United States Office of Research and EPA/540/R-06/003
Environmental Protection Development February 2006
Agency Washington, DC 20460
Innovative Technology
Verification Report
XRF Technologies for Measuring
Trace Elements in
Soil and Sediment
Niton XLi 700 Series
XRF Analyzer
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EPA/540/R-06/003
February 2006
Innovative Technology
Verification Report
Niton XLi 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 XLi 700 Series (XLi) 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 XLi 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 XLi 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 XLi portable analyzer features a choice of either a full suite of traditional isotope (the XLi) or a
miniaturized x-ray tube (the XLt which was evaluated in a separate report) for rapid chemical
characterization of soils, sediment, and other thick homogeneous samples. The pre-set factory calibration
allows simultaneous analysis of up to 25 elements, including all eight Resource Conservation and
Recovery Act (RCRA) metals, in bulk materials with no requirement for site-specific calibrations or
standards. Whether testing is performed in situ (directly onto the ground) or ex situ (bagged or prepared
samples), sophisticated software automatically compensates for matrix variations from sample to sample,
allowing the operator to simply "point and shoot" any bulk sample without unnecessary data entry or
additional calibrations capability is also available.
Niton's XLi 700 Series analyzers are easy to operate, light weight, ergonomic, and are an advanced
isotope-based environmental XRF instrument. Niton offers various isotope options to best optimize
performance for the environmental application.
This report describes the results of the evaluation of the XLi 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 XLi 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 6
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 40
6.2.1 Setup and Calibration 40
6.2.2 Demonstration Sample Processing 42
6.3 General Demonstration Results 43
6.4 Contact Information 43
VI
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Contents (Continued)
Chapter Page
7.0 PERFORMANCE EVALUATION 45
7.1 Primary Objective 1 - Method Detection Limits 45
7.2 Primary Objective 2 - Accuracy and Comparability 49
7.3 Primary Objective 3 - Precision 55
7.4 Primary Obj ective 4 - Impact of Chemical and Spectral Interferences 55
7.5 Primary Objective 5 - Effects of Soil Characteristics 55
7.6 Primary Objective 6 - Sample Throughput 61
7.7 Primary Objective 7 - Technology Cost 61
7.8 Secondary Objective 1 - Training Requirements 61
7.9 Secondary Objective 2 -Health and Safety 62
7.10 Secondary Objective 3 - Portability 63
7.11 Secondary Objective 4 - Durability 63
7.12 Secondary Objective 5 -Availability 63
8.0 ECONOMIC ANALYSIS 65
8.1 Equipment Costs 65
8.2 Supply Costs 65
8.3 Labor Costs 66
8.4 Comparison of XRF Analysis and Reference Laboratory Costs 67
9.0 SUMMARY OF TECHNOLOGY PERFORMANCE 69
10.0 REFERENCES 75
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 XLi XRF Analyzer Technical Specifications 41
7-1 Evaluation of Sensitivity - Method Detection Limits for Niton XLi 46
7-2 Comparison of Mean XLi MDLs to All-Instrument Mean MDLs and EPA
Method 6200 Data 48
7-3 Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data
for the Niton XLi 51
7-4 Summary of Correlation Evaluation forthe Niton XLi 52
7-5 Evaluation of Precision - Relative Standard Deviations for the Niton XLi 56
7-6 Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory
versus the XLi and All Demonstration Instruments 57
7-7 Effects of Interferent Elements on the RPDs (Accuracy) for Other Target Elements,
Niton XLi 58
7-8 Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Niton XLi 59
8-1 Equipment Costs 65
8-2 Time Required to Complete Analytical Activities 66
8-3 Comparison of XRF Technology and Reference Method Costs 68
9-1 Summary of Niton XLi Performance - Primary Objectives 70
9-2 Summary of Niton XLI Performance - Secondary Objectives 72
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 Niton XLi 700 Series Analyzer Set Up for Ex-Situ Analysis 40
6-2 Niton Technician Using a Stainless Steel Scoop to Fill a Sample Cup 42
6-3 Instrument Setup with Samples Awaiting Analysis 43
7-1 Linear Correlation Plot for Niton XLi Showing High Correlation for Selenium 50
7-2 Linear Correlation Plot for Niton XLi Showing Low Correlation and Variable Bias
For Vanadium 53
8-1 Comparison of Labor Requirements for the XLi versus Other XRF Instruments 67
9-1 Method Detection Limits (sensitivity), Accuracy, and Precision of the Niton XLi
in Comparison to the Average of All Eight XRF Instruments 73
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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 XLi 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
Table 1-1. Participating Technology Developers and Instruments
Developer Full Name
Elvatech, Ltd.
Innov-X Systems
NITON Analyzers, A
Division of Thermo
Electron Corrjoration
Oxford Instruments
Analytical, Ltd.
Rigaku, Inc.
RONTEC AG (acquired
byBrukerAXS,
1 1/2005)
Distributor in the
United States
Xcalibur XRF Services
Innov-X
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
XLt 700 Series
XLi 700 Series
X-Met 3000 TX
ED2000
ZSX Mini II
PicoTAX
Instrument Short
Name
ElvaX
XT400
XLt
XLi
X-Met
ED2000
ZSX Mini II
PicoTAX
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of the instrument (Chapter 6), a performance
evaluation (Chapter 7), a cost analysis (Chapter 8),
and a summary of the demonstration results (Chapter
9).
References are provided in Chapter 10. A
verification statement for the instrument is provided
as Appendix A. Comments from the instrument
developer on the demonstration and any exceptions to
EPA's evaluation are presented in Appendix B.
Appendices C, D, and E contain the data validation
summary report for the reference laboratory data and
detailed evaluations of instrument versus reference
laboratory results.
1.2 Description of the SITE Program
Performance verification of innovative environmental
technologies is an integral part of EPA's regulatory
and research mission. The SITE Program was
established by the EPA Office of Solid Waste and
Emergency Response and ORD under the Superfund
Amendments and Reauthorization Act of 1986. The
overall goal of the SITE Program is to conduct
performance verification studies and to promote
acceptance of innovative technologies that may be
used to achieve long-term protection of human health
and the environment. The program is designed to
meet three primary objectives: (1) identify and
remove obstacles to development and commercial
use of innovative technologies; (2) demonstrate
promising innovative technologies and gather reliable
information on performance and cost to support site
characterization and cleanup; and (3) maintain an
outreach program to operate existing technologies
and identify new opportunities for their use.
Additional information on the SITE Program is
available on the EPA ORD web site
(www.epa.gov/ord/SITE).
The intent of a SITE demonstration is to obtain
representative, high-quality data on the performance
and cost of one or more innovative technologies so
that potential users can assess a technology's
suitability for a specific application. The SITE
Program includes the following program elements:
• Monitoring and Measurement Technology
(MMT) Program - Evaluates technologies that
sample, detect, monitor, or measure hazardous
and toxic substances. These technologies are
expected to provide better, faster, or more cost-
effective methods for producing real-time data
during site characterization and remediation
studies than can conventional technologies.
• Remediation Technology Program -
Demonstrates innovative treatment technologies
to provide reliable data on performance, cost, and
applicability for site cleanups.
• Technology Transfer Program - Provides and
disseminates technical information in the form of
updates, brochures, and other publications that
promote the SITE Program and the participating
technologies.
The demonstration of XRF instruments was
conducted as part of the MMT Program, which is
administered by the Environmental Sciences Division
(ESD) of the National Exposure Research Laboratory
(NERL) in Las Vegas, Nevada. Additional
information on the NERL ESD is available on the
EPA web site (www.epa.gov/nerlesdl/). Tetra Tech
EM Inc. (Tetra Tech), an EPA contractor, provided
comprehensive technical support to the
demonstration.
1.3 Scope of the Demonstration
Conventional analytical methods for measuring the
concentrations of inorganic elements in soil and
sediment are time-consuming and costly. For this
reason, field-portable XRF instruments have been
proposed as an alternative approach, particularly
where rapid and cost-effective assessment of a site is
a goal. The use of a field XRF instrument for
elemental analysis allows field personnel to quickly
assess the extent of contamination by target elements
at a site. Furthermore, the near instantaneous data
provided by field-portable XRF instruments can be
used to quickly identify areas where there may be
increased risks and allow development of a more
focused and cost-effective sampling strategy for
conventional laboratory analysis.
EPA-sponsored demonstrations of XRF technologies
have been under way for more than a decade. The
first SITE MMT demonstration of XRF occurred in
1995, when six instruments were evaluated for their
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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.
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 abroad 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
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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
filled by electrons that cascade in from the outer
shells. The energy states of the electrons in the outer
shells are higher than those of the inner-shell
electrons, and the outer-shell electrons emit energy in
the form of x-rays as they cascade down. The energy
of this x-ray radiation is unique for each element.
An XRF analyzer consists of three major
components: (1) a source that generates x-rays (a
radioisotope or x-ray tube); (2) a detector that
converts x-rays emitted from the sample into
measurable electronic signals; and (3) a data
processing unit that records the emission or
fluorescence energy signals and calculates the
elemental concentrations in the sample.
Ejected K-shell electron
Incident radiation
L-shell electron
fills vacancy
, x-ray emitted
~ * Kax-ray Emitted
M-shell 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 increase because of sample hetero-
geneity or the presence of other elements in the
sample that fluoresce with similar x-ray energies.
The main variables that affect precision and accuracy
for XRF analysis are:
1. Physical matrix effects (variations in the physical
character of the sample).
2. Chemical matrix effects (absorption and
enhancement phenomena) and Spectral
interferences (peak overlaps).
3. Moisture content above 10 percent, which affects
x-ray transmission.
Because of these variables, it is important that each
field XRF characterization effort be guided by a well-
considered sampling and analysis plan. Sample
preparation and homogenization, instrument
calibration, and laboratory confirmation analysis are
all important aspects of an XRF sampling and
analysis plan. EPA SW-846 Method 6200 provides
additional guidance on sampling and analytical
methodology for XRF analysis.
1.5 Properties of the Target Elements
This section describes the target elements selected for
the technology demonstration and the typical
characteristics of each. Key criteria used in selecting
the target elements included:
• The frequency that the element is determined in
environmental applications of XRF instruments.
• The extent that the element poses an
environmental consequence, such as a potential
risk to human or environmental receptors.
• The ability of XRF technology to achieve
detection limits below typical remediation goals
and risk assessment criteria.
• The extent that the element may interfere with
the analysis of other target elements.
In considering these criteria, the critical target
elements selected for this study were antimony,
arsenic, cadmium, chromium, copper, iron, lead,
mercury, nickel, selenium, silver, vanadium, and
zinc. These 13 target elements are of significant
concern for site cleanups and human health risk
-------
assessments because most are highly toxic or
interfere with the analysis of other elements. The
demonstration therefore focused on the analysis of
these 13 elements in evaluating the various XRF
instruments.
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 in XRF analysis when the ratio of lead to
arsenic is 10 to 1 or more. Risk-based screening
levels and soil screening levels for arsenic may be
lower than the detection limits of field-portable XRF
instruments.
7.5.5 Cadmium
Naturally occurring cadmium in surface soils
typically ranges from 0.6 to 1.1 mg/kg;
concentrations greater than 4 mg/kg are potentially
phytotoxic. 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
therefore included in the study. Furthermore, iron is
often used as a target reference element in XRF
analysis.
Naturally occurring iron in surface soils typically
ranges from 7,000 to 550,000 mg/kg, with the iron
content originating primarily from parent rock.
Typical detection limits for field-portable XRF
instruments are in the range of 10 to 60 mg/kg. Iron
is easily analyzed by both ICP-AES and XRF;
however, neither technique can distinguish among
iron species in soil. Although iron in soil may pose
few environmental consequences, high levels of iron
may interfere with analyses of other elements in both
techniques (ICP-AES and XRF). Spectral
interference from iron is mitigated in ICP-AES
analysis by applying inter-element correction factors,
as required by the analytical method. Differences in
analytical results between ICP-AES and XRF for
other target elements are expected when
concentrations of iron are high in the soil matrix.
1.5.7 Lead
Naturally occurring lead in surface soils typically
ranges from 2 to 200 mg/kg; concentrations greater
than 50 mg/kg are potentially phytotoxic.
Concentrations greater than 400 mg/kg may result in
adverse effects in humans. Typical detection limits
for field-portable XRF instruments range from 10 to
20 mg/kg. Lead is a common contaminant at many
sites, and human and environmental exposure can
occur through many routes. Lead is frequently found
in mine waste, at lead-acid battery recycling
facilities, at oil refineries, and in lead-based paint.
Lead is successfully analyzed by ICP-AES and XRF;
however, spectral interferences between peaks for
lead and arsenic in XRF analysis can affect detection
limits and accuracy when the ratio of arsenic to lead
is 10 to 1 or more. Differences between ICP-AES
and XRF results are expected in the presence of high
concentrations of arsenic, especially when the ratio of
lead to arsenic is low.
1.5.8 Mercury
Naturally occurring mercury in surface soils typically
ranges from 0.01 to 0.3 mg/kg; concentrations greater
than 0.3 mg/kg are potentially phytotoxic.
Concentrations of mercury greater than 23 mg/kg and
concentrations of methyl mercury above 6.1 mg/kg
may result in adverse health effects in humans.
Typical detection limits for field-portable XRF
instruments range from 10 to 20 mg/kg. Elevated
concentrations of mercury are associated with
amalgamation of gold and with mine waste and
industrial facilities. Native surface soils are
commonly enriched by anthropogenic sources of
mercury. Anthropogenic sources include coal-fired
power plants and metal smelters. Mercury is too
volatile to withstand both the vigorous digestion and
extreme temperature involved with ICP-AES
analysis; therefore, the EPA-approved technique for
laboratory analysis of mercury is CVAA
spectroscopy. Mercury is successfully measured by
XRF, but differences between results obtained by
CVAA and XRF are expected when mercury levels
are high.
1.5.9 Nickel
Naturally occurring nickel in surface soils typically
ranges from 5 to 500 mg/kg; a concentration of 30
mg/kg is potentially phytotoxic. Concentrations
greater than 1,600 mg/kg may result in adverse health
effects in humans. Typical detection limits for field-
portable XRF instruments range from 10 to 60
mg/kg. Elevated concentrations of nickel are
associated with mine wastes and industrial facilities.
Nickel is a common environmental contaminant at
metal processing sites. It is successfully analyzed by
both ICP-AES and XRF with little interference;
therefore, a strong correlation between the methods is
expected.
1.5.10 Selenium
Naturally occurring selenium in surface soils
typically ranges from 0.1 to 2 mg/kg; concentrations
greater than 1 mg/kg are potentially phytotoxic. Its
toxicities are well documented for plants and
-------
livestock; however, it is also considered a trace
nutrient. Concentrations above 390 mg/kg may result
in adverse health effects in humans. Typical
detection limits for field-portable XRF instruments
range from 10 to 20 mg/kg. Most selenium is
associated with sulfur or sulfide minerals, where
concentrations can exceed 200 mg/kg. Selenium can
be measured by both ICP-AES and XRF; however,
detection limits using XRF usually exceed the
ecological risk-based screening levels for soil.
Analytical results for selenium using ICP-AES and
XRF are expected to be comparable.
7.5.77 Silver
Naturally occurring silver in surface soils typically
ranges from 0.01 to 5 mg/kg; concentrations greater
than 2 mg/kg are potentially phytotoxic. In addition,
concentrations that exceed 390 mg/kg may result in
adverse effects in humans. Typical detection limits
for field-portable XRF instruments range from 10 to
45 mg/kg. Silver is a common contaminant in mine
waste, in photographic film processing wastes, and at
metal processing sites. It is successfully analyzed by
ICP-AES and XRF; however, recovery may be
reduced in ICP-AES analysis because insoluble silver
chloride may form during acid digestion. Detection
limits using XRF may exceed the risk-based
screening levels for silver in soil.
1.5.12 Van adium
Naturally occurring vanadium in surface soils
typically ranges from 20 to 500 mg/kg;
concentrations greater than 2 mg/kg are potentially
phytotoxic, although specific phytotoxicity levels for
naturally occurring vanadium have not been
documented. Concentrations above 550 mg/kg may
result in adverse health effects in humans. Typical
detection limits for field-portable XRF instruments
range from 10 to 50 mg/kg. Vanadium can be
associated with manganese, potassium, and organic
matter and is typically concentrated in organic shales,
coal, and crude oil. It is successfully analyzed by
both ICP-AES and XRF with little interference.
7.5.75 Zinc
Naturally occurring zinc in surface soils typically
ranges from 10 to 300 mg/kg; concentrations greater
than 50 mg/kg are potentially phytotoxic. Zinc at
concentrations above 23,000 mg/kg may result in
adverse health effects in humans. Typical detection
limits for field-portable XRF instruments range from
10 to 30 mg/kg. Zinc is a common contaminant in
mine waste and at metal processing sites. In addition,
it is highly soluble, which is a common concern for
aquatic receptors. Zinc is successfully analyzed by
ICP-AES; however, spectral interferences between
peaks for copper and zinc may influence detection
limits and the accuracy of the XRF analysis.
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Chapter 2
Field Sample Collection Locations
Although the field demonstration took place at KARS
Park on Merritt Island, Florida, environmental
samples were collected at other sites around the
country to develop a demonstration sample that
incorporated a variety of soil/sediment types and
target element concentrations. This chapter describes
these sample collection sites, as well as the rationale
for the selection of each.
Several criteria were used to assess potential sample
collection sites, including:
• The ability to provide a variety of target elements
and soil/sediment matrices.
• The convenience and accessibility of the location
to the sampling team.
• Program support and the cooperation of the site
owner.
Nine sample collection sites were ultimately selected
for the demonstration; one was the KARS Park site
itself. These nine sites were selected to represent
variable soil textures (sand, silt, and clay) and iron
content, two factors that significantly affect
instrument performance.
Historical operations at these sites included mining,
smelting, steel manufacturing, and open burn pits;
one, KARS Park, was a gun range. Thus, these sites
incorporated a wide variety of metal contaminants in
soils and sediments. Both contaminated and
uncontaminated (background) samples were collected
at each site.
A summary of the sample collection sites is presented
in Table 2-1, which describes the types of metal-
contaminated soils or sediments that were found at
each site. This information is based on the historical
data that were provided by the site owners or by the
EPA remedial project managers.
2.1 Alton Steel Mill Site
The Alton Steel Mill site (formerly the Laclede Steel
site) is located at 5 Cut Street in Alton, Illinois. This
400-acre site is located in Alton's industrial corridor.
The Alton site was operated by Laclede Steel
Company from 1911 until it went bankrupt in July
2001. The site was purchased by Alton Steel, Inc.,
from the bankruptcy estate of Laclede Steel in May
2003. The Alton site is heir to numerous
environmental concerns from more than 90 years of
steel production; site contaminants include
polychlorinated biphenyls (PCBs) and heavy metals.
Laclede Steel was cited during its operating years for
improper management and disposal of PCB wastes
and electric arc furnace dust that contained heavy
metals such as lead and cadmium. A Phase I
environmental site assessment (ESA) was conducted
at the Alton site in May 2002, which identified
volatile organic compounds (VOCs), semivolatile
organic compounds (SVOCs), total priority pollutant
metals, and PCBs as potential contaminants of
concern at the site.
Based on the data gathered during the Phase I ESA
and on discussions with Alton personnel, several soil
samples were collected for the demonstration from
two areas at the Alton site, including the Rod
Patenting Building and the Tube Mill Building. The
soil in the areas around these two buildings had not
been remediated and was known to contain elevated
concentrations of arsenic, cadmium, chromium, lead,
nickel, zinc, and iron. The matrix of the
contaminated soil samples was a fine to medium
sand; the background soil sample was a sand loam.
Table 2-2 presents historical analytical data (the
maximum concentrations) for some of the target
elements detected at the Alton site.
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Table 2-1. Nature of Contamination in Soil and Sediment at Sample Collection Sites
Sample Collection Site
Alton Steel, Alton, IL
Burlington Northern-
ASARCO Smelter Site,
East Helena, MT
KARS Park - Kennedy
Space Center, Merritt
Island, FL
Leviathan Mine
Site/ Aspen Creek, Alpine
County, CA
Naval Surface Warfare
Center, Crane Division,
Crane, IN
Ramsay Flats-Silver Bow
Creek, Butte, MT
Sulphur Bank Mercury
Mine
Torch Lake Site (Great
Lakes Area of Concern),
Houghton County, MI
Wickes Smelter Site,
Jefferson City, MT
Source of Contamination
Steel manufacturing facility with metal arc
furnace dust. The site also includes a metal
scrap yard and a slag recovery facility.
Railroad yard staging area for smelter ores.
Contaminated soils resulted from dumping and
spilling concentrated ores.
Impacts to soil from historical facility
operations and a former gun range.
Abandoned open-pit sulfur and copper mine
that has contaminated a 9-mile stretch of
mountain creeks, including Aspen Creek, with
heavy metals.
Open disposal and burning of general refuse
and waste associated with aircraft
maintenance.
Silver Bow Creek was used as a conduit for
mining, smelting, industrial, and municipal
wastes.
Inactive mercury mine. Waste rock, tailings,
and ore are distributed in piles throughout the
property.
Copper mining produced mill tailings that were
dumped directly into Torch Lake,
contaminating the lake sediments and
shoreline.
Abandoned smelter complex with
contaminated soils and mineral-processing
wastes, including remnant ore piles,
decomposed roaster brick, slag piles and fines,
and amalgamation sediments.
Matrix
Soil
Soil
Soil
Soil and
Sediment
Soil
Soil and
Sediment
Soil
Sediment
Soil
Site-Specific Metals of Concern for XRF Demonstration
Sb
X
X
X
X
As
X
X
X
X
X
X
X
X
X
Cd
X
X
X
X
X
X
Cr
X
X
X
X
X
X
Cu
X
X
X
X
X
X
Fe
X
X
X
X
X
Pb
X
X
X
X
X
X
X
X
Hg
X
X
X
Ni
X
X
X
X
Se
X
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
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 Model
T 50A Turbula shaker-mixer. This shaker was
15
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capable of handling up to 50 gallons (190 liters) of
sample material; thus, this shaker could handle the
complete volume of each bulk sample. Bulk
samples of smaller volume were mixed and
homogenized using a Model T 10B Turbula shaker-
mixer that was capable of handling up to 10 gallons
(38 liters). Aliquots from each homogenized bulk
sample were then sampled and analyzed in triplicate
for the 13 target elements using ICP-AES and CVAA.
If the relative percent difference between the highest
and lowest result exceeded 10 percent for any element,
the entire batch was returned to the shaker-mixer for
additional homogenization. The entire processing
scheme for the bulk samples is shown in Figure 3-1.
Bulk samples
collected
k
Samples placed on
large trays to
promote drying
i
s~**
L
/Was \
Xdry? /
-Yes-
Material was sieved
through custom 1" screen
to remove large material.
Samples are
mixed and homogenized
using Model T 50A
Turbula shaker-mixer
Was
the material smaller
than 2mm?
the sample greater
than 10
gallons?
Material crushed using
stainless steel hammer mill
Samples are
mixed and homogenized
using Model T 10B
and Turbula shaker-mixer
Aliquots from each
homogenized soil and sediment batch
were sampled and analyzed
in triplicate using ICP-AES
and CVAA for th e target elements
Was
the percent difference
between the highest and
lowest result greater
than 10%?
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, and
• A temperate climate so that the demonstration
could occur on schedule in January.
