United States Office of Research and EPA/540/R-06/001 

 Environmental Protection Development February 2006 

 Agency Washington, DC 20460 

Innovative Technology 

Verification Report 

XRF Technologies for Measuring 

Trace Elements in 

Soil and Sediment 

Rigaku ZSX Mini II 

XRF Analyzer
EPA/540/R-06/001 

February 2006 

Innovative Technology 

Verification Report 

Rigaku ZSX Mini II 

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 
_____________________________________________________________________________

 ii 

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. 
_____________________________________________________________________________

 iii 

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 
______________________________________________________________________________

iv

Abstract 

The Rigaku ZSX Mini II (ZSX Mini II) XRF Services x-ray fluorescence (XRF) analyzer was demonstrated under the U.S. Environmental Protection Agency (EPA) Superfund Innovative Technology 

Evaluation (SITE) Program. The field portion of the demonstration was conducted in January 2005 at the 

Kennedy Athletic, Recreational and Social Park (KARS) at Kennedy Space Center on Merritt Island, 

Florida. The demonstration was designed to collect reliable performance and cost data for the ZSX Mini 

II 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 ZSX Mini II 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 

3050B/6010B, and using cold vapor atomic absorption (CVAA) spectroscopy for mercury only, in 

accordance with EPA Method 7471A. 

The ZSX Mini II is a “wavelength-dispersive” XRF analyzer that can analyze for elements ranging in 

mass from fluorine to uranium. The ZSX Mini II differentiates the x-ray energies emitted from a sample 

by dispersing the x-rays into different wavelength ranges using crystals. By contrast, more common 

“energy-dispersive” XRF analyzers differentiate between x-ray energies based on voltages measured by 

the detector. For some applications, wavelength-dispersive XRF analyzers can achieve high resolutions 

and very good sensitivity through the reduction of interelement interferences. 

Wavelength-dispersive XRFs have historically been large, laboratory-bound instruments with significant 

requirements for power and cooling. The ZSX Mini II is a smaller, transportable unit that can operate 

without additional cooling fluids on standard 110-volt circuits. The unit can employ an economical gas 

proportional counter as a detector rather than a diode detector with a multi-channel analyzer (common in 

energy-dispersive instruments) because wavelength resolution is achieved with the crystals. 

This report describes the results of the evaluation of the ZSX Mini II 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 ZSX Mini II 

analyzer is compiled and compared to both fixed laboratory costs and average XRF instrument costs. 
______________________________________________________________________________

v

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 
______________________________________________________________________________

vi

Contents (Continued) 

Chapter Page

 3.3 Demonstration Site and Logistics ....................................................................................20 

 3.3.1 Demonstration Site Selection..............................................................................20 

 3.3.2 Demonstration Site Logistics..............................................................................20 

 3.3.3 EPA Demonstration Team and Developer Field Team Responsibilities............21 

 3.3.4 Sample Management During the Field Demonstration.......................................21 

 3.3.5 Data Management...............................................................................................22 

4.0 EVALUATION DESIGN.............................................................................................................23 

 4.1 Evaluation Objectives ......................................................................................................23 

 4.2 Experimental Design........................................................................................................23 

 4.2.1 Primary Objective 1 – Method Detection Limits................................................24 

 4.2.2 Primary Objective 2 – Accuracy.........................................................................25 

 4.2.3 Primary Objective 3 – Precision .........................................................................26 

 4.2.4 Primary Objective 4 – Impact of Chemical and Spectral Interferences..............27 

 4.2.5 Primary Objective 5 – Effects of Soil Characteristics ........................................28 

 4.2.6 Primary Objective 6 – Sample Throughput ........................................................28 

 4.2.7 Primary Objective 7 – Technology Costs ...........................................................28 

 4.2.8 Secondary Objective 1 – Training Requirements ...............................................28 

 4.2.9 Secondary Objective 2 – Health and Safety .......................................................29 

 4.2.10 Secondary Objective 3 – Portability ...................................................................29 

 4.2.11 Secondary Objective 4 – Durability....................................................................29 

 4.2.12 Secondary Objective 5 – Availability.................................................................29 

 4.3 Deviations from the Demonstration Plan.........................................................................29 

 

5.0 REFERENCE LABORATORY ...................................................................................................31 

 5.1 Selection of Reference Methods ......................................................................................31 

 5.2 Selection of Reference Laboratory ..................................................................................32 

 5.3 QA/QC Results for Reference Laboratory.......................................................................33 

 5.3.1 Reference Laboratory Data Validation ...............................................................33 

 5.3.2 Reference Laboratory Technical Systems Audit ................................................34 

 5.3.3 Other Reference Laboratory Data Evaluations ...................................................34 

 5.4 Summary of Data Quality and Usability..........................................................................36 

6.0 TECHNOLOGY DESCRIPTION ................................................................................................39 

 

 6.1 General Description .........................................................................................................39 

 6.2 Instrument Operations during the Demonstration............................................................39 

 6.2.1 Setup and Calibration..........................................................................................39 

 6.2.2 Demonstration Sample Processing .....................................................................41 

 6.3 General Demonstration Results .......................................................................................41 

 6.4 Contact Information.........................................................................................................42 
______________________________________________________________________________

vii

Contents (Continued) 

Chapter Page

7.0 PERFORMANCE EVALUATION ..............................................................................................43 

 7.1 Primary Objective 1 – Method Detection Limits.............................................................43 

 7.2 Primary Objective 2 – Accuracy and Comparability .......................................................46 

 7.3 Primary Objective 3 – Precision ......................................................................................51 

 7.4 Primary Objective 4 – Impact of Chemical and Spectral Interferences...........................52

 7.5 Primary Objective 5 – Effects of Soil Characteristics .....................................................55 

 7.6 Primary Objective 6 – Sample Throughput .....................................................................59 

 7.7 Primary Objective 7 – Technology Cost..........................................................................59 

 7.8 Secondary Objective 1 – Training Requirements ............................................................59 

 7.9 Secondary Objective 2 – Health and Safety.....................................................................59 

 7.10 Secondary Objective 3 – Portability ................................................................................60 

 7.11 Secondary Objective 4 – Durability.................................................................................60 

 7.12 Secondary Objective 5 – Availability ..............................................................................60 

8.0 ECONOMIC ANALYSIS ............................................................................................................61 

 8.1 Equipment Costs..............................................................................................................61 

 8.2 Supply Costs ....................................................................................................................61 

 8.3 Labor Costs......................................................................................................................61 

 8.4 Comparison of XRF Analysis and Reference Laboratory Costs .....................................62 

 

9.0 SUMMARY OF TECHNOLOGY PERFORMANCE .................................................................65 

10.0 REFERENCES ............................................................................................................................71 

APPENDICES

Appendix A: Verification Statement 

Appendix B: Developer Discussion 

Appendix C: Data Validation Summary Report 

Appendix D: Developer and Reference Laboratory Data 

Appendix E: Statistical Data Summaries
______________________________________________________________________________

viii

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 Rigaku ZSX Mini II XRF Technical Specifications.....................................................................40 

7-1 Evaluation of Sensitivity – Method Detection Limits for the ZSX Mini II ..................................44 

7-2 Comparison of ZSX Mini 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 ZSX Mini II.......................................................................................................................49 

7-4 Summary of Correlation Evaluation for the ZSX Mini II.............................................................50 

7-5 Evaluation of Precision – Relative Standard Deviations for the ZSX Mimi II.............................53 

7-6 Evaluation of Precision – Relative Standard Deviations for the Reference Laboratory 

 versus the ZSX Mini II and All Demonstration Instruments ........................................................54 

7-7 Effects of Interferent Elements on the RPDs (Accuracy) for Other Target Elements ..................56 

7-8 Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Rigaku ZSX Mini II ............57 

8-1 Equipment Costs ...........................................................................................................................61 

8-2 Time Required to Complete Analytical Analysis .........................................................................62 

8-3 Comparison of XRF Technology and Reference Method Costs...................................................64 

9-1 Summary of Rigaku ZSX Mini II Performance – Primary Objectives.........................................66 

9-2 Summary of Rigaku ZSX Mini II Performance – Secondary Objectives.....................................68
______________________________________________________________________________

ix

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 Rigaku ZSX Mini II XRF Analyzer Set Up for Bench-Top Analysis ..........................................39 

6-2 Rigaku Technician Filling a Sample Cup For Analysis................................................................41 

6-3 Samples Placed into the 12-Position Sample Changer Awaiting Analysis...................................41 

7-1 Linear Correlation Plot for Lead Showing High Correlation........................................................48 

7-2 Linear Correlation Plot for Silver Indicating Low Overall Correlation with the Reference 

 Laboratory.....................................................................................................................................51 

8-1 Comparison of Activity Times for the ZSX Mini II versus Other XRF Instruments ...................63 

9-1 Method Detection Limits (sensitivity), Accuracy, and Precision of the ZSX Mini II 

 in Comparison to the Average of All Eight XRF Instruments......................................................69
______________________________________________________________________________

x

Acronyms, Abbreviations, and Symbols 

μg Micrograms 

μA 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
______________________________________________________________________________

xi

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 

MSD 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 
______________________________________________________________________________

xii

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 

r

2

 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 
______________________________________________________________________________

xiii

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 
______________________________________________________________________________

xiv

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; Jose Brum and George Fischer of Rigaku, 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. 
______________________________________________________________________________________

1 

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 

Rigaku ZSX Mini II 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 Distributor in the 

United States 

Developer Short 

Name 

Instrument Full 

Name 

Instrument Short 

Name 

Elvatech, Ltd. Xcalibur XRF Services Xcalibur ElvaX ElvaX 

Innov-X Systems Innov-X Systems Innov-X XT400 Series XT400 

NITON Analyzers, A 

Division of Thermo 

Electron Corporation 

NITON Analyzers, A 

Division of Thermo 

Electron Corporation

Niton XLt 700 Series 

XLi 700 Series 

XLt 

XLi 

Oxford Instruments 

Analytical, Ltd. 

Oxford Instruments 

Analytical, Ltd. 

Oxford X-Met 3000 TX 

ED2000

X-Met 

ED2000

Rigaku, Inc. Rigaku, Inc. Rigaku ZSX Mini II ZSX Mini II

RÖNTEC AG 

(acquired by Bruker 

AXS, 11/2005 

 RÖNTEC USA Rontec PicoTAX PicoTAX 
__________________________________________________________________________________

2 

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 costeffective 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/nerlesd1/). 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. 
__________________________________________________________________________________

3 

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, fieldportable 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-theart 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 3050B/6010B, and using cold vapor atomic 

absorption (CVAA) spectroscopy (for mercury only) 

in accordance with EPA Method 7471A. 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 xrays 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 
__________________________________________________________________________________

4 

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. 

Figure 1-1. The XRF process. 

Measurement times vary (typically ranging from 30 

to 600 seconds), based primarily on data quality 

objectives. Shorter analytical measurement times (30 

seconds) are generally used for initial screening, 

element identification, and hot-spot delineation, 

while longer measurement times (300 seconds or 

more) are typically used to meet higher goals for 

precision and accuracy. The length of the measuring 

time will also affect the detection limit; generally, the 

longer the measuring time, the lower the detection 

limit. However, detection limits for individual 

elements may be increased because of sample 

heterogeneity or the presence of other elements in the 

sample that fluoresce with similar x-ray energies. 

The main variables that affect precision and accuracy 

for XRF analysis are: 

1. Physical matrix effects (variations in the physical 

character of the sample). 

2. Chemical matrix effects (absorption and 

enhancement phenomena) and Spectral 

interferences (peak overlaps). 

3. Moisture content above 10 percent, which affects 

x-ray transmission. 

Because of these variables, it is important that each 

field XRF characterization effort be guided by a wellconsidered sampling and analysis plan. Sample 

preparation and homogenization, instrument 

calibration, and laboratory confirmation analysis are 

all important aspects of an XRF sampling and 

analysis plan. EPA SW-846 Method 6200 provides 

additional guidance on sampling and analytical 

methodology for XRF analysis. 

1.5 Properties of the Target Elements 

This section describes the target elements selected for 

the technology demonstration and the typical 

characteristics of each. Key criteria used in selecting 

the target elements included: 

• The frequency that the element is determined in 

environmental applications of XRF instruments. 

• The extent that the element poses an 

environmental consequence, such as a potential 

risk to human or environmental receptors. 

• The ability of XRF technology to achieve 

detection limits below typical remediation goals 

and risk assessment criteria. 

• The extent that the element may interfere with 

the analysis of other target elements. 

In considering these criteria, the critical target 

elements selected for this study were antimony, 

arsenic, cadmium, chromium, copper, iron, lead, 

mercury, nickel, selenium, silver, vanadium, and 

zinc. These 13 target elements are of significant 

concern for site cleanups and human health risk 

assessments because most are highly toxic or 

interfere with the analysis of other elements. The 

demonstration therefore focused on the analysis of 

these 13 elements in evaluating the various XRF 

instruments. 
__________________________________________________________________________________

5 

1.5.1 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. 

1.5.2 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. 

1.5.3 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 fieldportable XRF; however, action levels for cadmium 

may be lower than the detection limits of fieldportable 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). 

1.5.5 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. 

1.5.6 Iron 

Although iron is not considered an element that poses 

a significant environmental consequence, it interferes 

with measurement of other elements and was 
__________________________________________________________________________________

6 

therefore included in the study. Furthermore, iron is 

often used as a target reference element in XRF 

analysis. 

Naturally occurring iron in surface soils typically 

ranges from 7,000 to 550,000 mg/kg, with the iron 

content originating primarily from parent rock. 

Typical detection limits for field-portable XRF 

instruments are in the range of 10 to 60 mg/kg. Iron 

is easily analyzed by both ICP-AES and XRF; 

however, neither technique can distinguish among 

iron species in soil. Although iron in soil may pose 

few environmental consequences, high levels of iron 

may interfere with analyses of other elements in both 

techniques (ICP-AES and XRF). Spectral 

interference from iron is mitigated in ICP-AES 

analysis by applying inter-element correction factors, 

as required by the analytical method. Differences in 

analytical results between ICP-AES and XRF for 

other target elements are expected when 

concentrations of iron are high in the soil matrix. 

1.5.7 Lead 

Naturally occurring lead in surface soils typically 

ranges from 2 to 200 mg/kg; concentrations greater 

than 50 mg/kg are potentially phytotoxic. 

Concentrations greater than 400 mg/kg may result in 

adverse effects in humans. Typical detection limits 

for field-portable XRF instruments range from 10 to 

20 mg/kg. Lead is a common contaminant at many 

sites, and human and environmental exposure can 

occur through many routes. Lead is frequently found 

in mine waste, at lead-acid battery recycling 

facilities, at oil refineries, and in lead-based paint. 

Lead is successfully analyzed by ICP-AES and XRF; 

however, spectral interferences between peaks for 

lead and arsenic in XRF analysis can affect detection 

limits and accuracy when the ratio of arsenic to lead 

is 10 to 1 or more. Differences between ICP-AES 

and XRF results are expected in the presence of high 

concentrations of arsenic, especially when the ratio of 

lead to arsenic is low. 

1.5.8 Mercury 

Naturally occurring mercury in surface soils typically 

ranges from 0.01 to 0.3 mg/kg; concentrations greater 

than 0.3 mg/kg are potentially phytotoxic. 

Concentrations of mercury greater than 23 mg/kg and 

concentrations of methyl mercury above 6.1 mg/kg 

may result in adverse health effects in humans. 

Typical detection limits for field-portable XRF 

instruments range from 10 to 20 mg/kg. Elevated 

concentrations of mercury are associated with 

amalgamation of gold and with mine waste and 

industrial facilities. Native surface soils are 

commonly enriched by anthropogenic sources of 

mercury. Anthropogenic sources include coal-fired 

power plants and metal smelters. Mercury is too 

volatile to withstand both the vigorous digestion and 

extreme temperature involved with ICP-AES 

analysis; therefore, the EPA-approved technique for 

laboratory analysis of mercury is CVAA 

spectroscopy. Mercury is successfully measured by 

XRF, but differences between results obtained by 

CVAA and XRF are expected when mercury levels 

are high. 

1.5.9 Nickel 

Naturally occurring nickel in surface soils typically 

ranges from 5 to 500 mg/kg; a concentration of 30 

mg/kg is potentially phytotoxic. Concentrations 

greater than 1,600 mg/kg may result in adverse health 

effects in humans. Typical detection limits for fieldportable XRF instruments range from 10 to 60 

mg/kg. Elevated concentrations of nickel are 

associated with mine wastes and industrial facilities. 

Nickel is a common environmental contaminant at 

metal processing sites. It is successfully analyzed by 

both ICP-AES and XRF with little interference; 

therefore, a strong correlation between the methods is 

expected. 

1.5.10 Selenium 

Naturally occurring selenium in surface soils 

typically ranges from 0.1 to 2 mg/kg; concentrations 

greater than 1 mg/kg are potentially phytotoxic. Its 

toxicities are well documented for plants and 

livestock; however, it is also considered a trace 

nutrient. Concentrations above 390 mg/kg may result 

in adverse health effects in humans. Typical 

detection limits for field-portable XRF instruments 

range from 10 to 20 mg/kg. Most selenium is 

associated with sulfur or sulfide minerals, where 

concentrations can exceed 200 mg/kg. Selenium can 

be measured by both ICP-AES and XRF; however, 

detection limits using XRF usually exceed the 
__________________________________________________________________________________

7 

ecological risk-based screening levels for soil. 

Analytical results for selenium using ICP-AES and 

XRF are expected to be comparable. 

1.5.11 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 Vanadium 

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. 

1.5.13 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. 
__________________________________________________________________________________

8 

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9 

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 metalcontaminated 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. 
__________________________________________________________________________________________

10

Table 2-1. Nature of Contamination in Soil and Sediment at Sample Collection Sites 

Site-Specific Metals of Concern for 

Sample Collection Site Source of Contamination Matrix Sb As Cd Cr Cu Fe Pb Alton Steel, Alton, IL 

Steel manufacturing facility with metal arc furnace dust. The site also includes a metal scrap yard and a slag recovery facility. Soil X X X X X 

Burlington Northern–ASARCO Smelter Site, East Helena, MT 

Railroad yard staging area for smelter ores. Contaminated soils resulted from dumping and spilling concentrated ores. Soil X X X 

KARS Park – Kennedy Space Center, Merritt Island, FL 

Impacts to soil from historical facility operations and a former gun range. Soil X X X X X 

Leviathan Mine Site/Aspen Creek, Alpine County, CA 

Abandoned open-pit sulfur and copper mine that has contaminated a 9-mile stretch of 

mountain creeks, including Aspen Creek, with heavy metals. 

Soil and 

Sediment X X X X X 

Naval Surface Warfare Center, Crane Division, Crane, IN 

Open disposal and burning of general refuse and waste associated with aircraft maintenance. Soil X X X X X X X 

Ramsay Flats–Silver Bow Creek, Butte, MT 

Silver Bow Creek was used as a conduit for mining, smelting, industrial, and municipal wastes. 

Soil and 

Sediment X X X X X 

Sulphur Bank Mercury Mine 

Inactive mercury mine. Waste rock, tailings, and ore are distributed in piles throughout the property. Soil X X X 

Torch Lake Site (Great Lakes Area of Concern), Houghton County, MI 

Copper mining produced mill tailings that were dumped directly into Torch Lake, contaminating the lake sediments and shoreline. Sediment X X X X 

Wickes Smelter Site, Jefferson City, MT 

Abandoned smelter complex with contaminated soils and mineral-processing wastes, including remnant ore piles, decomposed roaster brick, slag piles and fines, and amalgamation sediments. Soil X X X X X X X 

Notes (in order of appearance in table): Sb: Antimony Cr: Chromium Pb: Lead Se: As: Arsenic Cu: Copper Hg: Mercury Ag: Cd: Cadmium Fe: Iron Ni: Nickel Zn: Note: Vanadium was not a chemical of concern at any of the sites and so does not appear on the table.
__________________________________________________________________________________

11

Table 2-2. Historical Analytical Data, Alton 

Steel Mill Site 

Metal Maximum Concentration (mg/kg) 

Arsenic 80.3 

Cadmium 97 

Chromium 1,551 

Lead 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, BNASARCO Smelter Site 

Metal Maximum Concentration (ppm) 

Arsenic 2,018 

Cadmium 876 

Lead 43,907 

2.3 Kennedy Athletic, Recreational and Social 

Park 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 Maximum Concentration (mg/kg) 

Antimony 8,500 

Arsenic 1,600 

Chromium 40.2 

Copper 290,000 

Lead 99,000 

Zinc 16,200 
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12

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 CaliforniaNevada 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 Maximum Concentration (mg/kg) 

Arsenic 2,510 

Cadmium 25.7 

Chromium 279 

Copper 837 

Nickel 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.
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13

Table 2-6. Historical Analytical Data, 

 NSWC Crane Division-Old Burn Pit 

Metal Maximum Concentration (mg/kg) 

Antimony 301 

Arsenic 26.8 

Cadmium 31.1 

Chromium 112 

Copper 1,520 

Iron 105,000 

Lead 16,900 

Mercury 0.43 

Nickel 62.6 

Silver 7.5 

Zinc 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 lowgradient 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 lowpermeability 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 Maximum Concentration (mg/kg) 

Arsenic 176 

Cadmium 141 

Copper 1,110 

Iron 20,891 

Lead 394 

Zinc 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. 
__________________________________________________________________________________

14

Table 2-8. Historical Analytical Data, Sulphur 

Bank Mercury Mine Site 

Metal Maximum Concentration 

(mg/kg) 

Antimony 3,724 

Arsenic 532 

Lead 900 

Mercury 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. 

