United States Office of Research and EPA/540/R-06/007
Environmental Protection Development February 2006
Agency Washington, DC 20460
Innovative Technology
Verification Report
XRF Technologies for Measuring
Trace Elements in
Soil and Sediment
Oxford ED2000
XRF Analyzer
- oSto s c,f.
J^W^
-------
EPA/540/R-06/007
February 2006
Innovative Technology
Verification Report
Oxford ED2000
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
-------
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
-------
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
-------
Abstract
The Oxford ED2000 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 ED2000 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 ED2000 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 Oxford ED2000 bench-top XRF analyzer is an energy dispersive XRF analyzer that can be operated
in a mobile laboratory or similar setting. The ED2000 can analyze up to 75 elements in a variety of
sample matrices, including contaminated soils and sediments, liquids, powders, granules, filter papers, or
films. The measurement of light-end elements (sodium to iron) can be determined when the samples are
prepared as pressed pellets. Oxford provides a calibration service as an option to customers for specific
projects and applications using this analyzer.
This report describes the results of the evaluation of the ED2000 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 ED2000
analyzer is compiled and compared to both fixed laboratory costs and average XRF instrument costs.
IV
-------
Contents
Chapter Page
Notice ii
Foreword iii
Abstract iv
Acronyms, Abbreviations, and Symbols x
Acknowledgements xiv
1.0 INTRODUCTION 1
1.1 Organization of this Report 1
1.2 Description of the SITE Program 2
1.3 Scope of the Demonstration 2
1.4 General Description of XRF Technology 3
1.5 Properties of the Target Elements 4
1.5.1 Antimony 5
1.5.2 Arsenic 5
1.5.3 Cadmium 5
1.5.4 Chromium 5
1.5.5 Copper 5
1.5.6 Iron 5
1.5.7 Lead 6
1.5.8 Mercury 6
1.5.9 Nickel 6
1.5.10 Selenium 6
1.5.11 Silver 7
1.5.12 Vanadium 7
1.5.13 Zinc 7
2.0 FIELD SAMPLE COLLECTION LOCATIONS 9
2.1 Alton Steel Mill Site 9
2.2 Burlington Northern-ASARCO Smelter Site 11
2.3 Kennedy Athletic, Recreational and Social Park Site 11
2.4 Leviathan Mine Site 12
2.5 Navy Surface Warfare Center, Crane Division Site 12
2.6 Ramsay Flats-Silver Bow Creek Site 13
2.7 Sulphur Bank Mercury Mine Site 13
2.8 Torch Lake Superfund Site 14
2.9 Wickes Smelter Site 14
3.0 FIELD DEMONSTRATION 15
3.1 Bulk Sample Processing 15
3.1.1 Bulk Sample Collection and Shipping 15
3.1.2 Bulk Sample Preparation and Homogenization 15
3.2 Demonstration Samples 17
3.2.1 Environmental Samples 17
3.2.2 Spiked Samples 17
3.2.3 Demonstration Sample Set 17
-------
Contents (Continued)
Chapter Page
3.3 Demonstration Site and Logistics 20
3.3.1 Demonstration Site Selection 20
3.3.2 Demonstration Site Logistics 20
3.3.3 EPA Demonstration Team and Developer Field Team Responsibilities 21
3.3.4 Sample Management during the Field Demonstration 21
3.3.5 Data Management 22
4.0 EVALUATION DESIGN 23
4.1 Evaluation Objectives 23
4.2 Experimental Design 23
4.2.1 Primary Objective 1 - Method Detection Limits 24
4.2.2 Primary Objective 2 -Accuracy 25
4.2.3 Primary Objective 3 - Precision 26
4.2.4 Primary Objective 4 - Impact of Chemical and Spectral Interferences 27
4.2.5 Primary Objective 5 - Effects of Soil Characteristics 28
4.2.6 Primary Objective 6 - Sample Throughput 28
4.2.7 Primary Objective 7 -Technology Costs 28
4.2.8 Secondary Objective 1 - Training Requirements 28
4.2.9 Secondary Objective 2 - Health and Safety 29
4.2.10 Secondary Objective 3 - Portability 29
4.2.11 Secondary Objective 4 - Durability 29
4.2.12 Secondary Objective 5 -Availability 29
4.3 Deviations from the Demonstration Plan 29
5.0 REFERENCE LABORATORY 31
5.1 Selection of Reference Methods 31
5.2 Selection of Reference Laboratory 32
5.3 QA/QC Results for Reference Laboratory 33
5.3.1 Reference Laboratory Data Validation 33
5.3.2 Reference Laboratory Technical Systems Audit 34
5.3.3 Other Reference Laboratory Data Evaluations 34
5.4 Summary of Data Quality and Usability 36
6.0 TECHNOLOGY DESCRIPTION 39
6.1 General Description 39
6.2 Instrument Operations during the Demonstration 39
6.2.1 Setup and Calibration 41
6.2.2 Demonstration Sample Processing 41
6.3 General Demonstration Results 42
6.4 Contact Information 42
VI
-------
Contents (Continued)
Chapter Page
7.0 PERFORMANCE EVALUATION 43
7.1 Primary Objective 1 - Method Detection Limits 43
7.2 Primary Objective 2 - Accuracy and Comparability 47
7.3 Primary Objective 3 - Precision 51
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 59
7.7 Primary Objective 7 - Technology Cost 59
7.8 Secondary Objective 1 - Training Requirements 60
7.9 Secondary Objective 2 -Health and Safety 60
7.10 Secondary Objective 3 - Portability 60
7.11 Secondary Objective 4 - Durability 61
7.12 Secondary Objective 5 -Availability 61
8.0 ECONOMIC ANALYSIS 63
8.1 Equipment Costs 63
8.2 Supply Costs 63
8.3 Labor Costs 63
8.4 Comparison of XRF Analysis and Reference Laboratory Costs 65
9.0 SUMMARY OF TECHNOLOGY PERFORMANCE 67
10.0 REFERENCES 73
APPENDICES
Appendix A: Verification Statement
Appendix B: Developer Discussion
Appendix C: Data Validation Summary Report
Appendix D: Developer and Reference Laboratory Data
Appendix E: Statistical Data Summaries
vn
-------
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 Oxford ED2000 XRF Analyzer Technical Specifications 40
7-1 Evaluation of Sensitivity - Method Detection Limits for the Oxford ED2000 44
7-2 Comparison of ED2000 MDLs to All-Instrument Mean MDLs and EPA
Method 6200 Data 46
7-3 Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data
for the Oxford ED2000 48
7-4 Summary of Correlation Evaluation forthe ED2000 49
7-5 Evaluation of Precision - Relative Standard Deviations for the Oxford ED2000 53
7-6 Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory
versus the ED2000 and All Demonstration Instruments 54
7-7 Effects of Interferent Elements on the RPDs (Accuracy) for Target Elements,
Oxford ED2000 56
7-8 Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Oxford ED2000 57
8-1 Equipment Costs 63
8-2 Time Required to Complete Analytical Activities 64
8-3 Comparison of XRF Technology and Reference Method Costs 66
9-1 Summary of Oxford ED2000 Performance - Primary Objectives 68
9-2 Summary of Oxford ED2000 Performance - Secondary Objectives 70
Vlll
-------
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 Oxford ED2000 Analyzer Setup for Bench-top Analysis 39
6-2 Oxford ED2000 Soil Pellet Sample Preparation 41
6-3 Oxford ED2000 Pelletized Samples for XRF Analysis 42
7-1 Linear Correlation Plot for Oxford ED2000 Showing High Correlation for Nickel 50
7-2 Linear Correlation Plot for Oxford ED2000 Showing Variability and High Bias for Arsenic 51
8-1 Comparison of Activity Times for the Oxford ED2000 versus Other XRF Instruments 65
9-1 Method Detection Limits (Sensitivity), Accuracy, and Precision of the ED2000
In Comparison to the Average of all Eight XRF Instruments 71
-------
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
-------
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
-------
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
-------
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
-------
Acknowledgements
This report was co-authored by Dr. Greg Swanson and Dr. Mark Colsman of Tetra Tech EM Inc. The
authors acknowledge the advice and support of the following individuals in preparing this report: Dr.
Stephen Billets and Mr. George Brilis of the U.S. Environmental Protection Agency's National Exposure
Research Laboratory; Dr. Sanjay Kamtekar and Dr. Rune Gehrlein of Oxford Instruments Analytical,
Inc.; 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
-------
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
Oxford ED2000 XRF analyzer based on the results
of the demonstration.
1.1 Organization of this Report
This report is organized to first present general
information pertinent to the demonstration. This
information is common to all eight ITVRs that were
developed from the XRF demonstration.
Specifically, this information includes an
introduction (Chapter 1), the locations where the field
samples were collected (Chapter 2), the field
demonstration (Chapter 3), the evaluation design
(Chapter 4), and the reference laboratory results
(Chapter 5).
The second part of this report provides information
relevant to the specific instrument that is the subject
of this ITVR. This information includes a description
of the instrument (Chapter 6), a performance
evaluation (Chapter 7), a cost analysis (Chapter 8),
and a summary of the demonstration results (Chapter
9).
Table 1-1. Participating Technology Developers and Instruments
Developer Full Name
Elvatech, Ltd.
Innov-X Systems
NITON Analyzers, A
Division of Thermo
Electron Corooration
Oxford Instruments
Analytical, Ltd.
Rigaku, Inc.
RONTEC AG
(acquired by Bruker
AXS, Inc., 11/2005)
Distributor in the
United States
Xcalibur XRF Services
Innov-X Systems
NITON Analyzers, A
Division of Thermo
Electron Corooration
Oxford Instruments
Analytical, Ltd.
Rigaku, Inc.
RONTEC USA
Developer Short
Name
Xcalibur
Innov-X
Niton
Oxford
Rigaku
Rontec
Instrument Full
Name
ElvaX
XT400 Series
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
-------
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
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 a broad range of soil/sediment types and
target element concentrations. To develop this
sample set, soil and sediment samples that contain the
target elements of concern were collected in bulk
quantities at nine sites from across the U.S. These
bulk samples of soil and sediment were
homogenized, characterized, and packaged into
demonstration samples for the evaluation. Some of
the batches of soil and sediment were spiked with
selected target elements to ensure that representative
concentration ranges were included for all target
elements and that the sample design was robust.
Replicate samples of the material in each batch were
included in the final set of demonstration samples to
assess instrument precision and detection limits. The
final demonstration sample set therefore included 326
samples.
Each developer analyzed all 326 samples during the
field demonstration using its XRF instrument and in
accordance with its standard operating procedure.
The field demonstration was conducted during the
week of January 24, 2005, at the Kennedy Athletic,
Recreational and Social (KARS) Park, which is part
of the Kennedy Space Center on Merritt Island,
Florida. Observers were assigned to each XRF
instrument during the field demonstration to collect
detailed information on the instrument and operating
procedures, including sample processing times, for
subsequent evaluation. The reference laboratory also
analyzed a complete set of the demonstration samples
for the target elements using acid digestion and
inductively coupled plasma-atomic emission
spectrometry (ICP-AES), in accordance with EPA
Method 3 05 OB/601 OB, and using cold vapor atomic
absorption (CVAA) spectroscopy (for mercury only)
in accordance with EPA Method 7471 A. By
assuming that the results from the reference
laboratory were essentially "true" values, instrument
accuracy was assessed by comparing the results
obtained using the XRF instrument with the results
from the reference laboratory. The data obtained
using the XRF instrument were also assessed in other
ways, in accordance with the objectives of the
demonstration, to provide information on instrument
precision, detection limits, and interferences.
1.4 General Description of XRF Technology
XRF spectroscopy is an analytical technique that
exposes a solid sample to an x-ray source. The x-
rays from the source have the appropriate excitation
energy that causes elements in the sample to emit
characteristic x-rays. A qualitative elemental
analysis is possible from the characteristic energy, or
wavelength, of the fluorescent x-rays emitted. A
quantitative elemental analysis is possible by
counting the number (intensity) of x-rays at a given
wavelength.
Three electron shells are generally involved in
emissions of x-rays during XRF analysis of samples:
the K, L, and M shells. Multiple-intensity peaks are
generated from the K, L, or M shell electrons in a
typical emission pattern, also called an emission
spectrum, for a given element. Most XRF analysis
focuses on the x-ray emissions from the K and L
shells because they are the most energetic lines. K
lines are typically used for elements with atomic
numbers from 11 to 46 (sodium to palladium), and L
lines are used for elements above atomic number 47
(silver). M-shell emissions are measurable only for
metals with an atomic number greater than 57
(lanthanum).
As illustrated in Figure 1-1, characteristic radiation
arises when the energy from the x-ray source exceeds
the absorption edge energy of inner-shell electrons,
ejecting one or more electrons. The vacancies are
-------
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
K_ x-ray emitted
* V ť S I I Kax-ray Emitted
M-shell electron
nils vacancy
Figure 1-1. The XRF process.
Measurement times vary (typically ranging from 30
to 600 seconds), based primarily on data quality
objectives. Shorter analytical measurement times (30
seconds) are generally used for initial screening,
element identification, and hot-spot delineation,
while longer measurement times (300 seconds or
more) are typically used to meet higher goals for
precision and accuracy. The length of the measuring
time will also affect the detection limit; generally, the
longer the measuring time, the lower the detection
limit. However, detection limits for individual
elements may be reduced because of sample
heterogeneity or the presence of other elements in the
sample that fluoresce with similar x-ray energies.
The main variables that affect precision and accuracy
for XRF analysis are:
1. Physical matrix effects (variations in the physical
character of the sample).
2. Chemical matrix effects (absorption and
enhancement phenomena) and spectral
interferences (peak overlaps).
3. Moisture content above 10 percent, which affects
x-ray transmission.
Because of these variables, it is important that each
field XRF characterization effort be guided by a well-
considered sampling and analysis plan. Sample
preparation and homogenization, instrument
calibration, and laboratory confirmation analysis are
all important aspects of an XRF sampling and
analysis plan. EPA SW-846 Method 6200 provides
additional guidance on sampling and analytical
methodology for XRF analysis.
1.5 Properties of the Target Elements
This section describes the target elements selected for
the technology demonstration and the typical
characteristics of each. Key criteria used in selecting
the target elements included:
The frequency that the element is determined in
environmental applications of XRF instruments.
The extent that the element poses an
environmental consequence, such as a potential
risk to human or environmental receptors.
The ability of XRF technology to achieve
detection limits below typical remediation goals
and risk assessment criteria.
The extent that the element may interfere with
the analysis of other target elements.
In considering these criteria, the critical target
elements selected for this study were antimony,
arsenic, cadmium, chromium, copper, iron, lead,
mercury, nickel, selenium, silver, vanadium, and
zinc. These 13 target elements are of significant
concern for site cleanups and human health risk
assessments because most are highly toxic or
interfere with the analysis of other elements. The
demonstration 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.
7.5.* Mercury
Naturally occurring mercury in surface soils typically
ranges from 0.01 to 0.3 mg/kg; concentrations greater
than 0.3 mg/kg are potentially phytotoxic.
Concentrations of mercury greater than 23 mg/kg and
concentrations of methyl mercury above 6.1 mg/kg
may result in adverse health effects in humans.
Typical detection limits for field-portable XRF
instruments range from 10 to 20 mg/kg. Elevated
concentrations of mercury are associated with
amalgamation of gold and with mine waste and
industrial facilities. Native surface soils are
commonly enriched by anthropogenic sources of
mercury. Anthropogenic sources include coal-fired
power plants and metal smelters. Mercury is too
volatile to withstand both the vigorous digestion and
extreme temperature involved with ICP-AES
analysis; therefore, the EPA-approved technique for
laboratory analysis of mercury is CVAA
spectroscopy. Mercury is successfully measured by
XRF, but differences between results obtained by
CVAA and XRF are expected when mercury levels
are high.
7.5.9 Nickel
Naturally occurring nickel in surface soils typically
ranges from 5 to 500 mg/kg; a concentration of 30
mg/kg is potentially phytotoxic. Concentrations
greater than 1,600 mg/kg may result in adverse health
effects in humans. Typical detection limits for field-
portable XRF instruments range from 10 to 60
mg/kg. Elevated concentrations of nickel are
associated with mine wastes and industrial facilities.
Nickel is a common environmental contaminant at
metal processing sites. It is successfully analyzed by
both ICP-AES and XRF with little interference;
therefore, a strong correlation between the methods is
expected.
7.5.70 Selenium
Naturally occurring selenium in surface soils
typically ranges from 0.1 to 2 mg/kg; concentrations
greater than 1 mg/kg are potentially phytotoxic. Its
toxicities are well documented for plants and
livestock; however, it is also considered a trace
nutrient. Concentrations above 390 mg/kg may result
in adverse health effects in humans. Typical
detection limits for field-portable XRF instruments
range from 10 to 20 mg/kg. Most selenium is
associated with sulfur or sulfide minerals, where
concentrations can exceed 200 mg/kg. Selenium can
be measured by both ICP-AES and XRF; however,
detection limits using XRF usually exceed the
-------
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.
-------
This page was left blank intentionally.
-------
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.
-------
Table 2-1. Nature of Contamination in Soil and Sediment at Sample Collection Sites
Sample Collection Site
Alton Steel, Alton, IL
Burlington Northern-
ASARCO Smelter Site,
East Helena, MT
KARS Park - Kennedy
Space Center, Merritt
Island, FL
Leviathan Mine
Site/ Aspen Creek, Alpine
County, CA
Naval Surface Warfare
Center, Crane Division,
Crane, IN
Ramsay Flats-Silver Bow
Creek, Butte, MT
Sulphur Bank Mercury
Mine
Torch Lake Site (Great
Lakes Area of Concern),
Houghton County, MI
Wickes Smelter Site,
Jefferson City, MT
Source of Contamination
Steel manufacturing facility with metal arc
furnace dust. The site also includes a metal
scrap yard and a slag recovery facility.
Railroad yard staging area for smelter ores.
Contaminated soils resulted from dumping and
spilling concentrated ores.
Impacts to soil from historical facility
operations and a former gun range.
Abandoned open-pit sulfur and copper mine
that has contaminated a 9-mile stretch of
mountain creeks, including Aspen Creek, with
heavy metals.
Open disposal and burning of general refuse
and waste associated with aircraft
maintenance.
Silver Bow Creek was used as a conduit for
mining, smelting, industrial, and municipal
wastes.
Inactive mercury mine. Waste rock, tailings,
and ore are distributed in piles throughout the
property.
Copper mining produced mill tailings that were
dumped directly into Torch Lake,
contaminating the lake sediments and
shoreline.
Abandoned smelter complex with
contaminated soils and mineral-processing
wastes, including remnant ore piles,
decomposed roaster brick, slag piles and fines,
and amalgamation sediments.
Matrix
Soil
Soil
Soil
Soil and
Sediment
Soil
Soil and
Sediment
Soil
Sediment
Soil
Site-Specific Metals of Concern for XRF Demonstration
Sb
X
X
X
X
As
X
X
X
X
X
X
X
X
X
Cd
X
X
X
X
X
X
Cr
X
X
X
X
X
X
Cu
X
X
X
X
X
X
Fe
X
X
X
X
X
Pb
X
X
X
X
X
X
X
X
Hg
X
X
X
Ni
X
X
X
X
Se
X
AŁ
X
X
Zn
X
X
X
X
X
X
Notes (in order of appearance in table):
Sb: Antimony Cr: Chromium Pb: Lead
As: Arsenic Cu: Copper Hg: Mercury
Cd: Cadmium Fe: Iron Ni: Nickel
Note: Vanadium was not a chemical of concern at any of the sites and so does not appear on the table.
Se: Selenium
Ag: Silver
Zn: Zinc
10
-------
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
-------
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
-------
Table 2-6. Historical Analytical Data,
NSWC Crane Division-Old Burn Pit
Metal
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Silver
Zinc
Maximum Concentration (mg/kg)
301
26.8
31.1
112
1,520
105,000
16,900
0.43
62.6
7.5
5,110
2.6 Ramsay Flats-Silver Bow Creek Site
The Ramsay Flats-Silver Bow Creek site was
selected to be included in the demonstration because
6 of the 13 target elements were detected in samples
of surface sediment collected previously at the site.
Silver Bow Creek originates north of Butte, Montana,
and is a tributary to the upper Clark Fork River.
More than 100 years of nearly continuous mining
have altered the natural environment surrounding the
upper Clark Fork River. Early wastes from mining,
milling, and smelting were dumped directly into
Silver Bow Creek and were subsequently transported
downstream. EPA listed Silver Bow Creek and a
contiguous portion of the upper Clark Fork River as a
Superfund site in 1983.
A large volume of tailings was deposited in a low-
gradient reach of Silver Bow Creek in the Ramsay
Flats area. Tailings at Ramsay Flats extend several
hundred feet north of the Silver Bow Creek channel.
About 18 inches of silty tailings overlie texturally
stratified natural sediments that consist of low-
permeability silt, silty clay, organic layers, and
stringers of fine sand.
Two sediment samples were collected from the
Ramsay Flats tailings area and were analyzed for a
suite of metals using a field-portable XRF. The
contaminated sediment sample was collected in
Silver Bow Creek adjacent to the mine tailings. The
matrix of this sediment sample was orange-brown
silty fine sand with interlayered black organic
material. The background sediment sample was
collected upstream of Butte, Montana. The matrix of
this sample was organic rich clayey silt with
approximately 25 percent fine sand. The maximum
concentrations of the target elements in the samples
are summarized in Table 2-7.
Table 2-7. Historical Analytical Data, Ramsay
Flats-Silver Bow Creek Site
Metal
Arsenic
Cadmium
Copper
Iron
Lead
Zinc
Maximum Concentration (mg/kg)
176
141
1,110
20,891
394
1,459
2.7 Sulphur Bank Mercury Mine Site
The Sulphur Bank Mercury Mine (SBMM) is a 160-
acre inactive mercury mine located on the eastern
shore of the Oaks Arm of Clear Lake in Lake County,
California, 100 miles north of San Francisco.
Between 1864 and 1957, SBMM was the site of
underground and open-pit mining at the hydrothermal
vents and hot springs. Mining disturbed about 160
acres of land at SBMM and generated large quantities
of waste rock (rock that did not contain economic
concentrations of mercury and was removed to gain
access to ore), tailings (the waste material from
processes that removed the mercury from ore), and
ore (rock that contained economic concentrations of
mercury that was mined and stockpiled for mercury
extraction). The waste rock, tailings, and ore are
distributed in piles throughout the property.
Table 2-8 presents historical analytical data (the
maximum concentrations) for the target elements
detected at elevated concentrations in surface
samples collected at SBMM. Two contaminated soil
samples and one background soil sample were
collected at various locations for the demonstration
project. The mercury sample was collected from the
ore stockpile and consisted of medium to coarse sand.
The second contaminated soil sample was collected
from the waste rock pile and consisted of coarse sand
and gravel with trace silt. The matrix of the
background soil sample was brown sandy loam.
13
-------
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
-------
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
Homogen ization
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.
15
-------
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
capable of handling up to 50 gallons (190 liters) of
sample material; thus, this shaker could handle the
complete volume of each bulk sample. Bulk samples
of smaller volume were mixed and homogenized
using a Model T 10B Turbula shaker-mixer that was
capable of handling up to 10 gallons (38 liters).
Aliquots from each homogenized bulk sample were
then sampled and analyzed in triplicate for the 13
target elements using ICP-AES and CVAA. If the
relative percent difference between the highest and
lowest result exceeded 10 percent for any element,
the entire batch was returned to the shaker-mixer for
additional homogenization. The entire processing
scheme for the bulk samples is shown in Figure 3-1.
Material was sieved
through custom 1" screen
to remove large material.
Was
the material smaller
than .2mm?
the sample greater
than 10
gallons?
Material crushed using
stainless steel hammer mill
Samples are
mixed and homogenized
using Model T 50A
Turbula shaker-mixer
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 the 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
-------
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
-------
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
-------
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
-------
3.3 Demonstration Site and Logistics
The field demonstration occurred during the week of
January 24, 2005. This section describes the
selection of the demonstration site and the logistics of
the field demonstration, including sample
management.
3.3.1 Demonstration Site Selection
The demonstration site was selected from among the
list of sample collection sites to simulate a likely field
deployment. The following criteria were used to
assess which of the nine sample collection sites might
best serve as the demonstration site:
Convenience and accessibility to participants in
the demonstration.
Ease of access to the site, with a reasonably sized
airport that can accommodate the travel
schedules for the participants.
Program support and cooperation of the site
owner.
Sufficient space and power to support developer
testing.
Adequate conference room space to support a
visitors day.
A temperate climate so that the demonstration
could occur on schedule in January.
After an extensive search for candidates, the site
selected for the field demonstration was KARS Park,
which is part of the Kennedy Space Center on Merritt
Island, Florida. KARS Park was selected as the
demonstration site for the following reasons:
Access and Site Owner Support
Representatives from NASA were willing to
support the field demonstration by providing
access to the site, assisting in logistical support
during the demonstration, and hosting a visitors
day.
Facilities Requirements and Feasibility The
recreation building was available and was of
sufficient size to accommodate all the demon-
stration 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
-------
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
-------
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 ExcelŽ spreadsheet. (The EPA/Tetra Tech
field team had provided a template.) Since each
instrument provided data in a different format, the
developer's field team was responsible for reducing
the data before they were submitted and for
transferring the data into the Excel spreadsheet.
The observer reviewed each data submittal for
completeness, and the data were then uploaded into a
master Excel spreadsheet on a laptop computer for
temporary storage. Only the EPA/Tetra Tech field
team had access to the master Excel spreadsheet
during the field demonstration.
Once the EPA/Tetra Tech field team returned to their
offices, the demonstration data were transferred to an
Microsoft AccessŽ database for permanent storage.
Each developer's data, as they existed in the Access
database, were then provided to the developer for
review. Any errors the developers identified were
corrected, and the database was then finalized. All
statistical analysis and data evaluation took place on
this final database.
22
-------
Chapter 4
Evaluation Design
This chapter presents the approach for evaluating the
performance of the XRF instruments. Specifically,
the sections below describe the objectives of the
evaluation and the experimental design.
The Demonstration and Quality Assurance Project
Plan (Tetra Tech 2005) provides additional details on
the overall demonstration approach. However, some
deviations from the plan, involving data evaluation
and laboratory audits, occurred after the
demonstration plan was written. For completeness,
the primary changes to the written plan are
documented in the final section of this chapter.
4.1 Evaluation Objectives
The overall purpose of the XRF technology
demonstration was to evaluate the performance of
various field XRF instruments in detecting and
quantifying trace elements in soils and sediments
from a variety of sites around the U.S. The
performance of each XRF instrument was evaluated
in accordance with primary and secondary objectives.
Primary objectives are critical to the evaluation and
require the use of quantitative results to draw
conclusions about an instrument's performance.
Secondary objectives pertain to information that is
useful but that will not necessarily require use of
quantitative results to draw conclusions about an
instrument's performance.
The primary and secondary objectives for the
evaluation are listed in Table 4-1. These objectives
were based on:
Input from MMT Program stakeholders,
including developers and EPA staff.
General expectations of users of field
measurement instruments.
The time available to complete the
demonstration.
The capabilities of the instruments that the
developers participating in the demonstration
intended to highlight.
4.2 Experimental Design
To address the first four primary objectives, each
XRF instrument analyzed the demonstration sample
set for the 13 target elements. The demonstration
samples originated from multiple sampling locations
across the country, as described in Chapter 2, to
provide a diverse set of soil and sediment matrices.
The demonstration sample set included both blended
environmental samples and spiked background
samples, as described in Chapter 3, to provide a wide
range of concentrations and combinations of
elements.
When the field demonstration was completed, the
results obtained using the XRF instruments were
compared with data from a reference laboratory to
evaluate the performance of each instrument in terms
of accuracy and comparability (Primary Objective 2).
The results for replicate samples were used to
evaluate precision in various concentration ranges
(Primary Objective 3) and the method detection
limits (MDL) (Primary Objective 1). Each of these
quantitative evaluations of instrument performance
was carried out for each target element. The effect of
chemical and spectral interferences and of soil
characteristics (Primary Objectives 4 and 5) were
evaluated to help explain extreme deviations or
outliers observed in the XRF results when compared
with the reference laboratory results.
A second important comparison involved the average
performance of all eight XRF instruments that
participated in the demonstration. For the first three
primary objectives (MDL, accuracy, precision), the
performance of each individual instrument was
compared to the overall average performance of all
eight instruments. Where the result of the instrument
under consideration was less than 10 percent different
than the average result for all eight instruments, the
result was considered "equivalent." A similar
comparison was conducted with respect to cost
(Primary Objective 7). These comparisons were
intended to illustrate the performance of each XRF
instrument in relation to its peers.
23
-------
The evaluation design for meeting each objective,
including data analysis procedures, is discussed in
more detail in the sections below. Where specific
deviations from these procedures were necessary for
the data set associated with specific instruments,
these deviations are described as part of the
performance evaluation in Chapter 7.
4.2.1 Primary Objective 1 Meth od Detection
Limits
The MDL for each target element was evaluated
based on the analysis of sets of seven replicate
samples that contained the target element at
concentrations near the detection limit. The MDL
was calculated using the procedures found in Title 40
Code of Federal Regulations (CFR) Part 136,
Appendix B, Revision 1.11. The following equation
was used:
MDL = t(n.u.a=0.99)(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
-------
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:
25
-------
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.
26
-------
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 therefore intended
to differentiate the instruments that incorporated
effective software for addressing chemical
interferences.
27
-------
4.2.5 Primary Objective 5 Effects of Soil
Characteristics
The demonstration sample set included soil and
sediment samples from nine locations across the U.S.
and a corresponding variety of soil types and
lithologies. The accuracy and precision statistics
(RPD and RSD) were grouped by soil type (sample
location) and the groups were compared to assess the
effects of soil characteristics. Outliers and
subpopulations in the RPD data sets, as identified
through graphical means (correlation plots and box
plots), were also examined for matrix effects.
4.2.6 Primary Objective 6 Sample Throughput
Sample throughput is a calculation of the total
number of samples that can be analyzed in a specified
time. The primary factors that affect sample
throughput are the time required to prepare a sample
for analysis, to conduct the analytical procedure for
each sample, and to process and tabulate the resulting
data. The time required to prepare and to analyze
demonstration samples was recorded each day that
demonstration samples were analyzed.
Sample throughput can also be affected by the time
required to set up and calibrate the instrument as well
as the time required for quality control. The time
required to perform these activities was also recorded
during the field demonstration.
An overall mean processing time per sample and an
overall sample throughput rate was calculated based
on the total time required to complete the analysis of
the demonstration sample set from initial instrument
setup through data reporting. The overall mean
processing time per sample was then used as the
primary basis for comparative evaluations.
4.2.7 Primary Objective 7 Technology Costs
The costs for analysis are an important factor in the
evaluation and include the cost for the instrument,
analytical supplies, and labor. The observer collected
information on each of these costs during the field
demonstration.
Based on input from each technology developer and
from distributors, the instrument cost was established
for purchase of the equipment and for daily, weekly,
and monthly rental. Some of the technologies are not
yet widely available, and the developer has not
established rental options. In these cases, an
estimated weekly rental cost was derived for the
summary cost evaluations based on the purchase
price for the instrument and typical rental to purchase
price ratios for similar instruments. The costs
associated with leasing agreements were also
specified in the report, if available.
Analytical supplies include sample cups, spoons, x-
ray film, MylarŽ, reagents, and personal protective
equipment. The rate that the supplies are consumed
was monitored and recorded during the field
demonstration. The cost of analytical supplies was
estimated per sample from these consumption data
and information on unit costs.
Labor includes the time required to prepare and
analyze the samples and to set up and dismantle the
equipment. The labor hours associated with
preparing and analyzing samples and with setting up
and dismantling the equipment were recorded during
the demonstration. The labor costs were calculated
based on this information and typical labor rates for a
skilled technician or chemist.
In addition to the assessment of the above-described
individual cost components, an overall cost for a field
effort similar to the demonstration was compiled and
compared to the cost of fixed laboratory analysis.
The results of the cost evaluation are presented in
Chapter 8.
4.2.8 Secondary Objective 1 Training
Requirements
Each XRF instrument requires that the operator be
trained to safely set up and operate the instrument.
The relative level of education and experience that is
appropriate to operate the XRF instrument was
assessed during the field demonstration.
The amount of specific training required depends on
the complexity of the instrument and the associated
software. Most developers have established training
programs. The time required to complete the
developer's training program was estimated and the
content of the training was identified.
28
-------
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
-------
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.
30
-------
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 3 05 OB/601 OB, 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
31
-------
the results. Since the matrices (soil 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
3 05 OB 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 3050B 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.
32
-------
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.
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
33
-------
(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 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
34
-------
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 Antimony
As Arsenic
Cd Cadmium
Cr Chromium
Cu Copper
Fe Iron
Pb Lead
Hg Mercury
Ni Nickel
Se Selenium
Ag Silver
V Vanadium
Zn Zinc
37
-------
Table 5-3. Precision of Reference Laboratory Results for Blends 1 through 70
Statistic
Number of %RSDs
Minimum %RSD
Maximum %RSD
Mean "/oRSD1
Median "/oRSD1
Sb
43
1.90
78.99
17.29
11.99
As
69
0.00
139.85
13.79
10.01
Cd
43
0.91
40.95
12.13
9.36
Cr
69
1.43
136.99
11.87
8.29
Cu
70
0.00
45.73
10.62
8.66
Fe
70
1.55
46.22
10.56
8.55
Pb
69
0.00
150.03
14.52
9.17
Hg
62
0.00
152.59
16.93
7.74
Ni
68
0.00
44.88
10.28
8.12
Se
35
0.00
37.30
13.24
9.93
Ag
44
1.02
54.21
12.87
8.89
V
69
0.00
43.52
9.80
8.34
Zn
70
0.99
48.68
10.94
7.54
Notes:
1 Values shown in bold fall outside precision criterion of less than or equal to 25 %RSD.
%RSD = Percent relative standard deviation.
Based on the three to seven replicate samples included in Blends 1 through 70.
Sb Antimony
As Arsenic
Cd Cadmium
Cr Chromium
Cu Copper
Fe Iron
Pb Lead
Hg Mercury
Ni Nickel
Se Selenium
Ag Silver
V Vanadium
Zn Zinc
38
-------
Chapter 6
Technology Description
The ED2000 XRF analyzer is manufactured by
Oxford Instruments Analytical Ltd (Oxford). This
chapter provides a technical description of the
ED2000 based on information obtained from Oxford
and observation of this analyzer during the field
demonstration. This chapter also identifies an
Oxford company contact, where additional technical
information may be obtained.
6.1 General Description
The Oxford ED2000 is an energy dispersive XRF
analyzer that can be operated as a bench-top unit in a
mobile laboratory or similar setting. The entire
analyzer system includes three major components:
(1) XRF spectrometer, (2) vacuum pump, and (3)
personal computer. Each ED2000 unit comes
equipped with a modem so that the instrument can be
controlled remotely for ease of operation. This
feature also allows qualified technicians to evaluate
system functionality and provide troubleshooting
guidance for inexperienced users from a remote
location.
The ED2000 can analyze up to 75 elements in a
variety of sample matrices, including contaminated
soils and sediments, liquids, powders, granules, filter
papers, or films. The measurement of light-end
elements (sodium to iron) can be determined when
the samples are prepared as pressed pellets. Oxford
provides a calibration service as an option to
customers using this analyzer.
The ED2000 system includes a SMART digital pulse
processor to handle count rates as high as 90,000
counts per second (CPS). The high count rates and
high detector resolutions provide improved precision
and lower detection levels compared to older Oxford
XRF analyzers. Oxford's XpertEase 32 software is
designed for detecting elements across the full
specification and allows automated processing to free
up the operator during routine analyses. Special
features of the ED2000 include a 16-position
automatic sample tray, 10 liter dewar to hold liquid
nitrogen to cool the detector, vacuum pump to
evacuate the sample chamber of the instrument to
reduce the formation of oxides in the sample matrix,
and a personal computer loaded with Microsoft
WindowsŽ XP and instrument calibration and
operational software. The ED2000 is shown in a
bench-top configuration in Figure 6-1. Technical
specifications for the ED2000 are provided in Table
6-1.
Figure 6-1. Oxford ED2000 analyzer set up for
bench-top analysis.
For the demonstration, a sample crusher/mixer and
sample press was included with the analyzer to
prepare sample pellets for analysis. However, it
should be noted that processing samples into pellets
is not required for routine sample analysis.
6.2 Instrument Operations during the
Demonstration
The ED2000 and accessories were shipped to the
demonstration site on three 4-foot by 4-foot wooden
pallets. One pallet contained the analyzer, which was
over-packed in a large cardboard box with Styrofoam
padding and strapped to the pallet. The two other
pallets contained the sample crusher/mixer, the
sample press, a computer, monitor, printer, and
disposable analytical supplies. Additionally, a local
supplier delivered a tank of liquid nitrogen, which is
used to cool the detector during analyses. Unpacking
39
-------
the three pallets and carrying the analyzer and
accessories into the demonstration building required
the help of four individuals. The analyzer, sample
crusher/mixer, and sample press each weighed over
150 pounds (70 kg).
Table 6-1. Oxford ED2000 XRF Analyzer Technical Specifications
Weight:
Dimensions:
Excitation Source:
Filters:
Detector:
Software:
Element Range:
Number of Elements:
Concentration Range:
Sample Form:
Sample Sizes:
Sample Chamber:
Computer:
Interface:
Operating Environment:
Power Requirements:
75 kilograms (XRF spectrometer only).
570 millimeters (mm) wide, 500 mm deep, and 200 mm high.
X-ray tube programmable 4-50kV, 1-1,000 uA (maximum 50 watts).