After an extensive search for candidates, the site
selected for the field demonstration was KARS Park,
which is part of the Kennedy Space Center on Merritt
Island, Florida. KARS Park was selected as the
demonstration site for the following reasons:
• Access and Site Owner Support —
Representatives from NASA were willing to
support the field demonstration by providing
access to the site, assisting in logistical support
during the demonstration, and hosting a visitors
day.
• Facilities Requirements and Feasibility — The
recreation building was available and was of
sufficient size to accommodate all the
demonstration participants. Furthermore, the
recreation building had adequate power to operate
all the XRF instruments simultaneously and all the
amenities to fully support the demonstration
participants, as well as visitors, in reasonable
comfort.
• Ease of Access to the Site — The park, located
about 45 minutes away from Orlando
International Airport, was selected because of its
easy accessibility by direct flight from many
airports in the country. In addition, many hotels
are located within 10 minutes of the site along
the coast at Cocoa Beach, in a popular tourist
area. Weather in this area of central Florida in
January is dry and sunny, with pleasant daytime
temperatures into the 70s (F) and cool nights.
3.3.2 Demonstration Site Logistics
The field demonstration was held in the recreation
building, which is just south of the gunnery range at
KARS Park. Photographs of the KARS Park
recreation building, where all the XRF instruments
were set up and operated, are shown in Figures 3-2
and 3-3.
A visitors day was held on January 26, 2005 when
about 25 guests came to the site to hear about the
demonstration and to observe the XRF instruments in
operation. Visitors day presentations were conducted
in a conference building adjacent to the recreation
building at KARS Park (see Figure 3-4). Presenta-
tions by NASA and EPA representatives were
followed by a tour of the XRF instruments in the
recreation building while demonstration samples
were being analyzed.
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
than the average result for all eight instruments, the
result was considered "equivalent." A similar
comparison was conducted with respect to cost
(Primary Objective 7). These comparisons were
23
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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
t
n
s
= method detection limit
= Student's t value for a 99
percent confidence level and
a standard deviation estimate
with n-1 degrees of freedom
= number of samples
= standard deviation.
Table 4-1. Evaluation Objectives
Objective
Primary Objective 1
Primary Objective 2
Primary Objective 3
Primary Objective 4
Primary Objective 5
Primary Objective 6
Primary Objective 7
Secondary Objective 1
Secondary Objective 2
Secondary Objective 3
Secondary Objective 4
Secondary Objective 5
Description
Determine the MDL for each target element.
Evaluate the accuracy and comparability of the XRF measurement to the results of
laboratory reference methods for a variety of contaminated soil and sediment
samples.
Evaluate the precision of XRF measurements for a variety of contaminated soil and
sediment samples.
Evaluate the effect of chemical and spectral interference on measurement of target
elements.
Evaluate the effect of soil characteristics on measurement of target elements.
Measure sample throughput for the measurement of target elements under field
conditions.
Estimate the costs associated with XRF field measurements.
Document the skills and training required to properly operate the instrument.
Document health and safety concerns associated with operating the instrument.
Document the portability of the instrument.
Evaluate the instrument's durability based on its materials of construction and
engineering design.
Document the availability of the instrument and of associated customer technical
support.
24
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Based on the data provided by the characterization
laboratory before the demonstration, a total of 12
sample blends (seven for soil and five for sediment)
were identified for use in the MDL determination.
The demonstration approach specified the analysis of
seven replicates for each of these sample blends by
both the developer and the reference laboratory. It
was predicted that these blends would allow the
determination of a minimum of one MDL for soil and
one MDL for sediment for each element, with the
exception of iron. This prediction was based on the
number of sample blends that contained
concentrations less than 50 percent lower or higher
than the lower limit of the Level 1 concentration
range (from 20 to 50 ppm, depending on the
element), as presented in Table 3-1.
After the field demonstration, the data sets obtained
by the developers and the reference laboratory for the
MDL sample blends were reviewed to confirm that
they were appropriate to use in calculating MDLs.
The requirements of 40 CFR 136, Appendix B, were
used as the basis for this evaluation. Specifically, the
CFR states that samples to be used for MDL
determinations should contain concentrations in the
range of 1 to 5 times the predicted MDL. On this
basis, and using a nominal predicted reporting limit
of 50 ppm for the target elements based on past XRF
performance and developer information, a
concentration of 250 ppm (5 times the "predicted"
nominal MDL) was used as a threshold in selecting
samples to calculate the MDL. Thus, each of the 12
MDL blends that contained mean reference
laboratory concentrations less than 250 ppm were
used in calculating MDLs for a given target element.
Blends with mean reference laboratory
concentrations greater than 250 ppm were discarded
for evaluating this objective.
For each target element, an MDL was calculated for
each sample blend with a mean concentration within
the prescribed range. If multiple MDLs could be
calculated for an element from different sample
blends, these results were averaged to arrive at an
overall mean MDL for the demonstration. The mean
MDL for each target element was then categorized as
either low (MDL less than 20 ppm), medium (MDL
between 20 and 100 ppm), or high (MDL exceeds
100 ppm). No blends were available to calculate a
detection limit for iron because all the blends
contained substantial native concentrations of iron.
4.2.2 Primary Objective 2 —Accuracy
Accuracy was assessed based on a comparison of the
results obtained by the XRF instrument with the
results from the reference laboratory for each of the
70 blends in the demonstration sample set. The
results from the reference laboratory were essentially
used as a benchmark in this comparison, and the
accuracy of the XRF instrument results was judged
against them. The limitations of this approach should
be recognized, however, because the reference
laboratory results were not actually "true values."
Still, there was a high degree of confidence in the
reference laboratory results for most elements, as
described in Chapter 5.
The following data analysis procedure was followed
for each of the 13 target elements to assess the
accuracy of an XRF instrument:
1. The results for replicate samples within a blend
were averaged for both the data from the XRF
instrument and the reference laboratory. Since
there were 70 sample blends, this step created a
maximum of 70 paired results for the assessment.
2. A blend that exhibited one or more non-detect
values in either the XRF instrument or the
reference laboratory analysis was excluded from
the evaluation.
3. A blend was excluded from the evaluation when
the average result from the reference laboratory
was below a minimum concentration. The
minimum concentration for exclusion from the
accuracy assessment was identified as the lower
limit of the lowest concentration range (Level 1
in Table 3-1), which is about 50 ppm for most
elements.
4. The mean result for a blend obtained with the
XRF instrument was compared with the
corresponding mean result from the reference
laboratory by calculating a relative percent
difference (RPD). This comparison was carried
out for each of the paired XRF and reference
laboratory results included in the evaluation (up
to 70 pairs) as follows:
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RPD
where
MR
MD
average (MR, MD)
= the mean reference
laboratory measurement
= the mean XRF instrument
measurement.
5. Steps 1 through 4 provided a set of up to 70
RPDs for each element (70 sample blends minus
the number excluded in steps 1 and 2). The
absolute value of each of the RPDs was taken
and summary statistics (minimum, maximum,
mean and median) were then calculated.
6. The accuracy of the XRF instrument for each
target element was then categorized, based on the
median of the absolute values of the RPDs, as
either excellent (RPD less than 10 percent), good
(RPD between 10 percent and 25 percent), fair
(RPD between 25 percent and 50 percent), or
poor (RPD above 50 percent).
7. The set of absolute values of the RPDs for each
instrument and element was further evaluated to
assess any trends in accuracy versus
concentration. These evaluations involved
grouping the RPDs by concentration range
(Levels 1 through 3 and 4, as presented in Table
3-1), preparing summary statistics for each range,
and assessing differences among the grouped
RPDs.
The absolute value of the RPDs was taken in step 5 to
provide a more sensitive indicator of the extent of
differences between the results from the XRF
instrument and the reference laboratory. However,
the absolute value of the RPDs does not indicate the
direction of the difference and therefore does not
reflect bias.
The populations of mean XRF and mean reference
laboratory results were assessed through linear
correlation plots to evaluate bias. These plots depict
the linear relationships between the results for the
XRF instrument and reference laboratory for each
target element using a linear regression calculation
with an associated correlation coefficient (r2). These
plots were used to evaluate the existence of general
bias between the data sets for the XRF instrument
and the reference laboratory.
4.2.3 Primary Objective 3 —Precision
The precision of the XRF instrument analysis for
each target element was evaluated by comparing the
results for the replicate samples in each blend. All 70
blends in the demonstration sample set (including
environmental and spiked samples) were included in
at least triplicate so that precision could be evaluated
across all concentration ranges and across different
matrices.
The precision of the data for a target element was
evaluated for each blend by calculating the mean
relative standard deviation (RSD) with the following
equation:
RSD =
SD
C
100
where
RSD = Relative standard deviation
SD = Standard deviation
C = Mean concentration.
The standard deviation was calculated using the
equation:
SD =
where
SD
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
-------
comparing the "certified values" for the spiked
samples with the reference laboratory results are
shown in Table 5-2. The target for percent recovery
was 75 to 125 percent. The mean percent recoveries
for 12 of the 13 target elements were well within this
accuracy goal. Only the mean recovery for antimony
was outside the goal (26.8 percent). The low mean
percent recovery for antimony supported the
recommendation made by the project team to conduct
a secondary comparison of XRF data to ERA-
certified spike values for antimony. This secondary
evaluation was intended to better understand the
impacts on the evaluation of the low bias for
antimony in the reference laboratory data. All other
recoveries were acceptable. Thus, this evaluation
further supports the conclusion that the reference data
set is of high quality.
Table 5-1. Number of Validation Qualifiers.
Element
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Totals
Number and Percentage of Qualified Results per QC type 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.
MSB Matrix spike duplicate.
QC Quality control.
1 This table presents the number of "U" (undetected) and "J" (estimated) qualifiers added to the
reference laboratory data during data validation. Though so qualified, these results are considered
usable for the demonstration. As is apparent in the "Totals" row at the bottom of this table, the
amount of data that required qualifiers for any specific QC type was invariably less than 10 percent.
No reference laboratory data were rejected (that is, qualified "R") during the data validation.
2 Percents for individual elements are calculated based on 326 results per element. Total
percents at the bottom of the table are calculated based on the total number of results for all
elements (4,238).
35
-------
All blends (1 through 70) were prepared and
delivered with multiple replicates. To assess
precision, percent RSDs were calculated for the
replicate sample results submitted by the reference
laboratory for each of the 70 blends. Table 5-3
presents the summary statistics for the reference
laboratory data for each of the 13 target elements.
These summary statistics indicate good precision in
that the median percent RSD was less than 10 percent
for 11 out of 13 target elements (and the median RSD
for the other two elements was just above 10
percent). Thus, this evaluation further supports the
conclusion that the reference data set is of high
quality.
ARDL, in Mount Vernon, Illinois, was selected as the
characterization laboratory to prepare environmental
samples for the demonstration. As part of its work,
ARDL analyzed several samples of each blend to
evaluate whether the concentrations of the target
elements and the homogeneity of the blends were
suitable for the demonstration. ARDL analyzed the
samples using the same methods as the reference
laboratory; however, the data from the
characterization laboratory were not validated and
were not intended to be equivalent to the reference
laboratory data. Rather, the intent was to use the
results obtained by the characterization laboratory as
an additional quality control check on the results
from the reference laboratory.
A review of the ARDL characterization data in
comparison to the reference laboratory data indicated
that ARDL obtained lower recoveries of several
elements. When expressed as a percent of the
average reference laboratory result (percent
recovery), the median ARDL result was below the
lower QC limit of 75 percent recovery for three
elements — chromium, nickel, and selenium. This
discrepancy between data from the reference
laboratory and ARDL was determined to have no
significant impact on reference laboratory data
quality for three reasons: (1) the ARDL data were
obtained on a rapid turnaround basis to evaluate
homogeneity — accuracy was not a specific goal, (2)
the ARDL data were not validated, and (3) all other
quality measurement for the reference laboratory data
indicated a high level of quality.
5.4 Summary of Data Quality and
Usability
A significant effort was undertaken to ensure that
data of high quality were obtained as the reference
data for this demonstration. The reference laboratory
data set was deemed valid, usable, and of high quality
based on the following:
• Comprehensive selection process for the
reference laboratory, with multiple levels of
evaluation.
• No data were rejected during data validation and
few data qualifiers were added.
• The observations noted during the reference
laboratory audit were only minor in nature; no
major findings or non-conformances were
documented.
• Acceptable accuracy (except for antimony, as
discussed in Section 5.3.3) of reference
laboratory results in comparison to spiked
certified values.
• Acceptable precision for the replicate samples in
the demonstration sample set.
Based on the quality indications listed above, the
reference laboratory data were used in the evaluation
of XRF demonstration data. A second comparison
was made between XRF data and certified values for
antimony (in Blends 46 through 70) to address the
low bias exhibited for antimony in the reference
laboratory data.
36
-------
Table 5-2. Percent Recovery for Reference Laboratory Results in Comparison to ERA Certified Spike Values for Blends 46 through 70
Statistic
Number of %R values
Minimum %R
Maximum %R
Mean "/oR1
Median "/oR1
Sb
16
12.0
36.1
26.8
28.3
As
14
65.3
113.3
88.7
90.1
Cd
20
78.3
112.8
90.0
87.3
Cr
12
75.3
108.6
94.3
97.3
Cu
20
51.7
134.3
92.1
91.3
Fe
NC
NC
NC
NC
NC
Pb
12
1.4
97.2
81.1
88.0
Hg
15
81.1
243.8
117.3
93.3
Ni
16
77.0
116.2
93.8
91.7
Se
23
2.2
114.2
89.9
93.3
Ag
20
32.4
100.0
78.1
84.4
V
15
58.5
103.7
90.4
95.0
Zn
10
0.0
95.2
90.6
91.3
Notes:
'Values shown in bold fall outside the 75 to 125 percent acceptance criterion for percent recovery.
ERA = Environmental Resource Associates, Inc.
NC = Not calculated.
%R = Percent recovery.
Source of certified values: Environmental Resource Associates, Inc.
Sb
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
-------
Chapter 6
Technology Description
The XLi 700 Series XRF analyzer is manufactured
by NITON Analyzers, a division of Thermo
Electron Corporation (Niton). This chapter
provides a technical description of the XLi based
on information obtained from Niton and obser-
vation of this analyzer during the field demon-
stration. This section also identifies a Niton
company contact, where additional technical
information may be obtained.
6.1 General Description
The Niton XLi is a small, field-portable, isotope-
based XRF instrument designed for chemical
characterization of soils, sediment, and other thick
homogeneous samples (plastics and metals). The
XLi can be outfitted with various isotope options
to best fit the environmental application needs of
the customer. Niton offers the XLi with a 40
milliCurie (mCi) 109cadmium (Cd) source for
standard elemental analysis of bulk materials. Up
to 15 elements can be analyzed using the 109Cd
source, including arsenic, chromium, copper, lead,
mercury, and zinc. Optional isotope sources that
can be fitted into the same analyzer are the 14 mCi
241americium (Am) source and the 20 mCi 55iron
(Fe) source. The 241Am source permits analysis
for five heavier elements: antimony, barium,
cadmium, silver, and tin. The 55Fe isotope source
permits analysis of four lighter elements: calcium,
potassium, titanium, and vanadium.
Niton also manufactures an XLi analyzer with a
patented Infiniton isotope source for general
analysis of up to 25 elements in bulk material
samples. The Infiniton XRF analyzer uses a 30
mCi 241Am source that essentially lasts indefinitely
because the source half-life equals 432.2 years.
The Infiniton XRF analyzer also includes unique
detector settings and software.
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 Bluetooth6 wireless
communication to a laptop or personal data assistant
(PDA).
The XLi 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-specific, or material-
specific, calibration; however, it is capable of handling
user-generated empirical calibrations, if required for
specific applications.
The XLi 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 (Figure 6-1). 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. In situ testing with the XLi allows for
semi-quantitative assessment of element concentrations
at multiple locations or over large areas in a short time.
For ex situ analysis, samples are prepared in x-ray
sample cups and placed in the sample drawer at the
bottom of the test stand, directly beneath the instrument
x-ray window. 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-portable XRF analyses use a combination of in situ
and ex situ sample testing.
The XLi 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, one for standard soil samples (optimum for
concentrations up to 1%) and one for industrial bulk
samples (optimum for concentration from 1 - 100%).
Additional user-defined calibrations can be programmed
and used under the bulk sample mode. In the thin film
mode, the XLi can be used to analyze thin samples (dust
wipes) and other filter media (PMi0 and PM2 5) for
airborne and risk assessment purposes.
39
-------
Figure 6-1. Niton XLi 700 Series analyzer set
up for-ex-situ analysis.
XRF analyses using the XLi can fully comply 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 XLi are presented in Table
6-1.
The XLi can be shipped via regular ground or air
transportation. The packages used to ship do not
need to be labeled as radioactive materials because
the isotope sources are contained in a shielded and
safe-locked unit.
Niton has no formal published standard operating
procedures for the XLi 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 system, and allow it
to warm up for 15 minutes.
2) Ensure the date and time is correct.
3) Run the detector calibration program that ensures the
electronics are stable and that the resolution of the
detector is appropriate (less than 225 electron volts
[eV] for the XLi).
4) 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.
5) Download and delete data after 3,000 readings have
been taken.
6.2 Instrument Operations during the
Demonstration
The instrument shipped to the demonstration site was a
standard XLi with 109Cd, 55Fe, and 241Am sources. The
instrument was packed in a Pelican case that was 8
inches tall by 20 inches wide and 16 inches deep. The
Pelican case was overpacked in a standard cardboard box
with additional packing. 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 XLi was used in the
ex situ, bulk analysis mode. Instrument setup 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 analyzer setup 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.
40
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Table 6-1. Niton XLi XRF Analyzer Technical Specifications
Weight:
Dimensions:
Excitation Source:
Detector:
Signal Processing:
Element Range:
Batteries:
Display:
Testing Modes:
Data Storage:
Standard Accessories:
1.7 pounds (0.8 kg)
Hand-held, approximately 1 1.5 x 3.5 x 3.0 inches (292 x 89 x 76 mm).
Primary: 241Am maximum 30mCi (1,110 MBq) — Infiniton, or 109Cd
maximum 40mCi (1,480 MBq).
Secondary: 241Am maximum 14mCi (520 MBq) or 55Fe maximum 20mCi (740
MBq).
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 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
hours (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-mm filter mode.
Internal: 3,000 readings with x-ray spectra (maximum).
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.
1 10/220 V AC battery charger/adapter.
PC interface cable.
NOT (Niton Data Transfer) PC software.
Safety lanyard.
Check/verification standards.
Integrated bar code scan engine/virtual keypad for rapid and reliable entry of
sample information.
41
-------
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 XLi's
calibration. 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 XLi
software allows for empirical calibrations and
corrections for any of the 25 elements. However, no
empirical calibration 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 XLi 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 XLi.
Before initiating sample processing, each sample set
was arranged in numerical order. Custody seals were
broken, and the soil samples placed in standard 32-
mm 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. Prepared samples were
placed in a queue and analyzed in order (Figure 6-3).
To initiate an analysis, the next sample in the queue
was placed in the environmental sample holder and
the drawer was closed. The sample analysis was
started from the laptop computer that was directly
connected to the analyzer. A total of 180 seconds (60
seconds for the 109Cd source, 60 seconds for the
241 Am source, and 60 seconds for the 55Fe source)
was selected as an appropriate analysis time to
simulate the duration a typical customer might
choose under normal field conditions. The Niton
software automatically sets the actual real time
needed to achieve 60 seconds of analysis time based
on the age of the isotope source. For example, the
actual real time to achieve 60 "source seconds" of
analysis would be approximately 120 seconds if an
XRF with a 109Cd source that is 18 months old (equal
to the half-life of the 109Cd source). The 109Cd and
55Fe sources were approximately 26 months old. The
total actual real time to achieve 180 source seconds
of analyses for the XLi analyzer used at the
demonstration therefore equaled about 330 seconds
(5.5 minutes).
At the end of the test, the sample number recording
screen was viewed on the laptop computer, and then
the sample number was entered and the results saved.
The Niton data transfer (NDT) software has the
option to save the data to the laptop computer
simultaneously as the results are saved on the
instrument. The data were written to the computer
using a comma separated value (CSV) format.
Figure 6-2. Niton technician using a stainless
steel scoop to fill a sample cup.
42
-------
Figure 6-3. Instrument setup with samples
awaiting analysis.
6.3
General Demonstration Results
The Niton operator for the XLi 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
soil and sediment materials were placed in the sample
cups. Samples with iron results above 50,000 parts
per million (ppm) (5 percent) and samples with lead
results above 10,000 ppm (1 percent) were identified
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 soils calibration for elements
below approximately 1 percent. However, the
industrial bulk calibration is considered more
accurate than the standard soils calibration for most
elements at concentrations above 1 percent. Iron is a
common element in soils and is typically above
10,000 ppm in all soils; therefore, the standard soil
calibration range for iron extends to 50,000 ppm.
6.4
Contact Information
Additional information on Niton's XLi 700 Series
XRF analyzer is available from the following source:
Mr. Dave Mercuro
Niton Analyzers
900 Middlesex Turnpike, Building #8
Billerica, MA01821
Telephone: (800) 875-1578, Ext. 333
Fax: 978-670-7430
Email: dmercuro@niton.com
Internet: www.niton.com
43
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This page was left blank intentionally.
44
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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 XLi
in Microsoft Excel® spreadsheet format was delivered
to the 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 XLi data set was reviewed and evaluated in
accordance with the primary and secondary
objectives of the demonstration. The findings of the
evaluation for each objective are presented below.
7.1 Primary Objective 1 — Method Detection
Limits
Samples were selected to calculate MDLs for each
target element from the 12 potential MDL sample
blends, as described in Section 4.2.1. The evaluation
and selection of data for the MDL calculation also
addressed results reported as "not detected" by Niton.