Table 2-9. Historical Analytical Data, Torch 

Lake Superfund Site 

Metal Maximum Concentration,(mg/kg) 

Arsenic 40 

Chromium 90 

Copper 5,850 

Lead 325 

Mercury 1.2 

Selenium 0.7 

Silver 6.2 

Zinc 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 Maximum Concentration (mg/kg) 

Antimony 79 

Arsenic 3,182 

Cadmium 70 

Chromium 13 

Copper 948 

Iron 24,780 

Lead 33,500 

Nickel 7.3 

Silver 83 

Zinc 5,299 
__________________________________________________________________________________ 

 15 

Chapter 3 

Field Demonstration

The field demonstration required a sample set and a 

single location (the demonstration site) where all the 

technology developers could assemble to analyze the 

sample set under the oversight of the EPA/Tetra Tech 

field team. This chapter describes how the sample 

set was created, how the demonstration site was 

selected, and how the field demonstration was 

conducted. Additional detail regarding these topics is 

available in the Demonstration and Quality 

Assurance Project Plan (Tetra Tech 2005). 

3.1 Bulk Sample Processing 

A set of samples that incorporated a variety of soil 

and sediment types and target element concentrations 

was needed to conduct a robust evaluation. The 

demonstration sample set was generated from the 

bulk soil and sediment samples that were collected 

from the nine sample collection sites described in 

Chapter 2. Both contaminated (environmental) and 

uncontaminated (background) bulk samples of soil 

and sediment were collected at each sample 

collection site. The background sample was used as 

source material for a spiked sample when the 

contaminated sample did not contain the required 

levels of target elements. By incorporating a spiked 

background sample into the sample set, the general 

characteristics of the soil and sediment sample matrix 

could be maintained. At the same time, this spiked 

sample assured that all target elements were present 

at the highest concentration levels needed for a robust 

evaluation. 

3.1.1 Bulk Sample Collection and Shipping 

Large quantities of soil and sediment were needed for 

processing into well-characterized samples for this 

demonstration. As a result, 14 soil samples and 11 

sediment samples were collected in bulk quantity 

from the nine sample collection sites across the U.S. 

A total of approximately 1,500 kilograms of 

unprocessed soil and sediment was collected, which 

yielded more than 1,000 kilograms of soil and 

sediment after the bulk samples had been dried. 

Each bulk soil sample was excavated using clean 

shovels and trowels and then placed into clean, 

plastic 5-gallon (19-liter) buckets at the sample 

collection site. The mass of soil and sediment in each 

bucket varied, but averaged about 25 kilograms per 

bucket. As a result, multiple buckets were needed to 

contain the entire quantity of each bulk sample. 

Once it had been filled, a plastic lid was placed on 

each bucket, the lid was secured with tape, and the 

bucket was labeled with a unique bulk sample 

number. Sediment samples were collected in a 

similar method at all sites except at Torch Lake, 

where sediments were collected using a Vibracore or 

Ponar sediment sampler operated from a boat. Each 

5-gallon bucket was overpacked in a plastic cooler 

and was shipped under chain of custody via overnight 

delivery to the characterization laboratory, Applied 

Research and Development Laboratory (ARDL). 

3.1.2 Bulk Sample Preparation and 

Homogenization 

Each bulk soil or sediment sample was removed from 

the multiple shipping buckets and then mixed and 

homogenized to create a uniform batch. Each bulk 

sample was then spread on a large tray at ARDL’s 

laboratory to promote uniform air drying. Some bulk 

samples of sediment required more than 2 weeks to 

dry because of the high moisture content. 

The air-dried bulk samples of soil and sediment were 

sieved through a custom-made screen to remove 

coarse material larger than about 1 inch. Next, each 

bulk sample was mechanically crushed using a 

hardened stainless-steel hammer mill until the 

particle size was sub-60-mesh sieve (less than 0.2 

millimeters). The particle size of the processed bulk 

soil and sediment was measured after each round of 

crushing using standard sieve technology, and the 

particles that were still larger than 60-mesh were 

returned to the crushing process. The duration of the 

crushing process for each bulk sample varied based 

on soil type and volume of coarse fragments. 
__________________________________________________________________________________ 

 16 

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. 

Figure 3-1. Bulk sample processing diagram.
__________________________________________________________________________________ 

 17 

3.2 Demonstration 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. 

3.2.2 Spiked Samples

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. 
______________________________________________________________________________ 

 18 

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 40 – 400 400 – 2,000 >2,000 

Arsenic 20 – 400 400 – 2,000 >2,000 

Cadmium 50 – 500 500 – 2,500 >2,500 

Chromium 50 – 500 500 – 2,500 >2,500 

Copper 50 – 500 500 – 2,500 >2,500 

Iron 60 – 5,000 5,000 – 25,000 25,000 – 40,000 >40,000 

Lead 20 – 1,000 1,000 – 2,000 2,000 – 10,000 >10,000 

Mercury 20 – 200 200 – 1,000 >1,000 

Nickel 50 – 250 250 – 1,000 >1,000 

Selenium 20 – 100 100 – 200 >200 

Silver 45 – 90 90 – 180 >180 

Vanadium 50 – 100 100 – 200 >200 

Zinc 30 – 1,000 1,000 – 3,500 3,500 – 8,000 >8,000 

SEDIMENT 

Antimony 40 – 250 250 – 750 >750 

Arsenic 20 – 250 250 – 750 >750 

Cadmium 50 – 250 250 – 750 >750 

Chromium 50 – 250 250 – 750 >750 

Copper 50 – 500 500 – 1,500 >1,500 

Iron 60 – 5,000 5,000 – 25,000 25,000 – 40,000 >40,000 

Lead 20 – 500 500 – 1,500 >1,500 

Mercury 20 – 200 200 – 500 >500 

Nickel 50 – 200 200 – 500 >500 

Selenium 20 – 100 100 – 200 >200 

Silver 45 – 90 90 – 180 >180 

Vanadium 50 – 100 100 – 200 >200 

Zinc 30 – 500 500 – 1,500 >1,500 
______________________________________________________________________________ 

 19 

Table 3-2. Number of Environmental Sample Blends and Demonstration Samples 

Sampling Location Number of 

Sample Blends 

Number of 

Demonstration Samples 

Alton Steel Mill Site 2 10 

Burlington Northern-ASARCO East 

Helena Site 5 29 

Kennedy Athletic, Recreational and 

Social Park Site 6 32 

Leviathan Mine Site 7 37 

Naval Surface Warfare Center, Crane 

Division Site 1 5 

Ramsay Flats—Silver Bow Creek 

Superfund Site 7 37 

Sulphur Bank Mercury Mine Site 9 47 

Torch Lake Superfund Site 3 19 

Wickes Smelter Site 5 31 

TOTAL * 45 247 

 * 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 

Number of 

Spiked Sample 

Blends 

Number of 

Demonstration Samples 

Alton Steel Mill Site 1 3 

Burlington Northern-ASARCO East 

Helena Site 2 6 

Leviathan Mine Site 5 15 

Naval Surface Warfare Center, Crane 

Division Site 2 6 

Ramsey Flats—Silver Bow Creek 

Superfund Site 6 22 

Sulphur Bank Mercury Mine Site 3 9 

Torch Lake Superfund Site 4 12 

Wickes Smelter Site 2 6 

TOTAL * 25 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. 
_____________________________________________________________________________

 20 

3.3 Demonstration Site and Logistics 

The field demonstration occurred during the week of 

January 24, 2005. This section describes the 

selection of the demonstration site and the logistics of 

the field demonstration, including sample 

management. 

3.3.1 Demonstration Site Selection 

The demonstration site was selected from among the 

list of sample collection sites to simulate a likely field 

deployment. The following criteria were used to 

assess which of the nine sample collection sites might 

best serve as the demonstration site: 

• Convenience and accessibility to participants in 

the demonstration. 

• Ease of access to the site, with a reasonably sized 

airport that can accommodate the travel 

schedules for the participants. 

• Program support and cooperation of the site 

owner. 

• Sufficient space and power to support developer 

testing. 

• Adequate conference room space to support a 

visitors day. 

• A temperate climate so that the demonstration 

could occur on schedule in January. 

After an extensive search for candidates, the site 

selected for the field demonstration was KARS Park, 

which is part of the Kennedy Space Center on Merritt 

Island, Florida. KARS Park was selected as the 

demonstration site for the following reasons: 

• Access and Site Owner Support — 

Representatives from NASA were willing to 

support the field demonstration by providing 

access to the site, assisting in logistical support 

during the demonstration, and hosting a visitors 

day. 

• Facilities Requirements and Feasibility — The 

recreation building was available and was of 

sufficient size to accommodate all the 

demonstration participants. Furthermore, the 

recreation building had adequate power to operate 

all the XRF instruments simultaneously and all the 

amenities to fully support the demonstration 

participants, as well as visitors, in reasonable 

comfort. 

• Ease of Access to the Site — The park, located 

about 45 minutes away from Orlando 

International Airport, was selected because of its 

easy accessibility by direct flight from many 

airports in the country. In addition, many hotels 

are located within 10 minutes of the site along 

the coast at Cocoa Beach, in a popular tourist 

area. Weather in this area of central Florida in 

January is dry and sunny, with pleasant daytime 

temperatures into the 70s (F) and cool nights. 

3.3.2 Demonstration Site Logistics 

The field demonstration was held in the recreation 

building, which is just south of the gunnery range at 

KARS Park. Photographs of the KARS Park 

recreation building, where all the XRF instruments 

were set up and operated, are shown in Figures 3-2 

and 3-3. 

A visitors day was held on January 26, 2005 when 

about 25 guests came to the site to hear about the 

demonstration and to observe the XRF instruments in 

operation. Visitors day presentations were conducted 

in a conference building adjacent to the recreation 

building at KARS Park (see Figure 3-4). Presentations by NASA and EPA representatives were 

followed by a tour of the XRF instruments in the 

recreation building while demonstration samples 

were being analyzed. 

Figure 3-2. KARS Park recreation building. 
_____________________________________________________________________________

 21 

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 Management during the 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 
_____________________________________________________________________________

 22 

that might provide the developer’s field team any 

insight as to the nature or content of the sample. 

Spiked samples were integrated with the 

environmental samples in a random manner so that 

the spiked samples could not be distinguished. 

The demonstration sample set was divided into 13 

subsets, or batches, for tracking during the field 

demonstration. The samples provided to each 

developer’s field team were randomly distributed in 

two fashions. First, the order of the jars within each 

batch was random, so that the sample order for a 

batch was different for each developer’s field team. 

Second, the distribution of sample batches was 

random, so that each developer’s field team received 

the sample batches in a different order. 

The observer provided the developer’s field team 

with one batch of samples at a time. When the 

developer’s field team reported that analysis of a 

batch was complete, the observer would reclaim all 

the unused sample material from that batch and then 

provide the next batch of samples for analysis. 

Chain-of-custody forms were used to document all 

sample transfers. When the analysis of all batches 

was complete, the observer assisted the developer’s 

field team in cleanup of the work area and 

repackaging the instrument and any associated 

equipment. The members of the developer’s field 

team were not allowed to take any part of the 

demonstration samples with them when they left the 

demonstration site. 

Samples that were not in the possession of the 

developer’s field team during the demonstration were 

held in a secure storage room adjacent to the 

demonstration work area (see Figure 3-5). The 

storage room was closed and locked except when the 

observer retrieved samples from the room. Samples 

were stored at room temperature during the 

demonstration, in accordance with the quality 

assurance/quality control (QA/QC) requirements 

established for the project. 

Figure 3-5. Sample storage room. 

3.3.5 Data Management 

Each of the developer’s field teams was able to 

complete analysis of all 326 samples during the field 

demonstration (or during the subsequent week, in one 

case when the developer’s field team arrived late at 

the demonstration site because of delays in 

international travel). The data produced by each 

developer’s field team were submitted during or at 

the end of the field demonstration in a standard 

Microsoft Excel® spreadsheet. (The EPA/Tetra Tech 

field team had provided a template.) Since each 

instrument provided data in a different format, the 

developer’s field team was responsible for reducing 

the data before they were submitted and for 

transferring the data into the Excel spreadsheet. 

The observer reviewed each data submittal for 

completeness, and the data were then uploaded into a 

master Excel spreadsheet on a laptop computer for 

temporary storage. Only the EPA/Tetra Tech field 

team had access to the master Excel spreadsheet 

during the field demonstration. 

Once the EPA/Tetra Tech field team returned to their 

offices, the demonstration data were transferred to an 

Microsoft Access® database for permanent storage. 

Each developer’s data, as they existed in the Access 

database, were then provided to the developer for 

review. Any errors the developers identified were 

corrected, and the database was then finalized. All 

statistical analysis and data evaluation took place on 

this final database.
_______________________________________________________________________________________

 23

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. 
__________________________________________________________________________________

 24

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 — Method 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-1,1-α=0.99)(s) 

 where 

MDL = method detection limit 

t = Student’s t value for a 99 

percent confidence level and 

a standard deviation estimate 

with n-1 degrees of freedom 

 n = number of samples 

s = standard deviation. 

Table 4-1. Evaluation Objectives 

Objective Description 

Primary Objective 1 Determine the MDL for each target element.

Primary Objective 2 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.

Primary Objective 3 Evaluate the precision of XRF measurements for a variety of contaminated soil and 

sediment samples.

Primary Objective 4 Evaluate the effect of chemical and spectral interference on measurement of target 

elements. 

Primary Objective 5 Evaluate the effect of soil characteristics on measurement of target elements.

Primary Objective 6 Measure sample throughput for the measurement of target elements under field 

conditions. 

Primary Objective 7 Estimate the costs associated with XRF field measurements. 

Secondary Objective 1 Document the skills and training required to properly operate the instrument.

Secondary Objective 2 Document health and safety concerns associated with operating the instrument.

Secondary Objective 3 Document the portability of the instrument.

Secondary Objective 4 Evaluate the instrument’s durability based on its materials of construction and 

engineering design.

Secondary Objective 5 Document the availability of the instrument and of associated customer technical 

support. 
__________________________________________________________________________________

 25

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:
__________________________________________________________________________________

 26 

___(MR – MD)_______

RPD = average (MR, MD) 

where 

MR = the mean reference 

laboratory measurement 

MD = 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: 

x 100

C

SD RSD =

where 

RSD = Relative standard deviation 

SD = Standard deviation 

C = Mean concentration. 

The standard deviation was calculated using the 

equation: 

( ) 2

1

1

2

1

1





 



 − − = ∑=

n

k

k CC

n

SD

where 

SD = Standard deviation 

n = Number of replicate 

 samples 

Ck = Concentration of sample K 

C = Mean concentration. 

The following specific procedure for data analysis 

was followed for each of the 13 target elements to 

assess XRF instrument precision: 

1. The RSD for the replicate samples in a blend was 

calculated for both data from the XRF instrument 

and the reference laboratory. Since there were 70 

sample blends, this step created a maximum of 

70 paired RSDs for the assessment. 
__________________________________________________________________________________

 27 

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 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. 
__________________________________________________________________________________

 28 

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, xray film, Mylar®, reagents, and personal protective 

equipment. The rate that the supplies are consumed 

was monitored and recorded during the field 

demonstration. The cost of analytical supplies was 

estimated per sample from these consumption data 

and information on unit costs. 

Labor includes the time required to prepare and 

analyze the samples and to set up and dismantle the 

equipment. The labor hours associated with 

preparing and analyzing samples and with setting up 

and dismantling the equipment were recorded during 

the demonstration. The labor costs were calculated 

based on this information and typical labor rates for a 

skilled technician or chemist. 

In addition to the assessment of the above-described 

individual cost components, an overall cost for a field 

effort similar to the demonstration was compiled and 

compared to the cost of fixed laboratory analysis. 

The results of the cost evaluation are presented in 

Chapter 8. 

4.2.8 Secondary Objective 1 — Training 

 Requirements 

Each XRF instrument requires that the operator be 

trained to safely set up and operate the instrument. 

The relative level of education and experience that is 

appropriate to operate the XRF instrument was 

assessed during the field demonstration. 

The amount of specific training required depends on 

the complexity of the instrument and the associated 

software. Most developers have established training 

programs. The time required to complete the 

developer’s training program was estimated and the 

content of the training was identified.
__________________________________________________________________________________

 29 

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 Secondary 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 Secondary 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 Secondary Objective 5 — Availability 

The availability of the instrument from the developer, 

distributors, and rental agencies was documented. 

The availability of replacement parts and instrumentspecific 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 
__________________________________________________________________________________

 30 

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 easyto-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. 
______________________________________________________________________________ 

 31 

Chapter 5 

Reference Laboratory 

As described in Chapter 4, a critical part of the 

evaluation was the comparison of the results obtained 

for the demonstration sample set by the XRF 

instrument with the results obtained by a fixed 

laboratory (the reference laboratory) using 

conventional analytical methods. Therefore, a 

significant effort was undertaken to ensure that data 

of the highest quality were obtained as the reference 

data for this demonstration. This effort included 

three main activities: 

• Selection of the most appropriate methods for 

obtaining reference data, 

• Selection of a high-quality reference laboratory, 

and 

• Validation of reference laboratory data and 

evaluation of QA/QC results. 

This chapter describes the information that confirms 

the validity, reliability, and usability of the reference 

laboratory data based on each of the three activities 

listed above (Sections 5.1, 5.2, and 5.3). Finally, this 

chapter presents conclusions (Section 5.4) on the 

level of data quality and the usability of the data 

obtained by the reference laboratory. 

5.1 Selection of Reference Methods 

Methods for analysis of elements in environmental 

samples, including soils and sediments, are well 

established in the environmental laboratory industry. 

Furthermore, analytical methods appropriate for soil 

and sediment samples have been promulgated by 

EPA in the compendium of methods, Test Methods 

for Evaluating Solid Waste, Physical/Chemical 

Methods (SW-846) (EPA 1996c). Therefore, the 

methods selected as reference methods for the 

demonstration were the SW-846 methods most 

typically applied by environmental laboratories to 

soil and sediment samples, as follows: 

• Inductively coupled plasma-atomic emission 

spectroscopy (ICP-AES), in accordance with 

EPA SW-846 Method 3050B/6010B, for all 

target elements except mercury 

• Cold vapor atomic absorption (CVAA) 

spectroscopy, in accordance with EPA SW-846 

Method 7471A, 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 6010B 

(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 (ICPMS) 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 
______________________________________________________________________________ 

 32 

that might bias 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 3050B was selected as the 

preparation method and involves digestion of the 

matrix using a combination of nitric and hydrochloric 

acids, with the addition of hydrogen peroxide to 

assist in degrading organic matter in the samples. 

Method 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 onsite 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. 
______________________________________________________________________________ 

 33 

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 Relative 

Importance 

Audits (on site) 40% 

Performance evaluation 

samples, including data package 

and electronic data deliverable 

50% 

Price 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 3050B/6010B 

and by CVAA using EPA SW-846 Method 7471A. 

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. 
______________________________________________________________________________ 

 34 

Only a small percentage of the reference laboratory 

data set was qualified as undetected as a result of 

blank contamination (3.3 percent) and estimated 

because of matrix spike and matrix spike duplicate 

(MS/MSD) recoveries (8.7 percent) and serial 

dilutions results (2.5 percent). Table 5.1 summarizes 

the number of validation qualifiers applied to the 

reference laboratory data according to QC type. Of 

the three QC types, only the MS/MSD recoveries 

warranted additional evaluation. The MS/MSD 

recoveries for antimony were marginally low 

(average recovery of 70.8 percent) when compared 

with the QC criterion of 75 to 125 percent recovery. 

It was concluded that low recoveries for antimony are 

common in analysis of soil and sediment by the 

prescribed methods and likely result from 

volatilization during the vigorous acid digestion 

process or spectral interferences found in soil and 

sediments matrices (or both). In comparison to 

antimony, high or low recoveries were observed only 

on an isolated basis for the other target metals (for 

example, lead and mercury) such that the mean and 

median percent recoveries were well within the 

required range. Therefore, the project team decided 

to evaluate the XRF data against the reference 

laboratory data for all 13 target elements and to 

evaluate the XRF data a second time against the ERA 

certified spike values for antimony only. These 

comparisons are discussed in Section 7.1. However, 

based on the validation of the complete reference 

data set and the low occurrence of qualified data, the 

reference laboratory data set as a whole was declared 

of high quality and of sufficient quality to make valid 

comparisons to XRF data. 

