples included in this
grouping include blends 7, 8, and 9, which contained
high concentrations of elements other than zinc, such
as arsenic, lead, and iron (see Section 7.5 below).
7.5 Primary Objective 5 — Effects of Soil
Characteristics
The population of RPDs between the XLt results and
the reference laboratory results were 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
demonstration data set as a whole. The site-specific
median RPDs are presented in Table 7-8, along with
descriptions of soil/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 mean RPD data sets for the
target elements. This evaluation focused on
correlating these values with sample types or
locations for multiple elements across the data set.
Outliers and extreme values are apparent in the
correlation plots (Figures E-l through E-13) and are
further depicted for the target elements on box and
whisker plots in Figure E-14.
Review of Table 7-8 and Figure E-14 indicates that
high relative median RPDs are observed in the
Wickes Smelter blends for a number of elements,
including arsenic, cadmium, copper, silver, and
vanadium. Evaluation of the outliers confirms this
observation, indicating that two or more of the
highest mean RPDs for these elements are from
Wickes Smelter blends 7, 8, or 9. During the
demonstration sample collection program (Chapter
2), the soil matrix from this site was described 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
compounds are thermally removed, leaving
concentrated heavy elements. In addition to arsenic,
copper, and zinc, this matrix was found to contain
high concentrations of lead and iron. These same
Wickes Smelter blends were identified in the
previous section as affecting instrument performance
for some target elements. Thus, the data presented in
Table 7-8 and Figure E-14 confirm that the complex
slag matrixes of blends 7, 8, and 9 have significant
effects on the accuracy of the XLt for some elements.
RPDs for several target elements are presented for
these blends in Table 7-9.
56
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Table 7-7. Effects of Interferent Elements on the RPDs (Accuracy) of Target Elements1
Parameter
Interferent/
Element Ratio
Number of
Samples
Median RPD of
Target Element2
Median Interferent
Concentration
Median Target
Element
Concentration
Lead Effects on Arsenic
<5 5-10 >10
29 7 5
12.9% 24.5% 46.7%
72 7460 2300
95 1038 98
Copper Effects on
Nickel
<5 5-10 >10
44 6 14
34.4% 35.8% 71.2%
127 1076 2117
186 176 108
Nickel Effects on
Copper
<5 5-10 >10
39 1 7
9.4% 7.9% 8.9%
150 387 1767
748 78 84
Zinc Effects on Copper
<5 5-10 >10
32 4 11
8.2% 59.3% 9.4%
163 4399 2300
944 944 123
Copper Effects on Zinc
<5 5-10 >10
47 3 11
8.8% 16.8% 14.3%
147 742 2167
823 102 137
Notes:
1 Concentrations are reported in units of milligrams per kilogram (rag/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.
57
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Table 7-8. Effect of Soil Type on the RPDs (Accuracy) for Target Elements
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 precipitate)
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
—
—
4
134.6%
1
100.5%
1
6.0%
4
116.8%
3
109.9%
5
125.9%
3
154.8%
3
138.2%
24
125.5%
Arsenic
—
—
6
16.2%
1
28.6%
—
_
9
10.3%
12
15.3%
5
13.5%
1
27.7%
6
51.4%
40
18.1%
Cadmium
2
14.9%
5
9.3%
1
11.0%
—
_
5
9.4%
4
10.2%
1
15.1%
2
15.5%
2
73.5%
22
10.8%
Chromium
2
20.9%
7
24.9%
1
29.5%
4
55.1%
7
11.7%
9
10.5%
11
11.2%
1
18.0%
3
21.4%
45
16.4%
Copper
3
9.4%
5
12.3%
3
12.4%
3
11.4%
5
9.3%
13
5.9%
2
19.6%
7
4.6%
6
28.5%
47
9.3%
Iron
3
14.1%
7
13.7%
o
6
13.0%
6
9.2%
12
27.6%
13
5.5%
12
6.4%
7
31.8%
7
16.9%
70
13.5%
Lead
3
9.9%
7
8.6%
o
5
22.3%
6
20.4%
8
21.2%
11
5.1%
5
20.1%
4
8.5%
7
12.4%
54
12.0%
58
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Table 7-8. Evaluation of the Effect of Soil Type on RPDs (Accuracy) of Target Elements (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 precipitate)
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
—
—
—
—
2
79.4%
—
_
4
69.1%
5
59.5%
12
107.5%
3
104.9%
—
—
26
88.8%
Nickel Selenium
3
39.0%
6
36.7%
3
27.6%
o
5
27.3%
11
39.4%
13
35.4%
11
32.5%
6
76.3%
6
45.4%
62
38.9%
1
5.4%
4
9.5%
2
14.8%
o
5
..
5
9.1%
5
9.1%
3
4.5%
4
10.8%
1
3.4%
25
6.8%
Silver
1
22.8%
4
19.6%
2
22.1%
—
_
4
14.0%
5
11.6%
1
77.7%
4
17.8%
3
43.4%
24
19.0%
Vanadium
2
70.5%
3
96.6%
1
93.9%
—
_
9
38.3%
4
81.1%
10
7.6%
7
42.0%
2
16.4%
38
40.5%
Zinc
3
3.3%
7
17.9%
3
7.0%
2
10.8%
8
17.1%
13
11.5%
10
4.4%
7
14.3%
7
16.7%
60
11.5%
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 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 (absolute value).
59
-------
Table 7-9. RPDs Calculated for Wickes Smelter Sample Blends for the Niton XLt
Blend
7
8
9
Median for
all blends
Arsenic
56.2%
102.6%
121.5%
18.1%
Cadmium
—
61.7%
85.4%
10.8%
Copper
38.6%
80.0%
108.3%
9.3%
Iron
55.9%
92.1%
108.6%
13.5%
Lead
12.4%
33.7%
56.3%
21.5%
Nickel
97.1%
—
146.5%
38.9%
Silver
—
43.4%
61.7%
19.0%
Zinc
36.9%
79.0%
108.9%
11.5%
Blend not included in accuracy evaluation.
Further review of extreme concentrations in the data
sets indicated that matrices from the Leviathan Mine
site may have also affected the accuracy of the XRF
measurements for a number of elements.
Specifically, one or more of the high outliers and
extreme values depicted on Figure E-14 for arsenic,
copper, nickel, and zinc were reported from samples
collected at the Leviathan Mine site (blends 34, 35,
55, and 58). Chapter 2 indicates that the matrices
from this site were clay soils that also included
precipitates and solids from acid mine leachate and
wastewater retention ponds. Many of the blends
contained extreme concentrations of iron (in the
range of 100,000 to 250,000 ppm). Although the
complexity of this matrix produced a number of
extreme values in the data sets, Table 7-8 indicates
minimal impacts to median RPDs when compared
with other sampling sites.
Other sampling sites and blends appeared to produce
high RPDs for some elements on an isolated basis, or
produced minor increases in mean or median RPDs.
For example, Torch Lake blends produced high
outliers for iron and selenium, and slight increases in
RPDs for both iron and nickel. These effects
appeared to be minor, however, and no other
generalized trends in XRF accuracy versus the
sample collection site or soil/sediment type could be
discerned, given that the ranges of RPDs observed for
some target elements were very broad. The spread in
the accuracy results is illustrated on the box and
whisker plot in Figure E-14. The plot shows that the
distributions of RPDs were sufficiently broad to
preclude the identification of any extreme values for
antimony, mercury, or vanadium.
7.6 Primary Objective 6 — Sample
Throughput
Niton provided a single instrument operator during
the field demonstration to perform all activities
associated with sample preparation, instrumental
analysis, and data reduction. The Niton XLt
instrument operator was able to analyze all 326
demonstration samples in 3 days at the demonstration
site. Once the XLt instrument had been set up and
operations had been streamlined, the Niton
instrument operator was able to analyze a maximum
of 146 samples during an extended work day.
Without an extended work day, it was estimated that
the Niton instrument operator would have averaged
about 91 samples per day.
This estimated sample throughput for a normal
working day was much higher than that observed for
the other instruments that participated in the
demonstration (average of 66 samples per day). This
was a particularly significant achievement given that
the other developers utilized two-person or even
three-person field teams. A detailed discussion of the
time required to complete the various steps of sample
analysis using the XLt 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 fully described in Chapter 8, Economic Analysis.
7.8 Secondary Objective 1 — Training
Requirements
The instrument operator must be suitably trained to
safely set up and operate the instrument to
successfully use XRF and obtain the level of data
quality required for specific projects. The amount of
training required depends on the complexity of the
instrument and the associated software.
Niton recommends that the operator have a high
school diploma and basic operational training. Field
or laboratory technicians are generally qualified to
operate this instrument. Additional understanding of
soil chemical and physical properties would be
60
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valuable for preparing site-specific calibrations and
for conducting specialty analyses. The operator of
the instrument during the demonstration held an M.S.
degree in earth sciences, with less than 1 year of
experience in operation of the XLt.
Niton offers free training on the use of field-portable
XRF analyzers for lead and other elements. Most
classes are 1 day unless otherwise indicated. Classes
are offered often (two to six classes per month) at
varying locations throughout the U.S. The course
materials include instrument theory, operation, and
application. In addition, the course material includes
radiation safety training, which some states require
for licensing on these instruments. The course covers
the following topics:
• Radiation safety
• X-ray fluorescence theory
• Hands-on training for lead-in-paint testing
• Hands-on-analysis of coatings for lead and other
elements
• On-site analysis of dust wipes, soil (EPA Method
6200), and paint chips
• On-site analysis of worker exposure cassettes for
airborne lead(National Institute of Occupational
Safety and Health [NIOSH] Method #7702)
• On-site measurement of total suspended
particulate (TSP) and fine particulate matter
filters for air monitoring
Participants are encouraged to bring samples to class
to analyze as part of the hands-on exercise for the
training. Niton also offers site-specific training by
request and will customize the training to the field
conditions, matrices, analytes, reporting limits, and
data quality levels required for individual project
objectives.
Niton has not established written standard operating
procedures (SOP) for the preparation or analysis of
soil or sediment samples using the XLt. However,
the instrument is accompanied by a clear and detailed
operating manual that presents the general steps in
analyzing soil and other environmental media.
Instrument software is also helpful in directing users
with intuitive operating menus. Niton and its
distributors offer on-site training and telephone
support to instrument users on an informal, as needed
basis.
In addition to the general instrument operational
instruction and training, the operator and data
manager must become familiar with Niton's data
acquisition software loaded onto the instrument.
Niton provides a copy of the NDT PC software for
each instrument. Although a PC is not required to
acquire data, a laptop PC can be useful because the
smaller instrument display can be projected onto the
larger PC screen for easier viewing. In addition, data
can be simultaneously recorded and stored in the PC,
thereby maximizing data collection efficiency while
minimizing the potential for lost data or transcription
errors.
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 XLt contains a miniature silver anode x-ray tube.
However, each instrument is equipped with trigger
locks and safety measures designed to minimize
possible exposure to the x-ray radiation. Niton
reports that risks from exposure to radiation are
minimal; the radiation measured around the
instrument during operation has been recorded at 0.1
milliRems per hour.
The second potential source of risk to XRF
instrument operators is exposure to reagent
chemicals. However, for the XLt, there are no risks
from reagents because no chemical reagents are
required for sample preparation.
61
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7.10 Secondary Objective 3 — Portability
Portability depends on the size, weight, number of
components, and power requirements of the
instrument, and the reagent 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 were also recorded. 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.
(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
XLt is defined as fully portable. It is a hand-held unit
that can be carried directly to the sampling location
for analysis of samples. The XLt is suitable for all
types of field analysis, ranging from "point-and-
shoot" readings on undisturbed soil surfaces to
processed soil samples in plastic bags or sample cups.
With an additional instrument stand, the XLt can also
be used in a hands-free, bench-top mode. This
instrument stand was used during the demonstration.
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 also was 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 outer construction of the XLt consists of a hard-
tooled plastic that is durable, weatherproof, and
impact-resistant. The instrument is intrinsically tight
and 100 percent waterproof. It can be submerged or
dropped in water with no damage to the inner
workings of the instrument. The external PC can be
attached via USB port and cable. If the PC data
acquisition system is used, it is recognized that the
PC may not be weatherproof and should be used only
in a protected environment. In addition, the
instrument can be outfitted with wireless
communications to further aid in data transfer.
However, these modes of operation were not assessed
during the demonstration.
Niton provides a 24-month limited warranty for the
XLt instrument. The warranty does not cover
batteries or accessories. Since x-ray tube sources are
new to the world of portable instrumentation, no clear
data have been obtained on the useful life that can be
assumed. The average lifespan of an x-ray tube in a
traditional bench-top device is 3 to 5 years.
Therefore, it is generally assumed among developers
of portable XRF instrumentation that the useful life
of an x-ray tube in these systems will be about 3-5
years.
7.12 Secondary Objective 5 — Availability
Niton was founded in 1987 and has two offices in the
U.S. and one office in Germany. Niton reports sales
of more than 1,000 new instruments each year both in
the U.S. and abroad. The XLt is also available for
purchase or rental from a nationwide network of
distributors, and many can provide on-site training.
The instrument can be repaired, maintained, and
calibrated by the distributors or at the factory in
Massachusetts. Niton also operates a telephone
helpline in both the U.S. and Europe.
62
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Chapter 8
Economic Analysis
This chapter provides cost information for the Niton
XLt 700 Series 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 XLt.
8.1 Equipment Costs
Capital equipment costs include either purchase or
rental of the XLt and any ancillary equipment that is
needed for specific analyses. (See Chapter 6 for a
description of available accessories.) Price
information for the analyzer and accessories was
obtained from Niton as well as from licensed Niton
distributors.
The XLt (with miniature x-ray tube) sells for a base
cost of $32,500. This cost includes the standard
accessories described in Chapter 6 of this report. The
instrument is shipped in a Pelican case, which holds
the instrument, environmental test stand, covers, and
communication cables. With the addition of the
PERFECT software, the cost to purchase the
equipment increases to $35,000. The Bluetooth0
wireless communication package adds $1,000 to the
equipment cost. A laptop computer may also be used
to run the instrument and manage the analytical data
at an additional cost.
The rental cost of the XLt instrument varies based on
model type and the degree of instrument and software
customization (such as site-specific calibrations or
quantitation algorithms), as required for specific
applications. This economic analysis assumed that
the instrument was applied "off the shelf and that no
additional customization costs were included. The
XLt analyzer that was used in the demonstration can
be rented for $1,500 per week or $5,500 per month.
Thus, purchase of the instrument could be justified as
more cost-effective than rental for field activities that
involve more than about 5 months of total field
analysis time.
The purchase price and shipping cost for the XLt
compare favorably with 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)
Weekly Rental
Autosampler (for
Overnight Analysis)
Niton XLt
$240
$32,500
$1,500
N/A
XRF
Demonstration
Average1
$410
$54,300
$2,813
N/A
Notes:
1 Average for all eight instruments in the
demonstration
N/A Not available or not applicable for this
comparison
The x-ray tube in the XLt is protected by a 2 year
warranty and is expected to last for 3 to 5 years,
assuming that the instrument is operated 2,000 hours
per year. The replacement cost, including a new
power supply, would be about $4,500.
8.2 Supply Costs
The supplies that were included in the cost estimate
include sample containers, Mylar® film, scoops, snap
rings, and disposable gloves. The rate of
consumption of these supplies was based on
observations during the field demonstration. Unit
prices for these supplies were based on price quotes
from independent vendors.
During the field demonstration, the XLt was operated
for 3 days to complete the analysis of the
demonstration sample set (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.
63
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8.3
Labor Costs
Labor costs were estimated based on the total time
required by the field team to complete the analysis of
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 set-up and calibration
• Sample preparation
• Sample analysis
• Daily shutdown and startup
• End of proj ect packing
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 XLt is
compared with the average of all XRF instruments in
Table 8-2 and with the range of all XRF instruments
in Figure 8-1. Specifically, the XLt compared
favorably against the other XRF instruments,
exhibiting lower-than-average times for all activities
except for daily shutdown and startup.
Table 8-2. Time Required to Complete
Analytical Activities1
Activity
Initial Set up and
Calibration
Sample Preparation
Sample Analysis
Daily Shut
Down/Start Up
End of Project
Packing
Total Processing
Time per Sample
Niton XLt
30
2.0
2.5
10
10
4.7
Average
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
64
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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
0 Niton XLt
I Range for all eight XRF instruments
80
Minutes
100
120
140
Figure 8-1. Comparison of activity times for the XLt versus other XRF instruments.
The Niton field team expended about 29 labor hours
to complete all sample processing activities during
the field demonstration using the XLt. This was
much lower than the overall average of 69 hours for
all instruments that participated in the demonstration.
The primary reasons that labor hours were lower for
the XLt include:
• Instrument run times (2 minutes) were
significantly less than other instruments.
• The instrument operation was simple enough that
a single technician performed all sample
preparation and analysis activities during the
demonstration.
• The software-based automation of the XLt
allowed the operator to reduce the data for
completed sample batches on a laptop PC while
the instrument was processing a new batch.
Overall, the XLt exhibited the fastest sample
processing time and the lowest labor hours of all the
instruments participating in the demonstration.
8.4 Comparison of XRF Analysis and
Reference Laboratory Costs
Two scenarios were evaluated to compare the cost for
XRF analysis using the XLt 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. 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.
65
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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 XLt was based
on equipment rental for 1 week, along with labor and
supplies estimates established during the field
demonstration. Labor costs were 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. The
IDW management cost was based on the average
IDW disposal cost per instrument during the
demonstration because IDW generation did not vary
significantly between instruments. Since the cost for
XRF analysis of one element or multiple elements
does not vary significantly (all target elements are
determined simultaneously when a sample is
analyzed), the XRF analysis cost was not adjusted for
one element versus 13 elements.
Table 8-3 summarizes the costs for the XLt versus
the cost for analysis in a fixed laboratory. This
comparison shows that the XLt compares favorably
to a fixed laboratory in terms of overall cost,
particularly when a large number of elements are to
be determined. Use of the XLt will likely produce
additional cost savings 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 XLt in the example scenario
(326 samples) was estimated at $5,706. 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, which typically cost more
than hand-held instruments like the XLt, were
included in the calculation of the average cost for all
XRF instruments. The XLt cost was slightly lower
than the three other hand-held instruments
participating in the demonstration.
Table 8-3. Comparison of XRF Technology and Reference Method Costs
Niton XLt
Shipping
Weekly Rental
Supplies
Labor
IDW
Total Niton XLt Analysis Cost
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 (13 elements)
Quantity
1
1
326
83
N/A
326
326
326
Item
Roundtrip
Week
Sample
Hours
N/A
Sample
Sample
Sample
Unit
Rate
$240
$1,500
$0.75
$43.75
N/A
$21
$36
$160
Total
$240
$1,500
$245
$3,631
$90
$5,706
$6,846
$6,846
$11,736
$52,160
$63,896
66
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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 Niton XLt 700 Series 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) that significantly reduced
uncertainties associated with the demonstration
sample set. These procedures minimized
heterogeneity impacts on method precision and on
the comparability between XRF data and reference
laboratory data. Thus, before XRF is used for large-
scale data collection, project teams are encouraged to
assess the effects of sampling uncertainty on data
quality and to adopt appropriate sample preparation
protocols, 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 that ensure 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 particularly 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 XLt analyzer for
each primary and secondary objective are
summarized in Tables 9-1 and 9-2. A performance
comparison between the XLt and the combined
performance of all eight vendors participating in the
XRF technology evaluation program is provided in
Figure 9-1. The comparisons in Figure 9-1 indicate
that relative to the program as a whole, the XLt
showed:
• Equivalent or better MDLs for 8 of the 13 target
metals (exceptions included antimony, cadmium,
copper, nickel, and selenium).
• Equivalent or better accuracy (RPDs) for 10 of
the 13 target metals (exceptions included
antimony, mercury, and nickel). Moreover, when
RPDs for antimony are calculated versus sample
spike levels rather than reference laboratory data
(which may be biased low), accuracy for
antimony improves to better than the program as
whole.
• Equivalent or better precision (RSDs) for 9 of the
13 target metals (exceptions included antimony,
copper, nickel, and silver).
As a hand-held instrument, the XLt is fully portable
and can be operated in the hand-held mode at a
sampling site. The reasons for the better-than-
average sensitivity, accuracy, and precision are not
known with any certainty but may relate to Niton's
well-established method procedures, calibration
protocols, and quantification algorithms for
environmental applications.
67
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Table 9-1. Summary of Niton XLt Performance - Primary Objectives
Objective
Performance Summary
PI: Method
Detection Limits
Mean MDLs for the 12 target elements ranged as follows (iron was not
included in the MDL evaluation):
o MDLs of 1 to 20 ppm: arsenic, lead, mercury, selenium, and
vanadium.
o MDLs of 20 to 50 ppm: copper, silver, and zinc.
o MDLs of 50 to 100 ppm: chromium and nickel.
o MDLs of greater than 100 ppm: antimony and cadmium.
MDLs for antimony (216 ppm) and cadmium (105 ppm) were based on
limited data (two MDL samples) and may be biased high because of the
high concentrations of other elements in these samples.
No significant differences were noted between MDLs for soil and sediment.
The calculated MDLs were comparable to the XLt's statistical LODs and
were generally below reference MDL data from EPA Method 6200.
P2: Accuracy and
Comparability
Median RPDs between the XLt and reference laboratory data revealed the
following, with lower RPDs indicating greater accuracy:
o RPDs of 1 to 10 percent: copper and selenium.
o RPDs of 10 to 25 percent: arsenic, cadmium, chromium, iron, lead,
silver, and zinc.
o RPDs of 25 to 50 percent: nickel and vanadium.
o RPDs greater than 50 percent: antimony and mercury.