Stability <0.2%/8 hrs. Silver x-ray tube target.
Fully programmable; 8 filter positions.
Patented Pentafet detector and digital pulse processor.
Guaranteed resolution of <150eV with 17,000 cps input rate.
Output count rate >90,000 cps. Liquid Nitrogen Dewar: 10-liter capacity.
Oxford owns the XpertEase Windows software package, which allows
qualitative, semi-quantitative, and full quantitative analysis. Special
features include pre-programmed analytical parameters; full spectrometer
control, data library, x-ray mathematical models.
Sodium to uranium.
Up to 75 elements for qualitative analysis and full quantitative analysis.
ppmto 100%.
Solids, liquids, powders, granules, filter papers, films.
From 0.2 mm to 250 mm diameter.
Air path, helium/vacuum options.
250 mm diameter x 90 mm deep.
Standard automated 16-position sample carousel. Options include 8-
position sample carousel and sample spinner.
IBM compatible computer, 2.8 GHz Pentium IV processor, 80 GB hard
disk, 128 MB RAM, including 15-inch SVGA color monitor, 105-key
keyboard, two-button mouse and associated ink jet printer.
External RS232 port.
Temperature: 5 to 30 °C; 20 to 80% relative (non-condensing).
1 10-125 or 220-250V AC, 50/60 Hz 10 amps.
40
-------
6.2.1 Set up and Calibration
Unpacking the analyzer and accessories required
approximately 1 hour and the primary assembling of
the XRF unit required an additional 2 hours. Due to
an unfortunate electrical shortage when the main
laptop PC was plugged in (European voltage turned
on, rather than U.S. voltage), the laptop PC was
damaged. As a result, the initial empirical calibration
curve, which was developed using the pre-
demonstration samples and stored on the laptop PC
hard drive, was not immediately available. The
empirical calibration information was sent to the
Oxford demonstration team via email and loaded
onto a second laptop PC the next day. For the
demonstration, approximately 6 hours were needed to
make the ED2000 operational. Oxford states that an
experienced technician can set up and calibrate the
ED2000 in one to four hours.The Oxford XpertEase
software was used to set up and operate the ED2000.
Each menu helps guide the user through the process
of turning on the x-ray tube and initializing the
spectrometer optics and detector. The elements and
their characteristic energy wavelengths for analysis
and the measurement units are selected using the
software. The Oxford empirical and factory
calibration curves were verified by analyzing some of
the pre-demonstration samples and National Institute
of Standards and Technology (NIST) standards. The
empirical calibration information was used for all
sample analyses during the demonstration.
6.2.2 Demonstration Sample Processing
Oxford sent a two-man team to the demonstration site
to process the demonstration samples using the
ED2000. The field team including a senior
instrument specialist, who operated the instrument
and reduced the data, and a senior sales
representative, who served as the sample preparation
technician.
Sample preparation by Oxford for this demonstration
involved pressing ground and homogenized soil and
sediment samples into pellets for analysis. However,
the ED2000 can accommodate non-pressed samples
in polyethylene cups and covered with MylarŽ film.
The initial pre-demonstration calibration curve was
developed using pelletized samples and Oxford
determined that using the same sample preparation
techniques was important for this demonstration in
order to minimize error and maximize precision and
accuracy.
The sample processing steps included weighing 9
grams of soil, adding five wax pellets, and placing
the mixture in a stainless steel dish. A titanium plug
was also placed in the dish with the sample and wax
to aid in crushing. The dish was covered and the
sample vigorously shaken in the sample
crusher/mixer for approximately 10 seconds. The
crushing and mixing helped to homogenize the
sample with the crushed wax, and further reduced the
particle size to approximately 70 microns. The
mixture was then placed in a stainless steel cylinder
and the sample pressed into a cylindrical shaped
pellet using an aluminum sample cup and a hydraulic
press (Figures 6-2 and 6-3.) The aluminum sample
cup did not affect the XRF analysis because the x-
rays only penetrate the sample approximately 2
millimeters and the pelletized samples were
approximately 10 millimeters thick. All re-usable
parts in contact with a soil or sediment sample were
cleaned with water and paper towels. For particularly
stubborn particles, a small amount of denatured
alcohol was used. The total time required to prepare
a sample for this demonstration ranged from 9 to 15
minutes.
Figure 6-2. Oxford ED2000 soil pellet sample
preparation.
41
-------
Figure 6-3. Oxford ED2000 pelletized samples for
XRF analysis.
A combination of NIST standards and pre-
demonstration samples were used to create the
calibration curve for the demonstration. The
calibration curve had 19 points of
concentration/response and was developed by
analyzing the known concentration samples for 215
seconds. Each demonstration analysis batch involved
filling the 16 position auto-sampler with 15
demonstration samples and one standard. Actual
XRF analysis time for each sample varied between
five to nine minutes with an average run time of
around eight minutes. Differences in analysis run
times resulted from the analyzer optimizing each
individual sample by selecting the number of filters
used and the number of counts per second. Samples
with large variability in element concentrations and
density required longer analysis times. After a
sixteen sample batch sequence was completed,
Oxford would review the data and save it to the
ED2000 operating system.
Another batch of 16 samples was loaded into the
autosampler and the analyses started. The XRF
demonstration analytical results were transferred to
the laptop PC daily for storage and manipulation.
Final demonstration data were transferred at the end
of the demonstration from a universal serial bus
(USB) portable storage drive to the database
maintained by Tetra Tech for all demonstration data.
The ED2000 operating system did experience several
software glitches that stopped the XRF analysis runs.
When this occurred, the system was rebooted and the
incomplete sample analyses were restarted. In
addition, the auto-sampler slot 8 experienced some
repeated problems accommodating samples which
required some system checks and runs of only 15
samples.
6.3
General Demonstration Results
The ED2000 required substantial effort to unpack,
assemble, and prepare for operation due to the
number of components and both the size and weight
of these components. Oxford prepared and analyzed
all 326 demonstration samples in 4 days (January 25
through 28, 2005) following a day spent resolving the
computer problems identified in Section 6.2.1. On
this basis, the observer estimated a routine
throughput of 50 to 60 samples per 8-hour day,
depending on the specific processing steps and the
analysis run time.
6.4 Contact Information
Additional information on Oxford's ED2000 XRF
analyzer is available from the following source:
Dr. John I.H. Patterson
Oxford Instruments Analytical
945 Busse Road
Elk Grove Village, IL 60007
Telephone: (800) 678-1117
Email: jpatterson@msys.oxinst.com
42
-------
Chapter 7
Performance Evaluation
As discussed in Chapter 6, Oxford analyzed all 326
demonstration samples of soil and sediment at the field
demonstration site between January 25 and 28, 2005.
The samples were analyzed in batches of 16 using the
instrument autosampler. Final data were transferred at
the end of the demonstration from a USB portable
storage drive to the database Tetra Tech maintained for
all demonstration data. All the data Oxford provided at
the close of the demonstration are tabulated and
compared with the reference laboratory data and the
ERA-certified spike concentrations, as applicable, in
Appendix D.
The ED2000 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. Oxford reported
no concentration data for some of the target elements in
these blends. In these cases, the ED2000's quantitation
algorithms could not resolve a signal for a specific
element that was greater than instrument "noise" at an
acceptable level of statistical significance. Additional
information on instrument algorithms and detection
thresholds is available from the developer; contact
information is provided at the end of Chapter 6. In
selecting samples from among the 12 blends to
calculate MDLs, blends were not used where the
developer reported no concentration for one or more of
the seven replicates.
The MDLs calculated for the ED2000 are presented in
Table 7-1. As shown, the data for the MDL blends
allowed only two MDLs (one for soil and one for
sediment) to be calculated for mercury. Between six
and 12 MDLs were calculated for the remaining target
elements. The mean MDLs in Table 7-1 are classified
as follows:
Very low (1 to 20 ppm): antimony, cadmium,
copper, selenium, silver, and vanadium.
Low (20 to 50 ppm): arsenic, chromium, lead,
mercury, nickel, and zinc.
Medium (50 to 100 ppm): none.
High (greater than 100 ppm): none.
No trends could be discerned in the MDLs calculated in
terms of sample matrix (soil versus sediment) or blend.
For antimony, however, the mean calculated MDL of
18 ppm was biased high by an extreme value of 69 ppm
calculated for Blend 65. This MDL was more than four
times higher than the next highest MDL of 16 ppm
calculated for antimony in Blend 12. Review of the
analytical data for Blend 65 indicated that the high
MDL was the result of a high relative degree of
imprecision in the replicate results the vendor reported
for this blend.
43
-------
Table 7-1. Evaluation of Sensitivity Method Detection Limits for the Oxford ED20001
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 ED2000 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 ED2000 MDL
Antimony
ED2000
MDL2
7
NC
11
NC
7
16
5
NC
NC
6
NC
69
18
ED2000
Cone3
17
ND
33
481
o
3
241
8
ND
ND
o
J
ND
54
Ref. Lab
Cone4
17
ND
8
118
ND
62
ND
ND
ND
ND
ND
11
Copper
ED2000
MDL2
9
15
26
NC
12
NC
25
NC
NC
9
20
27
18
ED2000
Cone3
47
58
179
2,716
40
953
51
1,997
1,696
41
111
87
Ref. Lab
Cone4
47
49
160
1,243
31
747
50
1,986
1,514
36
94
69
Arsenic
ED2000 ED2000 Ref. Lab
MDL2 Cone3 Cone4
23
21
NC
NC
10
NC
25
25
35
38
14
41
26
121
69
886
17,111
55
1,229
20
23
38
47
24
309
1.5
47
477
3,943
39
559
9
10
11
31
14
250
Lead
ED2000
MDL2
NC
68
NC
NC
30
NC
13
27
20
12
13
20
ED2000
Cone3
1,033
95
3,273
29,881
70
3,745
17
41
56
36
45
43
Ref. Lab
Cone4
1,200
78
3,986
33,429
72
4,214
17
33
51
26
27
25
25
Cadmium
ED2000 ED2000 Ref. Lab
MDL2 Cone3 Cone4
NC
3
3
7
NC
14
NC
NC
NC
NC
3
3
6
ND
2
10
49
ND
212
ND
ND
ND
ND
1
47
ND
1.9
12
91
0.96
263
ND
ND
ND
ND
ND
44
Mercury
ED2000
MDL2
NC
NC
NC
NC
NC
NC
11
NC
NC
NC
NC
34
23
ED2000
Cone3
ND
ND
ND
ND
ND
ND
54
ND
ND
ND
ND
24
Ref. Lab
Cone4
ND
ND
0.83
15
0.14
1.8
56
0.24
ND
ND
ND
32
Chromium
ED2000 ED2000 Ref. Lab
MDL2 Cone3 Cone4
67
81
79
74
16
18
40
25
28
12
99
39
48
351
107
109
71
101
81
228
79
160
89
107
329
167
121
133
55
116
101
150
63
133
75
102
303
Nickel
ED2000
MDL2
17
16
14
84
10
33
31
13
34
18
24
29
27
ED2000
Cone3
123
78
101
277
78
137
289
154
377
194
263
325
Ref. Lab
Cone4
83
60
70
57
60
91
213
72
196
174
202
214
44
-------
Table 7-1. Evaluation of Sensitivity Method Detection Limits for the Oxford ED20001 (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 ED2000 MDL
Selenium
ED2000 ED2000 Ref. Lab
MDL2 Cone3 Cone4
3
NC
NC
NC
NC
3
4
NC
NC
3
6
7
4
2
ND
ND
ND
ND
12
1
ND
ND
5
3
16
ND
ND
ND
ND
ND
15
ND
ND
ND
4.6
ND
22
Silver
ED2000 ED2000
MDL2 Cone3 Ref. Lab4
NC
NC
6
7
NC
2
NC
3
3
NC
2
7
4
ND
ND
11
69
ND
28
ND
3
4
ND
1
39
ND
0.93
14
144
ND
38
ND
ND
6.2
ND
ND
41
Vanadium
ED2000 ED2000 Ref. Lab
MDL2 Cone3 Cone4
NC
NC
6
7
NC
2
NC
3
3
NC
2
7
4
29
84
79
65
70
60
123
73
81
81
62
64
1.2
55
56
34
51
45
67
96
76
57
38
31
Zinc
ED2000 ED2000 Ref. Lab
MDL2 Cone3 Cone4
30
31
NC
NC
27
NC
22
55
45
29
34
NC
34
34
254
889
11,812
111
2,745
106
190
163
96
164
2175
24
229
886
5,657
92
2,114
90
160
137
69
137
1,843
Notes and abbreviations:
1 Detection limits and concentrations are milligrams per kilogram (mg/kg), or parts per million (ppm).
2 MDLs calculated from the 12 MDL sample blends for the ED2000 in this technology demonstration (in bold typeface for emphasis).
3 This column lists the mean concentration reported for this MDL sample blend by the ED2000.
4 This column lists the mean concentration reported for this MDL sample blend by the reference laboratory.
Cone Concentration
MDL Method detection limit.
NC The MDL was not calculated because reference laboratory concentrations exceeded five times the expected MDL range of 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.
45
-------
The mean MDLs calculated for the ED2000 are
compared in Table 7-2 with the mean MDLs for all
developers 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 ED2000 are
comparable to or lower than the demonstration-wide
means for all the target elements. The greatest
differences between the Oxford ED 2000 data and the
demonstration data as a whole are observed for
antimony, cadmium, silver, and vanadium, where the
ED2000 MDLs are one-third or less of the
demonstration-wide means. The ED2000 MDLs are
also significantly lower than the mean MDLs
calculated from EPA Method 6200 data for all of the
target elements. Reasons for the slightly increased
sensitivity of the ED2000 relative to other field
portable XRF instruments may include: (1) the high-
resolution, nitrogen-cooled detector that was used,
(2) the evacuation of the sample chamber in the
instrument to limit x-ray scattering by air during
analysis, and (3) the program-specific calibration by
the vendor using pre-demonstration samples (Chapter
6).
Table 7-2. Comparison of ED2000 MDLs to All -Instrument Mean MDLs and EPA Method 6200 Data1
Element
Antimony
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Oxford ED2000
Mean MDLs2
18
26
6
48
18
25
23
27
4
4
4
34
All XRF Instrument
Mean MDLs3
61
26
70
83
23
40
23
50
8
42
28
38
EPA Method 6200
Mean Detection Limits4
55 5
92
NR
376
171
78
NR
100 5
NR
NR
NR
89
Notes:
1 Detection limits are in units of milligrams per kilogram (mg/kg), or parts per million (ppm).
2 The mean MDLs calculated for this technology demonstration, as presented in Table 7-1.
3 The mean MDLs calculated for all eight XRF instruments participating in the technology
demonstration.
4 Mean values calculated from Table 4 of Method 6200 (EPA 1998, www.epa.gov/sw-846).
5 Only one value reported.
EPA U.S. Environmental Protection Agency.
MDL Method detection limit.
NR No MDLs or LODs reported for this element.
46
-------
7.2 Primary Objective 2 Accuracy and
Comparability
The number of demonstration sample blends that met
the criteria for evaluation of accuracy, as described in
Section 4.2.2, was generally in the range of 40 to 70
for most elements. However, somewhat low numbers
of acceptable blends were noted for antimony (29),
cadmium (26), mercury (26), selenium (25), and
silver (24). RPDs between the mean concentrations
reported by the ED2000 and the reference laboratory
were calculated for each blend that met the criteria
for an element.
Table 7-3 presents the median RPDs, along with the
number or RPD results used to calculate the median,
for each target element. These statistics are provided
for the demonstration as a whole, as well as for
subpopulations grouped by 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 (for all
demonstration blends and spikes):
Very good (median RPD less than 10 percent):
nickel.
Good (median RPD between 10 and 25 percent):
cadmium, chromium, copper, lead, mercury,
silver, and zinc.
Fair (median RPD between 25 percent and 50
percent): arsenic, selenium, and vanadium.
Poor (median RPD greater than 50 percent):
antimony and iron.
The median RPD was used for this evaluation
because it is less affected by extreme values than is
the mean. (The initial evaluation of the RPD
populations showed that they were right-skewed or
lognormal.) However, the classification of the
elements based on accuracy generally stayed the
same when the mean rather than the median RPD was
used for the evaluation (Appendix E).
Review of the median RPD values for the various
media and concentration subpopulations in Table 7-3
indicates that RPDs were generally higher in soil than
in sediment for arsenic, cadmium, chromium, and
silver. Therefore, the demonstration data set implies
that the ED2000 attained a lower level of accuracy
for these elements in soil. The only significant
difference or trend noted in terms of sample
concentration levels was a high relative median RPD
of 49.4 percent observed for mercury in Level 2
concentration soil samples (200 to 1,000 ppm).
Review of the data indicated that this value was
biased by high RPDs for multiple blends from the
Sulphur Bank mine site (Blends 23 through 26).
Section 5.3.3 indicated that reference laboratory data
for antimony were consistently biased low when
compared with the ERA-certified spike
concentrations. This effect may be caused when
antimony compounds used for spiking volatilize,
resulting in loss of antimony during the sample
digestion process at the reference laboratory.
Therefore, Table 7-3 includes a second accuracy
evaluation for antimony, comparing the ED2000
results with the ERA-certified values. As shown, this
comparison indicates far better performance for
antimony than does the comparison to the reference
laboratory results; the overall median RPD using the
ERA-certified values was 3.9 percent, compared with
an overall median of 117 percent using the reference
laboratory data. Compensating for potential
laboratory bias, use of the ERA-certified values
improves apparent XRF performance from antimony
from "poor" to "very good."
As an additional comparison, Table 7-3 presents the
overall average of the median RPDs for all eight XRF
instruments. Complete summary statistics for the
RPDs across all eight XRF instruments are included
in Appendix E (Table E-l). Table 7-3 indicates that
the median RPDs for the ED2000 were equivalent to
or lower than the all-instrument medians for the
majority of the target elements. For mercury and
nickel, the ED2000 median RPDs were significantly
lower, strongly implying a higher level of accuracy.
In contrast, higher median RPDs for the ED2000
relative to the all-instrument medians (indicating
lower accuracy) were observed for antimony, arsenic,
iron, and selenium.
In addition to calculating RPDs, the evaluation of
accuracy included preparing linear correlation plots
of ED2000 concentration values against the reference
laboratory values. These plots are presented for the
47
-------
Table 7-3. Evaluation of Accuracy Relative Percent Differences Versus Reference Laboratory Data for the Oxford ED2000
Matrix
Soil
Sediment
All Samples
All
Samples
Sample
Group
Level 1
Level 2
Level 3
Level 4
All Soil
Level 1
Level 2
Level 3
Level 4
All Sediment
ED2000
All XRF
Instruments
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Antimony
Ref
Lab
9
118.3%
5
115.5%
4
100.4%
18
114.9%
4
131.9%
3
147.6%
3
98.7%
-
11
131.5%
29
117.7%
206
84.3%
ERA
Spike
1
20.3%
1
26.0%
3
7.1%
5
20.3%
4
2 9%
3
0.4%
3
5.2%
-
11
2 2%
16
3.9%
110
70.6%
Arsenic
15
55.2%
4
74.8%
3
103.0%
22
68.7%
17
42.3%
4
12.0%
2
19.9%
-
23
37.3%
45
49.7%
320
26.2%
Cadmium
7
39.5%
7
28.8%
9
27.4%
16
35.6%
3
10.8%
4
1.1%
3
13.5%
-
10
6.3%
26
18.3%
209
16.7%
Chromium
28
40.5%
4
12.4%
0
30.7%
34
39.7%
20
24.8%
3
6.2%
3
5.4%
-
26
17.9%
60
24.8%
338
26.0%
Copper
16
14.7%
7
29.6%
2
8.9%
25
17.1%
7
15.3%
4
11.9%
10
7.3%
-
21
10.3%
46
13.5%
363
16.2%
Iron
5
175.1%
13
62.5%
13
61.0%
7
51.4%
38
62.3%
3
183.5%
18
90.3%
4
84.1%
6
65.9%
31
88.7%
69
78.1%
558
26.0%
Lead
16
17.1%
4
13.1%
8
13.1%
4
23.8%
32
14.7%
15
16.1%
4
5.9%
3
2.7%
-
22
11.5%
54
14.3%
392
21.5%
Mercury
7
4.6%
7
49.4%
2
19.7%
16
20.9%
3
28.8%
4
22 1%
3
23.1%
-
10
23.3%
26
23.3%
192
58.6%
Nickel
24
9.5%
5
10.5%
6
3.8%
35
8.4%
17
19.7%
6
4.8%
4
3.9%
-
27
8.6%
62
8.6%
403
25.4%
Selenium
4
30.9%
5
32.3%
4
27.7%
13
31.5%
5
30.7%
4
27.3%
3
31.4%
-
12
31.0%
25
31.4%
195
16.7%
Silver
3
43.4%
3
39.3%
6
18.2%
12
41.1%
5
11.7%
4
16.4%
3
34.5%
-
12
13.5%
24
23.0%
177
28.7%
Vanadium
13
41.4%
4
22.7%
4
27.8%
21
31.6%
6
19.6%
8
32.9%
3
18.0%
-
17
27 2%
38
30.1%
218
38.3%
Zinc
20
19.3%
6
24.3%
8
23.6%
34
22 7%
18
22 2%
5
8.8%
4
7.8%
-
27
17.4%
61
19.3%
471
19.4%
Notes:
All RPDs presented in this table are absolute values.
No samples reported by the reference laboratory in this concentration range.
ERA Environmental Resource Associates, Inc.
Not
NC calculated.
Number Number of samples appropriate for accuracy evaluation.
Ref Lab Reference laboratory (Shealy Environmental Services, Inc.)
RPD Relative percent difference.
48
-------
individual target elements in Figures E-l through E-
13 of Appendix E. The plots include a 45-degree line
that shows the "ideal" relationship between the
ED2000 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 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 mercury and nickel met all three of these
criteria. The correlation plot for nickel is displayed
in Figure 7-1 as an example of the correlations
obtained for these elements.
Table 7-4. Summary of Correlation Evaluation for the ED2000
Notes:
b
m
9
r
Target Element
Antimony (vs. Reference Lab)
Antimony (vs. ERA Certified Value)
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
m
2.99
0.90
1.75
0.93
0.83
0.98
1.91
1.06
0.88
1.02
0.73
0.95
1.12
1.66
b
60
100
106
-18
50
107
8735 1
-218 1
-4
21
1
-1
18
-271 1
r2
0.84
0.79
0.69
0.98
0.89
0.89
0.83
0.90
0.99
0.99
0.99
0.85
0.93
0.85
Correlation
Moderate
Moderate
Moderate
High
Moderate
Moderate
Moderate
High
High
High
High
Moderate
High
Moderate
Bias
High
High
..
..
..
High
..
Low
High
For iron, no MDL was calculated and the high intercept value was the result of the extreme range of
concentrations in the demonstration samples. To a lesser extent, high intercepts were also produced in
the lead and zinc plots from the large concentration ranges in the demonstration samples.
No bias observed.
Y-intercept of correlation line.
Slope of correlation line.
Correlation coefficient of correlation line.
49
-------
3500
3000
a.
X
0 2000
0
1
3
o
1000
500
Figure 7-1.
OIA ED2000
- Linear (OIA ED2000)
Linear correlation plot for Oxford ED2000
showing high correlation for nickel.
^
_^^,,/"*
R2 =0.99
*
^"""
* ^,^"
i*^
^^
S*^"
*^:
J^^
0
500 1000
1500 2000 2500
Reference Laboratory (ppm)
3000
3500
General observations from the correlation plots are as
follows:
The elements with a high relative degree of
correlation between the ED2000 and the
reference laboratory (r2 > 0.95) included
cadmium, lead, mercury, nickel, selenium, and
vanadium. Correlations for four other elements
(chromium, copper, silver, and zinc) also were
fairly high, with r2 values between 0.85 and 0.95.
Further review of the data indicated that removal
of lone high outliers from complex Blend 9
(Wickes Smelter slag) improve the r2 values for
copper, lead, and zinc to above 0.95. Thus, the
linear correlation evaluation corresponds with the
RPD evaluation in assessing the accuracy of the
XRF instrument as "good" to "fair" for all these
elements.
Elements with low relative correlations (r2 less
than 0.85) included antimony, arsenic, and iron.
The plot for arsenic is presented in Figure 7-2 as
an example of instrument performance for these
three elements, showing a high overall level of
scatter in the data (see Figures E-l and E-6 for
plots of antimony and iron). The correlation
plots again confirm the findings of the RPD
evaluation, which found high and variable
median RPDs for these elements (Table 7-3).
Figure E-l shows a second correlation analysis
was performed for antimony, comparing the
mean ED2000 concentrations for spiked blends
with the ERA-certified values rather than with
the mean concentrations reported by the
reference laboratory. However, as a result of a
few outlier data points, this analysis did not
improve the correlation coefficient for antimony,
which remained near 0.8. Use of the certified
values drastically improved the observed XRF
bias for antimony, however, reducing the slope of
the correlation line from 2.99 to near 0.9.
50
-------
Further review of the correlation plots reveals a
generalized bias in the XRF measurements for some
elements versus the laboratory method. With a slope
of 1.91 and a y-intercept of 8735 ppm, the best-fit
correlation line for iron displayed the highest positive
bias (Figure E-6). Similar positive biases (indicated
by slopes of 1.6 or more) were apparent for arsenic
and zinc. A positive bias is reasonable in XRF data
for many elements, given that the XRF measures total
element concentrations in the bulk soil. The
laboratory methods, conversely, measure only the
elements that can be extracted and solubilized from
the soil by the digestion process. However, the plots
for most of the other elements reveal only slight
biases (both high and low). A somewhat low bias
was observed for selenium with a slope of 0.73.
In conclusion, the evaluations of accuracy were
similar to the MDL evaluation in Section 7.1 in
showing an acceptable overall level of performance
by the ED2000 for the target elements. Correlations
with the reference laboratory were generally high,
and median RPDs were better for most of the
elements than those obtained by the eight
demonstration instruments combined. Factors such
as the high-resolution detection system and program-
specific calibration protocol (Chapter 6) may have
contributed to the high relative level of accuracy
attained by the ED2000. In contrast to vendor
claims, however, the ED2000 appeared to offer no
special advantage in performance for lighter elements
such as vanadium, chromium, iron, or even arsenic.
7.3 Primary Objective 3 Precision
As outlined in Section 4.2.3, precision of the ED2000
data set was evaluated by calculating RSDs for the
replicate measurements from each sample blend.
Median RSDs for the various concentration levels
and media (soil and sediment) are presented in Table
7-5. The table also presents the median RSDs for the
demonstration data set as a whole for the ED2000.
Additional summary statistics for the RSDs
(including minimum, maximum, and mean) are
provided in Appendix E (Table E-2).
Figure 7-2. Linear correlation plot for Oxford ED2000
showing variability and high bias for arsenic.
7000
6000 -
5000
4000
3000
2000 -
1000
OIA ED2000
45 Degrees
Linear (OIA ED2000)
y = 1.75x +106.47
R2=0.69
500
1000 1500 2000
Reference Laboratory (ppm)
2500
3000
51
-------
The RSD calculation found a high level of precision
for the ED2000 across all the target elements; the
highest median RSD was only 12.5 percent
(vanadium). The ranges into which the median RSDs
fell are summarized below:
Very low (median RSD between 0 and 5
percent): antimony, arsenic, cadmium, copper,
iron, mercury, nickel, selenium, silver, and zinc.
Low (median RSD between 5 and 10 percent):
chromium and lead.
Moderate (median RSD between 10 and 20
percent): vanadium.
High (median RSD greater than 20 percent):
none.
The median RSDs calculated for the soil and
sediment subsets were also below 10 percent for all
the elements except vanadium, where the median
RSDs were in the 10 to 17 percent range. No
significant differences were observed between the
RSDs for soil and sediment. Use of the mean RSDs
(Appendix E) as opposed to the median RSDs
indicated a similarly high level of precision in the
ED2000 results; mean RSDs were below 25 percent
for essentially all elements and data subpopulations.
The high overall level of precision may have been
facilitated by the high level of processing
(homogenizing, sieving, crushing, and drying)
performed on the sample blends before the
demonstration (Chapter 3). This observation is
consistent with previous SITE MMT 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 MMT 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 greatest for lead,
mercury, and vanadium, where the median RSDs
increased to between 10 and 20 percent in Level 1
blends. This observation indicates that, to a minor
extent, analytical precision for the ED2000 results is
concentration-dependent.
As an additional comparison, Table 7-5 also presents
the median RSDs calculated for all XRF instruments
that were part of the demonstration. Additional
summary statistics for the RSDs calculated across all
XRF instruments are included in Appendix E. Table
7-5 indicates that the median RSDs for the ED2000
were equivalent to or below the all-instrument
medians for all elements with the exception of lead
and vanadium, where slightly higher median RSDs
were observed. This observation indicates that the
additional sample processing and pelletization steps
Oxford performed during the demonstration may
have slightly improved data precision overall.
Table 7-6 presents median RSD statistics for the
reference laboratory for comparison to the ED2000
data and the results attained for all eight XRF
instruments combined. (Additional summary
statistics for the reference laboratory RSDs are
provided in Appendix E, Table E-3.) The median
RSDs attained by the ED2000 were lower than the
reference laboratory RSDs for all target elements
except vanadium. In comparison, the median RSDs
for all XRF instruments combined were equivalent to
or lower than the reference laboratory RSDs for 11 of
the 13 target elements (the exceptions were
chromium and vanadium).
52
-------
Table 7-5. Evaluation of Precision Relative Standard Deviations for the Oxford ED2000
Matrix
Soil
Sediment
All
Samples
All
Samples
Sample
Group
Level 1
Level 2
Level 3
Level 4
All Soil
Level 1
Level 2
Level 3
Level 4
All Sediment
ED2000
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
2.2%
5
2.8%
4
1.8%
18
2.6%
4
4.9%
4
1.6%
3
3.6%
11
2.8%
29
2.7%
206
6.1%
Arsenic
15
4.7%
4
1.7%
4
0.9%
23
3.1%
17
5.5%
4
1.3%
2
9.4%
23
5.0%
46
4.0%
320
8.2%
Cadmium
7
5.4%
7
2.3%
2
1.9%
16
2.9%
3
2.6%
4
2.2%
3
3.1%
10
2.6%
26
2.7%
209
3.6%
Chromium
28
5.7%
4
5.4%
2
1.3%
34
5.6%
21
9.2%
3
3.8%
3
2.4%
27
7.3%
61
5.6%
338
12.1%
Copper
16
5.3%
7
1.4%
2
2.3%
25
4.2%
8
4.8%
4
1.7%
10
1.4%
22
2.0%
47
2.6%
363
5.1%
Iron
5
0.7%
13
1.4%
13
3.1%
7
1.8%
38
1.6%
3
0.3%
19
1.5%
4
1.9%
6
2.1%
32
1.5%
70
1.5%
558
2.2%
Lead
16
13.5%
4
2.5%
8
1.7%
5
23.2%
33
8.4%
16
8.4%
4
1.9%
3
0.4%
23
4.9%
56
6.3%
392
4.9%
Mercury
7
14.8%
7
4.0%
2
3.6%
16
6.0%
3
16.4%
4
2.6%
3
1.6%
10
2.9%
26
4.7%
192
6.8%
Nickel
24
5.6%
5
3.7%
6
1.7%
35
4.7%
18
4.6%
6
3.0%
4
2.8%
28
4.1%
63
4.3%
403
7.0%
Selenium
4
4.0%
5
3.2%
4
2.0%
13
2.7%
5
5.1%
4
2.4%
3
1.8%
12
3.2%
25
2.8%
195
4.5%
Silver
3
3.8%
3
2.4%
6
2.3%
12
2.5%
5
4.2%
4
1.7%
3
2.9%
12
3.0%
24
2.8%
177
5.2%
Vanadium
13
17.2%
4
3.7%
4
5.2%
21
10.9%
6
18.3%
8
17.5%
3
7.1%
17
16.5%
38
12.5%
218
8.5%
Zinc
20
6.5%
6
1.7%
8
1.0%
34
3.7%
19
10.3%
5
1.7%
4
1.6%
28
6.1%
62
4.7%
471
5.3%
Notes:
Number
RSD
No samples reported by the reference laboratory in this concentration range.
Number of samples appropriate for precision evaluation.
Relative standard deviation
53
-------
Table 7-6. Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory Versus the ED2000 and All
Demonstration Instruments
Matrix
Soil
Sediment
All
Samples
All
Samples
All
Samples
Ref. Lab
Ref. Lab
Ref. Lab
ED2000
A11XRF
Instalments
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Antimony
17
9.8%
7
9.1%
24
9.5%
29
2.7%
206
6.1%
Arsenic
23
12.4%
24
9.2%
47
9.5%
46
4.0%
320
8.2%
Cadmium
15
9.0%
10
8.2%
25
9.0%
26
2.7%
209
3.6%
Chromium
34
10.6%
26
7.5%
60
8.4%
61
5.6%
338
12.1%
Copper
26
9.1%
21
8.9%
47
8.9%
47
2.6%
363
5.1%
Iron
38
8.7%
31
8.1%
69
8.5%
70
1.5%
558
2.2%
Lead
33
13.2%
22
7.4%
55
8.6%
56
6.3%
392
4.9%
Mercury
16
6.6%
10
6.9%
26
6.6%
26
4.7%
192
6.8%
Nickel
35
10.0%
27
7.3%
62
8.2%
63
4.3%
403
7.0%
Selenium
13
7.1%
12
7.6%
25
7.4%
25
2.8%
195
4.5%
Silver
13
7.5%
10
6.6%
23
7.1%
24
2.8%
177
5.2%
Vanadium
21
6.6%
17
8.1%
38
7.2%
38
12.5%
218
8.5%
Zinc
35
9.1%
27
6.9%
62
7.4%
62
4.7%
471
5.3%
Notes:
Ref. Lab.
XRF
Reference laboratory (Shealy Environmental Services, Inc.).
X-ray fluorescence.
54
-------
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 and are 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 table indicates a clear increase in
the median RPD for arsenic at the higher lead-to-
arsenic ratios. Specifically, a median RPD of 35
percent at low interferent ratios increases to 75
percent at moderate ratios and further to 138 percent
in the high interferent ratios. Using the criteria
applied in Section 7.2, high concentrations of lead
therefore diminish the accuracy of the ED2000 from
"fair" to "poor" for arsenic. Similarly, Table 7-7
indicates that high concentrations of copper reduce
instrument accuracy for nickel, although overall
accuracy remains "good" for the high-
ratio blends (with a median RPD of 24 percent). In
presenting statistics for unmodified RPDs as well as
the absolute values of the RPDs, Appendix E further
shows that the interferences by lead and copper tend
to increase the positive bias of the results for arsenic
and nickel (as indicated by more negative unmodified
RPDs).
Table 7-7 and Appendix E reveal no other trends in
RPDs that would indicate significant potential
interferences. Although interference effects were
limited for the ED2000, the data show significant
potential effects of high lead concentrations on
results for arsenic, despite the program-specific
calibration of the instrument that was based on pre-
demonstration samples.
7.5 Primary Objective 5 Effects of Soil
Characteristics
The population of RPDs between the results for the
ED2000 and the reference laboratory were further
evaluated against sampling site and soil type.
Separate sets of summary statistics were developed
for the median RPDs associated with each sampling
site for comparison to the other sites and to the
demonstration data set as a whole. The site-specific
median RPDs are presented in Table 7-8, along with
descriptions of soil and sediment type from
observations during sampling at each site. Complete
RPD summary statistics for each soil type (minimum,
maximum, and mean) are presented in Appendix E
(Table E-5).
Another perspective on the effects of soil type was
developed by graphically assessing outliers and
extreme values in the RPD data sets for each target
element. This evaluation focused on correlating
these extreme values with sample types or locations
for multiple elements across the data set. Some
outliers and extreme values are apparent in the
correlation plots (Figures E-l through E-13) and are
further depicted for the various elements on box and
whisker plots in Figure E-14.
55
-------
Table 7-7. Effects of Interferent Elements on the RPDs (Accuracy) for Target Elements, Oxford ED20001
Parameter
Interferent/
Element Ratio
Number of
Samples
Median RPD of
Target Element2
Median Interferent
Concentration
Median Target
Element
Concentration
Lead Effects on Arsenic
<5 5-10 >10
29 6 9
34.7% 74.8% 138.3%
76 5087 2239
148 1057 373
Copper Effects on
Nickel
<5 5-10 >10
43 5 14
7.2% 8.5% 23.6%
141 1160 2409
191 156 149
Nickel Effects on
Copper
<5 5-10 >10
37 1 8
13.5% 16.1% 12.6%
156 378 2284
1006 92 121
Zinc Effects on Copper
<5 5-10 >10
34 1 11
12.4% 11.3% 15.9%
207 889 3940
1093 179 135
Copper Effects on Zinc
<5 5-10 >10
48 3 10
21.0% 20.9% 17.3%
179 1259 2329
619 146 177
Notes:
1 Concentrations are reported in units of milligrams per kilogram (rag/kg), or parts per million (ppm).
2 All median RPDs presented in this table are based on the population of absolute values of the individual RPDs.
< Less than.
> Greater than.
RPD Relative percent difference.
56
-------
Table 7-8. Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Oxford ED2000
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Soil
Sediment
Soil
Site
AS
BN
CN
KP
LV
RF
SB
TL
WS
All
Matrix
Description
Fine to medium sand (steel
processing)
Sandy loam, low organic (ore
residuals)
Sandy loam (burn pit residue)
Soil: Fine to medium quartz sand.
Sed.: Sandy loam, high organic.