For many of the MDL blend results, element
concentrations were below the statistical limits of
detection (LOD) calculated by the XLi'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.Niton.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 XLi1
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 XLi 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 XLi MDL
Antimony
XLi
MDL2
NC
NC
NC
94
NC
97
NC
NC
NC
NC
NC
NC
966
XLi
Cone.3
ND
ND
ND
270
ND
238
ND
ND
ND
ND
ND
ND
Ref. Lab
Cone4
17
ND
8
118
ND
62
ND
ND
ND
ND
ND
11
Copper
XLi
MDL2
NC
NC
1465
NC
NC
NC
NC
NC
NC
NC
NC
NC
1466
XLi
Cone.3
ND
ND
176
2793
ND
941
ND
1997
1728
ND
ND
ND
Ref. Lab
Cone. 4
47
49
160
1,243
31
747
50
1,986
1,514
36
94
69
Arsenic
XLi
MDL2
NC
22
NC
NC
NC
NC
NC
NC
NC
NC
NC
71
466
XLi
Cone.3
ND
47
358
7571
ND
659
ND
ND
ND
ND
ND
297
Ref. Lab
Cone.4
1.5
47
477
3,943
39
559
9
10
11
31
14
250
Lead
XLi
MDL2
NC
33
NC
NC
31
NC
NC
41
22
NC
15
NC
28
XLi
Cone.3
1066
80
3933
53514
72
4696
ND
52
66
ND
43
ND
Ref. Lab
Cone. 4
1,200
78
3,986
33,429
72
4,214
17
33
51
26
27
25
Cadmium
XLi
MDL2
NC
NC
NC
NC
NC
120
NC
NC
NC
NC
NC
NC
1206
XLi
Cone.3
ND
ND
ND
ND
ND
321
ND
ND
ND
ND
ND
ND
Ref. Lab
Cone.4
ND
1.9
12
91
0.96
263
ND
ND
ND
ND
ND
44
Mercury
XLi
MDL2
NC
NC
NC
NC
NC
NC
13s
NC
NC
NC
NC
31
226
XLi
Cone.3
ND
ND
ND
ND
ND
ND
30
ND
ND
ND
ND
38
Ref. Lab
Cone.4
ND
ND
0.83
15
0.14
1.8
56
0.24
ND
ND
ND
32
Chromium
XLi
MDL2
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
228s
2286
XLi
Cone.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
299
Ref. Lab
Cone.4
167
121
133
55
116
101
150
63
133
75
102
303
Nickel
XLi
MDL2
NC
NC
NC
NC
NC
NC
90s
NC
NC
NC
98s
153
114
XLi
Cone.3
ND
ND
ND
ND
ND
ND
191
ND
ND
ND
192
206
Ref. Lab
Cone.4
83
60
70
57
60
91
213
72
196
174
202
214
46
-------
Table 7-1. Evaluation of Sensitivity — Method Detection Limits for the Niton XLi1 (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 XLi MDL
Selenium
XLi
MDL2
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
14
146
XLi
Cone.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
26
Ref. Lab
Cone. 4
ND
ND
ND
ND
ND
15
ND
ND
ND
4.6
ND
22
Silver
XLi
MDL2
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
XLi
Cone.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Ref. Lab
Cone. 4
ND
0.93
14
144
ND
38
ND
ND
6.2
ND
ND
41
Vanadium
XLi
MDL2
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
XLi
Cone. 3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Ref. Lab
Cone.4
1.2
55
56
34
51
45
67
96
76
57
38
31
Zinc
XLi
MDL2
NC
80
NC
NC
NC
NC
71s
91s
85s
NC
78
NC
81
XLi
Cone.3
ND
210
780
7986
ND
2640
106
144
175
ND
142
2052
Ref. Lab
Cone.4
24
229
886
5,657
92
2,114
90
160
137
69
137
1,843
Notes:
1 Detection limits and concentrations are in milligrams per kilogram (mg/kg), or parts per million (ppm).
2 MDLs calculated from the 12 MDL sample blends for the Niton XLi in this technology demonstration (in bold typeface for emphasis).
3 This column lists the mean concentration reported for this MDL sample blend by the Niton XLi.
4 This column lists the mean concentration reported for this MDL sample 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.
6 This MDL is considered highly uncertain because of the limited number of sample blends from which MDLs could be calculated for this
element.
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." Blends with one or more ND result as reported by the XRF were not used
for calculating the MDL for this element.
Ref. Lab. Reference laboratory.
47
-------
The mean MDLs calculated for the XLi are compared
in Table 7-2 with the mean LODs reported by Niton
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 XLi varied in
comparison to Niton's LODs and the mean MDLs
calculated from EPA Method 6200 data. For
antimony and cadmium, the mean MDLs were
clearly higher than the LODs and available Method
6200 data. The mean MDLs for arsenic and copper
were also somewhat elevated relative to the
instrument LODs.
When compared with the results for all eight XRF
instruments that participated in the demonstration, the
Table 7-2. Comparison of XLi MDLs to XLi LODs, All-Instrument MDLs, and EPA Method 6200 Data1
XLi exhibited high relative mean MDLs for seven of
the 10 target elements for which MDLs could be
calculated. The only elements for which the XLi had
comparable or lower MDLs were lead, mercury, and
selenium. Relative to the other demonstration
instruments, the XLi also exhibited low detection
frequencies in the MDL blends, such that fewer
MDLs could be calculated. On this basis, the XLi
appears to be less sensitive than many of the other
XRF instruments that participated in the
demonstration. It is possible that the lower
sensitivity of the XLi may relate to its use of isotope
sources rather than the x-ray tube sources used by the
rest of the demonstration instruments.
Element
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Niton XLi
Mean MDLs2
966
466
1206
2286
1466
28
226
114
146
NC
NC
81
Niton XLi
Mean LODs3
49
35
43
261
108
24
25
151
22
247
297
73
All XRF
Instrument
Mean MDLs4
61
26
70
83
23
40
23
50
8
42
28
38
EPA Method 6200
Mean Detection Limits5
55 7
92
NR
376
171
78
NR
100 7
NR
NR
NR
89
Notes:
i
EPA
LOD
MDL
NC
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 as 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).
This MDL is considered highly uncertain because of the limited number of sample blends from which MDLs
could be calculated for this element.
Only one value reported.
U.S. Environmental Protection Agency.
Limit of detection.
Method detection limit.
Not calculated.
Not reported; no MDLs reported for this element.
48
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7.2 Primary Objective 2 — Accuracy and
Comparability
The number of demonstration sample blends that met
the criteria for evaluation of accuracy, as described in
Section 4.2.2, was low for some elements. Due
primarily to limited instrument sensitivity, as
described in Section 7.2.1, only between five and 20
blends were included in the evaluation for chromium,
nickel, silver, and vanadium. RPDs between the
mean concentrations obtained from the XLi and the
reference laboratory were calculated for each blend
that met the criteria. Table 7-3 presents the median
RPDs for each target element, along with the number
of RPD results used to calculate the median. These
statistics are provided for all demonstration samples
as well as for subpopulations grouped by medium
(soil versus sediment) and concentration level
(Levels 1 through 4, as documented in Table 3-1).
Additional summary statistics for the RPDs
(minimum, maximum, and mean) are provided in
Appendix E (Table E-l).
Accuracy was classified as follows for the target
elements based on the overall median RPDs:
• Very good (median RPD less than 10 percent):
selenium.
• Good (median RPD between 10 percent and 25
percent): arsenic, cadmium, chromium, copper,
iron, lead, nickel, and zinc.
• Fair (median RPD between 25 percent and 50
percent): none.
• Poor (median RPD greater than 50 percent):
antimony, mercury, silver, and vanadium.
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 generally right-
skewed or lognormal.) However, the classification of
the elements based on accuracy generally stayed the
same when the mean rather than the median RPD was
used for the evaluation, although the means were
slightly higher overall (Table E-l). Review of the
median RPDs with respect to media type (soil versus
sediment) did not reveal any consistent trends. In
some cases the soil RPDs were lower; while in other
cases the sediment RPDs were lower. With regard to
concentration range, the low numbers of samples
with reported concentrations in the Level 1 range
(due to the XLi's high detection limits) effected the
assessment of trends in accuracy. However, the
following observations were made:
• A high median RPD was observed in the Level 3
soil samples for arsenic (with concentrations
greater than 2,000 ppm). This RPD appeared to
be skewed high by the results for sample blends 7
through 9 from the Wickes Smelter site, which
contained high concentrations of other elements
(such as lead, zinc, and iron).
• 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 observed. 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. However, this
trend in mercury RPDs is somewhat uncertain
due to the low numbers of samples with reported
concentrations in the Level 1 concentration
range.
The highest overall median RPD for an element was
109 percent (for antimony). 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 evaluation of accuracy for antimony,
comparing the results from the XLi with the ERA-
certified values. As shown, this comparison indicates
far belter performance for antimony than does the
comparison to the reference laboratory results, with
median RPDs of less than 10 percent for all media
and concentration levels. Furthermore, these results
suggest that the XLi may measure antimony in soil
and sediment more accurately than the fixed-
laboratory reference methods.
As an additional comparison, Table 7-3 also presents
the overall average of the median RPDs for all eight
49
-------
XRF instruments. Complete summary statistics for
the RPDs across all eight XRF instruments are
included in Appendix E (Table E-l). Table 7-3
indicates that the median RPDs for the XLi were
equivalent to or below the all-instrument medians for
most of the target elements. Only antimony,
cadmium, mercury, silver, and vanadium displayed
higher median RPDs for the XLi as compared to the
average of all eight instruments that participated in
the demonstration.
In addition to calculating RPDs, the evaluation of
accuracy included preparing linear correlation plots
of XLi 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 XLi
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), iron, nickel, and selenium met
all three of these criteria. The correlation plot for
selenium is displayed in Figure 7-1 as an example of
the correlations obtained for these elements.
Figure 7-1. Linear correlation plot for NITON XLi
showing high correlation for selenium
600 -r
500
400
300
200
100
Niton XLi
45 Degrees
Linear (Niton XLi)
50 100 150 200 250 300 350
Reference Laboratory (ppm)
400 450
500
50
-------
Table 7-3. Evaluation of Accuracy — Relative Percent Differences versus Reference Laboratory Data for the Niton XLi
Sample
Matrix Group Statistic
Soil Level 1 Number
Median
Level 2 Number
Median
Level 3 Number
Median
Level 4 Number
Median
All Soil Number
Median
Sediment Level 1 Number
Median
Level 2 Number
Median
Level 3 Number
Median
Level 4 Number
Median
All Sediment Number
Median
All
Samples Niton XLi Number
Median
All
Samples All XRF Number
Instruments Median
Antimony
RefLab
9
105.8%
5
117.3%
4
103.6%
-
--
18
107.5%
2
137.7%
4
127.1%
3
94.6%
--
-
9
111.7%
27
109.0%
206
84.3%
ERA
Spike
—
--
1
6.2%
3
5.4%
-
--
4
5.8%
2
7.8%
4
9.2%
3
2.7%
--
-
9
4.2%
13
5.4%
110
70.6%
Arsenic
7
22.9%
4
21.1%
4
55.7%
-
--
15
25.8%
9
8.3%
4
12.3%
2
16.6%
--
-
15
8.8%
30
15.9%
320
26.2%
Cadmium
4
18.9%
7
19.8%
2
22.3%
-
--
13
19.8%
2
26.1%
4
18.2%
3
21.2%
--
-
9
20.3%
22
19.9%
209
16.7%
Chromium
1
24. 1%
4
9.0%
2
35.8%
-
--
7
16.1%
0
NC
2
3.6%
3
20.2%
--
-
5
17.2%
12
16.6%
338
26.0%
Copper
4
30.0%
8
33.5%
2
18.9%
-
--
14
28.4%
3
20.5%
4
10.4%
10
5.1%
--
-
17
9.6%
31
13.2%
363
16.2%
Iron
5
4.2%
13
25.6%
13
4.7%
7
9.8%
38
11.1%
3
19.1%
19
22.0%
4
36.5%
6
19.1%
32
19.2%
70
17.8%
558
26.0%
Lead
10
25.2%
4
12.6%
8
12.2%
5
18.1%
27
17.8%
11
14.6%
4
5.5%
3
11.6%
--
-
18
10.7%
45
14.6%
392
21.5%
Mercury
3
35.0%
7
131.6%
2
136.9%
-
--
12
125.0%
2
29.3%
4
94.2%
3
103.4%
--
-
9
86.6%
21
103.4%
192
58.6%
Nickel
1
25.6%
4
13.0%
6
9.4%
-
--
11
11.8%
0
NC
5
12.9%
4
7.9%
--
-
9
9.2%
20
11.8%
403
25.4%
Selenium
3
13.4%
5
4.5%
4
5.5%
-
--
12
6.9%
5
15.7%
4
3.9%
3
5.6%
--
-
12
8.0%
24
6.9%
195
16.7%
Silver
0
NC
0
NC
3
23.7%
-
--
3
23.7%
0
NC
0
NC
2
83.4%
--
-
2
83.4%
5
54.9%
177
28.7%
Vanadium
0
NC
0
NC
2
47.1%
-
--
2
47.1%
0
NC
0
NC
3
64.1%
--
-
3
64.1%
5
54.1%
218
38.3%
Zinc
6
11.9%
6
16.1%
9
21.7%
-
--
21
12.7%
10
10.6%
5
5.8%
4
10.4%
--
-
19
9.8%
40
11.2%
471
19.4%
Notes:
All median RPDs presented in this table are based on the population of absolute values of the individual RPDs.
No samples reported by the reference laboratory in this concentration ranges.
ERA Environmental Resource Associates, Inc.
NC Not calculated.
Number Number of samples appropriate for accuracy evaluation.
RefLab Reference laboratory (Shealy Environmental Services, Inc.)
RPD Relative percent difference.
51
-------
Table 7-4. Summary of Correlation Evaluation for the Niton XLi
Notes:
Target
Element
Antimony
(Ref. Lab) 1
Antimony
(Cert. Val.) 1
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
m
2.93
0.96
1.94
1.35
0.70
1.08
1.15
1.65
0.20
0.99
0.97
0.24
2.66
1.39
b
46
-9
-200
-73
139
194
2589 2
-984
30
52
5
370
-367
-316
r2
0.92
1.0
0.94
0.98
0.92
0.85
0.95
0.94
0.98
0.96
0.98
0.90
0.74
0.95
Correlation
High
High
High
High
High
Moderate
High
High
High
High
High
High
Moderate
High
Bias
High
High
High
Low
..
—
High
Low
High
High3
High
m
9
r
For antimony, correlation was analyzed for the Niton XLi 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.
A high bias was indicated in the limited concentration range for which XLi results were available.
The regression line implies a potential low bias at lower concentrations, but no sample blends
were available for accuracy evaluation in that range (see Figure 7-2).
No bias observed.
Y-intercept of correlation line.
Slope of correlation line.
Correlation coefficient of correlation line.
52
-------
'—
<&
X
a
X
z
o
z
Figure 7-2. Linear correlation plot for NITON XLi
showing low correlation and variable bias for vanadium
1000 T-
900
800
700
600
500
400
300
200
100
0 -'
Niton XLi
45 Degrees
Linear (Niton XLi)
y=2.66x-366.85
R2 = 0.74
/ '
50 100 150 200 250 300
Reference Laboratory (ppm)
350
400
450
500
General 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 XLi data for arsenic,
lead, and zinc. However, further review of the
data indicated that removal of high outliers from
complex Blends 8 and 9 (Wickes Smelter slag)
improved the r2 values and reduced or eliminated
the positive bias for these elements.
• Mercury exhibited a high r2 value (0.98) but a
low bias (m = 0.2). Removing two extreme
Level 4 concentrations (Blends 21 and 22) from
the plots produced a much poorer correlation
coefficient (in the range of 0.79) without
improving the low bias.
• 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 greatly
diminished when the XLi results were compared
to the ERA-certified values. Comparison to the
ERA-certified values eliminated the high bias
and produced a better correlation (r2 = 1.00).
These findings agree with the RPD evaluation
above in showing better performance for
antimony by the XLi when ERA-certified spike
values are used to assess accuracy.
The regression lines suggested a very high bias
for silver and a bias for vanadium that changes
with concentration. However, these findings may
have been affected by the limited availability of
data in the various concentration ranges. Figure
7-2 shows the correlation plot for vanadium as an
example. As shown, the XLi results for
53
-------
vanadium exhibited a high bias, but the only data
available for the evaluation were from blends
with reference laboratory concentrations of 300
ppm and above. The lack of XLi results at lower
concentrations caused the linear regression line to
exhibit a low intercept and high slope, implying a
potential low bias at low concentrations.
In conclusion, the evaluations of accuracy showed an
acceptable overall level of performance by the XLi
for the target elements. Correlations with the
reference laboratory were generally high and, for
most elements, the median RPDs were better than the
average of all eight XRF instruments. Niton's proven
calibration and quantification algorithms for
environmental media may have contributed to the
high relative level of accuracy attained. However,
the low relative sensitivity of the XLi (that is, the
high relative MDLs) produced small data sets for
silver and vanadium and associated uncertainties in
the accuracy evaluation for these elements.
7.3 Primary Objective 3 — Precision
As described in Section 4.2.3, the precision of the
XLi was evaluated by calculating RSDs for the
replicate measurements from each sample blend.
Median RSDs for the various concentration levels
and media (soil and sediment), as well as for the
demonstration sample set as a whole, are presented in
Table 7-5. An expanded set of summary statistics for
the RSDs (including minimum, maximum, and mean)
is provided in Appendix E (Table E-2).
The RSD calculation revealed a high level of
precision for the XLi in that the overall median RSDs
were below 15 percent 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: iron, lead, and
zinc.
• RSD of 5 percent to 10 percent: antimony,
arsenic, cadmium, copper, mercury, nickel,
selenium, and vanadium.
• RSD of 10 percent to 20 percent: chromium and
silver.
• RSD of greater than 20 percent: none.
The median RSDs for the soil and sediment subsets
were also less than 15 percent with the exception of
silver in sediment (18.4 percent). The median RSDs
for sediment were slightly larger for some target
elements (chromium, lead, nickel, silver, vanadium,
and zinc) than the median RSDs for soil.
The high overall level of precision may have been
facilitated by the level of processing (homogenizing,
sieving, crushing, and drying) on the sample blends
before the demonstration (Chapter 3). This
observation is consistent with the previous SITE
MMT program demonstration of XRF technologies
that occurred in 1995 (EPA 1996a, 1996b, 1998a,
1998b, 1998c, and 1998d). The high level of sample
processing applied during both XRF technology
demonstrations was necessary to minimize the effects
of sample heterogeneity on the demonstration results
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 effect was observed for
multiple target elements in both soil and sediment,
but the effect was difficult to further assess due to the
limited numbers of samples available for some
elements and concentration levels. However, this
observation indicates that, to a minor extent,
analytical precision for the XLi may depend on
concentration.
As an additional comparison, Table 7-5 also presents
the overall average of the median RSDs for all XRF
instruments that participated in the demonstration.
Additional summary statistics for the RSDs across all
eight XRF instruments are included in Table E-2.
Table 7-5 indicates that the median RSDs for the XLi
were equivalent to or below the all-instrument
medians for eight of the 13 target elements. For the
54
-------
remaining elements (cadmium, chromium, mercury,
selenium, and silver), the median RSDs for the XLi
were only slightly above the all-instrument median
RSDs.
Table 7-6 presents median RSD statistics for the
reference laboratory and compares these to the
summary data for the XLi. (Additional summary
statistics are provided in Table E-3 of Appendix E.)
Table 7-6 indicates that the median RSDs for the XLi
were lower than the RSDs for the reference
laboratory for nine of the 13 target elements;
exceptions included chromium, mercury, silver, and
vanadium. Thus, the XLi exhibited slightly better
precision overall than the reference laboratory. In
comparison, the median RSDs for all XRF
instruments were equivalent to or lower than for the
reference laboratory for 11 of the 13 target elements
(the exceptions included chromium and vanadium).
7.4 Primary Objective 4 — Impact of
Chemical and Spectral Interferences
The RPD data from the accuracy evaluation were
further processed to assess the effects of
interferences. The RPD data for elements considered
susceptible to interferences were grouped and
compared based on the relative concentrations of
potentially interfering elements. Of specific interest
for the comparison were the potential effects of:
• High concentrations of lead on the RPDs for
arsenic
• High concentrations of nickel on the RPDs for
copper (and vice versa), 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.
Interferent-to-element ratios were calculated using
the mean concentrations the reference laboratory
reported for each blend, classified as low (less than
5X), moderate (5 to 10X), or high (greater than 10X).
Table 7-7 presents median RPD data for arsenic,
nickel, copper, and zinc that are grouped based on
this classification scheme. Additional summary
statistics are presented in Appendix E (Table E-4).
The tables confirm significant interference effects of
lead on arsenic. Specifically, as lead concentrations
increased to greater than 10 times the arsenic
concentration, the median RPD for arsenic increased
from 12.6 percent (well within the "good" range
defined in Section 7.2) to 48.3 percent (at the upper
end of the "fair" range). In contrast, high
concentrations of copper as a potential interferent do
not appear to affect the accuracy of the zinc
concentrations. The median RPD for zinc was
relatively unchanged between the low interferent-to-
element ratio (RPD =10.5 percent) and the high
interferent-to-element ratio (RPD = 11.9 percent).
Evaluation of the effects of copper on nickel, nickel
on copper, and zinc on copper also do not appear to
show significant effects; however, the low number of
samples prevents meaningful evaluation.
In presenting statistics for the raw RPDs as well as
the absolute values of the RPDs, Table E-4 further
shows that the interfering elements appeared to
produce an increasingly high bias in the arsenic data
(as indicated by lower raw RPDs). The
concentrations of copper, nickel, and zinc also
displayed a high bias, as indicated by negative raw
RPDs. The limited number of detected
concentrations for copper, nickel, and zinc when the
interferent concentration is moderate to high may be
the result of the low bias.
7.5 Primary Objective 5 — Effects of Soil
Characteristics
The population of RPDs between the results obtained
from the XLi and the reference laboratory was further
evaluated against sampling site and soil type.
Separate sets of summary statistics were developed
for the mean RPDs associated with each sampling
site for comparison to the other sites and to the data
set for all samples. The site-specific median RPDs
are presented in Table 7-8, along with descriptions of
soil or sediment type from observations during
sampling at each site. Complete RPD summary
statistics for each soil type (minimum, maximum, and
mean) are presented in Table E-5 of Appendix E
55
-------
Table 7-5. Evaluation of Precision — Relative Standard Deviations for the Niton XLi
Matrix
Soil
Sedime
nt
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 XLi
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
9
10.4%
5
6.8%
4
3.2%
—
—
18
7.8%
2
8.1%
4
10.4%
3
3.4%
—
—
9
6.2%
27
6.8%
206
6.1%
Arsenic
7
11.7%
4
6.4%
4
3.2%
—
—
15
6.4%
9
8.5%
4
6.2%
2
4.5%
—
—
15
7.2%
30
6.7%
320
8.2%
Cadmium
4
19.9%
7
6.8%
2
2.8%
—
—
13
8.0%
2
7.2%
4
7.3%
3
6.9%
—
—
9
7.1%
22
7.2%
209
3.6%
Chromium
1
27.6%
4
12.7%
2
4.9%
—
—
7
9.4%
0
NC
2
21.7%
3
14.6%
—
—
5
14.6%
12
14.1%
338
12.1%
Copper
4
9.7%
8
4.1%
2
3.0%
—
—
14
5.3%
3
6.5%
4
6.5%
10
4.6%
—
—
17
5.5%
31
5.5%
363
5.1%
Iron
5
4.2%
13
2.3%
13
1.9%
7
3.2%
38
2.4%
3
8.5%
19
2.4%
4
2.6%
6
1.8%
32
2.3%
70
2.4%
558
2.2%
Lead
10
13.4%
4
3.3%
8
2.3%
5
3.9%
27
3.9%
11
8.0%
4
3.7%
3
1.3%
—
—
18
6.1%
45
4.8%
392
4.9%
Mercury
3
14.6%
7
7.6%
2
3.7%
—
—
12
8.5%
2
19.4%
4
8.6%
3
4.3%
—
—
9
7.9%
21
7.9%
192
6.8%
Nickel
1
6.4%
4
9.6%
6
4.0%
—
—
11
5.9%
0
NC
5
12.4%
4
4.8%
—
—
9
9.1%
20
6.5%
403
7.0%
Selenium
3
15.3%
5
5.9%
4
2.5%
—
—
12
5.8%
5
7.6%
4
4.5%
3
1.9%
—
—
12
4.6%
24
5.8%
195
4.5%
Silver
0
NC
0
NC
3
10.2%
—
—
3
10.2%
0
NC
0
NC
2
18.4%
—
—
2
18.4%
5
13.8%
177
5.2%
Vanadium
0
NC
0
NC
2
4.5%
—
—
2
4.5%
0
NC
0
NC
3
14.3%
—
—
3
14.3%
5
8.6%
218
8.5%
Zinc
6
9.5%
6
2.6%
9
2.1%
—
—
21
2.7%
10
13.2%
5
3.5%
4
3.9%
—
—
19
5.8%
40
4.4%
471
5.3%
Notes:
Number
RSD
No samples reported by the reference laboratory in this concentration range.