Data review indicated that the reference laboratory results for some spiked
demonstration samples may be biased low for antimony due to the volatility
of the spiking compounds used. Data review indicated that the reference
laboratory results for some spiked demonstration samples may be biased
low for antimony due to the volatility of the spiking compounds used.
RPDs for antimony were quite high when the XLt data was compared to the
reference laboratory data (median RPD of 125 percent), but improved
considerably when compared to certified spike values (median RPD of 11
percent). Thus, the XLt appeared to be more accurate with respect to the
true concentration of antimony than the reference laboratory.
RPDs increased (that is, accuracy declined) with increasing concentrations
of silver and vanadium. RPDs for arsenic and cadmium were also skewed
high in some high concentration matrixes.
Correlation plots relative to reference laboratory data indicated:
o High correlations for 9 of the 13 target elements.
o Positive biases for arsenic, lead, nickel, and silver.
o Negative biases for mercury and vanadium.
P3: Precision
Median RSDs were good for all metals as follows:
o RSDs of 0 to 5 percent: cadmium, iron, lead, selenium, and zinc.
o RSDs of 5 to 10 percent: antimony, arsenic, chromium, copper,
mercury, nickel, silver, and vanadium.
o RSDs greater than 10 percent: none.
Median RSDs for the XLt were slightly lower than the reference laboratory.
68
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Table 9-1. Summary of Niton XLt Performance - Primary Objectives
Objective
Performance Summary
P4: Effects of
Sample
Interferences
High relative lead concentrations (more than 10 times) reduced
accuracy for arsenic results. Median RPDs for arsenic increased from
13 percent to 50 percent, and a larger positive bias was observed in the
arsenic results, as lead concentrations increased.
High relative copper concentrations (more than 10 times) similarly
reduced accuracy for nickel (median RPDs for nickel increased from 34
percent to 71 percent, and a larger positive bias was observed).
P5: Effects of Soil
Type
Low relative accuracy was observed for multiple elements in blends of
roaster slag from the Wickes Smelter site, which contained high overall
element concentrations.
High RPDs were also observed for multiple elements in blends from the
Leviathan Mine site, which included precipitates with high iron
concentrations.
P6: Sample
Throughput
With an average sample preparation time of 2.0 minutes and an
instrument analysis time of 2.5 minutes per sample, the total processing
time was 4.7 minutes per sample.
A maximum sample throughput of 146 samples per day was achieved
during an extended work day. A more typical sample throughput was
estimated to be 91 samples per day for an 8-hour work day.
The total processing time was the lowest and the daily sample
throughput was the highest of all eight instruments in the
demonstration.
P7: Costs
The base instrument cost was $32,500 (purchase) or $l,500/week
(rental), plus $240 shipping. This cost includes peripherals such as an
instrument stand, protective covers, communication cables, and 110 volt
AC adapter.
The XLt instrument operator expended approximately 29 labor hours to
complete the processing of the demonstration sample set (326 samples).
This was significantly lower than the average for all participating XRF
instruments of 69 labor hours.
Using the 1-week rental cost and adding labor and miscellaneous costs
($485 for shipping and supplies), a total project cost of $5,706 was
estimated for a project the size of the demonstration. In comparison, the
project cost averaged $8,932 for all participating XRF instruments and
the cost for fixed-laboratory analysis of all samples for 13 elements was
$63,896.
69
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Table 9-2. Summary of Niton XLt Performance - Secondary Objectives
Objective
Performance Summary
SI: Training
Requirements
Field or laboratory technicians with a high school diploma and basic
operational training are generally qualified to operate the XLt.
Niton offers free training on the use of field-portable XRF analyzers for
lead and other elements. Most are 1-day classes offered at varying
locations throughout the U.S. (two to six classes per month).
Niton also offers site-specific training by request and will customize the
training to the field conditions, matrices, analytes, reporting limits, and
data quality objectives for a project.
S2: Health and
Safety
The XLt is equipped with safety measures to minimize possible
exposure to emissions from the x-ray tube. Niton reports that the
resulting risks from radiation exposure are minimal (less than 0.1
milliRem per hour).
No chemicals are used during sample preparation or analysis that would
pose potential hazards.
S3: Portability
Based on dimensions, weight, and power requirements, the XLt is a
fully portable instrument. It can be used as a hand-held unit to analyze
undisturbed soil or bagged samples.
With an additional instrument stand, the XLt can be used in a hands-
free, bench-top mode.
S4: Durability
Niton instruments have a 24-month limited warranty for parts and labor.
The vendor estimates that the useful life of the x-ray tube source is 3-5
years.
The Niton XLt is impact-resistant and weatherproof. It is designed to
operate under wet and dirty conditions and may be used in adverse
weather conditions as it is dust and splash resistant.
S5: Availability
• Niton produces and sells more than 1,000 instruments a year through
offices in the U.S. and Germany.
• Rental instruments and supporting software are also available from
Niton or from numerous distributors throughout the U.S.
70
-------
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72
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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. 1998c. ScitectMAP Spectrum Analyzer Field
Portable X-Ray Fluorescence Analyzers.
EPA/600/R-97/147. 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-
MEI® 2000 X-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.
73
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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: XLt 700 Series XRF Analyzer
COMPANY: Niton Analyzers, A Division of Thermoelectron
ADDRESS: 900 Middlesex Turnpike, Building #8
Billerica, MA01821
Telephone: (800) 875-1578
Fax: 978-670-7430
Email: dmercurQ^nitorLConi
Internet: www.niton.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 Niton
XLt 700 Series portable x-ray fluorescence (XRF) analyzer for the analysis of 13 target elements in soil and
sediment, including antimony, arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver,
vanadium, and zinc.
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 XLt, 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
A-l
-------
blends were also spiked to further adjust and refine the concentration ranges of the target elements. Between three
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 Niton XLt 700 Series XRF
analyzer. More detailed discussion can be found in the Innovative Technology Verification Report - XRF
Technologies for Measuring Trace Elements in Soil and Sediment: Niton XLt XRF Analyzer (EPA/540/R-06/004).
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 XLt is a field portable instrument that features a miniaturized x-ray tube source and a Peltier-cooled Si-PiN x-
ray detector. The analyzer is factory-calibrated and programmed to analyze and report 25 elements. An optional
software package called PERFECT (Programmable Excitation by Regulation of Filters, Energy, Current, and Time)
is also available for analysis and reporting of light elements (including vanadium and chromium) and optimizing of
the detection limits for specific applications. Other features include an integrated touch-screen display; integrated
bar code reader and virtual keypad; remote operation and custom report generation capability from a Windows-
based PC; shielded bench-top test stand; and Bluetooth wireless communication to a laptop or personal data
assistant (PDA).
In soil and sediment applications, the XLt is designed to be used as either a hand-held instrument for analysis of
undisturbed or bagged soil, or as a bench-top instrument in a test stand for analysis of processed samples. The
analyzer is factory-calibrated, and it also accepts user-generated empirical calibrations, if required, for specific data
needs and applications.
VERIFICATION OF PERFORMANCE
Method detection limit: 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 XLt are listed below (lower MDLs indicate higher sensitivity).
Relative Sensitivity
High
Moderate
Low
Very Low
Mean MDL
1 - 20 ppm
20 - 50 ppm
50 - 100 ppm
> 100 ppm
Target Elements
Arsenic, Lead, Mercury, Selenium, and Vanadium.
Copper, Silver, and Zinc.
Chromium and Nickel.
Antimony and Cadmium.
Notes: ppm = Parts per million. Iron was not included in the MDL evaluation.
Accuracy: The determination of accuracy was based on the agreement of the XLt results with the reference
laboratory data. Accuracy was assessed by calculating the absolute relative percent difference (RPD) between the
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mean XRF concentration and the mean reference laboratory concentration for each blend. Accuracy of the XLt was
classified from high to very low for the different target elements as indicated in the table below based on the overall
median RPDs calculated for the demonstration.
Relative Accuracy
High
Moderate
Low
Very Low
Median RPD
0% - 10%
10% - 25%
25% - 50%
> 50%
Target Elements
Copper and Selenium.
Arsenic, Cadmium, Chromium,
Iron, Lead, Silver, and Zinc.
Nickel and Vanadium.
Antimony* and Mercury.
* Calculation of RPDs versus sample spike concentrations rather than reference laboratory results (due to potential low
bias in the reference laboratory results for antimony) improves accuracy from Very Low to Moderate.
Accuracy was also assessed through correlation plots between the mean XLt and mean reference laboratory
concentrations for the different sample blends. Correlation coefficients (r2) for linear regression analysis of the
plots are summarized below, along with the bias apparent from the plots in the XRF data versus the reference
laboratory data.
Correlation
Bias
>>
=
0
•1
0.88
High
tj
a
o>
£
o.
c.
o
U
0.87
--
1
0.94
--
•a
03
0.95
High
£>
0»
§
0.98
Low
~3
-i
20%
Target Elements
Cadmium, Iron, Lead, Selenium, and Zinc.
Antimony, Arsenic, Chromium, Copper, Mercury, Nickel,
Silver, and Vanadium.
None.
None.
Effects of Interferences: The RPDs from the accuracy evaluation 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. This evaluation found that high relative lead concentrations (> 10X) reduced the accuracy for
arsenic results in the XLt data set, increasing the median RPDs for arsenic from 13% (in the "moderate" range) to
50% (in the "low" range) as the lead concentration increases. Similarly, increasing copper concentrations reduce
accuracy for nickel, increasing median RPDs for nickel from 34% ("low") to 71% ("very low"). The interferences
produced increasing positive biases in the arsenic and nickel results.
Effects of Soil Characteristics: The RPDs from the accuracy evaluation were also further evaluated relative to
sampling site and soil type. This evaluation found low relative accuracy from the XLt for multiple elements in soils
impacted by minerals processing, which contained high overall element concentrations or high iron concentrations.
In particular, high RPD outliers were observed in the XLt data set for blends of roaster slag from the Wickes
Smelter site, and for blends from the Leviathan Mine that were impacted by iron-containing precipitates.
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Sample Throughput: The total processing time per sample was estimated at 4.7 minutes, which included 2.0
minutes of sample preparation and 2.5 minutes of instrument analysis time. The instrument analysis time and total
processing time were the lowest among the eight instruments participating in the demonstration. A sample
throughput of 91 samples per 8-hour work day was estimated. 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 preparation time.
Costs: A cost assessment identified a base purchase cost of $32,500 and typical rental cost of $l,500/week, plus
$240 shipping, for the XLt. A total cost of $5,706 (with a labor cost of $3,631 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 samples for the 13 target elements.
Skills and training required: Field or laboratory technicians with a high school diploma are generally qualified to
operate the XLt. Niton offers free 1-day training course on the use of field portable XRF analyzers for lead and
other elements. Niton and its distributors offer informal on-site training for specific customer and applications. In
addition, toll-free telephone support is also available.
Health and safety aspects: Health risks associated with exposure to X-ray tube emissions from the XLt are
minimized through shielding and other safety measures; the vendor reports that the resulting risks from radiation
exposure are very minimal (0.1 mrem/hr). No other risks or potential hazards associated with instrument operation
could be identified.
Portability: Based on dimensions, weight, and power requirements, the XLi is a fully portable instrument. It can
be used as a hand-held unit to analyze undisturbed soil or bagged samples. With an available instrument stand, the
XLi can be used in a hands-free, bench-top mode.
Durability: The instrument housing is impact-resistant and completely sealed for protection from moisture and
dust. It is designed to operate under wet and dirty conditions and can be submerged in water. Niton instruments
have a 24-month limited warranty for parts and labor. The useful life of the X-ray tube source is estimated by the
vendor to be 3-5 years.
Availability: Instruments, accessories, and supporting software are available for purchase or rental from Niton's
offices in the U.S. and Germany, or from numerous distributors throughout the U.S.
RELATIVE PERFORMANCE
The overall performance of the XLt relative to the average of all eight XRF instruments that participated in the
demonstration is shown below:
Sensitivity
Accuracy
Precision
Antimony
O
O
O
Arsenic
•
»
Same
Cadmium
O
»
»
Chromium
»
»
•
Copper
O
»
O
Iron
NC
»
Same
Lead
•
»
»
Mercury
•
O
»
Nickel
O
O
O
Selenium
O
»
Same
Silver
•
»
O
Vanadium
•
Same
»
Zinc
•
»
Same
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.
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APPENDIX B
DEVELOPER DISCUSSION
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DEVELOPER DISCUSSION
Thermo Electron NITON analyzers would like to thank the EPA and SITE program for the opportunity to
demonstrate our instrument's effectiveness for trace elemental analysis in soil and sediments. Overall, it proved
to be a useful exercise in determining our instrument's capabilities for field analysis. We would like to thank
everyone involved as we found the staff incredibly helpful in ensuring that the performance of our analyzers was
appropriately documented. Overall, Thermo Electron feels that the report adequately represents the utility of the
NITON analyzers in testing soils and sediments for common contaminants.
Our published limits of detection (LOD) for the 13 elements included in this study all correspond well with the