(Gun and skeet ranges)
Clay/clay loam, salt crust (iron
and other precipitate)
Silty fine sand (tailings)
Coarse sand and gravel (ore and
waste rock)
Silt and clay (slag-enriched)
Coarse sand and gravel (roaster
slag)
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Antimony
4
120.7%
2
88.7%
2
8.6%
4
107.7%
5
130.9%
7
115.5%
3
150.9%
2
122.4%
29
117.7%
Arsenic
1
182.8%
7
74.5%
1
49.7%
_
11
38.7%
12
37.0%
5
32.7%
2
123.2%
6
114.0%
45
49.7%
Cadmium
3
39.5%
5
35.2%
2
30.5%
_
5
7.4%
5
4.6%
1
0.7%
2
12.4%
2
51.1%
25
16.8%
Chromium
2
70.8%
7
22.9%
2
63.8%
4
64.4%
11
14.8%
12
11.8%
11
41.6%
5
23.2%
6
15.9%
60
24.8%
Copper
3
16.2%
6
24.5%
o
5
21.9%
2
21.6%
4
9.1%
13
13.6%
4
10.3%
7
7.6%
5
37.5%
47
13.6%
Iron
3
42.1%
7
59.5%
3
60.8%
6
179.6%
12
87.6%
13
86.1%
12
60.8%
7
98.4%
7
78.1%
70
78.4%
Lead
1
0.0%
2
9.7%
_
4
1.3%
5
23.5%
11
28.9%
3
87.7%
26
23.3%
57
-------
Table 7-8. Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Oxford ED2000 (Continued)
Matrix
Soil
Soil
Soil
Soil&
Sediment
Sediment
Sediment
Soil
Sediment
Soil
Site
AS
BN
CN
KP
LV
RF
SB
TL
WS
All
Matrix
Description
Fine to medium sand (steel
processing)
Sandy loam, low organic (ore
residuals)
Sandy loam (burn pit residue)
Soil: Fine to medium quartz sand.
Sed.: Sandy loam, high organic.
(Gun and skeet ranges)
Clay/clay loam, salt crust (iron
and other precipitate)
Silty fine sand (tailings)
Coarse sand and gravel (ore and
waste rock)
Silt and clay (slag-enriched)
Coarse sand and gravel (roaster
slag)
Statistic
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Number
Median
Mercury
1
0.0%
2
9.7%
_
4
1.3%
5
23.5%
11
28.9%
3
87.7%
26
23.3%
Nickel Selenium
3
5.2%
6
12.3%
o
5
10.5%
o
3
4.4%
11
19.5%
13
5.4%
11
4.0%
6
28.5%
7
19.1%
63
8.6%
1
32.3%
4
30.9%
2
29.4%
_
5
28.2%
5
31.4%
3
35.7%
4
25.8%
1
28.9%
25
31.4%
Silver
1
17.3%
4
41.1%
2
36.2%
_
4
14.2%
5
11.7%
1
65.4%
4
23.0%
3
54.6%
24
23.0%
Vanadium
1
27.2%
4
27.5%
1
3.7%
_
9
30.0%
3
35.7%
10
51.6%
7
12.0%
o
6
36.4%
38
30.1%
Zinc
3
12.4%
7
23.2%
3
22.6%
2
27.1%
10
34.6%
13
13.8%
11
16.9%
7
17.4%
6
20.9%
62
19.3%
Notes:
AS Alton Steel Mill
BN Burlington Northern railroad/ASARCO East.
CN Naval Surface Warfare Center, Crane Division.
KP KARS Park - Kennedy Space Center.
LV Leviathan Mine/Aspen Creek.
RF Ramsey Flats - Silver Bow Creek.
SB Sulphur Bank Mercury Mine.
TL Torch Lake Superfund Site.
WS Wickes Smelter Site.
Other Notes:
Number
RPD
No samples reported by the reference laboratory in this concentration range.
Number of demonstration samples evaluated.
Relative percent difference.
58
-------
Review of Table 7-8 reveals few extremes in
performance of the XRF instrument based on sample
matrix. Although elevated RPDs were observed in
some blends relative to the remainder of the data sets
for the target elements, few extremes were observed
that would indicate clear matrix effects. Moreover,
no specific sample sites appear to correlate with
abnormally good or poor performance across many or
all of the target elements. Instead, elevated median
RPDs for some target elements were observed on a
more limited basis in specific site blends. For
example, cadmium, copper, and silver displayed
elevated median RPDs in blends from the Wickes
Smelter site, whereas antimony, mercury, and nickel
displayed similar RPDs in blends from the Torch
Lake site. Iron exhibited an extreme median RPD of
179.6 percent in KARS Park blends, while vanadium
displayed a high relative median RPD of 51.6 percent
in blends from the Sulphur Bank Mercury Mine. In
some cases, the identification of a potential matrix
affect based on elevated or extreme RPDs was
limited by low sample numbers. For example, a high
RPD of 182.8 percent was observed for arsenic in an
Alton Steel site blend, but only a single sample from
this site had been assessed as acceptable for accuracy
evaluation (using the approach described in Section
4.2.2). Thus, the evaluation of matrix affects based
on median RPD was complex and showed no clear or
general trends.
Review of the box and whiskers plot (Figure E-14)
and the correlation plots from the accuracy evaluation
revealed no other general trends in RPDs relative to
sampling site. The outliers and extreme values
apparent in Figure E-14 were broadly distributed
among seven of the nine sampling sites. This
evaluation verified the slight prevalence of outliers in
the KARS Park blends (for iron) and in Wickes
Smelter blends (for multiple metals). As discussed in
Section 2.3, the KARS Park site was contaminated by
former gun range operations. Soil samples from this
site consisted of fine to medium quartz sand with
anticipated contamination from antimony, arsenic,
chromium, copper, lead, and zinc. In comparison, the
soil matrix from the Wickes Smelter site was
described as roaster slag, consisting of a black, fairly
coarse sand and gravel material that again contained
high concentrations of multiple target elements.
A smaller number of outlier blends apparent on
Figure E-14 were associated with the Leviathan Mine
site. However, sample matrix appeared to have a
minor effect on the overall accuracy of the XRF data.
The box and whiskers plot in Figure E-14 shows that
the broad overall distributions of RPDs for many
elements, such that relatively few high outliers or
extreme values could be identified. The distributions
of RPDs were sufficiently broad that no high outliers
or extreme values were discernable for antimony,
arsenic, and vanadium.
7.6 Primary Objective 6 Sample
Throughput
The Oxford two-person field team was able to
analyze all 326 demonstration samples in 5 days at
the demonstration site. Once the ED2000 instrument
had been set up and operations had been streamlined,
the Oxford field team was able to analyze a
maximum of 123 samples during an extended work
day. This sample throughput was achieved by using
different members of the field team to perform
sample preparation and instrumental analysis and by
using the autosampler to process samples through the
XRF spectrometer. Without an extended work day,
and taking into account instrument set-up and
demobilization time, it was estimated that the Oxford
field team would have averaged about 56 samples per
day.
This estimated sample throughput for a normal
working day was lower than that observed for the
other instruments that participated in the
demonstration (average of 66 samples per day). The
lower sample throughput was primarily the result of
the unique sample preparation process employed,
which involved pelletizing each sample prior to
instrumental analysis. If a powdered sample would
have been used instead, the sample throughput would
have increased.
A detailed discussion of the time required to
complete the various steps of sample analysis using
the ED2000 is included as part of the labor cost
analysis in Section 8.3.
7.7 Primary Objective 7 Technology Costs
The evaluations pertaining to this primary objective
are fully described in Chapter 8, Economic Analysis.
59
-------
7.8 Secondary Objective 1 Training
Requirements
The instrument operator must be suitably trained to
safely set up and operate the instrument to
successfully use XRF and obtain the level of data
quality required for specific projects. The amount of
training required depends on the complexity of the
instrument and the associated software.
Oxford recommends that the operator have a high
school diploma and basic operational training. Field
or laboratory technicians are generally qualified to
operate the instrument. The ED2000 comes equipped
with a modem that allows qualified Oxford
technicians to evaluate system functionality and to
provide troubleshooting guidance from a remote
location. During the demonstration, the Oxford staff
members who operated the instrument held Ph.D.
degrees in chemistry, with about 5 years of
experience in operation of the ED2000.
Oxford provides free on-site training for all
purchasers of the instrument. Topics vary based on
the end users' intended applications. The training
generally lasts 3 days; however, the training period
can be extended for very complex applications.
In addition to the general instrument operational
instruction and training, the operator and data
manager must be familiar with using a windows-
based personal computer (PC) to operate the ED2000
software (Xpert Ease).
7.9 Secondary Objective 2 Health and
Safety
The health and safety requirements for operation of
the instrument were identified. Included in the
evaluation were the potential risks from exposure to
radiation and to reagents. However, not included in
the evaluation were potential risks from exposure to
site-specific hazardous materials or to physical safety
hazards.
Two potential areas for operator risks were evaluated:
(1) radiation from the instrument itself, and (2)
exposure to any reagents used in preparing and
analyzing the samples. As mentioned above, any
potential risks from sample contaminants were not
addressed, simply because of the wide range in site
conditions where the instrument may be used.
The ED2000 contains an x-ray tube that is positioned
to deliver x-rays into a lead-shielded, sealed sample
chamber. Each instrument is equipped with a sample
chamber lock, and large lights indicate when x-rays
are being generated. The instrument will not operate
if the lock is not latched or if the lights are burned
out. The sample chamber lock, lead-shielded sample
chamber, and safety lights are designed to minimize
possible exposure to the x-ray radiation.
The second potential source of risk to XRF
instrument operators is exposure to reagent
chemicals. The two reagents used during the
demonstration are wax (for sample pellet preparation)
and liquid nitrogen (for cooling the detector). The
wax is not hazardous; however, care must be taken
when filling the detector's 10-liter reservoir (Dewar)
with liquid nitrogen because of its extremely low
temperature (-196°C or -321°F). The instrument
loses approximately 1 liter per day, requiring the
Dewar to be refilled every 10 days. In addition, the
instrument will not operate without enough liquid
nitrogen to cool the detectors. The risks from
exposure to radiation or to liquid nitrogen are
minimal when the instrument is operated according to
the manufacturer's recommendations, however.
7.10 Secondary Objective 3 Portability
Portability depends on the size, weight, number of
components, and power requirements of the
instrument, and the reagent required. The size of the
instrument, including physical dimensions and
weight, is presented in Table 6-1. The number of
components, power requirements, support structures,
and reagent requirements were also recorded. Two
distinctions were made during the demonstration
regarding portability:
(1) The instrument was considered fully portable if
the dimensions were such that the instrument
could be easily brought directly to the sample
location.
(2) The instrument was considered transportable if
the dimensions and power requirements were
such that the instrument could be moved to a
location near the sampling location, but required
a larger and more stable environment (for
example, a site trailer with AC power and stable
conditions).
60
-------
Based on the dimensions and power requirements,
the ED2000 is defined as transportable. It is capable
of being transported to a field trailer or other fixed
location with the required power supply and a stable,
weatherproof environment.
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) Oxford offers a 12-month
limited warranty on parts and labor. Additional
warranties, optional extended warranties, and service
contracts vary by country. Since x-ray tube sources
are new to the world of portable instrumentation, no
clear data have been obtained on the useful life that
can be assumed. The average lifespan of an x-ray
tube in the ED2000 is approximately 10,000 hours,
which is equivalent to approximately 7 years.
Oxford is continually upgrading both the instrument
and software to enhance environmental analysis. It is
expected that Oxford will continue to provide
upgrades to instruments and software as long as there
is a market for improved technologies.
The ED2000 instrument is made with hard-tool
plastic that is durable and impact-resistant under
nearly all field applications. The instrument is not
weatherproof and must be located in a stable,
weatherproof environment.
7.12 Secondary Objective 5 Availability
Oxford Instruments Analytical has offices
worldwide. New instruments are available from the
Oxford offices in Concord, Massachusetts, and Elk
Grove Village, Illinois. Oxford provides product
support for all instruments through service contracts
tailored to the client's needs. A network of 30
service representatives provide service and customer
support for instrument owners.
The ED2000 is available for lease or for long-term
rental on a case-specific basis. The ED2000 is not
available from third party vendors for lease or rental.
61
-------
This page was left blank intentionally.
62
-------
Chapter 8
Economic Analysis
This chapter provides cost information for the Oxford
ED2000 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 ED2000.
8.1 Equipment Costs
Capital equipment costs include either purchase or
rental of the ED2000 and any ancillary equipment
that is generally needed for sample analysis. (See
Chapter 6 for a description of available accessories.)
Information on purchase price for the analyzer and
accessories was obtained from Oxford.
The ED2000 instrument costs between $65,000 and
$85,000, depending on the configuration. The cost of
the unit used for the XRF demonstration is
approximately $80,000, including peripherals
(autosampler, sample crusher and mixer, sample
press, computer, monitor, and printer). At the time of
the demonstration, Oxford indicated that models are
not available for rental. For evaluation and
comparison purposes later in this Chapter, an
estimated rental cost was derived based on similar
XRF technologies where both purchase and rental
prices were available. Long-term lease programs are
also available through Oxford. Purchased models
include a 1-year parts and labor warranty; this
warranty may be extended for $9,000 per year. The
lifespan of the x-ray tube is about 5 to 7 years for
normal usage.
The purchase price and shipping cost for the Oxford
ED2000 exceed the average costs for all XRF
instruments that participated in the demonstration, as
shown in Table 8-1.
Table 8-1. Equipment Costs
Cost Element
Shipping
Capital Cost
(Purchase)
Weekly Rental
(estimated)
Autosampler (for
Overnight Analysis)
ED2000
$750
$80,000
$3,700
Included
XRF
Demonstration
Average 1
$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, MylarŽ film, spatulas or
scoops, wipes, and disposable gloves. The rate of
consumption for these supplies was based on
observations during the field demonstration. Unit
prices for these supplies were based on price quotes
from independent vendors of field equipment.
Additional costs include purchase of liquid nitrogen
for detector cooling and rental or purchase of sample
preparation equipment, if required for the intended
use.
The ED2000 was operated for 4 days to complete the
analysis of the demonstration sample set (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 $250
for 326 samples or $0.75 per sample.
8.3
Labor Costs
Labor costs were estimated based on the total time
required by the field team to complete the analysis of
all 326 samples and the number of people in the field
team, while making allowances for field team
63
-------
members that had responsibilities other than sample
processing during the demonstration. For example,
some developers sent sales representatives to the
demonstration to communicate with visitors and
provide outreach services; this type of staff time was
not included in the labor cost analysis.
While overall labor costs were based on the total time
required to process samples, the time required to
complete each definable activity was also measured
during the field demonstration. These activities
included:
Initial setup and calibration.
Sample preparation.
Sample analysis.
Daily shutdown and startup.
End of proj ect packing.
The estimated time to complete each of these
activities using the ED2000 is listed in Table 8-2.
The "total processing time per sample" was
calculated as the sum of all these activities assuming
that the activities were conducted sequentially;
therefore, it represents how much time it would take
a single trained analyst to complete these activities.
However, the "total processing time per sample" does
not include activities that were less definable in terms
of the amount of time taken, such as data
management and procurement of supplies, and is
therefore not a true total.
The time to complete all sample analysis using the
ED2000 is compared with the average of all XRF
instruments in Table 8-2 and is compared with the
range of all XRF instruments in Figure 8-1. In
comparison to other XRF analyzers, the ED2000
exhibited higher-than-average times for initial setup
and calibration, sample preparation and analysis, and
end of project packing. The ED2000 exhibited a
lower-than-average time for daily shutdown and
startup because the instrument was not shut down
each night.
Sample preparation included pressing samples into
pellets to maximize data quality. However, the
ED2000 does not require pelletized samples and can
accommodate powdered samples in polyethylene
cups, covered with MylarŽ film, for analysis. (The
majority of the technology developers in this
demonstration used powdered samples.) The sample
preparation time could have been reduced from 7
minutes to 2 minutes by changing to the powdered
sample approach.
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
ED2000
85
7.0
7.9
0
115
15.5
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
64
-------
Initial Set up and Calibration
Sample Preparation
Sample Analysis
Total Processing Time
Daily Shut Down/Start Up
End of project packing
20
40
60
80
Minutes
100
120
140
Figure 8-1. Comparison of activity times for the Oxford ED2000 versus other XRF instruments.
The Oxford field team expended about 93 labor hours
to complete all sample processing activities during
the field demonstration using the ED2000. This was
significantly higher than the overall average of 69
labor hours for all instruments that participated in the
demonstration. The primary reasons that labor hours
were higher for the ED2000 include:
The unique sample preparation process
employed, which involved pelletizing each
sample prior to instrumental analysis. If a
powdered sample would have been used instead,
the labor hours would have decreased.
The additional time required to set up the
multiple components of the ED2000 system and
to maintain these components during sample
processing.
8.4 Comparison of XRF Analysis and
Reference Laboratory Costs
Two scenarios were evaluated to compare the cost for
XRF analysis using the ED2000 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.
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 ED2000 was
based on equipment rental for 1 week, along with
labor and supplies estimates established during the
65
-------
field demonstration. The estimate used for rental of
the ED2000 was a hypothetical weekly rental rate
based on a survey of rental versus purchase costs of
other XRF instruments. Labor costs were estimated
based on the number of people in the field team and
the time spent during the field demonstration to
complete the analysis of the 326 demonstration
samples. 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
ED2000 analysis cost was not adjusted for one
element versus 13 elements.
Table 8-3 summarizes the costs for the ED2000
versus the cost for analysis in a fixed laboratory.
This comparison shows that the ED2000 compares
favorably to a fixed laboratory in terms of overall
cost when a large number of elements are to be
determined. The ED2000 compares unfavorably to a
fixed laboratory when one element is to be
determined. Use of the ED2000 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 ED2000 in the example
scenario (326 samples) was estimated at $11,645.
This estimate compares with the average of $8,932
for all XRF instruments that participated in the
demonstration. However, it should be noted that
bench-top instruments, such as the ED2000, are
known to cost more than the hand-held instruments
that were included in the average cost for all XRF
instruments. In comparison to other bench-top XRF
instruments, the cost of the ED2000 for the example
scenario was similar.
Table 8-3. Comparison of XRF Technology and Reference Method Costs
Analytical Approach
ED2000 (1 to 13 elements)
Shipping
Weekly Rental
Supplies
Labor
IDW
Total ED2000 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
148
N/A
326
326
326
Item
Roundtrip
Week
Sample
Hours
Each
Sample
Sample
Sample
Unit
Rate
$750
$3,700'
$0.75
$43.8
N/A
$21
$36
$160
Total
$750
$4,100
$245
$6,460
$90
$11,645
$6,846
$6,846
$11,736
$52,160
$63,896
Notes:
1 Estimated value as Oxford currently does not have a rental rate for the ED2000.
66
-------
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 Oxford ED2000 XRF
analyzer. The evaluation design incorporated 13
target elements, 70 distinct sample blends, and a total
of 326 samples. The blends included both soil and
sediment samples from nine sampling locations. A
rigorous program of sample preparation and
characterization, reference laboratory analysis,
QA/QC oversight, and data reduction supported the
evaluation of XRF instrument performance.
One important aspect of the demonstration was the
sample blending and processing procedures
(including drying, sieving, grinding, and
homogenization) that significantly reduced
uncertainties associated with the demonstration
sample set. The vendor performed additional
processing during the demonstration to homogenize
and press the samples into uniform pellets. 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 ED2000 for
each primary and secondary objective are
summarized in Tables 9-1 and 9-2. The ED2000 and
the combined performance of all eight vendors that
participated in the XRF technology evaluation
program are compared in Figure 9-1. The
comparison in Figure 9-1 indicates that, when
compared with the program as a whole, the ED2000
showed:
Equivalent or better MDLs for all 12 of the target
elements evaluated (iron was not included in the
MDL evaluation).
Equivalent or better accuracy (RPDs) for 9 of the
13 target elements (exceptions include antimony,
arsenic, iron, and selenium). Moreover, when
RPDs for antimony are calculated versus sample
spike levels rather than reference laboratory data
(which may be biased low), accuracy for
antimony improves to better than the program as
whole.
Equivalent or better precision (RSDs) for 11 of
the 13 target elements (exceptions include lead
and vanadium).
Factors that may have contributed to high relative
level of performance include: (1) samples were
processed into uniform pellets before they were
analyzed, (2) a program-specific instrument
calibration was generated using pre-demonstration
samples, (3) the sample analysis chamber was
evacuated to limit x-ray scattering by air, (4) a high-
resolution, cryogenically cooled detector was used,
and (5) the overall stability that is expected of a
bench-top XRF. As a bench-top instrument,
however, the ED2000 is not fully portable and
requires a stable operating environment.
67
-------
Table 9-1. Summary of Oxford ED2000 Performance - Primary Objectives
Objective
Performance Summary
PI: Method
Detection Limits
Mean MDLs for the target elements ranged as follows:
o MDLs of 1 to 20 ppm: antimony, cadmium, copper, selenium, silver, and
vanadium.
o MDLs of 20 to 50 ppm: arsenic, chromium, lead, mercury, nickel, and zinc.
o MDLs greater than 50 ppm: none.
(Iron was not included in the MDL evaluation.)
The MDL calculation for mercury was based on limited data (two MDL sample
blends).
No significant differences were noted between MDLs for soil and sediment, or among
different sample blends.
The MDLs calculated were significantly lower than reference MDL data from EPA
Method 6200.
P2: Accuracy and
Comparability
Median RPDs between the ED2000 and reference laboratory data revealed the
following, with lower RPDs indicating greater accuracy:
o RPDs of 1 to 10 percent: nickel.
o RPDs of 10 to 25 percent: cadmium, chromium, copper, lead, mercury, silver,
and zinc.
o RPDs of 25 to 50 percent: arsenic, selenium, and vanadium.
o RPDs of greater than 50 percent: antimony and iron.
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 high when the ED2000 data were
compared with the reference laboratory data (with a median RPD of 117 percent) but
improved considerably when compared with certified spike values (where the median
RPD was 3.9 percent). Thus, the ED2000 appeared to be more accurate in terms of the
true concentration of antimony than the reference laboratory.
Higher RPDs (that is, lower accuracy) were observed in soil than in sediment for
arsenic, cadmium, chromium, and silver.
Correlation plots relative to reference laboratory data indicated:
o Moderate to high correlations for all target elements.
o Positive biases for arsenic, iron, and zinc.
o Negative bias for selenium.
P3: Precision
Median RSDs were good for all target elements, as follows:
o RSDs below 5 percent: antimony, arsenic, cadmium, copper, iron, mercury,
nickel, selenium, silver, and zinc.
o RSDs between 5 and 10 percent: chromium and lead.
o The RSD between 10 and 20 percent: vanadium.
Median RSDs for the ED2000 for all elements except vanadium were lower than the
RSDs calculated for the reference laboratory data, indicating slightly better precision
for the XRF instrument.
P4: Effects of
Sample
Interferences
High relative concentrations of lead reduced accuracy for arsenic; median RPDs for
arsenic increased from 35 percent to 138 percent as the concentration of lead increased.
The lead interference produced a positive bias in the arsenic results.
High relative concentrations of copper (more than 10 times) slightly reduced accuracy
for nickel; the median RPDs increased from 7 percent to 24 percent. A positive bias in
the nickel results was produced by the copper interference.
68
-------
Table 9-1. Summary of Oxford ED2000 Performance - Primary Objectives (Continued)
Objective
Performance Summary
P5: Effects of Soil
Type
Outlier RPD values, indicating low relative accuracy, were observed for
iron in blends of sandy soil from the KARS Park site, a former gun
range.
High RPD outliers were also observed for copper, lead, nickel,
selenium, and zinc in blends from the Wickes Smelter site, a complex
roaster slag matrix that contained high concentrations of many
elements.
P6: Sample
Throughput
Oxford's sample preparation protocol during the demonstration
included palletizing each sample prior to analysis and took an average
of 7 minutes per sample.
With an average instrument analysis time of 7.9 minutes per sample, the
total sample processing time was 15.5 minutes per sample.
A maximum sample throughput of 123 samples was achieved during the
field demonstration on one extended work day. A typical average
sample throughput was estimated to be 53 samples per day for an 8-
hour work day.
P7: Costs
The purchase cost was $80,000 for the ED2000 as used in the
demonstration. This cost included an optional autosampler and
processing equipment to create sample pellets. Although long-term
leases are available, the vendor does not currently offer short-term
rental.
The Oxford field team expended approximately 93 labor hours to
complete the processing of the demonstration sample set (326 samples).
In comparison, the average for all participating XRF instruments was 69
labor hours. By approximating a 1-week rental cost (based on similar
XRF instruments) and adding labor and shipping/supplies costs, a total
project cost of $11,645 was estimated for a project the size of the
demonstration using the ED2000. In comparison, the average project
cost for all participating XRF instruments was $8,932 and the cost for
fixed-laboratory analysis of all 13 elements was $63,896.
69
-------
Table 9-2. Summary of Oxford ED2000 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 ED2000.
Oxford offers free training for instrument purchasers that generally lasts
about 3 days.
The ED2000 comes equipped with a modem that allows qualified
technicians to remotely troubleshoot the instrument and guide operators.
S2: Health and
Safety
The ED2000 is equipped with safety measures to minimize possible
exposure to emissions from the x-ray tube. The instrument cannot be
operated if these safety measures are disabled.
Users of the ED2000 must be able to safely manage and dispense
cryogenic liquids (nitrogen) to operate the detector.
S3: Portability
Based on dimensions, weight, and power requirements, the ED2000 is a
transportable (as opposed to fully portable) instrument. It is best used in
a field trailer or other fixed location with the required power supply and
a stable, weatherproof environment.
S4: Durability
The ED2000 instruments have a 12-month limited warranty for parts and
labor. Additional optional warranties and service contracts are available,
depending on the country where the instrument is purchased and used.
The average lifespan of an x-ray tube in the ED2000 is anticipated to be
10,000 hours (7 years)
The ED2000 is encased in durable hard-tool plastic but is not
weatherproof. It must be used in a stable environment.
S5: Availability
New instruments are available from the Oxford offices in Concord,
Massachusetts, and Oak Park, Illinois. A world-wide network of 30
service representatives provides service and customer support.
The ED2000 is available for lease or for long-term rental on a case-
specific basis. It is not available from third-party vendors.
70
-------
Comparison of Mean MDLs:
ED2000 vs. All Instruments
100
c ~
d I
ED2000 Mean MDL
D All Instrument Mean MDL
Target Element
Comparison of Median RPDs:
ED2000 vs. All Instruments
140.0%
120.0%
100.0%
80.0%
60.0%
40.0%
20.0%
0.0%
ED2000 Median RPD
D All Instrument Median RPD
Target Element
Comparison of Median RSDs:
ED2000 vs. All Instruments
Target Element
Figure 9-1. Method detection limits (sensitivity), accuracy, and precision of the ED2000 in
comparison to the average of all eight XRF instruments.
71
-------
This page was left blank intentionally.
72
-------
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-
METŽ 2000 X-Ray Fluorescence Technology.
EPA/600/R-03/149. May.
EPA. 2004b. Innovative Technology Verification
Report: Field Measurement Technology for
Mercury in Soil and Sediment - Niton's
XLi/XLt 700 Series X-Ray Fluorescence
Analyzers. EPA/600/R-03/148. May.
EPA. 2004c. USEPA Contract Laboratory Program
National Functional Guidelines for
Inorganic Data Review. Final. OSWER
9240.1-45. EPA 540-R-04-004. October.
73
-------
APPENDIX A
VERIFICATION STATEMENT
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
SITE Monitoring and Measurement Technology Program
Verification Statement
TECHNOLOGY TYPE: X-ray Fluorescence (XRF) Analyzer
APPLICATION: MEASUREMENT OF TRACE ELEMENTS IN SOIL AND SEDIMENT
TECHNOLOGY NAME: ED2000 XRF Analyzer
COMPANY: Oxford Instruments Analytical
ADDRESS: 945 Busse Road
Elk Grove Village, IL 60007
PHONE: 1-800-678-1117
WEB STIE: www.oxford-instruments.com
E-MAIL: sales@msys.oxinst.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 Oxford
Instruments Analytical (Oxford) ED2000 bench-top 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 technologies to measure 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 technology
developer, including Oxford, 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
A-l
-------
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 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 Oxford ED2000 XRF instrument.
More detailed discussion can be found in the Innovative Technology Verification Report - XRF Technologies for
Measuring Trace Elements in Soil and Sediment: Oxford ED2000 XRF Analyzer (EPA/540/R-06/007).
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 Oxford ED2000 XRF analyzer is an energy-dispersive XRF analyzer that can be operated as a bench-top unit
in a mobile or on-site laboratory. The ED2000 can analyze up to 75 elements in a variety of sample matrices,
including contaminated soils and sediments, liquids, powders, granules, filter papers, or films. Light-end
elements (sodium to iron) can be measured when the samples are prepared as pressed pellets. Samples were
pressed into pellets for this demonstration; however, this step is not required for routine analysis of soil or
sediment samples.
The Oxford ED2000 analyzer system includes a SMART digital pulse processor to handle count rates as high as
90,000 counts per second (CPS). The high count rates and high detector resolutions provide improved precision
and lower detection levels when compared with older Oxford XRF analyzers. Oxford also provides a calibration
service as an option to customers using this analyzer. Special features of the Oxford ED2000 include a 16-
position automatic sample tray, a 10 liter Dewar to hold liquid nitrogen to cool the detector, a vacuum pump to
evacuate the sample chamber of the XRF to reduce formation of oxides in the sample matrix, and a personal
computer loaded with Oxford's instrument calibration and XpertEase 32 software for automated data processing.
VERIFICATION OF PERFORMANCE
Method Detection Limit: MDLs were calculated using seven replicate analyses from each of 12 low-
concentration blends, according to the procedure described in Title 40 Code of Federal Regulations (CFR) Part
136, Appendix B, Revision 1.11. A mean MDL was further calculated for each element. The ranges into which
the mean MDLs fell for the ED2000 are summarized below (lower MDL values indicate higher sensitivity).
Relative Sensitivity
High
Moderate
Low
Very Low
Mean MDL
1-20 ppm
20 - 50 ppm
50 -100 ppm
> 100 ppm
Target Elements
Antimony, Cadmium, Copper, Selenium, Silver, and Vanadium.
Arsenic, Chromium, Lead, Mercury, Nickel, and Zinc.
None.
None.
Notes: ppm = Parts per million. Iron was not included in the MDL evaluation.
A-2
-------
Accuracy: Accuracy was evaluated based on the agreement of the XRF 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 ED2000 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
Nickel.
Cadmium, Chromium, Copper, Lead, Mercury
Silver, and Zinc.
Arsenic, Selenium, and Vanadium.
Antimony* andiron.
* 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 ED2000 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
*
1
"g
u
1
^
g
g
e
a
U
1
2
o
^
QJ
e.
e.
o
O
§
1
3
"3
Z
'3
OJ
55
g
§
>
u
N
0.84 0.69 0.98 0.89 0.89 0.83 0.90 0.99 0.99 0.99 0.85 0.93 0.85
High High - High - Low - - High
Notes: = No significant bias. * Correlation is 0.79 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 ED2000 was classified from high
to very low for the target elements, as indicated in the table below, based on the overall median RSDs. These
RSDs indicated a higher level of precision in the ED2000 than in the reference laboratory data for all target
elements except vanadium.
Relative Precision
High
Moderate
Low
Very Low
Median RSD
0% - 5%
5% - 10%
10% - 20%
> 20%
Target Elements
Antimony, Arsenic, Cadmium, Copper, Iron,
Mercury, Nickel, Selenium, Silver, and Zinc
Chromium and Lead.
Vanadium.
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. This evaluation found that accuracy for arsenic was reduced from "low" (median RPDs
between 25 and 50 percent) to "very low" (median RPDs greater than 50 percent) by high relative concentrations
of lead (greater than 10X the arsenic concentration). An existing high bias in the arsenic results was increased by
the interference. A more minor but similar effect was observed for copper as an interferent for nickel.
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 outlier RPD values indicating low relative accuracy for iron
in blends of sandy soil from the KARS Park site, a former gun range. High RPD outliers were also observed for
multiple elements in blends from the Wickes Smelter site, a complex roaster slag matrix.
A-3
-------
Sample Throughput: The total processing time per sample was estimated at 15.5 minutes, which included 7.0
minutes of sample preparation and 7.9 minutes of instrument analysis time. On this basis, a sample throughput of
53 samples per 8-hour work day was estimated with the use of the instrument's autosampler. As noted above,
however, the sample blends had undergone rigorous pre-processing before the demonstration. Sample throughput
would have decreased if these sample preparation steps (grinding, drying, sieving) had been performed during the
demonstration; these steps can add from 10 minutes to 2 hours to the sample processing time.
Costs: A cost assessment for the ED2000 identified a purchase cost of $80,000, plus $750 shipping, as equipped
for the demonstration. Using a hypothetical rental cost approximated from similar types of instruments, a total
cost of $11,645 (with a labor cost of $6,460 at $43.75/hr) was estimated for a project similar to the demonstration
(326 samples of soil and sediment). In comparison, the project cost averaged $8,932 for all eight XRF
instruments participating in the demonstration and $63,896 for fixed-laboratory analysis of all 13 target elements.
Skills and training required: Field or laboratory technicians with a high school diploma are generally qualified
to operate the ED2000. Oxford offers free training for instrument purchasers that generally lasts about 3 days,
and the instrument is equipped with a modem for remote troubleshooting and guidance.
Health and Safety Aspects: The ED2000 is equipped with safety measures to minimize possible exposure to
emissions from the x-ray tube. The instrument cannot be operated if these safety measures are disabled. Users of
the ED2000 must be able to safely manage and dispense cryogenic liquids (nitrogen) to operate the detector.
Portability: Based on dimensions, weight, and power requirements, the ED2000 is a transportable (as opposed to
fully portable) instrument. It is best used in a field trailer or other fixed location with the required power supply
and a stable, weatherproof environment.
Durability: The ED2000 is encased in durable hard-tool plastic but is not weatherproof. Oxford instruments
have a 12-month limited warranty for parts and labor. The developer estimates that the average lifespan of the x-
ray tube source is 10,000 hours or 7 years.
Availability: New instruments are available from the Oxford offices in Concord, Massachusetts, and Oak Park,
Illinois. A world-wide network of 30 service representatives provides service and customer support. Although
long-term leasing is possible, instruments are not currently available for rental.
RELATIVE PERFORMANCE
The overall performance of the ED2000 relative to the average of all eight XRF instruments that participated in
the demonstration is shown below:
Sensitivity
Accuracy
Precision
Antimony Arsenic
0
Same
0
Cadmium
Same
ť
Chromium
Same
Copper
Same
ť
Iron
NC
0
Lead
ť
0
Mercury
Same
ť
Nickel
ť
Selenium
0
Silver
ť
Vanadium
ť
0
Zinc
Same
Key:
Better
Worse
NC No MDL Calculated.
NOTICE: Verifications are based on an evaluation of technology performance under specific, predetermined criteria and the
appropriate quality assurance procedures. EPA makes no expressed or implied warranties as to the performance of the
technology and does not certify that a technology will always operate as verified. The end user is solely responsible for
complying with any and all applicable federal, state, and local requirements.
A-4
-------
APPENDIX B
DEVELOPER DISCUSSION
-------
DEVELOPER DISCUSSION
Oxford Instruments was pleased to participate in the SITE program demonstration of "XRF Technologies for
Measuring Trace Elements in Soil and Sediment". This demonstration provides significant information to the
potential users of XRF instrumentation for the investigation of heavy metal contamination in soil.
The ED2000 is a field transportable EDXRF instrument based on a high resolution detector which is designed
for operation in almost any environment. As such, this analyzer can be used either for direct screening of
samples at the site in a RV/mobile lab or it may be set up in a tent or make shift field laboratory. For this
evaluation, the instrument was set up in a field laboratory. Under normal operating conditions, such as a mobile
laboratory, the instrument can be operational in 10 minutes. If the instrument is shipped on site in different
components, then unpacking and assembly can be done within two hours and the instrument made operational in
less than 2 1A hrs. During this SITE program demonstration, unfortunately the computer power supply was
shorted out; replacing the computer with one of the existing lap-top computers compatible to the instrument and
loading the available empirical calibration files took some time.
The ED2000 offers optimized excitation conditions for different element groups. This increased the analysis
time per sample but provides better overall results. Based on the three criteria of MDL, Precision and Accuracy,
ED2000 performed well compare to other XRF instruments (as evident by Tables 7-2 to 7-5) due to the
optimized excitation, belter counting statistics and sample preparation. One can reduce the sample preparation
time to one minute by creating an empirical calibration as powders and measuring subsequent samples as
powders. Powder results can be improved further by tapping the samples in the sample cups to take out the air
pockets.
The results of this SITE study were essentially as expected. The MDLs calculated from the data for ED2000
were at least a factor of two better than the average of all other XRF instruments for antimony, cadmium, lead,
selenium, silver and vanadium and better than the MDL for the remaining elements except arsenic which was
equal in MDL of other XRF units. The precision data were better than reference lab and the average of the other
XRF instruments except for the lead and vanadium (11 elements out of 13). The precision for lead was slightly
worse than the average of all instruments at 6.3% vs. the average of 4.9%, however, this is quite acceptable for
environmental analysis and better than the precision obtained by the reference laboratory (8.6% RSD). The
vanadium excitation conditions were not optimized, as was done for other elements, in order to reduce the
analysis time (again, because of the time constraint caused by start-up problems). Adding a set of excitation
conditions will greatly improve the precision of the vanadium measurement at the expense of additional
measurement time. The accuracy data based on RPD values were better than or equal to average values of other
XRF instrments for nine elements out of thirteen. The accuracy can be improved significantly if site specific
empirical calibration is used. This can be achieved by taking a well analyzed set of samples from the site and
calibrating the instrument using them. This calibration can then be used to measure all the other samples with
the same matrix and will provide accurate results as the influence of the matrix will be compensated during the
calibration. Antimony results for ED 2000 were closer to the real ERA spike value than any other XRF
instruments or even the reference laboratory values.