Number of samples appropriate for precision evaluation.
Relative standard deviation
56
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Table 7-6. Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory versus the Niton XLi and All Demonstration
Instruments
Matrix
Soil
Sediment
All
Samples
All
Samples
All
Samples
Sample
Group
Ref. Lab
Ref. Lab
Ref. Lab
Niton
XLi
A11XRF
Instruments
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Antimony
17
9.8%
7
9.1%
24
9.5%
27
6.8%
206
6.1%
Arsenic
23
12.4%
24
9.2%
47
9.5%
30
6.7%
320
8.2%
Cadmium
15
9.0%
10
8.2%
25
9.0%
22
7.2%
209
3.6%
Chromium
34
10.6%
26
7.5%
60
8.4%
12
14.1%
338
12.1%
Copper
26
9.1%
21
8.9%
47
8.9%
31
5.5%
363
5.1%
Iron
38
8.7%
31
8.1%
69
8.5%
70
2.4%
558
2.2%
Lead
33
13.2%
22
7.4%
55
8.6%
45
4.8%
392
4.9%
Mercury
16
6.6%
10
6.9%
26
6.6%
21
7.9%
192
6.8%
Nickel
35
10.0%
27
7.3%
62
8.2%
20
6.5%
403
7.0%
Selenium
13
7.1%
12
7.6%
25
7.4%
24
5.8%
195
4.5%
Silver
13
7.5%
10
6.6%
23
7.1%
5
13.8%
177
5.2%
Vanadium
21
6.6%
17
8.1%
38
7.2%
5
8.6%
218
8.5%
Zinc
35
9.1%
27
6.9%
62
7.4%
40
4.4%
471
5.3%
57
-------
Table 7-7. Effects of Interferent Elements on the RPDs (Accuracy) for Other Target Elements for the Niton XLi1
Parameter
Interferent/
Element Ratio
Number of
Samples
Median RPD of
Target Element 2
Median Interferent
Concentration
Median Target
Element
Concentration
Lead Effects on Arsenic
<5 5-10 >10
23 6 1
12.6% 27.1% 48.3%
79 11510 24222
144 1635 3306
Copper Effects on Nickel3
<5 5-10 >10
17 1 2
9.2% 13.0% 13.0%
248 1960 5725
753 270 392
Nickel Effects on Copper3
<5 5-10 >10
30 0 1
12.7% NC 73.9%
306 NC 2443
1578 NC 182
Zinc Effects on Copper3
<5 5-10 >10
29 1 1
12.3% 98.9% 39.0%
201 13120 2287
1556 4315 218
Copper Effects on Zinc
<5 5-10 >10
32 2 6
10.5% 26.6% 11.9%
929 1434 2874
2247 179 168
Notes:
Concentrations are reported in units of milligrams per kilogram (rag/kg), or parts per million (ppm).
All median RPDs presented in this table are based on the population of absolute values of the individual RPDs.
Evaluation of interference effects for this element pair is hindered by the very low number of blends available at high interferent/element
Less than
ratios.
< Less than.
> Greater than.
RPD Relative percent difference.
58
-------
Table 7-8. Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Niton XLi1
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Soil
Sediment
Soil
Site
AS
BN
CN
KP
LV
RF
SB
TL
WS
All
Matrix
Description
Fine to medium sand (steel
processing)
Sandy loam, low organic (ore
residuals)
Sandy loam (burn pit residue)
Soil: Fine to medium quartz sand.
Sed.: Sandy loam, high organic.
(Gun and skeet ranges)
Clay/clay loam, salt crust (iron
and other precipitates)
Silty fine sand (tailings)
Coarse sand and gravel (ore and
waste rock)
Silt and clay (slag-enriched)
Coarse sand and gravel (roaster
slag)
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Antimony
—
—
4
116.8%
1
90.3%
2
8.3%
4
105.2%
3
94.6%
7
117.9%
3
144.9%
3
78.1%
27
109.0%
Arsenic
—
—
4
15.7%
1
25.8%
—
_
6
6.4%
10
14.1%
4
17.4%
—
~
5
48.3%
30
15.9%
Cadmium
2
24.6%
5
16.9%
2
18.7%
—
_
5
20.4%
4
22.7%
1
27.6%
2
14.2%
1
12.2%
22
19.9%
Chromium
—
—
2
2.1%
—
—
1
24.1%
4
2.2%
3
20.2%
1
28.4%
—
~
1
15.8%
12
16.6%
Copper
1
12.3%
4
22.5%
2
22.9%
2
20.7%
3
10.1%
8
12.4%
—
—
7
6.4%
4
59.7%
31
13.2%
Iron
3
14.8%
7
20.3%
o
3
25.2%
6
9.1%
12
26.1%
13
12.0%
12
4.5%
7
35.8%
7
27.5%
70
17.8%
Lead
3
11.4%
7
10.8%
o
5
42.5%
6
12.4%
4
30.4%
10
9.1%
1
35.5%
4
18.9%
7
18.1%
45
14.6%
59
-------
Table 7-8. Effect of Soil Type on RPDs (Accuracy) of Target Elements, Niton XLi (Continued)1
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Soil
Sediment
Soil
Site
AS
BN
CN
KP
LV
RF
SB
TL
WS
All
Matrix
Description
Fine to medium sand (steel
processing)
Sandy loam, low organic (ore
residuals)
Sandy loam (burn pit residue)
Soil: Fine to medium quartz sand.
Sed.: Sandy loam, high organic.
(Gun and skeet ranges)
Clay/clay loam, salt crust (iron
and other precipitates)
Silty fine sand (tailings)
Coarse sand and gravel (ore and
waste rock)
Silt and clay (slag-enriched)
Coarse sand and gravel (roaster
slag)
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Mercury
—
—
—
—
2
68.0%
—
_
4
78.6%
5
76.1%
8
136.0%
2
135.8%
—
—
21
103.4%
Nickel Selenium
1
11.8%
2
6.9%
1
29.0%
—
_
5
11.8%
6
9.5%
3
13.3%
—
~
2
10.9%
20
11.8%
1
1.5%
3
4.5%
2
16.1%
—
_
5
5.6%
5
12.0%
3
7.1%
4
11.5%
1
2.9%
24
6.9%
Silver
1
23.7%
1
89.5%
—
—
—
_
1
54.9%
1
111.9%
—
—
—
~
1
13.8%
5
54.9%
Vanadium
—
—
—
—
—
—
—
_
2
64.5%
1
30.5%
1
40.1%
—
~
1
54.1%
5
54.1%
Zinc
3
12.5%
5
21.7%
2
8.6%
—
_
4
15.4%
13
9.8%
2
6.6%
4
7.8%
7
24.2%
40
11.2%
Notes: AS Alton Steel Mill
BN Burlington Northern railroad/ASARCO East. Other Notes:
CN Naval Surface Warfare Center, Crane Division. J
KP KARS Park - Kennedy Space Center.
LV Leviathan Mine/Aspen Creek.
RF Ramsey Flats - Silver Bow Creek. Number
SB Sulphur Bank Mercury Mine. RPD
TL Torch Lake Superfund Site.
WS Wickes Smelter Site.
Evaluation of matrix effects for this element is hindered by the very low
number of blends available.
No samples reported by the reference laboratory in this concentration range
Number of demonstration samples evaluated.
Relative percent difference (absolute value).
60
-------
Another perspective on the effects of soil type was
developed by graphically assessing outliers and
extreme values in the RPD data sets for each target
element. This evaluation focused on correlating these
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
various elements on box and whisker plots in Figure
E-14.
Review of Table 7-8 indicates that the median RPDs
were highly variable and that trends or differences
between sample sites were difficult to discern.
Evaluations relative to sampling site were further
complicated by the low numbers of samples for many
target elements. (Table 7-8 indicates that only one to
three samples were available from many sampling
sites for evaluation of specific target elements.) The
only extremes were for arsenic and copper in blends
from the Wickes Smelter site. The median RPDs for
arsenic and copper in these blends was in the range of
50 percent as compared to a maximum of 26 percent
in the other blends. The soil matrix from this site was
described during the demonstration sample collection
program (Chapter 2) as roaster slag, consisting of a
black, fairly coarse sand and gravel material. This
slag is an intermediate product in processing ore,
wherein volatile sulfide materials are thermally
removed, leaving concentrated heavy elements. In
addition to arsenic, copper, and zinc, this matrix was
found to contain high concentrations of lead and iron.
Effects of the Wickes Smelter sample blends on XRF
data quality were noted earlier for arsenic, copper,
and other metals in the accuracy evaluation (Section
7.2).
Review of the box and whisker plot (Figure E-14) and
the correlation plots from the accuracy evaluation
revealed outliers and extreme values that were
distributed between four of the nine sampling sites.
Along with the Wickes Smelter blends, multiple
outliers were traceable to samples from the Torch
Lake, Leviathan Mine, and Crane Division sites.
However, the evaluation found that sample matrix
had a minor effect on the overall accuracy of the XRF
data given that the ranges of RPDs observed for the
target elements were very broad. The spread in the
accuracy results is illustrated on the box and whisker
plot in Figure E-14. The plot shows the broad
distributions of RPDs and illustrates that no high
outliers or extreme values were identified for
antimony, mercury, or silver. Although no specific
sampling sites were observed to cause the broad range
of RPDs for antimony or silver, further data review
indicated that the distribution of RPDs for mercury
was affected by a number of high RPDs observed for
blends from the Sulphur Bank mine site (Blends 19
through 26).
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 XLi
instrument operator was able to analyze all 326
demonstration samples in 4 days at the demonstration
site. Once the XLi instrument had been set up and
operations had been streamlined, the Niton instrument
operator was able to analyze a maximum of 92
samples during an extended work day. Without an
extended work day, it was estimated that the Niton
instrument operator would have averaged about 62
samples per day.
This estimated sample throughput for a normal
working day was similar to that observed for the other
instruments that participated in the demonstration
(average of 66 samples per day). However, this was a
significant achievement give 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 XLi is
included as part of the labor cost analysis in Section
8.3.
7.7 Primary Objective 7 — Technology Costs
The evaluations pertaining to this primary objective
are described in Chapter 8, Economic Analysis.
7.8 Secondary Objective 1 — Training
Requirements
Technology users must be suitably trained to set up
and operate the instrument to obtain the level of data
quality required for specific projects. The amount of
training required depends on the configuration and
complexity of the instrument, along with the
associated software.
61
-------
Niton recommends that the XLi operator have a high
school diploma and basic on-site operational training.
Field or laboratory technicians are generally qualified
to operate the XLi. Additional understanding of soil
chemical and physical properties would be valuable
for preparing site -specific calibrations and for
conducting specialty analyses. The operator of the
instrument during the demonstration had a B.S.
degree in chemistry and over 8 years of XRF
instrument experience. The skill level of this operator
was higher than is required to operate the XLi.
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 (SOPs) for the preparation or analysis of
soil or sediment samples using the XLi. 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 XLi holds up to three different radioisotope
sources. The following three sources were used
during the field demonstration: primary (109Cd) and
secondary (55Fe and 241Am). Each instrument is
equipped with a trigger locking mechanism and safety
measures designed into the hardware and software.
The developer reports that risks from exposure to
radiation are minimal; the radiation detected from
around the instrument during operation has been
recorded at 0.1 milliRem per hour.
62
-------
The second potential source of risk to XRF
instrument operators is exposure to reagent chemicals.
However, for the XLi, there are no risks from
reagents used in sample preparation because no
chemical reagents are required for sample
preparation.
7.10 Secondary Objective 3 — Portability
Portability depends on the size, weight, number of
components, and power requirements of the
instrument, and the reagents required. The size of the
instrument, including physical dimensions and
weight, is presented in Table 6-1. The number of
components, power requirements, support structures,
and reagent requirements are also listed in Table 6-1.
Two distinctions were made during the demonstration
regarding portability:
(1) The instrument was considered fully portable if
the dimensions were such that the instrument
could be easily brought directly to the sample
location by one person.
(2) The instrument was considered transportable if
the dimensions and power requirements were
such that the instrument could be moved to a
location near the sampling location, but required a
larger and more stable environment (for example,
a site trailer with AC power and stable
conditions).
Based on its dimensions and power requirements, the
XLi 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 XLi 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 XLi 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 XLi 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 shape of the XLi
was designed to fit within pipe portals and process
pipes. 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
XLi instrument. The warranty does not cover
batteries, radioisotope sources, or accessories. The
half-life of the Cd-109 source is about 18 months; the
half-life of the Fe-55 source is about 2.74 years; and
the half-life of the Am-241 source is about 432 years.
As such, the effective lifespan of the cadmium and
iron sources is less than 2 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 XLi 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.
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Chapter 8
Economic Analysis
This chapter provides cost information for the Niton
XLi 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 XLi.
8.1 Equipment Costs
Capital equipment costs include either purchase or
rental of the XLi and any ancillary equipment that is
generally needed for sample analysis. (See Chapter 6
for a description of available accessories.)
Information on purchase price and rental cost for the
analyzer and accessories was obtained from licensed
Niton distributors.
The XLi used at the demonstration costs
approximately $42,000, including the three
radioactive sources used; 109Cd, 55Fe, and 241Am. The
instrument with only the primary source (109Cd) costs
approximately $29,000. The base cost includes
peripherals such as the instrument stand, covers,
communication cables, and 110-volt adapter. A
laptop computer is also recommended to manipulate
the data but is not included in the base cost. The
instrument is available for rental by licensed Niton
distributors.
Purchased models include a 2-year warranty. The
half-life for the 109Cadium isotope is 18 months. As
the unit automatically adjusts for source decay, the
useful life of an isotope is based on the user's
throughput requirements. However, most find it
necessary to resource every 3-5 years. The half-life
for the 55Fe source is 2.74 years; and most find it
necessary to replace the x-ray source every 5-8 years.
The 241Am source would be expected to last
indefinitely because its half-life is 432.2 years.
The purchase price, rental cost, and shipping cost for
the XLi compare favorably with the average costs for
all XRF instruments that participated in the
demonstration, as shown in Table 8-1. Purchase of
the instrument could be justified as more cost
effective than rental only for field activities that
involve more than about 6 months of total field
analysis time.
Table 8-1. Equipment Costs
Cost Element
Shipping
Capital Cost
(Purchase)
Weekly Rental
Autosampler
(for Overnight
Analysis)
Niton XLi
$240
$42,000
$1,600
N/A
XRF
Demonstration
Average :
$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
8.2 Supply Costs
The supplies that were included in the cost estimate
include sample containers, Mylar® film, spatulas or
scoops, wipes, and disposable gloves. The rate of
consumption for these supplies was based on
observations during the field demonstration. Unit
prices for these supplies were based on price quotes
from independent vendors of field equipment.
The XLi was operated for 4 days to complete the
analysis of all 326 samples during the field
demonstration. 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.
65
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8.3
Labor Costs
therefore not a true total.
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 setup 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
The time to complete each activity using the XLi 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 XLi compared
favorably against the other XRF instruments,
exhibiting lower-than-average times for all activities
except for daily shutdown and startup. The field
observer noted that the sample analysis times
measured in the demonstration were lengthened by
the age of the radioactive sources. The observer
estimated that the older sources lengthened the
sample analysis time by about 2 minutes per sample.
Table 8-2. Time Required to Complete
Analytical Activities1
Activity
Initial Setup and
Calibration
Sample Preparation
Sample Analysis
Daily
Shutdown/Startup
End of Project
Packing
Total Processing
Time per Sample
Niton XLi
30
2.0
5.5
10
10
7.7
Average2
54
3.1
6.7
10
43
10.0
Notes:
1 All estimates are in minutes
2 Average for all eight XRF instruments in the
demonstration
66
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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
D Niton XLi ° 2°
| Range for all eight XRF instruments
40
60 80
Minutes
100
120
140
Figure 8-1. Comparison of activity times for the XLi versus other XRF instruments.
The Niton field team expended about 42 labor hours
to complete all sample processing activities during
the field demonstration using the XLi. This was
significantly 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 XLi include:
• Instrument run times (5.5 minutes) were
significantly less than many 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 XLi
allowed the operator to reduce the data for
completed sample batches on a laptop PC while
the instrument was processing a new batch.
Instrument run times and labor hours could have been
reduced if the radioactive sources used in the
instrument were new.
8.4 Comparison of XRF Analysis and
Reference Laboratory Costs
Two scenarios were evaluated to compare the cost for
XRF analysis using the XLi 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.
67
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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 XLi 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 fixed, based on the average
IDW disposal cost per instrument during the
demonstration, because IDW generation did not vary
significantly between instruments during the
demonstration. 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 XLi versus the
cost for analysis in a fixed laboratory. This
comparison shows that the XLi 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 XLi 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 XLi in the example scenario
(326 samples) was estimated at $6,390, whether one
or a number of elements was analyzed. This estimate
is less than 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 XLi, were included in the
calculation of the average cost for all XRF
instruments. In comparison to other hand-held XRF
instruments, the XLi cost for the example scenario
was similar.
Table 8-3. Comparison of XRF Technology and Reference Method Costs
Analytical Approach
Niton XLi (1 to 13 elements)
Shipping
Weekly Rental
Supplies
Labor
IDW
Total Niton XLi Analysis Cost (1 to 13 elements)
Fixed Laboratory (1 element)
(EPA Method 6010, ICP-AES)
Total Fixed Laboratory Costs (1 element)
Fixed Laboratory (13 elements)
Mercury (EPA Method 7471, CVAA)
All other Elements (EPA Method 6010, ICP-AES)
Total Fixed Laboratory Costs (13 elements)
Quantity
1
1
326
96
N/A
326
326
326
Item
Roundtrip
Week
Sample
Hours
N/A
Sample
Sample
Sample
Unit Rate
$240
$1,600
$0.75
$43.8
N/A
$21
$36
$160
Total
$240
$1,600
$245
$4,215
$90
$6,390
$6,846
$6,846
$11,736
$52,160
$63,896
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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 XLi XRF analyzer.
All primary and secondary objectives for the
performance evaluation were met.
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 the impacts
of heterogeneity on method precision and on the
comparability between XRF data and reference
laboratory data. In like manner, project teams are
encouraged to assess the effects of sampling
uncertainty on data quality and to adopt appropriate
sample preparation protocols before XRF is used for
large-scale data collection, particularly if the project
will involve comparisons to other methods (such as
off-site laboratories). An initial pilot-scale method
evaluation, carried out in cooperation with an
instrument vendor, can yield site-specific standard
operating procedures for sample preparation and
analysis to ensure that the XRF method will meet
data quality needs, such as accuracy and sensitivity
requirements. A pilot study can also help the project
team develop an initial understanding of the degree
of correlation between field and laboratory data. This
type of study is especially appropriate for sampling
programs that will involve complex soil or sediment
matrices with high concentrations of multiple
elements because the demonstration found that XRF
performance was more variable under these
conditions. Initial pilot studies can also be used to
develop site-specific calibrations, in accordance with
EPA Method 6200, that adjust instrument algorithms
to compensate for matrix effects.
The findings of the evaluation of the XLi for each
primary and secondary objective are summarized in
Tables 9-1 and 9-2. The XLi and the average
performance of all eight instruments that participated
in the XRF technology demonstration are compared
in Figure 9-1. The comparison in Figure 9-1
indicates that, when compared with the mean
performance of all eight XRF instruments, the XLi
showed:
• Equivalent or better MDLs for two elements,
including lead and mercury. (Iron was not
included in the MDL evaluation.)
• Equivalent or better accuracy (lower RPDs) for
nine of the 13 target elements. (Exceptions
include antimony, mercury, silver, and
vanadium.). 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 (lower RSDs) for
eight of the 13 target elements. (Exceptions
include cadmium, chromium, mercury, selenium,
and silver.)
The XLi is fully portable and can be operated in the
hand-held mode at a sampling site. Although good
overall performance was observed for this
instrument, sensitivity was lower overall (that is,
MDLs were higher) than for other XRF analyzers in
the performance evaluation, all of which used x-ray
tube sources rather than the radioisotope sources used
by the XLi. The low sensitivity of the instrument
resulted in small data sets for some target elements,
creating uncertainty in the findings for some primary
objectives.
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Table 9-1. Summary of Niton XLi Performance - Primary Objectives
Objective
Performance Summary
PI: Method
Detection Limits
A lack of detections in the MDL sample blends precluded the calculation of MDLs for
silver and vanadium. The low number of detections in the MDL blends produced
limited data for the other target elements as well, increasing the uncertainty associated
with the MDL evaluation.
Mean MDLs for the target elements ranged as follows:
o MDLs of 1 to 20 ppm: selenium.
o MDLs of 20 to 50 ppm: arsenic, lead, and mercury.
o MDLs of 50 to 100 ppm: antimony and zinc.
o MDLs of greater than 100 ppm: cadmium, chromium, copper, and nickel.
(Iron was not included in the MDL evaluation.)
The MDLs calculated for the XLi were generally lower than reference MDL data from
EPA Method 6200. Exceptions included antimony and cadmium, where higher MDLs
were observed with the XLi.
P2: Accuracy
and
Comparability
Median RPDs relative to reference laboratory data revealed the following, with lower
RPDs indicating greater accuracy:
o RPDs less than 10 percent: selenium.
o RPDs of 10 to 25 percent: arsenic, cadmium, chromium, copper, iron, lead,
nickel, and zinc.
o RPDs of 25 to 50 percent: none.
o RPDs of greater than 50 percent: antimony, mercury, silver, and vanadium.
Correlation plots relative to reference laboratory data indicated:
o High correlation coefficients (greater than 0.9) for 11 of the 13 target elements.
o Low to moderate correlation coefficients for copper and vanadium.
Furthermore, a moderate degree of correlation for mercury was artificially
improved by a few extreme concentrations.
o High biases in the XRF data versus the lab data for antimony, arsenic,
cadmium, lead, silver, vanadium, and zinc. For a number of these metals, the
high biases were largely created by extreme values associated with roaster slag
matrixes from the Wickes Smelter site. Low biases were observed for
chromium 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. RPDs for antimony were quite high when the XLi data was
compared to the reference laboratory data (median RPD of 109 percent), but improved
considerably when compared to certified spike values (median RPD of 5 percent).
Thus, the XLi appeared to be more accurate with respect to the true concentration of
antimony than the reference laboratory.
Significant uncertainty was introduced into the accuracy assessment for silver and
vanadium because the low sensitivity of the instrument limited the sample blends
available for evaluation.
P3: Precision
Median RSDs were good for all elements, as follows:
o RSDs less than 5 percent: iron, lead, and zinc.
o RSDs of 5 to 10 percent: antimony, arsenic, cadmium, copper, mercury,
nickel, selenium, and vanadium.
o RSDs of 10 to 20 percent: chromium and silver.
o RSDs greater than 20 percent: none.
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Table 9-1. Summary of Niton XLi Performance - Primary Objectives (continued)
Objective
Performance Summary
P3: Precision
(Continued)
RSDs were slightly higher (that is, precision was lower) in the lowest concentration
sample blends for many of the target elements, indicating a slight concentration
dependence for precision.
For nine of the 13 target elements, median RSDs for the XLi were lower than the
RSDs calculated for the reference laboratory data, indicating slightly better precision
for the XLi.
P4: Effects of
Sample
Interferences
High relative concentrations (greater than 10X) of lead as an interfering element
reduced accuracy for arsenic from "good" (median RPDs less than 25 percent) to
"fair" (median RPDs between 25 and 50 percent). Further, the high concentrations of
lead produced an increasingly low bias in arsenic results.