results in the report with the exception of chromium and cadmium. The method detection limits (MDL) for
chromium and cadmium were both reported higher than anticipated. However, given that most of these samples
had been intentionally spiked with high levels of various elements, it was not surprising that our performance
was inferior to what we typically expect in "real" samples. In this study, samples were required to serve more
than one purpose. Instead of merely attempting to determine a detection limit, one sample might be put to the
task of LOD and multi-element interference analysis. For elements such as antimony and cadmium, this proved
to be a problem for our analyzer.
Our analyzers report actual 3 sigma detection limits (
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APPENDIX C
DATA VALIDATION SUMMARY REPORT
-------
Contents
Chapter Page
Acronyms, Abbreviations, and Symbols ii
1.0 INTRODUCTION C-l
2.0 VALIDATION METHODOLOGY C-l
3.0 DATA VALIDATION 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
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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
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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
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• 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
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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).
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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
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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.
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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.
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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.
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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
LV-SO-34-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
Antimony
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
870
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
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-
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
j
C-26
-------
TABLE 5: DATA QUALIFICATION: 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
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
SB-SO-15-XX
Analyte
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
Iron
Result
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
51000
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
i
j
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
ej
i
j
j
j,e
j
i
j
j
C-27
-------
TABLE 5: DATA QUALIFICATION: SERIAL DILUTION EXCEEDANCES
(Continued)
Sample ID
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
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
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
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-
Comment
Code
i
j
j
j
ej
j
j
i
j
ej
j
j,e
i
j
j
j
j,e
J
ej
i
j
j
j
j
i
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, Xcalibur ElvaX and Reference Laboratory
Blend No.
i
i
i
i
i
i
i
i
i
i
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-XC
KP-SO-10-XC
KP-SO-15-XC
KP-SO-18-XC
KP-SO-22-XC
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-XC
KP-SO-13-XC
KP-SO-20-XC
KP-SO-24-XC
KP-SO-27-XC
KP-SO-29-XC
KP-SO-32-XC
KP-SO-04-XX
KP-SO-16-XX
KP-SO-23-XX
KP-SO-26-XX
KP-SO-31-XX
KP-SO-04-XC
KP-SO-16-XC
KP-SO-23-XC
KP-SO-26-XC
KP-SO-31-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
8.1 J+
6.1 J+
6.3 J+
6.7 J+
8.3 J+
8
12
6
8
6
17 J+
16 J+
19 J+
17 J+
15 J+
18 J+
16 J+
16
14
20
21
23
14
21
94 J+
93 J+
86 J+
90 J+
88
71
80
82
74
As
i j-
i j-
i j-
i j-
i j-
68
111
84
76
57
2 J-
1 J-
2 J-
1 J-
1 J-
2 J-
2 J-
83
98
73
85
43
44
0
3
3
3
4
28
176
70
77
63
0
Cd
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
25
23
0.1 U
0.045 U
0.1 U
0.1 U
0.05 U
0.1 U
0.045 U
26
26
30
0.046 U
0.063 U
0.048 U
0.061 U
0.1 U
36
62
82
24
Cr
290
300
340
250
260
306
323
298
277
326
170
180
160
160
170
150
180
198
219
193
205
182
217
216
180
200
180
210
140
163
168
185
171
146
Cu
26
26
26
24
29
17
14
16
22
16
48
52
46
49
45
42
50
39
39
35
33
43
37
40
200
230
190
230
200
172
149
183
176
156
Fe
1,400
1,600
1,600
1,200
1,300
1,292
1,287
1,407
1,206
1,389
990
980
910
900
970
870
970
906
1,001
933
930
922
964
914
1,300
1,400
1,300
1,500
1,100
1,057
981
1,079
1,088
903
Pb
620
560
510
500
650
478
527
541
518
551
1,200
1,200
1,300
1,100
1,200
1,200
1,200
1,192
1,248
1,156
1,150
1,252
1,279
1,168
5,800
6,100
5,300
6,500
5,700
5,603
5,618
5,944
6,142
5,458
Hg
0.059 U
0.028 U
0.029 U
0.016 U
0.027 U
2
0.027 U
0.037 U
0.03 U
0.017 U
0.021 U
0.013 U
0.014 U
3
0.018 U
0.016 U
0.017 U
0.013 U
0.017 U
5
3
3
5
D-l
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
i
i
i
i
i
i
i
i
i
i
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-XC
KP-SO-10-XC
KP-SO-15-XC
KP-SO-18-XC
KP-SO-22-XC
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-XC
KP-SO-13-XC
KP-SO-20-XC
KP-SO-24-XC
KP-SO-27-XC
KP-SO-29-XC
KP-SO-32-XC
KP-SO-04-XX
KP-SO-16-XX
KP-SO-23-XX
KP-SO-26-XX
KP-SO-31-XX
KP-SO-04-XC
KP-SO-16-XC
KP-SO-23-XC
KP-SO-26-XC
KP-SO-31-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
140
150
170
120
130
138
144
160
138
141
87
90
79
78
87
73
88
93
92
86
87
107
95
83
93
100
91
110
68
77
70
101
87
74
Se
0.25 U
0.22 U
0.25 U
0.25 U
0.25 U
38
14
0.21 U
0.25 U
0.25 U
0.25 U
0.25 U
0.25 U
0.51
11
35
23
50
0.28 U
0.25 U
0.25 U
0.22 U
0.25 U
25
6
54
59
51
Ag
0.25 U
0.25 U
0.25 U
0.25 U
0.25 U
13
14
0.25 U
0.25 U
0.25 U
0.25 U
0.25 U
0.25 U
0.25 U
13
4
5
3
12
6
0.16 J
0.16 J
0.13 J
0.17 J
0.4
11
20
4
12
V
2 J
2 J
2 J
2 J
2 J
0
0
0
0
0
1 J
1 J
1 J
1 J
1 J
1 J
1 J
0
0
0
0
0
0
0
1 J
1 J
1 J
1 J
2 J
34
0
0
0
0
Zn
11
12
15
11
11
41
0
33
21
37
26
24
25
22
24
22
24
67
75
56
60
78
55
60
45
47
41
52
38
82
80
79
94
68
D-2
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
KP-SO-03-XC
KP-SO-05-XC
KP-SO-09-XC
KP-SO-21-XC
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-XC
WS-SO-08-XC
WS-SO-12-XC
WS-SO-17-XC
WS-SO-27-XC
WS-SO-30-XC
WS-SO-35-XC
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-XC
WS-SO-05-XC
WS-SO-09-XC
WS-SO-14-XC
WS-SO-26-XC
WS-SO-31-XC
WS-SO-33-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
410
360
410
420
370
233
242
237
240
252
1.3 U
1.3
1.3 UJ
1.3 UJ
1.3 UJ
1.2 J-
1.3 UJ
1
1
1
1
3
1
1
8.9 J-
8.6 J-
7.1 J-
8.4 J-
7.6 J-
7.2 J-
6.9 J-
36
41
38
39
23
26
25
As
10
9
12
11
10
0
94
0
49
86
48
45
43
47
49
51
49
105
108
113
102
81
60
94
500
440
480
430
520
520
450 J-
473
537
490
427
297
252
195
Cd
0.1
0.074 U
0.13 U
0.094 U
0.098 U
32
1.9
2
1.8
1.9
2
2
2
31
25
41
30
12
12
12
11
12
12
11 J-
34
10
12
36
28
Cr
6
5
6
5
5
120
120
110
120
120
130
130
61
79
59
49
64
39
140
140
130
120
140
140
120 J-
52
56
72
64
51
45
Cu
780
670
780
780
700
614
641
609
641
666
50
47
45
49
51
53
51
68
73
69
70
61
56
61
170
160
160
150
160
170
150 J-
199
187
195
182
150
158
165
Fe
1,700
1,600
2,000
1,800
1,700
1,047
1,084
1,130
1,070
1,167
28,000
26,000
25,000
28,000
28,000
29,000
28,000
21,856
21,786
21,623
21,219
18,393
19,246
19,086
32,000
31,000
30,000
28,000
30,000
32,000
28,000 J-
23,201
23,725
23,021
22,896
19,241
19,974
20,042
Pb
18,000
19,000
24,000
22,000
19,000
18,603
19,642
19,166
19,206
20,448
110
71
65
70
72
81
74
202
180
164
181
172
149
152
4,300
4,000
4,000
3,700
4,000
4,200
3,700 J-
9,334
9,860
9,696
9,433
6,110
7,009
6,809
Hg
0.043 U
0.044 U
0.044 U
0.046 U
0.042 U
15
12
12
11
13
0.07 U
0.063 U
0.068 UJ
0.069 UJ
0.11 J-
0.069 UJ
0.071 UJ
3
5
0.86 J-
0.76 J-
0.89 J-
0.74 J-
0.83 J-
0.85 J-
0.87 J-
7
27
9
D-3
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
KP-SO-03-XC
KP-SO-05-XC
KP-SO-09-XC
KP-SO-21-XC
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-XC
WS-SO-08-XC
WS-SO-12-XC
WS-SO-17-XC
WS-SO-27-XC
WS-SO-30-XC
WS-SO-35-XC
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-XC
WS-SO-05-XC
WS-SO-09-XC
WS-SO-14-XC
WS-SO-26-XC
WS-SO-31-XC
WS-SO-33-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
4
3
4
3
4
2
2
3
2
3
61
58
55
59
61
65
62
39
57
39
38
55
35
70
75
71
70
64
70
72
65 J-
71
58
55
67
60
35
67
Se
0.42 U
0.25 U
0.24 U
0.25 U
0.25 U
275
230
231
240
211
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
34
15
5
1.6
1.3 U
1.3 U
1.3 U
1.3 U
1.2 U
1.3 U
43
19
16
Ag
0.82
0.73
0.82
0.84
0.76
42
31
13
25
27
0.93 J
0.86 J
0.94 J
0.89 J
0.9 J
1 J
1 J
10
11
10
10
6
6
15
15
14
13
14
15
13 J-
27
38
30
24
18
29
15
V
0 J
0 J
0 J
0 J
0 J
0
0
0
0
0
56
52
49
56
57
58
57
23
24
48
15
36
28
55
58
57
56
50
56
60
53 J-
23
36
13
46
31
64
0
Zn
100
92
110
110
100
176
123
154
178
196
230
220
210
230
230
240
240
380
387
385
384
345
345
348
930
900
870
820
900
950
830 J-
1,191
1,132
1,190
1,134
934
996
1,020
D-4
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
WS-SO-04-XC
WS-SO-15-XC
WS-SO-22-XC
WS-SO-34-XC
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-XC
WS-SO-16-XC
WS-SO-18-XC
WS-SO-21-XC
WS-SO-24-XC
WS-SO-29-XC
WS-SO-37-XC
WS-SO-13-XX
WS-SO-19-XX
WS-SO-28-XX
WS-SO-32-XX
WS-SO-36-XX
WS-SO-13-XC
WS-SO-19-XC
WS-SO-28-XC
WS-SO-32-XC
WS-SO-36-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
41 J-
45 J-
48 J-
41 J-
45 J-
144
152
140
137
136
130 J-
110 J-
130 J-
120 J-
97 J-
120 J-
120 J-
178
170
194
177
202
213
202
200 J-
150 J-
120 J-
190 J-
120 J-
208
178
258
237
260
As
1900
2000
2300
1900
2000
2,917
2,719
2,780
1,689
2,066
4200
3900
4100
3900
3600
3800
4100
5,187
4,682
3,655
4,194
4,123
3,683
4,497
5800
5000
4200
5500
3800
7,772
4,948
5,176
5,696
6,570
Cd
47
50
56
47
50
67
102
44
76
47
98
91
95
90
81
90
95
145
122
120
114
82
98
62
150
130
100
140
92
139
184
130
131
107
Cr
100
94
82
84
91
85
81
64
63
60
49
59
63
43
54
51
63
101
98
51
53
66
54
54
51
67
Cu
590
640
720
620
660
725
658
734
695
597
1,300
1,300
1,300
1,200
1,100
1,200
1,300
1,266
1,259
1,211
1,144
932
1,052
1,071
1800
1500
1200
1700
1100
1,511
1,559
1,207
1,331
1,260
Fe
32,000
34,000
37,000
33,000
36,000
29,297
25,925
29,457
27,447
23,244
44,000
42,000
44,000
40,000
38,000
40,000
42,000
33,774
34,523
31,756
32,103
24,425
27,220
28,622
47,000
39,000
33,000
44,000
30,000
35,738
39,189
27,159
29,668
29,661
Pb
18,000
20,000
24,000
17,000
22,000
42,266
39,796
42,430
37,445
30,445
35,000
24,000
37,000
43,000
27,000
42,000
26,000
64,837
61,339
59,680
56,773
40,706
48,582
48,690
45,000
24,000
30,000
30,000
45,000
47,796
48,951
39,360
41,616
39,863
Hg
5.8 J
6.5
5.8
4.8
5.4
90
65
17
15
17
14
16
15
14
30
46
43
116
100
28
11
12
11
11
13
84
90
52
48
D-5
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
WS-SO-04-XC
WS-SO-15-XC
WS-SO-22-XC
WS-SO-34-XC
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-XC
WS-SO-16-XC
WS-SO-18-XC
WS-SO-21-XC
WS-SO-24-XC
WS-SO-29-XC
WS-SO-37-XC
WS-SO-13-XX
WS-SO-19-XX
WS-SO-28-XX
WS-SO-32-XX
WS-SO-36-XX
WS-SO-13-XC
WS-SO-19-XC
WS-SO-28-XC
WS-SO-32-XC
WS-SO-36-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
66
62
58
57
60
42
38
79
67
65
57
60
62
51
54
55
63
95
85
42
42
90
80
39
75
74
59
73
55
112
43
90
97
100
Se
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.1 J
1.9
1.6
2.1
1.7
3
126
44
3.7
3.7
2.3
3.7
1.7
14
Ag
69 J-
76 J-
90 J-
72 J-
78 J-
105
99
104
86
59
150 J-
150 J-
140 J-
150 J-
140 J-
140 J-
140 J-
195
182
199
179
105
144
117
170 J-
160 J-
130 J-
190 J-
120 J-
206
223
137
163
144
V
42
44
52
44
47
0
0
0
0
0
36
35
36
33
30
33
34
0
17
41
0
12
0
0
24
20
16
23
15
0
0
0
73
77
Zn
3,000
3,100
3,400
3,000
3,200
4,227
4,061
4,265
4,070
3,534
6,000
5,700
5,900
5,500
5,200
5,500
5,800
7,030
6,880
6,777
6,552
5,451
5,972
5,885
9,000
7,700
6,100
8,500
5,700
9,997
10,289
8,400
8,948
8,632
D-6
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
BN-SO-10-XC
BN-SO-15-XC
BN-SO-18-XC
BN-SO-28-XC
BN-SO-31-XC
BN-SO-35-XC
BN-SO-02-XX
BN-SO-04-XX
BN-SO-17-XX
BN-SO-22-XX
BN-SO-27-XX
BN-SO-02-XC
BN-SO-04-XC
BN-SO-17-XC
BN-SO-22-XC
BN-SO-27-XC
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-XC
BN-SO-06-XC
BN-SO-08-XC
BN-SO-13-XC
BN-SO-20-XC
BN-SO-30-XC
BN-SO-34-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 U
1.5
1.3
1.4
10
4
8
8
0
7
9
11
9.1
9.3
7.3
9.6
12
13
13
4
23
65
60
57
65
57
64
68
61
66
63
70
62
63
62
As
38
50
34
37
35
41
37
47
64
79
74
89
84
89
140
120
110
98
110
164
160
130
203
155
620
600
570
320
540
630
630
684
751
731
715
752
597
652
Cd
0.94
1.2
0.82
0.89
0.87
1
0.98
11
25
33
25
50
42
39
34
39
26
39
46
73
64
290
280
270
150
260
300
290
298
284
319
326
321
307
312
Cr
120
110
110
110
100
140
120
86
64
82
101
92
85
78
90
79
79
65
78
43
56
62
50
36
120
94
100
98
88
100
110
75
104
91
60
76
61
44
Cu
32
35
29
29
28
33
30
26
37
31
30
39
46
45
170
140
140
110
130
149
146
162
158
156
840
810
750
410
730
860
830
850
869
851
848
837
837
873
Fe
24,000
24,000
22,000
22,000
22,000
26,000
23,000
17,877
18,087
18,208
18,517
18,150
18,130
18,569
28,000
24,000
23,000
20,000
24,000
17,560
18,022
18,512
18,691
18,679
25,000
24,000
22,000
17,000
22,000
26,000
25,000
21,467
21,431
21,601
21,842
21,577
21,784
22,434
Pb
63
140
56
59
58
65
60
115
126
93
84
88
163
134
840
700
680
590
660
1,155
1,154
1,176
1,137
1,192
4,700
4,500
4,300
2,400
4,100
4,800
4,700
6,485
6,565
6,593
6,781
6,406
6,448
6,660
Hg
0.13
0.14
0.15
0.13
0.16
0.14
0.15
2
5
0.37
0.36
0.39
0.37
0.38
1.6
2
2
1.6
1.6
1.6
2
11
9
D-7
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
BN-SO-10-XC
BN-SO-15-XC
BN-SO-18-XC
BN-SO-28-XC
BN-SO-31-XC
BN-SO-35-XC
BN-SO-02-XX
BN-SO-04-XX
BN-SO-17-XX
BN-SO-22-XX
BN-SO-27-XX
BN-SO-02-XC
BN-SO-04-XC
BN-SO-17-XC
BN-SO-22-XC
BN-SO-27-XC
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-XC
BN-SO-06-XC
BN-SO-08-XC
BN-SO-13-XC
BN-SO-20-XC
BN-SO-30-XC
BN-SO-34-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
63
54
58
59
54
71
63
54
69
60
85
66
71
61
54
48
47
40
46
32
33
57
59
34
100
92
94
71
84
99
100
83
72
79
69
86
76
82
Se
1.3 U
1.2 J
1.3 U
1.3
1.3 U
1.3 U
1.2 J
2
4.3
2.9
2.7
2.8
3.7
6
72
17
15
14
9.2
14
17
17
67
6
114
65
101
Ag
1.3 UJ
1.3 UJ
1.3 UJ
0.94 U
0.77 U
0.97 U
0.85 U
11
11
18
8
6
7.6
6.5
6.3
5.4
6.1
14
14
42
41
38
21
37
44
42
33
44
41
65
31
37
58
V
55
55
49
46
48
54
50
0
15
34
0
0
46
44
60
50
49
43
52
29
0
42
14
24
48
48
39
37
44
50
49
61
44
0
0
0
0
0
Zn
92
110
89
88
81
94
87
155
172
157
169
159
206
193
470
400
390
330
380
665
643
646
669
661
2,300
2,300
2,200
1,200
2,100
2,400
2,300
3,299
3,454
3,331
3,358
3,356
3,325
3,406
D-8
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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
16
16
16
16
16
16
16
16
16
16
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-XC
BN-SO-16-XC
BN-SO-21-XC
BN-SO-25-XC
BN-SO-33-XC
BN-SO-05-XX
BN-SO-19-XX
BN-SO-26-XX
BN-SO-29-XX
BN-SO-32-XX
BN-SO-05-XC
BN-SO-19-XC
BN-SO-26-XC
BN-SO-29-XC
BN-SO-32-XC
CN-SO-01-XX
CN-SO-04-XX
CN-SO-08-XX
CN-SO-10-XX
CN-SO-11-XX
CN-SO-01-XC
CN-SO-04-XC
CN-SO-08-XC
CN-SO-10-XC
CN-SO-11-XC
AS-SO-02-XX
AS-SO-06-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-13-XX
AS-SO-02-XC
AS-SO-06-XC
AS-SO-10-XC
AS-SO-11-XC
AS-SO-13-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
110 J-
120 J-
150 J-
82 J-
100 J-
100
99
105
103
100
160 J-
150 J-
150 J-
150 J-
160 J-
136
131
134
130
132
13 J-
13 J-
15 J-
13 J-
17 J-
16
19
19
14
21
2.6 UJ
2.4 UJ
1.9 J-
3.7 J-
2.4 UJ
14
12
12
14
13
As
990 J+
1,100 J+
1,300 J+
700 J
1,100
1,133
1,134
1,120
1,016
1,243
1,600
1,600
1,700
1,600
1,600
1,935
1,673
1,719
1,751
1,843
13
11
15
13
16
99
111
40
83
93
18
19
18
22
20
85
85
34
42
41
Cd
520
570
660
370 J-
640
601
561
586
592
599
850
860
900
880
860
808
811
821
834
852
21
21
25
22
30
20
19
20
50
52
48
63
57
64
33
63