In summary, the performance of the ED2000 was very good when compared to the other instruments in this
study. Even greater accuracy can be achieved by fine tuning of calibration parameters and use of matrix-
matched site-specific calibrations. The precision and MDL of the ED2000 was one of the best in the study;
therefore, the improvements available for the calibration will make the ED2000 one of the best instruments
available for the measurement of heavy metals in soil.
B-l
-------
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
-------
ABBREVIATIONS AND ACRONYMS
CCV Continuing calibration verification
CVAA Cold vapor atomic absorption
DVSR Data validation summary report
EPA U.S. Environmental Protection Agency
FAR Federal acquisition regulations
ICP-AES Inductively coupled plasma-atomic emission spectroscopy
ICS Interference check sample
ICV Initial calibration verification
LCS Laboratory control sample
LCSD Laboratory control sample duplicate
MDL Method detection limit
mg/kg Milligram per kilogram
MS Matrix spike
MSD Matrix spike duplicate
PARCC Precision, accuracy, representativeness, completeness, and comparability
PQL Practical quantitation limit
QA/QC Quality assurance and quality control
QAPP Quality assurance project plan
QC Quality control
RSD Relative standard deviation
RPD Relative percent difference
SDG Sample delivery group
Shealy Shealy Environmental Services, Inc.
SITE Superfund Innovative Technology Evaluation
Tetra Tech Tetra Tech EM Inc.
XRF X-ray fluorescence
11
-------
1.0 INTRODUCTION
This data validation summary report (DVSR) summarizes the reference laboratory quality control (QC)
data gathered during the x-ray fluorescence (XRF) technologies demonstration conducted under the U.S.
Environmental Protection Agency (EPA) Superfund Innovative Technology Evaluation (SITE) program.
The reference laboratory was procured following the federal acquisition regulations (FAR) and an
extensive selection process. Shealy Environmental Services, Inc. (Shealy), of Cayce, South Carolina, was
selected as the reference laboratory for this project. Thirteen target analytes were measured in reference
samples and include antimony, arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel,
selenium, silver, vanadium, and zinc. The laboratory reported results for 22 metals at the request of EPA;
however, for the purposes of meeting project objectives, only the data validation for the 13 target analytes
is summarized in this document. The objective of the validation is to determine the validity of the
reference data, as well as its usability in meeting the primary objective of comparing reference data to
XRF data generated during the demonstration. Shealy provided the data to Tetra Tech EM Inc. (Tetra
Tech) in electronic and hardcopy formats; a total of 13 sample delivery groups (SDG) contain all the data
for this project.
The DVSR consists of seven sections, including this introduction. Section 2.0 presents the data validation
methodology. Section 3.0 presents the results of the reference laboratory data validation. Section 4.0
summarizes the precision, accuracy, representativeness, completeness, and comparability (PARCC)
evaluation. Section 5.0 presents conclusions about the overall evaluation of the reference data. Section
6.0 lists the references used to prepare this DVSR. Tables are presented following Section 6.0.
2.0 VALIDATION METHODOLOGY
Data validation is the systematic process for reviewing and qualifying data against a set of criteria to
ensure that the reference data are adequate for the intended use. The data validation process assesses
acceptability of the data by evaluating the critical indicator parameters of PARCC. The laboratory
analytical data were validated according to the procedures outlined in the following documents:
"USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data
Review" (EPA 2004), hereinafter referred to as the "EPA guidance."
"Demonstration and Quality Assurance Project Plan, XRF Technologies for Measuring
Trace Elements in Soil and Sediment" (Tetra Tech 2005), hereinafter referred to as "the
QAPP."
Data validation occurred in the following two stages: (1) a cursory review of analytical reports and
quality assurance and quality control (QA/QC) information for 100 percent of the reference data and
(2) full validation of analytical reports, QA/QC information, and associated raw data for 10 percent of the
reference data as required by the QAPP (Tetra Tech 2005).
QA/QC criteria were reviewed in accordance with EPA guidance (EPA 2004) and the QAPP (Tetra Tech
2005). The cursory review for total metals consisted of evaluating the following requirements, as
applicable:
Holding times
C-l
-------
Initial and continuing calibrations
Laboratory blank results
Laboratory control sample (LCS) and laboratory control sample duplicates (LCSD) results
Matrix spike (MS) and matrix spike duplicate (MSB) results
Serial dilutions results
In addition to QA/QC criteria described above, the following criteria were reviewed during full
validation:
ICP interference check samples (ICS)
Target analyte identification and quantitation
Quantitation limit verification
Section 3.0 presents the results of the both the cursory review and full validation.
During data validation, worksheets were produced for each SDG that identify any QA/QC issues resulting
in data qualification. Data validation findings were written in 13 individual data validation reports (one
for each SDG). Data qualifiers were assigned to the results in the electronic database in accordance with
EPA guidelines (EPA 2004). In addition to data validation qualifiers, comment codes were added to the
database to indicate the primary reason for the validation qualifier. Table 1 defines data validation
qualifiers and comment codes that are applied to the data set. Details about specific QC issues can be
found in the individual SDG data validation reports and accompanying validation worksheets provided in
the Appendix.
The overall objective of data validation is to ensure that the quality of the reference data set is adequate
for the intended use, as defined by the QAPP (Tetra Tech 2005) for the PARCC parameters. Table 2
provides the QC criteria as defined by the QAPP. PARCC parameters were assessed by completing the
following tasks:
Reviewing precision and accuracy of laboratory QC data
Reviewing the overall analytical process, including holding time, calibration, analytical or
matrix performance, and analyte identification and quantitation
Assigning qualifiers to affected data when QA/QC criteria were not achieved
Reviewing and summarizing implications of the frequency and severity of qualifiers in the
validated data
Prior to the XRF demonstration, soil and sediment samples were collected from nine locations across the
U.S. and then blended, dried, sieved, and homogenized in the characterization laboratory to produce a set
of 326 reference samples. Each of these samples were subsequently analyzed by both the reference
C-2
-------
laboratory and all participating technology vendors. As such, 326 prepared soil/sediment samples were
delivered to Shealy for the measurement of total metals. The analytical program included the following
analyses and methods:
Total metal for 22 analytes by inductively coupled plasma atomic emission spectroscopy
(ICP-AES) according to EPA Methods 3050B/6010B (EPA 1996)
Total mercury by cold vapor atomic absorption spectroscopy (CVAA) according to EPA
Method 7471A (EPA 1996)
3.0 DATA VALIDATION RESULTS
The parameters listed in Section 2.0 were evaluated during cursory review and full validation of analytical
reports for all methods, as applicable. Each of the validation components discussed in this section is
summarized as follows:
Acceptable - All criteria were met and no data were qualified on that basis
Acceptable with qualification - Most criteria were met, but at least one data point was
qualified as estimated because of issues related to the review component
Since no data were rejected, all data were determined to be either acceptable or acceptable with
qualification. Sections 3.1 through 3.9 discuss each review component and the results of each. Tables
that summarize the data validation findings follow Section 6.0 of this DVSR. Only qualified data are
included in the tables. No reference laboratory data were rejected during the validation process. As such,
all results are acceptable with the qualification noted in the sections that follow.
3.1 Holding Time
Acceptable. The technical holding times were defined as the maximum time allowable between sample
collection and, as applicable, sample extraction, preparation, or analysis. The holding times used for
validation purposes were recommended in the specific analytical methods (EPA 1996) and were specified
in the QAPP (Tetra Tech 2005).
Because the soil and sediment samples were prepared prior to submission to the reference laboratory, and
because the preparation included drying to remove moisture, no chemical or physical (for example ice)
preservation was required. The holding time for sample digestion was 180 days for the ICP-AES
analyses and 28 days for mercury. All sample digestions and analyses were conducted within the
specified holding times. No data were qualified based on holding time exceedances. This fact contributes
to the high technical quality of the reference data.
3.2 Calibration
Acceptable. Laboratory instrument calibration requirements were established to ensure that analytical
instruments could produce acceptable qualitative and quantitative data for all target analytes. Initial
calibration demonstrates that the instrument is capable of acceptable performance at the beginning of an
analytical run, while producing a linear curve. Continuing calibration demonstrates that the instrument is
capable of repeating the performance established during the initial calibration (EPA 1996).
C-3
-------
For total metal analyses (ICP-AES and CVAA), initial calibration review included evaluating criteria for
the curve's correlation coefficient and initial calibration verification (ICV) percent recoveries. The ICV
percent recoveries verify that the analytical system is operating within the established calibration criteria
at the beginning of an analytical run. The continuing calibration review included evaluation of the criteria
for continuing calibration verification (CCV) percent recoveries. The CCV percent recoveries verify that
the analytical system is operating within the established calibration throughout the analytical run.
All ICV and CCV percent recoveries associated with the reference data were within acceptable limits of
90 to 110 percent. As such, no data were qualified or rejected because of calibration exceedances. This
fact contributes to the high technical quality of the data.
3.3 Laboratory Blanks
Acceptable with qualification. No field blanks were required by the QAPP, since samples were prepared
after collection and before submission to the reference laboratory. However, laboratory blanks were
prepared and analyzed to evaluate the existence and magnitude of contamination resulting from
laboratory activities. Blanks prepared and analyzed in the laboratory consisted of calibration and
preparation blanks. If a problem with any blank existed, all associated data were carefully evaluated to
assess whether the sample data were affected. At a minimum, calibration blanks were analyzed for every
10 analyses conducted on each instrument. Preparation blanks were prepared at a frequency of one per
preparation batch per matrix or every 20 samples, whichever is greater (EPA 1996).
When laboratory blank contamination was identified, sample results were compared to the practical
quantitation limit (PQL) and the maximum blank value as required by the validation guidelines (EPA
2004). Most of the blank detections were positive results (i.e. greater than the method detection limit
[MDL]), but less than the PQL. In these instances, if associated sample results were also less than the
PQL, they were qualified as undetected (U); with the comment code "b." In these same instances, if the
associated sample results were greater than the PQL, the reviewer used professional judgment to
determine if the sample results were adversely affected. If so, then the results were qualified as estimated
with the potential for being biased high (J+). If not, then no qualification was required.
In a few cases, the maximum blank value exceeded the PQL. In these cases, all associated sample results
less than the PQL were qualified as undetected (U) with the comment code "b." In cases where the
associated sample results were greater than the PQL, but less than the blank concentration, the results
were also qualified as undetected (U); with the comment code "b." If the associated sample results were
greater than both the PQL and the blank value, the reviewer used professional judgment to determine if
sample results were adversely affected. If so, then the results were qualified as estimated with the
potential for being biased high (J+); with the comment code "b." Sample results significantly above the
blank were not qualified.
In addition to laboratory blank contamination, negative drift greater than the magnitude of the PQL was
observed in some laboratory blanks. Associated sample data were qualified as undetected (U) if the
results were less than the PQL. Professional judgement was used to determine if the negative drift
adversely affected associated sample results greater than the PQL. If so, then sample results were
qualified as estimated with the potential for being biased low (J-) due to the negative drift of the
instrument baseline; with the comment code "b."
Of all target analyte data, 2.6 percent of the data was qualified as undetected because of laboratory blank
contamination (U, b), and less than 1 percent of the data was qualified as estimated (either J+, b or J-, b).
The low occurrence of results affected by blank contamination indicates that the general quality of the
C-4
-------
analytical data was not significantly compromised by blank contamination. Table 3 provides all results
that were qualified based on laboratory blanks.
3.4 Laboratory Control Samples
Acceptable. LCSs and LCSDs were prepared and analyzed with each batch of 20 or fewer samples of the
same matrix. All percent recoveries were within the QC limits of 80 to 120 percent; all relative percent
differences (RPD) between the LCD and LCSD values were less than the criterion of 20 percent. No data
were qualified or rejected on the basis of LCS/LCSD results. This fact contributes to the high technical
quality of the data.
3.5 Matrix Spike Samples
Acceptable with qualification. MS and MSB samples were prepared and analyzed with each batch of 20
or fewer samples of the same matrix. All percent recoveries were within the QC limits of 75 to 125
percent, and all RPDs between the MS and MSB values were less than the criterion of 25 percent, except
as discussed in the following paragraphs.
Sample results affected by MS and MSB percent recoveries issues were qualified as estimated and either
biased high (J+) if the recoveries were greater than 125 percent; or qualified as estimated and biased low
(J-) if the recoveries were less than 75 percent. In at least one case, the MS was higher than 125 percent
and the MSB was lower than 75 percent; the associated results were qualified as estimated (J) with no
distinction for potential bias. All data qualified on the basis of MS and MSB recovery were also assigned
the comment code "e." Of all target analyte data, less than 1 percent was qualified as estimated and
biased high (J+, e), while about 8 percent of the data were qualified as estimated and biased low (J-, e).
Antimony and silver were the most frequently qualified sample results. Based on experience, antimony
and silver soil recoveries are frequently low using the selected methods. Table 4 provides the results that
were qualified based on MS/MSB results.
The precision between MS and MSB results were generally acceptable. If the RPB between MS and
MSB results were greater than 25 percent, the data were already qualified based on exceedance of the
acceptance window for recovery. Therefore, no additional qualification was required for MS/MSB
precision.
No data were rejected on the basis of MS/MSB results. The relatively low occurrence of data
qualification due to MS/MSB recoveries and RPBs contribute to the high technical quality of the data.
3.6 Serial Dilution Results
Acceptable with qualification. Serial dilutions were conducted and analyzed by Shealy at a frequency of
1 per batch of 20 samples. The serial dilution analysis can evaluate whether matrix interference exists
and whether the accuracy of the analytical data is affected. For all target analyte data, less than 1 percent
of the data was qualified as estimated and biased high (J+, j), while about 2 percent of the data were
qualified as estimated and biased low (J-, j). Serial dilution results are used to determine whether
characteristics of the digest matrix, such as viscosity or the presence of analytes at high concentrations,
may interfere with the detected analytes. Qualifiers were applied to cases where interference was
suspected. However, the low incidence of apparent matrix interference contributes to the high technical
quality of the data. Table 5 provides the results that were qualified based on MS/MSB results.
C-5
-------
3.7 ICP Interference Check Samples
Acceptable. ICP results for each ICS were evaluated. The ICS verifies the validity of the laboratory's
inter-element and background correction factors. High levels of certain elements (including aluminum,
calcium, iron, and magnesium) can affect sample results if the inter-element and background correction
factors have not been optimized. Incorrect correction factors may result in false positives, false negatives,
or biased results. All ICS recoveries were within QC limits of 80 to 120 percent, and no significant biases
were observed due to potential spectral interference. No data were qualified or rejected because of ICS
criteria violations. This fact contributes to the high technical quality of the data.
3.8 Target Analyte Identification and Quantitation
Acceptable Identification is determined by measuring the characteristic wavelength of energy emitted by
the analyte (ICP) or absorbed by the analyte (CVAA). External calibration standards are used to quantify
the analyte concentration in the sample digest. Sample digest concentrations are converted to soil units
(milligrams per kilogram) and corrected for percent moisture. For 10 percent of the samples, results were
recalculated to verify the accuracy of reporting. All results were correctly calculated by the laboratory,
except for one mercury result, whose miscalculation was the result of an error in entering the dilution
factor. Shealy immediately resolved this error and corrected reports were provided. Since the result was
corrected, no qualification was required. No other reporting errors were observed.
For inorganic analyses, analytical instruments can make reliable qualitative identification of analytes at
concentrations below the PQL. Detected results below the PQL are considered quantitatively uncertain.
Sample results below the PQL were reported by the laboratory with a "J" qualifier. No additional
qualification was required.
3.9 Quantitation Limit Verification
Acceptable. Reference laboratory quantitation limits were specified in the QAPP (Tetra Tech 2005).
Circumstances that affected quantitation were limited and included dilution and percent moisture factors.
Since the samples were prepared prior to submission to the reference laboratory, moisture content was
very low and had little impact on quantitation limits. The laboratory did correct all quantitation limits for
moisture content. Due to the presence of percent-level analytes in some samples, dilutions were required.
However, the required PQLs for the reference laboratory were high enough that even with dilution and
moisture content factors applied, the reporting limits did not exceed those of the XRF instruments. This
allows for effective comparison of results between the reference laboratory and XRF instruments.
4.0 PRECISION, ACCURACY, REPRESENTATIVENESS, COMPLETENESS, AND
COMPARABILITY EVALUATION SUMMARY
All analytical data were reviewed for PARCC parameters to validate reference data. The following
sections discuss the overall data quality, including the PARCC parameters, as determined by the data
validation.
C-6
-------
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)
-------
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: SERIAL DILUTION 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: SERIAL DILUTION 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: SERIAL DILUTION 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: SERIAL DILUTION 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: SERIAL DILUTION 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,i
e
b,e
e
e
e
e
e
e
e
e
e
e
e
e
C-20
-------
TABLE 4: DATA QUALIFICATION: SERIAL DILUTION 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
j,e
e
e
b,e
b,e
e
e
e
e
e,j
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
e
C-21
-------
TABLE 4: DATA QUALIFICATION: SERIAL DILUTION 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: SERIAL DILUTION 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
e,j
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: SERIAL DILUTION 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: SERIAL DILUTION EXCEEDANCES (Continued))
Notes:
< = Less than
mg/kg = Milligram per kilogram
b = Data were qualified based on blank contamination
e = Data were additionally qualified based on matrix spike/matrix spike duplicate exceedances
j = Data were additionally qualified based on serial dilution exceedances
J = Result is estimated and biased could not be determined
J+ = Result is estimated and potentially biased high
J- = Result is estimated and potentially biased low
UJ = Result is undetected at estimated quantitation limit
C-25
-------
TABLE 5: DATA QUALIFICATION: SERIAL DILUTION EXCEEDANCES
Sample ID
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
AS-SO-09-XX
BN-SO-11-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
BN-SO-25-XX
KP-SE-14-XX
KP-SE-14-XX
KP-SE-14-XX
KP-SE-14-XX
KP-SE-14-XX
KP-SE-14-XX
LV-SE-29-XX
LV-SE-29-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-35-XX
LV-SE-35-XX
Analyte
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Vanadium
Zinc
Mercury
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Selenium
Silver
Vanadium
Zinc
Antimony
Chromium
Copper
Iron
Lead
Nickel
Lead
Mercury
Arsenic
Chromium
Iron
Nickel
Vanadium
Zinc
Result
25
100
390
250
94000
3200
170
9.6
65
6800
24
82
700
370
64
930
16000
5400
88
19
48
28
2900
11
46
2.7
520
680
23
7.2
1.5
31
74
24000
170
55
67
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J+
J-
J-
J-
J+
J-
J-
J-
J-
J-
J-
J-
Comment
Code
j
j
j
j
j
j
i
j
j
j
j
e,i
ej
j
j
j
j
j
i
j
j
j
j
i
j
j
j
ej
j
j
i
j
j
j
j
i
j
C-26
-------
TABLE 5: DATA 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
LV-SO-34-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-16-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
RF-SE-24-XX
SB-SO-02-XX
SB-SO-02-XX
SB-SO-02-XX
SB-SO-02-XX
SB-SO-15-XX
SB-SO-15-XX
SB-SO-15-XX
SB-SO-15-XX
Analyte
Antimony
Arsenic
Cadmium
Chromium
Iron
Lead
Nickel
Selenium
Vanadium
Zinc
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Vanadium
Zinc
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Vanadium
Zinc
Antimony
Arsenic
Lead
Mercury
Antimony
Arsenic
Chromium
Copper
Result
870
110
2300
2200
20000
3700
1900
220
230
48
85
72
310
820
73
16000
24
1700
130
32
760
130
6.5
74
860
24000
410
170
3.8
46
1400
44
23
22
130
600
170
91
30
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
J+
J+
J+
J+
J+
J+
J+
J+
J+
J-
J-
J-
J-
J+
J-
J-
J-
J-
Comment
Code
j
j
i
j
j
j
j
i
j
j
j
j
j
j
i
j
j
j
j
i
j
j
j
j
j
j
i
j
j
j
j
e,i
j
j
j
j,e
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-15-XX
SB-SO-15-XX
SB-SO-22-XX
SB-SO-22-XX
SB-SO-31-XX
SB-SO-31-XX
SB-SO-31-XX
SB-SO-31-XX
SB-SO-31-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
TL-SE-13-XX
WS-SO-01-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
WS-SO-33-XX
Analyte
Iron
Lead
Nickel
Vanadium
Zinc
Antimony
Zinc
Arsenic
Nickel
Selenium
Silver
Zinc
Antimony
Chromium
Copper
Iron
Lead
Silver
Vanadium