Interference effects associated with copper, nickel, and zinc could not be assessed in
detail because instrument sensitivity issues limited the number of sample blends
available for evaluation.
P5: Effects of Soil
Type
Low relative accuracy was observed for arsenic and copper in blends of roaster slag
from the Wickes Smelter site, which contained high overall element concentrations.
Multiple outliers were also traceable to samples from the Torch Lake, Leviathan
Mine, and Crane Division sites, and high-mercury blends from the Sulphur Bank
mine site increased the RPD range observed for mercury. Overall, however, sample
matrix had little observable effect on the accuracy of the XLi.
P6: Sample
Throughput
With an average sample preparation time of 2.0 minutes and an instrument analysis
time of 5.5 minutes per sample, the total processing time was 7.7 minutes per sample.
The instrument analysis time was lengthened by the use of old x-ray source materials,
which required long count times.
A maximum sample throughput of 92 samples per day was achieved during an
extended work day. A more typical sample throughput was estimated to be 62
samples per day for an 8-hour work day.
P7: Costs
Purchase cost is about $42,000 for the instrument as equipped in the demonstration
(with three radioactive sources). With one radioactive source, the purchase cost is
$29,000. Weekly rental cost for the instrument is $1,600. In addition to the
radioactive sources, this cost includes peripherals such as an instrument stand,
protective covers, communication cables, and 110 volt AC adapter.
Two of the radioactive sources available with the XLi have limited lifespans; the
109Cd source lasts 3 to 6 years and the 55Fe source lasts 5 to 10 years. Replacement
costs for these sources are $4000.
The Niton XLi instrument operator expended approximately 42 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 $6,390 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.
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Table 9-2. Summary of Niton XLi 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 XLi.
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 XLi has a trigger locking mechanism and other safety measures to minimize
exposure to the radioactive sources. Niton reports that risks from exposure to
radiation are minimal; the radiation detected from around the instrument during
operation has been recorded at 0.1 millirems 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 XLi 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 XLi can be used in a hands-free, bench-top
mode.
S4: Durability
Niton instruments have a 12-month limited warranty for parts and labor. The
warranty does not cover batteries, radioisotope sources, or accessories.
The XLi 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. The instrument can be connected to a PC or outfitted with wireless
communications for data transfer.
S5: Availability
Niton produces and sells more than 1,000 instruments a year through offices in the
U.S. and Germany.
Instruments, accessories, and supporting software are also available for purchase or
rental from Niton or from numerous distributors throughout the U.S.
72
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120%
100%
80
Comparison of Mean MDLs:
Niton XLi vs. All XRF Instruments
• NITON XLi Mean MDL
d All Instrument Mean MDL
Target Element
Comparison of Median RPDs:
Niton XLi vs. All XRF Instruments
NITON XLi Median RPD
All Instrument Median RPD
Target Element
Comparison of Median RSDs:
Niton XLi vs. All XRF Instruments
• NITON XLi Median RSD
DAM Instrument Median RSD
^
^
^ f ^ ^
*
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74
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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-MET® 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.
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APPENDIX A
VERIFICATION STATEMENT
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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: XLi 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: dmercuro@niton.com
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
XLi 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 XLi, during the field demonstration. These samples were derived from 70 different
blends and spiked blends of soil and sediment collected from nine sites across the U.S. The sample blends were
thoroughly dried, sieved, crushed, mixed, and characterized before they were used for the demonstration. Some
blends were also spiked to further adjust and refine the concentration ranges of the target elements. Between three
A-l
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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 XLi 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 XLi XRF Analyzer (EPA/540/R-06/003).
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 XLi is a small, field portable isotope-based XRF analyzer designed for chemical characterization of soils,
sediment, and other thick homogeneous samples (plastics and metals).. It can be outfitted with various isotope
options to best fit the environmental application needs of the customer. Niton offers the XLi with up to a 40
milliCurie (mCi) 109cadmium (Cd) source for standard elemental analyses of up to 15 elements. The instrument
used during the demonstration was equipped with a lOmCi source. Optional isotope sources that can be fitted into
the same XRF analyzer are the 14 mCi 241Americium (Am) source for heavy elements and the 20 mCi 55Iron (Fe)
source for light elements. Also available is a patented "Infiniton" 241Am source for general analysis of up to 25
elements in bulk samples.
Other features of the XLi include an integrated touch-screen display; completely sealed housing to protect the
analyzer from moisture and dust; lithium-ion batteries; 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). The instrument is factory-
calibrated to simultaneously analyze up to 25 elements, but is also capable of handling user-generated empirical
calibrations for specific 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 (lower MDLs
indicate higher sensitivity). The ranges into which the mean MDLs fell for the XLi are listed below. Silver and
vanadium were not detected by the XLi in the MDL blends and could not be evaluated.
Relative Sensitivity
High
Moderate
Low
Very Low
Mean MDL
1 - 20 ppm
20 - 50 ppm
50 - 100 ppm
> 100 ppm
Target Elements
Selenium.
Arsenic, Lead, and Mercury.
Antimony and Zinc.
Cadmium, Chromium, Copper, and Nickel.
Notes: ppm = Parts per million. Iron was not included in the MDL evaluation.
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Accuracy: Accuracy was evaluated based on the agreement of the XLi results with the reference laboratory data.
Accuracy was assessed by calculating the absolute relative percent difference (RPD) between the mean XRF and
the mean reference laboratory concentration for each blend. Accuracy of the XLi was classified from high to very
low for the various 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
Selenium.
Arsenic, Cadmium, Chromium, Copper, Iron,
Lead, Nickel, and Zinc.
None.
Antimony*, Mercury, Silver, and Vanadium.
* 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 High.
Accuracy was also assessed through correlation plots between the mean XLi and mean reference laboratory
concentrations for the various sample blends. Correlation coefficients (r2) for linear regression analysis of the
plots are summarized below, along with any significant biases apparent from the plots in the XRF data versus the
reference laboratory data.
Correlation
Bias
•K
>>
§
•§
0.92
High
1
<
0.94
High
s
a
1
•s
«
O
0.98
High
s
|
g
S
0.92
Low
e.
o
O
0.85
--
g
0.95
--
•e
OS
0.94
High
g
§
0.98
Low
^
z
0.96
--
'1
"3
CO
0.98
--
1
0.90
High
S
_g
•3
>•
0.74
High
CJ
0.95
High
Note: — = No significant bias. * Correlation is 1.0 with no observed bias when assessed versus sample spike concentrations.
Precision: Replicates were analyzed for all sample blends. Precision was evaluated by calculating the standard
deviation of the replicates, dividing by the average concentration of the replicates, and multiplying by 100 percent
to yield the relative standard deviation (RSD) for each blend. Precision of the XLi was classified from high to
very low for each target element, as indicated in the table below, based on the overall median RSDs. These results
indicated a higher level of precision in the XLi data than in the reference laboratory data for nine of the 13 target
elements.
Relative Precision
High
Moderate
Low
Very Low
Median RSD
0% - 5%
5% - 10%
10% - 20%
> 20%
Target Elements
Iron, Lead, and Zinc.
Antimony, Arsenic, Cadmium,
Vanadium.
Copper, Mercury, Nickel, Selenium, and
Chromium and Silver.
None.
Effects of Interferences: The RPDs from the evaluation of accuracy were further grouped and compared for a
few elements of concern (arsenic, nickel, copper, and zinc) based on the relative concentrations of potentially
interfering elements. Accuracy for arsenic was reduced from "moderate" (median RPDs less than 25 percent) to
"low" (median RPDs between 25 and 50 percent) by high relative concentrations of lead (greater than 10X the
arsenic concentration). Potential interference effects could not be assessed for copper, nickel, and zinc due to a
lack of detections reported by the XLi in the sample blends used for the interference evaluation.
Effects of Soil Characteristics: The RPDs from the evaluation of accuracy were also further evaluated in terms
of sampling site and soil type. This evaluation found high outlier RPD values, indicating low relative accuracy,
for arsenic and copper in blends of roaster slag from the Wickes Smelter site. These blends contained high overall
element concentrations. Overall, however, sample matrix had little observable effect on accuracy for the XRF
data.
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Sample Throughput: The total processing time per sample was estimated at 7.7 minutes, which included 2.0
minutes of sample preparation and 5.5 minutes of instrument analysis time. The instrument analysis time may
have been increased by the use of old radioisotope sources, which required longer count times. A sample
throughput of 53 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 for the XLi identified a purchase cost of $42,000 and a weekly rental cost of $1,600,
plus $240 shipping, as equipped for the demonstration. A total cost of $6,390 (with a labor cost of $4,215 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 XLi. 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: The XLi has a trigger locking mechanism to manually control source operation and
analysis. With this and other safety measures, Niton reports that risk from exposure to radiation is minimal
(approximately 0.1 millirems per hour).
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: Niton offers a 2-year warranty that does not cover batteries, radioisotope sources, or accessories. The
half-life for the 109Cadmium isotope is 18 months. As the unit automatically adjusts for source decay, the useful
life is of an isotope is based on the user's throughput requirements. However, most find it necessary to replace the
ex-ray source every 3-5 years. The half-life for the 55 Fe source is 2.74 years; and most find it necessary to
resource every 5-8 years. The 241Am source would be expected to last indefinitely because its half-life is 432.2
years. The instrument is environmentally sealed in a durable, hard-tool plastic and metal case.
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 performance of the XLi relative to the average of all eight XRF instruments that participated in the
demonstration is shown below:
Sensitivity
Accuracy
Precision
Antimony
0
0
Same
Arsenic
0
•
•
Cadmium
0
Same
0
Chromium
0
•
0
Copper
0
•
Same
Iron
NC
•
Same
Lead
Same
Mercury
Same
0
0
Nickel
0
•
•
Selenium
Same
•
0
Silver
NC
0
0
Vanadium
NC
0
Same
Zinc
0
•
•
Key:
Better
Worse
NC
No MDL Calculated.
NOTICE: Verifications are based on an evaluation of technology performance under specific, predetermined
criteria and the appropriate quality assurance procedures. EPA makes no expressed or implied warranties as to the
performance of the technology and does not certify that a technology will always operate as verified. The end user
is solely responsible for complying with any and all applicable federal, state, and local requirements.
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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 cadmium and antimony. The method detection limits (MDL) for
cadmium and antimony were 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-elenient 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).
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The low occurrence of results affected by blank contamination indicates that the general quality of the
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.
C-7
-------
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
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
Lead
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
40
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
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-
J-
Comment
Code
i
j
j
j
j
j
j
j
j
j
j
j
i
j
j
j
j
j
j
j
j
j
j
j
i
j
j
j
j
j
ej
j
j
j
j,e
j
i
j
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-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
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
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
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-
Comment
Code
i
j
j
ej
j
j
j
j
ej
j
j,e
j
i
j
j
j,e
j
ej
j
j
j
j
j
j
i
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, Niton XLi 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-BA
KP-SO-10-BA
KP-SO-15-BA
KP-SO-18-BA
KP-SO-22-BA
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-01-BA
KP-SO-11-BA
KP-SO-17-BA
KP-SO-25-BA
KP-SO-28-BA
KP-SO-30-BA
KP-SO-32-BA
KP-SO-04-XX
KP-SO-16-XX
KP-SO-23-XX
KP-SO-26-XX
KP-SO-31-XX
KP-SO-08-BA
KP-SO-13-BA
KP-SO-19-BA
KP-SO-24-BA
KP-SO-29-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
8.1 J+
6.1 J+
6.3 J+
6.7 J+
8.3 J+
< LOD : 44.07
< LOD : 39.90
< LOD : 42.33
< LOD : 42.38
-------
Appendix D. Analytical Data Summary, Niton XLi 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-BA
KP-SO-10-BA
KP-SO-15-BA
KP-SO-18-BA
KP-SO-22-BA
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-01-BA
KP-SO-11-BA
KP-SO-17-BA
KP-SO-25-BA
KP-SO-28-BA
KP-SO-30-BA
KP-SO-32-BA
KP-SO-04-XX
KP-SO-16-XX
KP-SO-23-XX
KP-SO-26-XX
KP-SO-31-XX
KP-SO-08-BA
KP-SO-13-BA
KP-SO-19-BA
KP-SO-24-BA
KP-SO-29-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
0.059 U
0.028 U
0.029 U
0.016 U
0.027 U
-------
Appendix D. Analytical Data Summary, Niton XLi 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-BA
KP-SO-03-BA
KP-SO-05-BA
KP-SO-09-BA
KP-SO-21-BA
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-BA
WS-SO-08-BA
WS-SO-12-BA
WS-SO-17-BA
WS-SO-27-BA
WS-SO-30-BA
WS-SO-35-BA
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-01-BA
WS-SO-07-BA
WS-SO-14-BA
WS-SO-18-BA
WS-SO-23-BA
WS-SO-26-BA
WS-SO-34-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
410
360
410
420
370
340
318
361
371
345
1.3 U
1.3
1.3 UJ
1.3 UJ
1.3 UJ
1.2 J-
1.3 UJ
-------
Appendix D. Analytical Data Summary, Niton XLi 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-BA
KP-SO-03-BA
KP-SO-05-BA
KP-SO-09-BA
KP-SO-21-BA
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-BA
WS-SO-08-BA
WS-SO-12-BA
WS-SO-17-BA
WS-SO-27-BA
WS-SO-30-BA
WS-SO-35-BA
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-01-BA
WS-SO-07-BA
WS-SO-14-BA
WS-SO-18-BA
WS-SO-23-BA
WS-SO-26-BA
WS-SO-34-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
0.043 U
0.044 U
0.044 U
0.046 U
0.042 U
< LOD : 30.91
< LOD : 29.42
-------
Appendix D. Analytical Data Summary, Niton XLi 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-02-BA
WS-SO-10-BA
WS-SO-16-BA
WS-SO-29-BA
WS-SO-33-BA
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-03-BA
WS-SO-05-BA
WS-SO-11-BA
WS-SO-20-BA
WS-SO-22-BA
WS-SO-25-BA
WS-SO-31-BA
WS-SO-13-XX
WS-SO-19-XX
WS-SO-28-XX
WS-SO-32-XX
WS-SO-36-XX
WS-SO-13-BA
WS-SO-19-BA
WS-SO-28-BA
WS-SO-32-BA
WS-SO-36-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
41 J-
45 J-
48 J-
41 J-
45 J-
124
142
163
136
150
130 J-
110 J-
130 J-
120 J-
97 J-
120 J-
120 J-
252
266
258
229
267
294
321
200 J-
150 J-
120 J-
190 J-
120 J-
379
344
313
315
370
As
1900
2000
2300
1900
2000
3,303
3,047
3,397
3,486
3,298
4200
3900
4100
3900
3600
3800
4100
7,400
7,700
7,400
8,100
7,300
7,700
7,400
5800
5000
4200
5500
3800
11,000
11,500
11,000
11,400
10,800
Cd
47
50
56
47
50
-------
Appendix D. Analytical Data Summary, Niton XLi 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-02-BA
WS-SO-10-BA
WS-SO-16-BA
WS-SO-29-BA
WS-SO-33-BA
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-03-BA
WS-SO-05-BA
WS-SO-11-BA
WS-SO-20-BA
WS-SO-22-BA
WS-SO-25-BA
WS-SO-31-BA
WS-SO-13-XX
WS-SO-19-XX
WS-SO-28-XX
WS-SO-32-XX
WS-SO-36-XX
WS-SO-13-BA
WS-SO-19-BA
WS-SO-28-BA
WS-SO-32-BA
WS-SO-36-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
5.8 J
6.5
5.8
4.8
5.4
43
-------
Appendix D. Analytical Data Summary, Niton XLi 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-BA
BN-SO-10-BA
BN-SO-15-BA
BN-SO-18-BA
BN-SO-28-BA
BN-SO-31-BA
BN-SO-35-BA
BN-SO-02-XX
BN-SO-04-XX
BN-SO-17-XX
BN-SO-22-XX
BN-SO-27-XX
BN-SO-06-BA
BN-SO-09-BA
BN-SO-14-BA
BN-SO-20-BA
BN-SO-25-BA
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-02-BA
BN-SO-07-BA
BN-SO-11-BA
BN-SO-16-BA
BN-SO-23-BA
BN-SO-27-BA
BN-SO-33-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 U
1.5
1.3
1.4
< LOD : 50.82
< LOD : 43.42
< LOD : 42.04
< LOD: 44.01
-------
Appendix D. Analytical Data Summary, Niton XLi 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-BA
BN-SO-10-BA
BN-SO-15-BA
BN-SO-18-BA
BN-SO-28-BA
BN-SO-31-BA
BN-SO-35-BA
BN-SO-02-XX
BN-SO-04-XX
BN-SO-17-XX
BN-SO-22-XX
BN-SO-27-XX
BN-SO-06-BA
BN-SO-09-BA
BN-SO-14-BA
BN-SO-20-BA
BN-SO-25-BA
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-02-BA
BN-SO-07-BA
BN-SO-11-BA
BN-SO-16-BA
BN-SO-23-BA
BN-SO-27-BA
BN-SO-33-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
0.13
0.14
0.15
0.13
0.16
0.14
0.15
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
Sample ID
BN-SO-07-XX
BN-SO-16-XX
BN-SO-21-XX
BN-SO-25-XX
BN-SO-33-XX
BN-SO-03-BA
BN-SO-08-BA
BN-SO-13-BA
BN-SO-22-BA
BN-SO-30-BA
BN-SO-05-XX
BN-SO-19-XX
BN-SO-26-XX
BN-SO-29-XX
BN-SO-32-XX
BN-SO-05-BA
BN-SO-19-BA
BN-SO-26-BA
BN-SO-29-BA
BN-SO-32-BA
CN-SO-01-XX
CN-SO-04-XX
CN-SO-08-XX
CN-SO-10-XX
CN-SO-11-XX
CN-SO-02-BA
CN-SO-04-BA
CN-SO-05-BA
CN-SO-09-BA
CN-SO-11-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
110 J-
120 J-
150 J-
82 J-
100 J-
426
419
379
427
481
160 J-
150 J-
150 J-
150 J-
160 J-
625
609
676
608
706
13 J-
13 J-
15 J-
13 J-
17 J-
< LOD : 56.72
95
88
66
116
As
990 J+
1,100 J+
1,300 J+
700 J
1,100
1,163
1,271
1,151
1,186
1,086
1,600
1,600
1,700
1,600
1,600
1,909
2,105
2,148
2,000
2,333
13
11