62
47
Cr
82
86
110
64 J-
100
74
57
105
39
86
79
82
86
84
87
63
45
45
190
200
210
200
240
158
179
179
170
155
180
190
180
230
200
146
225
172
154
175
Cu
1,400
1,500
1,700
930 J-
1,600
1,456
1,457
1,466
1,369
1,527
2,200
2,200
2,400
2,300
2,300
2,193
2,199
2,194
2,254
2,187
700
680
740
760
860
731
741
737
752
729
140
130
110
150
150
311
319
330
349
350
Fe
23,000
25,000
30,000
16,000 J-
27,000
23,645
23,360
24,645
22,952
25,053
26,000
26,000
27,000
26,000
26,000
26,751
27,009
26,274
27,470
26,292
38,000
37,000
43,000
39,000
47,000
34,316
34,495
32,236
33,088
33,039
48,000
52,000
45,000
52,000
52,000
33,843
36,284
36,503
38,108
36,984
Pb
6,900
8,100
8,900
5,400 J-
8,000
8,902
8,699
8,942
8,762
8,705
12,000
12,000
12,000
12,000
12,000
10,794
10,790
10,750
10,894
10,562
1,200
1,200
1,300
1,200
1,600
1,738
1,901
1,790
1,755
1,806
1,600
1,600
1,400
2,100
1,700
2,497
2,390
2,495
2,669
2,579
Hg
3.4
3.4
3.6
3.8
4
5
5
5.4
5.4
5.4
0.13
0.14
0.16
0.12
0.15
0.76
0.74
0.78
0.72
0.79
10
15
17
12
8
D-9
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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
16
16
16
16
16
16
16
16
16
16
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-XC
BN-SO-16-XC
BN-SO-21-XC
BN-SO-25-XC
BN-SO-33-XC
BN-SO-05-XX
BN-SO-19-XX
BN-SO-26-XX
BN-SO-29-XX
BN-SO-32-XX
BN-SO-05-XC
BN-SO-19-XC
BN-SO-26-XC
BN-SO-29-XC
BN-SO-32-XC
CN-SO-01-XX
CN-SO-04-XX
CN-SO-08-XX
CN-SO-10-XX
CN-SO-11-XX
CN-SO-01-XC
CN-SO-04-XC
CN-SO-08-XC
CN-SO-10-XC
CN-SO-11-XC
AS-SO-02-XX
AS-SO-06-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-13-XX
AS-SO-02-XC
AS-SO-06-XC
AS-SO-10-XC
AS-SO-11-XC
AS-SO-13-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni Se Ag V Zn
120 26 70 41 4,000
130 29 77 44 4,400
160 35 88 52 5,100
88 J- 19 J- 48 J- 28 J- 2,900 J-
150 34 81 48 5,100
100 47 75 31 5,643
71 15 73 41 5,547
103 20 76 0 5,498
99 66 0 5,524
117 84 0 5,746
160 48 110 39 6,700
160 48 120 39 6,700
160 49 120 40 7,000
160 48 120 41 6,800
160 48 120 39 6,700
113 100 123 0 7,367
134 72 106 0 7,318
107 117 0 7,323
126 128 0 7,482
125 115 30 7,359
240 2.2 12 21 3,100
240 1.5 12 22 2,900
280 1.3 U 15 26 3,200
240 1.9 14 22 3,000
320 1.3 U 16 27 3,500
198 18 48 3,910
183 23 0 3,742
184 55 3 51 3,732
185 15 56 3,451
217 3 0 3,451
91 2.6 U 4.5 42 3,300
93 2.6 U 4.8 44 3,500
84 1.1 U 4.4 42 3,000
120 1.1 U 5.6 54 3,800
100 3 5.2 50 3,800
92 5 60 3,543
86 0 3,424
95 00 3,321
86 10 0 3,440
86 80 3,539
D-10
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
19
19
19
19
19
19
19
19
19
19
Sample ID
AS-SO-01-XX
AS-SO-04-XX
AS-SO-07-XX
AS-SO-09-XX
AS-SO-12-XX
AS-SO-01-XC
AS-SO-04-XC
AS-SO-07-XC
AS-SO-09-XC
AS-SO-12-XC
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-XC
SB-SO-06-XC
SB-SO-14-XC
SB-SO-38-XC
SB-SO-41-XC
SB-SO-47-XC
SB-SO-51-XC
SB-SO-05-XX
SB-SO-18-XX
SB-SO-30-XX
SB-SO-40-XX
SB-SO-53-XX
SB-SO-05-XC
SB-SO-18-XC
SB-SO-30-XC
SB-SO-40-XC
SB-SO-53-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
3.8 J-
6.4 UJ
3.6 J-
2.6 UJ
2.6 UJ
4
6
6
1.2 UJ
1.7 J-
4.1 J-
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
6
0
3
4
9
15
4
1.6 J-
1.2 UJ
3.2 J-
2.2 J-
1.2 UJ
9
0
0
0
13
As
26
22
21
25 J-
29
74
46
45
46
85
9
8
9
10
9
8
9
50
63
82
72
63
77
60
9
10
7
9
10
70
82
65
72
46
Cd
100
110
97
100 J-
120
67
75
105
78
84
0.51 U
0.51 U
0.51 U
0.51 U
0.51 U
0.51 U
0.51 U
10
48
0.51 U
0.51 U
0.51 U
0.51 U
0.51 U
29
34
31
Cr
420
480
380
390 J-
440
371
364
415
523
313
150
140
150
150
160
140
160
104
115
130
148
160
183
119
140
150
94
120
140
132
68
62
153
106
Cu
250
260
240
250 J-
270
591
667
623
629
686
48
44
46
57
58
44
50
28
20
37
27
28
29
33
46
46
27
40
44
5
23
39
37
31
Fe
100,000
110,000
88,000
94,000 J-
93,000
74,049
79,399
78,896
83,038
82,623
38,000
35,000
37,000
37,000
40,000
34,000
40,000
27,814
27,713
27,854
27,016
26,866
27,284
27,183
35,000
38,000
22,000
33,000
37,000
25,964
23,181
25,684
25,849
26,290
Pb
3,200
3,300
2,900
3,200 J-
3,300
6,123
6,244
6,402
6,597
6,547
18
16
17
18
19
16
18
85
88
52
75
87
0
106
16
17
10
15
17
0
68
64
0
41
Hg
1.4
1.3
1.4
1.4
1.4
53
56
51
47
44
62
55
55
56
54
58
54
11
15
16
19
22
9
29
540
280
290
280
270
219
155
187
205
195
D-ll
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
19
19
19
19
19
19
19
19
19
19
Sample ID
AS-SO-01-XX
AS-SO-04-XX
AS-SO-07-XX
AS-SO-09-XX
AS-SO-12-XX
AS-SO-01-XC
AS-SO-04-XC
AS-SO-07-XC
AS-SO-09-XC
AS-SO-12-XC
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-XC
SB-SO-06-XC
SB-SO-14-XC
SB-SO-38-XC
SB-SO-41-XC
SB-SO-47-XC
SB-SO-51-XC
SB-SO-05-XX
SB-SO-18-XX
SB-SO-30-XX
SB-SO-40-XX
SB-SO-53-XX
SB-SO-05-XC
SB-SO-18-XC
SB-SO-30-XC
SB-SO-40-XC
SB-SO-53-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
180
200
160
170 J-
190
130
153
159
119
133
210
200
210
210
230
200
230
179
197
173
196
171
168
167
200
210
120
180
200
165
139
144
154
158
Se
2.6 U
6.2 U
2.7
2.6 U
2.6 U
24
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
54
1.3 U
1.3 U
1.3 J+
1.3 U
1.3 U
13
Ag
9.3
12
8.9
9.6 J-
3.2
3
4
9
9
7
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
4
6
6
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
8
16
8
V
66
72
63
65 J-
73
88
0
0
0
37
67
63
66
68
71
62
74
90
36
77
35
0
0
55
61
70
43
58
64
62
0
147
42
74
Zn
6,900
7,400
6,300
6,800 J-
7,500
2,484
2,195
2,196
1,858
2,034
90
82
95
91
96
82
93
109
98
108
114
98
114
102
80
84
50
74
81
92
89
90
106
88
D-12
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
Sample ID
SB-SO-08-XX
SB-SO-11-XX
SB-SO-21-XX
SB-SO-39-XX
SB-SO-42-XX
SB-SO-08-XC
SB-SO-11-XC
SB-SO-21-XC
SB-SO-39-XC
SB-SO-42-XC
SB-SO-22-XX
SB-SO-25-XX
SB-SO-27-XX
SB-SO-35-XX
SB-SO-44-XX
SB-SO-22-XC
SB-SO-25-XC
SB-SO-27-XC
SB-SO-35-XC
SB-SO-44-XC
SB-SO-23-XX
SB-SO-28-XX
SB-SO-32-XX
SB-SO-43-XX
SB-SO-48-XX
SB-SO-23-XC
SB-SO-28-XC
SB-SO-32-XC
SB-SO-43-XC
SB-SO-48-XC
SB-SO-02-XX
SB-SO-07-XX
SB-SO-10-XX
SB-SO-26-XX
SB-SO-50-XX
SB-SO-02-XC
SB-SO-07-XC
SB-SO-10-XC
SB-SO-26-XC
SB-SO-50-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
5.4 J-
5.7 J-
4.9 J
4.7 J-
4.6 J-
10
11
0
8
13
10 J
6.8 J+
6.7 J+
6 J+
6.8 J+
10
14
15
14
20
48 J-
42 J-
46 J-
40 J-
39 J-
35
39
38
34
39
44 J-
45 J
62 J
61 J
57 J
49
58
53
53
50
As
13
13
13
13
13
63
71
72
90
120
18
18
18
17
18
124
109
112
119
116
37
36
40
35
36
317
347
349
425
367
23 J-
22
26
30
27
99
72
52
46
74
Cd
0.51 U
0.51 U
0.51 U
0.51 U
0.51 U
26
0.51 U
0.51 U
0.51 U
0.51 U
0.51 U
0
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
0
12
0
40
0
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
35
38
24
Cr
120
140
130
140
140
109
97
51
133
132
120
120
120
110
120
51
20
53
61
21
21
23
20
21
36
25
130
120
140
160
140
115
118
122
101
134
Cu
39
46
43
46
45
25
26
18
27
5
37
37
37
35
37
16
3
20
22
25
7
7
7.6
6.7
6.9
1
0
0
1
0
43
38
44
50
46
30
26
38
40
39
Fe
32,000
36,000
34,000
34,000
35,000
24,137
24,094
22,026
23,521
24,055
29,000
29,000
29,000
28,000
29,000
18,480
19,155
19,141
19,400
19,543
4,500
4,400
4,900
4,200
4,500
2,818
2,961
2,881
2,850
2,881
35,000
35,000
41,000
46,000
42,000
28,994
29,271
29,497
27,573
28,740
Pb
17
20
18
19
18
0
0
0
0
0
22
22
22
21
22
0
0
0
0
0
36
36
40
34
36
0
0
0
0
0
22 J-
23
27
31
28
49
67
74
83
0
Hg
730
810
740
790
740
656
650
485
632
617
3300
3000
3100
3100
3000
1,057
1,107
1,128
1,233
1,283
8500
8800
8900
7600
8200
1,347
1,494
1,505
1,494
1,496
130 J+
270
220
260
200
74
87
69
62
74
D-13
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
Sample ID
SB-SO-08-XX
SB-SO-11-XX
SB-SO-21-XX
SB-SO-39-XX
SB-SO-42-XX
SB-SO-08-XC
SB-SO-11-XC
SB-SO-21-XC
SB-SO-39-XC
SB-SO-42-XC
SB-SO-22-XX
SB-SO-25-XX
SB-SO-27-XX
SB-SO-35-XX
SB-SO-44-XX
SB-SO-22-XC
SB-SO-25-XC
SB-SO-27-XC
SB-SO-35-XC
SB-SO-44-XC
SB-SO-23-XX
SB-SO-28-XX
SB-SO-32-XX
SB-SO-43-XX
SB-SO-48-XX
SB-SO-23-XC
SB-SO-28-XC
SB-SO-32-XC
SB-SO-43-XC
SB-SO-48-XC
SB-SO-02-XX
SB-SO-07-XX
SB-SO-10-XX
SB-SO-26-XX
SB-SO-50-XX
SB-SO-02-XC
SB-SO-07-XC
SB-SO-10-XC
SB-SO-26-XC
SB-SO-50-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
180
200
190
200
200
154
134
120
135
135
160
160
170
160
170
114
119
117
121
113
26
26
28
24
25
6
6
6
24
6
180
170
200
220
200
162
160
166
173
190
Se
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
52
25
0.22 J
0.26 U
0.36
0.26 U
0.26 U
1.2 U
1.4
2.8
3.4
2.9
12
Ag
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1
18
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
12
29
0.26 UJ
0.26 UJ
0.1 UJ
0.26 UJ
0.1 UJ
7
5
15
5
1.2 UJ
1.6
1.8
1.8
1.8
12
18
18
15
V
57
66
58
62
65
29
96
28
53
63
52
54
54
50
53
22
121
69
96
68
13
13
14
13
13
147
93
156
162
135
59
53
59
68
61
0
0
0
43
38
Zn
70
84
75
77
78
74
72
60
77
98
64 J-
63
65
62
64
58
67
57
60
67
8
8
9
8
8
18
0
0
13
0
88
86
100
110
100
113
114
117
103
114
D-14
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
24
24
24
24
24
24
24
24
24
24
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-01-XX
SB-SO-16-XX
SB-SO-24-XX
SB-SO-45-XX
SB-SO-52-XX
SB-SO-01-XC
SB-SO-16-XC
SB-SO-24-XC
SB-SO-45-XC
SB-SO-52-XC
SB-SO-13-XX
SB-SO-19-XX
SB-SO-33-XX
SB-SO-37-XX
SB-SO-55-XX
SB-SO-13-XC
SB-SO-19-XC
SB-SO-33-XC
SB-SO-37-XC
SB-SO-55-XC
SB-SO-12-XX
SB-SO-15-XX
SB-SO-17-XX
SB-SO-46-XX
SB-SO-54-XX
SB-SO-12-XC
SB-SO-15-XC
SB-SO-17-XC
SB-SO-46-XC
SB-SO-54-XC
KP-SE-08-XX
KP-SE-11-XX
KP-SE-17-XX
KP-SE-25-XX
KP-SE-30-XX
KP-SE-08-XC
KP-SE-11-XC
KP-SE-17-XC
KP-SE-25-XC
KP-SE-30-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
180 J
170 J
180 J
180 J
150 J
123
129
105
122
131
430 J
310 J
350 J
340 J
340 J
280
210
259
258
278
620 J
600 J-
800 J+
740 J+
280
428
419
257
417
425
6.2
5.6
4.9
6
5.7
13
16
17
12
14
As
65
64
66
63
62
83
108
103
88
94
160
100
110
130
120
194
174
195
172
195
190
170 J-
210
190
31
266
298
215
259
260
3
3
3
3
3
126
82
76
0
40
Cd
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
33
25
1 U
0.5 U
0.5 U
1 U
0.5 U
28
24
30
1 U
1 U
1 U
1 U
0.2 U
27
29
28
0.11 U
0.11 U
0.11 U
0.11 U
0.11 U
32
28
Cr
140
140
150
140
140
132
115
76
161
110
140
100
100
120
120
92
92
170
99
100
91 J-
110
120
25
132
133
32
133
204
88
96
98
99
83
96
94
92
113
93
Cu
46
45
49
45
47
44
30
25
37
38
46
32
33
39
37
32
22
19
35
35
33
30 J-
37
35
5.8
20
28
22
24
28
3.8
4.1
4.1
4.3
3.6
0
1
1
1
1
Fe
47,000
47,000
49,000
47,000
46,000
32,072
30,888
28,359
30,355
29,892
61,000
42,000
45,000
51,000
49,000
35,473
31,909
34,068
36,020
36,018
55,000
51,000 J-
61,000
57,000
8,600
39,828
39,562
33,967
39,119
39,886
840
940
940
960
830
966
940
1,036
1,039
1,048
Pb
30
30
32
30
29
67
0
0
83
76
36
25
28
31
29
58
0
0
76
105
43
40 J-
48
47
5 J-
91
0
0
80
84
300 J-
310 J-
300 J-
310 J-
300 J-
442
450
458
512
491
Hg
400
480
420
450
430
158
141
111
168
153
850
740
870
790
900
339
220
293
310
338
1,400
1,100
1,200
670
560
570
524
337
504
495
0.089 U
0.079 U
0.082 U
0.096 U
0.1 U
3
3
D-15
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
24
24
24
24
24
24
24
24
24
24
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-01-XX
SB-SO-16-XX
SB-SO-24-XX
SB-SO-45-XX
SB-SO-52-XX
SB-SO-01-XC
SB-SO-16-XC
SB-SO-24-XC
SB-SO-45-XC
SB-SO-52-XC
SB-SO-13-XX
SB-SO-19-XX
SB-SO-33-XX
SB-SO-37-XX
SB-SO-55-XX
SB-SO-13-XC
SB-SO-19-XC
SB-SO-33-XC
SB-SO-37-XC
SB-SO-55-XC
SB-SO-12-XX
SB-SO-15-XX
SB-SO-17-XX
SB-SO-46-XX
SB-SO-54-XX
SB-SO-12-XC
SB-SO-15-XC
SB-SO-17-XC
SB-SO-46-XC
SB-SO-54-XC
KP-SE-08-XX
KP-SE-11-XX
KP-SE-17-XX
KP-SE-25-XX
KP-SE-30-XX
KP-SE-08-XC
KP-SE-11-XC
KP-SE-17-XC
KP-SE-25-XC
KP-SE-30-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
190
190
200
190
190
170
139
130
149
151
180
120
130
150
140
125
121
100
132
128
110
100 J-
120
120
20
122
109
56
111
110
42
46
47
47
39
39
36
42
46
47
Se
1.8
1.9
2.5
2.8
1.8
4.4
2.5
3
2.5 U
2.5
2.5 U
3.4
2.8
2.6
0.5 U
0.27 U
0.43
0.27 U
0.26 U
0.24 U
2
41
41
Ag
2.3
2.2
2.3
2.1 J-
2.2
16
6
22
4
20
2.2 UJ
1.8
2 J
2 UJ
2.2 J
24
27
13
29
37
2.1 UJ
1.6 UJ
2.3 UJ
2.2 UJ
0.5 UJ
23
13
0.27 UJ
0.27 UJ
0.27 UJ
0.27 UJ
0.27 UJ
12
5
2
V
65
65
67
63
64
57
24
0
59
28
74
51
52
63
61
64
0
148
179
48
59
52 J-
60
57
11
0
40
0
33
9
4
4
4
4
4
26
0
0
0
32
Zn
95
97
95
93
90
96
84
67
91
96
70
51
56
58
60
56
57
57
68
57
42
36 J-
42
41
6
41
32
35
34
37
5
6
5
5
5
0
35
25
25
18
D-16
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
KP-SE-12-XC
KP-SE-14-XC
KP-SE-19-XC
KP-SE-28-XC
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-XC
TL-SE-10-XC
TL-SE-12-XC
TL-SE-15-XC
TL-SE-20-XC
TL-SE-24-XC
TL-SE-26-XC
TL-SE-03-XX
TL-SE-19-XX
TL-SE-23-XX
TL-SE-25-XX
TL-SE-31-XX
TL-SE-03-XC
TL-SE-19-XC
TL-SE-23-XC
TL-SE-25-XC
TL-SE-31-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
3.2
3.1
11 J-
3
3.3
4
5
13
5
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
0
5
7
5
10
9
16
2.5 U
2.5 U
2.5 U
2.5 U
2.5 U
11
6
10
11
9
As
2
2
2
2
2
70
27
107
81
36
10
10
10
9
10
11
10
58
0
53
30
45
78
42
9
10
9
10
10
67
32
74
27
79
Cd
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
11
26
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
12
1 U
1 U
1 U
1 U
1 U
12
16
Cr
34
42
46 J-
44
45
72
59
61
45
70
62
64
66
54
64
67
62
7
36
26
91
96
92
91
110
Cu
2.2
2.5
2.7 J+
2.3
2.3
8
1
1
1
1
1,900
2,000
2,100
1,800
2,000
2,100
2,000
2,586
2,606
2,626
2,461
2,718
2,911
2,631
1,600
1,700
1,600
1,600
1,800
1,879
2,405
2,272
2,281
2,096
Fe
480
510
520 J-
510
520
651
509
635
640
646
42,000
43,000
44,000
36,000
42,000
43,000
40,000
36,085
36,600
36,634
35,872
37,221
37,288
36,523
63,000
66,000
64,000
62,000
74,000
52,922
56,855
57,909
58,350
55,112
Pb
310 J-
320 J-
680 J-
330
320
405
343
423
452
453
32
35
34
28
32
37
34
98
144
133
122
119
135
195
12
13
12
11
13
139
60
106
115
160
Hg
0.053 U
0.06 U
0.065 U
0.044 U
0.056 U
3
2
2
0.26 J-
0.19 J-
0.22 J-
0.28 J-
0.26 J-
0.26 J-
0.24 J-
6
0.32 J-
0.32 J-
0.41 J-
0.44 J-
0.57 J-
D-17
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
KP-SE-12-XC
KP-SE-14-XC
KP-SE-19-XC
KP-SE-28-XC
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-XC
TL-SE-10-XC
TL-SE-12-XC
TL-SE-15-XC
TL-SE-20-XC
TL-SE-24-XC
TL-SE-26-XC
TL-SE-03-XX
TL-SE-19-XX
TL-SE-23-XX
TL-SE-25-XX
TL-SE-31-XX
TL-SE-03-XC
TL-SE-19-XC
TL-SE-23-XC
TL-SE-25-XC
TL-SE-31-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
16
20
23 J-
22
22
27
20
24
23
18
71
72
75
63
74
77
70
116
115
117
123
89
107
100
110
120
110
110
130
154
137
121
115
115
Se
0.26 U
0.26 U
0.26 U
0.26 U
0.26 U
11
47
27
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
5
2.5 U
2.5 U
2.5 U
2.5 U
2.5 U
3
Ag
0.26 UJ
0.26 UJ
0.26 UJ
0.26 U
0.26 U
3
3
1.3
1.2 U
1.2 U
1 U
1.2 U
1.3 U
1.2 U
13
15
25
17
0.94 U
1.1 U
1.3 U
0.94 U
1.2 U
6
41
23
54
15
V
2 J
2 J
3 J
2 J
2 J
0
0
0
21
0
95
95
100
84
100
100
96
0
0
0
0
0
0
54
140
150
150
150
170
0
0
0
0
66
Zn
6
8
7
7
6
33
25
30
38
35
160
160
170
140
160
170
160
183
180
165
179
174
168
192
200
210
200
200
230
113
98
95
93
97
D-18
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
TL-SE-11-XC
TL-SE-14-XC
TL-SE-18-XC
TL-SE-22-XC
TL-SE-27-XC
TL-SE-29-XC
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-XC
LV-SE-10-XC
LV-SE-22-XC
LV-SE-25-XC
LV-SE-31-XC
LV-SE-35-XC
LV-SE-50-XC
LV-SE-12-XX
LV-SE-26-XX
LV-SE-33-XX
LV-SE-39-XX
LV-SE-42-XX
LV-SE-12-XC
LV-SE-26-XC
LV-SE-33-XC
LV-SE-39-XC
LV-SE-42-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
0
7
3
4
9
12
10
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
2.5 U
5
9
10
5
0
0
0
2.6 U
2.6 U
2.6 U
2.6 U
2.7 U
8
7
10
11
As
9
15
10
10
11
10
11
68
86
58
51
37
16
45
28
34
30
31
32
31 J-
29
74
82
81
85
87
73
79
190
220
170
190
170
230
243
227
291
261
Cd
0.5 U
0.5 U
0.27 J
0.5 U
0.5 U
0.28 J
0.22 J
19
13
1
0.51 U
0.51 U
0.51 U
0.51 U
0.51 U
0.51 U
1 U
33
35
11
11
25
1 U
1 U
1 U
1 U
1.1 U
Cr
110
140
110
150
150
130
140
124
102
87
98
149
141
93
72
84
69
74
78
74 J-
74
39
46
44
49
55
64
52
58
50
98
133
81
Cu
1,400
1,600
1,500
1,300
1,700
1,500
1,600
1,462
1,883
1,900
1,876
1,865
1,932
1,809
33
42
33