Mercury
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Vanadium
Zinc
Result
51000
40
100
52
36
10
64
8
3200
28
160
3900
95
36
4400
22000
1100
160
59
5.8
450
11
120
150
28000
3700
65
13
53
830
Unit
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Validation
Qualifier
J-
J-
J-
J-
J-
J
J-
J-
J-
J-
J-
J-
J+
J+
J+
J+
J+
J
J+
J
J-
J-
J-
J-
J-
J-
J-
J-
J-
J-
Comment
Code
J
J
i
j
j
ej
j
i
j
j
ej
j
j,e
j
i
j
j
j,e
j
e,i
j
j
j
j
j
j
i
j
j
j
Notes:
mg/kg = Milligram per kilogram
e = Data were additionally qualified based on matrix spike/matrix spike duplicate
exceedances
j = Data were 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
C-28
-------
APPENDIX D
DEVELOPER AND REFERENCE LABORATORY DATA
-------
Appendix D. Analytical Data Summary, Oxford ED2000 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-OI
KP-SO-10-OI
KP-SO- 15-01
KP-SO-18-OI
KP-SO-22-OI
KP-SO-07-XX
KP-SO-13-XX
KP-SO-20-XX
KP-SO-24-XX
KP-SO-27-XX
KP-SO-29-XX
KP-SO-32-XX
KP-SO-07-OI
KP-SO-13-OI
KP-SO-20-OI
KP-SO-24-OI
KP-SO-27-OI
KP-SO-29-OI
KP-SO-32-OI
KP-SO-04-XX
KP-SO-16-XX
KP-SO-23-XX
KP-SO-26-XX
KP-SO-31-XX
KP-SO-04-OI
KP-SO-16-OI
KP-SO-23-OI
KP-SO-26-OI
KP-SO-31-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
8.1 J+
6.1 J+
6.3 J+
6.7 J+
8.3 J+
8.9
7.4
4.2
7.4
10.3
17.0 J+
16.0 J+
19.0 J+
17.0 J+
15.0 J+
18.0 J+
16.0 J+
17.3
19.0
20.5
16.2
13.0
18.3
17.6
94.0 J+
93.0 J+
86.0 J+
90.0 J+
88.0
85.6
93.4
95.5
90.6
88.4
As
0.7 J-
0.7 J-
0.8 J-
0.6 J-
0.7 J-
77.0
70.3
60.4
49.5
53.4
2.0 J-
1.4 J-
1.5 J-
1.4 J-
1.3 J-
1.5 J-
1.6 J-
108.4
119.3
131.8
116.3
122.2
125.9
122.9
2.8
2.9
2.6
3.7
28.0
624.9
616.9
644.9
615.7
598.6
Cd
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
1.6
0.2
0.2
0.1 U
0.0 U
0.1 U
0.1 U
0.1 U
0.1 U
0.0 U
0.1
0.0 U
0.1 U
0.0 U
0.1 U
0.1 U
0.7
0.2
0.2
0.9
Cr
290.0
300.0
340.0
250.0
260.0
505.2
574.0
513.1
512.2
506.6
170.0
180.0
160.0
160.0
170.0
150.0
180.0
370.0
318.7
381.1
341.6
358.4
335.1
352.1
180.0
200.0
180.0
210.0
140.0
265.5
272.0
270.3
263.6
302.8
Cu
26.0
26.0
26.0
24.0
29.0
32.0
27.9
23.3
27.9
28.5
48.0
52.0
46.0
49.0
45.0
42.0
50.0
47.8
47.4
48.2
42.0
50.2
43.3
48.6
200.0
230.0
190.0
230.0
200.0
240.5
235.6
230.9
237.4
227.5
Fe
1400.0
1600.0
1600.0
1200.0
1300.0
21280.0
21670.0
21450.0
21390.0
21330.0
990.0
980.0
910.0
900.0
970.0
870.0
970.0
21010.0
20610.0
20950.0
20740.0
20890.0
20740.0
20730.0
1300.0
1400.0
1300.0
1500.0
1100.0
21200.0
21230.0
21080.0
21230.0
21290.0
Pb
620.0
560.0
510.0
500.0
650.0
519.4
496.7
457.5
484.8
569.8
1200.0
1200.0
1300.0
1100.0
1200.0
1200.0
1200.0
1055.6
1029.9
1052.7
999.5
1002.9
1057.7
1032.0
5800.0
6100.0
5300.0
6500.0
5700.0
4284.2
4262.2
4287.8
4346.0
4083.2
D-l
-------
Appendix D. Analytical Data Summary, Oxford ED2000 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-OI
KP-SO-10-OI
KP-SO- 15-01
KP-SO-18-OI
KP-SO-22-OI
KP-SO-07-XX
KP-SO-13-XX
KP-SO-20-XX
KP-SO-24-XX
KP-SO-27-XX
KP-SO-29-XX
KP-SO-32-XX
KP-SO-07-OI
KP-SO-13-OI
KP-SO-20-OI
KP-SO-24-OI
KP-SO-27-OI
KP-SO-29-OI
KP-SO-32-OI
KP-SO-04-XX
KP-SO-16-XX
KP-SO-23-XX
KP-SO-26-XX
KP-SO-31-XX
KP-SO-04-OI
KP-SO-16-OI
KP-SO-23-OI
KP-SO-26-OI
KP-SO-31-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
0.1 U
0.0 U
0.0 U
0.0 U
0.0 U
0.3
5.9
0.0 U
0.0 U
0.0 U
0.0 U
0.0 U
0.0 U
0.0 U
5.3
0.0 U
0.0 U
0.0 U
0.0 U
0.0 U
8.5
Ni
140.0
150.0
170.0
120.0
130.0
145.2
134.0
142.6
138.1
139.4
87.0
90.0
79.0
78.0
87.0
73.0
88.0
98.6
97.9
104.8
106.8
97.3
98.4
90.4
93.0
100.0
91.0
110.0
68.0
80.9
102.0
101.4
95.2
103.3
Se
0.3 U
0.2 U
0.3 U
0.3 U
0.3 U
1.4
2.4
2.7
1.1
5.0
0.2 U
0.3 U
0.3 U
0.3 U
0.3 U
0.3 U
0.5
1.4
1.2
1.2
0.2
1.8
2.4
2.7
0.3 U
0.3 U
0.3 U
0.2 U
0.3 U
1.6
4.2
5.1
2.0
1.4
Ag
0.3 U
0.3 U
0.3 U
0.3 U
0.3 U
1.2
0.6
0.2
0.2
0.2
0.3 U
0.3 U
0.3 U
0.3 U
0.3 U
0.3 U
0.3 U
0.9
1.3
1.5
0.9
2.2
0.8
0.2 J
0.2 J
0.1 J
0.2 J
0.4
0.7
0.6
V
1.6 J
1.8 J
1.8 J
1.5 J
1.6 J
22.7
30.0
39.2
27.0
29.0
1.2 J
1.2 J
1.2 J
1.1 J
1.2 J
1.1 J
1.2 J
31.9
32.3
33.7
34.7
25.7
27.2
17.2
1.3 J
1.2 J
1.1 J
1.2 J
1.5 J
40.3
30.0
34.1
30.4
32.7
Zn
11.0
12.0
15.0
11.0
11.0
19.2
16.1
20.1
17.1
24.3
26.0
24.0
25.0
22.0
24.0
22.0
24.0
41.3
33.3
49.5
20.7
28.2
28.9
38.0
45.0
47.0
41.0
52.0
38.0
55.8
51.8
57.9
53.0
51.9
D-2
-------
Appendix D. Analytical Data Summary, Oxford ED2000 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-OI
KP-SO-03-OI
KP-SO-05-OI
KP-SO-09-OI
KP-SO-21-OI
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-OI
WS-SO-08-OI
WS-SO-12-OI
WS-SO-17-OI
WS-SO-27-OI
WS-SO-30-OI
WS-SO-35-OI
WS-SO-03-XX
WS-SO-05-XX
WS-SO-09-XX
WS-SO-14-XX
WS-SO-26-XX
WS-SO-31-XX
WS-SO-33-XX
WS-SO-03-OI
WS-SO-05-OI
WS-SO-09-OI
WS-SO-14-OI
WS-SO-26-OI
WS-SO-31-OI
WS-SO-33-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
410.0
360.0
410.0
420.0
370.0
471.4
463.7
460.9
454.6
478.3
1.3 U
1.3
1.3 UJ
1.3 UJ
1.3 UJ
1.2 J-
1.3 UJ
3.5
4.1
2.1
4.9
2.5
8.9 J-
8.6 J-
7.1 J-
8.4 J-
7.6 J-
7.2 J-
6.9 J-
34.5
36.4
29.7
32.5
37.8
28.7
29.6
As
9.7
8.8
12.0
11.0
9.5
2985.9
2829.4
3008.5
2925.3
3011.0
48.0
45.0
43.0
47.0
49.0
51.0
49.0
74.0
62.7
74.2
60.6
63.5
77.1
68.7
500.0
440.0
480.0
430.0
520.0
520.0
450.0 J-
905.1
883.7
861.0
864.8
873.1
921.1
892.1
Cd
0.1
0.1 U
0.1 U
0.1 U
0.1 U
2.4
0.2
1.5
1.3
0.9
1.9
2.0
1.8
1.9
2.0
2.0
2.0
1.7
1.2
2.0
0.7
1.1
4.0
1.9
12.0
12.0
12.0
11.0
12.0
12.0
11.0 J-
9.6
9.1
9.7
9.6
10.7
10.3
7.7
Cr
5.5
4.5
6.4
4.9
5.1
24.9
53.3
25.4
29.8
68.2
120.0
120.0
110.0
120.0
120.0
130.0
130.0
124.4
126.9
126.0
133.5
79.9
83.1
76.7
140.0
140.0
130.0
120.0
140.0
140.0
120.0 J-
140.9
130.5
123.8
119.9
83.3
84.4
83.2
Cu
780.0
670.0
780.0
780.0
700.0
998.6
1008.1
1024.4
1063.0
1040.5
50.0
47.0
45.0
49.0
51.0
53.0
51.0
56.2
59.8
63.9
54.5
65.0
51.5
58.3
170.0
160.0
160.0
150.0
160.0
170.0
150.0 J-
165.9
181.2
188.6
185.9
169.7
179.2
183.4
Fe
1700.0
1600.0
2000.0
1800.0
1700.0
22170.0
22520.0
22360.0
22230.0
22860.0
28000.0
26000.0
25000.0
28000.0
28000.0
29000.0
28000.0
53380.0
53270.0
52500.0
52260.0
42560.0
42830.0
42840.0
32000.0
31000.0
30000.0
28000.0
30000.0
32000.0
28000.0 J-
58370.0
59250.0
58800.0
58200.0
45820.0
44700.0
45520.0
Pb
18000.0
19000.0
24000.0
22000.0
19000.0
15320.4
14759.9
15190.4
15099.1
15113.5
110.0
71.0
65.0
70.0
72.0
81.0
74.0
84.3
78.6
70.4
108.3
80.8
127.2
114.4
4300.0
4000.0
4000.0
3700.0
4000.0
4200.0
3700.0 J-
3181.6
3243.2
3214.8
3280.1
3355.2
3298.1
3341.2
D-3
-------
Appendix D. Analytical Data Summary, Oxford ED2000 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-OI
KP-SO-03-OI
KP-SO-05-OI
KP-SO-09-OI
KP-SO-21-OI
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-OI
WS-SO-08-OI
WS-SO-12-OI
WS-SO-17-OI
WS-SO-27-OI
WS-SO-30-OI
WS-SO-35-OI
WS-SO-03-XX
WS-SO-05-XX
WS-SO-09-XX
WS-SO-14-XX
WS-SO-26-XX
WS-SO-31-XX
WS-SO-33-XX
WS-SO-03-OI
WS-SO-05-OI
WS-SO-09-OI
WS-SO-14-OI
WS-SO-26-OI
WS-SO-31-OI
WS-SO-33-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
0.0 U
0.0 U
0.0 U
0.0 U
0.0 U
0.1 U
0.1 U
0.1 UJ
0.1 UJ
0.1 J-
0.1 UJ
0.1 UJ
5.4
0.9 J-
0.8 J-
0.9 J-
0.7 J-
0.8 J-
0.9 J-
0.9 J-
Ni
3.6
3.1
4.2
3.3
3.5
47.8
30.5
34.4
27.6
53.9
61.0
58.0
55.0
59.0
61.0
65.0
62.0
51.1
58.5
64.7
57.5
52.4
57.0
50.7
75.0
71.0
70.0
64.0
70.0
72.0
65.0 J-
79.0
70.2
69.1
76.1
73.6
66.9
68.7
Se
0.4 U
0.3 U
0.2 U
0.3 U
0.3 U
4.0
3.8
1.8
1.4
2.1
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
0.0
1.2
0.5
1.1
0.6
0.8
1.6
1.3 U
1.3 U
1.3 U
1.3 U
1.2 U
1.3 U
1.4
0.4
3.2
3.8
1.6
3.1
Ag
0.8
0.7
0.8
0.8
0.8
0.2
1.0
0.7
0.4
1.1
0.9 J
0.9 J
0.9 J
0.9 J
0.9 J
1.0 J
1.0 J
0.9
1.0
1.7
0.0
0.5
0.9
15.0
15.0
14.0
13.0
14.0
15.0
13.0 J-
13.9
11.0
13.4
12.2
8.2
10.8
10.3
V
0.4 J
0.4 J
0.5 J
0.4 J
0.4 J
32.9
34.8
30.8
32.5
27.1
56.0
52.0
49.0
56.0
57.0
58.0
57.0
103.5
73.2
90.8
94.8
75.9
59.7
87.8
58.0
57.0
56.0
50.0
56.0
60.0
53.0 J-
97.7
88.2
92.0
62.5
75.9
65.0
68.7
Zn
100.0
92.0
110.0
110.0
100.0
137.2
125.8
156.6
151.1
158.0
230.0
220.0
210.0
230.0
230.0
240.0
240.0
245.6
237.1
261.1
260.7
252.0
265.0
257.0
930.0
900.0
870.0
820.0
900.0
950.0
830.0 J-
905.4
869.8
866.3
893.3
901.1
882.2
905.2
D-4
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
Sample ID
WS-SO-01-XX
WS-SO-04-XX
WS-SO-15-XX
WS-SO-22-XX
WS-SO-34-XX
WS-SO-01-OI
WS-SO-04-OI
WS-SO-15-OI
WS-SO-22-OI
WS-SO-34-OI
WS-SO-02-XX
WS-SO-16-XX
WS-SO-18-XX
WS-SO-21-XX
WS-SO-24-XX
WS-SO-29-XX
WS-SO-37-XX
WS-SO-02-OI
WS-SO-16-OI
WS-SO-18-OI
WS-SO-21-OI
WS-SO-24-OI
WS-SO-29-OI
WS-SO-37-OI
WS-SO-13-XX
WS-SO-19-XX
WS-SO-28-XX
WS-SO-32-XX
WS-SO-36-XX
WS-SO-13-OI
WS-SO-19-OI
WS-SO-28-OI
WS-SO-32-OI
WS-SO-36-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
41.0 J-
45.0 J-
48.0 J-
41.0 J-
45.0 J-
174.0
177.9
177.9
176.2
226.8
130.0 J-
110.0 J-
130.0 J-
120.0 J-
97.0 J-
120.0 J-
120.0 J-
358.0
365.5
658.7
365.6
358.0
629.3
635.3
200.0 J-
150.0 J-
120.0 J-
190.0 J-
120.0 J-
1612.9
945.2
976.0
971.0
As
1900.0
2000.0
2300.0
1900.0
2000.0
6263.0
6274.6
6313.4
6380.5
6301.4
4200.0
3900.0
4100.0
3900.0
3600.0
3800.0
4100.0
17068.7
17233.1
17370.3
17250.2
16963.6
16976.2
16911.8
5800.0
5000.0
4200.0
5500.0
3800.0
24834.6
24753.2
25297.7
24868.2
Cd
47.0
50.0
56.0
47.0
50.0
33.9
30.1
34.6
33.8
32.6
98.0
91.0
95.0
90.0
81.0
90.0
95.0
47.7
49.6
50.6
45.5
46.1
51.9
48.5
150.0
130.0
100.0
140.0
92.0
215.2
0.3
69.3
67.3
72.6
Cr
100.0
94.0
82.0
84.0
91.0
103.8
107.3
107.1
115.8
58.9
49.0
59.0
63.0
43.0
54.0
51.0
63.0
86.6
85.2
46.4
88.4
97.4
44.7
46.4
53.0
66.0
54.0
54.0
51.0
94.6
13.7
41.4
39.2
41.5
Cu
590.0
640.0
720.0
620.0
660.0
991.5
978.5
1000.9
1038.5
1021.3
1300.0
1300.0
1300.0
1200.0
1100.0
1200.0
1300.0
2763.5
2694.3
2724.0
2712.3
2695.8
2699.1
2719.7
1800.0
1500.0
1200.0
1700.0
1100.0
3926.4
3969.2
4085.8
4060.4
Fe
32000.0
34000.0
37000.0
33000.0
36000.0
82320.0
82870.0
80860.0
84150.0
62420.0
44000.0
42000.0
44000.0
40000.0
38000.0
40000.0
42000.0
123610.0
122680.0
92790.0
126730.0
124800.0
86890.0
87470.0
47000.0
39000.0
33000.0
44000.0
30000.0
138890.0
18510.0
97470.0
98170.0
99560.0
Pb
18000.0
20000.0
24000.0
17000.0
22000.0
11083.3
11310.0
11532.1
11536.1
17939.5
35000.0
24000.0
37000.0
43000.0
27000.0
42000.0
26000.0
18337.4
18406.6
46619.7
18222.9
18467.6
44284.4
44831.3
45000.0
24000.0
30000.0
30000.0
45000.0
18011.3
61960.0
63414.9
62815.5
D-5
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
7
7
7
7
7
7
7
7
7
7
8
8
8
8
8
8
8
8
8
8
8
8
8
8
9
9
9
9
9
9
9
9
9
9
Sample ID
WS-SO-01-XX
WS-SO-04-XX
WS-SO-15-XX
WS-SO-22-XX
WS-SO-34-XX
WS-SO-01-OI
WS-SO-04-OI
WS-SO-15-OI
WS-SO-22-OI
WS-SO-34-OI
WS-SO-02-XX
WS-SO-16-XX
WS-SO-18-XX
WS-SO-21-XX
WS-SO-24-XX
WS-SO-29-XX
WS-SO-37-XX
WS-SO-02-OI
WS-SO-16-OI
WS-SO-18-OI
WS-SO-21-OI
WS-SO-24-OI
WS-SO-29-OI
WS-SO-37-OI
WS-SO-13-XX
WS-SO-19-XX
WS-SO-28-XX
WS-SO-32-XX
WS-SO-36-XX
WS-SO-13-OI
WS-SO-19-OI
WS-SO-28-OI
WS-SO-32-OI
WS-SO-36-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
5.8 J
6.5
5.8
4.8
5.4
15.3
17.0
15.0
17.0
14.0
16.0
15.0
14.0
11.0
12.0
11.0
11.0
13.0
0.7
Ni
66.0
62.0
58.0
57.0
60.0
119.6
143.9
122.6
127.7
98.7
57.0
60.0
62.0
51.0
54.0
55.0
63.0
169.4
235.6
198.1
209.7
231.7
201.9
247.9
75.0
74.0
59.0
73.0
55.0
317.3
9.7
307.4
325.6
324.0
Se
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
7.1
5.8
4.5
1.3 U
1.1 J
1.9
1.6
2.1
1.7
3.0
12.1
12.8
5.3
5.8
3.7
3.7
2.3
3.7
1.7
12.3
0.7
7.7
Ag
69.0 J-
76.0 J-
90.0 J-
72.0 J-
78.0 J-
43.8
44.9
44.2
44.6
42.3
150.0 J-
150.0 J-
140.0 J-
150.0 J-
140.0 J-
140.0 J-
140.0 J-
66.9
67.5
70.4
69.4
67.1
71.3
72.4
170.0 J-
160.0 J-
130.0 J-
190.0 J-
120.0 J-
245.1
76.1
78.4
80.5
V
42.0
44.0
52.0
44.0
47.0
112.6
112.9
72.2
94.2
54.5
36.0
35.0
36.0
33.0
30.0
33.0
34.0
68.6
89.5
47.8
68.6
74.9
60.2
45.8
24.0
20.0
16.0
23.0
15.0
94.6
37.3
49.8
57.9
55.5
Zn
3000.0
3100.0
3400.0
3000.0
3200.0
4583.5
4760.6
4809.9
4734.2
4705.4
6000.0
5700.0
5900.0
5500.0
5200.0
5500.0
5800.0
11539.1
11591.0
12337.3
11869.8
11707.8
11875.1
11766.6
9000.0
7700.0
6100.0
8500.0
5700.0
20334.5
20711.8
20903.9
21042.3
D-6
-------
Appendix D. Analytical Data Summary, Oxford ED2000 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-OI
BN-SO-10-OI
BN-SO- 15-01
BN-SO-18-OI
BN-SO-28-OI
BN-SO-31-OI
BN-SO-35-OI
BN-SO-02-XX
BN-SO-04-XX
BN-SO-17-XX
BN-SO-22-XX
BN-SO-27-XX
BN-SO-02-OI
BN-SO-04-OI
BN-SO-17-OI
BN-SO-22-OI
BN-SO-27-OI
BN-SO-03-XX
BN-SO-06-XX
BN-SO-08-XX
BN-SO-13-XX
BN-SO-20-XX
BN-SO-30-XX
BN-SO-34-XX
BN-SO-03-OI
BN-SO-06-OI
BN-SO-08-OI
BN-SO-13-OI
BN-SO-20-OI
BN-SO-30-OI
BN-SO-34-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 U
1.5
1.3
1.4
6.5
5.2
0.2
2.3
2.8
3.4
1.9
11.0
9.1
9.3
7.3
9.6
30.7
33.2
30.1
38.2
29.5
65.0
60.0
57.0
65.0
57.0
64.0
68.0
240.8
243.7
231.8
242.3
248.3
240.8
236.6
As
38.0
50.0
34.0
37.0
35.0
41.0
37.0
53.9
56.4
56.9
57.6
48.4
55.3
56.6
140.0
120.0
110.0
98.0
110.0
192.9
213.4
203.8
201.6
206.7
620.0
600.0
570.0
320.0
540.0
630.0
630.0
1222.6
1216.8
1249.2
1235.4
1223.7
1207.8
1247.6
Cd
0.9
1.2
0.8
0.9
0.9
1.0
1.0
0.4
1.6
2.4
0.6
2.2
1.5
50.0
42.0
39.0
34.0
39.0
31.4
34.7
33.0
33.8
35.1
290.0
280.0
270.0
150.0
260.0
300.0
290.0
218.1
213.5
206.0
209.4
217.2
209.0
212.5
Cr
120.0
110.0
110.0
110.0
100.0
140.0
120.0
96.0
96.5
108.0
95.3
105.9
102.8
102.5
90.0
79.0
79.0
65.0
78.0
68.9
75.3
74.7
75.8
65.1
120.0
94.0
100.0
98.0
88.0
100.0
110.0
80.6
92.4
75.0
77.8
77.5
77.3
83.2
Cu
32.0
35.0
29.0
29.0
28.0
33.0
30.0
45.5
44.3
40.5
37.4
38.0
40.5
35.4
170.0
140.0
140.0
110.0
130.0
164.3
148.9
149.3
152.5
149.8
840.0
810.0
750.0
410.0
730.0
860.0
830.0
941.0
972.8
953.9
953.1
955.3
931.1
963.9
Fe
24000.0
24000.0
22000.0
22000.0
22000.0
26000.0
23000.0
42290.0
41200.0
40820.0
42180.0
42030.0
41220.0
42620.0
28000.0
24000.0
23000.0
20000.0
24000.0
41901.0
43010.0
41860.0
42120.0
42190.0
25000.0
24000.0
22000.0
17000.0
22000.0
26000.0
25000.0
42780.0
44240.0
43670.0
42550.0
45500.0
43960.0
43140.0
Pb
63.0
140.0
56.0
59.0
58.0
65.0
60.0
75.2
75.7
61.7
60.8
86.2
62.5
64.7
840.0
700.0
680.0
590.0
660.0
648.7
612.9
639.5
657.7
643.1
4700.0
4500.0
4300.0
2400.0
4100.0
4800.0
4700.0
3666.3
3763.7
3750.3
3743.0
3785.4
3816.9
3689.0
D-7
-------
Appendix D. Analytical Data Summary, Oxford ED2000 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-OI
BN-SO-10-OI
BN-SO- 15-01
BN-SO-18-OI
BN-SO-28-OI
BN-SO-31-OI
BN-SO-35-OI
BN-SO-02-XX
BN-SO-04-XX
BN-SO-17-XX
BN-SO-22-XX
BN-SO-27-XX
BN-SO-02-OI
BN-SO-04-OI
BN-SO-17-OI
BN-SO-22-OI
BN-SO-27-OI
BN-SO-03-XX
BN-SO-06-XX
BN-SO-08-XX
BN-SO-13-XX
BN-SO-20-XX
BN-SO-30-XX
BN-SO-34-XX
BN-SO-03-OI
BN-SO-06-OI
BN-SO-08-OI
BN-SO-13-OI
BN-SO-20-OI
BN-SO-30-OI
BN-SO-34-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
0.1
0.1
0.2
0.1
0.2
0.1
0.2
3.9
3.2
4.8
5.1
0.4
0.4
0.4
0.4
0.4
8.4
0.5
1.6
2.0
2.0
1.6
1.6
1.6
2.0
7.0
5.7
Ni
63.0
54.0
58.0
59.0
54.0
71.0
63.0
60.6
69.1
67.6
64.6
62.8
63.3
67.2
54.0
48.0
47.0
40.0
46.0
55.2
57.9
57.6
59.4
56.8
100.0
92.0
94.0
71.0
84.0
99.0
100.0
114.5
128.6
99.1
101.3
110.2
99.2
105.9
Se
1.3 U
1.2 J
1.3 U
1.3
1.3 U
1.3 U
1.2 J
1.2
2.3
0.3
2.4
1.9
1.3
4.3
2.9
2.7
2.8
3.7
1.0
1.8
0.5
3.0
17.0
15.0
14.0
9.2
14.0
17.0
17.0
11.1
11.8
11.5
12.1
12.6
10.8
13.2
Ag
1.3 UJ
1.3 UJ
1.3 UJ
0.9 U
0.8 U
1.0 U
0.9 U
1.8
0.9
0.9
0.6
0.8
1.1
7.6
6.5
6.3
5.4
6.1
5.2
3.5
4.3
5.1
6.1
42.0
41.0
38.0
21.0
37.0
44.0
42.0
28.8
27.9
26.7
28.0
29.0
28.4
28.7
V
55.0
55.0
49.0
46.0
48.0
54.0
50.0
76.6
77.9
62.6
76.6
78.4
45.8
72.9
60.0
50.0
49.0
43.0
52.0
63.5
51.5
69.2
84.4
75.7
48.0
48.0
39.0
37.0
44.0
50.0
49.0
69.5
64.2
48.7
63.6
55.0
58.0
59.4
Zn
92.0
110.0
89.0
88.0
81.0
94.0
87.0
102.7
111.5
111.9
99.9
126.0
114.3
111.7
470.0
400.0
390.0
330.0
380.0
446.5
468.1
452.9
450.5
455.8
2300.0
2300.0
2200.0
1200.0
2100.0
2400.0
2300.0
2712.0
2718.4
2767.3
2757.9
2757.3
2820.3
2684.0
D-8
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
16
16
16
16
16
16
16
16
16
16
Sample ID
BN-SO-07-XX
BN-SO-16-XX
BN-SO-21-XX
BN-SO-25-XX
BN-SO-33-XX
BN-SO-07-OI
BN-SO-16-OI
BN-SO-21-OI
BN-SO-25-OI
BN-SO-33-OI
BN-SO-05-XX
BN-SO-19-XX
BN-SO-26-XX
BN-SO-29-XX
BN-SO-32-XX
BN-SO-05-OI
BN-SO-19-OI
BN-SO-26-OI
BN-SO-29-OI
BN-SO-32-OI
CN-SO-01-XX
CN-SO-04-XX
CN-SO-08-XX
CN-SO-10-XX
CN-SO-11-XX
CN-SO-01-OI
CN-SO-04-OI
CN-SO-08-OI
CN-SO-10-OI
CN-SO-11-OI
AS-SO-02-XX
AS-SO-06-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-13-XX
AS-SO-02-OI
AS-SO-06-OI
AS-SO-10-OI
AS-SO-11-OI
AS-SO-13-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
110.0 J-
120.0 J-
150.0 J-
82.0 J-
100.0 J-
465.9
486.5
489.4
482.2
458.3
160.0 J-
150.0 J-
150.0 J-
150.0 J-
160.0 J-
779.7
748.3
801.7
771.4
785.5
13.0 J-
13.0 J-
15.0 J-
13.0 J-
17.0 J-
66.2
63.7
66.1
59.9
62.7
2.6 UJ
2.4 UJ
1.9 J-
3.7 J-
2.4 UJ
2.6
6.5
4.9
5.0
As
990.0 J+
1100.0 J+
1300.0 J+
700.0 J
1100.0
2264.2
2276.5
2264.1
2267.2
2280.0
1600.0
1600.0
1700.0
1600.0
1600.0
3755.9
3767.8
3770.1
3818.8
3956.6
13.0
11.0
15.0
13.0
16.0
123.9
134.3
133.5
148.5
154.4
18.0
19.0
18.0
22.0
20.0
233.9
226.3
237.8
212.6
244.8
Cd
520.0
570.0
660.0
370.0 J-
640.0
389.5
389.4
392.3
388.0
375.5
850.0
860.0
900.0
880.0
860.0
507.5
496.9
507.9
521.9
491.5
21.0
21.0
25.0
22.0
30.0
17.9
20.7
19.4
19.4
17.4
50.0
52.0
48.0
63.0
57.0
40.9
41.7
41.3
0.1
40.3
Cr
82.0
86.0
110.0
64.0 J-
100.0
81.8
62.4
68.9
72.5
75.5
86.0
79.0
82.0
86.0
84.0
65.5
55.8
94.2
56.8
55.7
190.0
200.0
210.0
200.0
240.0
190.4
176.4
181.7
177.0
181.8
180.0
190.0
180.0
230.0
200.0
113.9
116.6
114.0
121.6
121.0
Cu
1400.0
1500.0
1700.0
930.0 J-
1600.0
1844.8
1824.6
1845.9
1811.6
1842.9
2200.0
2200.0
2400.0
2300.0
2300.0
3096.0
3086.3
3045.2
3044.6
3090.3
700.0
680.0
740.0
760.0
860.0
728.8
782.4
717.2
782.4
721.8
140.0
130.0
110.0
150.0
150.0
132.1
135.9
145.5
126.5
133.5
Fe
23000.0
25000.0
30000.0
16000.0 J-
27000.0
45040.0
44590.0
44500.0
45010.0
44250.0
26000.0
26000.0
27000.0
26000.0
26000.0
46890.0
46140.0
72630.0
46810.0
46420.0
38000.0
37000.0
43000.0
39000.0
47000.0
46740.0
46110.0
46250.0
45200.0
45930.0
48000.0
52000.0
45000.0
52000.0
52000.0
48090.0
45720.0
46870.0
48780.0
46450.0
Pb
6900.0
8100.0
8900.0
5400.0 J-
8000.0
6402.2
6428.6
6420.8
6434.6
6460.2
12000.0
12000.0
12000.0
12000.0
12000.0
10106.0
9893.2
10213.3
9877.2
10171.6
1200.0
1200.0
1300.0
1200.0
1600.0
1096.9
1102.2
1057.6
1048.2
1043.5
1600.0
1600.0
1400.0
2100.0
1700.0
1515.5
1440.4
1507.2
1540.5
1501.9
D-9
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
13
13
13
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
16
16
16
16
16
16
16
16
16
16
Sample ID
BN-SO-07-XX
BN-SO-16-XX
BN-SO-21-XX
BN-SO-25-XX
BN-SO-33-XX
BN-SO-07-OI
BN-SO-16-OI
BN-SO-21-OI
BN-SO-25-OI
BN-SO-33-OI
BN-SO-05-XX
BN-SO-19-XX
BN-SO-26-XX
BN-SO-29-XX
BN-SO-32-XX
BN-SO-05-OI
BN-SO-19-OI
BN-SO-26-OI
BN-SO-29-OI
BN-SO-32-OI
CN-SO-01-XX
CN-SO-04-XX
CN-SO-08-XX
CN-SO-10-XX
CN-SO-11-XX
CN-SO-01-OI
CN-SO-04-OI
CN-SO-08-OI
CN-SO-10-OI
CN-SO-11-OI
AS-SO-02-XX
AS-SO-06-XX
AS-SO-10-XX
AS-SO-11-XX
AS-SO-13-XX
AS-SO-02-OI
AS-SO-06-OI
AS-SO-10-OI
AS-SO-11-OI
AS-SO-13-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
3.4
3.4
3.6
3.8
4.0
5.0
5.0
5.4
5.4
5.4
0.1
0.1
0.2
0.1
0.2
2.1
0.8
0.7
0.8
0.7
0.8
1.6
5.5
0.7
Ni
120.0
130.0
160.0
88.0 J-
150.0
160.7
152.0
150.6
166.5
150.0
160.0
160.0
160.0
160.0
160.0
215.9
184.8
195.7
192.3
199.2
240.0
240.0
280.0
240.0
320.0
252.2
251.7
257.3
247.5
232.9
91.0
93.0
84.0
120.0
100.0
118.9
86.6
97.9
104.2
106.6
Se
26.0
29.0
35.0
19.0 J-
34.0
22.8
19.9
21.0
19.6
20.8
48.0
48.0
49.0
48.0
48.0
40.6
37.9
37.2
31.9
29.8
2.2
1.5
1.3 U
1.9
1.3 U
1.6
2.5
3.5
3.3
2.6 U
2.6 U
1.1 U
1.1 U
3.0
1.5
2.0
4.7
1.8
Ag
70.0
77.0
88.0
48.0 J-
81.0
48.5
44.2
48.9
47.5
46.4
110.0
120.0
120.0
120.0
120.0
65.0
61.5
63.2
65.4
63.5
12.0
12.0
15.0
14.0
16.0
8.3
11.8
8.3
10.4
8.1
4.5
4.8
4.4
5.6
5.2
2.8
1.3
2.3
2.2
V
41.0
44.0
52.0
28.0 J-
48.0
46.3
53.5
49.5
54.8
55.8
39.0
39.0
40.0
41.0
39.0
61.3
62.3
79.0
63.7
54.5
21.0
22.0
26.0
22.0
27.0
10.9
32.4
26.5
11.6
34.7
42.0
44.0
42.0
54.0
50.0
46.6
53.7
45.1
58.9
44.8
Zn
4000.0
4400.0
5100.0
2900.0 J-
5100.0
5431.7
5453.9
5388.1
5384.0
5477.9
6700.0
6700.0
7000.0
6800.0
6700.0
8647.5
8504.3
8629.0
8680.1
8715.8
3100.0
2900.0
3200.0
3000.0
3500.0
3685.1
3582.7
3559.9
3530.5
3577.6
3300.0
3500.0
3000.0
3800.0
3800.0
4085.7
3745.3
3971.3
3872.2
4027.5
D-10
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
19
19
19
19
19
19
19
19
19
19
Sample ID
AS-SO-01-XX
AS-SO-04-XX
AS-SO-07-XX
AS-SO-09-XX
AS-SO-12-XX
AS-SO-01-OI
AS-SO-04-OI
AS-SO-07-OI
AS-SO-09-OI
AS-SO-12-OI
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-OI
SB-SO-06-OI
SB-SO-14-OI
SB-SO-38-OI
SB-SO-41-OI
SB-SO-47-OI
SB-SO-51-OI
SB-SO-05-XX
SB-SO-18-XX
SB-SO-30-XX
SB-SO-40-XX
SB-SO-53-XX
SB-SO-05-OI
SB-SO-18-OI
SB-SO-30-OI
SB-SO-40-OI
SB-SO-53-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
3.8 J-
6.4 UJ
3.6 J-
2.6 UJ
2.6 UJ
5.8
6.1
10.8
7.9
4.5
1.2 UJ
1.7 J-
4.1 J-
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
7.3
5.8
10.2
9.5
8.1
6.3
6.1
1.6 J-
1.2 UJ
3.2 J-
2.2 J-
1.2 UJ
19.7
15.9
13.6
14.4
14.9
As
26.0
22.0
21.0
25.0 J-
29.0
563.2
564.6
528.4
541.1
532.9
8.8
8.2
8.6
9.6
9.1
7.8
9.1
36.0
13.6
16.0
15.5
23.4
17.2
15.0
9.2
10.0
6.9
8.5
10.0
19.5
18.9
18.7
24.1
19.2
Cd
100.0
110.0
97.0
100.0 J-
120.0
74.6
72.5
65.7
70.5
69.8
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
0.5
0.1
0.6
1.0
0.0
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
1.2
0.0
Cr
420.0
480.0
380.0
390.0 J-
440.0
153.3
156.8
160.1
162.7
152.9
150.0
140.0
150.0
150.0
160.0
140.0
160.0
220.3
213.1
229.4
220.7
250.2
238.3
220.8
140.0
150.0
94.0
120.0
140.0
214.4
229.3
220.7
234.2
219.1
Cu
250.0
260.0
240.0
250.0 J-
270.0
313.5
290.1
287.2
310.6
293.0
48.0
44.0
46.0
57.0
58.0
44.0
50.0
40.5
48.7
59.9
57.9
46.3
44.2
58.7
46.0
46.0
27.0
40.0
44.0
45.3
59.6
50.0
43.4
35.8
Fe
100000.0
110000.0
88000.0
94000.0 J-
93000.0
61940.0
64380.0
62830.0
63230.0
63890.0
38000.0
35000.0
37000.0
37000.0
40000.0
34000.0
40000.0
66390.0
70040.0
71090.0
68920.0
69150.0
70290.0
70050.0
35000.0
38000.0
22000.0
33000.0
37000.0
68690.0
68600.0
68280.0
69150.0
67100.0
Pb
3200.0
3300.0
2900.0
3200.0 J-
3300.0
3146.2
3069.8
3165.0
3118.5
3141.5
18.0
16.0
17.0
18.0
19.0
16.0
18.0
16.9
20.1
12.2
13.7
14.4
18.7
24.4
16.0
17.0
10.0
15.0
17.0
24.9
36.8
40.0
13.9
14.4
D-ll
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
17
17
17
17
17
17
17
17
17
17
18
18
18
18
18
18
18
18
18
18
18
18
18
18
19
19
19
19
19
19
19
19
19
19
Sample ID
AS-SO-01-XX
AS-SO-04-XX
AS-SO-07-XX
AS-SO-09-XX
AS-SO-12-XX
AS-SO-01-OI
AS-SO-04-OI
AS-SO-07-OI
AS-SO-09-OI
AS-SO-12-OI
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-OI
SB-SO-06-OI
SB-SO-14-OI
SB-SO-38-OI
SB-SO-41-OI
SB-SO-47-OI
SB-SO-51-OI
SB-SO-05-XX
SB-SO-18-XX
SB-SO-30-XX
SB-SO-40-XX
SB-SO-53-XX
SB-SO-05-OI
SB-SO-18-OI
SB-SO-30-OI
SB-SO-40-OI
SB-SO-53-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
1.4
1.3
1.4
1.4
1.4
8.3
7.0
62.0
55.0
55.0
56.0
54.0
58.0
54.0
54.3
51.5
52.7
61.4
50.1
53.4
52.9
540.0
280.0
290.0
280.0
270.0
363.2
361.0
371.6
361.1
351.9
Ni
180.0
200.0
160.0
170.0 J-
190.0
218.2
222.1
195.6
223.5
204.8
210.0
200.0
210.0
210.0
230.0
200.0
230.0
207.7
200.1
216.5
194.1
219.4
204.1
194.8
200.0
210.0
120.0
180.0
200.0
187.6
190.6
195.7
195.2
185.3
Se
2.6 U
6.2 U
2.7
2.6 U
2.6 U
1.9
4.5
3.7
0.4
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
2.1
2.6
1.2
0.9
3.2
0.1
0.3
1.3 U
1.3 U
1.3 J+
1.3 U
1.3 U
0.3
3.8
2.7
1.0
Ag
9.3
12.0
8.9
9.6 J-
3.2
4.2
3.8
3.2
4.0
4.2
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
0.5
1.1
0.2
2.3
1.3
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
0.6
1.0
1.8
0.1
V
66.0
72.0
63.0
65.0 J-
73.0
46.6
49.9
56.0
51.7
53.5
67.0
63.0
66.0
68.0
71.0
62.0
74.0
113.7
118.5
143.7
114.3
114.4
114.1
140.7
61.0
70.0
43.0
58.0
64.0
125.6
122.1
123.0
125.0
112.2
Zn
6900.0
7400.0
6300.0
6800.0 J-
7500.0
10002.5
9861.4
9715.6
9796.8
9773.8
90.0
82.0
95.0
91.0
96.0
82.0
93.0
114.0
104.0
114.0
111.8
103.7
102.5
95.3
80.0
84.0
50.0
74.0
81.0
120.6
94.3
95.1
104.2
99.7
D-12
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
Sample ID
SB-SO-08-XX
SB-SO-11-XX
SB-SO-21-XX
SB-SO-39-XX
SB-SO-42-XX
SB-SO-08-OI
SB-SO-11-OI
SB-SO-21-OI
SB-SO-39-OI
SB-SO-42-OI
SB-SO-22-XX
SB-SO-25-XX
SB-SO-27-XX
SB-SO-35-XX
SB-SO-44-XX
SB-SO-22-OI
SB-SO-25-OI
SB-SO-27-OI
SB-SO-35-OI
SB-SO-44-OI
SB-SO-23-XX
SB-SO-28-XX
SB-SO-32-XX
SB-SO-43-XX
SB-SO-48-XX
SB-SO-23-OI
SB-SO-28-OI
SB-SO-32-OI
SB-SO-43-OI
SB-SO-48-OI
SB-SO-02-XX
SB-SO-07-XX
SB-SO-10-XX
SB-SO-26-XX
SB-SO-50-XX
SB-SO-02-OI
SB-SO-07-OI
SB-SO-10-OI
SB-SO-26-OI
SB-SO-50-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
5.4 J-
5.7 J-
4.9 J
4.7 J-
4.6 J-
35.3
42.9
36.7
40.4
34.9
10.0 J
6.8 J+
6.7 J+
6.0 J+
6.8 J+
67.8
69.9
67.6
66.6
69.6
48.0 J-
42.0 J-
46.0 J-
40.0 J-
39.0 J-
134.0
183.9
180.4
141.4
198.3
44.0 J-
45.0 J
62.0 J
61.0 J
57.0 J
262.9
250.4
254.2
254.2
251.2
As
13.0
13.0
13.0
13.0
13.0
33.7
57.6
20.6
35.7
56.7
18.0
18.0
18.0
17.0
18.0
56.1
52.5
41.5
43.7
51.9
37.0
36.0
40.0
35.0
36.0
129.3
132.1
126.1