15
13
16
< LOD : 77.21
< LOD : 77.79
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
Sample ID
BN-SO-07-XX
BN-SO-16-XX
BN-SO-21-XX
BN-SO-25-XX
BN-SO-33-XX
BN-SO-03-BA
BN-SO-08-BA
BN-SO-13-BA
BN-SO-22-BA
BN-SO-30-BA
BN-SO-05-XX
BN-SO-19-XX
BN-SO-26-XX
BN-SO-29-XX
BN-SO-32-XX
BN-SO-05-BA
BN-SO-19-BA
BN-SO-26-BA
BN-SO-29-BA
BN-SO-32-BA
CN-SO-01-XX
CN-SO-04-XX
CN-SO-08-XX
CN-SO-10-XX
CN-SO-11-XX
CN-SO-02-BA
CN-SO-04-BA
CN-SO-05-BA
CN-SO-09-BA
CN-SO-11-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
3.4
3.4
3.6
3.8
4
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
16
16
16
16
16
16
16
16
16
16
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
Sample ID
AS-SO-02-XX
AS-SO-06-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-13-XX
AS-SO-02-BA
AS-SO-06-BA
AS-SO-10-BA
AS-SO-11-BA
AS-SO-13-BA
AS-SO-01-XX
AS-SO-04-XX
AS-SO-07-XX
AS-SO-09-XX
AS-SO-12-XX
AS-SO-01-BA
AS-SO-03-BA
AS-SO-05-BA
AS-SO-08-BA
AS-SO-09-BA
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-BA
SB-SO-06-BA
SB-SO-14-BA
SB-SO-38-BA
SB-SO-41-BA
SB-SO-47-BA
SB-SO-51-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
2.6 UJ
2.4 UJ
1.9 J-
3.7 J-
2.4 UJ
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
16
16
16
16
16
16
16
16
16
16
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
Sample ID
AS-SO-02-XX
AS-SO-06-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-13-XX
AS-SO-02-BA
AS-SO-06-BA
AS-SO-10-BA
AS-SO-11-BA
AS-SO-13-BA
AS-SO-01-XX
AS-SO-04-XX
AS-SO-07-XX
AS-SO-09-XX
AS-SO-12-XX
AS-SO-01-BA
AS-SO-03-BA
AS-SO-05-BA
AS-SO-08-BA
AS-SO-09-BA
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-BA
SB-SO-06-BA
SB-SO-14-BA
SB-SO-38-BA
SB-SO-41-BA
SB-SO-47-BA
SB-SO-51-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
0.76
0.74
0.78
0.72
0.79
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
19
19
19
19
19
19
19
19
19
19
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
Sample ID
SB-SO-05-XX
SB-SO-18-XX
SB-SO-30-XX
SB-SO-40-XX
SB-SO-53-XX
SB-SO-01-BA
SB-SO-10-BA
SB-SO-21-BA
SB-SO-31-BA
SB-SO-45-BA
SB-SO-08-XX
SB-SO-11-XX
SB-SO-21-XX
SB-SO-39-XX
SB-SO-42-XX
SB-SO-05-BA
SB-SO-16-BA
SB-SO-26-BA
SB-SO-35-BA
SB-SO-53-BA
SB-SO-22-XX
SB-SO-25-XX
SB-SO-27-XX
SB-SO-35-XX
SB-SO-44-XX
SB-SO-08-BA
SB-SO-19-BA
SB-SO-29-BA
SB-SO-40-BA
SB-SO-55-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
1.6 J-
1.2 UJ
3.2 J-
2.2 J-
1.2 UJ
< LOD : 52.07
< LOD : 48.04
< LOD : 49.98
< LOD : 46.26
< LOD : 49.59
5.4 J-
5.7 J-
4.9 J
4.7 J-
4.6 J-
< LOD : 56.08
101
< LOD : 52.86
< LOD : 55.75
< LOD : 53.79
10 J
6.8 J+
6.7 J+
6 J+
6.8 J+
86
88
101
95
62
As
9
10
7
9
10
< LOD: 23.51
< LOD : 23.77
< LOD: 24. 55
< LOD : 24.56
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
19
19
19
19
19
19
19
19
19
19
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
Sample ID
SB-SO-05-XX
SB-SO-18-XX
SB-SO-30-XX
SB-SO-40-XX
SB-SO-53-XX
SB-SO-01-BA
SB-SO-10-BA
SB-SO-21-BA
SB-SO-31-BA
SB-SO-45-BA
SB-SO-08-XX
SB-SO-11-XX
SB-SO-21-XX
SB-SO-39-XX
SB-SO-42-XX
SB-SO-05-BA
SB-SO-16-BA
SB-SO-26-BA
SB-SO-35-BA
SB-SO-53-BA
SB-SO-22-XX
SB-SO-25-XX
SB-SO-27-XX
SB-SO-35-XX
SB-SO-44-XX
SB-SO-08-BA
SB-SO-19-BA
SB-SO-29-BA
SB-SO-40-BA
SB-SO-55-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
540
280
290
280
270
82
86
87
90
81
730
810
740
790
740
221
232
219
262
245
3300
3000
3100
3100
3000
512
536
540
503
547
Ni
200
210
120
180
200
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
24
24
24
24
24
24
24
24
24
24
Sample ID
SB-SO-23-XX
SB-SO-28-XX
SB-SO-32-XX
SB-SO-43-XX
SB-SO-48-XX
SB-SO-23-BA
SB-SO-28-BA
SB-SO-32-BA
SB-SO-43-BA
SB-SO-48-BA
SB-SO-02-XX
SB-SO-07-XX
SB-SO-10-XX
SB-SO-26-XX
SB-SO-50-XX
SB-SO-09-BA
SB-SO-18-BA
SB-SO-30-BA
SB-SO-39-BA
SB-SO-44-BA
SB-SO-01-XX
SB-SO-16-XX
SB-SO-24-XX
SB-SO-45-XX
SB-SO-52-XX
SB-SO-07-BA
SB-SO-20-BA
SB-SO-27-BA
SB-SO-37-BA
SB-SO-49-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
48 J-
42 J-
46 J-
40 J-
39 J-
247
231
231
235
225
44 J-
45 J
62 J
61 J
57 J
288
240
227
279
271
180 J
170 J
180 J
180 J
150 J
602
693
680
682
645
As
37
36
40
35
36
48
38
49
67
45
23 J-
22
26
30
27
32
< LOD : 26.83
< LOD : 25.83
32
29
65
64
66
63
62
77
61
76
65
81
Cd
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
24
24
24
24
24
24
24
24
24
24
Sample ID
SB-SO-23-XX
SB-SO-28-XX
SB-SO-32-XX
SB-SO-43-XX
SB-SO-48-XX
SB-SO-23-BA
SB-SO-28-BA
SB-SO-32-BA
SB-SO-43-BA
SB-SO-48-BA
SB-SO-02-XX
SB-SO-07-XX
SB-SO-10-XX
SB-SO-26-XX
SB-SO-50-XX
SB-SO-09-BA
SB-SO-18-BA
SB-SO-30-BA
SB-SO-39-BA
SB-SO-44-BA
SB-SO-01-XX
SB-SO-16-XX
SB-SO-24-XX
SB-SO-45-XX
SB-SO-52-XX
SB-SO-07-BA
SB-SO-20-BA
SB-SO-27-BA
SB-SO-37-BA
SB-SO-49-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
8500
8800
8900
7600
8200
1,635
1,806
1,697
1,707
1,768
130 J+
270
220
260
200
54
38
45
46
40
400
480
420
450
430
80
67
71
60
74
Ni
26
26
28
24
25
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
25
25
25
25
25
25
25
25
25
25
26
26
26
26
26
26
26
26
26
26
27
27
27
27
27
27
27
27
27
27
Sample ID
SB-SO-13-XX
SB-SO-19-XX
SB-SO-33-XX
SB-SO-37-XX
SB-SO-55-XX
SB-SO-02-BA
SB-SO-11-BA
SB-SO-24-BA
SB-SO-33-BA
SB-SO-50-BA
SB-SO-12-XX
SB-SO-15-XX
SB-SO-17-XX
SB-SO-46-XX
SB-SO-54-XX
SB-SO-12-BA
SB-SO-15-BA
SB-SO-17-BA
SB-SO-46-BA
SB-SO-54-BA
KP-SE-08-XX
KP-SE-11-XX
KP-SE-17-XX
KP-SE-25-XX
KP-SE-30-XX
KP-SE-04-BA
KP-SE-12-BA
KP-SE-20-BA
KP-SE-27-BA
KP-SE-31-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
430 J
310 J
350 J
340 J
340 J
1,367
1,344
1,290
1,487
1,363
620 J
600 J-
800 J+
740 J+
280
2,168
1,966
2,103
2,056
2,028
6.2
5.6
4.9
6
5.7
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
25
25
25
25
25
25
25
25
25
25
26
26
26
26
26
26
26
26
26
26
27
27
27
27
27
27
27
27
27
27
Sample ID
SB-SO-13-XX
SB-SO-19-XX
SB-SO-33-XX
SB-SO-37-XX
SB-SO-55-XX
SB-SO-02-BA
SB-SO-11-BA
SB-SO-24-BA
SB-SO-33-BA
SB-SO-50-BA
SB-SO-12-XX
SB-SO-15-XX
SB-SO-17-XX
SB-SO-46-XX
SB-SO-54-XX
SB-SO-12-BA
SB-SO-15-BA
SB-SO-17-BA
SB-SO-46-BA
SB-SO-54-BA
KP-SE-08-XX
KP-SE-11-XX
KP-SE-17-XX
KP-SE-25-XX
KP-SE-30-XX
KP-SE-04-BA
KP-SE-12-BA
KP-SE-20-BA
KP-SE-27-BA
KP-SE-31-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
850
740
870
790
900
108
126
114
119
113
1,400
1,100
1,200
670
560
188
181
147
182
172
0.089 U
0.079 U
0.082 U
0.096 U
0.1 U
< LOD : 13.43
< LOD : 12.78
< LOD : 13.22
< LOD : 12.40
< LOD : 12.78
Ni
180
120
130
150
140
-------
Appendix D. Analytical Data Summary, Niton XLi 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-07-BA
KP-SE-14-BA
KP-SE-16-BA
KP-SE-23-BA
KP-SE-26-BA
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-BA
TL-SE-10-BA
TL-SE-12-BA
TL-SE-15-BA
TL-SE-20-BA
TL-SE-24-BA
TL-SE-26-BA
TL-SE-03-XX
TL-SE-19-XX
TL-SE-23-XX
TL-SE-25-XX
TL-SE-31-XX
TL-SE-03-BA
TL-SE-19-BA
TL-SE-23-BA
TL-SE-25-BA
TL-SE-31-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
3.2
3.1
11 J-
3
3.3
-------
Appendix D. Analytical Data Summary, Niton XLi 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-07-BA
KP-SE-14-BA
KP-SE-16-BA
KP-SE-23-BA
KP-SE-26-BA
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-BA
TL-SE-10-BA
TL-SE-12-BA
TL-SE-15-BA
TL-SE-20-BA
TL-SE-24-BA
TL-SE-26-BA
TL-SE-03-XX
TL-SE-19-XX
TL-SE-23-XX
TL-SE-25-XX
TL-SE-31-XX
TL-SE-03-BA
TL-SE-19-BA
TL-SE-23-BA
TL-SE-25-BA
TL-SE-31-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
0.053 U
0.06 U
0.065 U
0.044 U
0.056 U
< LOD : 14.27
< LOD : 14.07
-------
Appendix D. Analytical Data Summary, Niton XLi 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-05-BA
TL-SE-07-BA
TL-SE-13-BA
TL-SE-16-BA
TL-SE-21-BA
TL-SE-28-BA
TL-SE-30-BA
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-BA
LV-SE-10-BA
LV-SE-22-BA
LV-SE-25-BA
LV-SE-31-BA
LV-SE-35-BA
LV-SE-50-BA
LV-SE-12-XX
LV-SE-26-XX
LV-SE-33-XX
LV-SE-39-XX
LV-SE-42-XX
LV-SE-01-BA
LV-SE-06-BA
LV-SE-17-BA
LV-SE-37-BA
LV-SE-49-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
-------
Appendix D. Analytical Data Summary, Niton XLi 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-05-BA
TL-SE-07-BA
TL-SE-13-BA
TL-SE-16-BA
TL-SE-21-BA
TL-SE-28-BA
TL-SE-30-BA
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-BA
LV-SE-10-BA
LV-SE-22-BA
LV-SE-25-BA
LV-SE-31-BA
LV-SE-35-BA
LV-SE-50-BA
LV-SE-12-XX
LV-SE-26-XX
LV-SE-33-XX
LV-SE-39-XX
LV-SE-42-XX
LV-SE-01-BA
LV-SE-06-BA
LV-SE-17-BA
LV-SE-37-BA
LV-SE-49-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
0.074 U
0.021 U
0.08 U
0.025 U
0.082 U
0.02 U
0.076 U
< LOD : 24.30
< LOD : 24.34
29
< LOD : 23.79
< LOD: 23. 51
24
46
0.02 U
0.023 U
1.1
1
1
1.4
1.2
< LOD : 19.07
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
34
34
34
34
34
34
34
34
34
34
35
35
35
35
35
35
35
35
35
35
36
36
36
36
36
36
36
36
36
36
Sample ID
LV-SE-09-XX
LV-SE-19-XX
LV-SE-27-XX
LV-SE-36-XX
LV-SE-38-XX
LV-SE-03-BA
LV-SE-11-BA
LV-SE-24-BA
LV-SE-32-BA
LV-SE-42-BA
LV-SE-07-XX
LV-SE-18-XX
LV-SE-23-XX
LV-SE-45-XX
LV-SE-48-XX
LV-SE-07-BA
LV-SE-18-BA
LV-SE-23-BA
LV-SE-45-BA
LV-SE-48-BA
LV-SE-01-XX
LV-SE-14-XX
LV-SE-21-XX
LV-SE-24-XX
LV-SE-32-XX
LV-SE-05-BA
LV-SE-19-BA
LV-SE-27-BA
LV-SE-39-BA
LV-SE-51-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
6.7 U
6.7 U
6.7 U
6.7 U
6.7 U
< LOD : 60.54
< LOD : 52.64
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
34
34
34
34
34
34
34
34
34
34
35
35
35
35
35
35
35
35
35
35
36
36
36
36
36
36
36
36
36
36
Sample ID
LV-SE-09-XX
LV-SE-19-XX
LV-SE-27-XX
LV-SE-36-XX
LV-SE-38-XX
LV-SE-03-BA
LV-SE-11-BA
LV-SE-24-BA
LV-SE-32-BA
LV-SE-42-BA
LV-SE-07-XX
LV-SE-18-XX
LV-SE-23-XX
LV-SE-45-XX
LV-SE-48-XX
LV-SE-07-BA
LV-SE-18-BA
LV-SE-23-BA
LV-SE-45-BA
LV-SE-48-BA
LV-SE-01-XX
LV-SE-14-XX
LV-SE-21-XX
LV-SE-24-XX
LV-SE-32-XX
LV-SE-05-BA
LV-SE-19-BA
LV-SE-27-BA
LV-SE-39-BA
LV-SE-51-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
6
7.2
11
8.5
7.9
< LOD : 30.74
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
37
37
37
37
37
37
37
37
37
37
38
38
38
38
38
38
38
38
38
38
39
39
39
39
39
39
39
39
39
39
39
39
39
39
Sample ID
LV-SE-08-XX
LV-SE-16-XX
LV-SE-28-XX
LV-SE-30-XX
LV-SE-47-XX
LV-SE-08-BA
LV-SE-16-BA
LV-SE-28-BA
LV-SE-30-BA
LV-SE-47-BA
LV-SE-11-XX
LV-SE-29-XX
LV-SE-44-XX
LV-SE-46-XX
LV-SE-52-XX
LV-SE-04-BA
LV-SE-15-BA
LV-SE-20-BA
LV-SE-34-BA
LV-SE-43-BA
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-BA
RF-SE-12-BA
RF-SE-23-BA
RF-SE-36-BA
RF-SE-42-BA
RF-SE-45-BA
RF-SE-53-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
37
37
37
37
37
37
37
37
37
37
38
38
38
38
38
38
38
38
38
38
39
39
39
39
39
39
39
39
39
39
39
39
39
39
Sample ID
LV-SE-08-XX
LV-SE-16-XX
LV-SE-28-XX
LV-SE-30-XX
LV-SE-47-XX
LV-SE-08-BA
LV-SE-16-BA
LV-SE-28-BA
LV-SE-30-BA
LV-SE-47-BA
LV-SE-11-XX
LV-SE-29-XX
LV-SE-44-XX
LV-SE-46-XX
LV-SE-52-XX
LV-SE-04-BA
LV-SE-15-BA
LV-SE-20-BA
LV-SE-34-BA
LV-SE-43-BA
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-BA
RF-SE-12-BA
RF-SE-23-BA
RF-SE-36-BA
RF-SE-42-BA
RF-SE-45-BA
RF-SE-53-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
5.2
5.4
5.4
6.3
4.9
25
< LOD : 20.08
< LOD : 19.46
22
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
40
40
40
40
40
40
40
40
40
40
41
41
41
41
41
41
41
41
41
41
42
42
42
42
42
42
42
42
42
42
Sample ID
RF-SE-03-XX
RF-SE-28-XX
RF-SE-38-XX
RF-SE-49-XX
RF-SE-55-XX
RF-SE-08-BA
RF-SE-15-BA
RF-SE-32-BA
RF-SE-44-BA
RF-SE-51-BA
RF-SE-06-XX
RF-SE-13-XX
RF-SE-27-XX
RF-SE-31-XX
RF-SE-58-XX
RF-SE-02-BA
RF-SE-18-BA
RF-SE-22-BA
RF-SE-38-BA
RF-SE-48-BA
RF-SE-02-XX
RF-SE-22-XX
RF-SE-25-XX
RF-SE-30-XX
RF-SE-57-XX
RF-SE-09-BA
RF-SE-17-BA
RF-SE-28-BA
RF-SE-40-BA
RF-SE-50-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
< LOD : 47.78
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
40
40
40
40
40
40
40
40
40
40
41
41
41
41
41
41
41
41
41
41
42
42
42
42
42
42
42
42
42
42
Sample ID
RF-SE-03-XX
RF-SE-28-XX
RF-SE-38-XX
RF-SE-49-XX
RF-SE-55-XX
RF-SE-08-BA
RF-SE-15-BA
RF-SE-32-BA
RF-SE-44-BA
RF-SE-51-BA
RF-SE-06-XX
RF-SE-13-XX
RF-SE-27-XX
RF-SE-31-XX
RF-SE-58-XX
RF-SE-02-BA
RF-SE-18-BA
RF-SE-22-BA
RF-SE-38-BA
RF-SE-48-BA
RF-SE-02-XX
RF-SE-22-XX
RF-SE-25-XX
RF-SE-30-XX
RF-SE-57-XX
RF-SE-09-BA
RF-SE-17-BA
RF-SE-28-BA
RF-SE-40-BA
RF-SE-50-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
0.48
0.57
0.41
0.43
0.42
23
29
26
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
43
43
43
43
43
43
43
43
43
43
44
44
44
44
44
44
44
44
44
44
45
45
45
45
45
45
45
45
45
45
46
46
46
46
46
46
Sample ID
RF-SE-15-XX
RF-SE-24-XX
RF-SE-32-XX
RF-SE-43-XX
RF-SE-59-XX
RF-SE-03-BA
RF-SE-16-BA
RF-SE-27-BA
RF-SE-35-BA
RF-SE-54-BA
RF-SE-05-XX
RF-SE-26-XX
RF-SE-39-XX
RF-SE-44-XX
RF-SE-56-XX
RF-SE-01-BA
RF-SE-11-BA
RF-SE-20-BA
RF-SE-33-BA
RF-SE-59-BA
RF-SE-04-XX
RF-SE-14-XX
RF-SE-19-XX
RF-SE-34-XX
RF-SE-52-XX
RF-SE-04-BA
RF-SE-14-BA
RF-SE-19-BA
RF-SE-34-BA
RF-SE-52-BA
BN-SO-11-XX
BN-SO-14-XX
BN-SO-23-XX
BN-SO-04-BA
BN-SO-12-BA
BN-SO-24-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
43
43
43
43
43
43
43
43
43
43
44
44
44
44
44
44
44
44
44
44
45
45
45
45
45
45
45
45
45
45
46
46
46
46
46
46
Sample ID
RF-SE-15-XX
RF-SE-24-XX
RF-SE-32-XX
RF-SE-43-XX
RF-SE-59-XX
RF-SE-03-BA
RF-SE-16-BA
RF-SE-27-BA
RF-SE-35-BA
RF-SE-54-BA
RF-SE-05-XX
RF-SE-26-XX
RF-SE-39-XX
RF-SE-44-XX
RF-SE-56-XX
RF-SE-01-BA
RF-SE-11-BA
RF-SE-20-BA
RF-SE-33-BA
RF-SE-59-BA
RF-SE-04-XX
RF-SE-14-XX
RF-SE-19-XX
RF-SE-34-XX
RF-SE-52-XX
RF-SE-04-BA
RF-SE-14-BA
RF-SE-19-BA
RF-SE-34-BA
RF-SE-52-BA
BN-SO-11-XX
BN-SO-14-XX
BN-SO-23-XX
BN-SO-04-BA
BN-SO-12-BA
BN-SO-24-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
2.6
2.3
2.8
2.7
0.085 U
26
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
47
47
47
47
47
47
48
48
48
48
48
48
49
49
49
49
49
49
50
50
50
50
50
50
51
51
51
51
51
51
Sample ID
BN-SO-09-XX
BN-SO-12-XX
BN-SO-24-XX
BN-SO-17-BA
BN-SO-21-BA
BN-SO-34-BA
SB-SO-09-XX
SB-SO-20-XX
SB-SO-31-XX
SB-SO-13-BA
SB-SO-25-BA
SB-SO-56-BA
SB-SO-29-XX
SB-SO-36-XX
SB-SO-56-XX
SB-SO-04-BA
SB-SO-34-BA
SB-SO-42-BA
SB-SO-04-XX
SB-SO-34-XX
SB-SO-49-XX
SB-SO-22-BA
SB-SO-36-BA
SB-SO-52-BA
WS-SO-07-XX
WS-SO-11-XX
WS-SO-25-XX
WS-SO-04-BA
WS-SO-15-BA
WS-SO-37-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
750 J-
750 J-
810 J-
2,304
2,318
2,421
1.3 UJ
1.3 UJ
1.3 UJ
< LOD : 48.72
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
47
47
47
47
47
47
48
48
48
48
48
48
49
49
49
49
49
49
50
50
50
50
50
50
51
51
51
51
51
51
Sample ID
BN-SO-09-XX
BN-SO-12-XX
BN-SO-24-XX
BN-SO-17-BA
BN-SO-21-BA
BN-SO-34-BA
SB-SO-09-XX
SB-SO-20-XX
SB-SO-31-XX
SB-SO-13-BA
SB-SO-25-BA
SB-SO-56-BA
SB-SO-29-XX
SB-SO-36-XX
SB-SO-56-XX
SB-SO-04-BA
SB-SO-34-BA
SB-SO-42-BA
SB-SO-04-XX
SB-SO-34-XX
SB-SO-49-XX
SB-SO-22-BA
SB-SO-36-BA
SB-SO-52-BA
WS-SO-07-XX
WS-SO-11-XX
WS-SO-25-XX
WS-SO-04-BA
WS-SO-15-BA
WS-SO-37-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
0.39
0.34
0.37
< LOD : 22.96
< LOD : 22.66
< LOD : 23.34
30
10
32
27
< LOD: 20.55
29
7.9 J
36
9
24
36
< LOD : 20.20
40
36
36
30
30
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
52
52
52
52
52
52
53
53
53
53
53
53
54
54
54
54
54
54
55
55
55
55
55
55
56
56
56
56
56
56
Sample ID
WS-SO-10-XX
WS-SO-20-XX
WS-SO-23-XX
WS-SO-09-BA
WS-SO-21-BA
WS-SO-24-BA
AS-SO-03-XX
AS-SO-05-XX
AS-SO-08-XX
AS-SO-04-BA
AS-SO-07-BA
AS-SO-12-BA
LV-SO-03-XX
LV-SO-40-XX
LV-SO-49-XX
LV-SO-13-BA
LV-SO-26-BA
LV-SO-40-BA
LV-SO-04-XX
LV-SO-34-XX
LV-SO-37-XX
LV-SO-09-BA
LV-SO-21-BA
LV-SO-46-BA
CN-SO-03-XX
CN-SO-06-XX
CN-SO-07-XX
CN-SO-03-BA
CN-SO-06-BA
CN-SO-07-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
1.3 U
1.3 U
1.3 U
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
52
52
52
52
52
52
53
53
53
53
53
53
54
54
54
54
54
54
55
55
55
55
55
55
56
56
56
56
56
56
Sample ID
WS-SO-10-XX
WS-SO-20-XX
WS-SO-23-XX
WS-SO-09-BA
WS-SO-21-BA
WS-SO-24-BA
AS-SO-03-XX
AS-SO-05-XX
AS-SO-08-XX
AS-SO-04-BA
AS-SO-07-BA
AS-SO-12-BA
LV-SO-03-XX
LV-SO-40-XX
LV-SO-49-XX
LV-SO-13-BA
LV-SO-26-BA
LV-SO-40-BA
LV-SO-04-XX
LV-SO-34-XX
LV-SO-37-XX
LV-SO-09-BA
LV-SO-21-BA
LV-SO-46-BA
CN-SO-03-XX
CN-SO-06-XX
CN-SO-07-XX
CN-SO-03-BA
CN-SO-06-BA
CN-SO-07-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
0.058 U
0.06 U
0.05 U
< LOD : 20.62
< LOD : 20.76
< LOD : 19.94
3.7 J-
2.5 J-
2.5 J-
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
57
57
57
57
57
57
58
58
58
58
58
58
59
59
59
59
59
59
60
60
60
60
60
60
61
61
61
61
61
61
Sample ID
CN-SO-02-XX
CN-SO-05-XX
CN-SO-09-XX
CN-SO-01-BA
CN-SO-08-BA
CN-SO-10-BA
LV-SE-06-XX
LV-SE-13-XX
LV-SE-41-XX
LV-SE-12-BA
LV-SE-36-BA
LV-SE-52-BA
LV-SE-05-XX
LV-SE-20-XX
LV-SE-43-XX
LV-SE-14-BA
LV-SE-33-BA
LV-SE-38-BA
LV-SE-15-XX
LV-SE-17-XX
LV-SE-51-XX
LV-SE-29-BA
LV-SE-41-BA
LV-SE-44-BA
TL-SE-05-XX
TL-SE-09-XX
TL-SE-13-XX
TL-SE-01-BA
TL-SE-11-BA
TL-SE-29-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
230
130
120
386
441
443
30
31
30
138
150
145
92
140 J+
160 J+
537
411
436
290 J+
280 J+
210 J+
767
794
742
100 J+
100 J+
95 J+
602
613
545
As
19
6
6
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
57
57
57
57
57
57
58
58
58
58
58
58
59
59
59
59
59
59
60
60
60
60
60
60
61
61
61
61
61
61
Sample ID
CN-SO-02-XX
CN-SO-05-XX
CN-SO-09-XX
CN-SO-01-BA
CN-SO-08-BA
CN-SO-10-BA
LV-SE-06-XX
LV-SE-13-XX
LV-SE-41-XX
LV-SE-12-BA
LV-SE-36-BA
LV-SE-52-BA
LV-SE-05-XX
LV-SE-20-XX
LV-SE-43-XX
LV-SE-14-BA
LV-SE-33-BA
LV-SE-38-BA
LV-SE-15-XX
LV-SE-17-XX
LV-SE-51-XX
LV-SE-29-BA
LV-SE-41-BA
LV-SE-44-BA
TL-SE-05-XX
TL-SE-09-XX
TL-SE-13-XX
TL-SE-01-BA
TL-SE-11-BA
TL-SE-29-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
270 J-
280 J-
260 J-
81
92
93
610 J-
640 J-
610 J-
198
205
189
2.6 J-
2.8
2.8
29
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
62
62
62
62
62
62
63
63
63
63
63
63
64
64
64
64
64
64
65
65
65
65
65
65
65
65
65
65
65
65
65
65
Sample ID
TL-SE-06-XX
TL-SE-17-XX
TL-SE-28-XX
TL-SE-02-BA
TL-SE-08-BA
TL-SE-22-BA
TL-SE-07-XX
TL-SE-21-XX
TL-SE-30-XX
TL-SE-14-BA
TL-SE-18-BA
TL-SE-27-BA
TL-SE-02-XX
TL-SE-08-XX
TL-SE-16-XX
TL-SE-06-BA
TL-SE-09-BA
TL-SE-17-BA
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-05-BA
RF-SE-21-BA
RF-SE-25-BA
RF-SE-31-BA
RF-SE-41-BA
RF-SE-47-BA
RF-SE-57-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
1.2 U
1.2 U
1.2 U
< LOD : 64.70
< LOD : 63.48
< LOD : 60.89
30
33
31
204
214
170
77
66
73
522
485
484
12
10
11
11
13
11
8.9
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
62
62
62
62
62
62
63
63
63
63
63
63
64
64
64
64
64
64
65
65
65
65
65
65
65
65
65
65
65
65
65
65
Sample ID
TL-SE-06-XX
TL-SE-17-XX
TL-SE-28-XX
TL-SE-02-BA
TL-SE-08-BA
TL-SE-22-BA
TL-SE-07-XX
TL-SE-21-XX
TL-SE-30-XX
TL-SE-14-BA
TL-SE-18-BA
TL-SE-27-BA
TL-SE-02-XX
TL-SE-08-XX
TL-SE-16-XX
TL-SE-06-BA
TL-SE-09-BA
TL-SE-17-BA
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-05-BA
RF-SE-21-BA
RF-SE-25-BA
RF-SE-31-BA
RF-SE-41-BA
RF-SE-47-BA
RF-SE-57-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
2.2
2.6
2.8
< LOD : 22.02
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
66
66
66
66
66
66
67
67
67
67
67
67
68
68
68
68
68
68
69
69
69
69
69
69
70
70
70
70
70
70
Sample ID
RF-SE-08-XX
RF-SE-10-XX
RF-SE-33-XX
RF-SE-13-BA
RF-SE-29-BA
RF-SE-56-BA
RF-SE-16-XX
RF-SE-41-XX
RF-SE-48-XX
RF-SE-06-BA
RF-SE-26-BA
RF-SE-55-BA
RF-SE-18-XX
RF-SE-35-XX
RF-SE-54-XX
RF-SE-24-BA
RF-SE-39-BA
RF-SE-46-BA
RF-SE-20-XX
RF-SE-46-XX
RF-SE-51-XX
RF-SE-10-BA
RF-SE-37-BA
RF-SE-49-BA
RF-SE-21-XX
RF-SE-40-XX
RF-SE-47-XX
RF-SE-30-BA
RF-SE-43-BA
RF-SE-58-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Sb
14
12
13
61
-------
Appendix D. Analytical Data Summary, Niton XLi and Reference Laboratory (Continued)
Blend
No.