5.3.2 Reference Laboratory Technical 

 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 3050B and 6010B and for 

total mercury by EPA Method 7471A. All decisionmaking 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 ERAcertified 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 
______________________________________________________________________________ 

 35 

comparing the “certified values” for the spiked 

samples with the reference laboratory results are 

shown in Table 5-2. The target for percent recovery 

was 75 to 125 percent. The mean percent recoveries 

for 12 of the 13 target elements were well within this 

accuracy goal. Only the mean recovery for antimony 

was outside the goal (26.8 percent). The low mean 

percent recovery for antimony supported the 

recommendation made by the project team to conduct 

a secondary comparison of XRF data to ERAcertified 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 

Number and Percentage of Qualified Results per QC type 1

Method Blank MS/MSD Serial Dilution 

Element Number Percent2

 Number Percent2 Number Percent2

Antimony 5 1.5 199 61.0 8 2.4 

Arsenic 12 3.7 3 0.9 10 3.1 

Cadmium 13 4.0 0 0 6 1.8 

Chromium 0 0 0 0 10 3.1 

Copper 1 0.3 0 0 8 2.4 

Iron 0 0 0 0 10 3.1 

Lead 0 0 34 10.5 11 3.4 

Mercury 68 20.9 31 9.5 4 1.2 

Nickel 0 0 0 0 10 3.1 

Selenium 16 4.9 0 0 3 0.9 

Silver 22 6.7 102 31.3 7 2.1 

Vanadium 0 0 0 0 9 2.8 

Zinc 1 0.3 0 0 10 3.1 

Totals 138 3.3 369 8.7 106 2.5 

Notes: 

MS Matrix spike. 

MSD Matrix spike duplicate. 

QC Quality control. 

1

 This table presents the number of “U” (undetected) and “J” (estimated) qualifiers added to the 

reference laboratory data during data validation. Though so qualified, these results are considered 

usable for the demonstration. As is apparent in the “Totals” row at the bottom of this table, the 

amount of data that required qualifiers for any specific QC type was invariably less than 10 percent. 

No reference laboratory data were rejected (that is, qualified “R”) during the data validation. 

2

 Percents for individual elements are calculated based on 326 results per element. Total 

 percents at the bottom of the table are calculated based on the total number of results for all 

 elements (4,238).
__________________________________________________________________________________ 

 36 

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. 
__________________________________________________________________________________________

37

Table 5-2. Percent Recovery for Reference Laboratory Results in Comparison to ERA Certified Spike Values for Ble

Statistic Sb As Cd Cr Cu Fe Pb Hg Ni Se Ag 

Number of %R values 16 14 20 12 20 NC 12 15 16 23 20 Minimum %R 12.0 65.3 78.3 75.3 51.7 NC 1.4 81.1 77.0 2.2 32.4 Maximum %R 36.1 113.3 112.8 108.6 134.3 NC 97.2 243.8 116.2 114.2 100.0 Mean %R1 26.8 88.7 90.0 94.3 92.1 NC 81.1 117.3 93.8 89.9 78.1 Median %R1 28.3 90.1 87.3 97.3 91.3 NC 88.0 93.3 91.7 93.3 84.4 

Notes: 

1Values 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 
__________________________________________________________________________________________

38

Table 5-3. Precision of Reference Laboratory Results for Blends 1 through 70 

Statistic Sb As Cd Cr Cu Fe Pb Hg Ni Se Ag 

Number of %RSDs 43 69 43 69 70 70 69 62 68 35 4Minimum %RSD 1.90 0.00 0.91 1.43 0.00 1.55 0.00 0.00 0.00 0.00 1.0Maximum %RSD 78.99 139.85 40.95 136.99 45.73 46.22 150.03 152.59 44.88 37.30 54.2Mean %RSD1 17.29 13.79 12.13 11.87 10.62 10.56 14.52 16.93 10.28 13.24 12.8Median %RSD1 11.99 10.01 9.36 8.29 8.66 8.55 9.17 7.74 8.12 9.93 8.8Notes: 1Values 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 
________________________________________________________________________________________ 

 39 

Chapter 6 

Technology Description 

The ZSX Mini II XRF analyzer is manufactured by 

Rigaku, Inc. This chapter provides a technical 

description of the ZSX Mini II based on information 

obtained from Rigaku and observation of this 

analyzer during the field demonstration. This section 

also identifies a Rigaku company contact, where 

additional technical information may be obtained. 

6.1 General Description 

The ZSX Mini II is a wavelength-dispersive XRF 

analyzer that operates differently from an energydispersive XRF analyzer. Wavelength-dispersive 

XRF analyzers differentiate the x-ray energies 

emitted from a sample by dispersing the x-rays into 

different wavelength ranges using crystals. 

Conversely, energy-dispersive XRF analyzers 

differentiate between x-ray energies emitted based on 

the voltages measured by the detector. For some 

applications, wavelength-dispersive XRF analyzers 

can achieve high resolutions and good sensitivity. 

For example, laboratory-grade wavelength-dispersive 

XRF analyzers have resolved significant 

concentrations of arsenic and lead in many sample 

matrixes that pose challenges to energy-dispersive 

instruments. 

Wavelength-dispersive XRFs have historically 

been large, laboratory-bound instruments with 

significant requirements for power and cooling. 

The ZSX Mini II, however, is a smaller, 

transportable unit that can operate without 

additional cooling fluids on standard 110-volt 

circuits. The unit can employ an economical 

gas proportional counter as a detector rather than a 

diode detector with a multi-channel analyzer (used by 

energy-dispersive analyzers) because wavelength 

resolution is achieved with the crystals. The ZSX 

Mini II is shown in a benchtop configuration in 

Figure 6-1. Technical specifications for the ZSX 

Mini II are presented in Table 6-1. 

Figure 6-1. Rigaku ZSX Mini II XRF analyzer set 

up for bench-top analysis. 

6.2 Instrument Operations during the 

Demonstration 

The ZSX Mini II and accessories were shipped by a 

professional freight service to the demonstration site 

in two wooden shipping crates with styrofoam 

padding. The ZSX Mini II is transportable; however, 

a sturdy table is required for bench-top configuration 

because it weighs approximately 260 pounds (120 

kg). Peripheral equipment included the 12-position 

sample changer; a vacuum pump used to evacuate the 

sample chamber to reduce formation of oxides in the 

sample matrix; and a personal computer (PC) loaded 

with Microsoft Windows XP® and the ZSX Mini II 

calibration and operational software. 

6.2.1 Setup and Calibration 

Rigaku assembled the ZSX Mini II and initialized the 

application software in about 1.5 hours. An 

experienced technician can set up the analyzer in 1 to 

2 hours; an inexperienced technician may need 2 to 3
________________________________________________________________________________________ 

 40 

Table 6-1. Rigaku ZSX Mini II XRF Technical Specifications 

 Weight: 260 pounds (120 kg). 

 Dimensions: 570 millimeters (mm) wide, 500 mm deep, 250 mm high 

 Excitation Source: 50-Watt, 40-kilovolt (kV), 1.25-milli-amp, air-cooled endwindow x-ray tube (with palladium or rhodium as an anode 

material). 

 X-ray Optics: Analyzing crystals for x-ray dispersion include lithium fluoride 

(LiF), pentaerythritol (PeT), and thallium acid phthalate (TAP) 

operating on a revolving changer. Optional crystals include 

RX35 and germanium. 

 Detector: Scintillation detector for analysis of titanium through uranium. 

Can be equipped with a gas proportional counter for light 

elements, requiring management of argon/methane carrier gas. 

Optional vacuum or helium environments for enhanced 

performance in analyzing light elements. 

 Signal Processing: Digital signal processing unit. 

 Software: Windows XP-based, multi-function software package for 

instrument control, spectra accumulation, calibration, and 

quantification (includes fundamental parameters methods). 

 Element Range: From fluorine to uranium. 

Operating Environment: Temperature: 15 to 28 °C; less than 75 percent relative humidity 

(non-condensing). 

 Sample Container: 25-mm plastic sample cups with polypropylene windows. 

 Variants: ZSX Mini II with single sample changer. (Sample spinner is 

available.) 

ZSX Mini II with 12-position sample changer. 

ZSX Mini II can be adapted to accommodate oversize or 

irregular objects. 

 Power: AC single phase 110 Volts, 10 Amps, 50/60 Hertz 

hours for setup. A factory-new XRF analyzer may 

take 4 to 6 hours to uncrate, set up, and initialize all 

computer software. The Rigaku XRF analyzer 

software was observed to be self-explanatory in terms 

of analyzer start up. Menus guided the user through 

turning on the x-ray tube and initializing the XRF 

spectrometer optics and detector. The 13 individual 

elements, their characteristic energy wavelengths for 

monitoring, and the units of measure were selected 

using the software. 

The ZSX Mini II can be calibrated using the 

fundamental parameters procedure or empirically 

using reference standards and site-specific calibration 

materials. The ZSX Mini II used the factory 

calibration for this demonstration and verified the 

results using a calibration reference material provided 

by the U.S. Geological Survey. After the analyzer 

was set up at the demonstration site, the stored 

calibration curve information was used to calibrate 

the instrument, and known reference materials were 

analyzed to verify that the calibration curve was 

loaded. A single empirical calibration curve was 

used for all analysis during the demonstration. Other 

quality control samples used during the 

demonstration included a silicon dioxide blank and 

other standard reference materials as calibration 

verification checks. 
__________________________________________________________________________________ 

 41 

6.2.2 Demonstration Sample Processing 

Rigaku sent a two-man team to the demonstration site 

to process the demonstration samples using the ZSX 

Mini II. The field team including an instrument 

applications specialist, who operated the instrument 

and reduced the data, and a sales representative, who 

served as the sample preparation technician. 

Sample preparation by Rigaku for this demonstration 

involved assembling the polypropylene sample cups; 

attaching a snap ring to support a Mylar® film across 

one end, filling the cup with the sample, and 

attaching a Teflon® film across the other end (see 

Figure 6-2). The Teflon® film was perforated to 

allow venting and minimize rupture of the sample 

when a vacuum was applied during analysis. A 

unique sample identification (ID) number was 

marked in permanent marker on the Teflon® film for 

sample identification. The sequence of events for 

each sample batch involved: 

• Loading a batch of 12 sample cups into the 12-

position sample changer and placing it into the 

XRF analyzer (see Figure 6-3). 

• Starting the XRF analysis included sequential 

readings of wavelength and the intensity of the 

characteristic fluorescence produced by each 

sample. The intensity of the fluorescence at the 

characteristic wavelength for each element was 

converted to milligrams per kilogram based on 

the calibration. 

• Reviewing the data after the sample batch had 

been analyzed and verifying the sample ID 

numbers. 

• Downloading data for each sample batch onto a 

Microsoft Excel® spreadsheet. 

• Transferring the daily results from the ZSX Mini 

II data processor to a USB portable storage 

device for transfer to the demonstration oversight 

team. 

Each day, the results from the previous day were 

transferred to the Tetra Tech demonstration team via 

a USB portable storage drive. 

Figure 6-2. Rigaku technician filling a sample cup 

for analysis. 

Figure 6.3. Samples placed into the 12-position 

sample changer awaiting analysis. 

6.3 General Demonstration Results 

Rigaku analyzed all 326 soil and sediment samples in 

4 days using the ZSX Mini II wavelength-dispersive 

XRF analyzer. Rigaku was able to prepare, analyze, 

and report 80 to 90 samples in a 12-hour day during 

the demonstration. (Rigaku had expected to analyze 

about 120 to 150 samples each day.) 

Data processing for the demonstration samples was 

completed within the ZSX Mini II data processor that 

is part of the XRF analyzer. The ZSX Mini II data 

processor stopped acquiring data several times during 

the demonstration, which required re-analysis of 
__________________________________________________________________________________ 

 42 

entire sample batches. Data acquisition issues 

continued to plague the analyzer even after the ZSX 

Mini II computer had been replaced, new application 

names for each batch had been created and saved, 

and smaller batch sizes run. The computer issue was 

random, except that it always stopped while the 

instrument was analyzing for vanadium. It was 

unclear whether the issue was related to hardware or 

software. 

6.4 Contact Information 

Additional information on Rigaku’s ZSX Mini II 

XRF analyzer is available from the following source: 

Mr. Jose Brum 

Rigaku Inc. 

14 Ruth Circle 

Haverhill, Massachusetts 01832 

Telephone: (978) 374-7725 

Email: jbrum@RigakuMSC.com
______________________________________________________________________________

 43 

Chapter 7 

Performance Evaluation 

As discussed in Chapter 6, Rigaku analyzed all 326 

demonstration samples of soil and sediment at the 

field demonstration site between January 24 and 27, 

2005. A complete set of electronic data in Microsoft 

Excel® spreadsheet format was delivered to the EPA 

and Tetra Tech field team before Rigaku demobilized 

from the site on January 28, 2005. All data Rigaku 

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 data set for the ZSX Mini II 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. Rigaku 

reported the instrument response for each target 

element in each sample; the instrument response — 

whether positive or negative — was used to calculate 

the MDL. 

The MDLs calculated for the ZSX Mini II are 

presented in Table 7-1. As shown, the data for the 

MDL blends allowed between eight and 12 individual 

MDLs to be calculated for each target element. (Iron 

was not included in the MDL evaluation, as was 

discussed in Section 4.2.1.) The mean MDLs in 

Table 7-1 are classified as follows: 

• Very low (1 to 20 ppm): copper, mercury, 

nickel, selenium, and zinc. 

• Low (20 to 50 ppm): arsenic, lead, silver, and 

vanadium. 

• Medium (50 to 100 ppm): antimony, cadmium, 

and chromium. 

• High (greater than 100 ppm): none. 

Instrument response remained fairly consistent, with 

very few extreme values, for the target elements in 

the “very low” and “low” categories. No trends 

could be discerned in terms of sample matrix (soil 

versus sediment) or blend. For antimony and 

cadmium, however, the MDLs may be inflated by 

analytical results that were biased high. For the 12 

MDL sample blends, the ZSX Mini II measured 

concentrations of antimony that ranged from 124 

ppm to 565 ppm with a mean of 283 ppm, while the 

reference laboratory reported seven non-detect 

concentrations and a maximum concentration of 118 

ppm. Similarly, the ZSX Mini II measured 

concentrations of cadmium that ranged from 328 ppm 

to 896 ppm with a mean of 609 ppm, while the 

reference laboratory reported six non-detect 

concentrations and a maximum concentration of 91 

ppm. It is possible that a systematic high bias in the 

ZSX Mini II was a cause of the high MDLs for 

antimony and cadmium. (The correlation plots in 

Section 7.2 below also indicated positive biases at 

low concentrations for these and other target 

elements.) The mean MDL for chromium (61 ppm) 

appears to reasonably represent true instrument 

sensitivity for this element because the 

concentrations reported from the ZSX Mini II for the 

detection limit blends did not illustrate any major 

discrepancies when compared to the results from the 

reference laboratory. 
_____________________________________________________________________________________________

Draft Final 44 

Table 7-1. Evaluation of Sensitivity — Method Detection Limits for the ZSX Mini II1

 Antimony Arsenic Cadmium 

Matrix Blend No. 

Calc. 

MDL2

ZSX Mini 

Conc.3

Ref. Lab 

Conc4

Calc. 

MDL2

ZSX Mini 

Conc. 3

Ref. Lab 

Conc. 4

Calc. 

MDL2

ZSX Mini 

Conc. 3

Ref. Lab 

Conc. 4

Ca

MD

Soil 2 111 451 17 34 102 1.5 118 896 ND 1Soil 5 43 159 ND 45 58 47 34 603 1.9 6Soil 6 77 456 8 NC 213 477 35 578 12 4Soil 8 306 450 118 NC 1,537 3,943 32 328 91 7Soil 10 66 211 ND 44 48 39 109 661 0.96 6Soil 12 105 565 62 NC 306 559 NC 671 263 9Soil 18 65 200 ND 20 17 9 60 601 ND 3Sediment 29 41 124 ND 20 -21 10 41 490 ND 3Sediment 31 43 170 ND 40 -11 11 30 534 ND 5Sediment 32 40 191 ND 22 34 31 62 618 ND 3Sediment 39 45 208 ND 61 13 14 41 645 ND 4Sediment 65 92 205 11 NC 181 250 62 681 44 NMean 86 36 57 6

Copper Lead Mercury 

Matrix Blend No. 

Calc. 

MDL2

ZSX Mini 

Conc. 3

Ref. Lab 

Conc. 4

Calc. 

MDL2

ZSX Mini 

Conc. 3

Ref. Lab 

Conc. 4

Calc. 

MDL2

ZSX Mini 

Conc. 3

Ref. Lab 

Conc. 4

Ca

MD

Soil 2 15 60 47 NC 780 1,200 18 62 ND 1Soil 5 13 42 49 17 6 78 8 26 ND Soil 6 9 99 160 NC 1,993 3,986 11 27 0.83 1Soil 8 NC 739 1,243 NC 17,262 33,429 13 19 15 Soil 10 10 25 31 13 -14 72 15 27 0.14 Soil 12 NC 494 747 NC 2,180 4,214 21 26 1.8 1Soil 18 5 30 50 26 -50 17 15 44 56 1Sediment 29 NC 930 1,986 27 -65 33 17 6 0.24 Sediment 31 NC 708 1,514 22 -56 51 27 15 ND 1Sediment 32 11 27 36 20 -38 26 7 32 ND Sediment 39 13 68 94 20 -29 27 31 48 ND 1Sediment 65 8 56 69 19 -22 25 21 58 32 2Mean 11 21 17 1
_____________________________________________________________________________________________

Draft Final 45 

Table 7-1. Evaluation of Sensitivity — Method Detection Limits for the ZSX Mini II1 (Continued

Selenium Silver Vanadium 

Matrix Blend No. 

Calc. 

MDL2

ZSX Mini 

Conc. 3

Ref. Lab 

Conc. 4

Calc. 

MDL2

ZSX Mini 

Conc. 3

Ref. Lab 

Conc 4

Calc. 

MDL2

ZSX Mini 

Conc. 3

Ref. Lab 

Conc. 4

Ca

MD

Soil 2 4 16 ND 37 305 ND 14 22 1.2 2Soil 5 3 8 ND 20 207 0.93 29 73 55 1Soil 6 4 8 ND 15 196 14 24 69 56 NSoil 8 4 17 ND 8 115 144 16 59 34 NSoil 10 3 6 ND 22 226 ND 21 67 51 2Soil 12 4 11 15 19 201 38 19 62 45 NSoil 18 3 6 ND 17 207 ND 41 119 67 Sediment 29 4 1 ND 24 170 ND 22 141 96 1Sediment 31 3 2 ND 9 188 6.2 17 122 76 Sediment 32 4 7 4.6 18 215 ND 12 85 57 3Sediment 39 8 10 ND 27 217 ND 15 55 38 1Sediment 65 6 16 22 30 226 41 15 51 31 NMean 4 21 20 1

Notes: 1 Detection limits and concentrations are milligrams per kilogram (mg/kg), or parts per million (ppm). 2 Cells that appear in bold typeface show MDLs calculated for the ZSX Mini II from the 12 MDL sample blends in this t3 This column lists the mean concentration reported for this MDL sample blend by the ZSX Mini II. 4 This column lists the mean concentration reported for this MDL sample blend by the reference laboratory. 

Calc. Calculated. Conc. Concentration. MDL Method detection limit. NC The MDL was not calculated because reference laboratory concentrations exceeded five times the expected MDL rang

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 

for calculating the MDL for this element. 

Ref. Lab. Reference laboratory. 
__________________________________________________________________________________

 46 

The mean MDLs calculated for the ZSX Mini II are 

compared in Table 7-2 with the mean MDLs for all 

eight XRF instruments that participated in the 

demonstration and with the mean MDLs derived 

from performance data presented in EPA Method 

6200 (EPA 1998e). As shown, the mean MDLs for 

the ZSX Mini II are generally lower than were 

calculated from EPA Method 6200 data. The 

exception is antimony where, as noted above, high 

bias for the ZSX Mini II data appears to have 

produced a mean MDL that is higher than the 

available Method 6200 data. When compared with 

the all-instrument mean MDLs, the ZSX Mini II 

exhibited high relative mean MDLs for antimony and 

arsenic. Mean MDLs for the ZSX Mini II were less 

than one-half the all-instrument means for copper, 

nickel, selenium, silver, and zinc. 

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, were adequate for all the target 

elements and ranged from 24 (mercury) to 70 (iron). 

RPDs between the mean concentrations obtained 

from the ZSX Mini II 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 of 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-1). 

Table 7-2. Comparison of ZSX Mini II MDLs to All–Instrument Mean MDLs and EPA Method 6200 Data1 

Element 

ZSX Mini II 

Mean MDLs2

All XRF Instrument 

Mean MDLs3

EPA Method 6200 

Mean Detection Limits4

Antimony 86 61 55 5

Arsenic 36 26 92 

Cadmium 57 70 NR 

Chromium 61 83 376 

Copper 11 23 171 

Lead 21 40 78 

Mercury 17 23 NR 

Nickel 11 50 100 5

Selenium 4 8 NR 

Silver 21 42 NR 

Vanadium 20 28 NR 

Zinc 16 38 89 

Notes: 

1

 Detection limits are in units of milligrams per kilogram (mg/kg), or parts per million (ppm). 