134.3
132.2
23.0 J-
22.0
26.0
30.0
27.0
39.7
40.9
40.6
56.3
48.1
Cd
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
1.6
0.4
0.2
1.3
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
1.7
1.7
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
0.3
0.8
2.2
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
1.6
0.9
1.1
Cr
120.0
140.0
130.0
140.0
140.0
213.3
198.0
220.3
209.7
220.4
120.0
120.0
120.0
110.0
120.0
175.9
170.4
178.3
176.9
186.6
21.0
21.0
23.0
20.0
21.0
74.6
96.2
86.3
73.8
86.2
130.0
120.0
140.0
160.0
140.0
224.9
207.3
207.7
212.8
227.5
Cu
39.0
46.0
43.0
46.0
45.0
46.1
60.1
47.2
45.7
44.4
37.0
37.0
37.0
35.0
37.0
54.9
37.6
42.5
43.3
39.2
7.0
7.0
7.6
6.7
6.9
5.7
21.0
19.5
18.3
10.4
43.0
38.0
44.0
50.0
46.0
61.3
48.8
48.5
46.9
52.3
Fe
32000.0
36000.0
34000.0
34000.0
35000.0
65310.0
58240.0
64410.0
65030.0
61850.0
29000.0
29000.0
29000.0
28000.0
29000.0
57150.0
57149.0
57690.0
57840.0
56090.0
4500.0
4400.0
4900.0
4200.0
4500.0
24750.0
24490.0
24360.0
24590.0
24410.0
35000.0
35000.0
41000.0
46000.0
42000.0
75760.0
72940.0
72930.0
70140.0
72860.0
Pb
17.0
20.0
18.0
19.0
18.0
14.8
29.7
23.1
24.3
17.2
22.0
22.0
22.0
21.0
22.0
21.3
23.8
26.9
20.1
18.2
36.0
36.0
40.0
34.0
36.0
46.7
38.5
35.9
46.4
31.3
22.0 J-
23.0
27.0
31.0
28.0
28.4
30.5
25.1
28.2
22.7
D-13
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
20
20
20
20
20
20
20
20
20
20
21
21
21
21
21
21
21
21
21
21
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
Sample ID
SB-SO-08-XX
SB-SO-11-XX
SB-SO-21-XX
SB-SO-39-XX
SB-SO-42-XX
SB-SO-08-OI
SB-SO-11-OI
SB-SO-21-OI
SB-SO-39-OI
SB-SO-42-OI
SB-SO-22-XX
SB-SO-25-XX
SB-SO-27-XX
SB-SO-35-XX
SB-SO-44-XX
SB-SO-22-OI
SB-SO-25-OI
SB-SO-27-OI
SB-SO-35-OI
SB-SO-44-OI
SB-SO-23-XX
SB-SO-28-XX
SB-SO-32-XX
SB-SO-43-XX
SB-SO-48-XX
SB-SO-23-OI
SB-SO-28-OI
SB-SO-32-OI
SB-SO-43-OI
SB-SO-48-OI
SB-SO-02-XX
SB-SO-07-XX
SB-SO-10-XX
SB-SO-26-XX
SB-SO-50-XX
SB-SO-02-OI
SB-SO-07-OI
SB-SO-10-OI
SB-SO-26-OI
SB-SO-50-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
730.0
810.0
740.0
790.0
740.0
1034.4
937.1
965.4
1007.1
1028.1
3300.0
3000.0
3100.0
3100.0
3000.0
2328.2
2285.3
2323.4
2390.0
2260.0
8500.0
8800.0
8900.0
7600.0
8200.0
7042.3
7317.5
7973.4
7597.2
7886.8
130.0 J+
270.0
220.0
260.0
200.0
132.1
130.4
115.1
136.6
137.7
Ni
180.0
200.0
190.0
200.0
200.0
197.9
177.1
175.8
183.5
197.2
160.0
160.0
170.0
160.0
170.0
174.5
159.0
170.3
161.1
165.4
26.0
26.0
28.0
24.0
25.0
38.6
36.7
43.1
45.4
38.9
180.0
170.0
200.0
220.0
200.0
197.3
180.6
192.0
192.6
197.0
Se
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3
2.7
4.9
2.8
1.5
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
2.6
0.7
2.1
0.3
0.2 J
0.3 U
0.4
0.3 U
0.3 U
0.2
1.7
4.1
3.4
1.2 U
1.4
2.8
3.4
2.9
3.4
2.5
2.0
0.8
Ag
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.4
1.5
0.4
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
1.3
0.4
0.5
0.3 UJ
0.3 UJ
0.1 UJ
0.3 UJ
0.1 UJ
0.1
1.0
1.0
1.2 UJ
1.6
1.8
1.8
1.8
0.6
1.3
0.9
V
57.0
66.0
58.0
62.0
65.0
45.7
82.1
69.9
82.0
67.0
52.0
54.0
54.0
50.0
53.0
71.8
65.3
62.5
46.9
78.6
13.0
13.0
14.0
13.0
13.0
59.0
53.0
59.0
68.0
61.0
115.6
118.8
108.5
116.9
94.9
Zn
70.0
84.0
75.0
77.0
78.0
93.1
80.2
87.4
93.0
83.7
64.0 J-
63.0
65.0
62.0
64.0
74.9
84.4
82.4
88.9
85.6
8.4
7.8
8.5
8.3
7.8
4.7
7.2
30.2
24.6
1.8
88.0
86.0
100.0
110.0
100.0
128.4
121.3
134.2
116.5
107.6
D-14
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
24
24
24
24
24
24
24
24
24
24
25
25
25
25
25
25
25
25
25
25
26
26
26
26
26
26
26
26
26
26
27
27
27
27
27
27
27
27
27
27
Sample ID
SB-SO-01-XX
SB-SO-16-XX
SB-SO-24-XX
SB-SO-45-XX
SB-SO-52-XX
SB-SO-01-OI
SB-SO-16-OI
SB-SO-24-OI
SB-SO-45-OI
SB-SO-52-OI
SB-SO-13-XX
SB-SO-19-XX
SB-SO-33-XX
SB-SO-37-XX
SB-SO-55-XX
SB-SO-13-OI
SB-SO-19-OI
SB-SO-33-OI
SB-SO-37-OI
SB-SO-55-OI
SB-SO-12-XX
SB-SO-15-XX
SB-SO-17-XX
SB-SO-46-XX
SB-SO-54-XX
SB-SO-12-OI
SB-SO-15-OI
SB-SO-17-OI
SB-SO-46-OI
SB-SO-54-OI
KP-SE-08-XX
KP-SE-11-XX
KP-SE-17-XX
KP-SE-25-XX
KP-SE-30-XX
KP-SE-08-OI
KP-SE-11-OI
KP-SE-17-OI
KP-SE-25-OI
KP-SE-30-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
180.0 J
170.0 J
180.0 J
180.0 J
150.0 J
658.0
620.5
639.1
617.7
620.4
430.0 J
310.0 J
350.0 J
340.0 J
340.0 J
1252.9
1357.7
1345.4
1331.8
1319.1
620.0 J
600.0 J-
800.0 J+
740.0 J+
280.0
2219.2
2192.0
2189.3
2178.1
2176.4
6.2
5.6
4.9
6.0
5.7
2.1
5.2
5.7
6.7
4.7
As
65.0
64.0
66.0
63.0
62.0
71.4
62.8
66.7
88.3
89.9
160.0
100.0
110.0
130.0
120.0
146.2
143.9
158.3
151.4
153.9
190.0
170.0 J-
210.0
190.0
31.0
201.1
217.4
224.6
225.5
231.9
2.6
2.6
2.6
2.8
2.8
40.7
46.8
49.0
44.1
49.5
Cd
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
1.9
0.0
1.0 U
0.5 U
0.5 U
1.0 U
0.5 U
0.7
1.1
1.0 U
1.0 U
1.0 U
1.0 U
0.2 U
1.1
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
0.4
0.9
Cr
140.0
140.0
150.0
140.0
140.0
210.4
213.2
215.3
202.0
214.7
140.0
100.0
100.0
120.0
120.0
181.3
172.0
171.8
174.9
179.9
100.0
91.0 J-
110.0
120.0
25.0
183.9
169.8
166.7
178.1
177.7
88.0
96.0
98.0
99.0
83.0
210.8
212.3
198.0
208.8
223.0
Cu
46.0
45.0
49.0
45.0
47.0
44.1
44.0
47.4
55.4
60.4
46.0
32.0
33.0
39.0
37.0
50.4
52.2
45.7
49.0
46.2
33.0
30.0 J-
37.0
35.0
5.8
50.3
39.2
43.3
47.2
50.2
3.8
4.1
4.1
4.3
3.6
7.8
1.0
5.7
6.0
0.3
Fe
47000.0
47000.0
49000.0
47000.0
46000.0
77950.0
81100.0
81380.0
79520.0
79290.0
61000.0
42000.0
45000.0
51000.0
49000.0
91850.0
93070.0
93530.0
94500.0
90560.0
55000.0
51000.0 J-
61000.0
57000.0
8600.0
108480.0
107370.0
105190.0
104380.0
104310.0
840.0
940.0
940.0
960.0
830.0
21030.0
20980.0
20860.0
20970.0
21170.0
Pb
30.0
30.0
32.0
30.0
29.0
31.6
25.7
25.6
26.6
21.5
36.0
25.0
28.0
31.0
29.0
27.4
32.4
30.9
38.5
36.2
43.0
40.0 J-
48.0
47.0
5.2 J-
52.4
46.9
52.2
54.7
43.6
300.0 J-
310.0 J-
300.0 J-
310.0 J-
300.0 J-
360.6
349.1
327.6
325.5
327.7
D-15
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
24
24
24
24
24
24
24
24
24
24
25
25
25
25
25
25
25
25
25
25
26
26
26
26
26
26
26
26
26
26
27
27
27
27
27
27
27
27
27
27
Sample ID
SB-SO-01-XX
SB-SO-16-XX
SB-SO-24-XX
SB-SO-45-XX
SB-SO-52-XX
SB-SO-01-OI
SB-SO-16-OI
SB-SO-24-OI
SB-SO-45-OI
SB-SO-52-OI
SB-SO-13-XX
SB-SO-19-XX
SB-SO-33-XX
SB-SO-37-XX
SB-SO-55-XX
SB-SO-13-OI
SB-SO-19-OI
SB-SO-33-OI
SB-SO-37-OI
SB-SO-55-OI
SB-SO-12-XX
SB-SO-15-XX
SB-SO-17-XX
SB-SO-46-XX
SB-SO-54-XX
SB-SO-12-OI
SB-SO-15-OI
SB-SO-17-OI
SB-SO-46-OI
SB-SO-54-OI
KP-SE-08-XX
KP-SE-11-XX
KP-SE-17-XX
KP-SE-25-XX
KP-SE-30-XX
KP-SE-08-OI
KP-SE-11-OI
KP-SE-17-OI
KP-SE-25-OI
KP-SE-30-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
400.0
480.0
420.0
450.0
430.0
213.8
225.3
218.3
235.7
230.6
850.0
740.0
870.0
790.0
900.0
401.0
387.4
392.4
407.6
393.4
1400.0
1100.0
1200.0
670.0
560.0
558.4
534.2
531.5
525.9
560.7
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
5.5
3.3
2.0
Ni
190.0
190.0
200.0
190.0
190.0
167.6
191.1
171.5
168.6
183.4
180.0
120.0
130.0
150.0
140.0
160.1
166.2
164.7
164.0
155.2
110.0
100.0 J-
120.0
120.0
20.0
132.9
119.9
128.1
127.3
117.0
42.0
46.0
47.0
47.0
39.0
59.4
59.9
58.7
58.8
63.1
Se
1.8
1.9
2.5
2.8
1.8
3.4
0.8
1.9
1.1
4.4
2.5
3.0
2.5 U
2.5
1.5
1.1
3.5
1.8
1.0
2.5 U
3.4
2.8
2.6
0.5 U
1.8
1.4
0.4
1.4
0.1
0.3 U
0.4
0.3 U
0.3 U
0.2 U
1.2
0.2
2.2
1.3
1.9
Ag
2.3
2.2
2.3
2.1 J-
2.2
0.2
0.4
0.0
2.2 UJ
1.8
2.0 J
2.0 UJ
2.2 J
0.0
0.3
1.2
1.8
2.1 UJ
1.6 UJ
2.3 UJ
2.2 UJ
0.5 UJ
2.8
0.6
0.1
0.3 UJ
0.3 UJ
0.3 UJ
0.3 UJ
0.3 UJ
0.7
0.0
0.5
0.1
1.1
V
65.0
65.0
67.0
63.0
64.0
132.3
97.2
97.6
75.2
131.2
74.0
51.0
52.0
63.0
61.0
120.4
109.8
137.2
115.3
96.7
59.0
52.0 J-
60.0
57.0
11.0
83.9
93.2
111.0
97.9
84.3
3.7
4.0
4.0
4.1
3.6
37.4
33.0
38.9
30.2
40.3
Zn
95.0
97.0
95.0
93.0
90.0
109.0
98.4
117.9
103.0
105.5
70.0
51.0
56.0
58.0
60.0
82.8
64.0
87.9
68.9
72.4
42.0
36.0 J-
42.0
41.0
6.0
62.9
84.8
67.5
69.8
69.9
4.8
5.7
4.7
4.8
4.5
15.6
11.8
7.5
2.8
7.4
D-16
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
28
28
28
28
28
28
28
28
28
28
29
29
29
29
29
29
29
29
29
29
29
29
29
29
30
30
30
30
30
30
30
30
30
30
Sample ID
KP-SE-01-XX
KP-SE-12-XX
KP-SE-14-XX
KP-SE-19-XX
KP-SE-28-XX
KP-SE-01-OI
KP-SE- 12-01
KP-SE-14-OI
KP-SE- 19-01
KP-SE-28-OI
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-OI
TL-SE-10-OI
TL-SE-12-OI
TL-SE-15-OI
TL-SE-20-OI
TL-SE-24-OI
TL-SE-26-OI
TL-SE-03-XX
TL-SE-19-XX
TL-SE-23-XX
TL-SE-25-XX
TL-SE-31-XX
TL-SE-03-OI
TL-SE-19-OI
TL-SE-23-OI
TL-SE-25-OI
TL-SE-31-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
3.2
3.1
11.0 J-
3.0
3.3
5.6
3.8
2.1
4.3
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
5.3
1.1
3.4
1.7
2.5 U
2.5 U
2.5 U
2.5 U
2.5 U
2.4
0.2
As
1.5
1.5
1.9
1.5
1.6
37.2
51.5
44.1
42.1
41.3
9.8
10.0
10.0
8.8
10.0
11.0
9.9
29.3
12.6
26.4
35.2
21.0
17.6
17.4
9.3
9.6
9.1
9.9
10.0
36.0
0.2
19.4
15.1
46.6
Cd
0.1 U
0.1 U
0.1 U
0.1 U
0.1 U
0.7
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
1.3
0.1
1.8
2.2
0.8
0.0
1.0 U
1.0 U
1.0 U
1.0 U
1.0 U
0.0
0.5
Cr
34.0
42.0
46.0 J-
44.0
45.0
93.9
112.5
99.4
99.1
102.5
62.0
64.0
66.0
54.0
64.0
67.0
62.0
90.4
75.1
89.2
74.0
70.9
81.8
72.8
91.0
96.0
92.0
91.0
110.0
105.8
13.7
95.9
105.1
98.4
Cu
2.2
2.5
2.7 J+
2.3
2.3
4.9
1.6
1.4
5.6
1900.0
2000.0
2100.0
1800.0
2000.0
2100.0
2000.0
1975.7
1988.7
2023.3
2027.1
1973.1
2021.3
1971.2
1600.0
1700.0
1600.0
1600.0
1800.0
1647.9
1633.6
1659.9
1655.3
1634.6
Fe
480.0
510.0
520.0 J-
510.0
520.0
19990.0
20080.0
20040.0
19920.0
20040.0
42000.0
43000.0
44000.0
36000.0
42000.0
43000.0
40000.0
83270.0
83230.0
80650.0
83220.0
83270.0
82930.0
81600.0
63000.0
66000.0
64000.0
62000.0
74000.0
118620.0
18510.0
119440.0
122170.0
118700.0
Pb
310.0 J-
320.0 J-
680.0 J-
330.0
320.0
329.8
339.9
358.2
314.4
326.1
32.0
35.0
34.0
28.0
32.0
37.0
34.0
37.3
53.6
45.8
27.0
35.9
46.9
43.6
12.0
13.0
12.0
11.0
13.0
26.6
20.6
23.4
13.0
D-17
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
28
28
28
28
28
28
28
28
28
28
29
29
29
29
29
29
29
29
29
29
29
29
29
29
30
30
30
30
30
30
30
30
30
30
Sample ID
KP-SE-01-XX
KP-SE-12-XX
KP-SE-14-XX
KP-SE-19-XX
KP-SE-28-XX
KP-SE-01-OI
KP-SE- 12-01
KP-SE- 14-01
KP-SE- 19-OI
KP-SE-28-OI
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-OI
TL-SE-10-OI
TL-SE-12-OI
TL-SE- 15-01
TL-SE-20-OI
TL-SE-24-OI
TL-SE-26-OI
TL-SE-03-XX
TL-SE-19-XX
TL-SE-23-XX
TL-SE-25-XX
TL-SE-31-XX
TL-SE-03-OI
TL-SE-19-OI
TL-SE-23-OI
TL-SE-25-OI
TL-SE-31-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
0.1 U
0.1 U
0.1 U
0.0 U
0.1 U
3.7
7.5
0.3 J-
0.2 J-
0.2 J-
0.3 J-
0.3 J-
0.3 J-
0.2 J-
3.5
9.3
10.1
6.9
8.7
4.9
0.3 J-
0.3 J-
0.4 J-
0.4 J-
0.6 J-
2.6
1.6
3.7
Ni
16.0
20.0
23.0 J-
22.0
22.0
27.2
38.1
24.9
26.0
32.3
71.0
72.0
75.0
63.0
74.0
77.0
70.0
93.3
87.2
96.7
88.9
92.4
98.5
95.6
110.0
120.0
110.0
110.0
130.0
139.7
131.5
135.5
163.4
136.4
Se
0.3 U
0.3 U
0.3 U
0.3 U
0.3 U
2.2
2.4
1.1
2.8
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.6
0.7
3.7
3.2
1.3
1.9
2.5 U
2.5 U
2.5 U
2.5 U
2.5 U
1.8
0.3
1.7
0.6
Ag
0.3 UJ
0.3 UJ
0.3 UJ
0.3 U
0.3 U
0.9
0.7
1.6
1.3
1.2 U
1.2 U
1.0 U
1.2 U
1.3 U
1.2 U
1.7
2.4
3.8
1.9
3.4
2.1
3.7
0.9 U
1.1 U
1.3 U
0.9 U
1.2 U
1.8
2.5
3.2
2.1
2.0
V
2.3 J
2.4 J
2.5 J
2.3 J
2.4 J
29.8
37.5
26.5
17.9
30.7
95.0
95.0
100.0
84.0
100.0
100.0
96.0
76.1
90.9
61.1
55.7
83.7
46.2
95.7
140.0
150.0
150.0
150.0
170.0
114.8
37.3
108.5
95.5
91.7
Zn
5.8
7.7
7.1
7.3
6.3
15.2
9.5
0.6
11.1
5.6
160.0
160.0
170.0
140.0
160.0
170.0
160.0
165.7
218.0
203.6
196.4
189.4
183.2
177.0
200.0
210.0
200.0
200.0
230.0
218.9
235.4
240.2
233.0
232.3
D-18
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
31
31
31
31
31
31
31
31
31
31
31
31
31
31
32
32
32
32
32
32
32
32
32
32
32
32
32
32
33
33
33
33
33
33
33
33
33
33
Sample ID
TL-SE-01-XX
TL-SE-11-XX
TL-SE-14-XX
TL-SE-18-XX
TL-SE-22-XX
TL-SE-27-XX
TL-SE-29-XX
TL-SE-01-OI
TL-SE-11-OI
TL-SE-14-OI
TL-SE- 18-01
TL-SE-22-OI
TL-SE-27-OI
TL-SE-29-OI
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-OI
LV-SE-10-OI
LV-SE-22-OI
LV-SE-25-OI
LV-SE-31-OI
LV-SE-35-OI
LV-SE-50-OI
LV-SE-12-XX
LV-SE-26-XX
LV-SE-33-XX
LV-SE-39-XX
LV-SE-42-XX
LV-SE-12-OI
LV-SE-26-OI
LV-SE-33-OI
LV-SE-39-OI
LV-SE-42-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
0.3
3.7
1.4
1.9
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
2.5 U
1.7
2.5
6.8
0.4
2.1
3.5
2.4
2.6 U
2.6 U
2.6 U
2.6 U
2.7 U
4.5
2.9
5.4
1.6
3.2
As
9.3
15.0
10.0
9.9
11.0
10.0
11.0
51.5
25.4
50.8
46.9
31.4
34.2
28.1
28.0
34.0
30.0
31.0
32.0
31.0 J-
29.0
41.0
47.5
43.5
47.2
31.7
71.6
47.9
190.0
220.0
170.0
190.0
170.0
218.3
211.4
199.2
226.1
228.4
Cd
0.5 U
0.5 U
0.3 J
0.5 U
0.5 U
0.3 J
0.2 J
0.1
0.1
1.5
0.7
2.9
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
1.0 U
0.7
1.3
1.0 U
1.0 U
1.0 U
1.0 U
1.1 U
0.8
0.8
0.4
0.3
1.0
Cr
110.0
140.0
110.0
150.0
150.0
130.0
140.0
160.9
162.9
146.4
154.5
156.2
168.8
172.3
72.0
84.0
69.0
74.0
78.0
74.0 J-
74.0
89.5
95.7
86.8
83.9
90.2
91.1
86.3
55.0
64.0
52.0
58.0
50.0
84.3
86.0
78.8
102.3
83.5
Cu
1400.0
1600.0
1500.0
1300.0
1700.0
1500.0
1600.0
1671.8
1661.6
1734.2
1715.7
1681.0
1703.6
1704.2
33.0
42.0
33.0
36.0
36.0
35.0
34.0
38.9
37.3
40.6
41.4
43.7
44.8
37.1
34.0
39.0
31.0
35.0
30.0
43.0
46.6
37.9
44.5
47.7
Fe
19000.0
28000.0
18000.0
24000.0
26000.0
19000.0
23000.0
70690.0
73470.0
71320.0
76820.0
77070.0
75080.0
75700.0
23000.0
28000.0
23000.0
25000.0
25000.0
24000.0 J-
24000.0
57320.0
55750.0
56620.0
57560.0
56340.0
55180.0
56140.0
72000.0
83000.0
66000.0
74000.0
65000.0
140770.0
146680.0
143070.0
143440.0
136600.0
Pb
48.0 J-
54.0 J-
50.0 J-
46.0 J-
54.0 J-
51.0 J-
51.0 J-
58.8
62.4
46.2
59.5
52.2
51.1
62.9
20.0 J-
25.0 J-
22.0 J-
23.0 J-
49.0 J-
22.0 J-
24.0 J-
33.5
38.6
38.2
37.4
40.1
36.0
29.2
19.0 J-
25.0 J-
21.0 J-
22.0 J-
22.0 J-
22.6
26.4
19.9
47.9
34.7
D-19
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
31
31
31
31
31
31
31
31
31
31
31
31
31
31
32
32
32
32
32
32
32
32
32
32
32
32
32
32
33
33
33
33
33
33
33
33
33
33
Sample ID
TL-SE-01-XX
TL-SE-11-XX
TL-SE-14-XX
TL-SE-18-XX
TL-SE-22-XX
TL-SE-27-XX
TL-SE-29-XX
TL-SE-01-OI
TL-SE-11-OI
TL-SE-14-OI
TL-SE- 18-01
TL-SE-22-OI
TL-SE-27-OI
TL-SE-29-OI
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-OI
LV-SE-10-OI
LV-SE-22-OI
LV-SE-25-OI
LV-SE-31-OI
LV-SE-35-OI
LV-SE-50-OI
LV-SE-12-XX
LV-SE-26-XX
LV-SE-33-XX
LV-SE-39-XX
LV-SE-42-XX
LV-SE-12-OI
LV-SE-26-OI
LV-SE-33-OI
LV-SE-39-OI
LV-SE-42-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
0.1 U
0.0 U
0.1 U
0.0 U
0.1 U
0.0 U
0.1 U
3.0
8.5
0.0 U
0.0 U
1.1
1.0
1.0
1.4
1.2
2.1
9.4
2.8
3.0
5.6
6.0
6.8
8.0
4.3
8.4
6.2
3.5
3.2
Ni
180.0
210.0
180.0
190.0
210.0
200.0
200.0
213.1
221.1
193.0
220.1
216.6
206.3
223.5
160.0
200.0
170.0
170.0
180.0
170.0 J-
170.0
143.8
147.3
143.4
136.1
145.7
144.6
131.1
71.0
83.0
66.0
74.0
67.0
101.4
104.3
106.6
103.3
114.7
Se
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
2.0
1.1
1.4
1.0
1.6
3.8
4.7
5.2
5.1
5.1
5.0
3.3
6.0
5.9
3.2
4.9
4.1
5.2
5.1
3.0
6.1
2.8
5.1
3.4
5.7
4.6
2.4
4.3
3.6
Ag
5.7 J-
5.5 J-
5.7 J-
6.3 J-
6.5 J-
7.8 J-
5.9 J-
3.7
4.1
5.7
3.2
5.0
5.6
3.8
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
2.5 U
0.6
0.6
2.6 U
2.6 U
2.6 U
2.6 U
2.7 U
0.3
0.3
0.4
0.4
1.1
V
75.0
85.0
73.0
70.0
80.0
67.0
80.0
96.0
98.2
60.1
82.3
81.3
68.3
79.5
53.0
66.0
51.0
56.0
58.0
55.0 J-
57.0
77.4
59.3
109.5
87.2
70.0
75.7
84.4
72.0
86.0
67.0
74.0
64.0
132.7
124.5
139.1
103.7
114.4
Zn
130.0
140.0
140.0
120.0
150.0
140.0
140.0
155.9
149.9
160.3
158.9
194.1
159.7
162.5
65.0
77.0
66.0
70.0
70.0
67.0 J-
65.0
94.3
98.5
95.1
89.9
83.1
113.6
95.9
66.0
75.0
59.0
66.0
57.0
104.6
82.3
90.6
86.5
111.3
D-20
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
34
34
34
34
34
34
34
34
34
34
35
35
35
35
35
35
35
35
35
35
36
36
36
36
36
36
36
36
36
36
37
37
37
37
37
37
37
37
37
37
Sample ID
LV-SE-09-XX
LV-SE-19-XX
LV-SE-27-XX
LV-SE-36-XX
LV-SE-38-XX
LV-SE-09-OI
LV-SE-19-OI
LV-SE-27-OI
LV-SE-36-OI
LV-SE-38-OI
LV-SE-07-XX
LV-SE-18-XX
LV-SE-23-XX
LV-SE-45-XX
LV-SE-48-XX
LV-SE-07-OI
LV-SE- 18-01
LV-SE-23-OI
LV-SE-45-OI
LV-SE-48-OI
LV-SE-01-XX
LV-SE-14-XX
LV-SE-21-XX
LV-SE-24-XX
LV-SE-32-XX
LV-SE-01-OI
LV-SE-14-OI
LV-SE-21-OI
LV-SE-24-OI
LV-SE-32-OI
LV-SE-08-XX
LV-SE-16-XX
LV-SE-28-XX
LV-SE-30-XX
LV-SE-47-XX
LV-SE-08-OI
LV-SE-16-OI
LV-SE-28-OI
LV-SE-30-OI
LV-SE-47-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
6.7 U
6.7 U
6.7 U
6.7 U
6.7 U
0.7
5.3
4.1
1.1
4.6
6.7 UJ
6.7 UJ
6.6 UJ
6.7 UJ
6.6 UJ
5.2
2.9
5.2
0.5
1.5 UJ
1.5 UJ
1.5 UJ
1.5 UJ
1.4 UJ
2.3
0.9
1.4
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
11.1
10.9
8.2
10.3
11.2
As
450.0
500.0
530.0
550.0
480.0
494.0
494.9
486.4
492.1
490.2
780.0
800.0
660.0
650.0
680.0
751.6
731.7
717.7
742.2
733.3
6.1
5.0
6.5
4.9
5.6
8.6
1.1
1.7
30.0
29.0
31.0
30.0
31.0
60.4
60.2
63.8
49.0
52.2
Cd
2.7 U
2.7 U
2.7 U
2.7 U
2.7 U
0.5
1.3
0.2
0.6
2.7 U
2.7 U
2.6 U
2.7 U
2.6 U
0.9
1.1
0.4
1.1
0.8
0.7
0.8
0.7
0.9
0.6
0.5
0.5 U
0.5 U
0.5 U
0.5 U
0.5 U
0.0
1.9
1.3
0.5
Cr
48.0
55.0
56.0
60.0
52.0
85.5
94.0
102.2
104.7
86.9
57.0
61.0
53.0
50.0
52.0
98.0
107.4
100.5
99.6
139.2
4.4
4.2
4.4
3.9
4.4
16.9
17.1
15.9
16.0
15.9
54.0
53.0
59.0
58.0
56.0
86.7
86.2
85.2
86.1
86.1
Cu
34.0
37.0
39.0
40.0
36.0
67.3
55.2
62.5
48.0
45.2
48.0
49.0
40.0
40.0
42.0
69.0
61.5
60.8
69.4
69.8
18.0
16.0
19.0
15.0
16.0
15.7
14.0
18.3
16.3
11.7
23.0
22.0
25.0
25.0
23.0
28.9
34.9
33.7
38.5
30.2
Fe
150000.0
160000.0
180000.0
180000.0
160000.0
340860.0
339190.0
339390.0
342120.0
340830.0
200000.0
210000.0
170000.0
170000.0
180000.0
464910.0
451600.0
456600.0
449880.0
447660.0
1100.0
980.0
970.0
840.0
860.0
19400.0
19390.0
19380.0
19430.0
19410.0
23000.0
22000.0
25000.0
24000.0
23000.0
59160.0
55510.0
58660.0
59350.0
58020.0
Pb
14.0 J-
17.0 J-
16.0 J-
21.0 J-
15.0 J-
21.6
28.8
17.0
16.2
19.0
11.0
11.0
7.7
7.6
8.9
5.7
9.4
13.6
17.0
14.0
18.0
14.0
14.0
15.0
13.9
20.3
18.2
16.3
55.0
53.0
59.0
58.0
57.0
84.0
89.9
81.6
75.3
83.6
D-21
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
34
34
34
34
34
34
34
34
34
34
35
35
35
35
35
35
35
35
35
35
36
36
36
36
36
36
36
36
36
36
37
37
37
37
37
37
37
37
37
37
Sample ID
LV-SE-09-XX
LV-SE-19-XX
LV-SE-27-XX
LV-SE-36-XX
LV-SE-38-XX
LV-SE-09-OI
LV-SE-19-OI
LV-SE-27-OI
LV-SE-36-OI
LV-SE-38-OI
LV-SE-07-XX
LV-SE-18-XX
LV-SE-23-XX
LV-SE-45-XX
LV-SE-48-XX
LV-SE-07-OI
LV-SE- 18-01
LV-SE-23-OI
LV-SE-45-OI
LV-SE-48-OI
LV-SE-01-XX
LV-SE-14-XX
LV-SE-21-XX
LV-SE-24-XX
LV-SE-32-XX
LV-SE-01-OI
LV-SE-14-OI
LV-SE-21-OI
LV-SE-24-OI
LV-SE-32-OI
LV-SE-08-XX
LV-SE-16-XX
LV-SE-28-XX
LV-SE-30-XX
LV-SE-47-XX
LV-SE-08-OI
LV-SE-16-OI
LV-SE-28-OI
LV-SE-30-OI
LV-SE-47-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
6.0
7.2
11.0
8.5
7.9
7.0
2.2
4.4
13.7
5.5
5.4
5.0
5.6
7.3
2.8
2.3
4.1
4.3
0.1 U
0.1 U
0.0 U
0.1 U
0.1 U
0.8
3.2
1.3
5.2
5.4
5.4
6.3
4.9
1.1
6.5
7.4
Ni
55.0
65.0
64.0
70.0
75.0
141.2
134.0
133.2
130.3
136.4
58.0
60.0
50.0 J
50.0 J
50.0 J
133.3
151.7
135.1
174.7
151.3
49.0
46.0
49.0
44.0
47.0
45.1
46.2
39.1
48.0
47.0
110.0
110.0
120.0
120.0
120.0
126.0
122.8
129.7
137.2
132.0
Se
6.7 U
5.9 J
6.7 U
11.0
6.7 U
3.6
0.0
2.8
0.6
6.4
10.0
12.0
9.6
8.2
7.6
4.5
7.5
4.2
4.1
2.2
1.5 U
1.5 U
1.5 U
1.5 U
1.4 U
2.7
1.8
0.3
1.0
4.8
5.0
5.8
5.6
4.2
6.8
3.8
6.2
4.3
5.1
Ag
6.7 U
6.7 U
6.7 U
6.7 U
6.7 U
0.2
1.5
6.7 U
6.7 U
6.6 U
6.7 U
6.6 U
0.7
0.0
0.3
1.5 U
1.5 U
1.5 U
1.5 U
1.4 U
0.3
0.7
0.2
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
0.6
0.8
1.3
0.3
V
100.0
110.0
120.0
120.0
100.0
135.0
166.8
141.3
134.6
166.7
130.0
140.0
120.0
120.0
120.0
193.4
142.1
210.5
240.1
184.6
1.6 J
1.4 J
1.6 J
1.4 J
1.3 J
34.0
35.9
37.0
38.6
31.9
44.0
42.0
48.0
48.0
45.0
72.8
41.2
59.0
72.9
49.9
Zn
51.0 J
55.0 J
58.0 J
60.0 J
54.0 J
87.0
98.2
91.2
84.8
89.5
24.0 J
52.0 J
18.0 J
19.0 J
30.0 J
66.1
64.9
56.4
85.0
68.1
14.0 J
12.0 J
14.0 J
12.0 J
19.0
16.7
19.1
18.2
18.5
20.1
61.0
59.0
65.0
66.0
65.0
84.7
95.0
92.8
79.2
103.3
D-22
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
38
38
38
38
38
38
38
38
38
38
39
39
39
39
39
39
39
39
39
39
39
39
39
39
40
40
40
40
40
40
40
40
40
40
Sample ID
LV-SE-ll-XX
LV-SE-29-XX
LV-SE-44-XX
LV-SE-46-XX
LV-SE-52-XX
LV-SE-11-OI
LV-SE-29-OI
LV-SE-44-OI
LV-SE-46-OI
LV-SE-52-OI
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-OI
RF-SE- 12-01
RF-SE-23-OI
RF-SE-36-OI
RF-SE-42-OI
RF-SE-45-OI
RF-SE-53-OI
RF-SE-03-XX
RF-SE-28-XX
RF-SE-38-XX
RF-SE-49-XX
RF-SE-55-XX
RF-SE-03-OI
RF-SE-28-OI
RF-SE-38-OI
RF-SE-49-OI
RF-SE-55-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
1.4 UJ
1.4 UJ
1.4 U
0.9 U
1.4 U
3.5
2.3
1.3 U
1.2 U
0.3 U
1.2 U
1.3 UJ
1.3 UJ
1.3 UJ
1.5
0.8
1.7
0.1
4.1
0.0
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
1.2 UJ
4.3
1.0
2.8
1.9
3.5
As
150.0
150.0
140.0
110.0
160.0
153.6
160.3
162.4
171.0
155.4
12.0
14.0
0.3 U
12.0
14.0
15.0
14.0
20.3
24.6
19.6
22.2
27.2
32.0
21.0
27.0
31.0
27.0
31.0
24.0
46.2
50.6
49.9
57.5
47.1
Cd
6.6
6.3
6.1
5.0
6.8
5.3
5.9
7.0
4.8
8.0
0.5 U
0.5 U
0.1 U
0.5 U
0.6
0.5 U
0.6 U
0.6
0.7
0.3
2.5
2.6
2.0
0.4
1.3
1.5
1.2
1.5
1.1
2.0
2.0
2.1
2.6
0.2
Cr
120.0
120.0
120.0
92.0
130.0
133.3
121.0
123.9
123.2
127.1
92.0
100.0
0.3 U
91.0
110.0
110.0
110.0
125.4
104.7
37.7
119.0
126.5
115.7
120.9
93.0
100.0
90.0
100.0
91.0
111.0
102.5
118.2
101.6
119.8
Cu
270.0
260.0
250.0
200.0
280.0
271.0
265.8
284.5
272.4
276.7
81.0
110.0
0.2 U
82.0
95.0
100.0
95.0
116.6
106.5
109.5
110.3
99.3
117.6
115.5
200.0
220.0
190.0
220.0
180.0
235.8
238.1
233.2
227.5
242.3
Fe
42000.0
42000.0
40000.0
32000.0
44000.0
57390.0
54730.0
52330.0
54660.0
51000.0
17000.0
20000.0
3.9 J
17000.0
19000.0
21000.0
19000.0
48420.0
47030.0
24450.0
48460.0
46700.0
47550.0
46950.0
17000.0
18000.0
16000.0
18000.0
15000.0
44980.0
44870.0
44630.0
44250.0
44690.0
Pb
7.2
7.2 J+
7.8
5.9
7.8
22.5
15.5
18.1
7.6
26.2
24.0
25.0
0.3 U
22.0
28.0
33.0
28.0
42.3
43.9
50.7
45.4
40.5
44.2
51.3
88.0
99.0
83.0
97.0
75.0
92.3
100.3
108.8
92.4
107.0
D-23
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
38
38
38
38
38
38
38
38
38
38
39
39
39
39
39
39
39
39
39
39
39
39
39
39
40
40
40
40
40
40
40
40
40
40
Sample ID
LV-SE-ll-XX
LV-SE-29-XX
LV-SE-44-XX
LV-SE-46-XX
LV-SE-52-XX
LV-SE-11-OI
LV-SE-29-OI
LV-SE-44-OI
LV-SE-46-OI
LV-SE-52-OI
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-OI
RF-SE- 12-01
RF-SE-23-OI
RF-SE-36-OI
RF-SE-42-OI
RF-SE-45-OI
RF-SE-53-OI
RF-SE-03-XX
RF-SE-28-XX
RF-SE-38-XX
RF-SE-49-XX
RF-SE-55-XX
RF-SE-03-OI
RF-SE-28-OI
RF-SE-38-OI
RF-SE-49-OI
RF-SE-55-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
2.8
1.5 J-
1.5
1.4
21.0
1.4
3.0
0.6
0.1 U
0.1 U
2.4
0.1 U
0.1 U
0.1 U
0.1 U
1.6
8.8
0.0
0.5
0.6
0.4
0.4
0.4
1.9
2.3
0.3
11.5
Ni
870.0
860.0
830.0
660.0
910.0
889.8
852.1
823.3
856.5
835.9
180.0
210.0
2.0 U
180.0
210.0
220.0
210.0
185.6
172.5
175.4
195.0
176.6
181.4
176.6
150.0
160.0
140.0
170.0
140.0
147.0
129.6
135.5
135.7
134.2
Se
1.3 U
1.2 U
1.4 U
0.9 U
1.4 U
2.4
0.5
2.5
1.4
0.9
1.3 U
1.2 U
0.3 U
1.0 U
1.3 U
1.3 U
1.3 U
1.3
2.9
2.3
1.5
3.1
6.2
0.4
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
2.9
1.0
2.0
2.4
2.2
Ag
1.4 U
1.4 U
1.4 U
0.9 U
1.4 U
0.6
1.3 U
1.2 U
0.4
1.2 U
1.3 U
1.3 U
1.3 U
0.9
0.8
2.5
1.7
0.5
0.7
0.7
1.2 U
1.2 U
1.2 U
1.2 U
1.2 U
1.8
0.5
1.8
3.0
0.0
V
35.0
35.0
34.0
27.0
38.0
63.6
75.5
63.4
46.6
53.0
34.0
38.0
2.5 U
34.0
40.0
43.0
40.0
59.1
66.4
47.8
58.8
66.5
82.8
54.7
40.0
44.0
39.0
43.0
35.0
69.9
72.7
85.7
55.4
44.0
Zn
200.0
200.0
190.0
150.0
210.0
238.2
240.0
226.9
224.6
215.1
130.0
140.0
0.6 U
120.0
140.0
150.0
140.0
172.4
153.8
150.9
161.4
159.5
172.7
179.7
300.0
320.0
300.0
330.0
280.0
343.9
344.4
357.9
375.3
335.7
D-24
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
41
41
41
41
41
41
41
41
41
41
42
42
42
42
42
42
42
42
42
42
43
43
43
43
43
43
43
43
43
43
44
44
44
44
44
44
44
44
44
44
Sample ID
RF-SE-06-XX
RF-SE-13-XX
RF-SE-27-XX
RF-SE-31-XX
RF-SE-58-XX
RF-SE-06-OI
RF-SE- 13-01
RF-SE-27-OI
RF-SE-31-OI
RF-SE-58-OI
RF-SE-02-XX
RF-SE-22-XX
RF-SE-25-XX
RF-SE-30-XX
RF-SE-57-XX
RF-SE-02-OI
RF-SE-22-OI
RF-SE-25-OI
RF-SE-30-OI
RF-SE-57-OI
RF-SE-15-XX
RF-SE-24-XX
RF-SE-32-XX
RF-SE-43-XX
RF-SE-59-XX
RF-SE-15-OI
RF-SE-24-OI
RF-SE-32-OI
RF-SE-43-OI
RF-SE-59-OI
RF-SE-05-XX
RF-SE-26-XX
RF-SE-39-XX
RF-SE-44-XX
RF-SE-56-XX
RF-SE-05-OI
RF-SE-26-OI
RF-SE-39-OI
RF-SE-44-OI
RF-SE-56-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
3.9
4.2
4.1
4.3
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
4.6
8.4
7.6
4.2
8.2
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
1.3 UJ
9.3
6.7
10.8
3.4
10.4
4.1 J+
2.2 J+
2.9 J+
2.7 J+
3.5 J+
8.8
6.1
7.0
4.7
11.0
As
70.0
76.0
64.0
39.0
71.0
100.9
111.3
122.4
110.8
115.4
110.0
99.0
88.0
89.0
89.0
129.5
150.3
152.8
166.1
131.4
120.0
130.0 J+
120.0
130.0
140.0
209.8
192.6
197.3
192.1
182.2
160.0
140.0
160.0
140.0
180.0
216.1
220.8
235.8
216.8
240.4
Cd
3.6
3.7
3.1
1.8
3.6
2.7
4.1
3.8
1.9
2.3
5.4
4.7
4.0
4.3
4.5
3.7
2.2
3.5
4.1
5.3
6.2
6.5 J+
5.1
5.7
5.9
6.4
7.7
6.0
7.5
6.7
9.1
8.4
9.3
8.2
9.6
7.3
6.4
7.3
9.2
9.8
Cr
90.0
92.0
78.0
63.0
89.0
95.8
97.2
92.0
94.0
102.1
93.0
84.0
78.0
78.0
79.0
97.2
50.5
89.3
88.0
86.5
72.0
74.0 J+
64.0
68.0
73.0
116.6
78.6
90.1
84.4
96.5