36
36
35
34
6
30
25
23
21
20
5
34
39
31
35
30
32
32
35
43
26
Fe
19,000
28,000
18,000
24,000
26,000
19,000
23,000
26,263
34,010
33,304
32,929
33,004
32,418
31,056
23,000
28,000
23,000
25,000
25,000
24,000 J-
24,000
19,902
20,112
19,644
20,308
19,882
20,470
19,573
72,000
83,000
66,000
74,000
65,000
51,313
53,305
53,895
54,680
54,288
Pb
48 J-
54 J-
50 J-
46 J-
54 J-
51 J-
51 J-
154
145
141
193
181
187
119
20 J-
25 J-
22 J-
23 J-
49 J-
22 J-
24 J-
80
0
59
125
57
96
69
19 J-
25 J-
21 J-
22 J-
22 J-
155
120
183
0
104
Hg
0.074 U
0.021 U
0.08 U
0.025 U
0.082 U
0.02 U
0.076 U
5
5
3
4
18
1
0.02 U
0.023 U
1.1
1
1
1.4
1.2
13
7
6
19
5.6
6
6.8
8
4.3
D-19
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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-XC
TL-SE-11-XC
TL-SE-14-XC
TL-SE-18-XC
TL-SE-22-XC
TL-SE-27-XC
TL-SE-29-XC
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-XC
LV-SE-10-XC
LV-SE-22-XC
LV-SE-25-XC
LV-SE-31-XC
LV-SE-35-XC
LV-SE-50-XC
LV-SE-12-XX
LV-SE-26-XX
LV-SE-33-XX
LV-SE-39-XX
LV-SE-42-XX
LV-SE-12-XC
LV-SE-26-XC
LV-SE-33-XC
LV-SE-39-XC
LV-SE-42-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
180
210
180
190
210
200
200
156
220
198
199
206
232
209
160
200
170
170
180
170 J-
170
115
119
106
141
111
116
113
71
83
66
74
67
71
72
72
102
99
Se
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
64
37
3.8
4.7
5.2
5.1
5.1
5
3.3
3
6.1
2.8
5.1
3.4
22
Ag
5.7 J-
5.5 J-
5.7 J-
6.3 J-
6.5 J-
7.8 J-
5.9 J-
33
21
24
26
23
26
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
2.5 U
11
6
7
10
8
2
21
2.6 U
2.6 U
2.6 U
2.6 U
2.7 U
3
4
5
2
V
75
85
73
70
80
67
80
0
0
64
54
0
65
44
53
66
51
56
58
55 J-
57
55
73
23
0
0
45
82
72
86
67
74
64
25
27
0
0
0
Zn
130
140
140
120
150
140
140
97
104
107
93
107
109
104
65
77
66
70
70
67 J-
65
115
97
127
124
113
91
100
66
75
59
66
57
48
37
40
31
41
D-20
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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
37
37
37
37
37
37
37
37
37
37
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-XC
LV-SE-19-XC
LV-SE-27-XC
LV-SE-36-XC
LV-SE-38-XC
LV-SE-07-XX
LV-SE-18-XX
LV-SE-23-XX
LV-SE-45-XX
LV-SE-48-XX
LV-SE-07-XC
LV-SE-18-XC
LV-SE-23-XC
LV-SE-45-XC
LV-SE-48-XC
LV-SE-01-XX
LV-SE-14-XX
LV-SE-21-XX
LV-SE-24-XX
LV-SE-32-XX
LV-SE-01-XC
LV-SE-14-XC
LV-SE-21-XC
LV-SE-24-XC
LV-SE-32-XC
LV-SE-08-XX
LV-SE-16-XX
LV-SE-28-XX
LV-SE-30-XX
LV-SE-47-XX
LV-SE-08-XC
LV-SE-16-XC
LV-SE-28-XC
LV-SE-30-XC
LV-SE-47-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
6.7 U
6.7 U
6.7 U
6.7 U
6.7 U
0
11
10
15
0
6.7 UJ
6.7 UJ
6.6 UJ
6.7 UJ
6.6 UJ
12
11
22
35
28
1.5 UJ
1.5 UJ
1.5 UJ
1.5 UJ
1.4 UJ
118
80
98
98
107
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
0
1
1
6
0
As
450
500
530
550
480
513
517
488
545
503
780
800
660
650
680
692
670
705
642
585
6
5
7
5
6
91
70
72
66
73
30
29
31
30
31
69
83
71
57
93
Cd
2.7 U
2.7 U
2.7 U
2.7 U
2.7 U
24
18
0
2.7 U
2.7 U
2.6 U
2.7 U
2.6 U
12
9
0.76
0.74
0.84
0.68
0.87
28
0.52 U
0.52 U
0.52 U
0.52 U
0.52 U
36
52
34
Cr
48
55
56
60
52
270
384
86
92
57
61
53
50
52
314
702
346
4
4
4
4
4
54
53
59
58
56
40
58
Cu
34
37
39
40
36
40
2
3
36
4
48
49
40
40
42
47
2
28
54
1
18
16
19
15
16
1
14
0
0
1
23
22
25
25
23
6
5
5
5
23
Fe
150,000
160,000
180,000
180,000
160,000
105,797
104,569
103,211
107,069
105,744
200,000
210,000
170,000
170,000
180,000
132,559
133,997
129,948
120,254
124,294
1,100
980
970
840
860
416
446
455
437
433
23,000
22,000
25,000
24,000
23,000
20,743
20,064
20,981
20,597
19,257
Pb
14 J-
17 J-
16 J-
21 J-
15 J-
0
166
257
0
0
11
11
8
8
9
270
356
192
0
445
17
14
18
14
14
43
22
22
27
32
55
53
59
58
57
137
177
165
193
145
Hg
6
7.2
11
8.5
7.9
5.5
5.4
5
5.6
7.3
109
0.098 U
0.056 U
0.048 U
0.053 U
0.052 U
3
2
5.2
5.4
5.4
6.3
4.9
8
12
7
D-21
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX 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
37
37
37
37
37
37
37
37
37
37
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-XC
LV-SE-19-XC
LV-SE-27-XC
LV-SE-36-XC
LV-SE-38-XC
LV-SE-07-XX
LV-SE-18-XX
LV-SE-23-XX
LV-SE-45-XX
LV-SE-48-XX
LV-SE-07-XC
LV-SE-18-XC
LV-SE-23-XC
LV-SE-45-XC
LV-SE-48-XC
LV-SE-01-XX
LV-SE-14-XX
LV-SE-21-XX
LV-SE-24-XX
LV-SE-32-XX
LV-SE-01-XC
LV-SE-14-XC
LV-SE-21-XC
LV-SE-24-XC
LV-SE-32-XC
LV-SE-08-XX
LV-SE-16-XX
LV-SE-28-XX
LV-SE-30-XX
LV-SE-47-XX
LV-SE-08-XC
LV-SE-16-XC
LV-SE-28-XC
LV-SE-30-XC
LV-SE-47-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
55
65
64
70
75
74
74
75
73
74
58
60
50 J
50 J
50 J
55
54
57
65
111
49
46
49
44
47
21
25
17
31
15
110
110
120
120
120
122
84
102
108
96
Se
6.7 U
5.9 J
6.7 U
11
6.7 U
111
10
10
12
9.6
8.2
7.6
5
9
1.5 U
1.5 U
1.5 U
1.5 U
1.4 U
4.8
5
5.8
5.6
4.2
6
Ag
6.7 U
6.7 U
6.7 U
6.7 U
6.7 U
13
14
10
6.7 U
6.7 U
6.6 U
6.7 U
6.6 U
1.5 U
1.5 U
1.5 U
1.5 U
1.4 U
9
4
19
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
4
0
9
15
2
V
100
110
120
120
100
0
0
0
0
0
130
140
120
120
120
0
0
0
15
0
2 J
1 J
2 J
1 J
1 J
0
0
0
0
0
44
42
48
48
45
46
32
16
36
32
Zn
51 J
55 J
58 J
60 J
54 J
24 J
52 J
18 J
19 J
30 J
0
14 J
12 J
14 J
12 J
19
22
53
0
0
29
61
59
65
66
65
116
103
100
92
107
D-22
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
38
38
38
38
38
38
38
38
38
38
39
39
39
39
39
39
39
39
39
39
39
39
39
39
40
40
40
40
40
40
40
40
40
40
Sample ID
LV-SE-ll-XX
LV-SE-29-XX
LV-SE-44-XX
LV-SE-46-XX
LV-SE-52-XX
LV-SE-11-XC
LV-SE-29-XC
LV-SE-44-XC
LV-SE-46-XC
LV-SE-52-XC
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-XC
RF-SE-12-XC
RF-SE-23-XC
RF-SE-36-XC
RF-SE-42-XC
RF-SE-45-XC
RF-SE-53-XC
RF-SE-03-XX
RF-SE-28-XX
RF-SE-38-XX
RF-SE-49-XX
RF-SE-55-XX
RF-SE-03-XC
RF-SE-28-XC
RF-SE-38-XC
RF-SE-49-XC
RF-SE-55-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
1.4 UJ
1.4 UJ
1.4 U
0.88 U
1.4 U
17
13
9
11
1.3 U
1.2 U
0.25 U
1.2 U
1.3 UJ
1.3 UJ
1.3 UJ
0
0
0
0
4
9
0
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1
5
10
1
1
As
150
150
140
110
160
218
228
195
199
167
12
14
0 U
12
14
15
14
63
72
54
63
34
64
73
27
31
27
31
24
80
53
65
64
99
Cd
6.6
6.3
6.1
5
6.8
0.5 U
0.5 U
0.1 U
0.5 U
0.56
0.52 U
0.57 U
10
11
30
1.3
1.5
1.2
1.5
1.1
51
12
Cr
120
120
120
92
130
57
41
92
100
0 U
91
110
110
110
48
70
80
88
51
118
70
93
100
90
100
91
106
80
73
41
Cu
270
260
250
200
280
212
202
176
200
186
81
110
0.2 U
82
95
100
95
56
52
72
67
75
59
55
200
220
190
220
180
210
211
228
200
209
Fe
42,000
42,000
40,000
32,000
44,000
30,708
30,725
26,884
27,483
29,383
17,000
20,000
4 J
17,000
19,000
21,000
19,000
15,548
16,025
16,718
15,862
17,031
16,455
16,043
17,000
18,000
16,000
18,000
15,000
15,187
15,903
16,972
15,568
16,258
Pb
7
7 J+
8
6
8
0
0
0
96
24
25
0 U
22
28
33
28
108
96
97
56
60
119
88
99
83
97
75
188
204
197
178
219
Hg
2.8
1.5 J-
1.5
1.4
21
0.091 U
0.099 U
2.4
0.081 U
0.084 U
0.084 U
0.084 U
7
7
4
8
4
86
0.48
0.57
0.41
0.43
0.42
9
7
8
Ni
870
860
830
660
910
608
636
508
567
551
180
210
2 U
180
210
220
210
132
135
155
124
165
141
144
150
160
140
170
140
117
116
123
117
118
D-23
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
38
38
38
38
38
38
38
38
38
38
39
39
39
39
39
39
39
39
39
39
39
39
39
39
40
40
40
40
40
40
40
40
40
40
Sample ID
LV-SE-ll-XX
LV-SE-29-XX
LV-SE-44-XX
LV-SE-46-XX
LV-SE-52-XX
LV-SE-11-XC
LV-SE-29-XC
LV-SE-44-XC
LV-SE-46-XC
LV-SE-52-XC
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-XC
RF-SE-12-XC
RF-SE-23-XC
RF-SE-36-XC
RF-SE-42-XC
RF-SE-45-XC
RF-SE-53-XC
RF-SE-03-XX
RF-SE-28-XX
RF-SE-38-XX
RF-SE-49-XX
RF-SE-55-XX
RF-SE-03-XC
RF-SE-28-XC
RF-SE-38-XC
RF-SE-49-XC
RF-SE-55-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
870
860
830
660
910
608
636
508
567
551
180
210
2 U
180
210
220
210
132
135
155
124
165
141
144
150
160
140
170
140
117
116
123
117
118
Se
1.3 U
1.2 U
1.4 U
0.88 U
1.4 U
1.3 U
1.2 U
0.25 U
1 U
1.3 U
1.3 U
1.3 U
6
14
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
Ag
1.4 U
1.4 U
1.4 U
0.88 U
1.4 U
7
0
0
1.3 U
1.2 U
0.37
1.2 U
1.3 U
1.3 U
1.3 U
25
4
4
14
3
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
6
3
8
V
35
35
34
27
38
0
0
0
0
61
34
38
3 U
34
40
43
40
0
35
49
0
33
0
26
40
44
39
43
35
42
61
0
9
0
Zn
200
200
190
150
210
191
202
202
189
187
130
140
1 U
120
140
150
140
171
190
219
227
248
217
185
300
320
300
330
280
481
486
552
530
534
D-24
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
41
41
41
41
41
41
41
41
41
41
42
42
42
42
42
42
42
42
42
42
43
43
43
43
43
43
43
43
43
43
Sample ID
RF-SE-06-XX
RF-SE-13-XX
RF-SE-27-XX
RF-SE-31-XX
RF-SE-58-XX
RF-SE-06-XC
RF-SE-13-XC
RF-SE-27-XC
RF-SE-31-XC
RF-SE-58-XC
RF-SE-02-XX
RF-SE-22-XX
RF-SE-25-XX
RF-SE-30-XX
RF-SE-57-XX
RF-SE-02-XC
RF-SE-22-XC
RF-SE-25-XC
RF-SE-30-XC
RF-SE-57-XC
RF-SE-15-XX
RF-SE-24-XX
RF-SE-32-XX
RF-SE-43-XX
RF-SE-59-XX
RF-SE-15-XC
RF-SE-24-XC
RF-SE-32-XC
RF-SE-43-XC
RF-SE-59-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
2
7
2
6
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
2
10
2
7
2
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
6
3
3
10
12
As
70
76
64
39
71
96
92
92
123
89
110
99
88
89
89
143
179
107
125
123
120
130 J+
120
130
140
180
207
148
168
152
Cd
3.6
3.7
3.1
1.8
3.6
22
2
5.4
4.7
4
4.3
4.5
4
22
25
6.2
6.5 J+
5.1
5.7
5.9
21
38
Cr
90
92
78
63
89
78
97
59
93
84
78
78
79
58
79
80
101
72
74 J+
64
68
73
49
75
36
Cu
490
530
440
250
500
468
485
485
523
520
740
670
580
610
610
599
649
649
637
637
820
860 J+
770
840
890
887
889
901
938
928
Fe
20,000
21,000
18,000
12,000
21,000
16,459
16,918
17,224
17,807
17,583
24,000
22,000
19,000
21,000
21,000
17,633
17,877
18,000
18,543
17,762
23,000
24,000 J+
20,000
22,000
23,000
19,197
19,447
19,415
19,857
19,383
Pb
230
230
200
120
230
356
452
381
392
501
330
300
270
290
300
478
467
497
542
505
390
410 J+
330
350
380
661
654
703
678
686
Hg
l.l
1.2
1.2
1.1
1.2
5
1.6
1.7
1.5
1.5
1.5
7
2.6
2.3
2.8
2.7
0.085 U
8
D-25
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
41
41
41
41
41
41
41
41
41
41
42
42
42
42
42
42
42
42
42
42
43
43
43
43
43
43
43
43
43
43
Sample ID
RF-SE-06-XX
RF-SE-13-XX
RF-SE-27-XX
RF-SE-31-XX
RF-SE-58-XX
RF-SE-06-XC
RF-SE-13-XC
RF-SE-27-XC
RF-SE-31-XC
RF-SE-58-XC
RF-SE-02-XX
RF-SE-22-XX
RF-SE-25-XX
RF-SE-30-XX
RF-SE-57-XX
RF-SE-02-XC
RF-SE-22-XC
RF-SE-25-XC
RF-SE-30-XC
RF-SE-57-XC
RF-SE-15-XX
RF-SE-24-XX
RF-SE-32-XX
RF-SE-43-XX
RF-SE-59-XX
RF-SE-15-XC
RF-SE-24-XC
RF-SE-32-XC
RF-SE-43-XC
RF-SE-59-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
150
160
130
86
150
108
122
100
115
107
180
160
140
150
150
105
150
140
131
112
160
170 J+
140
150
160
125
140
127
127
136
Se
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
24
1.3 U
1.3 U
1.5
1.3 U
2
4
23
1.4
1.3 U
1.3 U
1.3 U
1.3 U
14
Ag
1.3 U
1.3
1.3 U
1.3 U
1.3 U
24
22
5
25
2.7
2.3
1.7
1.9
2.2
9
10
3
3.6
3.8 J+
4.2
4
4.5
4
16
19
22
V
44
45
39
28
46
50
0
14
33
23
50
44
40
44
44
0
0
0
0
0
45
46 J+
36
40
42
0
22
0
40
48
Zn
740
790
670
420
770
1,092
1,173
1,090
1,156
1,231
1,100
990
890
960
1,000
1,295
1,445
1,371
1,452
1,465
1,300
1,400 J-
1,100
1,200
1,300
1,768
1,861
1,857
1,939
1,868
D-26
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
44
44
44
44
44
44
44
44
44
44
45
45
45
45
45
45
45
45
45
45
46
46
46
46
46
46
47
47
47
47
47
47
Sample ID
RF-SE-05-XX
RF-SE-26-XX
RF-SE-39-XX
RF-SE-44-XX
RF-SE-56-XX
RF-SE-05-XC
RF-SE-26-XC
RF-SE-39-XC
RF-SE-44-XC
RF-SE-56-XC
RF-SE-04-XX
RF-SE-14-XX
RF-SE-19-XX
RF-SE-34-XX
RF-SE-52-XX
RF-SE-04-XC
RF-SE-14-XC
RF-SE-19-XC
RF-SE-34-XC
RF-SE-52-XC
BN-SO-11-XX
BN-SO-14-XX
BN-SO-23-XX
BN-SO-11-XC
BN-SO-14-XC
BN-SO-23-XC
BN-SO-09-XX
BN-SO-12-XX
BN-SO-24-XX
BN-SO-09-XC
BN-SO-12-XC
BN-SO-24-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
4.1 J+
2.2 J+
2.9 J+
2.7 J+
3.5 J+
3
9
12
7
12
3.2 J+
4.4 J+
3.7 J+
2.9 J+
3.4 J+
4
5
15
17
16
4 J-
3.5 J-
1.2 UJ
5
8
0
750 J-
750 J-
810 J-
374
366
348
As
160
140
160
140
180
163
225
209
231
212
230
260
250
210
220
303
274
284
343
311
2,900
2,800
2,800
4,644
4,470
4,327
97
89
97
60
52
70
Cd
9.1
8.4
9.3
8.2
9.6
15
30
24
12
12
13
10
11
27
12
25
720
690
700
951
850
818
2,700
2,600
2,900
3,128
3,078
2,870
Cr
69
64
73
64
75
40
43
86
46
45
42
47
48
39
42
51
47
49
820
800
800
519
507
533
2,900
2,800
3,000
1,613
1,605
1,563
Cu
1,000
990
1,100
970
1200
1,115
1,133
1,157
1,171
1,138
1,500
1,700
1,700
1,400
1,500
1,637
1,635
1,673
1,727
1,720
120
120
120
431
406
423
100
96
100
76
67
75
Fe
26,000
23,000
26,000
24,000
27,000
20,304
20,882
21,647
21,394
20,900
27,000
30,000
30,000
24,000
26,000
22,522
23,684
22,966
23,564
23,725
23,000
22,000
23,000
24,935
24,994
25,464
22,000
21,000
23,000
15,548
15,511
15,803
Pb
450
440
490
420
490
729
683
769
657
694
730
800
800
660
720
1,023
1,118
1,145
1,069
56
51
52
0
61
77
4,700
4,500
4,900
7,409
7,237
7,395
Hg
2.6
2.5
2.2
2.3
2.2
7
5
4.2
4.7
3.9
4.5
4.1
1,100
24 J-
26
31
25
43
37
0.39
0.34
0.37
D-27
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
44
44
44
44
44
44
44
44
44
44
45
45
45
45
45
45
45
45
45
45
46
46
46
46
46
46
47
47
47
47
47
47
Sample ID
RF-SE-05-XX
RF-SE-26-XX
RF-SE-39-XX
RF-SE-44-XX
RF-SE-56-XX
RF-SE-05-XC
RF-SE-26-XC
RF-SE-39-XC
RF-SE-44-XC
RF-SE-56-XC
RF-SE-04-XX
RF-SE-14-XX
RF-SE-19-XX
RF-SE-34-XX
RF-SE-52-XX
RF-SE-04-XC
RF-SE-14-XC
RF-SE-19-XC
RF-SE-34-XC
RF-SE-52-XC
BN-SO-11-XX
BN-SO-14-XX
BN-SO-23-XX
BN-SO-11-XC
BN-SO-14-XC
BN-SO-23-XC
BN-SO-09-XX
BN-SO-12-XX
BN-SO-24-XX
BN-SO-09-XC
BN-SO-12-XC
BN-SO-24-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
150
140
150
140
160
105
107
94
107
112
130
140
140
120
130
117
105
126
125
137
2,900
2,800
2,800
2,533
2,429
2,460
1,500
1,400
1,600
1,158
1,194
1,169
Se
3.1
2.8
2.6
2.4
1.8
1
2.8
3
4.1
1.9
2
140
130
130
260
208
206
290
290
300
717
624
611
Ag
7.4 J-
7.2 J-
8.2 J-
7.2 J-
8.3 J-
11
17
6
7
12 J-
13 J-
14 J-
10 J-
11 J-
42
25
33
12
9
140 J-
140 J-
130 J-
166
142
135
100 J-
210 J-
140 J-
520
512
447
V
48
42
49
44
51
50
0
12
0
40
46
51
52
42
47
48
34
0
0
0
150
150
150
48
75
76
340
310
350
99
40
75
Zn
1,800
1,700
1,900
1,600
1,900
2,313
2,307
2,279
2,351
2,222
2,400
2,600
2,700
2,200
2,300
2,884
3,004
2,922
2,971
2,916
3,900
3,800
3,800
5,392
5,294
5,306
81
74
81
104
110
116
D-28
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
48
48
48
48
48
48
49
49
49
49
49
49
50
50
50
50
50
50
51
51
51
51
51
51
52
52
52
52
52
52
53
53
53
53
53
53
Sample ID
SB-SO-09-XX
SB-SO-20-XX
SB-SO-31-XX
SB-SO-09-XC
SB-SO-20-XC
SB-SO-31-XC
SB-SO-29-XX
SB-SO-36-XX
SB-SO-56-XX
SB-SO-29-XC
SB-SO-36-XC
SB-SO-56-XC
SB-SO-04-XX
SB-SO-34-XX
SB-SO-49-XX
SB-SO-04-XC
SB-SO-34-XC
SB-SO-49-XC
WS-SO-07-XX
WS-SO-11-XX
WS-SO-25-XX
WS-SO-07-XC
WS-SO-11-XC
WS-SO-25-XC
WS-SO-10-XX
WS-SO-20-XX
WS-SO-23-XX
WS-SO-10-XC
WS-SO-20-XC
WS-SO-23-XC
AS-SO-03-XX
AS-SO-05-XX
AS-SO-08-XX
AS-SO-03-XC
AS-SO-05-XC
AS-SO-08-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
1.3 UJ
1.3 UJ
1.3 UJ
3
11
0
1.2 U
1.2 U
1.2 U
0
0
0
940
980
700
522
528
3.8
1.2 U
1.2 U
16
17
13
1.3 U
1.3 U
1.3 U
22
23
21
1.2 U
1.2 U
1.2 U
4
1
1
As
9
11
8 J-
67
62
68
9
8
10
74
52
95
13
12
12
121
121
85
53
46
59
95
138
44
83
100
110
80
56
44
14
9
10
101
67
55
Cd
0.51 U
0.51 U
0.51 U
10
13
0.5 U
0.5 U
0.5 U
9
28
17
2,800
2,500
2,500
3,100
2,907
3,174
1.9
1.4
3.1
1.8
1.9
2.1
11
40
50
1,300
900
930
1,167
1,184
1,217
Cr
130
170
140
160
64
104
140
120
150
75
150
144
2,800
2,500
2,400
1,800
1,691
1,770
640
570
730
499
476
379
67
81
82
93
52
80
33
23
24
59
Cu
120
150
130
414
379
393
130
100
140
408
424
419
100
91
89
80
72
71
4,400
3,900
4,900
9,740
9,332
6,663
76
90
96
286
288
271
6,200
4,500
4,600
8,843
9,977
9,488
Fe
35,000
44,000
38,000
38,474
32,246
35,657
41,000
33,000
42,000
36,179
37,462
38,650
38,000
34,000
33,000
24,853
23,843
24,585
25,000
19,000
24,000
20,630
19,876
16,469
19,000
23,000
23,000
26,434
25,411
24,797
15,000
11,000
11,000
11,957
12,322
12,255
Pb
19
24
21
32
0
0
19
15
20
41
55
40
21
18
18
68
20
51
1,700
1,500
1,900
5,119
4,887
3,193