66
66
66
66
66
66
67
67
67
67
67
67
68
68
68
68
68
68
69
69
69
69
69
69
70
70
70
70
70
70
Sample ID
RF-SE-08-XX
RF-SE-10-XX
RF-SE-33-XX
RF-SE-13-BA
RF-SE-29-BA
RF-SE-56-BA
RF-SE-16-XX
RF-SE-41-XX
RF-SE-48-XX
RF-SE-06-BA
RF-SE-26-BA
RF-SE-55-BA
RF-SE-18-XX
RF-SE-35-XX
RF-SE-54-XX
RF-SE-24-BA
RF-SE-39-BA
RF-SE-46-BA
RF-SE-20-XX
RF-SE-46-XX
RF-SE-51-XX
RF-SE-10-BA
RF-SE-37-BA
RF-SE-49-BA
RF-SE-21-XX
RF-SE-40-XX
RF-SE-47-XX
RF-SE-30-BA
RF-SE-43-BA
RF-SE-58-BA
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Reference Laboratory
Reference Laboratory
Reference Laboratory
Niton LLC XLi
Niton LLC XLi
Niton LLC XLi
Hg
29
27
28
40
49
40
260
230
250
102
104
87
600
650
670
262
241
257
0.48
0.45
0.48
< LOD : 20.41
42
29
320
280
320
136
137
140
Ni
250
220
240
258
295
256
1,700 J-
1,900
2,000
1,764
1,756
1,753
390
350
420
431
341
414
1,400
650
1,200
1,295
1,187
1,316
220
250
250
234
295
290
Se
42
39
41
46
51
51
1.2 U
1.2 U
2.2
-------
APPENDIX E
STATISTICAL DATA SUMMARIES
-------
Figure E-l: Linear Correlation Plot for Antimony
3500
3000
2500
2000
1500
1000
500
y = 0.96x- 8.731
R2 = 1.00
^
• Niton XLi vs Reference Laboratory
A Niton XLi vs Certified Value
45 Degrees
Linear (Niton XLi vs Reference Laboratory)
• — Linear (Niton XLi vs Certified Value)
500
1000 1500 2000 2500
Reference Laboratoy or Certified Value (ppm)
3000
3500
Figure E-2: Linear Correlation Plot for Arsenic
12000 i
10000
I
X
3
X
§
8000
6000
4000
2000
Niton XLi
45 Degrees
Linear (Niton XLi)
X
X -N
y = 1.94x-200.44
R2 = 0.94
1000
2000 3000 4000
Reference Laboratory (ppm)
5000
6000
E-l
-------
Figure E-3: Linear Correlation Plot for Cadmium
4000 T
3500
3000
Niton XLi
45 Degrees
Linear (Niton XLi)
y = 1.35x-72.70
R2 = 0.98
2500
2000
, 1500
1000
500
x- •
0 -
500
1000 1500 2000
Reference Laboratory (ppm)
2500
3000
Figure E-4: Linear Correlation Plot for Chromium
3500
3000
2500
2000
1500
1000
500
Niton XLi
45 Degrees
Linear (Niton XLi)
0 -I-
0
500 1000 1500 2000 2500
Reference Laboratory (ppm)
y =0.70x + 138.68
R2 = 0.92
3000
3500
E-2
-------
Figure E-5: Linear Correlation Plot for Copper
7000
6000
5000
4000
X
a
3000
2000
1000
Niton XLi
45 Degrees
Linear (Niton XLi)
1000
2000 3000 4000
Reference Laboratory (ppm)
y = 1.08x +194.81
R2=0.85
5000
6000
250000 -,
200000
3
X
a 100000
50000
Figure E-6: Linear Correlation Plot for Iron
Niton XLi
45 Degrees
Linear (Niton XLi)
y = 1.15x + 2589.23
R2 = 0.95
0 20000 40000 60000 80000 100000 120000 140000 160000 180000 200000
Reference Laboratory (ppm)
E-3
-------
80000
p, 50000
e.
•—
•A
jxj 40000
X
e
o 30000
s
90000
10000
o
sooo
7000
6000 -
B.
*"" 5000 -
&
X
2 4000 -
r^
O
2000 -
0 -1
c
1
(
0
Figure E-7: Linear Correlation Plot for Lead
• Niton XLi
•
45De§rees y = 1.65x- 984.35
— — Linear (Niton XLi) R2=0.94
^
**
^
^^'
** •
0*
S- m
«•"•""
_— • •
) 5000 10000 15000 20000 25000 30000 35000 40000
Reference Laboratory (ppin)
Figure E-8: Linear Correlation Plot for Mercury
• Niton XLi |
^— ^— Linear (Niton XLi)
y = 0.20x+ 29.98
R2 = 0.98
— •
*+*v* — ~~~~~~
1000 2000 3000 4000 5000 6000 7000 8000 9000
Reference Laboratory (ppin)
E-4
-------
Figure E-9: Linear Correlation Plot for Nickel
3500 -,
3000
2500
2000
1500
o
Z
1000
500
0 -r
0
Niton XLi
45 Degrees
Linear (Niton XLi)
y =0.99x + 52.19
R2 = 0.96
500
1000 1500 2000 2500
Reference Laboratory (ppin)
3000
3500
700 -,
600 --
500
X 300
e
o
200
100
Figure E-10: Linear Correlation Plot for Selenium
Niton XLi
45 Degrees
Linear (Niton XLi)
y = 0.97x + 4.82
R2 = 0.98
0 50 100 150 200 250 300 350 400 450 500
Reference Laboratory (ppin)
E-5
-------
Figure E-ll: Linear Correlation Plot for Silver
500 -,
450
400
350
a 300
250
e 200
o
150
100
50
0 -
500
a 400 ^
300 -
200
100 -
0
Niton XLi
45 Degrees
Linear (Niton XLi)
0 50 100 150 200 250 300 350 400 450
Reference Laboratory (ppm)
Figure E-12: Linear Correlation Plot for Vanadium
1000 -!
900
800 -
700 -
Niton XLi
45 Degrees
Linear (Niton XLi)
0 50 100 150 200 250 300 350 400 450 500
Reference Laboratory (ppm)
E-6
-------
14000 T~-~~ —
1 9000
1 0000
/— \
C 8000
'—
X 6000 -
X
2 4000
9000
0 -
2000
Figure
• Niton XLi
45 Degrees
— — Linear (Niton XLi)
E-13: Linear Correlation Plot for Tine
•
y = 1.39x-
R2-0
^*f
^''
**><<*
•** • " •
^
1000 2000
3000 4000 5000 6000 7000 80
Reference Laboratory (ppm)
315. 9?|
95 |
00
E-7
-------
Box Plot for Relative Percent Difference (RPD)
Niton XLi
Median; Box: 25%-75%; Whisker: Non-Outlier Range
180%
O5
O
x
x -.
c -I
o K
.*;
z
0)
t
ra
tory
(CV)
NJ
O
x
= o
!3
"S o>
m
ues
Va
and the Referenc
and Certified Va
a
a.
a:
c
ra
0)
S
00
O
x
*.
O
x
-20%
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 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, Niton XLi Data Set.
E-8
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Niton XLi
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
4.0%
169.0%
92.4%
105.8%
5
90.3%
122.9%
113.0%
117.3%
4
96.5%
109.0%
103.2%
103.6%
—
~
—
~
—
18
4.0%
169.0%
100.5%
107.5%
ERA Spike
~
—
~
—
—
1
6.2%
6.2%
6.2%
6.2%
3
0.7%
6.3%
4.1%
5.4%
—
~
—
~
—
4
0.7%
6.3%
4.6%
5.8%
Arsenic
7
1.6%
29.0%
17.7%
22.9%
4
12.1%
28.5%
20.7%
21.1%
4
14.9%
78.5%
51.2%
55.7%
—
~
—
~
—
15
1.6%
78.5%
27.4%
25.8%
Cadmium
4
12.2%
34.8%
21.2%
18.9%
7
2.6%
37.5%
17.7%
19.8%
2
16.9%
27.6%
22.3%
22.3%
—
~
—
~
—
13
2.6%
37.5%
19.5%
19.8%
Chromium
1
24.1%
24.1%
24.1%
24.1%
4
1.5%
16.1%
8.9%
9.0%
2
28.4%
43.2%
35.8%
35.8%
—
~
—
~
—
7
1.5%
43.2%
18.7%
16.1%
Copper
4
5.8%
73.9%
34.9%
30.0%
8
6.8%
98.9%
42.1%
33.5%
2
12.3%
25.4%
18.9%
18.9%
—
~
—
~
—
14
5.8%
98.9%
36.7%
28.4%
Iron
5
0.2%
16.4%
6.4%
4.2%
13
5.6%
64.9%
28.4%
25.6%
13
0.4%
51.7%
11.7%
4.7%
7
0.2%
39.8%
15.1%
9.8%
38
0.2%
64.9%
17.4%
11.1%
Lead
10
1.3%
107.0%
28.7%
25.2%
4
2.9%
18.1%
11.6%
12.6%
8
0.7%
37.9%
13.5%
12.2%
5
8.3%
68.1%
31.7%
18.1%
27
0.7%
107.0%
22.2%
17.8%
Mercury
O
5
20.6%
55.2%
36.9%
35.0%
7
101.0%
150.9%
127.4%
131.6%
2
131.9%
141.8%
136.9%
136.9%
—
~
—
~
—
12
20.6%
150.9%
106.4%
125.0%
E-9
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Niton XLi
(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
1
25.6%
25.6%
25.6%
25.6%
4
7.6%
29.0%
15.7%
13.0%
6
1.0%
32.1%
12.0%
9.4%
~
~
~
~
—
11
1.0%
32.1%
14.6%
11.8%
Selenium
3
6.6%
21.2%
13.7%
13.4%
5
1.5%
18.8%
6.7%
4.5%
4
0.0%
21.4%
8.1%
5.5%
—
~
~
~
—
12
0.0%
21.4%
8.9%
6.9%
Silver
0
NC
NC
NC
NC
0
NC
NC
NC
NC
3
13.8%
89.5%
42.3%
23.7%
~
~
~
~
—
3
13.8%
89.5%
42.3%
23.7%
Vanadium
0
NC
NC
NC
NC
0
NC
NC
NC
NC
2
40.1%
54.1%
47.1%
47.1%
~
~
~
~
—
2
40.1%
54.1%
47.1%
47.1%
Zinc
6
2.7%
87.6%
22.5%
11.9%
6
5.3%
39.2%
18.0%
16.1%
9
6.6%
55.8%
23.4%
21.7%
~
~
~
~
—
21
2.7%
87.6%
21.6%
12.7%
E-10
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Niton XLi
(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
2
130.5%
144.9%
137.7%
137.7%
4
105.7%
149.4%
127.3%
127.1%
3
93.8%
98.8%
95.7%
94.6%
~
~
—
~
—
9
93.8%
149.4%
119.1%
111.7%
ERA Spike
2
4.1%
11.5%
7.8%
7.8%
4
2.6%
18.8%
9.9%
9.2%
3
0.1%
4.2%
2.3%
2.7%
~
~
—
~
—
9
0.1%
18.8%
6.9%
4.2%
Arsenic
9
0.2%
33.4%
12.4%
8.3%
4
1.2%
17.2%
10.8%
12.3%
2
8.8%
24.4%
16.6%
16.6%
~
~
—
~
—
15
0.2%
33.4%
12.5%
8.8%
Cadmium
2
13.6%
38.6%
26.1%
26.1%
4
14.8%
37.3%
22.2%
18.2%
3
15.8%
24.2%
20.4%
21.2%
~
~
—
~
—
9
13.6%
38.6%
22.4%
20.3%
Chromium
0
NC
NC
NC
NC
2
2.4%
4.8%
3.6%
3.6%
3
17.2%
23.3%
20.2%
20.2%
~
~
—
~
—
5
2.4%
23.3%
13.6%
17.2%
Copper
3
10.1%
25.8%
18.8%
20.5%
4
5.6%
14.2%
10.2%
10.4%
10
0.3%
16.2%
6.3%
5.1%
~
~
—
—
—
17
0.3%
25.8%
9.4%
9.6%
Iron
3
14.1%
27.6%
20.3%
19.1%
19
8.1%
77.5%
25.6%
22.0%
4
3.8%
66.5%
35.8%
36.5%
6
7.9%
23.3%
17.9%
19.1%
32
3.8%
77.5%
25.0%
19.2%
Lead
11
1.5%
47.7%
20.0%
14.6%
4
2.6%
9.2%
5.7%
5.5%
3
9.0%
27.2%
15.9%
11.6%
~
~
—
~
—
18
1.5%
47.7%
16.2%
10.7%
Mercury
2
16.5%
42.1%
29.3%
29.3%
4
76.1%
152.2%
104.2%
94.2%
3
86.6%
119.4%
103.1%
103.4%
~
~
—
~
—
9
16.5%
152.2%
87.2%
86.6%
E-ll
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Niton XLi
(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
0
NC
NC
NC
NC
5
2.2%
14.3%
9.3%
12.9%
4
6.0%
15.5%
9.3%
7.9%
~
—
~
~
—
9
2.2%
15.5%
9.3%
9.2%
Selenium
5
6.6%
25.9%
15.2%
15.7%
4
0.1%
16.5%
6.1%
3.9%
3
1.8%
12.0%
6.5%
5.6%
—
—
~
~
—
12
0.1%
25.9%
10.0%
8.0%
Silver
0
NC
NC
NC
NC
0
NC
NC
NC
NC
2
54.9%
111.9%
83.4%
83.4%
~
—
~
~
—
2
54.9%
111.9%
83.4%
83.4%
Vanadium
0
NC
NC
NC
NC
0
NC
NC
NC
NC
o
5
30.5%
64.9%
53.2%
64.1%
~
—
~
~
—
o
5
30.5%
64.9%
53.2%
64.1%
Zinc
10
1.9%
41.8%
15.1%
10.6%
5
0.2%
19.9%
7.1%
5.8%
4
6.9%
11.1%
9.7%
10.4%
~
—
~
~
—
19
0.2%
41.8%
11.9%
9.8%
E-12
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Niton XLi
(Continued)
Matrix
All
Samples
All
Samples
Cone
Range
Niton XLi
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
RefLab
27
4.0%
169.0%
106.7%
109.0%
206
0.1%
181.5%
80.6%
84.3%
ERA Spike
13
0.1%
18.8%
6.2%
5.4%
110
0.1%
162.0%
62.7%
70.6%
Arsenic
30
0.2%
78.5%
20.0%
15.9%
320
0.2%
182.8%
36.6%
26.2%
Cadmium
22
2.6%
38.6%
20.7%
19.9%
209
0.1%
168.1%
29.6%
16.7%
Chromium
12
1.5%
43.2%
16.6%
16.6%
338
0.1%
151.7%
30.8%
26.0%
Copper
31
0.3%
98.9%
21.7%
13.2%
363
0.2%
111.1%
24.6%
16.2%
Iron
70
0.2%
77.5%
20.8%
17.8%
558
0.0%
190.1%
35.4%
26.0%
Lead
45
0.7%
107.0%
19.8%
14.6%
392
0.1%
135.2%
30.9%
21.5%
Mercury
21
16.5%
152.2%
98.1%
103.4%
192
0.0%
158.1%
62.5%
58.6%
E-13
-------
Table E-l. Evaluation of Accuracy Relative Percent Differences Versus Reference Laboratory Data Calculated for the Niton XLi
(Continued)
Matrix
All
Samples
All
Samples
Cone
Range
Niton XLi
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
20
1.0%
32.1%
12.2%
11.8%
403
0.3%
146.5%
31.0%
25.4%
Selenium
24
0.0%
25.9%
9.5%
6.9%
195
0.0%
127.1%
32.0%
16.7%
Silver
5
13.8%
111.9%
58.8%
54.9%
177
0.0%
129.7%
36.0%
28.7%
Vanadium
5
30.5%
64.9%
50.7%
54.1%
218
0.1%
129.5%
42.2%
38.3%
Zinc
40
0.2%
87.6%
17.0%
11.2%
471
0.0%
138.0%
26.3%
19.4%
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 due to lack of XRF data.
Number Number of demonstration samples evaluated.