69.0
64.0
73.0
64.0
75.0
87.4
83.4
79.3
96.1
89.3
Cu
490.0
530.0
440.0
250.0
500.0
542.9
537.3
540.1
521.5
537.1
740.0
670.0
580.0
610.0
610.0
705.1
717.7
703.3
713.4
720.1
820.0
860.0 J+
770.0
840.0
890.0
983.2
965.8
932.8
960.4
947.4
1000.0
990.0
1100.0
970.0
1200.0
1159.9
1136.0
1155.4
1179.8
1168.7
Fe
20000.0
21000.0
18000.0
12000.0
21000.0
46580.0
46500.0
46340.0
45460.0
46260.0
24000.0
22000.0
19000.0
21000.0
21000.0
48620.0
31760.0
48040.0
46570.0
48400.0
23000.0
24000.0 J+
20000.0
22000.0
23000.0
49510.0
51360.0
49800.0
50410.0
50550.0
26000.0
23000.0
26000.0
24000.0
27000.0
51340.0
51710.0
52140.0
52130.0
53460.0
Pb
230.0
230.0
200.0
120.0
230.0
243.5
237.4
226.6
217.1
242.9
330.0
300.0
270.0
290.0
300.0
314.7
312.1
289.2
296.4
313.8
390.0
410.0 J+
330.0
350.0
380.0
418.7
413.2
392.0
397.7
432.7
450.0
440.0
490.0
420.0
490.0
467.5
445.0
448.9
433.9
439.5
D-25
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
41
41
41
41
41
41
41
41
41
41
42
42
42
42
42
42
42
42
42
42
43
43
43
43
43
43
43
43
43
43
44
44
44
44
44
44
44
44
44
44
Sample ID
RF-SE-06-XX
RF-SE-13-XX
RF-SE-27-XX
RF-SE-31-XX
RF-SE-58-XX
RF-SE-06-OI
RF-SE- 13-01
RF-SE-27-OI
RF-SE-31-OI
RF-SE-58-OI
RF-SE-02-XX
RF-SE-22-XX
RF-SE-25-XX
RF-SE-30-XX
RF-SE-57-XX
RF-SE-02-OI
RF-SE-22-OI
RF-SE-25-OI
RF-SE-30-OI
RF-SE-57-OI
RF-SE-15-XX
RF-SE-24-XX
RF-SE-32-XX
RF-SE-43-XX
RF-SE-59-XX
RF-SE-15-OI
RF-SE-24-OI
RF-SE-32-OI
RF-SE-43-OI
RF-SE-59-OI
RF-SE-05-XX
RF-SE-26-XX
RF-SE-39-XX
RF-SE-44-XX
RF-SE-56-XX
RF-SE-05-OI
RF-SE-26-OI
RF-SE-39-OI
RF-SE-44-OI
RF-SE-56-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
l.l
1.2
1.2
1.1
1.2
1.6
1.7
1.5
1.5
1.5
1.6
1.7
7.6
2.6
2.3
2.8
2.7
0.1 U
0.6
17.8
2.3
2.6
2.5
2.2
2.3
2.2
13.4
11.8
11.2
Ni
150.0
160.0
130.0
86.0
150.0
151.8
136.4
135.1
136.8
130.0
180.0
160.0
140.0
150.0
150.0
142.6
145.2
148.2
138.9
144.8
160.0
170.0 J+
140.0
150.0
160.0
154.3
146.9
158.3
161.6
161.3
150.0
140.0
150.0
140.0
160.0
142.3
135.2
131.5
140.6
139.3
Se
1.3 U
1.3 U
1.3 U
1.3 U
1.3 U
5.4
1.7
1.9
2.0
2.1
1.3 U
1.3 U
1.5
1.3 U
2.0
1.9
1.9
1.6
4.7
4.5
1.4
1.3 U
1.3 U
1.3 U
1.3 U
5.9
2.5
1.9
2.6
2.5
3.1
2.8
2.6
2.4
1.8
3.8
3.4
0.6
2.4
3.0
Ag
1.3 U
1.3
1.3 U
1.3 U
1.3 U
3.4
2.4
4.7
3.1
3.6
2.7
2.3
1.7
1.9
2.2
4.4
5.2
4.6
6.0
3.7
3.6
3.8 J+
4.2
4.0
4.5
5.3
5.9
6.4
6.2
5.9
7.4 J-
7.2 J-
8.2 J-
7.2 J-
8.3 J-
8.1
7.2
9.1
5.4
5.4
V
44.0
45.0
39.0
28.0
46.0
70.5
75.8
71.1
70.0
63.6
50.0
44.0
40.0
44.0
44.0
66.3
48.6
69.3
77.1
74.6
45.0
46.0 J+
36.0
40.0
42.0
73.6
97.5
68.3
72.6
64.9
48.0
42.0
49.0
44.0
51.0
67.7
85.8
85.1
85.1
89.1
Zn
740.0
790.0
670.0
420.0
770.0
792.5
791.5
785.2
761.6
790.2
1100.0
990.0
890.0
960.0
1000.0
1006.3
1005.6
1010.9
1045.4
1034.5
1300.0
1400.0 J-
1100.0
1200.0
1300.0
1361.1
1347.2
1365.8
1318.2
1384.3
1800.0
1700.0
1900.0
1600.0
1900.0
1716.7
1809.6
1768.3
1724.8
1796.4
D-26
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
45
45
45
45
45
45
45
45
45
45
46
46
46
46
46
46
47
47
47
47
47
47
48
48
48
48
48
48
49
49
49
49
49
49
Sample ID
RF-SE-04-XX
RF-SE-14-XX
RF-SE-19-XX
RF-SE-34-XX
RF-SE-52-XX
RF-SE-04-OI
RF-SE- 14-01
RF-SE- 19-01
RF-SE-34-OI
RF-SE-52-OI
BN-SO-11-XX
BN-SO-14-XX
BN-SO-23-XX
BN-SO- 11-01
BN-SO-14-OI
BN-SO-23-OI
BN-SO-09-XX
BN-SO-12-XX
BN-SO-24-XX
BN-SO-09-OI
BN-SO-12-OI
BN-SO-24-OI
SB-SO-09-XX
SB-SO-20-XX
SB-SO-31-XX
SB-SO-09-OI
SB-SO-20-OI
SB-SO-31-OI
SB-SO-29-XX
SB-SO-36-XX
SB-SO-56-XX
SB-SO-29-OI
SB-SO-36-OI
SB-SO-56-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
3.2 J+
4.4 J+
3.7 J+
2.9 J+
3.4 J+
9.2
9.0
9.0
12.3
13.7
4.0 J-
3.5 J-
1.2 UJ
6.5
3.2
2.7
750.0 J-
750.0 J-
810.0 J-
1713.5
1534.4
1643.9
1.3 UJ
1.3 UJ
1.3 UJ
8.0
9.5
5.3
1.2 U
1.2 U
1.2 U
5.3
3.4
7.8
As
230.0
260.0
250.0
210.0
220.0
342.9
346.8
338.8
338.5
339.0
2900.0
2800.0
2800.0
3235.5
3231.5
3221.1
97.0
89.0
97.0
733.8
957.9
669.7
8.9
11.0
8.0 J-
19.7
9.6
11.2
9.4
7.8
9.5
18.3
9.7
Cd
12.0
12.0
13.0
10.0
11.0
10.3
10.4
9.8
9.7
12.2
720.0
690.0
700.0
508.5
532.5
537.7
2700.0
2600.0
2900.0
1618.2
1548.2
1538.9
0.5 U
0.5 U
0.5 U
1.0
0.1
0.5 U
0.5 U
0.5 U
0.1
1.4
0.2
Cr
42.0
47.0
48.0
39.0
42.0
73.4
51.4
69.7
60.2
50.9
820.0
800.0
800.0
430.3
439.9
415.1
2900.0
2800.0
3000.0
1567.5
1620.3
1617.5
130.0
170.0
140.0
219.8
240.3
210.7
140.0
120.0
150.0
239.1
228.1
225.7
Cu
1500.0
1700.0
1700.0
1400.0
1500.0
1608.9
1587.0
1620.4
1650.1
1640.8
120.0
120.0
120.0
127.7
157.0
137.4
100.0
96.0
100.0
107.1
159.7
112.8
120.0
150.0
130.0
130.6
110.0
108.4
130.0
100.0
140.0
151.7
160.7
141.3
Fe
27000.0
30000.0
30000.0
24000.0
26000.0
54830.0
54920.0
55290.0
55250.0
55440.0
23000.0
22000.0
23000.0
38940.0
39550.0
38650.0
22000.0
21000.0
23000.0
42410.0
40760.0
42800.0
35000.0
44000.0
38000.0
70440.0
72670.0
72080.0
41000.0
33000.0
42000.0
72470.0
73250.0
71990.0
Pb
730.0
800.0
800.0
660.0
720.0
677.1
688.4
679.8
709.1
694.5
56.0
51.0
52.0
63.3
79.5
61.0
4700.0
4500.0
4900.0
4126.8
4642.8
4074.6
19.0
24.0
21.0
9.3
14.4
19.2
19.0
15.0
20.0
26.9
24.9
33.8
D-27
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
45
45
45
45
45
45
45
45
45
45
46
46
46
46
46
46
47
47
47
47
47
47
48
48
48
48
48
48
49
49
49
49
49
49
Sample ID
RF-SE-04-XX
RF-SE-14-XX
RF-SE-19-XX
RF-SE-34-XX
RF-SE-52-XX
RF-SE-04-OI
RF-SE- 14-01
RF-SE- 19-01
RF-SE-34-OI
RF-SE-52-OI
BN-SO-11-XX
BN-SO-14-XX
BN-SO-23-XX
BN-SO- 11-01
BN-SO-14-OI
BN-SO-23-OI
BN-SO-09-XX
BN-SO-12-XX
BN-SO-24-XX
BN-SO-09-OI
BN-SO-12-OI
BN-SO-24-OI
SB-SO-09-XX
SB-SO-20-XX
SB-SO-31-XX
SB-SO-09-OI
SB-SO-20-OI
SB-SO-31-OI
SB-SO-29-XX
SB-SO-36-XX
SB-SO-56-XX
SB-SO-29-OI
SB-SO-36-OI
SB-SO-56-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
4.2
4.7
3.9
4.5
4.1
0.2
7.8
15.0
8.7
8.0
24.0 J-
26.0
31.0
26.5
21.3
33.2
0.4
0.3
0.4
30.0
10.0
32.0
43.0
33.8
33.4
7.9 J
36.0
9.0
51.8
47.2
29.2
Ni
130.0
140.0
140.0
120.0
130.0
148.8
138.9
138.1
126.9
144.0
2900.0
2800.0
2800.0
2888.6
2895.5
2819.1
1500.0
1400.0
1600.0
1459.2
1878.4
1429.0
2900.0
3700.0
3200.0 J-
3248.3
3202.3
3169.4
200.0
160.0
210.0
215.9
209.6
208.2
Se
2.8
3.0
4.1
1.9
2.0
3.3
2.5
0.8
2.2
3.9
140.0
130.0
130.0
96.0
92.9
100.5
290.0
290.0
300.0
209.6
257.7
207.0
26.0
30.0
28.0 J-
19.7
20.2
20.2
160.0
130.0
160.0
104.4
98.3
104.2
Ag
12.0 J-
13.0 J-
14.0 J-
10.0 J-
11.0 J-
10.7
8.4
10.1
8.8
8.6
140.0 J-
140.0 J-
130.0 J-
87.9
90.8
96.5
100.0 J-
210.0 J-
140.0 J-
171.7
166.0
165.5
160.0 J-
140.0 J-
160.0 J-
308.7
293.6
304.6
1.2 UJ
1.2 UJ
1.2 UJ
0.6
0.0
V
46.0
51.0
52.0
42.0
47.0
103.5
74.8
72.0
65.5
79.9
150.0
150.0
150.0
121.0
119.5
126.3
340.0
310.0
350.0
267.3
243.8
268.1
120.0
160.0
140.0
216.3
223.2
206.2
400.0
320.0
410.0
473.7
445.6
428.4
Zn
2400.0
2600.0
2700.0
2200.0
2300.0
2329.1
2343.8
2311.1
2389.6
2322.1
3900.0
3800.0
3800.0
4647.0
4559.5
4642.6
81.0
74.0
81.0
93.2
167.9
126.9
3600.0
4500.0
3900.0 J-
4268.1
4300.9
4260.1
3900.0
3200.0
4100.0
4359.3
4279.2
4217.8
D-28
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
50
50
50
50
50
50
51
51
51
51
51
51
52
52
52
52
52
52
53
53
53
53
53
53
54
54
54
54
54
54
55
55
55
55
55
55
Sample ID
SB-SO-04-XX
SB-SO-34-XX
SB-SO-49-XX
SB-SO-04-OI
SB-SO-34-OI
SB-SO-49-OI
WS-SO-07-XX
WS-SO-11-XX
WS-SO-25-XX
WS-SO-07-OI
WS-SO-11-OI
WS-SO-25-OI
WS-SO-10-XX
WS-SO-20-XX
WS-SO-23-XX
WS-SO-10-OI
WS-SO-20-OI
WS-SO-23-OI
AS-SO-03-XX
AS-SO-05-XX
AS-SO-08-XX
AS-SO-03-OI
AS-SO-05-OI
AS-SO-08-OI
LV-SO-03-XX
LV-SO-40-XX
LV-SO-49-XX
LV-SO-03-OI
LV-SO-40-OI
LV-SO-49-OI
LV-SO-04-XX
LV-SO-34-XX
LV-SO-37-XX
LV-SO-04-OI
LV-SO-34-OI
LV-SO-37-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
940.0
980.0
700.0
2840.8
2769.4
2771.2
3.8
1.2 U
1.2 U
4.5
2.1
2.8
1.3 U
1.3 U
1.3 U
5.0
1.4
1.7
1.2 U
1.2 U
1.2 U
4.8
7.6
6.1
1.6
2.7
7.4
19.7
22.5
12.6
860.0
870.0 J-
590.0
2249.8
2200.1
2156.3
As
13.0
12.0
12.0
0.7
9.5
53.0
46.0
59.0
324.4
304.9
315.1
83.0
100.0
110.0
441.3
425.9
430.3
14.0
9.3
10.0
28.3
40.0
43.0
42.0
42.0
43.0
69.2
82.6
91.7
120.0
110.0 J-
84.0
700.9
744.2
768.8
Cd
2800.0
2500.0
2500.0
2609.2
2560.6
2577.6
1.9
1.4
3.1
4.4
1.9
0.2
1.8
1.9
2.1
3.1
1.9
2.2
1300.0
900.0
930.0
895.3
869.5
882.2
590.0
580.0
600.0
550.3
560.5
533.1
2400.0
2300.0 J-
1700.0
2254.8
2242.9
2184.4
Cr
2800.0
2500.0
2400.0
2687.1
2666.4
2645.2
640.0
570.0
730.0
704.5
690.1
401.2
67.0
81.0
82.0
113.0
98.8
112.9
33.0
23.0
24.0
52.7
50.3
60.4
600.0
590.0
610.0
637.4
674.5
677.3
2300.0
2200.0 J-
1600.0
2169.5
2390.5
2515.7
Cu
100.0
91.0
89.0
104.9
73.3
83.0
4400.0
3900.0
4900.0
4304.9
4328.2
4460.6
76.0
90.0
96.0
133.7
125.3
123.9
6200.0
4500.0
4600.0
4414.7
4292.8
4184.1
130.0
130.0
130.0
146.4
144.5
138.9
98.0
87.0
66.0
117.1
123.8
151.4
Fe
38000.0
34000.0
33000.0
66020.0
64740.0
68740.0
25000.0
19000.0
24000.0
55080.0
55110.0
41300.0
19000.0
23000.0
23000.0
55940.0
55170.0
55130.0
15000.0
11000.0
11000.0
34450.0
33500.0
33910.0
24000.0
24000.0
25000.0
68020.0
67730.0
69260.0
22000.0
20000.0 J-
16000.0
66090.0
66320.0
67770.0
Pb
21.0
18.0
18.0
26.7
32.3
24.9
1700.0
1500.0
1900.0
1800.8
1848.5
1906.3
1900.0
2300.0
2500.0
2286.2
2397.2
2312.8
160.0
110.0
120.0
181.0
154.4
154.2
94.0
92.0
98.0
134.0
103.3
117.1
4000.0
3700.0 J-
2800.0
4103.5
3982.0
4052.7
D-29
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
50
50
50
50
50
50
51
51
51
51
51
51
52
52
52
52
52
52
53
53
53
53
53
53
54
54
54
54
54
54
55
55
55
55
55
55
Sample ID
SB-SO-04-XX
SB-SO-34-XX
SB-SO-49-XX
SB-SO-04-OI
SB-SO-34-OI
SB-SO-49-OI
WS-SO-07-XX
WS-SO-11-XX
WS-SO-25-XX
WS-SO-07-OI
WS-SO-11-OI
WS-SO-25-OI
WS-SO-10-XX
WS-SO-20-XX
WS-SO-23-XX
WS-SO-10-OI
WS-SO-20-OI
WS-SO-23-OI
AS-SO-03-XX
AS-SO-05-XX
AS-SO-08-XX
AS-SO-03-OI
AS-SO-05-OI
AS-SO-08-OI
LV-SO-03-XX
LV-SO-40-XX
LV-SO-49-XX
LV-SO-03-OI
LV-SO-40-OI
LV-SO-49-OI
LV-SO-04-XX
LV-SO-34-XX
LV-SO-37-XX
LV-SO-04-OI
LV-SO-34-OI
LV-SO-37-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
40.0
36.0
36.0
50.1
51.4
42.7
0.3
0.3
0.3
0.1 U
0.1 U
0.1 U
3.7 J-
2.5 J-
2.5 J-
8.5
48.0 J-
46.0 J-
52.0 J-
56.0
40.9
52.6
130.0 J-
130.0 J-
130.0 J-
120.2
136.5
129.7
Ni
3300.0
3000.0
2800.0
3088.3
2983.5
3000.1
260.0
240.0
300.0
332.2
329.5
307.0
290.0
350.0
380.0
404.4
411.0
395.9
520.0
370.0
380.0
472.8
429.9
426.5
2000.0
1900.0
2000.0
2199.3
2248.6
2235.0
2000.0
1900.0 J-
1400.0
2268.3
2306.9
2447.0
Se
390.0
360.0
330.0
247.4
251.0
254.2
1.2 U
1.2 U
1.2 U
1.4
280.0
340.0
360.0
243.4
246.4
243.0
200.0
140.0
140.0
116.3
113.9
116.2
120.0
120.0
120.0
90.9
91.9
88.1
230.0
220.0 J-
170.0
187.4
180.2
189.9
Ag
1.3 UJ
1.3 UJ
1.2 UJ
0.8
400.0 J-
340.0 J-
450.0 J-
363.8
361.4
306.9
1.3 UJ
1.3 UJ
1.3 UJ
480.0 J-
330.0 J-
280.0 J-
311.7
302.9
301.4
210.0 J-
210.0 J-
220.0 J-
177.7
178.8
172.0
1.2 UJ
1.2 UJ
1.2 U
0.4
V
58.0
52.0
52.0
110.6
79.1
93.4
48.0
43.0
54.0
84.6
103.4
52.2
260.0
320.0
330.0
449.2
447.8
417.3
29.0
23.0
23.0
45.6
53.0
39.4
120.0
120.0
120.0
171.0
160.6
131.3
260.0
230.0 J-
180.0
279.3
298.3
335.3
Zn
86.0
77.0
72.0
99.4
88.1
81.1
180.0
160.0
200.0
199.6
194.7
193.1
1900.0
2300.0
2500.0
3045.9
3116.2
3017.2
350.0
250.0
260.0
282.4
256.9
290.7
3700.0
3700.0
3800.0
4743.4
4833.5
4819.4
53.0
48.0 J-
37.0
91.2
95.4
98.7
D-30
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
56
56
56
56
56
56
57
57
57
57
57
57
58
58
58
58
58
58
59
59
59
59
59
59
60
60
60
60
60
60
61
61
61
61
61
61
Sample ID
CN-SO-03-XX
CN-SO-06-XX
CN-SO-07-XX
CN-SO-03-OI
CN-SO-06-OI
CN-SO-07-OI
CN-SO-02-XX
CN-SO-05-XX
CN-SO-09-XX
CN-SO-02-OI
CN-SO-05-OI
CN-SO-09-OI
LV-SE-06-XX
LV-SE-13-XX
LV-SE-41-XX
LV-SE-06-OI
LV-SE-13-OI
LV-SE-41-OI
LV-SE-05-XX
LV-SE-20-XX
LV-SE-43-XX
LV-SE-05-OI
LV-SE-20-OI
LV-SE-43-OI
LV-SE-15-XX
LV-SE-17-XX
LV-SE-51-XX
LV-SE- 15-01
LV-SE-17-OI
LV-SE-51-OI
TL-SE-05-XX
TL-SE-09-XX
TL-SE-13-XX
TL-SE-05-OI
TL-SE-09-OI
TL-SE-13-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
22.0
20.0
20.0
64.7
66.1
64.9
230.0
130.0
120.0
353.5
350.6
335.6
30.0
31.0
30.0
157.6
141.8
141.0
92.0
140.0 J+
160.0 J+
504.8
499.8
487.9
290.0 J+
280.0 J+
210.0 J+
776.5
788.3
735.2
100.0 J+
100.0 J+
95.0 J+
662.3
648.5
646.3
As
87.0
91.0
90.0
152.0
146.4
146.7
19.0
6.2
6.0
16.2
19.1
27.3
23.0
24.0
21.0
271.7
255.6
274.5
20.0
31.0
24.0
16.9
7.6
34.8
32.0
31.0
26.0
45.0
39.5
47.2
34.0
33.0
31.0
157.8
165.3
159.9
Cd
63.0
64.0
63.0
57.1
51.4
52.0
820.0
630.0
580.0
418.8
448.9
428.0
160.0
160.0
150.0
177.3
165.5
164.0
440.0
680.0
550.0
550.0
553.9
543.1
1300.0
1300.0
1100.0
1086.8
1098.1
1048.8
0.3 J
0.2 J
0.5 J
Cr
17.0
18.0
19.0
46.0
42.4
48.0
290.0
26.0
21.0
33.7
27.7
30.9
540.0
540.0
480.0
538.3
522.8
572.6
840.0
1400.0
1100.0
958.8
1040.9
1036.6
83.0
79.0
72.0
84.7
88.6
91.6
40.0
39.0
36.0 J+
62.7
64.3
56.8
Cu
72.0
74.0
72.0
105.1
103.9
106.7
140.0
160.0
140.0
188.0
171.3
189.0
30.0
30.0
26.0
42.1
49.5
43.2
39.0
60.0
47.0
55.8
69.7
61.2
2300.0
2200.0
2000.0
1980.8
2006.2
2069.5
4900.0
4800.0
4400.0 J+
3874.4
3894.7
3879.4
Fe
15000.0
16000.0
17000.0
40660.0
40690.0
41270.0
22000.0
23000.0
19000.0
40540.0
39970.0
39340.0
18000.0
18000.0
16000.0
56000.0
56230.0
54990.0
16000.0
22000.0
19000.0
55690.0
55900.0
55540.0
22000.0
21000.0
19000.0
54390.0
55080.0
53940.0
24000.0
23000.0
22000.0 J+
60550.0
61530.0
61090.0
Pb
130.0
130.0
130.0
156.7
177.5
169.2
490.0
25.0
23.0
57.4
37.7
34.0
1600.0
1600.0
1500.0
1843.0
1830.6
1834.6
14.0
21.0
17.0
37.7
47.5
32.3
18.0
17.0 J-
15.0
41.0
38.8
24.9
1200.0
1200.0
1100.0 J+
1116.0
1142.5
1099.4
D-31
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
56
56
56
56
56
56
57
57
57
57
57
57
58
58
58
58
58
58
59
59
59
59
59
59
60
60
60
60
60
60
61
61
61
61
61
61
Sample ID
CN-SO-03-XX
CN-SO-06-XX
CN-SO-07-XX
CN-SO-03-OI
CN-SO-06-OI
CN-SO-07-OI
CN-SO-02-XX
CN-SO-05-XX
CN-SO-09-XX
CN-SO-02-OI
CN-SO-05-OI
CN-SO-09-OI
LV-SE-06-XX
LV-SE-13-XX
LV-SE-41-XX
LV-SE-06-OI
LV-SE-13-OI
LV-SE-41-OI
LV-SE-05-XX
LV-SE-20-XX
LV-SE-43-XX
LV-SE-05-OI
LV-SE-20-OI
LV-SE-43-OI
LV-SE-15-XX
LV-SE-17-XX
LV-SE-51-XX
LV-SE- 15-01
LV-SE-17-OI
LV-SE-51-OI
TL-SE-05-XX
TL-SE-09-XX
TL-SE-13-XX
TL-SE-05-OI
TL-SE-09-OI
TL-SE-13-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
34.0 J-
40.0 J-
36.0 J-
45.9
51.6
32.5
270.0 J-
280.0 J-
260.0 J-
293.9
262.2
276.3
610.0 J-
640.0 J-
610.0 J-
617.5
604.8
621.8
2.6 J-
2.8
2.8
2.0
6.5
500.0
490.0
470.0
479.6
483.0
472.5
980.0
820.0
990.0
726.2
750.1
736.2
Ni
74.0
76.0
75.0
113.6
107.3
108.8
530.0
360.0
330.0
369.4
365.2
363.5
360.0
360.0
320.0
432.1
411.6
420.5
400.0
660.0
530.0
511.6
511.7
535.2
230.0
220.0
200.0
210.4
204.7
213.6
54.0
53.0
49.0
79.5
61.9
71.7
Se
36.0
38.0
37.0
30.8
32.0
31.1
190.0
190.0
170.0
123.2
120.3
115.5
160.0
160.0
150.0
130.9
125.0
122.0
340.0
500.0
420.0
293.6
283.2
286.8
92.0
89.0
76.0
54.5
57.6
52.0
130.0
130.0
120.0
82.3
84.1
84.0
Ag
90.0
94.0
91.0
68.7
68.0
68.8
68.0
78.0
74.0
45.9
49.2
46.4
110.0
110.0
99.0
104.1
100.4
97.9
49.0
75.0 J-
60.0 J-
57.3
55.9
54.3
300.0 J-
200.0 J-
250.0 J-
353.3
364.3
345.2
180.0 J-
170.0 J-
160.0 J
126.4
125.5
122.3
V
30.0
32.0
33.0
51.8
49.6
58.1
160.0
160.0
140.0
144.3
145.3
153.7
480.0
470.0
420.0
601.7
569.9
655.9
340.0
530.0
430.0
489.3
488.6
543.2
180.0
170.0
160.0
177.9
180.9
195.6
66.0
63.0
59.0 J+
59.4
68.2
39.1
Zn
58.0
59.0
58.0
100.1
94.3
88.9
1900.0
2200.0
2100.0
2652.8
2610.1
2518.4
52.0
51.0
46.0
89.0
88.5
71.6
1800.0
2800.0
2300.0
2531.5
2580.9
2619.8
62.0
58.0
54.0
65.3
83.0
76.5
100.0
100.0
96.0
126.5
99.1
104.4
D-32
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
62
62
62
62
62
62
63
63
63
63
63
63
64
64
64
64
64
64
65
65
65
65
65
65
65
65
65
65
65
65
65
65
Sample ID
TL-SE-06-XX
TL-SE-17-XX
TL-SE-28-XX
TL-SE-06-OI
TL-SE-17-OI
TL-SE-28-OI
TL-SE-07-XX
TL-SE-21-XX
TL-SE-30-XX
TL-SE-07-OI
TL-SE-21-OI
TL-SE-30-OI
TL-SE-02-XX
TL-SE-08-XX
TL-SE-16-XX
TL-SE-02-OI
TL-SE-08-OI
TL-SE-16-OI
RF-SE-01-XX
RF-SE-09-XX
RF-SE-11-XX
RF-SE-17-XX
RF-SE-29-XX
RF-SE-37-XX
RF-SE-50-XX
RF-SE-01-OI
RF-SE-09-OI
RF-SE-11-OI
RF-SE-17-OI
RF-SE-29-OI
RF-SE-37-OI
RF-SE-50-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
1.2 U
1.2 U
1.2 U
1.0
30.0
33.0
31.0
219.1
232.8
219.6
77.0
66.0
73.0
603.1
605.0
589.5
12.0
10.0
11.0
11.0
13.0
11.0
8.9
41.6
43.7
95.4
74.1
38.7
39.7
43.7
As
86.0
85.0
89.0
318.7
289.1
338.6
11.0
13.0
11.0
14.5
25.5
48.2
15.0
10.0
15.0
38.8
14.9
29.1
230.0
260.0
240.0
250.0
280.0
260.0
230.0
308.9
316.6
331.9
290.1
308.2
300.7
306.7
Cd
350.0
340.0
360.0
332.3
341.1
323.9
48.0
51.0
47.0
40.9
42.3
39.8
160.0
180.0
170.0
139.3
137.8
141.5
40.0
45.0
43.0
43.0
49.0
45.0
40.0
45.0
47.2
46.6
45.8
47.0
47.4
48.2
Cr
34.0
33.0
34.0
62.0
65.2
69.4
66.0
73.0
64.0
104.2
87.9
82.1
64.0
74.0
69.0
108.0
101.4
77.8
280.0
310.0
300.0
300.0
330.0
320.0
280.0
327.7
318.3
342.3
343.5
325.4
309.6
336.2
Cu
2000.0
2100.0
2100.0
2192.7
2221.5
2330.4
2200.0
2300.0
2200.0
2415.1
2421.4
2391.5
3100.0
3200.0
3100.0
3238.1
3247.2
3260.3
63.0
71.0
72.0
67.0
75.0
72.0
65.0
80.0
76.6
98.3
84.9
99.1
87.8
85.0
Fe
22000.0
21000.0
22000.0
59820.0
59180.0
77260.0
37000.0
44000.0
36000.0
113930.0
118970.0
110890.0
32000.0
45000.0
38000.0
120700.0
118120.0
123390.0
14000.0
16000.0
15000.0
15000.0
17000.0
16000.0
14000.0
41740.0
42800.0
73730.0
59910.0
42030.0
41500.0
41950.0
Pb
1700.0
1700.0
1700.0
1748.3
1747.3
1735.1
13.0
15.0
14.0
14.3
19.2
17.6
12.0
11.0
13.0
15.7
8.9
14.8
22.0
26.0
25.0
26.0
26.0
27.0
23.0
45.3
40.9
50.6
41.8
43.4
46.5
29.9
D-33
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
62
62
62
62
62
62
63
63
63
63
63
63
64
64
64
64
64
64
65
65
65
65
65
65
65
65
65
65
65
65
65
65
Sample ID
TL-SE-06-XX
TL-SE-17-XX
TL-SE-28-XX
TL-SE-06-OI
TL-SE-17-OI
TL-SE-28-OI
TL-SE-07-XX
TL-SE-21-XX
TL-SE-30-XX
TL-SE-07-OI
TL-SE-21-OI
TL-SE-30-OI
TL-SE-02-XX
TL-SE-08-XX
TL-SE-16-XX
TL-SE-02-OI
TL-SE-08-OI
TL-SE-16-OI
RF-SE-01-XX
RF-SE-09-XX
RF-SE-11-XX
RF-SE-17-XX
RF-SE-29-XX
RF-SE-37-XX
RF-SE-50-XX
RF-SE-01-OI
RF-SE-09-OI
RF-SE-11-OI
RF-SE-17-OI
RF-SE-29-OI
RF-SE-37-OI
RF-SE-50-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
2.2
2.6
2.8
10.9
4.2
2.4
40.0
120.0
100.0
39.2
28.1
34.2
400.0
350.0
420.0
122.2
132.1
127.3
47.0
45.0
52.0
20.0
20.0
22.0
19.0
31.2
23.1
16.4
4.8
24.5
34.5
33.9
Ni
44.0
43.0
44.0
74.3
69.5
57.4
94.0
100.0
93.0
137.5
136.8
132.2
99.0
100.0
100.0
149.0
143.2
127.0
200.0
220.0
210.0
210.0
240.0
220.0
200.0
232.9
228.1
237.8
224.2
223.6
208.9
219.8
Se
45.0
44.0
45.0
33.6
31.8
33.1
120.0
140.0
120.0
106.3
102.4
99.1
44.0
39.0
44.0
38.0
37.4
41.3
21.0
23.0
20.0
22.0
26.0
23.0
20.0
15.0
15.7
19.9
15.6
17.1
12.5
15.1
Ag
56.0
56.0
57.0
48.3
47.4
50.9
63.0
67.0
62.0
51.0
55.2
52.0
120.0
130.0
120.0
93.4
94.2
95.1
37.0
42.0
40.0
40.0
44.0
44.0
38.0
37.7
43.0
35.9
40.3
38.9
40.2
39.9
V
78.0
78.0
81.0
73.1
84.0
93.3
110.0
120.0
100.0
48.5
108.6
117.2
110.0
120.0
110.0
135.7
87.6
141.8
29.0
32.0
29.0
30.0
35.0
32.0
29.0
55.2
68.4
60.7
61.9
66.2
67.8
66.3
Zn
83.0
81.0
83.0
120.9
118.3
108.3
160.0
170.0
160.0
184.2
228.7
196.6
160.0
170.0
160.0
226.7
185.6
219.9
1700.0
1900.0
1800.0
1800.0
2100.0
1900.0
1700.0
2198.0
2216.3
2209.0
2148.0
2138.2
2154.9
2162.9
D-34
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
66
66
66
66
66
66
67
67
67
67
67
67
68
68
68
68
68
68
69
69
69
69
69
69
70
70
70
70
70
70
Sample ID
RF-SE-08-XX
RF-SE-10-XX
RF-SE-33-XX
RF-SE-08-OI
RF-SE- 10-01
RF-SE-33-OI
RF-SE- 16-XX
RF-SE-41-XX
RF-SE-48-XX
RF-SE- 16-01
RF-SE-41-OI
RF-SE-48-OI
RF-SE-18-XX
RF-SE-35-XX
RF-SE-54-XX
RF-SE-18-OI
RF-SE-35-OI
RF-SE-54-OI
RF-SE-20-XX
RF-SE-46-XX
RF-SE-51-XX
RF-SE-20-OI
RF-SE-46-OI
RF-SE-51-OI
RF-SE-21-XX
RF-SE-40-XX
RF-SE-47-XX
RF-SE-21-OI
RF-SE-40-OI
RF-SE-47-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Sb
14.0
12.0
13.0
60.4
62.9
63.3
85.0 J-
100.0
100.0
293.6
299.8
310.4
320.0
300.0
320.0
835.4
876.3
852.6
550.0
270.0
480.0
5606.5
1165.0
1132.4
1.3 U
1.3 U
1.3 U
0.2
7.8
8.3
As
460.0
400.0
440.0
613.8
621.5
610.1
72.0 J-
82.0
87.0
103.6
101.4
99.6
810.0
740.0
880.0
1000.1
1057.4
970.8
1300.0
590.0
1100.0
996.5
1259.3
1322.6
62.0
70.0
72.0
378.5
359.3
380.9
Cd
67.0
58.0
64.0
69.3
68.9
72.3
310.0 J-
360.0
380.0
343.8
342.5
354.5
770.0
700.0
840.0
723.5
761.2
721.2
540.0
240.0
450.0
287.3
476.1
467.9
1700.0
1900.0
1900.0
758.8
1781.6
1790.1
Cr
510.0
440.0
490.0
497.8
513.7
520.6
820.0 J-
950.0
1000.0
891.7
881.3
851.8
950.0
860.0
1000.0
873.6
912.1
895.9
94.0
44.0
77.0
96.0
90.2
106.0
76.0
85.0
90.0
138.0
96.1
93.3
Cu
1800.0
1500.0
1700.0
1977.6
2022.9
1939.8
73.0 J-
85.0
90.0
88.6
85.9
82.1
78.0
70.0
86.0
90.0
100.8
84.2
93.0
40.0
77.0
59.3
86.9
89.6
1000.0
1100.0
1200.0
1312.8
1244.5
1218.7
Fe
18000.0
16000.0
18000.0
45260.0
44750.0
44880.0
16000.0 J-
18000.0
19000.0
43130.0
43810.0
42480.0
16000.0
15000.0
18000.0
41660.0
42010.0
41150.0
20000.0
8900.0
17000.0
237540.0
43920.0
46080.0
16000.0
18000.0
19000.0
59140.0
45590.0
45670.0
Pb
580.0
510.0
570.0
574.6
594.1
566.4
24.0 J-
25.0
27.0
38.6
36.6
50.4
860.0
780.0
920.0
783.4
781.3
784.8
28.0
13.0
23.0
58.5
44.8
33.0
2100.0
2400.0
2400.0
2273.3
2258.6
2186.2
D-35
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Blend No.
66
66
66
66
66
66
67
67
67
67
67
67
68
68
68
68
68
68
69
69
69
69
69
69
70
70
70
70
70
70
Sample ID
RF-SE-08-XX
RF-SE-10-XX
RF-SE-33-XX
RF-SE-08-OI
RF-SE- 10-01
RF-SE-33-OI
RF-SE- 16-XX
RF-SE-41-XX
RF-SE-48-XX
RF-SE- 16-01
RF-SE-41-OI
RF-SE-48-OI
RF-SE-18-XX
RF-SE-35-XX
RF-SE-54-XX
RF-SE-18-OI
RF-SE-35-OI
RF-SE-54-OI
RF-SE-20-XX
RF-SE-46-XX
RF-SE-51-XX
RF-SE-20-OI
RF-SE-46-OI
RF-SE-51-OI
RF-SE-21-XX
RF-SE-40-XX
RF-SE-47-XX
RF-SE-21-OI
RF-SE-40-OI
RF-SE-47-OI
Source of Data
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Reference Laboratory
Reference Laboratory
Reference Laboratory
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Oxford Instrument Analytical ED 2000
Hg
29.0
27.0
28.0
30.9
35.9
31.9
260.0
230.0
250.0
299.8
295.6
310.4
600.0
650.0
670.0
795.7
838.8
797.1
0.5
0.5
0.5
2.2
320.0
280.0
320.0
395.1
397.8
378.3
Ni
250.0
220.0
240.0
252.2
252.9
268.1
1700.0 J-
1900.0
2000.0
1800.8
1804.6
1739.7
390.0
350.0
420.0
386.0
368.5
379.3
1400.0
650.0
1200.0
1191.9
1245.9
1281.9
220.0
250.0
250.0
241.7
221.4
223.2
Se
42.0
39.0
41.0
29.5
31.4
28.6
1.2 U
1.2 U
2.2
2.5
3.6
4.4
140.0
140.0
160.0
104.2
106.8
104.8
380.0
170.0
320.0
249.3
239.6
241.3
440.0
480.0
510.0
351.8
349.9
340.6
Ag
0.4 U
0.3 U
0.3 U
0.1
3.8
130.0 J-
140.0
150.0
130.5
130.5
134.5
140.0
150.0
180.0
176.2
184.0
174.2
59.0
26.0
48.0
28.6
45.1
44.6
120.0
100.0
120.0
114.4
270.5
271.9
V
120.0
100.0
120.0
177.0
166.7
169.8
32.0 J-
39.0
40.0
67.8
56.3
65.5
390.0
340.0
410.0
459.1
485.1
420.9
36.0
16.0
30.0
60.1
64.4
57.1
130.0
150.0
150.0
244.6
189.9
182.4
Zn
120.0
110.0
130.0
140.5
151.2
121.4
760.0 J-
830.0
880.0
910.7
889.6
896.1
120.0
110.0
120.0
132.9
167.2
139.4
1400.0
650.0
1200.0
1407.3
1377.9
1407.1
100.0
120.0
120.0
157.8
141.3
120.4
D-36
-------
Appendix D. Analytical Data Summary, Oxford ED2000 and Reference Laboratory (Continued)
Notes:
All concentrations reported in milligrams per kilogram (mg/kg), or parts per million (ppm).
J Estimated concentration
J+ Concentration is considered estimated and biased high
J- Concentration is considered estimated and biased low
U Analyte is not detected; the associated concentration value is the sample reporting limit
D-37
-------
APPENDIX E
STATISTICAL DATA SUMMARIES
-------
3000
Figure E-l: Linear Correlation Plot for Antimony
2500
! 2000
ft
o 1500
1000
500
* /
^
500
-/-
y = 2.99x + 60.45
R2=0.84
y = 0.8953x + 100.69
R2 = 0.7891
OIA ED2000 vs Reference Laboraory
45 degrees
OIA ED2000 vs Certified Values
- Linear (OIA ED2000 vs Reference
Laboraory)
- Linear (OIA ED2000 vs Certified Values)
1000 1500 2000 2500
Reference Laboratoy or Certified Value (ppin)
3000
3500
7000
6000
Figure E-2: Linear Correlation Plot for Arsenic
5000
I
e.
4000
o
o
o
3000
2000
1000
OIA ED2000
45 Degrees
Linear (OIA ED2000)
y = 1.75x + 106.471
R2 = 0.69 I
1000 1500 2000
Reference Laboratory (ppin)
E-l
-------
Figure E-3: Linear Correlation Plot for Cadmium
3000
2500
2000 -
OIA ED2000
45 Degrees
Linear (OIA ED2000)
-500
Reference Laboratory (ppin)
3500
3000
Figure E-4: Linear Correlation Plot for Chromium
OIA ED2000
45 Degrees
Linear (OIA ED2000)
250° -
e.
2000 -
1500 -
1000 -
500
1000 1500 2000
Reference Laboratory (ppin)
E-2
-------
Figure E-5: Linear Correlation Plot for Copper
6000
5000 -
g, 4000
e.
X
o 3000
o
C4
O
a
Ť 2000
1000 -
OIA ED2000
45 Degrees
Linear (OIA ED2000)
y = 0.98x + 107.44|
R2 = 0.89
2000 3000 4000
Reference Laboratory (ppin)
500000
450000
400000
350000
300000
250000
200000
150000
100000
50000
0
Figure E-6: Linear Correlation Plot for Iron
OIA ED2000
45 Degrees
- Linear (OIA ED2000)
y
= 1.91x
R2 =
+ 8735.39
0.83
0 20000 40000 60000 80000 100000 120000 140000 160000 180000 200000
Reference Laboratory (ppin)
E-3
-------
Figure E-7: Linear Correlation Plot for Lead
60000
50000
40000
X
o 30000
o
o
O
a
3 20000
o
10000
OIA ED2000
45 Degrees
- Linear (OIA ED2000)
y = 1.06x-217.94
R2 = 0.90
5000 10000 15000 20000 25000
Reference Laboratory (ppin)
30000
35000
40000
g,
e.