1,900
2,300
2,500
5,426
4,817
4,721
160
110
120
208
211
218
Hg
30
10
32
34
7.9 J
36
9
15
19
26
40
36
36
34
484
44
0.26
0.27
0.25
9
0.058 U
0.06 U
0.05 U
20
18
3.7 J-
2.5 J-
2.5 J-
5
D-29
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
48
48
48
48
48
48
49
49
49
49
49
49
50
50
50
50
50
50
51
51
51
51
51
51
52
52
52
52
52
52
53
53
53
53
53
53
Sample ID
SB-SO-09-XX
SB-SO-20-XX
SB-SO-31-XX
SB-SO-09-XC
SB-SO-20-XC
SB-SO-31-XC
SB-SO-29-XX
SB-SO-36-XX
SB-SO-56-XX
SB-SO-29-XC
SB-SO-36-XC
SB-SO-56-XC
SB-SO-04-XX
SB-SO-34-XX
SB-SO-49-XX
SB-SO-04-XC
SB-SO-34-XC
SB-SO-49-XC
WS-SO-07-XX
WS-SO-11-XX
WS-SO-25-XX
WS-SO-07-XC
WS-SO-11-XC
WS-SO-25-XC
WS-SO-10-XX
WS-SO-20-XX
WS-SO-23-XX
WS-SO-10-XC
WS-SO-20-XC
WS-SO-23-XC
AS-SO-03-XX
AS-SO-05-XX
AS-SO-08-XX
AS-SO-03-XC
AS-SO-05-XC
AS-SO-08-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
2900
3700
3200 J-
2,715
2,375
2,499
200
160
210
146
166
169
3,300
3,000
2,800
2,718
2,565
2,648
260
240
300
437
420
310
290
350
380
328
312
319
520
370
380
607
675
605
Se
26
30
28 J-
28
31
21
160
130
160
381
369
383
390
360
330
912
855
960
1.2 U
1.2 U
1.2 U
9
280
340
360
1,175
998
1,017
200
140
140
334
307
339
Ag
160 J-
140 J-
160 J-
387
300
335
1.2 UJ
1.2 UJ
1.2 UJ
3
4
5
1.3 UJ
1.3 UJ
1.2 UJ
65
400 J-
340 J-
450 J-
542
537
378
1.3 UJ
1.3 UJ
1.3 UJ
19
8
16
480 J-
330 J-
280 J-
366
544
377
V
120
160
140
41
0
144
400
320
410
199
225
97
58
52
52
0
76
96
48
43
54
39
9
0
260
320
330
151
106
117
29
23
23
13
0
0
Zn
3,600
4,500
3,900 J-
4,097
3,934
4,005
3,900
3,200
4,100
4,175
4,103
4,111
86
77
72
70
62
63
180
160
200
306
327
279
1,900
2,300
2,500
3,742
3,763
3,736
350
250
260
532
599
556
D-30
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
54
54
54
54
54
54
55
55
55
55
55
55
56
56
56
56
56
56
57
57
57
57
57
57
58
58
58
58
58
58
59
59
59
59
59
59
Sample ID
LV-SO-03-XX
LV-SO-40-XX
LV-SO-49-XX
LV-SO-03-XC
LV-SO-40-XC
LV-SO-49-XC
LV-SO-04-XX
LV-SO-34-XX
LV-SO-37-XX
LV-SO-04-XC
LV-SO-34-XC
LV-SO-37-XC
CN-SO-03-XX
CN-SO-06-XX
CN-SO-07-XX
CN-SO-03-XC
CN-SO-06-XC
CN-SO-07-XC
CN-SO-02-XX
CN-SO-05-XX
CN-SO-09-XX
CN-SO-02-XC
CN-SO-05-XC
CN-SO-09-XC
LV-SE-06-XX
LV-SE-13-XX
LV-SE-41-XX
LV-SE-06-XC
LV-SE-13-XC
LV-SE-41-XC
LV-SE-05-XX
LV-SE-20-XX
LV-SE-43-XX
LV-SE-05-XC
LV-SE-20-XC
LV-SE-43-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
1.6
2.7
7.4
6
4
1
860
870 J-
590
347
335
344
22
20
20
11
12
8
230
130
120
74
78
78
30
31
30
40
38
45
92
140 J+
160 J+
90
93
103
As
42
42
43
61
75
65
120
110 J-
84
90
52
39
87
91
90
169
201
163
19
6
6
79
80
51
23
24
21
87
54
74
20
31
24
93
74
59
Cd
590
580
600
670
730
604
2,400
2,300 J-
1,700
3,054
2,985
3,095
63
64
63
77
68
94
820
630
580
677
695
667
160
160
150
269
234
235
440
680
550
657
745
743
Cr
600
590
610
346
393
346
2,300
2,200 J-
1,600
1,351
1,443
1,423
17
18
19
290
26
21
38
35
540
540
480
341
379
365
840
1,400
1,100
652
714
709
Cu
130
130
130
451
449
413
98
87
66
61
48
72
72
74
72
93
82
93
140
160
140
336
308
296
30
30
26
3
4
16
39
60
47
225
231
233
Fe
24,000
24,000
25,000
34,877
35,004
30,730
22,000
20,000 J-
16,000
20,656
20,387
20,591
15,000
16,000
17,000
16,552
15,546
17,267
22,000
23,000
19,000
22,137
20,389
20,290
18,000
18,000
16,000
17,343
17,202
18,059
16,000
22,000
19,000
25,232
24,839
24,954
Pb
94
92
98
173
153
197
4,000
3,700 J-
2,800
8,958
8,837
8,918
130
130
130
272
256
294
490
25
23
0
0
43
1,600
1,600
1,500
3,778
3,596
3,754
14
21
17
101
63
107
Hg
48 J-
46 J-
52 J-
13
130 J-
130 J-
130 J-
37
38
21
34 J-
40 J-
36 J-
10
7
15
270 J-
280 J-
260 J-
98
110
98
610 J-
640 J-
610 J-
245
225
249
2.6 J-
2.8
2.8
8
D-31
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
54
54
54
54
54
54
55
55
55
55
55
55
56
56
56
56
56
56
57
57
57
57
57
57
58
58
58
58
58
58
59
59
59
59
59
59
Sample ID
LV-SO-03-XX
LV-SO-40-XX
LV-SO-49-XX
LV-SO-03-XC
LV-SO-40-XC
LV-SO-49-XC
LV-SO-04-XX
LV-SO-34-XX
LV-SO-37-XX
LV-SO-04-XC
LV-SO-34-XC
LV-SO-37-XC
CN-SO-03-XX
CN-SO-06-XX
CN-SO-07-XX
CN-SO-03-XC
CN-SO-06-XC
CN-SO-07-XC
CN-SO-02-XX
CN-SO-05-XX
CN-SO-09-XX
CN-SO-02-XC
CN-SO-05-XC
CN-SO-09-XC
LV-SE-06-XX
LV-SE-13-XX
LV-SE-41-XX
LV-SE-06-XC
LV-SE-13-XC
LV-SE-41-XC
LV-SE-05-XX
LV-SE-20-XX
LV-SE-43-XX
LV-SE-05-XC
LV-SE-20-XC
LV-SE-43-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni Se Ag V Zn
2,000 120 210 J- 120 3,700
1,900 120 210 J- 120 3,700
2,000 120 220 J- 120 3,800
1,795 320 204 41 4,677
1,815 291 223 99 4,664
1,650 270 191 81 4,653
2,000 230 1.2 UJ 260 53
1,900 J- 220 J- 1.2 UJ 230 J- 48 J-
1,400 170 1.2 U 180 37
1,834 502 107 57
1,791 549 19 105 38
1,875 586 22 133 63
74 36 90 30 58
76 38 94 32 59
75 37 91 33 58
81 22 114 33 132
78 46 99 23 140
102 41 108 29 140
530 190 68 160 1,900
360 190 78 160 2,200
330 170 74 140 2,100
327 406 82 75 3,552
308 385 73 67 3,580
289 388 92 78 3,451
360 160 110 480 52
360 160 110 470 51
320 150 99 420 46
299 406 148 194 64
305 343 139 207 79
331 329 139 217 64
400 340 49 340 1,800
660 500 75 J- 530 2,800
530 420 60 J- 430 2,300
411 1,189 65 151 3,269
427 1,255 74 211 3,354
420 1,210 77 173 3,300
D-32
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
60
60
60
60
60
60
61
61
61
61
61
61
62
62
62
62
62
62
63
63
63
63
63
63
64
64
64
64
64
64
Sample ID
LV-SE-15-XX
LV-SE-17-XX
LV-SE-51-XX
LV-SE-15-XC
LV-SE-17-XC
LV-SE-51-XC
TL-SE-05-XX
TL-SE-09-XX
TL-SE-13-XX
TL-SE-05-XC
TL-SE-09-XC
TL-SE-13-XC
TL-SE-06-XX
TL-SE-17-XX
TL-SE-28-XX
TL-SE-06-XC
TL-SE-17-XC
TL-SE-28-XC
TL-SE-07-XX
TL-SE-21-XX
TL-SE-30-XX
TL-SE-07-XC
TL-SE-21-XC
TL-SE-30-XC
TL-SE-02-XX
TL-SE-08-XX
TL-SE-16-XX
TL-SE-02-XC
TL-SE-08-XC
TL-SE-16-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
290 J+
280 J+
210 J+
150
152
119
100 J+
100 J+
95 J+
134
128
125
1.2 U
1.2 U
1.2 U
16
17
21
30
33
31
48
50
52
77
66
73
101
123
120
As
32
31
26
70
72
129
34
33
31
53
65
87
86
85
89
67
63
126
11
13
11
74
69
54
15
10
15
55
71
33
Cd
1,300
1,300
1,100
1,365
1,362
1,186
0.34 J
0.24 J
0.45 J
350
340
360
463
501
520
48
51
47
58
42
44
160
180
170
159
214
213
Cr
83
79
72
69
45
40
39
36 J+
34
33
34
20
66
73
64
16
13
64
74
69
43
12
Cu
2,300
2,200
2,000
2,440
2,459
2,275
4,900
4,800
4,400 J+
6,233
6,272
6,013
2000
2100
2100
2,895
2,729
2,659
2200
2300
2200
3,700
3,736
3,573
3,100
3,200
3,100
4,258
5,452
5,324
Fe
22,000
21,000
19,000
18,435
18,517
17,652
24,000
23,000
22,000 J+
22,153
21,976
22,026
22,000
21,000
22,000
22,639
21,993
21,638
37,000
44,000
36,000
53,232
53,772
52,769
32,000
45,000
38,000
45,180
54,821
52,189
Pb
18
17 J-
15
47
80
0
1,200
1,200
1,100 J+
2,327
2,295
2,354
1,700
1,700
1,700
4,143
4,379
4,711
13
15
14
73
117
129
12
11
13
144
73
43
Hg
500
490
470
247
236
212
980
820
990
424
434
450
2.2
2.6
2.8
40
120
100
41
19
23
400
350
420
152
163
192
D-33
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
60
60
60
60
60
60
61
61
61
61
61
61
62
62
62
62
62
62
63
63
63
63
63
63
64
64
64
64
64
64
Sample ID
LV-SE-15-XX
LV-SE-17-XX
LV-SE-51-XX
LV-SE-15-XC
LV-SE-17-XC
LV-SE-51-XC
TL-SE-05-XX
TL-SE-09-XX
TL-SE-13-XX
TL-SE-05-XC
TL-SE-09-XC
TL-SE-13-XC
TL-SE-06-XX
TL-SE-17-XX
TL-SE-28-XX
TL-SE-06-XC
TL-SE-17-XC
TL-SE-28-XC
TL-SE-07-XX
TL-SE-21-XX
TL-SE-30-XX
TL-SE-07-XC
TL-SE-21-XC
TL-SE-30-XC
TL-SE-02-XX
TL-SE-08-XX
TL-SE-16-XX
TL-SE-02-XC
TL-SE-08-XC
TL-SE-16-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
230
220
200
187
184
166
54
53
49
116
120
103
44
43
44
90
71
65
94
100
93
152
118
122
99
100
100
181
155
176
Se
92
89
76
76
95
70
130
130
120
190
216
180
45
44
45
83
31
50
120
140
120
404
421
483
44
39
44
77
92
66
Ag
300 J-
200 J-
250 J-
513
577
437
180 J-
170 J-
160 J
224
254
227
56
56
57
86
85
89
63
67
62
117
99
130
120
130
120
171
227
227
V
180
170
160
94
127
69
66
63
59 J+
0
0
0
78
78
81
0
0
13
110
120
100
0
0
58
110
120
110
65
0
0
Zn
62
58
54
27
53
0
100
100
96
86
104
99
83
81
83
105
116
117
160
170
160
95
94
115
160
170
160
91
93
91
D-34
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
65
65
65
65
65
65
65
65
65
65
65
65
65
65
66
66
66
66
66
66
67
67
67
67
67
67
68
68
68
68
68
68
Sample ID
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-XC
RF-SE-09-XC
RF-SE-11-XC
RF-SE-17-XC
RF-SE-29-XC
RF-SE-37-XC
RF-SE-50-XC
RF-SE-08-XX
RF-SE-10-XX
RF-SE-33-XX
RF-SE-08-XC
RF-SE-10-XC
RF-SE-33-XC
RF-SE-16-XX
RF-SE-41-XX
RF-SE-48-XX
RF-SE-16-XC
RF-SE-41-XC
RF-SE-48-XC
RF-SE-18-XX
RF-SE-35-XX
RF-SE-54-XX
RF-SE-18-XC
RF-SE-35-XC
RF-SE-54-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb
12
10
11
11
13
11
8.9
8
11
10
11
0
0
4
14
12
13
21
21
19
85 J-
100
100
52
52
57
320
300
320
160
164
165
As
230
260
240
250
280
260
230
406
424
433
406
418
447
437
460
400
440
737
784
709
72 J-
82
87
114
109
142
810
740
880
1,208
1,239
1,238
Cd
40
45
43
43
49
45
40
49
69
52
59
69
66
62
67
58
64
65
75
73
310 J-
360
380
421
463
432
770
700
840
899
942
918
Cr
280
310
300
300
330
320
280
158
232
213
270
192
219
219
510
440
490
337
355
324
820 J-
950
1,000
664
617
640
950
860
1,000
615
681
621
Cu
63
71
72
67
75
72
65
205
216
209
220
212
216
211
1,800
1,500
1,700
2,066
2,205
2,138
73 J-
85
90
112
97
104
78
70
86
30
44
37
Fe
14,000
16,000
15,000
15,000
17,000
16,000
14,000
15,474
15,814
15,982
16,378
16,296
16,332
16,381
18,000
16,000
18,000
12,810
13,872
13,548
16,000 J-
18,000
19,000
14,873
14,638
14,899
16,000
15,000
18,000
11,932
12,298
12,444
Pb
22
26
25
26
26
27
23
33
77
27
82
70
32
37
580
510
570
1,023
987
1,068
24 J-
25
27
44
74
36
860
780
920
1,267
1,329
1,346
Hg
47
45
52
20
20
22
19
7
19
7
16
17
6
14
29
27
28
16
8
11
260
230
250
102
107
111
600
650
670
221
242
243
D-35
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
65
65
65
65
65
65
65
65
65
65
65
65
65
65
66
66
66
66
66
66
67
67
67
67
67
67
68
68
68
68
68
68
Sample ID
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-XC
RF-SE-09-XC
RF-SE-11-XC
RF-SE-17-XC
RF-SE-29-XC
RF-SE-37-XC
RF-SE-50-XC
RF-SE-08-XX
RF-SE-10-XX
RF-SE-33-XX
RF-SE-08-XC
RF-SE-10-XC
RF-SE-33-XC
RF-SE-16-XX
RF-SE-41-XX
RF-SE-48-XX
RF-SE-16-XC
RF-SE-41-XC
RF-SE-48-XC
RF-SE-18-XX
RF-SE-35-XX
RF-SE-54-XX
RF-SE-18-XC
RF-SE-35-XC
RF-SE-54-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni
200
220
210
210
240
220
200
169
182
192
189
186
178
183
250
220
240
233
252
247
1,700 J-
1,900
2,000
1,663
1,618
1,608
390
350
420
276
340
307
Se
21
23
20
22
26
23
20
31
59
42
39
41
28
6
1.2 U
1.2 U
2.2
140
140
160
265
257
268
Ag
37
42
40
40
44
44
38
46
42
27
49
62
43
52
0.39 U
0.34 U
0.33 U
13
5
130 J-
140
150
156
166
169
140
150
180
258
268
260
V
29
32
29
30
35
32
29
0
48
0
0
0
0
0
120
100
120
59
61
37
32 J-
39
40
21
0
54
390
340
410
142
142
132
Zn
1,700
1,900
1,800
1,800
2,100
1,900
1,700
3,293
3,500
3,405
3,473
3,421
3,423
3,463
120
110
130
81
107
105
760 J-
830
880
1,373
1,401
1,377
120
110
120
164
176
153
D-36
-------
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
69
69
69
69
69
69
70
70
70
70
70
70
Sample ID
RF-SE-20-XX
RF-SE-46-XX
RF-SE-51-XX
RF-SE-20-XC
RF-SE-46-XC
RF-SE-51-XC
RF-SE-21-XX
RF-SE-40-XX
RF-SE-47-XX
RF-SE-21-XC
RF-SE-40-XC
RF-SE-47-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Sb As Cd Cr Cu Fe Pb Hg
550 1300 540 94 93 20,000 28 0.48
270 590 240 44 40 8,900 13 0.45
480 1100 450 77 77 17,000 23 0.48
219 1,760 576 43 144 16,036 13
232 1,858 619 73 139 16,115 89 19
232 1,774 595 76 136 16,229 76 12
1.3 U 62 1,700 76 1,000 16,000 2,100 320
1.3 U 70 1,900 85 1,100 18,000 2,400 280
1.3 U 72 1,900 90 1,200 19,000 2,400 320
19 85 2,180 50 1,060 13,404 3,814 95
20 122 2,314 91 1,101 13,281 3,973 93
19 116 2,295 53 1,093 13,555 3,841 92
Appendix D. Analytical Data Summary, Xcalibur ElvaX and Reference Laboratory (Continued)
Blend No.
69
69
69
69
69
69
70
70
70
70
70
70
Sample ID
RF-SE-20-XX
RF-SE-46-XX
RF-SE-51-XX
RF-SE-20-XC
RF-SE-46-XC
RF-SE-51-XC
RF-SE-21-XX
RF-SE-40-XX
RF-SE-47-XX
RF-SE-21-XC
RF-SE-40-XC
RF-SE-47-XC
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Reference Laboratory
Reference Laboratory
Reference Laboratory
Xcalibur XRF Services
Xcalibur XRF Services
Xcalibur XRF Services
Ni Se Ag V Zn
1,400 380 59 36 1,400
650 170 26 16 650
1,200 320 48 30 1,200
1,079 828 80 0 2,094
1,056 912 69 0 2,115
1,075 818 84 0 2,054
220 440 120 130 100
250 480 100 150 120
250 510 120 150 120
179 1,232 305 58 107
193 1,299 325 52 61
211 1,321 312 59 117
Notes:
All concentrations reported in milligrams per kilogram (mg/kg), or parts per million (ppm).
Sample results for which "0" or no value was reported were considered nondetections as reported by Xcalibur.
Reference laboratory data qualifiers were as follows:
J Estimated concentration.
J+ Concentration is considered estimated and biased high.
J- Concentration is considered estimated and biased low.
U Analyte is not detected; the associated concentration value is the sample reporting limit.
D-37
-------
APPENDIX E
STATISTICAL DATA SUMMARIES
-------
Figure E-l: Linear Correlation Plot for Antimony
4000
3500
3000
2500
X 2000
^
e 1500
o
Z 1000
500
0
v — ^ 4(W + 1 9R QS
R2 ~~ 0 88
A ,1
/
A/
%
V/A rfr^"
H*1^
ۥ***
^
1
^'
^
i
y = 1.12x+ 18.34
R2 ~ 0 99 «*
m^^
^<"
A Niton XLt vs Reference Laboratory
45 degrees
• Niton XLt vs Certified Values
= = = Linear (Niton XLt vs Reference Laboratory)
500
1000 1500 2000 2500
Reference Laboratory or Certified Value (ppm)
3000
3500
7000 -,
6000
I
5000
4000
3000
2000
1000 -
Figure E-2: Linear Correlation Plot for Arsenic
Xcalibur ElvaX
45 Degrees
Linear (Xcalibur ElvaX)
y = 1.23x +35.06
R2 = 0.97
"<--"
1000
2000 3000 4000
Reference Laboratory (ppm)
5000
6000
E-l
-------
3500 -i—
Qfinn
?snn
&
&
2 2000 -
X
X
«
^ i son
X 1000
son
0
c
Figure E-3:
• Xcalibur ElvaX
^— ^— Linear (Xcalibur ElvaX)
Linear Correlation Plot for Cadmium
,
/'
jr
X
X
v = 1.24x-24.87
R2 = 0.98
X •
_Jf B
v'^
500 1000 1500 2000
Reference Laboratory (ppm)
2500
3000
3500
1000
2500 -
s
'—
& 2000
X
X
«
^
W ^5QQ
5
a
3
X 1000
500
o
Figure E-4
• Xcalibur ElvaX
—————45 Degrees
^— ^— Linear (Xcalibur ElvaX)
Linear Correlation Plot for Chromium
y = 0.62x + 34.93
R2 = 0.98
^-".
m^^"
. - **•
^'~
\*--"
0
500 1000
1500 2000 2500 3000 3500
Reference Laboratory (ppm)
E-2
-------
10000 -j
QOOO
8000 -
Q.
Q.
b 6000 -
X
'a 5000 -
>
a
h 4000 -
.0
a
03
;> 3000
2000 -
1000
0 _
C
Figure
• Xcalibur ElvaX
45 Degrees
— — Linear (Xcalibur ElvaX)
.<'
s-'f:
*^*"
1000 2
E-5: Linear Correlation Plot for Copper
•
•
+
S
s
,' .
s'
^
0
20000 40000 60000 80000 100000 120000 140000 160000
Reference Laboratory (ppm)
180000 200000
E-3
-------
^nnnn
snnnn
& 40000
&
X
"a 30000
_>
1
a 20000 -
X
10000 -
0 i
c
Figure E-7: Linear Correlation Plot for Lead
• Xcalibur ElvaX
45 Degrees
— — Linear (Xcalibur ElvaX)
^
.
S
^ I
y-1.4
R2
1
Ox + 324.06
= 0.94
• ^ *~
s
s
^ - m
"'
5000 10000 15000 20000 25000 30000 35000
Reference Laboratory (ppni)
40000
Figure E-8: Linear Correlation Plot for Mercury
QftOO -— .
8000
•7000
• Xcalibur ElvaX
— — — — 45 Degrees
^— ^— Linear (Xcalibur ElvaX)
£ 6000
a.
P4 SOOO
x DUUU
X
•^ 4000
1
X
°000
1000 " m
0 •
0
~~ ~~
— —
y = 0.19x +
R2 = 0.
—
1000 2000 3000 4000 5000 6000 7000 8000
Reference Laboratory (ppm)
113.65
^2
•
9000
E-4
-------
3500
,-v 2500
a.
2 7000
x /uuu
X
03
W 1500
cs
X 1000
son
o
1200
1000
S
<£ xoo
X 8UU
X
>;
^ 600 -
X 400 -
200
o
C
C
Figure E-9: Linear Correlation Plot for Nickel
• Xcalibur ElvaX
—————— 45 Deerees
— — Linear (Xcalibur ElvaX)
^
^
• - ^^
' ^
^ •
» *^
J*^"
500 1000 1500 2000 2500
Reference Laboratory (ppm)
Figure E-10: Linear Correlation Plot for Selenium
• Xcalibur ElvaX S
—————45 Degrees • >
S
— — Linear (Xcalibur ElvaX) /
• /
''m
/ •
• s --"-''
s?
/ "..,-•••'
•M ' - "
•niUP^"
100 200 300 400 5
Reference Laboratory (ppm)
3
y
30
..."
^ *
^ m
y = 0.85x+ 15.5
R2 = 0.99
000 35
= 2.99x- 96.99
R2 = 0.96
6C
1
00
0
E-5
-------
son
5, 400 -
&
X
X 300 -
3
3
"a 200 -
100
o
c
son ^
|J"°
ft
X
3 200 -
a
100 -
50 -
0 -
C
S
-.