Ref 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 Niton XLi
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
3.5%
17.6%
10.7%
10.4%
5
5.3%
8.6%
6.8%
6.8%
4
1.7%
7.8%
4.0%
3.2%
~
~
—
~
—
18
1.7%
17.6%
8.1%
7.8%
Arsenic
7
5.8%
28.4%
13.6%
11.7%
4
5.7%
7.6%
6.5%
6.4%
4
0.6%
5.0%
3.0%
3.2%
~
~
—
~
—
15
0.6%
28.4%
8.9%
6.4%
Cadmium
4
11.9%
34.0%
21.4%
19.9%
7
2.1%
13.6%
7.1%
6.8%
2
1.3%
4.3%
2.8%
2.8%
~
~
—
~
—
13
1.3%
34.0%
10.9%
8.0%
Chromium
1
27.6%
27.6%
27.6%
27.6%
4
6.4%
21.4%
13.3%
12.7%
2
3.6%
6.2%
4.9%
4.9%
~
~
—
~
—
7
3.6%
27.6%
12.9%
9.4%
Copper
4
8.1%
15.3%
10.7%
9.7%
8
1.6%
14.2%
5.7%
4.1%
2
1.2%
4.8%
3.0%
3.0%
~
~
—
~
—
14
1.2%
15.3%
6.8%
5.3%
Iron
5
3.0%
8.0%
5.3%
4.2%
13
1.1%
11.2%
3.1%
2.3%
13
0.9%
8.9%
2.4%
1.9%
7
1.6%
10.9%
3.9%
3.2%
38
0.9%
11.2%
3.3%
2.4%
Lead
10
3.8%
23.8%
12.4%
13.4%
4
1.9%
4.9%
3.4%
3.3%
8
0.9%
3.1%
2.3%
2.3%
5
0.8%
7.4%
4.0%
3.9%
27
0.8%
23.8%
6.5%
3.9%
Mercury
3
11.6%
19.2%
15.1%
14.6%
7
4.4%
14.1%
8.5%
7.6%
2
3.6%
3.8%
3.7%
3.7%
~
~
—
~
—
12
3.6%
19.2%
9.3%
8.5%
E-15
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Niton XLi (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
1
6.4%
6.4%
6.4%
6.4%
4
6.7%
12.1%
9.5%
9.6%
6
1.4%
5.9%
3.9%
4.0%
~
~
~
~
—
11
1.4%
12.1%
6.2%
5.9%
Selenium
o
3
14.3%
17.3%
15.6%
15.3%
5
0.7%
6.3%
5.0%
5.9%
4
0.4%
3.7%
2.3%
2.5%
~
~
~
~
—
12
0.4%
17.3%
6.7%
5.8%
Silver
0
NC
NC
NC
NC
0
NC
NC
NC
NC
3
5.0%
14.2%
9.8%
10.2%
~
~
~
~
—
3
5.0%
14.2%
9.8%
10.2%
Vanadium
0
NC
NC
NC
NC
0
NC
NC
NC
NC
2
4.1%
4.8%
4.5%
4.5%
~
~
~
~
—
2
4.1%
4.8%
4.5%
4.5%
Zinc
6
6.2%
12.5%
9.5%
9.5%
6
1.5%
4.6%
3.0%
2.6%
9
0.6%
4.9%
2.3%
2.1%
~
~
~
~
—
21
0.6%
12.5%
4.5%
2.7%
E-16
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Niton XLi (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
2
4.3%
11.9%
8.1%
8.1%
4
4.5%
15.4%
10.1%
10.4%
3
1.3%
6.2%
3.6%
3.4%
~
~
—
~
—
9
1.3%
15.4%
7.5%
6.2%
Arsenic
9
4.4%
23.9%
10.3%
8.5%
4
3.4%
8.0%
5.9%
6.2%
2
2.4%
6.6%
4.5%
4.5%
~
~
—
~
—
15
2.4%
23.9%
8.3%
7.2%
Cadmium
2
6.1%
8.2%
7.2%
7.2%
4
1.7%
13.4%
7.4%
7.3%
3
1.1%
7.3%
5.1%
6.9%
~
~
—
~
—
9
1.1%
13.4%
6.6%
7.1%
Chromium
0
NC
NC
NC
NC
2
11.6%
31.8%
21.7%
21.7%
3
13.6%
16.5%
14.9%
14.6%
~
~
—
~
—
5
11.6%
31.8%
17.6%
14.6%
Copper
o
3
5.8%
21.1%
11.1%
6.5%
4
4.1%
7.4%
6.1%
6.5%
10
0.8%
6.9%
4.5%
4.6%
~
~
—
~
—
17
0.8%
21.1%
6.0%
5.5%
Iron
o
3
7.3%
19.8%
11.9%
8.5%
19
1.2%
4.2%
2.3%
2.4%
4
2.2%
4.7%
3.0%
2.6%
6
0.6%
2.4%
1.7%
1.8%
32
0.6%
19.8%
3.2%
2.3%
Lead
11
3.3%
25.5%
9.5%
8.0%
4
2.4%
5.4%
3.8%
3.7%
3
1.0%
1.7%
1.3%
1.3%
~
~
—
~
—
18
1.0%
25.5%
6.9%
6.1%
Mercury
2
12.4%
26.3%
19.4%
19.4%
4
1.4%
19.7%
9.6%
8.6%
3
4.0%
5.2%
4.5%
4.3%
~
~
—
~
—
9
1.4%
26.3%
10.1%
7.9%
E-17
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Niton XLi (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
0
NC
NC
NC
NC
5
8.3%
23.7%
15.8%
12.4%
4
0.3%
9.1%
4.7%
4.8%
-
~
~
~
—
9
0.3%
23.7%
10.9%
9.1%
Selenium
5
3.4%
17.1%
9.9%
7.6%
4
0.9%
10.5%
5.1%
4.5%
o
3
0.7%
2.7%
1.8%
1.9%
-
~
~
~
—
12
0.7%
17.1%
6.3%
4.6%
Silver
0
NC
NC
NC
NC
0
NC
NC
NC
NC
2
13.8%
23.0%
18.4%
18.4%
-
~
~
~
—
2
13.8%
23.0%
18.4%
18.4%
Vanadium
0
NC
NC
NC
NC
0
NC
NC
NC
NC
3
8.6%
25.1%
16.0%
14.3%
-
~
~
~
—
3
8.6%
25.1%
16.0%
14.3%
Zinc
10
5.3%
19.6%
12.9%
13.2%
5
1.2%
7.5%
3.9%
3.5%
4
2.8%
5.8%
4.1%
3.9%
-
~
~
~
—
19
1.2%
19.6%
8.7%
5.8%
E-18
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Niton XLi (Continued)
Matrix
All Samples
All Samples
Cone
Range
Niton XLi
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
27
1.3%
17.6%
7.9%
6.8%
206
0.5%
97.7%
8.9%
6.1%
Arsenic
30
0.6%
28.4%
8.6%
6.7%
320
0.2%
71.7%
11.2%
8.2%
Cadmium
22
1.1%
34.0%
9.1%
7.2%
209
0.4%
92.8%
8.2%
3.6%
Chromium
12
3.6%
31.8%
14.9%
14.1%
338
0.6%
116.3%
15.9%
12.1%
Copper
31
0.8%
21.1%
6.4%
5.5%
363
0.1%
58.3%
7.5%
5.1%
Iron
70
0.6%
19.8%
3.3%
2.4%
558
0.1%
101.8%
5.2%
2.2%
Lead
45
0.8%
25.5%
6.6%
4.8%
392
0.2%
115.6%
9.3%
4.9%
Mercury
21
1.4%
26.3%
9.6%
7.9%
192
1.0%
137.1%
14.3%
6.8%
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Niton XLi (Continued)
Matrix
All Samples
All Samples
Cone
Range
Niton XLi
All Instruments
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
20
0.3%
23.7%
8.3%
6.5%
403
0.3%
164.2%
10.8%
7.0%
Selenium
24
0.4%
17.3%
6.5%
5.8%
195
0.1%
98.8%
7.2%
4.5%
Silver
5
5.0%
23.0%
13.2%
13.8%
177
0.6%
125.3%
10.3%
5.2%
Vanadium
5
4.1%
25.1%
11.4%
8.6%
218
0.4%
86.1%
12.5%
8.5%
Zinc
40
0.6%
19.6%
6.5%
4.4%
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 due to 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
23
-33.4%
8.5%
-11.4%
-12.6%
0.2%
33.4%
14.2%
12.6%
ND
936
219
79
42
3288
402
144
5- 10
6
-78.5%
28.5%
-27.9%
-21.1%
12.1%
78.5%
37.4%
27.1%
3933
70720
25980
11510
358
11140
3833
1635
>10
1
-48.3%
-48.3%
-48.3%
-48.3%
48.3%
48.3%
48.3%
48.3%
24222
24222
24222
24222
3306
3306
3306
3306
Copper Effects on Nickel
<5
17
-32.1%
29.0%
-3.9%
-6.5%
1.0%
32.1%
12.1%
9.2%
182
1268
487
248
206
3032
1264
753
5-10
1
-13.0%
-13.0%
-13.0%
-13.0%
13.0%
13.0%
13.0%
13.0%
1960
1960
1960
1960
270
270
270
270
>10
2
-14.2%
-11.8%
-13.0%
-13.0%
11.8%
14.2%
13.0%
13.0%
5682
5767
5725
5725
308
476
392
392
Nickel Effects on Copper
<5
30
-98.9%
9.6%
-18.3%
-12.7%
0.3%
98.9%
20.0%
12.7%
ND
753
397
306
170
5767
1869
1578
5-10
0
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
NC
>10
1
-73.9%
-73.9%
-73.9%
-73.9%
73.9%
73.9%
73.9%
73.9%
2443
2443
2443
2443
182
182
182
182
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
29
-76.8%
9.6%
-16.7%
-12.3%
0.3%
76.8%
18.5%
12.3%
ND
8593
1475
201
170
5767
1784
1556
5- 10
1
-98.9%
-98.9%
-98.9%
-98.9%
98.9%
98.9%
98.9%
98.9%
13120
13120
13120
13120
4315
4315
4315
4315
>10
1
-39.0%
-39.0%
-39.0%
-39.0%
39.0%
39.0%
39.0%
39.0%
2287
2287
2287
2287
218
218
218
218
Copper Effects on Zinc
<5
32
-87.6%
12.7%
-13.6%
-10.0%
0.2%
87.6%
16.9%
10.5%
ND
4315
1214
929
118
13120
3015
2247
5-10
2
-41.8%
11.5%
-15.1%
-15.1%
11.5%
41.8%
26.6%
26.6%
1268
1599
1434
1434
173
185
179
179
>10
6
-41.0%
-2.0%
-14.0%
-11.9%
2.0%
41.0%
14.0%
11.9%
1960
5767
3545
2874
125
325
187
168
Notes:
1. Concentrations are reported in units of milligrams per kilogram (mg/kg), or parts per million (ppm).
2. Table presents statistics for unmodified RPDs as well as absolute value RPDs.
< Less than.
> Greater than.
RPD Relative percent difference.
NC Not calculated due to lack of XRF data.
ND Nondetect.
XRF X-ray fluorescence.
E-22
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Site
AS
BN
CN
KP
LV
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)
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
Reference Laboratory
RPD
..
~
~
~
—
4
-122.9%
-101.2%
-114.4%
-116.8%
1
-90.3%
-90.3%
-90.3%
-90.3%
2
-4.0%
12.7%
4.3%
4.3%
4
-130.5%
-96.5%
-109.4%
-105.2%
RPD ABS Val
..
~
~
~
—
4
101.2%
122.9%
114.4%
116.8%
1
90.3%
90.3%
90.3%
90.3%
2
4.0%
12.7%
8.3%
8.3%
4
96.5%
130.5%
109.4%
105.2%
Certified Value
RPD
..
~
~
~
—
1
6.3%
6.3%
6.3%
6.3%
1
6.2%
6.2%
6.2%
6.2%
..
~
~
4
-0.7%
8.1%
3.9%
4.1%
RPD ABS Val
..
~
~
~
—
1
6.3%
6.3%
6.3%
6.3%
1
6.2%
6.2%
6.2%
6.2%
..
~
~
4
0.7%
8.1%
4.3%
4.1%
Arsenic
Reference Laboratory
RPD
..
~
~
~
—
4
-25.8%
-12.1%
-17.3%
-15.7%
1
-25.8%
-25.8%
-25.8%
-25.8%
..
~
~
6
-33.4%
8.5%
-8.5%
-0.7%
RPD ABS Val
..
~
~
~
—
4
12.1%
25.8%
17.3%
15.7%
1
25.8%
25.8%
25.8%
25.8%
..
~
~
6
0.2%
33.4%
12.7%
6.4%
E-23
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Site
AS
BN
CN
KP
LV
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)
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
Cadmium
Reference Laboratory
RPD
2
-31.3%
17.9%
-6.7%
-6.7%
5
-19.9%
8.0%
-10.6%
-16.9%
2
-34.8%
2.6%
-16.1%
-16.1%
..
~
~
5
-38.6%
-15.8%
-26.5%
-20.4%
RPD ABS Val
2
17.9%
31.3%
24.6%
24.6%
5
4.5%
19.9%
13.8%
16.9%
2
2.6%
34.8%
18.7%
18.7%
..
~
~
5
15.8%
38.6%
26.5%
20.4%
Chromium
Reference Laboratory
RPD
..
~
~
~
—
2
16.1%
43.2%
29.6%
-1.5%
—
~
~
-
—
1
24.1%
24.1%
24.1%
24.1%
4
-2.4%
17.2%
2.8%
-1.8%
RPD ABS Val
..
~
~
~
—
2
16.1%
43.2%
29.6%
2.1%
—
~
~
~
—
1
24.1%
24.1%
24.1%
24.1%
4
1.5%
17.2%
5.8%
2.2%
Copper
Reference Laboratory
RPD RPD ABS Val
1
-12.3%
-12.3%
-12.3%
-12.3%
4
-31.4%
-21.0%
-24.3%
-22.5%
2
-39.0%
6.8%
-16.1%
-16.1%
2
-35.7%
5.8%
-15.0%
-15.0%
3
-73.9%
-3.0%
-29.0%
-10.1%
1
12.3%
12.3%
12.3%
12.3%
4
21.0%
31.4%
24.3%
22.5%
2
6.8%
39.0%
22.9%
22.9%
2
5.8%
35.7%
20.7%
20.7%
3
3.0%
73.9%
29.0%
10.1%
E-24
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Site
AS
BN
CN
KP
LV
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)
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
Iron
Reference Laboratory
RPD
3
-39.6%
0.2%
-18.1%
-14.8%
7
-33.4%
-5.6%
-19.2%
-20.3%
3
-42.9%
2.9%
-21.7%
-25.2%
6
-19.1%
0.2%
-9.1%
-9.1%
12
-64.9%
27.6%
-26.3%
-23.9%
RPD ABS Val
3
0.2%
39.6%
18.2%
14.8%
7
5.6%
33.4%
19.2%
20.3%
3
2.9%
42.9%
23.7%
25.2%
6
0.2%
19.1%
9.2%
9.1%
12
7.9%
64.9%
30.9%
26.1%
Lead
Reference Laboratory
RPD
3
-25.4%
2.9%
-11.3%
-11.4%
7
-27.4%
-0.7%
-10.7%
-10.8%
3
-42.5%
107.0%
25.9%
13.4%
6
-8.3%
18.0%
7.0%
12.4%
4
-37.9%
-25.0%
-30.9%
-30.4%
RPD ABS Val
3
2.9%
25.4%
13.2%
11.4%
7
0.7%
27.4%
10.7%
10.8%
3
13.4%
107.0%
54.3%
42.5%
6
7.2%
18.0%
12.1%
12.4%
4
25.0%
37.9%
30.9%
30.4%
Mercury
Reference Laboratory
RPD
..
~
~
~
—
..
~
~
~
—
2
35.0%
101.0%
68.0%
68.0%
..
~
~
4
20.6%
103.4%
70.3%
78.6%
RPD ABS Val
..
~
~
~
—
..
~
~
~
—
2
35.0%
101.0%
68.0%
68.0%
..
~
~
4
20.6%
103.4%
70.3%
78.6%
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
Sediment
Site
AS
BN
CN
KP
LV
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)
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
Reference Laboratory
RPD
1
-11.8%
-11.8%
-11.8%
-11.8%
2
-6.8%
6.9%
0.1%
0.1%
1
29.0%
29.0%
29.0%
29.0%
..
~
5
-32.1%
9.2%
-11.1%
-11.8%
RPD ABS Val
1
11.8%
11.8%
11.8%
11.8%
2
6.8%
6.9%
6.9%
6.9%
1
29.0%
29.0%
29.0%
29.0%
..
~
5
6.5%
32.1%
14.8%
11.8%
Selenium
Reference Laboratory
RPD
1
-1.5%
-1.5%
-1.5%
-1.5%
3
-21.2%
4.5%
-5.6%
0.0%
2
-13.4%
18.8%
2.7%
2.7%
..
~
5
-21.4%
9.4%
-2.1%
-1.5%
RPD ABS Val
1
1.5%
1.5%
1.5%
1.5%
3
0.0%
21.2%
8.5%
4.5%
2
13.4%
18.8%
16.1%
16.1%
..
~
5
1.5%
21.4%
8.1%
5.6%
Silver
Reference Laboratory
RPD
1
-23.7%
-23.7%
-23.7%
-23.7%
1
-89.5%
-89.5%
-89.5%
-89.5%
—
~
~
~
—
..
~
1
-54.9%
-54.9%
-54.9%
-54.9%
RPD ABS Val
1
23.7%
23.7%
23.7%
23.7%
1
89.5%
89.5%
89.5%
89.5%
—
~
~
~
—
..
~
1
54.9%
54.9%
54.9%
54.9%
E-26
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Site
AS
BN
CN
KP
LV
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)
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
Vanadium
Reference Laboratory
RPD
..
~
~
~
—
..
~
~
~
—
—
~
~
~
—
..
~
2
-64.9%
-64.1%
-64.5%
-64.5%
RPD ABS Val
..
~
~
~
—
..
~
~
~
—
—
~
~
~
—
..
~
2
64.1%
64.9%
64.5%
64.5%
Zinc
Reference Laboratory
RPD
3
-30.0%
-5.3%
-15.9%
-12.5%
5
-23.6%
2.7%
-15.4%
-21.7%
2
-10.1%
-7.0%
-8.6%
-8.6%
..
~
4
-87.6%
-1.9%
-30.1%
-15.4%
RPD ABS Val
3
5.3%
30.0%
15.9%
12.5%
5
2.7%
23.6%
16.4%
21.7%
2
7.0%
10.1%
8.6%
8.6%
..
~
4
1.9%
87.6%
30.1%
15.4%
E-27
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Sediment
Soil
Sediment
Soil
Site
RF
SB
TL
WS
All
Matrix
Description
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
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
3
-105.7%
-93.8%
-98.0%
-94.6%
7
-169.0%
-106.0%
-126.9%
-117.9%
3
-149.4%
-142.6%
-145.6%
-144.9%
3
-105.8%
-75.2%
-86.4%
-78.1%
27
-169.0%
12.7%
-105.8%
-109.0%
RPD ABS Val
3
93.8%
105.7%
98.0%
94.6%
7
106.0%
169.0%
126.9%
117.9%
3
142.6%
149.4%
145.6%
144.9%
3
75.2%
105.8%
86.4%
78.1%
27
4.0%
169.0%
106.7%
109.0%
Certified Value
RPD
3
-2.6%
2.7%
0.1%
0.1%
1
5.4%
5.4%
5.4%
5.4%
3
10.2%
18.8%
13.5%
11.5%
..
~
~
~
—
13
-2.6%
18.8%
5.7%
5.4%
RPD ABS Val
3
0.1%
2.7%
1.8%
2.6%
1
5.4%
5.4%
5.4%
5.4%
3
10.2%
18.8%
13.5%
11.5%
..
~
~
~
—
13
0.1%
18.8%
6.2%
5.4%
Arsenic
Reference Laboratory
RPD
10
-27.8%
8.3%
-10.5%
-14.1%
4
-29.0%
-3.7%
-16.9%
-17.4%
—
~
~
~
—
5
-78.5%
28.5%
-32.0%
-48.3%
30
-78.5%
28.5%
-15.9%
-15.2%
RPD ABS Val
10
4.3%
27.8%
14.0%
14.1%
4
3.7%
29.0%
16.9%
17.4%
—
~
~
~
—
5
1.6%
78.5%
44.0%
48.3%
30
0.2%
78.5%
20.0%
15.9%
E-28
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Sediment
Soil
Sediment
Soil
Site
RF
SB
TL
WS
All
Matrix
Description
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
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Cadmium
Reference Laboratory
RPD
4
-37.3%
-16.2%
-24.7%
-22.7%
1
-27.6%
-27.6%
-27.6%
-27.6%
2
-14.8%
-13.6%
-14.2%
-14.2%
1
-12.2%
-12.2%
-12.2%
-12.2%
22
-38.6%
17.9%
-18.1%
-19.9%
RPD ABS Val
4
16.2%
37.3%
24.7%
22.7%
1
27.6%
27.6%
27.6%
27.6%
2
13.6%
14.8%
14.2%
14.2%
1
12.2%
12.2%
12.2%
12.2%
22
2.6%
38.6%
20.7%
19.9%
Chromium
Reference Laboratory
RPD
3
4.8%
23.3%
16.1%
20.2%
1
28.4%
28.4%
28.4%
28.4%
—
~
~
~
—
1
15.8%
15.8%
15.8%
15.8%
12
-2.4%
43.2%
15.6%
16.6%
RPD ABS Val
3
4.8%
23.3%
16.1%
20.2%
1
28.4%
28.4%
28.4%
28.4%
—
~
~
~
—
1
15.8%
15.8%
15.8%
15.8%
12
1.5%
43.2%
16.6%
16.6%
Copper
Reference Laboratory
RPD
8
-25.8%
0.3%
-12.8%
-12.4%
..
~
~
~
—
7
-13.2%
9.6%
-2.4%
-2.2%
4
-98.9%
-25.4%
-60.9%
-59.7%
31
-98.9%
9.6%
-20.1%
-13.2%
RPD ABS Val
8
0.3%
25.8%
12.9%
12.4%
..
~
~
~
—
7
0.6%
13.2%
6.2%
6.4%
4
25.4%
98.9%
60.9%
59.7%
31
0.3%
98.9%
21.7%
13.2%
E-29
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Sediment
Soil
Sediment
Soil
Site
RF
SB
TL
WS
All
Matrix
Description
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
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Iron
Reference Laboratory
RPD
13
-28.6%
-3.8%
-14.2%
-12.0%
12
-34.1%
10.2%
-4.4%
-2.8%
7
-77.5%
-17.9%
-45.4%
-35.8%
7
-51.7%
0.4%
-25.8%
-27.5%
70
-77.5%
27.6%
-19.4%
-17.1%
RPD ABS Val
13
3.8%
28.6%
14.2%
12.0%
12
0.4%
34.1%
7.5%
4.5%
7
17.9%
77.5%
45.4%
35.8%
7
0.4%
51.7%
25.9%
27.5%
70
0.2%
77.5%
20.8%
17.8%
Lead
Reference Laboratory
RPD
10
-47.7%
3.5%
-11.8%
-9.1%
1
-35.5%
-35.5%
-35.5%
-35.5%
4
-43.5%
-2.6%
-21.0%
-18.9%
7
-68.1%
1.3%
-24.2%
-18.1%
45
-68.1%
107.0%
-11.5%
-10.8%
RPD ABS Val
10
1.5%
47.7%
12.5%
9.1%
1
35.5%
35.5%
35.5%
35.5%
4
2.6%
43.5%
21.0%
18.9%
7
1.3%
68.1%
24.6%
18.1%
45
0.7%
107.0%
19.8%
14.6%
Mercury
Reference Laboratory
RPD
5
-42.1%
86.6%
38.1%
76.1%
8
105.5%
150.9%
133.1%
136.0%
2
119.4%
152.2%
135.8%
135.8%
..
~
~
~
—
21
-42.1%
152.2%
92.6%
103.4%
RPD ABS Val
5
16.5%
86.6%
61.5%
76.1%
8
105.5%
150.9%
133.1%
136.0%
2
119.4%
152.2%
135.8%
135.8%
..
~
~
~
—
21
16.5%
152.2%
98.1%
103.4%
E-30
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Sediment
Soil
Sediment
Soil
Site
RF
SB
TL
WS
All
Matrix
Description
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
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
Reference Laboratory
RPD
6
-15.5%
6.0%
-5.6%
-7.6%
3
-25.6%
13.3%
-3.8%
1.0%
—
~
~
~
—
2
-14.2%
-7.6%
-10.9%
-10.9%
20
-32.1%
29.0%
-5.2%
-7.2%
RPD ABS Val
6
2.2%
15.5%
9.0%
9.5%
3
1.0%
25.6%
13.3%
13.3%
—
~
~
~
—
2
7.6%
14.2%
10.9%
10.9%
20
1.0%
32.1%
12.2%
11.8%
Selenium
Reference Laboratory
RPD
5
-18.6%
1.8%
-8.9%
-12.0%
3
6.6%
8.2%
7.3%
7.1%
4
-25.9%
16.5%
-2.0%
0.8%
1
2.9%
2.9%
2.9%
2.9%
24
-25.9%
18.8%
-2.1%
-0.1%
RPD ABS Val
5
0.1%
18.6%
9.6%
12.0%
3
6.6%
8.2%
7.3%
7.1%
4
5.0%
25.9%
13.5%
11.5%
1
2.9%
2.9%
2.9%
2.9%
24
0.0%
25.9%
9.5%
6.9%
Silver
Reference Laboratory
RPD
1
-111.9%
-111.9%
-111.9%
-111.9%
..
~
~
~
—
—
~
~
~
—
1
-13.8%
-13.8%
-13.8%
-13.8%
5
-111.9%
-13.8%
-58.8%
-54.9%
RPD ABS Val
1
111.9%
111.9%
111.9%
111.9%
..
~
~
~
—
—
~
~
-
—
1
13.8%
13.8%
13.8%
13.8%
5
13.8%
111.9%
58.8%
54.9%
E-31
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Matrix
Sediment
Soil
Sediment
Soil
Site
RF
SB
TL
WS
All
Matrix
Description
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
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Vanadium
Reference Laboratory
RPD
1
-30.5%
-30.5%
-30.5%
-30.5%
1
-40.1%
-40.1%
-40.1%
-40.1%
—
—
~
~
—
1
-54.1%
-54.1%
-54.1%
-54.1%
5
-64.9%
-30.5%
-50.7%
-54.1%
RPD ABS Val
1
30.5%
30.5%
30.5%
30.5%
1
40.1%
40.1%
40.1%
40.1%
—
—
~
~
—
1
54.1%
54.1%
54.1%
54.1%
5
30.5%
64.9%
50.7%
54.1%
Zinc
Reference Laboratory
RPD
13
-41.8%
10.1%
-8.4%
-8.6%
2
-6.6%
6.6%
0.0%
0.0%
4
-41.0%
11.5%
-8.9%
-3.0%
7
-55.8%
12.7%
-20.5%
-24.2%
40
-87.6%
12.7%
-13.7%
-10.5%
RPD ABS Val
13
0.2%
41.8%
11.9%
9.8%
2
6.6%
6.6%
6.6%
6.6%
4
2.0%
41.0%
14.6%
7.8%
7
8.3%
55.8%
26.5%
24.2%
40
0.2%
87.6%
17.0%
11.2%
E-32
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Site Abbreviations:
AS Alton Steel Mill
BN Burlington Northern Railroad/ASARCO East
CN Naval Surface Warfare Center, Crane Division
KP KARS Park - Kennedy Space Center
LV Leviathan Mine/Aspen Creek
RF Ramsey Flats - Silver Bow Creek
SB Sulfur Bank Mercury
TL Torch Lake Superfund Site
WS Wickes Smelter Site
Other Notes:
Number Number of demonstration samples evaluated.
RPD Relative percent difference (unmodified).
RPD Abs Relative percent difference (absolute value).
E-33
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