2

 The mean MDLs calculated for this technology demonstration, as presented in Table 7-1. 

3

 The mean MDLs calculated for all eight XRF instruments that participated in the technology demonstration. 

4

 Mean values calculated from Table 4 of Method 6200 (EPA 1998e, www.epa.gov/sw-846). 

5

 Only one value reported. 

EPA U.S. Environmental Protection Agency. 

MDL Method detection limit. 

NR Not reported; no MDLs reported for this element. 
__________________________________________________________________________________

 47 

Accuracy was classified as follows for the target 

elements based on the overall median RPDs: 

• Very good: (median RPD less than 10 percent): 

none. 

• Good (median RPD between 10 and 25 percent): 

none. 

• Fair (median RPD between 25 percent and 50 

percent): arsenic, chromium, copper, silver, 

vanadium, and zinc. 

• Poor (median RPD greater than 50 percent): 

antimony, cadmium, iron, lead, mercury, nickel, 

and selenium. 

The highest overall median RPD of 101 percent was 

calculated for selenium. 

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 (Table E-1). The ability to 

evaluate the classification by medium (soil versus 

sediment) or by concentration range is limited by the 

variability of the data set. 

The only significant difference or trend noted in 

terms of sample matrix or concentration levels were 

low relative median RPDs in the Level 1 

concentration samples when compared with the 

higher concentration levels. This effect was observed 

for a majority of the target elements (10 of 13) in soil 

and a smaller number (four) in sediment. For many 

target elements (arsenic, chromium, copper, iron, 

lead, selenium, and zinc), the effect was significant 

with median RPDs falling into the “good” to “very 

good” categories as compared with generally “poor” 

accuracy in the higher concentration levels. This 

observation implies that the ZSX Mini II may 

provide greater accuracy for less complex sample 

matrixes that contain lower concentrations of target 

elements. The developer may need to further refine 

instrument calibration and quantitation algorithms to 

better analyze samples that contain high 

concentrations of multiple target elements. 

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 by 

volatilization of the antimony compounds used for 

spiking, resulting in loss of antimony during the 

sample digestion process at the reference laboratory. 

Therefore, Table 7-3 includes a second accuracy 

evaluation for antimony, comparing the results from 

the ZSX Mini II with the ERA-certified values. 

However, use of these values did not improve the 

RPDs for antimony. 

As an additional comparison, Table 7-3 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-1). Table 7-3 indicates that 

the median RPDs for the ZSX Mini II were well 

above the all-instrument medians for 12 of the 13 

target elements (vanadium was the only exception). 

These observations included the RPDs for antimony 

calculated versus the ERA-certified spike values, 

which were significantly lower than the RPDs versus 

the reference laboratory data for many of the other 

XRF instruments participating in the demonstration. 

In addition to calculating RPDs, the evaluation of 

accuracy included preparing linear correlation plots 

of ZSX Mini II concentration values against the 

reference laboratory values. These plots are 

presented for the individual target elements in 

Figures E-1 through E-13 of Appendix E. The plots 

include a 45-degree line that shows the “ideal” 

relationship between the ZSX Mini II 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 indicates 

that no target elements met all three accuracy criteria. 
__________________________________________________________________________________

 48 

Figure 7-1: Linear correlation plot for lead

 indicating low instrument bias.

y = 0.54x - 92.44

R2 = 0.99

0

5000

10000

15000

20000

25000

30000

35000

40000

0 5000 10000 15000 20000 25000 30000 35000 40000

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)

The correlation coefficients for arsenic, chromium, 

copper, iron, lead, mercury, nickel, selenium, and 

zinc were greater than 0.9, indicating a consistent 

instrument response to differences in concentration. 

However, the slopes (m) for each of these target 

elements were between 0.27 and 0.59, indicating a 

consistent low bias. Furthermore, only copper had a 

y-intercept that was less than the detection limit. A 

correlation plot for lead is presented in Figure 7-1 as 

an example of representative instrument performance 

for this group of target elements. 

Overall correlation of the ZSX Mini II data with the 

reference laboratory was low for antimony, cadmium, 

silver, and vanadium. High intercepts combined with 

low slopes for cadmium and vanadium actually 

meant that a significant positive bias changed to a 

significant negative bias as concentrations increased 

for these elements. The correlation coefficients for 

antimony and silver were 0.1 or less, indicating that 

the instrument response essentially did not correlate 

with the reference laboratory data. On this basis, it 

appears that the ZSX Mini II does not provide 

accurate data for antimony and silver, in that its data 

cannot be correlated with other reference methods. 

The correlation plot for silver is presented in Figure 

7-2 as an example. 
 ________________________________________________________________________________________________

49

Table 7-3. Evaluation of Accuracy — Relative Percent Differences Versus Reference Laboratory Data for the 

Sample Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Selenium 

Matrix Group Statistic Ref Lab ERA Spike Soil Level 1 Number 8 1 8 7 23 16 5 4 7 23 4 

Median 161.2% 84.9% 14.0% 116.1% 21.0% 32.2% 93.3% 84.1% 24.3% 50.0% 77.6% 

Level 2 Number 5 1 4 7 4 8 13 4 6 5 5 

Median 32.1% 84.8% 74.4% 21.4% 60.4% 49.3% 48.6% 68.9% 106.6% 60.6% 102.3% 

Level 3 Number 4 3 4 2 2 2 13 8 2 6 4 

Median 28.8% 108.3% 82.4% 49.7% 80.5% 33.0% 60.3% 65.1% 112.1% 74.1% 105.9% 

Level 4 Number -- -- -- -- -- -- 7 5 -- -- -- 

Median -- -- -- -- -- -- 70.8% 64.5% -- -- -- 

All Soil Number 17 5 16 16 29 26 38 21 15 34 13 

Median 116.8% 96.1% 71.3% 49.7% 29.3% 40.0% 58.5% 66.7% 78.3% 57.7% 101.5% 

Sediment Level 1 Number 4 4 8 3 7 8 3 6 2 18 5 

Median 174.4% 101.7% 47.3% 123.3% 9.3% 26.7% 122.4% 82.0% 67.5% 62.0% 89.6% 

Level 2 Number 4 4 3 4 3 4 19 4 4 6 4 

Median 79.9% 83.3% 47.7% 65.0% 52.7% 39.7% 33.4% 70.3% 87.1% 57.1% 108.4% 

Level 3 Number 3 3 2 3 3 10 4 3 3 4 3 

Median 20.6% 116.2% 29.1% 20.9% 52.2% 71.4% 42.7% 54.7% 71.4% 66.0% 109.1% 

Level 4 Number -- -- -- -- -- -- 6 -- -- -- -- 

Median -- -- -- -- -- -- 70.5% -- -- -- -- 

All Sediment Number 11 11 13 10 13 22 32 13 9 28 12 

Median 84.3% 108.9% 45.5% 65.0% 43.7% 40.0% 38.0% 71.4% 71.4% 63.1% 103.2% 

All Samples ZSX Mini Number 28 16 29 26 42 48 70 34 24 62 25 

Median 92.2% 102.2% 49.2% 60.9% 37.2% 40.0% 52.4% 66.8% 74.2% 60.4% 101.5% 

All Samples All XRF Number 206 110 320 209 338 363 558 392 192 403 195 

 Instruments Median 84.3% 70.6% 26.2% 16.7% 26.0% 16.2% 26.0% 21.5% 58.6% 25.4% 16.7% 

Notes: All median RPDs presented in this table are absolute values. 

-- No samples reported by the reference laboratory in this concentration range. 

ERA Environmental Resource Associates, Inc. 

NC Not calculated. Number Number of samples appropriate for accuracy evaluation. Ref Reference laboratory (Shealy Environmental Services, Inc.). 

RPD Relative percent difference. 
________________________________________________________________________________________

 50 

Table 7-4. Summary of Correlation Evaluation for the ZSX Mini II 

Notes: 

1 The bias for this element is indeterminate because of the lack of correlation observed with the reference 

laboratory data. 

2

 The bias for this element tended to be high at low concentrations (because of a high intercept) and low 

at high concentrations (because of a low slope). Overall correlation with the reference laboratory was 

moderate to low for this element. 

3 For iron, no MDL was calculated and the high intercept value was the result of the extreme range of 

concentrations in the demonstration samples. 

b Y-intercept of correlation line. 

m Slope of correlation line. 

r

2

 Correlation coefficient of correlation line. 

Target Element m b r2 Correlation Bias 

Antimony (vs. 

Reference Lab) 0.51 296 0.11 Low Indeterminate 1

Antimony (vs. ERA 

Certified Value) 0.02 258 0 None Indeterminate 1

Arsenic 0.45 32 0.90 High Low 

Cadmium 0.42 573 0.82 Moderate Variable 2

Chromium 0.43 63 0.95 High Low 

Copper 0.59 5 0.95 High Low 

Iron 0.38 5610 3 0.93 High Low 

Lead 0.54 92 0.99 High Low 

Mercury 0.30 29 0.98 High Low 

Nickel 0.42 32 0.93 High Low 

Selenium 0.27 8 0.97 High Low 

Silver 0.04 198 0.01 None Indeterminate 1

Vanadium 0.56 53 0.73 Moderate Variable 2

Zinc 0.47 47 0.97 High Low 
______________________________________________________________________________

 51 

Figure 7-2. Linear correlation plot for Rigaku indicating

 low overall correlation with the reference laboratory for silver.

y = 0.04x + 197.88

R2 = 0.01

0

50

100

150

200

250

300

350

400

450

0 50 100 150 200 250 300 350 400 450

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)

In conclusion, the demonstration found potential 

issues with accuracy for the ZSX Mini II. Median 

RPDs tended to be higher than the other XRF 

technologies demonstrated, remaining in the “fair” to 

“poor” range for all target elements. The correlation 

plots further showed that, although satisfactory 

correlations with reference laboratory data were 

obtained for many of the target elements, a 

significant and consistent low bias was observed 

(thus producing the high RPDs). The correlation 

analysis indicated biases that varied from high to low 

as concentrations increased for some elements, and 

further showed very poor overall agreement of the 

ZSX Mini II data with the reference laboratory data 

for both antimony and silver. The developer 

indicates that poor performance is expected for 

antimony, silver, and cadmium because the 

instrument does not have a primary beam filter to 

remove interference lines from the x-ray tube 

(Appendix B). For the remaining target elements, it 

is possible that a refined, project-specific instrument 

calibration could have improved the comparability of 

the data from the ZSX Mini II with that of the 

reference laboratory. 

7.3 Primary Objective 3 — Precision 

As described in Section 4.2.3, the precision of the 

ZSX Mini II 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 ZSX Mini II. Additional summary 

statistics for the RSDs (including minimum, 

maximum, and mean) are provided in Appendix E 

(Table E-2). 

The RSD calculation found a high level of precision 

for the ZSX Mini II across all target elements. 

Median RSDs for the demonstration data ranged only 

as high as 14.7 percent (chromium). The ranges into 

which the median RSDs fell are summarized below: 
______________________________________________________________________________

 52 

• Very low (median RSD between 0 and 5 

percent): cadmium, copper, iron, lead, mercury, 

nickel, selenium, silver, and zinc. 

• Low (median RSD between 5 and 10 percent): 

antimony and vanadium. 

• Moderate (median RSD between 10 and 20 

percent): arsenic and chromium. 

• High (median RSD greater than 20 percent): 

none. 

No differences were observed between the RSDs for 

soil and sediment. Use of the mean as opposed to the 

median RSDs (Table E-2) indicated a similarly high 

level of precision in the results from the ZSX Mini II 

for all elements except mercury. The high overall 

level of precision may have been facilitated by the 

level of processing (homogenizing, sieving, crushing, 

and drying) performed on the sample blends before 

the demonstration (Chapter 3). This observation is 

consistent with the previous SITE MMT Program 

demonstration of XRF technologies that occurred in 

1995 (EPA 1996a, 1996b, 1998a, 1998b, 1998c, and 

1998d). The high level of sample processing applied 

during both XRF technology demonstrations was 

necessary to minimize the effects of sample 

heterogeneity on the demonstration results and on 

comparability with the reference laboratories. During 

project design, site investigation teams that intend to 

compare XRF and laboratory data should similarly 

assess the need for sample processing steps to 

manage sample heterogeneity and improve data 

comparability. 

Further review of the median RSDs in Table 7-5 

based on concentration range reveals slightly higher 

RSDs (in other words, lower precision) for the target 

elements in Level 1 samples when compared with the 

rest of the data set. This effect was greatest for 

arsenic, chromium, 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 ZSX Mini II 

is concentration-dependent. Furthermore, precision 

shows the opposite trend from accuracy in that 

accuracy is higher at low concentrations for many 

target elements (Section 7.2), while precision is 

lower. Even for the Level 1 samples, however, the 

effect of concentration on precision was small; the 

mean RSDs for the target elements remained 

relatively good, with the highest RSD at 17.8 percent 

(for chromium in sediment). 

As an additional comparison, Table 7-5 also presents 

the median RSDs calculated for all XRF instruments 

that participated in the demonstration. Additional 

summary statistics for the RSDs calculated across all 

XRF instruments combined are included in Table E2. Table 7-5 indicates that the median RSDs for the 

ZSX Mini II were equivalent to or below the allinstrument medians for all elements except arsenic 

and chromium, for which slightly higher median 

RSDs were observed. 

Table 7-6 presents median RSD statistics for the 

reference laboratory and compares these to the 

summary data for the ZSX Mini II. These reference 

laboratory median RSD statistics were calculated 

using the same blends as were used in the RSD 

statistics for the ZSX Mini II. (Additional summary 

statistics are provided in Table E-3 of Appendix E.) 

Table 7-6 indicates that the median RSDs for the 

ZSX Mini II were equivalent to or lower than the 

reference laboratory RSDs for 12 of 13 target 

elements. (Only the RSD for chromium was slightly 

higher for the ZSX Mini II.) Thus, the ZSX Mini II 

exhibited slightly better precision overall than the 

reference laboratory. In comparison to the median 

RSDs for the ZSX Mini II, Table 7-6 shows that the 

median RSDs for all XRF instruments participating 

in the demonstration were lower than the reference 

laboratory RSDs for 11 out of the 13 target elements 

(the exceptions were chromium and vanadium). 

7.4 Primary Objective 4 — Impact of 

Chemical and Spectral Interferences 

The RPD data from the accuracy evaluation were 

further processed to assess the effects of 

interferences. The RPD data for elements considered 

susceptible to interferences were grouped and 

compared based on the relative concentrations of 

potentially interfering elements. Of specific interest 

for the comparison were the potential effects of: 

• High concentrations of lead on the RPDs for 

 arsenic, 

• High concentrations of nickel on the RPDs for 

copper (and vice versa), and 

• High concentrations of zinc on RPDs for copper 

(and vice versa). 
_________________________________________________________________________________________________

53

Table 7-5. Evaluation of Precision — Relative Standard Deviations for the ZSX Mini II

 Sample Matrix Group Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel SeSoil Level 1 Number 8 8 7 23 16 5 4 7 23 

Median 6.2% 13.0% 1.8% 14.8% 4.5% 1.0% 7.5% 9.6% 4.7% 7

 Level 2 Number 5 4 7 4 8 13 4 6 5 

Median 6.9% 3.2% 2.2% 4.3% 1.9% 0.5% 2.1% 5.2% 2.3% 3

 Level 3 Number 4 4 2 2 2 13 8 2 6 

Median 4.9% 1.7% 1.1% 2.7% 0.6% 0.6% 1.8% 2.4% 1.3% 

 Level 4 Number -- -- -- -- -- 7 5 -- -- 

Median -- -- -- -- -- 0.7% 0.8% -- -- 

 All Soil Number 17 16 16 29 26 38 21 15 34 

Median 6.3% 6.1% 1.8% 13.0% 3.4% 0.6% 1.8% 5.3% 3.9% 3

Sediment Level 1 Number 4 8 3 7 8 3 6 2 18 

Median 11.0% 15.8% 1.2% 17.8% 3.4% 0.4% 4.0% 7.6% 4.0% 1

 Level 2 Number 4 3 4 3 4 19 4 4 6 

Median 5.5% 11.2% 1.9% 9.1% 2.1% 0.7% 2.3% 7.3% 5.2% 7

 Level 3 Number 3 2 3 3 10 4 3 3 4 

Median 7.2% 9.9% 3.0% 18.2% 1.7% 1.1% 2.6% 3.6% 1.6% 3

 Level 4 Number -- -- -- -- -- 6 -- -- -- 

Median -- -- -- -- -- 0.7% -- -- -- 

All Sediment Number 11 13 10 13 22 32 13 9 28 

Median 7.2% 14.4% 1.3% 17.8% 2.1% 0.7% 2.6% 4.5% 3.7% 7

All Samples ZSX Mini Number 28 29 26 42 48 70 34 24 62 

Median 6.4% 10.1% 1.6% 14.7% 2.3% 0.6% 2.0% 4.9% 3.7% 3

All Samples All XRF Number 206 320 209 338 363 558 392 192 403  Instruments Median 6.1% 8.2% 3.6% 12.1% 5.1% 2.2% 4.9% 6.8% 7.0% 4Notes:

-- No samples reported by the reference laboratory in this concentration ranges. 

Number Number of samples appropriate for precision evaluation.

RSD Relative standard deviation 
_________________________________________________________________________________________________

54

 Table 7-6. Evaluation of Precision – Relative Standard Deviations for the Reference Laboratory versus the Z

All Demonstration Instruments 

Matrix Sample Group Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Selen

Number 17 23 15 34 26 38 33 16 35 1

Soil Ref Lab 

Median 9.8% 12.4% 9.0% 10.6% 9.1% 8.7% 13.2% 6.6% 10.0% 7.1

Number 7 24 10 26 21 31 22 10 27 1

Sediment 

Ref Lab 

Median 9.1% 9.2% 8.2% 7.5% 8.9% 8.1% 7.4% 6.9% 7.3% 7.6

 All Number 24 47 25 60 47 69 55 26 62 2Samples 

Ref Lab 

Median 9.5% 9.5% 9.0% 8.4% 8.9% 8.5% 8.6% 6.6% 8.2% 7.4

 All Number 28 29 26 42 48 70 34 24 62 2Samples 

ZSX Mini 

Median 6.4% 10.1% 1.6% 14.7% 2.3% 0.6% 2.0% 4.9% 3.7% 3.9

 All Number 206 320 209 338 363 558 392 192 403 19Samples 

All XRF Instruments Median 6.1% 8.2% 3.6% 12.1% 5.1% 2.2% 4.9% 6.8% 7.0% 4.5

Notes: Number Number of demonstration samples evaluated. Ref. Lab. Reference laboratory. XRF X-ray fluorescence
_____________________________________________________________________________

 55 

Interferent-to-element ratios were calculated using 

the mean concentrations reported for each blend by 

the reference laboratory, 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 that the median RPD for arsenic 

was lower (that is, accuracy was higher) at the higher 

lead-to-arsenic ratios than at the low or moderate 

lead-to-arsenic ratios. Typically, the opposite trend is 

expected: high lead concentrations will tend to cause 

a high bias and thereby reduce accuracy in XRF 

measurements of arsenic. However, Section 7.2 

listed arsenic among the elements for which the ZSX 

Mini II results were consistently biased low (Figure 

E-2). Thus, any high bias caused by the effects of 

lead may have offset the inherent low bias in the 

instrument (for example, from calibration or 

quantitation protocols) to produce results closer to the 

reference laboratory. Similar effects were indicated 

in the other interferent/element pairs in that median 

RPDs remained equivalent or declined slightly as 

interferent concentrations increased. Overall, 

therefore, the low accuracy of the ZSX Mini II data 

set appears to have complicated the evaluation of 

interelement interferences, and may mask the effects 

of such interferences. 

7.5 Primary Objective 5 — Effects of Soil 

Characteristics 

The population of RPDs between the ZSX Mini II 

results and the reference laboratory results were 

further evaluated against sampling site and soil type. 

Separate sets of summary statistics were developed 

for the mean RPDs associated with each sampling 

site for comparison to the other sites and to the 

demonstration data set as a whole. The site-specific 

median RPDs are presented in Table 7-8, along with 

descriptions of soil or sediment type from 

observations during sampling at each site. Complete 

RPD summary statistics for each soil type (minimum, 

maximum, and mean) are presented in Appendix E 

(Table E-5). 

Another perspective on the effects of soil type was 

developed by graphically assessing outliers and 

extreme values in the mean RPD data sets for the 

target elements. This evaluation focused on 

correlating these values with sample types or 

locations for multiple elements across the data set. 

Outliers and extreme values are apparent in the 

correlation plots (Figures E-1 through E-13) and are 

further depicted for the various elements on box and 

whisker plots in Figure E-14. 