Figure
• Xcalibur ElvaX
— — Linear (Xcalibur ElvaX)
«
^ .."»:""
xx.-%/-
50 100 If
Figure E-]
• Xcalibur ElvaX
^— ^— Linear (Xcalibur ElvaX)
v - '
-- -*""•
50 100 150
E-ll: Linear Correlation Plot for Silver
• ^
i ^S~
^
S m
^
. •
0 200 250 300 350 <•
Reference Laboratory (ppni)
2: Linear Correlation Plot for Vanadium
^^
200 250 300 350 400
Reference Laboratory (ppni)
y - 1.28x + ;
R2 -0.6
100 4<
y = 0.33x + 2
R2 = 0.80
•
450 5(
J9.99
5
0
5.81
)0
E-6
-------
Figure E-13: Linear Correlation Plot for Zinc
10000
8000 -
O 7000
fe 6000 -
a 5000 -
b 4000
.&
$ 3000 -
2000
1000
0 J
c
• Xcalibur ElvaX
— — Linear (Xcalibur ElvaX)
•
y = 1.03x + 223.1l|
R2 = 0.85 1
^<
S* - '
m ^
" l". ^ ^ ^
« "^ • «
• *^-
*
1000 2000
3000 4000 5000
Reference Laboratory (ppin)
6000 7000 8000
E-7
-------
Box Plot for Relative Percent Difference (RPD)
Xcalibur ElvaX
Median; Box: 25%-75%; Whisker: Non-Outlier Range
1 OU /O
160%
3 140%
re ""'
> £^ >" 1 90°/
u o 0 '^u/°
fli m
£ 2
* o g 100%
a) re re
0) -1 >
| g -o 80%
m S it
d o> "£ 60%
ft 0) O
ill 40%
0) *-
S T3
= 20%
TO
0%
-9DO/,
i i ! 22-SB !
i i i 0 i
; 1 ! V
j j 9 |
i j JL i
i i Up !
'! >! T '*
i j i j
i ! 9 i
i j. |
^
*
D [
•
j ~q j.
i 0
1 21 -SB
i 6-WS
t <;
] +
1 F
[
1
Inl L
= I -
i ! i
>
n
J
c
J
aeltv
9
c
!-
: J
! ! !
_ { i i
! 47-iBN !
| 9 |
! T ! 17-iAS
L i T -i
1 i 1
i t
] | J
•61-iTb-
Tr
-. 64-i-TL
9 \
j i
I
8 n
9 1
q
L
D
Q
1 p
t 1
J
*f
3
JL
n
} * I
! ! ! !
Sb-RL As Cr Fe Hg Se V
Sb-CV Cd Cu Pb Ni Ag 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 results and
sampling site associated with each Blend number.
Figure E-14. Box and Whiskers Plot for Mean RPD Values Showing Outliers and Extremes
for Target Elements, Xcalibur ElvaX Data Set.
E-8
-------
Table E-l. Evaluation of Accuracy - Relative Percent Difference versus Reference Laboratory Data Calculated for the Xcalibur ElvaX
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
9
2.6%
105.4%
43.7%
47.0%
5
10.2%
70.2%
32.2%
31.7%
o
3
43.9%
77.4%
64.4%
71.9%
~
~
—
~
—
17
2.6%
105.4%
44.0%
43.9%
ERA Spike
1
154.4%
154.4%
154.4%
154.4%
1
6.2%
6.2%
6.2%
6.2%
2
0.7%
6.3%
3.5%
3.5%
~
~
—
~
—
4
0.7%
154.4%
41.9%
6.2%
Arsenic
15
33.7%
163.0%
62.6%
53.8%
4
8.4%
22.2%
15.6%
15.9%
4
8.4%
45.0%
23.4%
20.1%
~
~
—
~
—
23
8.4%
163.0%
47.6%
45.0%
Cadmium
7
0.2%
29.4%
17.3%
16.4%
7
0.4%
35.2%
13.5%
12.4%
2
10.1%
16.3%
13.2%
13.2%
~
~
—
~
—
16
0.2%
35.2%
15.1%
13.9%
Chromium
23
2.3%
87.2%
28.4%
21.2%
4
35.6%
49.6%
41.2%
39.9%
2
37.6%
58.1%
47.9%
47.9%
~
~
—
~
—
29
2.3%
87.2%
31.5%
29.4%
Copper
16
9.9%
111.1%
61.2%
62.7%
8
1.3%
15.7%
7.0%
5.7%
2
59.7%
64.4%
62.0%
62.0%
~
~
—
~
—
26
1.3%
111.1%
44.6%
26.6%
Iron
5
0.3%
46.2%
24.7%
25.5%
13
1.1%
33.9%
13.8%
10.3%
13
2.1%
40.3%
24.6%
29.1%
7
18.9%
43.6%
28.5%
30.9%
38
0.3%
46.2%
21.6%
24.1%
Lead
7
8.3%
75.3%
51.3%
50.5%
4
0.5%
88.5%
40.4%
36.2%
8
2.2%
87.1%
50.9%
55.5%
5
5.0%
62.3%
29.6%
22.3%
24
0.5%
88.5%
44.8%
47.0%
Mercury
5
26.6%
133.5%
99.0%
107.9%
7
22.5%
99.6%
75.2%
90.4%
2
91.0%
140.5%
115.7%
115.7%
~
~
—
~
—
14
22.5%
140.5%
89.5%
96.2%
E-9
-------
Table E-l. Evaluation of Accuracy - Relative Percent Difference versus Reference Laboratory Data Calculated for the Xcalibur ElvaX
(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
24
1.5%
35.4%
17.7%
16.7%
5
6.1%
39.1%
28.2%
30.9%
6
3.7%
25.4%
15.4%
13.6%
—
—
~
—
—
35
1.5%
39.1%
18.8%
17.0%
Selenium
2
0.9%
3.7%
2.3%
2.3%
5
51.2%
86.3%
72.5%
72.7%
4
75.7%
106.0%
89.6%
88.3%
—
—
~
—
—
11
0.9%
106.0%
66.0%
75.7%
Silver
3
2.6%
16.2%
10.1%
11.6%
3
0.0%
15.4%
7.7%
7.6%
7
3.6%
106.7%
35.1%
16.5%
—
—
~
—
—
13
0.0%
106.7%
23.0%
12.4%
Vanadium
3
13.2%
50.4%
33.0%
35.4%
3
47.6%
77.4%
65.2%
70.6%
4
64.2%
129.5%
87.7%
78.6%
—
—
~
—
—
10
13.2%
129.5%
64.6%
67.4%
Zinc
20
0.1%
80.6%
30.9%
21.6%
6
0.8%
52.2%
31.5%
35.2%
9
0.3%
105.7%
26.6%
22.2%
—
—
~
—
—
35
0.1%
105.7%
29.9%
22.3%
E-10
-------
Table E-l. Evaluation of Accuracy - Relative Percent Difference versus Reference Laboratory Data Calculated for the Xcalibur ElvaX
(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 ERA Spike
3 3
30.6% 4.1%
45.5% 100.0%
39.9% 38.5%
43.8% 11.5%
4 4
27.0% 2.6%
55.7% 18.8%
39.9% 9.9%
38.4% 9.2%
3 3
59.9% 0.1%
63.0% 4.2%
61.7% 2.3%
62.3% 2.7%
„
„
„
„
—
10 10
27.0% 0.1%
63.0% 100.0%
46.4% 16.2%
45.6% 6.2%
Arsenic
17
1.9%
104.0%
55.9%
42.5%
4
2.2%
52.7%
28.7%
29.9%
2
41.1%
57.3%
49.2%
49.2%
—
—
~
—
—
23
1.9%
104.0%
50.6%
42.5%
Cadmium
3
11.8%
44.3%
23.4%
14.0%
4
22.5%
37.1%
29.7%
29.6%
3
5.6%
21.0%
14.8%
17.7%
—
—
~
—
—
10
5.6%
44.3%
23.3%
21.7%
Chromium
6
4.8%
30.7%
19.4%
20.6%
3
34.0%
35.9%
34.8%
34.6%
3
36.2%
46.8%
40.2%
37.8%
—
—
~
—
—
12
4.8%
46.8%
28.5%
32.4%
Copper
8
4.6%
101.8%
43.0%
33.0%
4
1.2%
8.3%
4.8%
4.8%
10
7.3%
48.7%
26.7%
27.2%
—
—
~
—
—
22
1.2%
101.8%
28.7%
25.1%
Iron
o
3
10.9%
73.9%
34.7%
19.2%
19
1.2%
34.7%
15.0%
14.0%
4
16.2%
30.9%
23.3%
23.0%
6
12.4%
44.8%
28.5%
30.6%
32
1.2%
73.9%
20.4%
17.6%
Lead
12
5.7%
121.2%
67.0%
68.1%
o
3
42.5%
66.4%
56.2%
59.9%
o
3
51.0%
88.7%
73.7%
81.2%
—
—
~
—
—
18
5.7%
121.2%
66.3%
66.9%
Mercury
3
80.5%
103.7%
91.3%
89.8%
4
70.9%
106.7%
84.0%
79.2%
3
72.3%
92.4%
84.4%
88.5%
—
—
~
—
—
10
70.9%
106.7%
86.3%
84.5%
E-ll
-------
Table E-l. Evaluation of Accuracy - Relative Percent Difference versus Reference Laboratory Data Calculated for the Xcalibur ElvaX
(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
3.6%
73.9%
26.3%
22.1%
6
2.9%
22.8%
15.3%
17.4%
4
1.2%
36.0%
18.5%
18.5%
—
~
~
~
—
28
1.2%
73.9%
22.8%
20.0%
Selenium
3
6.5%
59.5%
28.7%
20.0%
4
42.6%
110.0%
72.0%
67.7%
3
91.7%
98.5%
95.9%
97.4%
—
~
~
~
—
10
6.5%
110.0%
66.2%
69.1%
Silver
4
16.1%
57.1%
42.6%
48.6%
4
15.5%
51.1%
31.9%
30.4%
o
5
50.3%
93.9%
70.8%
68.3%
—
~
~
~
—
11
15.5%
93.9%
46.4%
50.3%
Vanadium
0
NC
NC
NC
NC
o
3
55.1%
87.0%
72.1%
74.2%
o
5
75.8%
93.1%
84.1%
83.3%
—
~
~
~
—
6
55.1%
93.1%
78.1%
79.5%
Zinc
17
2.1%
70.9%
34.6%
33.9%
5
34.9%
63.4%
47.8%
50.8%
4
18.6%
60.1%
35.0%
30.6%
—
~
~
~
—
26
2.1%
70.9%
37.2%
37.2%
E-12
-------
Table E-l. Evaluation of Accuracy - Relative Percent Difference versus Reference Laboratory Data Calculated for the Xcalibur ElvaX
(Continued)
Matrix
All Samples
All Samples
Cone
Range
Xcalibur ElvaX
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
RefLab
27
2.6%
105.4%
44.9%
45.5%
206
0.1%
181.5%
80.6%
84.3%
ERA Spike
14
0.1%
154.4%
23.6%
6.2%
110
0.1%
162.0%
62.7%
70.6%
Arsenic
46
1.9%
163.0%
49.1%
44.2%
320
0.2%
182.8%
36.6%
26.2%
Cadmium
26
0.2%
44.3%
18.3%
16.3%
209
0.1%
168.1%
29.6%
16.7%
Chromium
41
2.3%
87.2%
30.6%
30.7%
338
0.1%
151.7%
30.8%
26.0%
Copper
48
1.2%
111.1%
37.3%
25.1%
363
0.2%
111.1%
24.6%
16.2%
Iron
70
0.3%
73.9%
21.1%
19.5%
558
0.0%
190.1%
35.4%
26.0%
Lead
42
0.5%
121.2%
54.0%
54.6%
392
0.1%
135.2%
30.9%
21.5%
Mercury
24
22.5%
140.5%
88.2%
90.7%
192
0.0%
158.1%
62.5%
58.6%
Table E-l. Evaluation of Accuracy - Relative Percent Difference versus Reference Laboratory Data Calculated for the Xcalibur ElvaX
(Continued)
Matrix
All Samples
All Samples
Cone
Range
Xcalibur ElvaX
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
63
1.2%
73.9%
20.6%
17.5%
403
0.3%
146.5%
31.0%
25.4%
Selenium
21
0.9%
110.0%
66.1%
75.7%
195
0.0%
127.1%
32.0%
16.7%
Silver
24
0.0%
106.7%
33.7%
18.3%
177
0.0%
129.7%
36.0%
28.7%
Vanadium
16
13.2%
129.5%
69.6%
74.0%
218
0.1%
129.5%
42.2%
38.3%
Zinc
61
0.1%
105.7%
33.0%
32.5%
471
0.0%
138.0%
26.3%
19.4%
E-13
-------
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 Resource Associates, Inc.
NC Not calculated because of a lack of XRF data.
Number Number of demonstration samples evaluated.
Ref Lab Reference laboratory (Shealy Environmental Services, Inc.).
RPD Relative percent difference.
XRF X-ray fluorescence.
E-14
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Xcalibur ElvaX
Matrix
Soil
Cone
Range
Low
Medium
High
Very 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
9
3.0%
24.2%
10.7%
6.7%
5
1.6%
11.0%
5.3%
3.0%
3
1.8%
19.0%
8.1%
3.6%
—
~
~
—
—
17
1.6%
24.2%
8.6%
6.5%
Arsenic
15
6.4%
51.3%
21.4%
16.1%
4
5.9%
34.7%
14.0%
7.7%
4
3.5%
21.8%
14.3%
16.0%
—
~
~
—
—
23
3.5%
51.3%
18.9%
14.8%
Cadmium
7
4.7%
35.2%
20.8%
20.5%
7
1.8%
9.4%
4.1%
2.2%
2
4.5%
4.5%
4.5%
4.5%
—
~
~
—
—
16
1.8%
35.2%
11.4%
6.3%
Chromium
23
6.5%
48.5%
23.4%
20.9%
4
2.5%
14.1%
6.9%
5.5%
2
1.7%
3.2%
2.4%
2.4%
—
~
-
—
—
29
1.7%
48.5%
19.7%
17.7%
Copper
16
2.0%
20.5%
7.4%
6.2%
8
1.2%
11.3%
5.2%
3.8%
2
6.0%
19.5%
12.8%
12.8%
—
~
~
—
—
26
1.2%
20.5%
7.1%
6.0%
Iron
5
1.8%
7.7%
4.8%
4.4%
13
0.7%
11.7%
3.5%
2.7%
13
1.5%
15.5%
5.5%
3.8%
7
2.8%
12.2%
5.7%
4.5%
38
0.7%
15.5%
4.8%
4.1%
Lead
7
1.9%
25.2%
9.3%
7.0%
4
3.5%
23.9%
9.0%
4.2%
8
0.7%
19.3%
5.0%
2.6%
5
1.1%
15.8%
8.7%
10.4%
24
0.7%
25.2%
7.7%
4.6%
Mercury
5
26.2%
137.1%
54.3%
37.7%
7
7.1%
18.1%
13.3%
12.6%
2
4.6%
8.0%
6.3%
6.3%
—
~
~
—
—
14
4.6%
137.1%
26.9%
15.7%
E-15
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Xcalibur ElvaX (Continued)
Matrix
Soil
Cone
Range
Low
Medium
High
Very 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
24
2.9%
37.7%
14.3%
10.3%
5
2.6%
17.7%
8.1%
6.3%
6
1.6%
6.8%
3.5%
2.6%
~
~
~
~
—
35
1.6%
37.7%
11.6%
7.9%
Selenium
2
18.9%
35.1%
27.0%
27.0%
5
2.0%
13.6%
6.5%
5.2%
4
5.8%
9.1%
7.9%
8.3%
~
~
~
~
—
11
2.0%
35.1%
10.7%
8.5%
Silver
3
8.6%
21.4%
13.8%
11.5%
3
7.2%
10.9%
8.5%
7.3%
7
7.9%
23.8%
16.8%
19.2%
~
~
~
~
—
13
7.2%
23.8%
14.2%
11.5%
Vanadium
3
43.4%
52.3%
48.4%
49.4%
3
7.7%
40.8%
23.9%
23.3%
4
13.5%
42.0%
28.3%
28.9%
~
~
~
~
—
10
7.7%
52.3%
33.0%
39.9%
Zinc
20
1.8%
24.4%
9.4%
8.1%
6
0.4%
7.3%
3.2%
2.3%
9
0.3%
10.8%
4.0%
1.8%
~
~
~
~
—
35
0.3%
24.4%
7.0%
6.4%
E-16
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Xcalibur ElvaX (Continued)
Matrix
Sediment
Cone
Range
Low
Medium
High
Very 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
3
3.8%
9.0%
6.0%
5.1%
4
3.5%
10.7%
6.7%
6.3%
3
1.6%
13.2%
6.1%
3.4%
—
~
—
~
—
10
1.6%
13.2%
6.3%
5.2%
Arsenic
17
6.3%
41.3%
19.2%
18.5%
4
3.7%
7.2%
5.0%
4.6%
2
1.4%
2.9%
2.2%
2.2%
—
~
—
~
—
23
1.4%
41.3%
15.2%
14.1%
Cadmium
3
7.4%
16.0%
10.5%
8.1%
4
3.6%
7.0%
5.4%
5.5%
3
2.3%
7.9%
4.5%
3.2%
—
~
—
~
—
10
2.3%
16.0%
6.6%
6.5%
Chromium
6
9.0%
37.2%
27.0%
30.0%
3
4.7%
16.0%
8.7%
5.4%
3
3.7%
5.7%
4.8%
5.0%
—
~
—
~
—
12
3.7%
37.2%
16.9%
12.5%
Copper
8
2.3%
18.1%
7.8%
6.1%
4
1.9%
3.3%
2.4%
2.3%
10
2.3%
13.1%
5.6%
4.3%
—
~
—
~
—
22
1.9%
18.1%
5.8%
4.3%
Iron
3
3.4%
9.8%
6.0%
4.9%
19
0.4%
8.2%
2.5%
2.2%
4
0.9%
9.8%
3.9%
2.4%
6
1.4%
6.2%
3.3%
3.2%
32
0.4%
9.8%
3.1%
2.5%
Lead
12
2.9%
47.0%
16.2%
12.5%
3
1.3%
3.9%
2.8%
3.2%
3
2.2%
6.5%
3.8%
2.7%
—
~
—
~
—
18
1.3%
47.0%
11.9%
6.4%
Mercury
3
35.5%
44.0%
40.8%
42.8%
4
1.9%
12.1%
6.5%
5.9%
3
3.0%
5.2%
4.5%
5.2%
—
~
—
~
—
10
1.9%
44.0%
16.1%
6.5%
E-17
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Xcalibur ElvaX (Continued)
Matrix
Sediment
Cone
Range
Low
Medium
High
Very 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
0.9%
35.4%
11.1%
9.9%
6
4.0%
10.5%
6.4%
5.9%
4
1.1%
8.7%
3.4%
1.8%
~
~
~
~
—
28
0.9%
35.4%
9.0%
8.2%
Selenium
3
16.0%
48.6%
27.3%
17.3%
4
2.3%
11.4%
8.2%
9.6%
3
2.8%
6.1%
4.2%
3.6%
~
~
~
~
—
10
2.3%
48.6%
12.7%
9.6%
Silver
4
2.2%
13.6%
8.6%
9.4%
4
3.4%
15.5%
7.5%
5.6%
3
2.0%
13.8%
6.3%
3.2%
~
~
~
~
—
11
2.0%
15.5%
7.6%
7.0%
Vanadium
0
NC
NC
NC
NC
3
7.2%
30.0%
21.0%
25.7%
3
4.4%
16.9%
9.0%
5.6%
~
~
~
~
—
6
4.4%
30.0%
15.0%
12.1%
Zinc
17
1.2%
31.5%
10.2%
8.3%
5
1.1%
5.2%
3.2%
3.3%
4
1.3%
2.1%
1.7%
1.8%
~
~
~
~
—
26
1.1%
31.5%
7.6%
5.8%
E-18
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Xcalibur ElvaX (Continued)
Matrix
All Samples
All Samples
Cone
Range
Xcalibur ElvaX
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
27
1.6%
24.2%
7.8%
5.4%
206
0.5%
97.7%
8.9%
6.1%
Arsenic
46
1.4%
51.3%
17.1%
14.1%
320
0.2%
71.7%
11.2%
8.2%
Cadmium
26
1.8%
35.2%
9.6%
6.5%
209
0.4%
92.8%
8.2%
3.6%
Chromium
41
1.7%
48.5%
18.9%
17.2%
338
0.6%
116.3%
15.9%
12.1%
Copper
48
1.2%
20.5%
6.5%
4.9%
363
0.1%
58.3%
7.5%
5.1%
Iron
70
0.4%
15.5%
4.0%
3.2%
558
0.1%
101.8%
5.2%
2.2%
Lead
42
0.7%
47.0%
9.5%
6.0%
392
0.2%
115.6%
9.3%
4.9%
Mercury
24
1.9%
137.1%
22.4%
12.5%
192
1.0%
137.1%
14.3%
6.8%
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Xcalibur ElvaX (Continued)
Matrix
All Samples
All Samples
Cone
Range
Xcalibur ElvaX
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
63
0.9%
37.7%
10.4%
8.0%
403
0.3%
164.2%
10.8%
7.0%
Selenium
21
2.0%
48.6%
11.7%
8.9%
195
0.1%
98.8%
7.2%
4.5%
Silver
24
2.0%
23.8%
11.2%
9.4%
177
0.6%
125.3%
10.3%
5.2%
Vanadium
16
4.4%
52.3%
26.2%
24.5%
218
0.4%
86.1%
12.5%
8.5%
Zinc
61
0.3%
31.5%
7.2%
6.1%
471
0.1%
192.9%
8.0%
5.3%
Notes:
Cone
NC
Number
RSD
XRF
No samples reported by the reference laboratory in this concentration range.