9000 -,
8000 -
7000 -
6000 -
5000 -
o 4000 -
o
o
§ 3000 -
2000 -
1000 -
0
-1000 J
Figure E-8: Linear Correlation Plot for Mercury
OIA ED2000
45 Degrees
Linear (OIA ED2000)
Reference Laboratory (ppin)
E-4
-------
Figure E-9: Linear Correlation Plot for Nickel
4000
3500
3000
5 2500 -
o 2000 -
o
1500
1000
500
OIA ED2000
45 Degrees
Linear (OIA ED2000)
500 1000 1500 2000 2500
Reference Laboratory (ppin)
3000
3500
600
500
I 40° -
o.
o 300
o
o
s
a
3 200 -
100
Figure E-10: Linear Correlation Plot for Selenium
OIA ED2000
45 Degrees
Linear (OIA ED2000)
y = 0.73x + 1.36
R2 = 0.99
100 200 300 400
Reference Laboratory (ppin)
E-5
-------
Figure E-ll: Linear Correlation Plot for Silver
450
400
350 -
OIA ED2000
45 Degrees
Linear (OIA ED2000)
y = 0.95x- 0.61
R2 = 0.85
50 100 150 200 250 300
Reference Laboratory (ppin)
350 400
700
600
500
I
e.
400
o
o
| 300
H
200
100
Figure E-12: Linear Correlation Plot for Vanadium
OIA ED2000
45 Degrees
- Linear (OIA ED2000)
150 200 250 300 350
Reference Laboratory (ppin)
E-6
-------
Figure E-13: Linear Correlation Plot for Zinc
25000
20000
I
o.
15000
o
o
o
10000
5000
OIA ED2000
45 Degrees
Linear (OIA ED2000)
y = 1.66x- 271.56
R2 = 0.85
1000 2000 3000 4000 5000 6000 7000 8000
Reference Laboratory (ppm)
E-7
-------
Box Plot for Relative Percent Difference (RPD)
Oxford ED2000
Median; Box: 25%-75%; Whisker: Non-Outlier Range
Ł.Ł\> /O
200%
o 180%
o
Ł Ł* 160%
f O
1 1 3 140%
= -0 ^
| .3 g 120%
.5 g -o
m = Ł 100%
= "5(3 80%
S ^ i 60%
Q. ~
= 40%
C ťť
ra
| 20%
0%
9rw,
i
[
j
i
i
-1 |-
- °
If 1
! P
.... 57.
C
(
D
T
T
|
2~8TKP~
$ 1-JKP.2
f
"BQj
)
AS" ~r
3
_._.§4luS- -
r -
. 7-V
> ^55-
] JL
r T ^
i
5 o-r^,<*
5 27-KP
RF
57.CN
64
r (
j 09^r
/s t
V i T
n :
IQI
' T' ' """
-KP
-KP L
8--^/S-
TL
l_35rl=V-
* 34-
60-
L C
vs .
LV
LV
1 r1
j |n[61:
"TLl
i
T
[
:
L
:
8-\i
1
!S
bb-
51
/S
"
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 and analytical data associated with each Blend number.
Figure E-14. Box and Whiskers Plot for Mean RPD Values Showing Outliers and
Extremes for Target Elements, Oxford ED2000 Data Set.
E-8
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data Calculated for the Oxford ED2000
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
Ref
Lab
9
0.6%
161.6%
99.3%
118.3%
5
73.7%
133.9%
112.2%
115.5%
4
71.7%
113.1%
96.4%
100.4%
~
18
0.6%
161.6%
102.2%
114.9%
ERA
Spike
1
20.3%
20.3%
20.3%
20.3%
1
26.0%
26.0%
26.0%
26.0%
3
0.1%
42.1%
16.4%
7.1%
~
5
0.1%
42.1%
19.1%
20.3%
Arsenic
15
16.9%
182.8%
82.3%
55.2%
4
60.0%
80.7%
72.6%
74.8%
3
13.1%
125.1%
80.4%
103.0%
~
~
~
22
13.1%
182.8%
80.3%
68.7%
Cadmium
7
16.8%
61.3%
37.8%
39.5%
7
4.3%
53.1%
27.1%
28.8%
2
0.7%
54.2%
27.4%
27.4%
~
16
0.7%
61.3%
31.8%
35.6%
Chromium
28
8.3%
114.0%
39.6%
40.5%
4
7.7%
61.2%
23.4%
12.4%
2
3.8%
57.7%
30.7%
30.7%
~
~
~
34
3.8%
114.0%
37.2%
39.7%
Copper
16
1.0%
43.9%
17.7%
14.7%
7
0.2%
74.4%
32.8%
29.6%
2
0.8%
17.1%
8.9%
8.9%
~
~
25
0.2%
74.4%
21.2%
17.1%
Iron
5
138.0%
182.7%
168.7%
175.1%
13
53.1%
110.1%
73.9%
62.5%
13
54.9%
80.4%
63.9%
61.0%
7
5.4%
90.0%
48.5%
51.4%
38
5.4%
182.7%
78.3%
62.3%
Lead
16
1.2%
122.6%
23.0%
17.1%
4
8.6%
19.4%
13.6%
13.1%
8
1.6%
32.1%
13.5%
13.1%
4
11.2%
45.7%
26.1%
23.8%
32
1.2%
122.6%
19.8%
14.7%
Mercury
7
0.0%
41.9%
13.1%
4.6%
7
2.7%
70.7%
40.0%
49.4%
2
10.5%
28.9%
19.7%
19.7%
~
~
16
0.0%
70.7%
25.7%
20.9%
E-9
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data Calculated for the Oxford ED2000
(Continued)
Matrix
Soil
Cone
Range
Level 1
Level 2
Level 3
Level 4
All Soil
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
24
1.1%
117.0%
22.1%
9.5%
5
4.6%
19.1%
11.5%
10.5%
6
0.3%
28.0%
8.3%
3.8%
~
~
~
35
0.3%
117.0%
18.2%
8.4%
Selenium
4
16.7%
33.2%
27.9%
30.9%
5
28.2%
42.0%
34.5%
32.3%
4
10.6%
35.7%
25.4%
27.7%
~
~
~
~
13
10.6%
42.0%
29.7%
31.5%
Silver
3
42.9%
54.6%
47.0%
43.4%
3
28.9%
59.7%
42.7%
39.3%
6
11.2%
70.2%
32.9%
18.2%
~
~
~
~
12
11.2%
70.2%
38.9%
41.1%
Vanadium
13
11.8%
69.0%
42.4%
41.4%
4
3.7%
42.4%
22.9%
22.7%
4
17.6%
36.4%
27.4%
27.8%
~
~
~
~
~
21
3.7%
69.0%
35.8%
31.6%
Zinc
20
0.4%
72.0%
25.5%
19.3%
6
12.4%
40.2%
24.3%
24.3%
8
6.7%
70.5%
26.9%
23.6%
~
~
~
~
34
0.4%
72.0%
25.6%
22.7%
E-10
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data Calculated for the Oxford ED2000
(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
Ref
Lab
4
130.9%
150.9%
136.4%
131.9%
3
104.1%
157.1%
136.3%
147.6%
3
92.7%
143.5%
111.6%
98.7%
~
~
11
92.7%
157.1%
127.8%
131.5%
ERA
Spike
4
1.7%
29.5%
9.2%
2.9%
3
0.1%
0.4%
0.3%
0.4%
3
4.3%
74.8%
28.1%
5.2%
~
~
~
11
0.1%
74.8%
11.1%
2.2%
Arsenic
17
12.3%
168.7%
61.1%
42.3%
4
2.1%
34.7%
15.2%
12.0%
2
17.9%
21.9%
19.9%
19.9%
~
~
~
23
2.1%
168.7%
49.5%
37.3%
Cadmium
3
7.5%
19.7%
12.7%
10.8%
4
0.1%
5.1%
1.9%
1.1%
3
4.6%
23.8%
14.0%
13.5%
~
~
~
10
0.1%
23.8%
8.7%
6.3%
Chromium
20
0.1%
77.6%
28.9%
24.8%
3
4.6%
8.3%
6.4%
6.2%
3
4.7%
9.5%
6.5%
5.4%
~
~
26
0.1%
77.6%
23.7%
17.9%
Copper
7
3.4%
23.1%
13.9%
15.3%
4
9.8%
13.6%
11.8%
11.9%
10
0.6%
19.0%
7.9%
7.3%
~
~
21
0.6%
23.1%
10.7%
10.3%
Iron
3
181.3%
190.1%
185.0%
183.5%
18
70.5%
150.8%
93.9%
90.3%
4
67.2%
103.6%
84.7%
84.1%
6
29.8%
83.8%
59.2%
65.9%
31
29.8%
190.1%
94.8%
88.7%
Lead
15
2.4%
72.2%
25.1%
16.1%
4
4.1%
8.6%
6.1%
5.9%
3
2.5%
15.8%
7.0%
2.7%
~
22
2.4%
72.2%
19.2%
11.5%
Mercury
3
16.1%
87.7%
44.2%
28.8%
4
1.7%
101.6%
36.9%
22.1%
3
0.9%
23.5%
15.8%
23.1%
~
~
~
10
0.9%
101.6%
32.8%
23.3%
E-ll
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data Calculated for the Oxford ED2000
(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
17
0.3%
94.3%
24.7%
19.7%
6
2.3%
19.5%
7.2%
4.8%
4
2.0%
13.5%
5.8%
3.9%
~
27
0.3%
94.3%
18.0%
8.6%
Selenium
5
8.5%
44.1%
29.4%
30.7%
4
21.0%
41.1%
29.2%
27.3%
3
17.5%
37.3%
28.7%
31.4%
~
12
8.5%
44.1%
29.2%
31.0%
Silver
5
3.2%
19.3%
11.6%
11.7%
4
5.3%
30.7%
17.2%
16.4%
3
12.8%
63.6%
37.0%
34.5%
~
~
~
12
3.2%
63.6%
19.8%
13.5%
Vanadium
6
5.5%
51.4%
22.9%
19.6%
8
7.1%
51.7%
29.3%
32.9%
3
15.7%
28.6%
20.8%
18.0%
~
~
~
17
5.5%
51.7%
25.6%
27.2%
Zinc
18
10.9%
50.3%
25.4%
22.2%
5
3.2%
25.3%
11.8%
8.8%
4
1.0%
16.5%
8.3%
7.8%
~
~
~
27
1.0%
50.3%
20.4%
17.4%
E-12
-------
Table E-l. Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data Calculated for the Oxford ED2000
(Continued)
Matrix
All Samples
All Samples
Cone
Range
ED2000
All
Developers
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
Ref
Lab
29
0.6%
161.6%
111.9%
117.7%
206
0.1%
181.5%
80.6%
84.3%
ERA
Spike
16
0.1%
74.8%
13.6%
3.9%
110
0.1%
162.0%
62.7%
70.6%
Arsenic
45
2.1%
182.8%
64.6%
49.7%
320
0.2%
182.8%
36.6%
26.2%
Cadmium
26
0.1%
61.3%
22.9%
18.3%
209
0.1%
168.1%
29.6%
16.7%
Chromium
60
0.1%
114.0%
31.4%
24.8%
338
0.1%
151.7%
30.8%
26.0%
Copper
46
0.2%
74.4%
16.4%
13.5%
363
0.2%
111.1%
24.6%
16.2%
Iron
69
5.4%
190.1%
85.7%
78.1%
558
0.0%
190.1%
35.4%
26.0%
Lead
54
1.2%
122.6%
19.6%
14.3%
392
0.1%
135.2%
30.9%
21.5%
Mercury
26
0.0%
101.6%
28.4%
23.3%
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 Oxford ED2000
(Continued)
Matrix
All Samples
All Samples
Cone
Range
ED2000
All Developers
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
62
0.3%
117.0%
18.1%
8.6%
403
0.3%
146.5%
31.0%
25.4%
Selenium
25
8.5%
44.1%
29.4%
31.4%
195
0.0%
127.1%
32.0%
16.7%
Silver
24
3.2%
70.2%
29.3%
23.0%
177
0.0%
129.7%
36.0%
28.7%
Vanadium
38
3.7%
69.0%
31.2%
30.1%
218
0.1%
129.5%
42.2%
38.3%
Zinc
61
0.4%
72.0%
23.3%
19.3%
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 because of a 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 Oxford ED2000
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
1.2%
31.1%
8.2%
2.2%
5
2.5%
3.1%
2.8%
2.8%
4
0.8%
5.5%
2.5%
1.8%
~
~
~
18
0.8%
31.1%
5.4%
2.6%
Arsenic
15
1.8%
19.2%
7.4%
4.7%
4
0.3%
2.5%
1.6%
1.7%
4
0.2%
1.0%
0.7%
0.9%
~
~
~
23
0.2%
19.2%
5.2%
3.1%
Cadmium
7
2.1%
92.8%
24.5%
5.4%
7
1.5%
3.6%
2.3%
2.3%
2
1.0%
2.8%
1.9%
1.9%
~
~
~
~
16
1.0%
92.8%
12.0%
2.9%
Chromium
28
2.5%
64.1%
10.9%
5.7%
4
2.9%
28.6%
10.6%
5.4%
2
0.8%
1.9%
1.3%
1.3%
~
~
~
34
0.8%
64.1%
10.3%
5.6%
Copper
16
1.3%
22.8%
8.3%
5.3%
7
0.8%
4.4%
1.9%
1.4%
2
1.9%
2.7%
2.3%
2.3%
~
~
~
~
25
0.8%
22.8%
6.0%
4.2%
Iron
5
0.4%
1.2%
0.7%
0.7%
13
0.8%
15.8%
2.5%
1.4%
13
0.9%
48.5%
9.6%
3.1%
7
1.2%
17.4%
4.0%
1.8%
38
0.4%
48.5%
5.0%
1.6%
Lead
16
2.6%
34.6%
14.7%
13.5%
4
2.4%
2.9%
2.6%
2.5%
8
0.3%
7.3%
2.3%
1.7%
5
1.4%
48.2%
23.5%
23.2%
33
0.3%
48.2%
11.6%
8.4%
Mercury
7
6.4%
22.6%
14.0%
14.8%
7
1.9%
7.0%
4.0%
4.0%
2
2.1%
5.1%
3.6%
3.6%
~
~
~
~
16
1.9%
22.6%
8.3%
6.0%
E-15
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Oxford ED2000 (Continued)
Matrix
Soil
Cone
Range
Low
Medium
High
Very High
All Soil
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
24
1.9%
53.9%
8.1%
5.6%
5
0.8%
5.8%
3.3%
3.7%
6
1.1%
15.8%
4.3%
1.7%
~
~
~
~
~
35
0.8%
53.9%
6.8%
4.7%
Selenium
4
1.4%
12.6%
5.5%
4.0%
5
1.2%
4.0%
2.8%
3.2%
4
0.8%
12.7%
4.4%
2.0%
~
~
~
~
~
13
0.8%
12.7%
4.1%
2.7%
Silver
3
2.3%
4.0%
3.4%
3.8%
3
0.6%
4.8%
2.6%
2.4%
6
1.8%
9.4%
3.5%
2.3%
~
~
~
~
~
12
0.6%
9.4%
3.2%
2.5%
Vanadium
13
4.5%
23.1%
15.0%
17.2%
4
2.9%
13.3%
5.9%
3.7%
4
4.1%
9.4%
6.0%
5.2%
~
~
~
~
~
21
2.9%
23.1%
11.5%
10.9%
Zinc
20
1.7%
28.9%
7.8%
6.5%
6
1.6%
3.4%
2.1%
1.7%
8
0.5%
2.2%
1.2%
1.0%
~
~
~
~
~
34
0.5%
28.9%
5.3%
3.7%
E-16
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Oxford ED2000 (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
4
2.5%
41.0%
13.3%
4.9%
4
1.3%
2.8%
1.8%
1.6%
3
2.4%
97.7%
34.6%
3.6%
~
~
~
~
11
1.3%
97.7%
14.9%
2.8%
Arsenic
17
1.1%
69.9%
10.7%
5.5%
4
0.7%
4.2%
1.9%
1.3%
2
4.4%
14.5%
9.4%
9.4%
~
~
~
~
23
0.7%
69.9%
9.1%
5.0%
Cadmium
3
1.3%
4.3%
2.8%
2.6%
4
1.0%
26.0%
7.9%
2.2%
3
2.4%
41.1%
15.5%
3.1%
~
~
~
10
1.0%
41.1%
8.6%
2.6%
Chromium
21
0.6%
47.0%
12.4%
9.2%
3
2.3%
4.7%
3.6%
3.8%
3
2.2%
4.6%
3.0%
2.4%
~
~
~
~
27
0.6%
47.0%
10.4%
7.3%
Copper
8
1.6%
21.3%
7.1%
4.8%
4
1.0%
3.9%
2.1%
1.7%
10
0.3%
3.2%
1.4%
1.4%
~
~
~
22
0.3%
21.3%
3.6%
2.0%
Iron
3
0.1%
0.5%
0.3%
0.3%
19
0.3%
101.8%
11.2%
1.5%
4
0.5%
3.6%
1.9%
1.9%
6
0.4%
45.5%
9.3%
2.1%
32
0.1%
101.8%
8.6%
1.5%
Lead
16
2.9%
37.3%
11.8%
8.4%
4
0.2%
2.5%
1.6%
1.9%
3
0.3%
2.1%
0.9%
0.4%
~
~
23
0.2%
37.3%
8.6%
4.9%
Mercury
3
8.0%
44.5%
23.0%
16.4%
4
1.1%
3.9%
2.6%
2.6%
3
1.4%
3.0%
2.0%
1.6%
~
~
10
1.1%
44.5%
8.5%
2.9%
E-17
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Oxford ED2000 (Continued)
Matrix
Sediment
Cone
Range
Low
Medium
High
Very High
All Sediment
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
18
2.1%
12.4%
5.5%
4.6%
6
2.2%
4.9%
3.2%
3.0%
4
2.0%
3.7%
2.8%
2.8%
~
~
~
~
28
2.0%
12.4%
4.6%
4.1%
Selenium
5
2.8%
14.2%
6.5%
5.1%
4
1.2%
3.6%
2.4%
2.4%
3
1.7%
2.1%
1.9%
1.8%
~
~
~
~
12
1.2%
14.2%
4.0%
3.2%
Silver
5
2.7%
23.8%
8.0%
4.2%
4
0.9%
3.1%
1.9%
1.7%
3
2.7%
41.4%
15.7%
2.9%
~
~
~
12
0.9%
41.4%
7.9%
3.0%
Vanadium
6
11.5%
26.9%
18.8%
18.3%
8
3.1%
40.9%
19.2%
17.5%
3
6.2%
7.1%
6.8%
7.1%
~
~
~
~
17
3.1%
40.9%
16.9%
16.5%
Zinc
19
3.4%
13.4%
9.3%
10.3%
5
1.2%
1.8%
1.5%
1.7%
4
1.3%
2.4%
1.7%
1.6%
~
~
~
~
28
1.2%
13.4%
6.8%
6.1%
E-18
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Oxford ED2000 (Continued)
Matrix
All Samples
All Samples
Cone
Range
ED2000
All Developers
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Antimony
29
0.8%
97.7%
9.0%
2.7%
206
0.5%
97.7%
8.9%
6.1%
Arsenic
46
0.2%
69.9%
7.1%
4.0%
320
0.2%
71.7%
11.2%
8.2%
Cadmium
26
1.0%
92.8%
10.7%
2.7%
209
0.4%
92.8%
8.2%
3.6%
Chromium
61
0.6%
64.1%
10.4%
5.6%
338
0.6%
116.3%
15.9%
12.1%
Copper
47
0.3%
22.8%
4.9%
2.6%
363
0.1%
58.3%
7.5%
5.1%
Iron
70
0.1%
101.8%
6.7%
1.5%
558
0.1%
101.8%
5.2%
2.2%
Lead
56
0.2%
48.2%
10.4%
6.3%
392
0.2%
115.6%
9.3%
4.9%
Mercury
26
1.1%
44.5%
8.4%
4.7%
192
1.0%
137.1%
14.3%
6.8%
E-19
-------
Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for Oxford ED2000 (Continued)
Matrix
All Samples
All Samples
Cone
Range
ED2000
All Developers
Statistic
Number
Minimum
Maximum
Mean
Median
Number
Minimum
Maximum
Mean
Median
Nickel
63
0.8%
53.9%
5.8%
4.3%
403
0.3%
164.2%
10.8%
7.0%
Selenium
25
0.8%
14.2%
4.1%
2.8%
195
0.1%
98.8%
7.2%
4.5%
Silver
24
0.6%
41.4%
5.6%
2.8%
177
0.6%
125.3%
10.3%
5.2%
Vanadium
38
2.9%
40.9%
13.9%
12.5%
218
0.4%
86.1%
12.5%
8.5%
Zinc
62
0.5%
28.9%
6.0%
4.7%
471
0.1%
192.9%
8.0%
5.3%
Notes:
NC
Number
RSD
XRF
No samples reported by the reference laboratory in this concentration range.
Not calculated because of a lack of XRF data.
Number of demonstration samples evaluated.
Relative standard deviation.
X-ray fluorescence.
E-20
-------
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%
E-21
-------
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-22
-------
Table E-4. Evaluation of the Effects of Inteferent Metals on RPDs (Accuracy) of Other Target Elements 1
Parameter
Interferent/Metal Ratio
Number of Samples
RPD of Target Metal
RPD of Target Metal
(Absolute Value)
Interferent
Concentration Range
Target Metal
Concentration Range
Statistic
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Lead Effects on Arsenic
<5
29
-112.2%
23.4%
-33.4%
-34.7%
2.1%
112.2%
35.1%
34.7%
26
783
188
76
20
3229
354
148
5-10
6
-125.1%
-55.2%
-78.4%
-74.8%
55.2%
125.1%
78.4%
74.8%
640
29881
9004
5087
204
3814
1481
1057
>10
9
-168.7%
-103.0%
-137.0%
-138.3%
103.0%
168.7%
137.0%
138.3%
1119
12680
3570
2239
161
6307
1077
373
Copper Effects on Nickel
<5
43
-94.3%
20.6%
-8.6%
-3.4%
0.3%
94.3%
13.2%
7.2%
51
1259
253
141
56
3207
595
191
5-10
5
-17.0%
7.2%
-5.5%
-8.5%
0.3%
17.0%
8.3%
8.5%
953
1980
1349
1160
108
258
175
156
>10
14
-117.0%
3.3%
-36.4%
-23.6%
3.3%
117.0%
36.9%
23.6%
1006
4365
2624
2409
71
443
189
149
Nickel Effects on Copper
<5
37
-74.4%
19.0%
-14.9%
-11.3%
0.2%
74.4%
16.4%
13.5%
71
852
206
156
51
4365
1341
1006
5-10
1
-16.1%
-16.1%
-16.1%
-16.1%
16.1%
16.1%
16.1%
16.1%
378
378
378
378
92
92
92
92
>10
8
-43.9%
13.6%
-11.1%
-10.6%
3.4%
43.9%
16.2%
12.6%
1240
3207
2285
2284
79
143
114
121
E-23
-------
Table E-4. Evaluation of the Effects of Inteferent Metals on RPDs (Accuracy) of Other Target Elements l (Continued)
Parameter
Interferent/Metal Ratio
Number of Samples
RPD of Target Metal
RPD of Target Metal
(Absolute Value)
Interferent
Concentration Range
Target Metal
Concentration Range
Statistic
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Minimum
Maximum
Mean
Median
Zinc Effects on Copper
<5
34
-74.4%
19.0%
-13.7%
-10.7%
0.2%
74.4%
16.7%
12.4%
54
11812
1416
207
51
4365
1438
1093
5-10
1
-11.3%
-11.3%
-11.3%
-11.3%
11.3%
11.3%
11.3%
11.3%
889
889
889
889
179
179
179
179
>10
11
-37.5%
13.6%
-13.2%
-15.9%
1.0%
37.5%
15.8%
15.9%
899
9830
3807
3940
79
299
141
135
Copper Effects on Zinc
<5
48
-72.0%
4.2%
-24.3%
-21.0%
0.4%
72.0%
24.5%
21.0%
51
3072
562
179
54
11812
1932
619
5-10
3
-34.9%
-10.9%
-22.3%
-20.9%
10.9%
34.9%
22.3%
20.9%
1027
1646
1311
1259
140
232
173
146
>10
10
-33.8%
3.6%
-17.0%
-17.3%
3.6%
33.8%
17.8%
17.3%
1696
4365
2814
2329
75
277
168
177
Notes:
1. Concentrations are reported in units of milligrams per kilogram (mg/kg), or parts per million (ppm).
2. Table presents statistics for raw (unmodified) RPDs as well as absolute value RPDs.
< Less than
> Greater than
RPD Relative percent difference
NC Not calculated because of a lack of XRF data
ND Nondetect
XRF X-ray fluorescence
E-24
-------
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
-133.9%
-71.7%
-111.7%
-120.7%
2
-103.8%
-73.7%
-88.7%
-88.7%
2
-16.7%
-0.6%
-8.6%
-8.6%
4
-131.5%
-96.0%
-110.8%
-107.7%
RPD ABS Val
~
~
~
4
71.7%
133.9%
111.7%
120.7%
2
73.7%
103.8%
88.7%
88.7%
2
0.6%
16.7%
8.6%
8.6%
4
96.0%
131.5%
110.8%
107.7%
Certified Value
RPD
~
~
~
1
42.1%
42.1%
42.1%
42.1%
2
20.3%
26.0%
23.2%
23.2%
4
-0.1%
4.3%
1.7%
1.3%
RPD ABS Val
~
~
~
1
42.1%
42.1%
42.1%
42.1%
2
20.3%
26.0%
23.2%
23.2%
4
0.1%
4.3%
1.8%
1.3%
Arsenic
Reference Laboratory
RPD
1
-182.8%
-182.8%
-182.8%
-182.8%
7
-157.2%
-13.1%
-70.0%
-74.5%
1
-49.7%
-49.7%
-49.7%
-49.7%
11
-168.7%
23.4%
-48.0%
-38.7%
RPD ABS Val
1
182.8%
182.8%
182.8%
182.8%
7
13.1%
157.2%
70.0%
74.5%
1
49.7%
49.7%
49.7%
49.7%
11
2.1%
168.7%
52.7%
38.7%
E-25
-------
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
5
-143.5%
-92.7%
-120.7%
-130.9%
7
-161.6%
-104.7%
-122.5%
-115.5%
3
-157.1%
-147.6%
-151.9%
-150.9%
2
-123.7%
-121.2%
-122.4%
-122.4%
29
-161.6%
-0.6%
-111.9%
-117.7%
RPD ABS Val
5
92.7%
143.5%
120.7%
130.9%
7
104.7%
161.6%
122.5%
115.5%
o
6
147.6%
157.1%
151.9%
150.9%
2
121.2%
123.7%
122.4%
122.4%
29
0.6%
161.6%
111.9%
117.7%
Certified Value
RPD
5
-74.8%
5.2%
-20.6%
-3.6%
1
7.1%
7.1%
7.1%
7.1%
3
-1.7%
0.1%
-0.7%
-0.4%
~
~
~
~
16
-74.8%
42.1%
-0.2%
0.3%
RPD ABS Val
5
0.4%
74.8%
22.7%
5.2%
1
7.1%
7.1%
7.1%
7.1%
o
3
0.1%
1.7%
0.7%
0.4%
~
~
~
~
16
0.1%
74.8%
13.6%
3.9%
Arsenic
Reference Laboratory
RPD
12
-138.3%
-17.9%
-43.9%
-37.0%
5
-112.2%
-16.9%
-47.3%
-32.7%
2
-132.5%
-113.8%
-123.2%
-123.2%
6
-142.7%
-36.6%
-98.9%
-114.0%
45
-182.8%
23.4%
-63.4%
-49.7%
RPD ABS Val
12
17.9%
138.3%
43.9%
37.0%
5
16.9%
112.2%
47.3%
32.7%
2
113.8%
132.5%
123.2%
123.2%
6
36.6%
142.7%
98.9%
114.0%
45
2.1%
182.8%
64.6%
49.7%
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
Cadmium
Reference Laboratory
RPD
o
6
16.7%
48.7%
35.0%
39.5%
5
21.3%
54.2%
38.5%
35.2%
2
16.8%
44.2%
30.5%
30.5%
-
~
5
-7.5%
13.5%
2.1%
1.4%
RPD ABS Val
3
16.7%
48.7%
35.0%
39.5%
5
21.3%
54.2%
38.5%
35.2%
2
16.8%
44.2%
30.5%
30.5%
-
5
1.4%
13.5%
6.8%
7.4%
Chromium
Reference Laboratory
RPD
2
50.2%
91.5%
70.8%
70.8%
7
8.3%
61.2%
29.7%
22.9%
2
13.6%
114.0%
63.8%
63.8%
4
-77.6%
-40.6%
-61.8%
-64.4%
11
-66.5%
9.5%
-24.0%
-14.8%
RPD ABS Val
2
50.2%
91.5%
70.8%
70.8%
7
8.3%
61.2%
29.7%
22.9%
2
13.6%
114.0%
63.8%
63.8%
4
40.6%
77.6%
61.8%
64.4%
11
4.6%
66.5%
25.7%
14.8%
Copper
Reference Laboratory
RPD
3
-16.2%
17.1%
0.6%
1.0%
6
-29.6%
-10.3%
-21.6%
-24.5%
3
-36.6%
0.2%
-19.4%
-21.9%
2
-32.2%
-11.0%
-21.6%
-21.6%
4
-43.9%
7.1%
-13.7%
-9.1%
RPD ABS Val
3
1.0%
17.1%
11.4%
16.2%
6
10.3%
29.6%
21.6%
24.5%
3
0.2%
36.6%
19.6%
21.9%
2
11.0%
32.2%
21.6%
21.6%
4
7.1%
43.9%
17.3%
9.1%
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
Iron
Reference Laboratory
RPD
13
-150.8%
-67.2%
-88.7%
-86.1%
12
-138.0%
-51.4%
-68.7%
-60.8%
7
-107.3%
-40.8%
-86.8%
-98.4%
7
-90.0%
-54.9%
-74.7%
-78.1%
70
-190.1%
42.1%
-84.3%
-78.4%
RPD ABS Val
13
67.2%
150.8%
88.7%
86.1%
12
51.4%
138.0%
68.7%
60.8%
7
40.8%
107.3%
86.8%
98.4%
7
54.9%
90.0%
74.7%
78.1%
70
5.4%
190.1%
85.6%
78.4%
Lead
Reference Laboratory
RPD
13
-72.2%
8.6%
-19.1%
-9.9%
7
-30.8%
39.5%
-0.1%
-2.9%
4
-22.3%
4.1%
-7.8%
-6.5%
6
-20.0%
45.7%
7.3%
3.4%
55
-72.2%
122.6%
-2.7%
-2.5%
RPD ABS Val
13
2.4%
72.2%
22.3%
9.9%
7
1.2%
39.5%
15.4%
10.4%
4
2.5%
22.3%
9.8%
7.3%
6
4.3%
45.7%
18.2%
15.4%
55
1.2%
122.6%
20.2%
14.5%
Mercury
Reference Laboratory
RPD
5
-24.0%
28.8%
-11.0%
-20.1%
11
-41.9%
70.7%
16.7%
10.5%
3
23.1%
101.6%
70.8%
87.7%
~
~
~
26
-41.9%
101.6%
12.4%
0.9%
RPD ABS Val
5
16.1%
28.8%
22.5%
23.5%
11
4.6%
70.7%
35.3%
28.9%
o
5
23.1%
101.6%
70.8%
87.7%
~
~
~
26
0.0%
101.6%
28.4%
23.3%
E-28
-------
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
3
-16.7%
-4.6%
-8.8%
-5.2%
6
-21.0%
-1.2%
-11.8%
-12.3%
3
-37.8%
10.5%
-7.0%
6.1%
3
-17.6%
1.5%
-6.8%
-4.4%
11
-94.3%
20.6%
-22.7%
-12.4%
RPD ABS Val
o
6
4.6%
16.7%
8.8%
5.2%
6
1.2%
21.0%
11.8%
12.3%
o
6
6.1%
37.8%
18.1%
10.5%
o
6
1.5%
17.6%
7.8%
4.4%
11
2.0%
94.3%
27.4%
19.5%
Selenium
Reference Laboratory
RPD
1
32.3%
32.3%
32.3%
32.3%
4
26.5%
32.1%
30.1%
30.9%
2
16.7%
42.0%
29.4%
29.4%
~
~
5
10.6%
44.1%
28.4%
28.2%
RPD ABS Val
1
32.3%
32.3%
32.3%
32.3%
4
26.5%
32.1%
30.1%
30.9%
2
16.7%
42.0%
29.4%
29.4%
~
~
5
10.6%
44.1%
28.4%
28.2%
Silver
Reference Laboratory
RPD
1
17.3%
17.3%
17.3%
17.3%
4
-11.2%
59.7%
32.7%
41.1%
2
28.9%
43.4%
36.2%
36.2%
~
~
4
-34.5%
19.1%
-0.2%
7.4%
RPD ABS Val
1
17.3%
17.3%
17.3%
17.3%
4
11.2%
59.7%
38.3%
41.1%
2
28.9%
43.4%
36.2%
36.2%
~
~
4
5.3%
34.5%
17.1%
14.2%
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
Nickel
Reference Laboratory
RPD
13
-13.5%
11.1%
1.1%
2.3%
11
-28.3%
8.4%
-3.4%
0.3%
6
-34.5%
-8.6%
-25.5%
-28.5%
7
-117.0%
7.2%
-47.5%
-19.1%
63
-117.0%
20.6%
-14.2%
-5.4%
RPD ABS Val
13
0.3%
13.5%
6.4%
5.4%
11
0.3%
28.3%
6.9%
4.0%
6
8.6%
34.5%
25.5%
28.5%
7
3.4%
117.0%
49.5%
19.1%
63
0.3%
117.0%
18.0%
8.6%
Selenium
Reference Laboratory
RPD
5
17.5%
33.2%
29.1%
31.4%
3
33.2%
37.8%
35.6%
35.7%
4
8.5%
41.1%
25.3%
25.8%
1
28.9%
28.9%
28.9%
28.9%
25
8.5%
44.1%
29.4%
31.4%
RPD ABS Val
5
17.5%
33.2%
29.1%
31.4%
o
6
33.2%
37.8%
35.6%
35.7%
4
8.5%
41.1%
25.3%
25.8%
1
28.9%
28.9%
28.9%
28.9%
25
8.5%
44.1%
29.4%
31.4%
Silver
Reference Laboratory
RPD
5
-63.6%
11.7%
-11.1%
3.2%
1
-65.4%
-65.4%
-65.4%
-65.4%
4
14.2%
30.7%
22.7%
23.0%
o
5
14.2%
70.2%
46.4%
54.6%
24
-65.4%
70.2%
13.7%
15.8%
RPD ABS Val
5
3.2%
63.6%
19.5%
11.7%
1
65.4%
65.4%
65.4%
65.4%
4
14.2%
30.7%
22.7%
23.0%
3
14.2%
70.2%
46.4%
54.6%
24
3.2%
70.2%
29.3%
23.0%
E-30
-------
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
1
27.2%
27.2%
27.2%
27.2%
4
-31.6%
24.8%
-4.1%
-4.9%
1
3.7%
3.7%
3.7%
3.7%
~
~
9
-51.4%
-8.3%
-29.7%
-30.0%
RPD ABS Val
1
27.2%
27.2%
27.2%
27.2%
4
20.4%
31.6%
26.7%
27.5%
1
3.7%
3.7%
3.7%
3.7%
~
~
9
8.3%
51.4%
29.7%
30.0%
Zinc
Reference Laboratory
RPD
3
-33.9%
3.6%
-14.3%
-12.4%
7
-48.7%
-14.3%
-24.9%
-23.2%
3
-47.3%
-13.3%
-27.7%
-22.6%
2
-34.9%
-19.2%
-27.1%
-27.1%
10
-69.6%
-11.4%
-35.5%
-34.6%
RPD ABS Val
3
3.6%
33.9%
16.6%
12.4%
7
14.3%
48.7%
24.9%
23.2%
3
13.3%
47.3%
27.7%
22.6%
2
19.2%
34.9%
27.1%
27.1%
10
11.4%
69.6%
35.5%
34.6%
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
3
-40.7%
-18.0%
-31.4%
-35.7%
10
-69.0%
-11.8%
-44.6%
-51.6%
7
-7.1%
51.7%
12.9%
12.0%
3
-41.4%
-34.0%
-37.2%
-36.4%
38
-69.0%
51.7%
-21.5%
-29.3%
RPD ABS Val
o
6
18.0%
40.7%
31.4%
35.7%
10
11.8%
69.0%
44.6%
51.6%
7
5.5%
51.7%
18.4%
12.0%
o
6
34.0%
41.4%
37.2%
36.4%
38
3.7%
69.0%
31.2%
30.1%
Zinc
Reference Laboratory
RPD
13
-25.3%
4.2%
-12.3%
-13.8%
11
-72.0%
-6.7%
-23.2%
-16.9%
7
-33.8%
-10.9%
-19.6%
-17.4%
6
-70.5%
-0.4%
-26.9%
-20.9%
62
-72.0%
4.2%
-22.9%
-19.3%
RPD ABS Val
13
1.0%
25.3%
13.1%
13.8%
11
6.7%
72.0%
23.2%
16.9%
7
10.9%
33.8%
19.6%
17.4%
6
0.4%
70.5%
26.9%
20.9%
62
0.4%
72.0%
23.2%
19.3%
E-32
-------
Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued)
Notes:
AS
BN
CN
KP
LV
RF
SB
TL
WS
Other Notes:
Number
RPD
RPD ABS Val
Alton Steel Mill
Burlington Northern Railroad/ASARCO East
Naval Surface Warfare Center, Crane Division
KARS Park - Kennedy Space Center
Leviathan Mine/Aspen Creek
Ramsey Flats - Silver Bow Creek
Sulphur Bank Mercury Mine
Torch Lake Superfund Site
Wickes Smelter Site
No samples reported by the reference laboratory in this concentration range.
Number of demonstration samples evaluated.
Relative Percent Difference (raw value).
Relative Percent Difference (absolute value).
E-33
------- |