Review of Table 7-8 indicates that the median RPDs 

were highly variable and that trends or differences 

between sample sites were difficult to discern. For 

many target elements, evaluations relative to 

sampling site were further complicated by the low 

numbers of samples (Table 7-8 indicates that only 1 

to 3 samples were available from many sampling 

sites for evaluation of specific target elements.) The 

degree of variation in RPDs for the target elements 

was greatest in the samples from KARS Park, where 

the median RPDs ranged from 11.8 percent (nickel) 

to 153 percent (antimony). Other sample sites for 

which the range of RPDs across the different target 

elements was greater than 100 percent included: 

Alton Steel, Burlington Northern, Sulphur Bank, and 

Torch Lake. The smallest RPD range was observed 

for the Ramsey Flats site, where a minimum RPD of 

29.7 percent was noted for vanadium and a maximum 

RPD of 78.5 percent was calculated for lead. 

These observations indicate that the relatively low 

accuracy and consistently low bias of the Rigaku data 

may have masked any effects of soil type on the 

results. 

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 high outliers and extreme values 

apparent in Figure E-14 were distributed among the 

KARS Park, Alton Steel, Sulphur Bank, and 

Leviathan Mine sites. However, the plots further 

demonstrate that sample matrix appeared to have 

little overall effect on the accuracy of the XRF data. 

Figure E-14 shows the broad overall distributions of 

RPDs for many elements such that relatively few 

high outliers or extreme values could be identified. 

The identification of high statistical outliers or 

extreme values was precluded for eight of the target 

elements, including antimony, cadmium, chromium, 

lead, mercury, selenium, silver, and vanadium. 
_______________________________________________________________________________________________

56 

Table 7-7. Effects of Interferent Elements on the RPDs (Accuracy) for Other Target Elements1 

Parameter Lead Effects on Arsenic Copper Effects on Nickel Nickel Effects on Copper Zinc Effects on Copper 

Interferent/ 

Element Ratio 

<5 5 – 10 >10 <5 5 – 10 >10 <5 5 – 10 >10 <5 5 – 10 >10 

Number of 

Samples 15 7 7 43 5 14 39 1 8 35 2 11 

Median RPD of 

Target Element2 45.5% 76.5% 16.3% 62.7% 55.3% 53.3% 46.1% 31.1% 30.1% 40.2% 44.1% 31.0% 

Median Interferent 

Concentration 173 3716 1390 62 700 1017 80 203 963 92 2190 1430 

Median Target 

Element 

Concentration 92 487 93 99 88 60 565 57 70 567 532 77 

Notes: 1 Concentrations are reported in units of milligrams per kilogram (mg/kg), or parts per million (ppm). 2 All median RPDs presented in this table are based on the population of absolute values of the individual RPDs. 

< Less than. > Greater than. RPD Relative percent difference.
_______________________________________________________________________________________________

57 

Table 7-8. Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Rigaku ZSX Mini II 

Matrix Antimony Arsenic Cadmium Chromium Copper 

Matrix Site Description Statistic Soil AS Fine to medium sand (steel Number -- -- 3 2 3 

processing) Median -- -- 116.1% 43.4% 74.3% 

Soil BN Sandy loam, low organic (ore Number 4 6 5 4 6 

residuals) Median 146.1% 64.4% 26.8% 51.4% 40.0% 

Soil Number CN Sandy loam (burn pit residue) 2 1 2 1 3 

Median 87.4% 3.3% 93.1% 16.5% 31.0% 

Soil & Number 2 -- -- 3 2 Sediment 

KP Soil: Fine to medium quartz sand.

Sed.: Sandy loam, high organic. (Gun and skeet ranges) Median 153.4% -- -- 37.0% 19.8% 

Sediment Number LV Clay/clay loam, salt crust (iron 4 3 5 7 4 

and other precipitates) Median 33.7% 82.3% 36.4% 62.9% 40.9% 

Sediment Number RF Silty fine sand (tailings) 5 10 5 6 13 

Median 75.6% 40.2% 65.4% 42.2% 31.1% 

Soil Number SB Coarse sand and gravel (ore and 5 2 1 10 4 

waste rock) Median 54.1% 92.1% 42.2% 7.8% 46.9% 

Sediment Number TL Silt and clay (slag-enriched) 3 1 2 2 7 

Median 90.6% 56.8% 82.7% 14.1% 72.5% 

Soil Number WS Coarse sand and gravel (roaster 3 6 3 7 6 

slag) Median 116.8% 79.3% 112.8% 29.3% 44.1% 

 All Number 28 29 26 42 48 

Median 92.2% 49.2% 60.9% 37.2% 40.0% 
_______________________________________________________________________________________________

58 

Table 7-8. Effect of Soil Type on RPDs (Accuracy) of Target Elements, Rigaku ZSX Mini II (Continu

Notes: Other Notes: AS Alton Steel Mill -- No samples reported by the reference laboratory in t

BN Burlington Northern railroad/ASARCO East. Number Number of demonstration samples evaluated. CN Naval Surface Warfare Center, Crane Division. RPD Relative percent difference. 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. 

Matrix Mercury Nickel Selenium Silver Vana

Matrix Site Description Statistic Soil AS Fine to medium sand (steel Number -- 3 1 1 1 

processing) Median -- 71.3% 97.5% 40.4% 13.

Soil BN Sandy loam, low organic (ore Number 1 6 4 4 4 

residuals) Median 39.9% 62.0% 96.2% 42.8% 26.

Soil Number CN Sandy loam (burn pit residue) 2 3 2 2 1 

Median 42.1% 71.5% 87.9% 91.0% 26.

Soil & Number -- 3 -- -- -Sediment 

KP Soil: Fine to medium quartz sand.

Sed.: Sandy loam, high organic. (Gun and skeet ranges) Median -- 11.8% -- -- -

Sediment Number LV Clay/clay loam, salt crust (iron 4 11 5 4 9 

and other precipitates) Median 52.8% 65.5% 100.3% 34.7% 19.

Sediment Number RF Silty fine sand (tailings) 5 13 5 5 3 

Median 59.0% 55.9% 97.6% 64.0% 29.

Soil Number SB Coarse sand and gravel (ore and 10 10 3 1 9 

waste rock) Median 112.1% 65.3% 106.6% 38.3% 60.

Sediment Number TL Silt and clay (slag-enriched) 2 6 4 4 7 

Median 128.8% 66.8% 120.3% 58.8% 41.

Soil Number WS Coarse sand and gravel (roaster -- 7 1 4 3 

slag) Median -- 37.6% 101.5% 48.3% 27.

 All Number 24 62 25 25 3

Median 74.2% 60.4% 101.5% 45.1% 35.
__________________________________________________________________________________

 59

7.6 Primary Objective 6 — Sample 

Throughput 

The Rigaku two-person field team was able to 

analyze all 326 demonstration samples in 4 days at 

the demonstration site. Once the ZSX Mini II 

instrument had been set up and operations had been 

streamlined, the Rigaku field team was able to 

analyze a maximum of 107 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 Rigaku field team would have 

averaged about 69 samples per day.This estimated 

sample throughput for a normal working day was 

similar to that observed for the other instruments that 

participated in the demonstration (average of 66 

samples per day). 

A detailed discussion of the time required to 

complete the various steps of sample analysis using 

the ZSX Mini II is included as part of the labor cost 

analysis in Section 8.3. 

7.7 Primary Objective 7 — Technology Costs 

The evaluations pertaining to this primary objective 

are fully described in Chapter 8, Economic Analysis. 

7.8 Secondary Objective 1 — Training 

Requirements

The instrument operator must be suitably trained to 

set up and operate the instrument to obtain the level 

of data quality required for specific projects. The 

amount of training required depends on the 

configuration and complexity of the instrument along 

with the associated software. Most developers have 

established standard training programs. 

Rigaku recommends that the operator have a high 

school diploma and basic operational training. Field 

or laboratory technicians are generally qualified to 

operate this instrument. The Rigaku staff member 

who operated the instrument during the 

demonstration held a B.S. degree in chemistry, with 

several years of experience in operation of the ZSX 

Mini II. 

Rigaku recommends that operators complete at least 

the training Rigaku offers for instrument users. 

When an instrument is purchased, a Rigaku service 

engineer will set it up and provide basic instruction 

on operation and safety. After about a week, a 

Rigaku application specialist will come to the site 

where the instrument will be used to provide a 3-day 

comprehensive training course adapted for the user’s 

specific application. Additional 3-day training 

classes are offered for $1,800. Participants are 

encouraged to bring samples to class to analyze as 

part of the hands-on exercise for the training. A 

built-in modem allows a support technician to operate 

and troubleshoot the instrument from a remote 

location. 

In addition to the general instrument operational 

instruction and training, the operator and data 

manager must be familiar with using a personal 

computer (PC) to acquire and manage analytical data 

obtained from the instrument. Rigaku provides a 

copy of its instrument software with each instrument 

purchase. The software allows direct transfer to 

analytical results from the instrument to the PC, 

thereby minimizing the potential for lost data. 

7.9 Secondary Objective 2 — Health and 

Safety 

Included in the health and safety evaluation were the 

potential risks from: (1) potential radiation hazards 

from the instrument itself, and (2) exposure to any 

reagents used in preparing and analyzing the samples. 

However, the evaluation did not include potential 

risks from exposure to site-specific hazardous 

materials, such as sample contaminants, or to 

physical safety hazards. These factors were excluded 

because of the wide and unpredictable range of sites 

and conditions that could be encountered in the field 

during an actual project application of the instrument. 

The ZSX Mini II contains an x-ray tube that is 

positioned to deliver x-rays into a lead-shielded 

sealing 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. 

The sample chamber lock, lead-shielded sample 

chamber, and safety lights are designed to minimize 

possible exposure to the x-ray radiation. 
__________________________________________________________________________________

 60

The second potential source of risk to XRF 

instrument operators is exposure to reagent chemicals 

used in sample preparation. However, for the ZSX 

Mini II, there are no risks from this source because 

no chemical reagents are required for sample 

preparation. The sample chamber may be placed in a 

vacuum or purged with inert gas such as helium in 

some applications (for example, to improve data 

quality for lighter elements). As an inert gas, helium 

is relatively harmless, as long as users apply standard 

safety procedures for management and use of highpressure gas cylinders. The risks from exposure to 

radiation or to helium are likewise minimal when the 

instrument is operated according to the 

manufacturer’s recommendations. 

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 are also listed in Table 6-1. 

Two distinctions were made during the 

demonstration regarding portability: 

(1) The instrument was considered fully portable if 

the dimensions were such that the instrument 

could be easily brought directly to the sample 

location by one person. 

(2) The instrument was considered transportable if 

the dimensions and power requirements were 

such that the instrument could be moved to a 

location near the sampling location, but required 

a larger and more stable environment (for 

example, a site trailer with AC power and stable 

conditions). 

Based on the dimensions and power requirements, 

the ZSX Mini II 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). 

Rigaku provides 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. 

Rigaku indicated that the lifespan of an x-ray tube in 

the ZSX Mini II can be as high as 10,000 hours of 

operation. 

Rigaku is continually upgrading both the instrument 

and software to enhance environmental analysis. It is 

expected that Rigaku will continue to provide 

upgrades to instruments and software as long as there 

is a market for improved technologies. 

The ZSX Mini II 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 

environment. 

7.12 Secondary Objective 5 — Availability 

Rigaku LLC was founded in 1931 and has six 

salespersons in the U.S. and many more worldwide. 

Rigaku provides product support for all instruments 

through service contracts tailored to the client’s 

needs. A network of 35 service representatives 

provides service and customer support for instrument 

owners. 

The ZSX Mini II is available for lease or for longterm rental on a case-specific basis. The ZSX Mini II 

is not available from third-party vendors for lease or 

rental.

 
________________________________________________________________________________________ 

 61 

Chapter 8 

Economic Analysis

This chapter provides cost information for the Rigaku 

ZSX Mini II 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 ZSX Mini II instrument. 

8.1 Equipment Costs 

Capital equipment costs include either purchase or 

rental of the ZSX Mini II 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 

Rigaku. 

The ZSX Mini II instrument costs between $80,000 

and $85,000, depending on the configuration. The 

cost includes peripherals such as the x-ray 

spectrometer, 12-postion sample changer, vacuum 

pump, and personal computer loaded with the 

appropriate operational software. At the time of the 

demonstration, Rigaku indicated that models are not 

available for rental. However, long-term lease 

programs are available through Rigaku. 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. Purchased models 

include a 1-year parts and labor warranty. The 

lifespan of the x-ray tube is about 4 to 5 years for 

normal usage. 

The purchase price and shipping cost for the ZSX 

Mini II 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 ZSX Mini II 

XRF 

Demonstration 

Average * 

Shipping $500 $410 

Capital Cost 

(Purchase) 

 $82,500 $54,300 

Weekly Rental $4,300 $2,813 

Autosampler 

(for Overnight 

Analysis) 

 Included N/A 

Notes: 

* Average for all eight demonstration vendors 

N/A Not available or not applicable for this 

comparison 

8.2 Supply Costs 

The supplies that were included in the cost estimate 

include sample containers, Mylar® film, spatulas or 

scoops, wipes, and disposable gloves. The rate of 

consumption for these supplies was based on 

observations during the field demonstration. Unit 

prices for these supplies were based on price quotes 

from independent vendors of field equipment. 

Additional costs include purchase of helium or P-10 

(argon/methane) gas if an oxygen-free environment is 

best suited for the analysis. 

The ZSX Mini II 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 

members that had responsibilities other than sample 
__________________________________________________________________________________ 

 62 

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 project packing 

The estimated time required to complete each of 

these activities using the ZSX Mini II 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 

ZSX Mini II 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 ZSX Mini II 

exhibited higher-than-average times for initial setup 

and calibration and for end of project packing. The 

ZSX Mini II exhibited lower-than-average times for 

sample preparation, sample analysis, daily shutdown 

and startup, and total processing time per sample. 

Table 8-2. Time Required to Complete Analytical 

Activities1

Activity ZSX Mini II Average2

Initial Setup and 

Calibration 90 54 

Sample Preparation 2.2 3.1 

Sample Analysis 5.7 6.7 

Daily Shutdown/Startup 0 10 

End of Project Packing 147 43 

Total Processing Time 

per Sample 8.6 10.0 

Notes: 

1

 All estimates are in minutes 

2

 Average for all eight XRF instruments in the 

demonstration 

The Rigaku field team expended about 67 labor hours 

to complete all sample processing activities during 

the field demonstration using the ZSX Mini II. This 

was similar to the overall average of 69 labor hours 

for all instruments that participated in the 

demonstration. 

8.4 Comparison of XRF Analysis and 

Reference Laboratory Costs 

Two scenarios were evaluated to compare the cost for 

XRF analysis using the ZSX Mini II 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. 
__________________________________________________________________________________ 

 63 

0 20 40 60 80 100 120 140

Minutes

End of project packing

Daily Shut Down/Start Up

Total Processing Time

Sample Analysis

Sample Preparation

Initial Set up and Calibration

Figure 8-1. Comparison of activity times for the ZSX Mini II versus other XRF instruments. 

Typical unit costs for fixed-laboratory analysis using 

the reference methods were estimated using 

information on average cost 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 offsite fixed laboratory analysis, such as sample 

packaging and shipment. 

The cost for XRF analysis using the ZSX Mini II was 

based on equipment rental for 1 week, along with 

labor and supplies estimates established during the 

field demonstration. As noted previously, the 

estimate used a hypothetical rental rate for the ZSX 

Mini II 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 fixedlaboratory 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 ZSX Mini II analysis cost was not 

adjusted for one element versus 13 elements. 

Table 8-3 summarizes the costs for the ZSX Mini II 

versus the cost for analysis in a fixed laboratory. 

This comparison shows that the ZSX Mini II 

ZSX Mini II 

Range for all eight XRF instruments 
__________________________________________________________________________________ 

 64 

compares favorably to a fixed laboratory in terms of 

overall cost when a large number of elements are to 

be determined. The ZSX Mini II compares 

unfavorably to a fixed laboratory when one element 

is to be determined. Use of the ZSX Mini II 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 ZSX Mini II in the example 

scenario (326 samples) was estimated at $10,421. 

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 ZSX Mini II, 

typically 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 ZSX Mini II for the 

example scenario was similar. 

Table 8-3. Comparison of XRF Technology and Reference Method Costs

Analytical Approach Quantity Item 

Unit 

Rate Total

 

ZSX Mini II (1 to 13 elements) 

Shipping 1 Roundtrip $500 $500

Weekly Rental1 1 Week $4,3001 $4,300

Supplies 326 Sample $0.75 $245

Labor 54 Hours $43.75 $5,286

IDW N/A N/A N/A $90

Total ZSX Mini II Analysis Cost (1 to 13 

elements) $10,421

 

Fixed Laboratory (1 element) 

(EPA Method 6010, ICP-AES) 326 Sample $21 $6,846

Total Fixed Laboratory Costs (1 element) $6,846

 

Fixed Laboratory (13 elements) 

Mercury (EPA Method 7471, CVAA) 326 Sample $36 $11,736

All other Elements (EPA Method 6010, ICP-AES) 326 Sample $160 $52,160

Total Fixed Laboratory Costs (13 elements) $63,896

Notes: 

1

 Estimated value as Rigaku currently does not have a rental rate for the ZSX Mini II. 
__________________________________________________________________________________ 

 65 

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 Rigaku ZSX Mini II XRF 

analyzer. The evaluation design incorporated 13 

target elements, 70 distinct sample blends, and a total 

of 326 samples. The blends included both soil and 

sediment samples from nine sampling locations. A 

rigorous program of sample preparation and 

characterization, reference laboratory analysis, 

QA/QC oversight, and data reduction supported the 

evaluation of XRF instrument performance. 

One important aspect of the demonstration was the 

sample blending and processing procedures 

(including drying, sieving, grinding, and 

homogenization) that significantly reduced 

uncertainties associated with the demonstration 

sample set. These procedures minimized 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 ZSX Mini II 

analyzer for each primary and secondary objective 

are summarized in Tables 9-1 and 9-2. The ZSX 

Mini II and the combined performance of all eight 

instruments 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 mean performance of all eight 

XRF instruments, the ZSX Mini II showed: 

• Equivalent or better MDLs for all target elements 

except antimony and arsenic (iron was not 

included in the MDL evaluation). 

• Equivalent or poorer accuracy (RPDs) for 12 of 

the 13 target elements (vanadium was the 

exception). When RPDs for antimony were 

calculated versus sample spike levels rather than 

reference laboratory data (which may be biased 

low), accuracy for antmony remained low 

relative to the program as whole. 

• Equivalent or better precision (RSDs) for 11 of 

the 13 target elements (arsenic and chromium 

were the exceptions). 

Bench-top instruments, such as the ZSX Mini II, 

typically provide improved MDLs in comparison to 

portable instruments, and so the better than average 

performance in this area was expected. As a benchtop instrument, however, the ZSX Mini II is not fully 

portable and requires a stable operating environment. 

The reasons for the poorer than average accuracy for 

most elements are not known with any certainty but 

may relate to the algorithms employed to quantify 

target elements or to inadequate calibration. 
__________________________________________________________________________________ 

 66 

Table 9-1. Summary of Rigaku ZSX Mini II Performance – Primary Objectives 

Objective Performance Summary 

P1: Method 

Detection Limits 

• Mean MDLs for the target elements ranged as follows: 

o MDLs of 1 to 20 ppm: copper, mercury, nickel, selenium, and 

zinc. 

o MDLs of 20 to 50 ppm: arsenic, lead, silver, and vanadium. 

o MDLs of 50 to 100 ppm: antimony, cadmium, and chromium. 

o MDLs greater than 100 ppm: none. 

(Iron was not included in the MDL evaluation.) 

• The MDLs for antimony and cadmium may be inflated by high biases in 

the XRF results in some of the MDL sample blends. 

• No significant differences were noted between MDLs for soil and 

sediment, or among different sample blends. 

• For all the target elements except antimony, the MDLs calculated were 

lower than reference MDL data from EPA Method 6200. 

P2: Accuracy and 

Comparability 

• Median RPDs between the ZSX Mini II and reference laboratory data 

revealed the following, with lower RPDs indicating greater accuracy: 

o RPDs less than 25 percent: none. 

o RPDs of 25 to 50 percent: arsenic, chromium, copper, silver, 

vanadium, and zinc. 

o RPDs greater than 50 percent: antimony, cadmium, iron, lead, 

mercury, nickel, and selenium. 

• 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. However, unlike a 

number of other instruments in the XRF technology demonstration, high 

RPDs for antimony were not improved for the ZSX Mini II when 

calculated relative to certified spike values rather than reference 

laboratory results. 

• Lower RPDs (that is, higher accuracy) were noted in low concentration 

samples versus higher concentration samples for multiple target 

elements in both soil and sediment. 

• Correlation plots relative to reference laboratory data indicated: 

o Significant negative biases for most of the target elements (or, 

for cadmium and vanadium, biases that change from high to 

low as concentrations increase). 

o Poor to no correlation with the reference laboratory results for 

antimony and silver. 