Concentration.
Not calculated because of a lack of XRF data.
Number of demonstration samples evaluated.
Relative standard deviation.
X-ray fluorescence.
E-19
-------
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
Nickel
35
0.0%
44.9%
11.4%
10.0%
27
0.6%
35.8%
9.4%
7.3%
62
0.0%
44.9%
10.6%
8.2%
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-20
-------
Table E-4. Evaluation of the Effects of Interferent Elements on RPDs (Accuracy) of Other Target Elements1
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
-163.0%
8.1%
-55.0%
-45.1%
2.2%
163.0%
55.5%
45.1%
ND
1314
299
152
67
4480
452
178
5-10
7
-33.7%
22.2%
-11.7%
-9.7%
8.4%
33.7%
18.0%
21.5%
1163
54373
19071
8802
163
6033
2068
1129
>10
10
-104.0%
53.8%
-22.9%
-31.9%
1.9%
104.0%
52.2%
50.6%
2326
38476
8482
4699
59
2434
310
70
Copper Effects on Nickel
<5
44
-24.1%
39.1%
14.0%
16.7%
1.2%
39.1%
18.4%
17.2%
ND
1085
193
73
48
2644
476
146
5-10
5
-3.6%
33.9%
12.1%
15.7%
2.9%
33.9%
14.7%
15.7%
852
2137
1372
1143
78
244
152
131
>10
14
-73.9%
27.7%
-17.3%
-21.7%
4.0%
73.9%
29.6%
27.6%
682
9436
3473
2298
58
629
172
122
Nickel Effects on Copper
<5
39
-108.7%
53.0%
-22.2%
-11.2%
1.2%
108.7%
31.4%
21.0%
ND
629
163
128
29
9436
1669
852
5-10
1
70.7%
70.7%
70.7%
70.7%
70.7%
70.7%
70.7%
70.7%
307
307
307
307
37
37
37
37
>10
8
-111.1%
32.4%
-40.3%
-44.9%
22.8%
111.1%
61.7%
49.4%
1070
2644
1888
1793
60
438
213
122
E-21
-------
Table E-4. Evaluation of the Effects of Interferent Elements on RPDs (Accuracy) of Other Target Elements1 (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
-64.4%
70.7%
-4.2%
-7.3%
1.2%
70.7%
23.0%
21.0%
ND
7370
1267
177
29
9436
1760
909
5-10
2
-9.9%
6.1%
-1.9%
-1.9%
6.1%
9.9%
8.0%
8.0%
1085
9253
5169
5169
177
1374
775
775
>10
11
-111.1%
-23.3%
-87.9%
-99.1%
23.3%
111.1%
87.9%
99.1%
1384
5331
3447
3528
104
639
336
332
Copper Effects on Zinc
<5
49
-80.6%
105.7%
-24.4%
-25.3%
0.1%
105.7%
32.0%
32.5%
ND
2205
386
177
36
9253
1944
1085
5-10
3
-47.1%
70.9%
13.8%
17.6%
17.6%
70.9%
45.2%
47.1%
634
2187
1302
1085
95
165
120
99
>10
9
-65.0%
56.2%
-0.4%
2.3%
2.3%
65.0%
34.7%
31.3%
1818
9436
4692
3670
92
562
183
103
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 because of a lack of XRF data.
ND Nondetect.
XRF X-ray fluorescence.
E-22
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements
Matrix
Soil
Soil
Soil
Soil&
Sediment
Site
AS
BN
CN
KP
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.)
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
~
~
~
—
4
-2.7%
71.9%
23.6%
12.6%
2
67.6%
70.2%
68.9%
68.9%
1
48.2%
48.2%
48.2%
48.2%
RPD ABS Val
~
~
~
—
4
2.7%
71.9%
24.9%
12.6%
2
67.6%
70.2%
68.9%
68.9%
1
48.2%
48.2%
48.2%
48.2%
Certified Value
RPD
~
~
~
—
1
6.3%
6.3%
6.3%
6.3%
2
6.2%
154.4%
80.3%
80.3%
-
RPD ABS
Val
~
~
~
—
1
6.3%
6.3%
6.3%
6.3%
2
6.2%
154.4%
80.3%
80.3%
-
Arsenic
Reference Laboratory
RPD
1
-82.6%
-82.6%
-82.6%
-82.6%
7
-63.7%
43.3%
-19.9%
-22.1%
1
-66.2%
-66.2%
-66.2%
-66.2%
~
RPD ABS
Val
1
82.6%
82.6%
82.6%
82.6%
7
8.4%
63.7%
32.3%
33.7%
1
66.2%
66.2%
66.2%
66.2%
~
Cadmium
Reference Laboratory
RPD
3
-13.1%
25.0%
4.0%
0.2%
5
-21.6%
5.3%
-9.8%
-10.1%
2
-23.0%
-0.4%
-11.7%
-11.7%
~
RPD ABS Val
3
0.2%
25.0%
12.8%
13.1%
5
5.3%
21.6%
11.9%
10.1%
2
0.4%
23.0%
11.7%
11.7%
~
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
Site
AS
BN
CN
KP
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.)
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
2
6.1%
11.6%
8.8%
8.8%
5
31.6%
58.1%
42.1%
43.2%
1
21.2%
21.2%
21.2%
21.2%
4
-20.1%
8.9%
-5.5%
-5.4%
RPDABS
Val
2
6.1%
11.6%
8.8%
8.8%
5
31.6%
58.1%
42.1%
43.2%
1
21.2%
21.2%
21.2%
21.2%
4
4.8%
20.1%
10.0%
7.5%
Copper
Reference Laboratory
RPD
3
-86.3%
-59.7%
-76.5%
-83.7%
6
-111.1%
30.4%
-17.3%
-6.6%
3
-72.5%
1.3%
-30.7%
-21.0%
2
15.7%
22.8%
19.2%
19.2%
RPDABS
Val
3
59.7%
86.3%
76.5%
83.7%
6
2.0%
111.1%
28.5%
12.1%
3
1.3%
72.5%
31.6%
21.0%
2
15.7%
22.8%
19.2%
19.2%
Iron
Reference Laboratory
RPD
3
1.3%
31.2%
17.4%
19.7%
7
-10.3%
33.9%
11.3%
5.7%
3
-2.8%
19.8%
6.3%
1.9%
6
-19.2%
46.2%
8.2%
3.9%
RPDABS
Val
3
1.3%
31.2%
17.4%
19.7%
7
1.1%
33.9%
14.8%
10.3%
3
1.9%
19.8%
8.2%
2.8%
6
0.3%
46.2%
18.3%
15.1%
Lead
Reference Laboratory
RPD
3
-67.0%
-40.2%
-51.8%
-48.1%
6
-50.5%
10.9%
-31.7%
-43.8%
2
-71.2%
-32.2%
-51.7%
-51.7%
6
-43.0%
8.3%
-5.6%
0.8%
RPDABS
Val
3
40.2%
67.0%
51.8%
48.1%
6
10.9%
50.5%
35.3%
43.8%
2
32.2%
71.2%
51.7%
51.7%
6
0.5%
43.0%
10.8%
5.3%
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
Site
AS
BN
CN
KP
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.)
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
~
~
~
—
1
-26.6%
-26.6%
-26.6%
-26.6%
2
90.4%
107.9%
99.2%
99.2%
~
RPDABS
Val
~
~
~
—
1
26.6%
26.6%
26.6%
26.6%
2
90.4%
107.9%
99.2%
99.2%
~
Nickel
Reference Laboratory
RPD
3
-39.1%
25.8%
-1.3%
9.3%
6
-9.8%
27.7%
16.5%
20.1%
3
-14.8%
30.9%
14.6%
27.6%
3
-9.8%
12.0%
0.2%
-1.5%
RPDABS
Val
3
9.3%
39.1%
24.7%
25.8%
6
9.8%
27.7%
19.8%
20.1%
3
14.8%
30.9%
24.4%
27.6%
3
1.5%
12.0%
7.8%
9.8%
Selenium
Reference Laboratory
RPD
1
-68.5%
-68.5%
-68.5%
-68.5%
2
-75.7%
-51.2%
-63.4%
-63.4%
2
-72.7%
0.9%
-35.9%
-35.9%
~
RPD ABS Val
1
68.5%
68.5%
68.5%
68.5%
2
51.2%
75.7%
63.4%
63.4%
2
0.9%
72.7%
36.8%
36.8%
-
Silver
Reference Laboratory
RPD
1
-16.5%
-16.5%
-16.5%
-16.5%
4
-106.7%
0.0%
-29.2%
-5.1%
2
-15.4%
-11.6%
-13.5%
-13.5%
~
RPD ABS Val
1
16.5%
16.5%
16.5%
16.5%
4
0.0%
106.7%
29.2%
5.1%
2
11.6%
15.4%
13.5%
13.5%
~
E-25
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Soil
Soil
Soil&
Sediment
Site
AS
BN
CN
KP
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.)
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
~
~
~
~
2
77.4%
129.5%
103.4%
103.4%
1
70.6%
70.6%
70.6%
70.6%
-
RPDABS
Val
~
~
~
~
2
77.4%
129.5%
103.4%
103.4%
1
70.6%
70.6%
70.6%
70.6%
-
Zinc
Reference Laboratory
RPD
3
-65.0%
105.7%
13.8%
0.8%
7
-61.6%
-8.3%
-36.8%
-33.4%
3
-80.6%
-15.2%
-49.4%
-52.2%
2
-57.3%
-47.1%
-52.2%
-52.2%
RPDABS
Val
3
0.8%
105.7%
57.1%
65.0%
7
8.3%
61.6%
36.8%
33.4%
3
15.2%
80.6%
49.4%
52.2%
2
47.1%
57.3%
52.2%
52.2%
E-26
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Sediment
Sediment
Soil
Sediment
Soil
Site
LV
RF
SB
TL
WS
All
Matrix
Description
Clay /clay loam, salt
crust (iron and other
precipitate)
Silty fine sand (tailings)
Coarse sand and gravel
(ore and waste rock)
Silt and clay (slag-
enriched)
Coarse sand and gravel
(roaster slag)
Samples
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
4
35.9%
49.6%
42.2%
41.6%
4
-43.8%
63.0%
34.3%
59.0%
6
-68.5%
43.9%
9.7%
23.0%
3
-45.7%
-27.0%
-39.4%
-45.5%
3
-105.4%
-37.6%
-63.3%
-47.0%
27
-105.4%
77.4%
11.3%
14.9%
RPDABS
Val
4
35.9%
49.6%
42.2%
41.6%
4
43.8%
63.0%
56.2%
59.0%
6
2.6%
68.5%
32.5%
32.9%
3
27.0%
45.7%
39.4%
45.5%
3
37.6%
105.4%
63.3%
47.0%
27
2.6%
105.4%
44.9%
45.5%
Certified Value
RPD
4
-108.4%
32.4%
-15.1%
7.8%
4
-2.6%
98.9%
24.8%
1.4%
~
~
~
~
3
10.2%
18.8%
13.5%
11.5%
~
~
~
—
14
-2.6%
154.4%
23.0%
6.2%
RPDABS
Val
4
9.9%
108.4%
44.0%
28.9%
4
0.1%
98.9%
26.1%
2.7%
~
~
~
~
o
3
10.2%
18.8%
13.5%
11.5%
~
~
~
—
14
0.1%
154.4%
23.5%
6.2%
Arsenic
Reference Laboratory
RPD
12
-31.8%
73.9%
16.5%
17.3%
12
-88.4%
-25.7%
-44.8%
-41.8%
5
-163.0%
-39.2%
-76.5%
-48.6%
2
-70.4%
1.9%
-34.3%
-34.3%
7
-66.4%
47.4%
-14.3%
-18.6%
46
-163.0%
53.8%
-41.4%
-41.0%
RPDABS
Val
12
1.2%
73.9%
27.5%
28.4%
12
25.7%
88.4%
44.8%
41.8%
5
39.2%
163.0%
76.5%
48.6%
2
1.9%
70.4%
36.2%
36.2%
7
8.4%
66.4%
34.2%
22.2%
46
1.9%
163.0%
49.1%
44.2%
Cadmium
Reference Laboratory
RPD
4
-97.3%
-59.2%
-81.2%
-84.2%
5
-37.1%
-11.8%
-22.0%
-21.0%
1
-16.3%
-16.3%
-16.3%
-16.3%
2
-34.3%
-14.0%
-24.1%
-24.1%
o
5
-29.4%
-12.2%
-18.7%
-14.7%
26
-44.3%
25.0%
-15.9%
-15.5%
RPD ABS Val
4
59.2%
97.3%
81.2%
84.2%
5
11.8%
37.1%
22.0%
21.0%
1
16.3%
16.3%
16.3%
16.3%
2
14.0%
34.3%
24.1%
24.1%
o
5
12.2%
29.4%
18.7%
14.7%
26
0.2%
44.3%
18.3%
16.3%
E-27
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Sediment
Sediment
Soil
Sediment
Soil
Site
LV
RF
SB
TL
WS
All
Matrix
Description
Clay /clay loam, salt
crust (iron and other
precipitate)
Silty fine sand (tailings)
Coarse sand and gravel
(ore and waste rock)
Silt and clay (slag-
enriched)
Coarse sand and gravel
(roaster slag)
Samples
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
3
70.9%
121.0%
93.5%
88.5%
8
11.7%
37.8%
29.8%
32.4%
10
-34.8%
87.2%
21.8%
19.5%
1
15.6%
15.6%
15.6%
15.6%
6
-41.9%
80.4%
28.5%
30.1%
41
-41.9%
87.2%
25.3%
28.1%
RPDABS
Val
3
70.9%
121.0%
93.5%
88.5%
8
11.7%
37.8%
29.8%
32.4%
10
9.0%
87.2%
28.8%
22.9%
1
15.6%
15.6%
15.6%
15.6%
6
2.3%
80.4%
42.4%
38.7%
41
2.3%
87.2%
30.6%
30.7%
Copper
Reference Laboratory
RPD
11
-24.1%
39.1%
8.9%
11.5%
13
-101.8%
70.7%
-11.0%
-8.3%
4
-108.7%
53.0%
-33.0%
-38.1%
7
-48.7%
-18.2%
-32.1%
-28.6%
6
-105.3%
9.2%
-28.3%
-7.6%
48
-111.1%
70.7%
-23.3%
-11.4%
RPDABS
Val
11
3.7%
39.1%
18.7%
14.3%
13
1.2%
101.8%
28.5%
11.6%
4
22.8%
108.7%
70.9%
76.1%
7
18.2%
48.7%
32.1%
28.6%
6
5.4%
105.3%
33.4%
9.5%
48
1.2%
111.1%
37.3%
25.1%
Iron
Reference Laboratory
RPD
5
-97.4%
6.5%
-68.8%
-84.1%
13
-5.3%
28.8%
13.9%
16.2%
12
3.2%
44.0%
29.7%
33.7%
7
-34.7%
15.7%
-9.0%
-1.9%
7
-16.4%
32.4%
19.3%
23.8%
70
-34.7%
73.9%
14.4%
17.6%
RPDABS
Val
5
6.5%
97.4%
71.3%
84.1%
13
5.0%
28.8%
15.5%
16.2%
12
3.2%
44.0%
29.7%
33.7%
7
1.9%
34.7%
18.2%
15.7%
7
16.4%
32.4%
24.0%
23.8%
70
0.3%
73.9%
21.1%
19.5%
Lead
Reference Laboratory
RPD
4
-68.3%
3.6%
-27.4%
-22.4%
10
-76.3%
-42.5%
-58.6%
-59.0%
~
~
~
~
4
-121.2%
-66.4%
-95.1%
-96.4%
7
-88.5%
-22.3%
-63.3%
-70.5%
42
-121.2%
10.9%
-52.8%
-54.6%
RPD ABS Val
4
3.6%
68.3%
29.1%
22.4%
10
42.5%
76.3%
58.6%
59.0%
~
~
~
~
4
66.4%
121.2%
95.1%
96.4%
7
22.3%
88.5%
63.3%
70.5%
42
0.5%
121.2%
54.0%
54.6%
E-28
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Sediment
Sediment
Soil
Sediment
Soil
Site
LV
RF
SB
TL
WS
All
Matrix
Description
Clay /clay loam, salt
crust (iron and other
precipitate)
Silty fine sand (tailings)
Coarse sand and gravel
(ore and waste rock)
Silt and clay (slag-
enriched)
Coarse sand and gravel
(roaster slag)
Samples
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
3
70.9%
121.0%
93.5%
88.5%
5
79.3%
106.7%
89.7%
89.8%
10
-133.5%
140.5%
64.0%
92.4%
o
5
72.3%
103.7%
85.0%
79.1%
—
~
~
~
—
24
-133.5%
140.5%
74.8%
90.1%
RPDABS
Val
3
70.9%
121.0%
93.5%
88.5%
5
79.3%
106.7%
89.7%
89.8%
10
22.5%
140.5%
90.7%
96.2%
o
5
72.3%
103.7%
85.0%
79.1%
—
~
~
~
—
24
22.5%
140.5%
88.2%
90.7%
Nickel
Reference Laboratory
RPD
11
-24.1%
39.1%
8.9%
11.5%
13
-2.9%
34.5%
17.7%
19.9%
11
-7.5%
35.4%
19.0%
17.5%
6
-73.9%
-3.6%
-35.5%
-36.4%
7
-37.3%
23.2%
-4.4%
4.0%
63
-73.9%
39.1%
6.9%
13.6%
RPDABS
Val
11
3.7%
39.1%
18.7%
14.3%
13
1.2%
34.5%
18.1%
19.9%
11
7.5%
35.4%
20.4%
17.5%
6
3.6%
73.9%
35.5%
36.4%
7
4.0%
37.3%
18.6%
16.3%
63
1.2%
73.9%
20.6%
17.5%
Selenium
Reference Laboratory
RPDABS
RPD Val
5 5
-97.4% 6.5%
6.5% 97.4%
-68.8% 71.3%
-84.1% 84.1%
3 3
-98.5% 56.8%
-56.8% 98.5%
-82.3% 82.3%
-91.7% 91.7%
3 3
-86.5% 3.7%
3.7% 86.5%
-56.4% 58.8%
-86.3% 86.3%
4 4
-110.0% 20.0%
-20.0% 110.0%
-58.0% 58.0%
-51.1% 51.1%
1 1
-106.0% 106.0%
-106.0% 106.0%
-106.0% 106.0%
-106.0% 106.0%
21 21
-110.0% 0.9%
6.5% 110.0%
-65.0% 66.1%
-75.7% 75.7%
Silver
Reference Laboratory
RPD RPD ABS Val
4 4
-68.3% 3.6%
3.6% 68.3%
-27.4% 29.1%
-22.4% 22.4%
4 4
-93.9% 15.5%
-15.5% 93.9%
-53.6% 53.6%
-52.6% 52.6%
1 1
-75.8% 75.8%
-75.8% 75.8%
-75.8% 75.8%
-75.8% 75.8%
4 4
-57.1% 32.1%
-32.1% 57.1%
-45.7% 45.7%
-46.8% 46.8%
4 4
-20.2% 10.5%
-10.5% 20.2%
-14.8% 14.8%
-14.3% 14.3%
24 24
-106.7% 0.0%
3.6% 106.7%
-33.4% 33.7%
-18.3% 18.3%
E-29
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Sediment
Sediment
Soil
Sediment
Soil
Site
LV
RF
SB
TL
WS
All
Matrix
Description
Clay /clay loam, salt
crust (iron and other
precipitate)
Silty fine sand (tailings)
Coarse sand and gravel
(ore and waste rock)
Silt and clay (slag-
enriched)
Coarse sand and gravel
(roaster slag)
Samples
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
5
47.6%
83.3%
65.2%
64.2%
3
74.2%
93.1%
84.8%
87.0%
3
-35.4%
73.8%
17.2%
13.2%
~
~
~
~
2
50.4%
83.4%
66.9%
66.9%
16
-35.4%
129.5%
65.2%
74.0%
RPDABS
Val
5
47.6%
83.3%
65.2%
64.2%
3
74.2%
93.1%
84.8%
87.0%
3
13.2%
73.8%
40.8%
35.4%
~
~
~
~
2
50.4%
83.4%
66.9%
66.9%
16
13.2%
129.5%
69.6%
74.0%
Zinc
Reference Laboratory
RPD
8
-48.4%
48.8%
-19.0%
-27.4%
13
-63.4%
20.3%
-33.2%
-38.4%
11
-22.8%
18.9%
-3.8%
-0.3%
7
-31.3%
70.9%
23.3%
28.5%
7
-51.3%
-11.8%
-32.5%
-24.9%
61
-80.6%
105.7%
-19.0%
-22.8%
RPDABS
Val
8
2.1%
48.8%
31.2%
34.2%
13
17.6%
63.4%
39.0%
38.4%
11
0.1%
22.8%
9.3%
7.8%
7
2.3%
70.9%
35.2%
31.3%
7
11.8%
51.3%
32.5%
24.9%
61
0.1%
105.7%
33.0%
32.5%
E-30
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
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 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 (raw value).
RPD ABS Val Relative percent difference (absolute value).
E-31
------- |