P3: Precision • Median RSDs were good for all elements, as follows: 

o RSDs of 0 to 5 percent: cadmium, copper, iron, mercury, 

nickel, selenium, silver, and zinc. 

o RSDs of 5 to 10 percent: antimony and vanadium. 

o RSDs of 10 to 20 percent: arsenic and chromium. 

• In contrast to accuracy, the precision of the ZSX Mini II improved 

slightly as concentration increased. 

• Median RSDs for the ZSX Mini II for all elements except chromium 

were equivalent to or lower than the RSDs calculated for the reference 

laboratory data, indicating slightly better precision for the XRF 

instrument. 
__________________________________________________________________________________ 

 67 

Table 9-1. Summary of Rigaku ZSX Mini II Performance – Primary Objectives (continued) 

Objective Performance Summary 

P4: Effects of 

Sample 

Interferences 

• High relative concentrations of lead appeared to slightly improve 

accuracy for arsenic, reducing the instrument’s negative bias. Median 

RPDs for arsenic decreased from 45.5 percent to 16.3 percent as the 

concentration of lead increased. 

• Overall, significant interference effects could not be determined 

because of the low accuracy of the XRF data. 

P5: Effects of Soil 

Type 

• The degree of variation in RPDs for the target elements was greatest in 

the samples from KARS Park, a former gun range, where the median 

RPDs ranged from 11.8 percent (nickel) to 153 percent (antimony). 

Other sample sites for which the range of RPDs across the different 

target elements was greater than 100 percent included: Alton Steel, 

Burlington Northern, Sulphur Bank, and Torch Lake. 

• The high outliers and extreme values were distributed among the KARS 

Park, Alton Steel, Sulphur Bank, and Leviathan Mine sites. However, 

the evaluation found that sample matrix had little overall effect on 

accuracy for the ZSX Mini II, given the broad overall ranges of RPDs 

observed. 

P6: Sample 

Throughput 

• With an average sample preparation time of 2.2 minutes and an 

instrument analysis time of 5.7 minutes per sample, the total sample 

processing time was 8.6 minutes per sample. 

• A maximum sample throughput of 107 samples was achieved during the 

field demonstration on one extended work day. A typical average 

sample throughput was estimated to be 69 samples per day for an 8-

hour work day. 

P7: Costs • Instrument purchase cost was about $82,500. This cost included an 

optional autosampler, vacuum pump, and personal computer. 

According to the developer, short-term and long-term leases are 

available, but no rates were provided. 

• The Rigaku field team expended approximately 67 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 $10,421was estimated for a project the size of the 

demonstration using the ZSX Mini II. 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. 
__________________________________________________________________________________ 

 68 

Table 9-2. Summary of Rigaku ZSX Mini II Performance – Secondary Objectives 

Objective Performance Summary 

S1: Training 

Requirements 

• Field or laboratory technicians with a high school diploma and basic 

operational training are generally qualified to operate the ZSX Mini II. 

• Rigaku offers free instrument setup for purchasers, followed by 

customized training that generally lasts about 3 days. 

• The ZSX Mini II comes equipped with a modem that allows qualified 

technicians to remotely troubleshoot the instrument and guide operators. 

S2: Health and 

Safety 

• The ZSX Mini II 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 ZSX Mini II should be able to safely manage high pressure 

gas cylinders (helium) if an inert atmosphere is desired for sample 

analysis. 

S3: Portability • Based on dimensions, weight, and power requirements, the ZSX Mini II 

is a transportable (as opposed to fully portable) instrument. It is best 

used in a field trailer or other fixed location. 

S4: Durability • The ZSX Mini II has 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 ZSX Mini II is anticipated to 

be 10,000 hours (7 years) 

• The ZSX Mini II is encased in durable hard-tool plastic but is not 

weatherproof. It must be used in a stable, sheltered environment. 

S5: Availability • Rigaku maintains offices in the U.S. and Europe for its XRF division, 

with 10 sales representatives distributed across North America and 

Europe. A world-wide network of 35 service representatives provides 

service and customer support. 

• The ZSX Mini II is available for short-term rental or long-term lease. 

Rates vary and are project-specific. The instrument is not available from 

third-party vendors. 
__________________________________________________________________________________ 

 69 

Comparison of Mean MDLs: 

ZSX Mini II vs. All Developers

0

20

40

60

80

100

Antimony

Arsenic

Cadmium

Chromium

Copper

Lead

Mercury

Nickel

Selenium

Silver

Vanadium

Zinc

Target Metal

Mean MDL in 

Parts Per Million

ZSX Mini II Mean MDL

All Developer Mean MDL

Comparison of Median RPDs: 

ED2000 vs. All Developers

0.0%

20.0%

40.0%

60.0%

80.0%

100.0%

120.0%

Antimony

Arsenic

Cadmium

Chromium

Copper

Iron

Lead

Mercury

Nickel

Selenium

Silver

Vanadium

Zinc

Target Metal

Relative Percent 

Difference (RPD)

ZSX Mini II Median RPD

All Developer Median RPD

Comparison of Median RSDs: 

ED2000 vs. All Developers

0.0%

2.0%

4.0%

6.0%

8.0%

10.0%

12.0%

14.0%

16.0%

18.0%

Antimony

Arsenic

Cadmium

Chromium

Copper

Iron

Lead

Mercury

Nickel

Selenium

Silver

Vanadium

Zinc

Target Metal

Relative Standard Deviation 

(RSD), Percent

ZSX Mini II Median RSD

All Developer Median RSD

Figure 9-1. Method detection limits (sensitivity), accuracy, and precision of the ZSX Mini II in 

comparison to the average of all eight XRF instruments. 
_________________________________________________________________________________ 

 70 

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__________________________________________________________________________________

 71 

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 

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Environmental Protection Agency, 

Superfund Innovative Technology 

Evaluation Program. March. 

U.S. Environmental Protection Agency (EPA). 

1996a. TN Spectrace TN 9000 and TN Pb 

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 (SW846). December. 

EPA. 1998a. Environmental Technology 

Verification Report; Field Portable X-ray 

Fluorescence Analyzer, Metorex X-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. Scitect MAP 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 QA00 Update. 

EPA/600/R-96/084. July. 

EPA. 2004a. Innovative Technology Verification 

Report: Field Measurement Technology for 

Mercury in Soil and Sediment - Metorex’s 

X-MET® 2000 X-Ray Fluorescence 

Technology. EPA/600/R-03/149. May. 

EPA. 2004b. Innovative Technology Verification 

Report: Field Measurement Technology for 

Mercury in Soil and Sediment - Niton’s 

XLi/XLt 700 Series X-Ray Fluorescence 

Analyzers. EPA/600/R-03/148. May. 

EPA. 2004c. USEPA Contract Laboratory 

Program National Functional Guidelines for 

Inorganic Data Review. Final. OSWER 

9240.1-45. EPA 540-R-04-004. October. 
 

APPENDIX A 

VERIFICATION STATEMENT
 A-1 

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

Office of Research and Development 

Washington, DC 20460 

SITE Monitoring and Measurement Technology Program 

Verification Statement 

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 Rigaku Incorporated 

ZSX Mini II 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 trace elements in soil and sediment was conducted 

from January 24 through 28, 2005, at the Kennedy Athletic, Recreational and Social (KARS) Park, which is part of 

the Kennedy Space Center on Merritt Island, Florida. A total of 326 samples were analyzed by each XRF technology 

developer, including Rigaku, during the field demonstration. These samples were derived from 70 different blends 

and spiked blends of soil and sediment collected from nine sites across the U.S. The sample blends were thoroughly 

dried, sieved, crushed, mixed, and characterized before they were used for the demonstration. Some blends were also 

TECHNOLOGY TYPE: X-ray Fluorescence (XRF) Analyzer 

APPLICATION: MEASUREMENT OF TRACE ELEMENTS IN SOIL AND SEDIMENT 

TECHNOLOGY NAME: ZSX Mini II 

COMPANY: Rigaku Incorporated 

ADDRESS: 9009 New Trails Drive 

 The Woodlands, TX 77381-5209 

PHONE: 281-363-1033 

WEB SITE: www.rigakumsc.com/xrf 

E-MAIL: info@rigakumsc.com 
 A-2 

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 

3050B/6010B 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 Rigaku ZSX Mini II XRF 

instrument. More detailed discussion can be found in the Innovative Technology Verification Report – XRF 

Technologies for Measuring Trace Elements in Soil and Sediment: Rigaku ZSX Mini II XRF Analyzer 

(EPA/540/R-06/001). 

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 ZSX Mini II differs from the other XRF technologies evaluated in the SITE MMT demonstration in that it is a 

“wavelength-dispersive” XRF analyzer. Wavelength-dispersive XRF analyzers differentiate the x-ray energies 

emitted from a sample by dispersing them into different wavelength ranges using crystals. The other seven 

technologies participating in the demonstration were “energy-dispersive” XRF analyzers that differentiate x-ray 

energies based on voltages measured by the detector. Wavelength dispersive XRFs have historically been large, 

laboratory-bound instruments with significant requirements for power and cooling. The ZSX Mini II is a smaller, 

transportable unit that can operate at room temperature on standard 110-volt circuits. The ZSX Mini II has a sample 

chamber that can: accommodate up to 12 samples, be adapted for irregularly-shaped objects, operate under vacuum 

or helium environments (enhancing performance for light elements), and spin samples during analysis (with an 

available spinner accessory). Up to five types of analyzing crystals are available for x-ray dispersion, including 

lithium fluoride, pentaerythritol, thallium acid phthalate, RX35, and germanium. Multiple crystals can be used for a 

single analysis using a revolving changer. In contrast to energy-dispersive instruments, the unit employs an 

economical gas proportional counter as a detector rather than a diode array/multi-channel analyzer detector because 

wavelength resolution is achieved with the crystals. 

VERIFICATION OF PERFORMANCE 

Method Detection Limit: MDLs were calculated using seven replicate analyses from each of 12 low-concentration 

sample blends, according to the procedure described in Title 40 Code of Federal Regulations (CFR) Part 136, 

Appendix B, Revision 1.11. A mean MDL was further calculated for each target element. The ranges into which the 

mean MDLs fell for the ZSX Mini II are listed below (lower MDL values indicate better sensitivity). 

Relative Sensitivity Mean MDL Target Elements 

High 1 - 20 ppm Copper, Mercury, Nickel, Selenium, and Zinc. 

Moderate 20 – 50 ppm Arsenic, Lead, Silver, and Vanadium. 

Low 50 – 100 ppm Antimony, Cadmium, and Chromium. 

Very Low >100 ppm None. 

Notes: ppm = Parts per million. Iron was not included in the MDL evaluation. 
 A-3 

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 

ZSX Mini II 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 Median RPD Target Elements 

High 0% - 10% None. 

Moderate 10% - 25% None. 

Low 25% - 50% Arsenic, Chromium, Copper, Silver, Vanadium, and Zinc. 

Very Low > 50% Antimony*, Cadmium, Iron, Lead, Mercury, Nickel, and 

Selenium. 

* Calculation of RPDs versus sample spike concentrations rather than reference laboratory results (due to potential low bias in 

the reference laboratory results for antimony) failed to improve accuracy. 

Accuracy was also assessed through correlation plots between the mean ZSX Mini II 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. Antimony* Arsenic Cadmium Chromium Copper 

Iron 

Lead 

Mercury 

Nickel 

Selenium 

Silver 

Vanadium 

Zinc 

Correlation 0.11 0.90 0.82 0.95 0.95 0.93 0.99 0.98 0.93 0.97 0.01 0.73 0.97 

Bias Indet. Low Var. Low Low Low Low Low Low Low Indet. Var. Low 

Notes: Indet. = Indeterminate due to low correlation. Var. = Bias varies from high to low as concentration increases. 

* Correlation did not improve when compared to sample spike concentrations as opposed to reference laboratory data. 

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 

ZSX Mini II was classified from high to very low for each target element, as indicated in the table below, 

based on the overall median RSDs. The calculated RSDs indicated a higher level of precision in the ZSX 

Mini II than in the reference laboratory data for all target elements except arsenic and chromium. 

Relative Precision Median RSD Target Elements 

High 0% - 5% Cadmium, Copper, Iron, Lead, Mercury, Nickel, Selenium, 

Silver, and Zinc 

Moderate 5% - 10% Antimony and Vanadium. 

Low 10% - 20% Arsenic and Chromium. 

Very Low > 20% 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 high relative lead concentrations (more than 

10X), a potential interferent for arsenic, actually improved the apparent accuracy for arsenic results in the 

ZSX Mini II data set (decreasing the median RPDs for arsenic from 45 percent to 16 percent) by 

counteracting the inherently low instrument bias. Similar but smaller effects were observed on nickel, 

copper, and zinc results for other interfering elements. 

Effects of Soil Characteristics: The RPDs from the evaluation of accuracy were also further evaluated 

in terms of sampling site and soil type. This evaluation found high variability in RPD values for multiple 

target elements in sandy soil from the KARS Park site, a former gun range. Extreme RPD ranges and 
 A-4 

high RPD outliers were also observed on a more limited basis in blends from other sampling sites; 

however, sample matrix had little overall effect on accuracy for the ZSX Mini II, given the broad overall 

ranges of RPDs observed. 

Sample Throughput: The total processing time per sample was estimated at 8.6 minutes, which 

included 2.2 minutes of sample preparation and 5.7 minutes of instrument analysis time. A sample 

throughput of 69 samples per 8-hour work day was estimated with the use of the instrument’s 

autosampler. As noted above, however, the sample blends had undergone rigorous pre-processing before 

the demonstration. Sample throughput would have decreased if these sample preparation steps (grinding, 

drying, sieving) had been performed during the demonstration; these steps can add from 10 minutes to 2 

hours to the sample processing time. 

Costs: A cost assessment identified a purchase cost of $82,500 plus $500 shipping for the ZSX Mini II. 

Using a hypothetical rental cost approximated from similar types of instruments, a total cost of $10,421 

(with a labor cost of $5,286 at $43.75/hr) associated with sample preparation and analysis was estimated 

for a project similar to the demonstration (326 samples of soil and sediment). In comparison, the project 

cost averaged $8,932 for all eight XRF instruments participating in the demonstration and $63,896 for 

fixed-laboratory analysis of all samples for the 13 target elements. 

Skills and training required: Field or laboratory technicians with a high school diploma are generally 

qualified to operate the ZSX Mini II. Rigaku offers free training for instrument purchasers that generally 

lasts about 3 days, and the instrument is equipped with a modem for remote troubleshooting. 

Health and Safety Aspects: The ZSX Mini II 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 ZSX Mini II must be able to safely manage high-pressure gas cylinders (if inert 

atmosphere analysis is desired). 

Portability: Based on dimensions, weight, and power requirements, the ZSX Mini II 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 ZSX Mini II is encased in durable hard-tool plastic but is not weatherproof. Rigaku 

offers a 12-month limited warranty for parts and labor. The average lifespan of the x-ray tube source is 

estimated at 10,000 hours or 7 years. 

Availability: New instruments are available from the Rigaku offices in The Woodlands, Texas, and 

London. Customers are supported by world-wide network of 10 sales and 35 service representatives. 

RELATIVE PERFORMANCE 

ZSX Mini II overall performance relative to the XRF demonstration as a whole (all 8 instruments) is as 

follows: 

 Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Selenium Silver Vanadium Zinc 

Sensitivity о о ● ● ● ● ● ● ● ● ● ● ●

Accuracy о о о о о о о о о о о ● о

Precision Same о ● о ● ● ● ● ● ● ● ● ●

Key: ● Better о Worse 

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.
 

APPENDIX B 

DEVELOPER DISCUSSION
 B-1 

DEVELOPER DISCUSSION 

Although we did not match well with the unknowns certified results, our instrument tracked well with the 

assayed numbers. In other words, as they went up or down in concentration, so did we. 

 

From our point of view the test went well; the ZSX Mini II demonstrated better sensitivity and repeatability 

versus all other instruments. 

The ZSX Mini II has proven to be excellent for analysis of heavy elements such as Cu, Fe, Ti, or Zr. Elements 

such as Ag, Cd and Sb were our worst performers for the reason that the ZSX Mini II does not have a Primary 

Beam Filter. These elements are not possible at low concentrations on the ZSX Mini II due to either sensitivity 

or interference from tube lines. 

The lack of finite standard concentration values was of prime concern for us in this test. The supplied reference 

materials had a range for the element concentrations, not exact values. We are curious as to how the other 

vendors obtained more accurate results as the ZSX Mini II always out performs all these instruments in regular 

competitions. Perhaps we missed some information on this setup? 

One of the categories was on portability of the unit. The notation concerning how many people it takes to move 

the unit indicates that the ZSX Mini II is not field portable. The definition of “field portable” is relative. Its 

portability is shown in the fact that it was shipped to this site, set up and the tests run in a short period of time. It 

is not an instrument that is hand carried but definitely portable within the definition of portable for this 

application and is readily placed in a van, or other smaller vehicles. This is not possible with the larger, full 

power XRF systems. 

For the item where the Mini II was noted as requiring facilities like a stable platform, gas, electricity and 

temperature controlled environment. Other systems at the site also required many of these facilities while still 

others needed acids, fume hoods, hot plates, etc. 

Rigaku feels that we participated in this test with the intent of simulating a field situation. Although the samples 

were ground – this would not necessarily be found in the field - they were run as loose powders as would be 

expected in a remote environment. Our main concern is the method on which we had based our calibrations. The 

fact that we were poor only in the accuracy aspect relates to improper concentration values of the calibration 

reference materials. As stated earlier, the Mini II is produced for just such tests and has a proven track record for 

such analyses. 

We thank you for allowing us to participate in this exercise and look forward to any further experiments you 

may have in the future. 

 
 

APPENDIX C 

DATA VALIDATION SUMMARY REPORT
 i

Contents 

Chapter Page

Acronyms, Abbreviations, and Symbols.....................................................................................................iii 

1.0 INTRODUCTION .......................................................................................................................... C-1 

2.0 VALIDATION METHODOLOGY................................................................................................ C-1 

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
 ii

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 
C-1 

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-2 

• 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 (MSD) 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-3 

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-4 

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-5 

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 MSD 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 MSD values were less than the criterion of 25 percent, except 

as discussed in the following paragraphs. 

Sample results affected by MS and MSD 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 MSD 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 MSD 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/MSD results. 

The precision between MS and MSD results were generally acceptable. If the RPD between MS and 

MSD 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/MSD 

precision. 

No data were rejected on the basis of MS/MSD results. The relatively low occurrence of data 

qualification due to MS/MSD recoveries and RPDs 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/MSD results. 
C-6 

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-7 

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-8 

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. 
 

TABLES
C-9 

TABLE 1: DATA VALIDATION QUALIFIERS AND COMMENT CODES 

Qualifier Definition 

No Qualifier Indicates that the data are acceptable both qualitatively and quantitatively. 

U Indicates compound was analyzed for but not detected above the concentration listed. 

The value listed is the sample quantitation limit. 

J Indicates an estimated concentration value. The result is considered qualitatively 

acceptable, but quantitatively unreliable. 

J+ The result is an estimated quantity, but the result may be biased high. 

J- The result is an estimated quantity, but the result may be biased low. 

UJ Indicates an estimated quantitation limit. The compound was analyzed for, but was 

considered non-detected. 

R The data are unusable (compound may or may not be present). Resampling and 

reanalysis is necessary for verification. 

Comment Code Definition 

a Surrogate recovery exceeded (not applicable to this data set) 

b Laboratory method blank and common blank contamination 

c Calibration criteria exceeded 

d Duplicate precision criteria exceeded 

e Matrix spike or laboratory control sample recovery exceeded 

f Field blank contamination (not applicable to this data set) 

g Quantification below reporting limit 

h Holding time exceeded 

i Internal standard criteria exceeded (not applicable to this data set) 

j Other qualification (will be specified in report) 
C-10 

TABLE 2: QC CRITERIA 

Parameter Method QC Check Frequency Criterion Corrective Action 

Reference Method 

Method and instrument blanks 

One per analytical batch of 20 or less 

Less than the reporting limit 

1. Check calculat2. Assess and elim

contamination 

3. Reanalyze blan4. Inform Tetra T5. Flag affected r

MS/MSD One per 

analytical batch of 20 or less 

75 to 125 percent recovery RPD ≤ 25 

1. Check calculat2. Check LCS/LC

duplicate resulthey meet crite

3. Inform Tetra T4. Flag affected r

LCS/LCSD One per 

analytical batch of 20 or less 

80 to 120 percent recovery RPD ≤ 20 

1. Check calculati2. Check instrume

and adjust as ne

3. Check MS/MSD 

results to determcriterion 

4. Inform Tetra Te5. Redigest and re

of samples 

6. Flag affected re

Target Metals (12 ICP metals and Hg) 

3050B/6010B and 7471A 

Performance audit samples 

One per analytical batch of 20 or less 

Within acceptance limits 

1. Evaluated by T2. Inform laborato

changes 

3. Flag affected re

Percent moisture Laboratory 

duplicates 

One per analytical batch of 20 or less 

RPD ≤ 20 1. Check calculati

2. Reanalyze samp3. Inform Tetra Te4. Flag affected re
C-11 

TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Comment 

Code 

AS-SO-04-XX Selenium 6.2 mg/kg U b 

AS-SO-06-XX Antimony 2.4 mg/kg UJ b, e 

AS-SO-10-XX Selenium 1.1 mg/kg U b 

AS-SO-11-XX Selenium 1.1 mg/kg U b 

AS-SO-13-XX Antimony 2.4 mg/kg UJ b, e 

BN-SO-18-XX Silver 0.94 mg/kg U b 

BN-SO-28-XX Silver 0.77 mg/kg U b 

BN-SO-31-XX Silver 0.97 mg/kg U b 

BN-SO-35-XX Silver 0.85 mg/kg U b 

KP-SE-01-XX Mercury 0.053 mg/kg U b 

KP-SE-11-XX Mercury 0.079 mg/kg U b 

KP-SE-12-XX Mercury 0.06 mg/kg U b 

KP-SE-14-XX Mercury 0.065 mg/kg U b 

KP-SE-17-XX Mercury 0.082 mg/kg U b 

KP-SE-19-XX Mercury 0.044 mg/kg U b 

KP-SE-25-XX Mercury 0.096 mg/kg U b 

KP-SE-25-XX Selenium 0.26 mg/kg U b 

KP-SE-28-XX Mercury 0.056 mg/kg U b 

KP-SE-30-XX Mercury 0.1 mg/kg U b 

KP-SE-30-XX Selenium 0.24 mg/kg U b 

KP-SO-02-XX Mercury 0.043 mg/kg U b 

KP-SO-02-XX Selenium 0.42 mg/kg U b 

KP-SO-03-XX Cadmium 0.074 mg/kg U b 

KP-SO-03-XX Mercury 0.044 mg/kg U b 

KP-SO-04-XX Cadmium 0.046 mg/kg U b 

KP-SO-04-XX Mercury 0.018 mg/kg U b 

KP-SO-04-XX Selenium 0.28 mg/kg U b 

KP-SO-05-XX Cadmium 0.13 mg/kg U b 

KP-SO-05-XX Mercury 0.044 mg/kg U b 

KP-SO-05-XX Selenium 0.24 mg/kg U b 

KP-SO-06-XX Arsenic 0.73 mg/kg J- b 

KP-SO-06-XX Mercury 0.059 mg/kg U b 

KP-SO-07-XX Arsenic 2 mg/kg J- b 

KP-SO-07-XX Mercury 0.027 mg/kg U b 

KP-SO-07-XX Selenium 0.21 mg/kg U b 

KP-SO-09-XX Cadmium 0.094 mg/kg U b 

KP-SO-09-XX Mercury 0.046 mg/kg U b 
TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION 

(Continued) 

C-12 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Comment 

Code 

KP-SO-10-XX Arsenic 0.7 mg/kg J- b 

KP-SO-10-XX Mercury 0.028 mg/kg U b 

KP-SO-10-XX Selenium 0.22 mg/kg U b 

KP-SO-13-XX Arsenic 1.4 mg/kg J- b 

KP-SO-13-XX Cadmium 0.045 mg/kg U b 

KP-SO-13-XX Mercury 0.037 mg/kg U b 

KP-SO-15-XX Arsenic 0.76 mg/kg J- b 

KP-SO-15-XX Mercury 0.029 mg/kg U b 

KP-SO-16-XX Cadmium 0.063 mg/kg U b 

KP-SO-16-XX Mercury 0.016 mg/kg U b 

KP-SO-18-XX Arsenic 0.56 mg/kg J- b 

KP-SO-18-XX Mercury 0.016 mg/kg U b 

KP-SO-20-XX Arsenic 1.5 mg/kg J- b 

KP-SO-20-XX Mercury 0.03 mg/kg U b 

KP-SO-21-XX Cadmium 0.098 mg/kg U b 

KP-SO-21-XX Mercury 0.042 mg/kg U b 

KP-SO-22-XX Arsenic 0.7 mg/kg J- b 

KP-SO-22-XX Mercury 0.027 mg/kg U b 

KP-SO-23-XX Cadmium 0.048 mg/kg U b 

KP-SO-23-XX Mercury 0.017 mg/kg U b 

KP-SO-24-XX Arsenic 1.4 mg/kg J- b 

KP-SO-24-XX Mercury 0.017 mg/kg U b 

KP-SO-26-XX Cadmium 0.061 mg/kg U b 

KP-SO-26-XX Mercury 0.013 mg/kg U b 

KP-SO-26-XX Selenium 0.22 mg/kg U b 

KP-SO-27-XX Arsenic 1.3 mg/kg J- b 

KP-SO-27-XX Cadmium 0.05 mg/kg U b 

KP-SO-27-XX Mercury 0.021 mg/kg U b 

KP-SO-29-XX Arsenic 1.5 mg/kg J- b 

KP-SO-29-XX Mercury 0.013 mg/kg U b 

KP-SO-31-XX Mercury 0.017 mg/kg U b 

KP-SO-32-XX Arsenic 1.6 mg/kg J- b 

KP-SO-32-XX Cadmium 0.045 mg/kg U b 

KP-SO-32-XX Mercury 0.014 mg/kg U b 

LV-SE-02-XX Mercury 0.02 mg/kg U b 

LV-SE-10-XX Mercury 0.023 mg/kg U b 

LV-SE-11-XX Selenium 1.3 mg/kg U b 
TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION 

(Continued) 

C-13 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Comment 

Code 

LV-SE-14-XX Mercury 0.056 mg/kg U b 

LV-SE-21-XX Mercury 0.048 mg/kg U b 

LV-SE-24-XX Mercury 0.053 mg/kg U b 

LV-SE-29-XX Selenium 1.2 mg/kg U b 

LV-SE-32-XX Mercury 0.052 mg/kg U b 

RF-SE-07-XX Mercury 0.091 mg/kg U b 

RF-SE-08-XX Silver 0.39 mg/kg U b 

RF-SE-10-XX Silver 0.34 mg/kg U b 

RF-SE-12-XX Mercury 0.099 mg/kg U b 

RF-SE-23-XX Copper 0.2 mg/kg U b 

RF-SE-23-XX Zinc 0.6 mg/kg U b 

RF-SE-33-XX Silver 0.33 mg/kg U b 

RF-SE-36-XX Mercury 0.081 mg/kg U b 

RF-SE-36-XX Selenium 1 mg/kg U b 

RF-SE-45-XX Cadmium 0.52 mg/kg U b 

RF-SE-53-XX Cadmium 0.57 mg/kg U b 

SB-SO-03-XX Antimony 1.2 mg/kg UJ b, e 

SB-SO-12-XX Silver 2.1 mg/kg UJ b 

SB-SO-13-XX Silver 2.2 mg/kg UJ b 

SB-SO-15-XX Silver 1.6 mg/kg UJ b 

SB-SO-17-XX Silver 2.3 mg/kg UJ b, e 

SB-SO-18-XX Antimony 1.2 mg/kg UJ b, e 

SB-SO-30-XX Selenium 1.3 mg/kg J+ b 

SB-SO-32-XX Silver 0.1 mg/kg UJ b, e 

SB-SO-37-XX Silver 2 mg/kg UJ b 

SB-SO-46-XX Silver 2.2 mg/kg UJ b, e 

SB-SO-48-XX Silver 0.1 mg/kg UJ b, e 

SB-SO-53-XX Antimony 1.2 mg/kg UJ b, e 

TL-SE-01-XX Mercury 0.074 mg/kg U b 

TL-SE-03-XX Mercury 0.32 mg/kg J- b 

TL-SE-03-XX Silver 0.94 mg/kg U b 

TL-SE-04-XX Mercury 0.26 mg/kg J- b 

TL-SE-10-XX Mercury 0.19 mg/kg J- b 

TL-SE-11-XX Mercury 0.021 mg/kg U b 

TL-SE-12-XX Mercury 0.22 mg/kg J- b 

TL-SE-14-XX Mercury 0.08 mg/kg U b 

TL-SE-15-XX Mercury 0.28 mg/kg J- b 
TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION 

(Continued) 

C-14 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Comment 

Code 

TL-SE-15-XX Silver 1 mg/kg U b 

TL-SE-18-XX Mercury 0.025 mg/kg U b 

TL-SE-19-XX Mercury 0.32 mg/kg J- b 

TL-SE-19-XX Silver 1.1 mg/kg U b 

TL-SE-20-XX Mercury 0.26 mg/kg J- b 

TL-SE-22-XX Mercury 0.082 mg/kg U b 

TL-SE-23-XX Mercury 0.41 mg/kg J- b 

TL-SE-23-XX Silver 1.3 mg/kg U b 

TL-SE-24-XX Mercury 0.26 mg/kg J- b 

TL-SE-24-XX Silver 1.3 mg/kg U b 

TL-SE-25-XX Mercury 0.44 mg/kg J- b 

TL-SE-25-XX Silver 0.94 mg/kg U b 

TL-SE-26-XX Mercury 0.24 mg/kg J- b 

TL-SE-27-XX Mercury 0.02 mg/kg U b 

TL-SE-29-XX Mercury 0.076 mg/kg U b 

TL-SE-31-XX Mercury 0.57 mg/kg J- b 

TL-SE-31-XX Silver 1.2 mg/kg U b 

WS-SO-06-XX Mercury 0.07 mg/kg U b 

WS-SO-08-XX Mercury 0.063 mg/kg U b 

WS-SO-10-XX Mercury 0.058 mg/kg U b 

WS-SO-12-XX Mercury 0.068 mg/kg UJ b, e 

WS-SO-17-XX Mercury 0.069 mg/kg UJ b, e 

WS-SO-20-XX Mercury 0.06 mg/kg U b 

WS-SO-23-XX Mercury 0.05 mg/kg U b 

WS-SO-30-XX Mercury 0.069 mg/kg UJ b, e 

WS-SO-31-XX Selenium 1.2 mg/kg U b 

WS-SO-35-XX Mercury 0.071 mg/kg UJ b, e 

Notes: 

mg/kg = Milligrams per kilogram 

b = Data were qualified based on blank contamination 

e = Data were additionally qualified based on matrix spike/matrix spike duplicate exceedances 

J+ = Result is estimated and potentially biased high 

J- = Result is estimated and potentially biased low 

UJ = Result is undetected at estimated quantitation limits 
C-15 

TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

AS-SO-01-XX Antimony 3.8 mg/kg J- e 

AS-SO-02-XX Antimony <2.6 mg/kg UJ e 

AS-SO-03-XX Mercury 3.7 mg/kg J- e 

AS-SO-03-XX Silver 480 mg/kg J- e 

AS-SO-04-XX Antimony <6.4 mg/kg UJ e 

AS-SO-05-XX Mercury 2.5 mg/kg J- e 

AS-SO-05-XX Silver 330 mg/kg J- e 

AS-SO-06-XX Antimony 2.4 mg/kg UJ b, e 

AS-SO-07-XX Antimony 3.6 mg/kg J- e 

AS-SO-08-XX Mercury 2.5 mg/kg J- e 

AS-SO-08-XX Silver 280 mg/kg J- e 

AS-SO-09-XX Antimony <2.6 mg/kg UJ e 

AS-SO-10-XX Antimony 1.9 mg/kg J- e 

AS-SO-11-XX Antimony 3.7 mg/kg J- e 

AS-SO-12-XX Antimony <2.6 mg/kg UJ e 

AS-SO-13-XX Antimony 2.4 mg/kg UJ b, e 

BN-SO-01-XX Antimony <1.3 mg/kg UJ e 

BN-SO-01-XX Silver <1.3 mg/kg UJ e 

BN-SO-05-XX Antimony 160 mg/kg J- e 

BN-SO-07-XX Antimony 110 mg/kg J- e 

BN-SO-07-XX Silver 990 mg/kg J+ e 

BN-SO-09-XX Antimony 750 mg/kg J- e 

BN-SO-09-XX Silver 100 mg/kg J- e 

BN-SO-10-XX Antimony <1.3 mg/kg UJ e 

BN-SO-10-XX Silver <1.3 mg/kg UJ e 

BN-SO-11-XX Antimony 4 mg/kg J- e 

BN-SO-11-XX Silver 140 mg/kg J- e 

BN-SO-12-XX Antimony 750 mg/kg J- e 

BN-SO-12-XX Silver 210 mg/kg J- e 

BN-SO-14-XX Antimony 3.5 mg/kg J- e 

BN-SO-14-XX Silver 140 mg/kg J- e 

BN-SO-15-XX Antimony <1.3 mg/kg UJ e 

BN-SO-15-XX Silver <1.3 mg/kg UJ e 

BN-SO-16-XX Antimony 120 mg/kg J- e 

BN-SO-16-XX Arsenic 1100 mg/kg J+ e 

BN-SO-19-XX Antimony 150 mg/kg J- e 

BN-SO-21-XX Antimony 150 mg/kg J- e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-16 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

BN-SO-21-XX Arsenic 1300 mg/kg J+ e 

BN-SO-23-XX Antimony <1.2 mg/kg UJ e 

BN-SO-23-XX Silver 130 mg/kg J- e 

BN-SO-24-XX Antimony 810 mg/kg J- e 

BN-SO-24-XX Silver 140 mg/kg J- e 

BN-SO-25-XX Antimony 82 mg/kg J- e, j 

BN-SO-25-XX Arsenic 700 mg/kg J e, j 

BN-SO-26-XX Antimony 150 mg/kg J- e 

BN-SO-29-XX Antimony 150 mg/kg J- e 

BN-SO-32-XX Antimony 160 mg/kg J- e 

BN-SO-33-XX Antimony 100 mg/kg J- e 

CN-SO-01-XX Antimony 13 mg/kg J- e 

CN-SO-02-XX Mercury 270 mg/kg J- e 

CN-SO-03-XX Mercury 34 mg/kg J- e 

CN-SO-04-XX Antimony 13 mg/kg J- e 

CN-SO-05-XX Mercury 280 mg/kg J- e 

CN-SO-06-XX Mercury 40 mg/kg J- e 

CN-SO-07-XX Mercury 36 mg/kg J- e 

CN-SO-08-XX Antimony 15 mg/kg J- e 

CN-SO-09-XX Mercury 260 mg/kg J- e 

CN-SO-10-XX Antimony 13 mg/kg J- e 

CN-SO-11-XX Antimony 17 mg/kg J- e 

KP-SE-01-XX Lead 310 mg/kg J- e 

KP-SE-01-XX Silver <0.26 mg/kg UJ e 

KP-SE-08-XX Lead 300 mg/kg J- e 

KP-SE-08-XX Silver <0.27 mg/kg UJ e 

KP-SE-11-XX Lead 310 mg/kg J- e 

KP-SE-11-XX Silver <0.27 mg/kg UJ e 

KP-SE-12-XX Lead 320 mg/kg J- e 

KP-SE-12-XX Silver <0.26 mg/kg UJ e 

KP-SE-14-XX Lead 680 mg/kg J- e, j 

KP-SE-14-XX Silver <0.26 mg/kg UJ e 

KP-SE-17-XX Lead 300 mg/kg J- e 

KP-SE-17-XX Silver <0.27 mg/kg UJ e 

KP-SE-25-XX Lead 310 mg/kg J- e 

KP-SE-25-XX Silver <0.27 mg/kg UJ e 

KP-SE-30-XX Lead 300 mg/kg J- e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-17 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

KP-SE-30-XX Silver <0.27 mg/kg UJ e 

KP-SO-04-XX Antimony 94 mg/kg J+ e 

KP-SO-06-XX Antimony 8.1 mg/kg J+ e 

KP-SO-07-XX Antimony 17 mg/kg J+ e 

KP-SO-10-XX Antimony 6.1 mg/kg J+ e 

KP-SO-13-XX Antimony 16 mg/kg J+ e 

KP-SO-15-XX Antimony 6.3 mg/kg J+ e 

KP-SO-16-XX Antimony 93 mg/kg J+ e 

KP-SO-18-XX Antimony 6.7 mg/kg J+ e 

KP-SO-20-XX Antimony 19 mg/kg J+ e 

KP-SO-22-XX Antimony 8.3 mg/kg J+ e 

KP-SO-23-XX Antimony 86 mg/kg J+ e 

KP-SO-24-XX Antimony 17 mg/kg J+ e 

KP-SO-26-XX Antimony 90 mg/kg J+ e 

KP-SO-27-XX Antimony 15 mg/kg J+ e 

KP-SO-29-XX Antimony 18 mg/kg J+ e 

KP-SO-32-XX Antimony 16 mg/kg J+ e 

LV-SE-01-XX Antimony <1.5 mg/kg UJ e 

LV-SE-02-XX Antimony <1.3 mg/kg UJ e 

LV-SE-02-XX Lead 20 mg/kg J- e 

LV-SE-02-XX Silver <1.3 mg/kg UJ e 

LV-SE-05-XX Mercury 2.6 mg/kg J- e 

LV-SE-06-XX Mercury 610 mg/kg J- e 

LV-SE-07-XX Antimony <6.7 mg/kg UJ e 

LV-SE-08-XX Antimony <1.3 mg/kg UJ e 

LV-SE-09-XX Lead 14 mg/kg J- e 

LV-SE-10-XX Antimony <1.3 mg/kg UJ e 

LV-SE-10-XX Lead 25 mg/kg J- e 

LV-SE-10-XX Silver <1.3 mg/kg UJ e 

LV-SE-11-XX Antimony <1.4 mg/kg UJ e 

LV-SE-12-XX Lead 19 mg/kg J- e 

LV-SE-13-XX Mercury 640 mg/kg J- e 

LV-SE-14-XX Antimony <1.5 mg/kg UJ e 

LV-SE-15-XX Antimony 290 mg/kg J+ e 

LV-SE-15-XX Silver 300 mg/kg J- e 

LV-SE-16-XX Antimony <1.3 mg/kg UJ e 

LV-SE-17-XX Antimony 280 mg/kg J+ e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-18 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

LV-SE-17-XX Lead 17 mg/kg J- e 

LV-SE-17-XX Silver 200 mg/kg J- e 

LV-SE-18-XX Antimony <6.7 mg/kg UJ e 

LV-SE-19-XX Lead 17 mg/kg J- e 

LV-SE-20-XX Antimony 140 mg/kg J+ e 

LV-SE-20-XX Silver 75 mg/kg J- e 

LV-SE-21-XX Antimony <1.5 mg/kg UJ e 

LV-SE-22-XX Antimony <1.3 mg/kg UJ e 

LV-SE-22-XX Lead 22 mg/kg J- e 

LV-SE-22-XX Silver <1.3 mg/kg UJ e 

LV-SE-23-XX Antimony <6.6 mg/kg UJ e 

LV-SE-24-XX Antimony <1.5 mg/kg UJ e 

LV-SE-25-XX Antimony <1.3 mg/kg UJ e 

LV-SE-25-XX Lead 23 mg/kg J- e 

LV-SE-25-XX Silver <1.3 mg/kg UJ e 

LV-SE-26-XX Lead 25 mg/kg J- e 

LV-SE-27-XX Lead 16 mg/kg J- e 

LV-SE-28-XX Antimony <1.3 mg/kg UJ e 

LV-SE-29-XX Antimony <1.4 mg/kg UJ e 

LV-SE-30-XX Antimony <1.3 mg/kg UJ e 

LV-SE-31-XX Antimony <1.3 mg/kg UJ e 

LV-SE-31-XX Lead 49 mg/kg J- e 

LV-SE-31-XX Silver <1.3 mg/kg UJ e 

LV-SE-32-XX Antimony <1.4 mg/kg UJ e 

LV-SE-33-XX Lead 21 mg/kg J- e 

LV-SE-35-XX Antimony <1.3 mg/kg UJ e 

LV-SE-35-XX Lead 22 mg/kg J- e 

LV-SE-35-XX Silver <1.3 mg/kg UJ e 

LV-SE-36-XX Lead 21 mg/kg J- e 

LV-SE-38-XX Lead 15 mg/kg J- e 

LV-SE-39-XX Lead 22 mg/kg J- e 

LV-SE-41-XX Mercury 610 mg/kg J- e 

LV-SE-42-XX Lead 22 mg/kg J- e 

LV-SE-43-XX Antimony 160 mg/kg J+ e 

LV-SE-43-XX Silver 60 mg/kg J- e 

LV-SE-45-XX Antimony <6.7 mg/kg UJ e 

LV-SE-47-XX Antimony <1.3 mg/kg UJ e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-19 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

LV-SE-48-XX Antimony <6.6 mg/kg UJ e 

LV-SE-50-XX Lead 24 mg/kg J- e 

LV-SE-51-XX Antimony 210 mg/kg J+ e 

LV-SE-51-XX Silver 250 mg/kg J- e 

LV-SO-03-XX Mercury 48 mg/kg J- e 

LV-SO-03-XX Silver 210 mg/kg J- e 

LV-SO-04-XX Mercury 130 mg/kg J- e 

LV-SO-04-XX Silver <1.2 mg/kg UJ e 

LV-SO-34-XX Mercury 130 mg/kg J- e 

LV-SO-34-XX Silver <1.2 mg/kg UJ e 

LV-SO-37-XX Mercury 130 mg/kg J- e 

LV-SO-40-XX Mercury 46 mg/kg J- e 

LV-SO-40-XX Silver 210 mg/kg J- e 

LV-SO-49-XX Mercury 52 mg/kg J- e 

LV-SO-49-XX Silver 220 mg/kg J- e 

RF-SE-02-XX Antimony <1.3 mg/kg UJ e 

RF-SE-03-XX Antimony <1.2 mg/kg UJ e 

RF-SE-04-XX Antimony 3.2 mg/kg J+ e 

RF-SE-04-XX Silver 12 mg/kg J- e 

RF-SE-05-XX Antimony 4.1 mg/kg J+ e 

RF-SE-05-XX Silver 7.4 mg/kg J- e 

RF-SE-06-XX Antimony <1.3 mg/kg UJ e 

RF-SE-13-XX Antimony <1.3 mg/kg UJ e 

RF-SE-14-XX Antimony 4.4 mg/kg J+ e 

RF-SE-14-XX Silver 13 mg/kg J- e 

RF-SE-15-XX Antimony <1.3 mg/kg UJ e 

RF-SE-19-XX Antimony 3.7 mg/kg J+ e 

RF-SE-19-XX Silver 14 mg/kg J- e 

RF-SE-22-XX Antimony <1.3 mg/kg UJ e 

RF-SE-24-XX Antimony <1.3 mg/kg UJ e 

RF-SE-25-XX Antimony <1.3 mg/kg UJ e 

RF-SE-26-XX Antimony 2.2 mg/kg J+ e 

RF-SE-26-XX Silver 7.2 mg/kg J- e 

RF-SE-27-XX Antimony <1.3 mg/kg UJ e 

RF-SE-28-XX Antimony <1.2 mg/kg UJ e 

RF-SE-30-XX Antimony <1.3 mg/kg UJ e 

RF-SE-31-XX Antimony <1.3 mg/kg UJ e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-20 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

RF-SE-32-XX Antimony <1.3 mg/kg UJ e 

RF-SE-34-XX Antimony 2.9 mg/kg J+ e 

RF-SE-34-XX Silver 10 mg/kg J- e 

RF-SE-38-XX Antimony <1.2 mg/kg UJ e 

RF-SE-39-XX Antimony 2.9 mg/kg J+ e 

RF-SE-39-XX Silver 8.2 mg/kg J- e 

RF-SE-42-XX Antimony <1.3 mg/kg UJ e 

RF-SE-43-XX Antimony <1.3 mg/kg UJ e 

RF-SE-44-XX Antimony 2.7 mg/kg J+ e 

RF-SE-44-XX Silver 7.2 mg/kg J- e 

RF-SE-45-XX Antimony <1.3 mg/kg UJ e 

RF-SE-49-XX Antimony <1.2 mg/kg UJ e 

RF-SE-52-XX Antimony 3.4 mg/kg J+ e 

RF-SE-52-XX Silver 11 mg/kg J- e 

RF-SE-53-XX Antimony <1.3 mg/kg UJ e 

RF-SE-55-XX Antimony <1.2 mg/kg UJ e 

RF-SE-56-XX Antimony 3.5 mg/kg J+ e 

RF-SE-56-XX Silver 8.3 mg/kg J- e 

RF-SE-57-XX Antimony <1.3 mg/kg UJ e 

RF-SE-58-XX Antimony <1.3 mg/kg UJ e 

RF-SE-59-XX Antimony <1.3 mg/kg UJ e 

SB-SO-01-XX Antimony 180 mg/kg J e 

SB-SO-02-XX Antimony 44 mg/kg J- e, j 

SB-SO-02-XX Silver <1.2 mg/kg UJ e 

SB-SO-03-XX Antimony 1.2 mg/kg UJ b, e 

SB-SO-04-XX Silver <1.3 mg/kg UJ e 

SB-SO-05-XX Antimony 1.6 mg/kg J- e 

SB-SO-06-XX Antimony 1.7 mg/kg J- e 

SB-SO-07-XX Antimony 45 mg/kg J e 

SB-SO-08-XX Antimony 5.4 mg/kg J- e 

SB-SO-09-XX Antimony <1.3 mg/kg UJ e 

SB-SO-09-XX Silver 160 mg/kg J- e 

SB-SO-10-XX Antimony 62 mg/kg J e 

SB-SO-11-XX Antimony 5.7 mg/kg J- e 

SB-SO-12-XX Antimony 620 mg/kg J e 

SB-SO-13-XX Antimony 430 mg/kg J e 

SB-SO-14-XX Antimony 4.1 mg/kg J- e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-21 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

SB-SO-15-XX Antimony 600 mg/kg J- j, e 

SB-SO-16-XX Antimony 170 mg/kg J e 

SB-SO-17-XX Antimony 800 mg/kg J+ e 

SB-SO-17-XX Silver 2.3 mg/kg UJ b, e 

SB-SO-18-XX Antimony 1.2 mg/kg UJ b, e 

SB-SO-19-XX Antimony 310 mg/kg J e 

SB-SO-20-XX Antimony <1.3 mg/kg UJ e 

SB-SO-20-XX Silver 140 mg/kg J- e 

SB-SO-21-XX Antimony 4.9 mg/kg J e 

SB-SO-22-XX Antimony 10 mg/kg J e, j 

SB-SO-23-XX Antimony 48 mg/kg J- e 

SB-SO-23-XX Silver <0.26 mg/kg UJ e 

SB-SO-24-XX Antimony 180 mg/kg J e 

SB-SO-25-XX Antimony 6.8 mg/kg J+ e 

SB-SO-26-XX Antimony 61 mg/kg J e 

SB-SO-27-XX Antimony 6.7 mg/kg J+ e 

SB-SO-28-XX Antimony 42 mg/kg J- e 

SB-SO-28-XX Silver <0.26 mg/kg UJ e 

SB-SO-29-XX Silver <1.2 mg/kg UJ e 

SB-SO-30-XX Antimony 3.2 mg/kg J- e 

SB-SO-31-XX Antimony <1.3 mg/kg UJ e 

SB-SO-31-XX Silver 160 mg/kg J- e, j 

SB-SO-32-XX Antimony 46 mg/kg J- e 

SB-SO-32-XX Silver 0.1 mg/kg UJ b, e 

SB-SO-33-XX Antimony 350 mg/kg J e 

SB-SO-33-XX Silver 2 mg/kg J e 

SB-SO-34-XX Silver <1.3 mg/kg UJ e 

SB-SO-35-XX Antimony 6 mg/kg J+ e 

SB-SO-36-XX Silver <1.2 mg/kg UJ e 

SB-SO-37-XX Antimony 340 mg/kg J e 

SB-SO-38-XX Antimony <1.3 mg/kg UJ e 

SB-SO-39-XX Antimony 4.7 mg/kg J- e 

SB-SO-40-XX Antimony 2.2 mg/kg J- e 

SB-SO-41-XX Antimony <1.3 mg/kg UJ e 

SB-SO-42-XX Antimony 4.6 mg/kg J- e 

SB-SO-43-XX Antimony 40 mg/kg J- e 

SB-SO-43-XX Silver <0.26 mg/kg UJ e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-22 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

SB-SO-44-XX Antimony 6.8 mg/kg J+ e 

SB-SO-45-XX Antimony 180 mg/kg J e 

SB-SO-45-XX Silver 2.1 mg/kg J- e 

SB-SO-46-XX Antimony 740 mg/kg J+ e 

SB-SO-46-XX Silver 2.2 mg/kg UJ b, e 

SB-SO-47-XX Antimony <1.3 mg/kg UJ e 

SB-SO-48-XX Antimony 39 mg/kg J- e 

SB-SO-48-XX Silver 0.1 mg/kg UJ b, e 

SB-SO-49-XX Silver <1.2 mg/kg UJ e 

SB-SO-50-XX Antimony 57 mg/kg J e 

SB-SO-51-XX Antimony <1.3 mg/kg UJ e 

SB-SO-52-XX Antimony 150 mg/kg J e 

SB-SO-53-XX Antimony 1.2 mg/kg UJ b, e 

SB-SO-54-XX Lead 5.2 mg/kg J- e 

SB-SO-54-XX Silver <0.5 mg/kg UJ e 

SB-SO-55-XX Antimony 340 mg/kg J e 

SB-SO-55-XX Silver 2.2 mg/kg J e 

SB-SO-56-XX Silver <1.2 mg/kg UJ e 

TL-SE-01-XX Antimony <1.2 mg/kg UJ e 

TL-SE-01-XX Lead 48 mg/kg J- e 

TL-SE-01-XX Silver 5.7 mg/kg J- e 

TL-SE-05-XX Antimony 100 mg/kg J+ e 

TL-SE-05-XX Silver 180 mg/kg J- e 

TL-SE-09-XX Antimony 100 mg/kg J+ e 

TL-SE-09-XX Silver 170 mg/kg J- e 

TL-SE-11-XX Antimony <1.2 mg/kg UJ e 

TL-SE-11-XX Lead 54 mg/kg J- e 

TL-SE-11-XX Silver 5.5 mg/kg J- e 

TL-SE-13-XX Antimony 95 mg/kg J+ j, e 

TL-SE-13-XX Silver 160 mg/kg J j, e 

TL-SE-14-XX Antimony <1.2 mg/kg UJ e 

TL-SE-14-XX Lead 50 mg/kg J- e 

TL-SE-14-XX Silver 5.7 mg/kg J- e 

TL-SE-18-XX Antimony <1.2 mg/kg UJ e 

TL-SE-18-XX Lead 46 mg/kg J- e 

TL-SE-18-XX Silver 6.3 mg/kg J- e 

TL-SE-22-XX Antimony <1.2 mg/kg UJ e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-23 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

TL-SE-22-XX Lead 54 mg/kg J- e 

TL-SE-22-XX Silver 6.5 mg/kg J- e 

TL-SE-27-XX Antimony <1.2 mg/kg UJ e 

TL-SE-27-XX Lead 51 mg/kg J- e 

TL-SE-27-XX Silver 7.8 mg/kg J- e 

TL-SE-29-XX Antimony <1.2 mg/kg UJ e 

TL-SE-29-XX Lead 51 mg/kg J- e 

TL-SE-29-XX Silver 5.9 mg/kg J- e 

WS-SO-01-XX Antimony 41 mg/kg J- e 

WS-SO-01-XX Mercury 5.8 mg/kg J e, j 

WS-SO-01-XX Silver 69 mg/kg J- e 

WS-SO-02-XX Antimony 130 mg/kg J- e 

WS-SO-02-XX Silver 150 mg/kg J- e 

WS-SO-03-XX Antimony 8.9 mg/kg J- e 

WS-SO-03-XX Mercury 0.86 mg/kg J- e 

WS-SO-04-XX Antimony 45 mg/kg J- e 

WS-SO-04-XX Silver 76 mg/kg J- e 

WS-SO-05-XX Antimony 8.6 mg/kg J- e 

WS-SO-05-XX Silver 0.76 mg/kg J- e 

WS-SO-07-XX Silver 400 mg/kg J- e 

WS-SO-09-XX Antimony 7.1 mg/kg J- e 

WS-SO-09-XX Mercury 0.89 mg/kg J- e 

WS-SO-10-XX Silver <1.3 mg/kg UJ e 

WS-SO-11-XX Silver 340 mg/kg J- e 

WS-SO-12-XX Antimony <1.3 mg/kg UJ e 

WS-SO-12-XX Mercury 0.068 mg/kg UJ b, e 

WS-SO-13-XX Antimony 200 mg/kg J- e 

WS-SO-13-XX Silver 170 mg/kg J- e 

WS-SO-14-XX Antimony 8.4 mg/kg J- e 

WS-SO-14-XX Mercury 0.74 mg/kg J- e 

WS-SO-15-XX Antimony 48 mg/kg J- e 

WS-SO-15-XX Silver 90 mg/kg J- e 

WS-SO-16-XX Antimony 110 mg/kg J- e 

WS-SO-16-XX Silver 150 mg/kg J- e 

WS-SO-17-XX Antimony <1.3 mg/kg UJ e 

WS-SO-17-XX Mercury 0.069 mg/kg UJ b, e 

WS-SO-18-XX Antimony 130 mg/kg J- e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-24 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Validation 

Code 

WS-SO-18-XX Silver 140 mg/kg J- e 

WS-SO-19-XX Antimony 150 mg/kg J- e 

WS-SO-19-XX Silver 160 mg/kg J- e 

WS-SO-20-XX Silver <1.3 mg/kg UJ e 

WS-SO-21-XX Antimony 120 mg/kg J- e 

WS-SO-21-XX Silver 150 mg/kg J- e 

WS-SO-22-XX Antimony 41 mg/kg J- e 

WS-SO-22-XX Silver 72 mg/kg J- e 

WS-SO-23-XX Silver <1.3 mg/kg UJ e 

WS-SO-24-XX Antimony 97 mg/kg J- e 

WS-SO-24-XX Silver 140 mg/kg J- e 

WS-SO-25-XX Silver 450 mg/kg J- e 

WS-SO-26-XX Antimony 7.6 mg/kg J- e 

WS-SO-26-XX Mercury 0.83 mg/kg J- e 

WS-SO-27-XX Antimony <1.3 mg/kg UJ e 

WS-SO-27-XX Mercury 0.11 mg/kg J- e 

WS-SO-28-XX Antimony 120 mg/kg J- e 

WS-SO-28-XX Silver 130 mg/kg J- e 

WS-SO-29-XX Antimony 120 mg/kg J- e 

WS-SO-29-XX Silver 140 mg/kg J- e 

WS-SO-30-XX Antimony 1.2 mg/kg J- e 

WS-SO-30-XX Mercury 0.069 mg/kg UJ b, e 

WS-SO-31-XX Antimony 7.2 mg/kg J- e 

WS-SO-31-XX Mercury 0.85 mg/kg J- e 

WS-SO-32-XX Antimony 190 mg/kg J- e 

WS-SO-32-XX Silver 190 mg/kg J- e 

WS-SO-33-XX Antimony 6.9 mg/kg J- e 

WS-SO-33-XX Mercury 0.87 mg/kg J- e 

WS-SO-34-XX Antimony 45 mg/kg J- e 

WS-SO-34-XX Silver 78 mg/kg J- e 

WS-SO-35-XX Antimony <1.3 mg/kg UJ e 

WS-SO-35-XX Mercury 0.071 mg/kg UJ b, e 

WS-SO-36-XX Antimony 120 mg/kg J- e 

WS-SO-36-XX Silver 120 mg/kg J- e 

WS-SO-37-XX Antimony 120 mg/kg J- e 

WS-SO-37-XX Silver 140 mg/kg J- e 
TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES 

(Continued) 

C-25 

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-26 

TABLE 5: DATA QUALIFICATION: SERIAL DILUTION EXCEEDANCES 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Comment 

Code 

AS-SO-09-XX Arsenic 25 mg/kg J- j 

AS-SO-09-XX Cadmium 100 mg/kg J- j 

AS-SO-09-XX Chromium 390 mg/kg J- j 

AS-SO-09-XX Copper 250 mg/kg J- j 

AS-SO-09-XX Iron 94000 mg/kg J- j 

AS-SO-09-XX Lead 3200 mg/kg J- j 

AS-SO-09-XX Nickel 170 mg/kg J- j 

AS-SO-09-XX Silver 9.6 mg/kg J- j 

AS-SO-09-XX Vanadium 65 mg/kg J- j 

AS-SO-09-XX Zinc 6800 mg/kg J- j 

BN-SO-11-XX Mercury 24 mg/kg J- j 

BN-SO-25-XX Antimony 82 mg/kg J- e, j 

BN-SO-25-XX Arsenic 700 mg/kg J e, j 

BN-SO-25-XX Cadmium 370 mg/kg J- j 

BN-SO-25-XX Chromium 64 mg/kg J- j 

BN-SO-25-XX Copper 930 mg/kg J- j 

BN-SO-25-XX Iron 16000 mg/kg J- j 

BN-SO-25-XX Lead 5400 mg/kg J- j 

BN-SO-25-XX Nickel 88 mg/kg J- j 

BN-SO-25-XX Selenium 19 mg/kg J- j 

BN-SO-25-XX Silver 48 mg/kg J- j 

BN-SO-25-XX Vanadium 28 mg/kg J- j 

BN-SO-25-XX Zinc 2900 mg/kg J- j 

KP-SE-14-XX Antimony 11 mg/kg J- j 

KP-SE-14-XX Chromium 46 mg/kg J- j 

KP-SE-14-XX Copper 2.7 mg/kg J+ j 

KP-SE-14-XX Iron 520 mg/kg J- j 

KP-SE-14-XX Lead 680 mg/kg J- e, j 

KP-SE-14-XX Nickel 23 mg/kg J- j 

LV-SE-29-XX Lead 7.2 mg/kg J+ j 

LV-SE-29-XX Mercury 1.5 mg/kg J- j 

LV-SE-35-XX Arsenic 31 mg/kg J- j 

LV-SE-35-XX Chromium 74 mg/kg J- j 

LV-SE-35-XX Iron 24000 mg/kg J- j 

LV-SE-35-XX Nickel 170 mg/kg J- j 

LV-SE-35-XX Vanadium 55 mg/kg J- j 

LV-SE-35-XX Zinc 67 mg/kg J- j 

LV-SO-34-XX Antimony 870 mg/kg J- j 
TABLE 5: DATA QUALIFICATIONS: SERIAL DILUTION EXCEEDANCES (Continued) 

 

C-27 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Comment 

Code 

LV-SO-34-XX Arsenic 110 mg/kg J- j 

LV-SO-34-XX Cadmium 2300 mg/kg J- j 

LV-SO-34-XX Chromium 2200 mg/kg J- j 

LV-SO-34-XX Iron 20000 mg/kg J- j 

LV-SO-34-XX Lead 3700 mg/kg J- j 

LV-SO-34-XX Nickel 1900 mg/kg J- j 

LV-SO-34-XX Selenium 220 mg/kg J- j 

LV-SO-34-XX Vanadium 230 mg/kg J- j 

LV-SO-34-XX Zinc 48 mg/kg J- j 

RF-SE-16-XX Antimony 85 mg/kg J- j 

RF-SE-16-XX Arsenic 72 mg/kg J- j 

RF-SE-16-XX Cadmium 310 mg/kg J- j 

RF-SE-16-XX Chromium 820 mg/kg J- j 

RF-SE-16-XX Copper 73 mg/kg J- j 

RF-SE-16-XX Iron 16000 mg/kg J- j 

RF-SE-16-XX Lead 24 mg/kg J- j 

RF-SE-16-XX Nickel 1700 mg/kg J- j 

RF-SE-16-XX Silver 130 mg/kg J- j 

RF-SE-16-XX Vanadium 32 mg/kg J- j 

RF-SE-16-XX Zinc 760 mg/kg J- j 

RF-SE-24-XX Arsenic 130 mg/kg J+ j 

RF-SE-24-XX Cadmium 6.5 mg/kg J+ j 

RF-SE-24-XX Chromium 74 mg/kg J+ j 

RF-SE-24-XX Copper 860 mg/kg J+ j 

RF-SE-24-XX Iron 24000 mg/kg J+ j 

RF-SE-24-XX Lead 410 mg/kg J+ j 

RF-SE-24-XX Nickel 170 mg/kg J+ j 

RF-SE-24-XX Silver 3.8 mg/kg J+ j 

RF-SE-24-XX Vanadium 46 mg/kg J+ j 

RF-SE-24-XX Zinc 1400 mg/kg J- j 

SB-SO-02-XX Antimony 44 mg/kg J- e, j 

SB-SO-02-XX Arsenic 23 mg/kg J- j 

SB-SO-02-XX Lead 22 mg/kg J- j 

SB-SO-02-XX Mercury 130 mg/kg J+ j 

SB-SO-15-XX Antimony 600 mg/kg J- j, e 

SB-SO-15-XX Arsenic 170 mg/kg J- j 

SB-SO-15-XX Chromium 91 mg/kg J- j 

SB-SO-15-XX Copper 30 mg/kg J- j 

SB-SO-15-XX Iron 51000 mg/kg J- j 
TABLE 5: DATA QUALIFICATIONS: SERIAL DILUTION EXCEEDANCES (Continued) 

 

C-28 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Comment 

Code 

SB-SO-15-XX Lead 40 mg/kg J- j 

SB-SO-15-XX Nickel 100 mg/kg J- j 

SB-SO-15-XX Vanadium 52 mg/kg J- j 

SB-SO-15-XX Zinc 36 mg/kg J- j 

SB-SO-22-XX Antimony 10 mg/kg J e, j 

SB-SO-22-XX Zinc 64 mg/kg J- j 

SB-SO-31-XX Arsenic 8 mg/kg J- j 

SB-SO-31-XX Nickel 3200 mg/kg J- j 

SB-SO-31-XX Selenium 28 mg/kg J- j 

SB-SO-31-XX Silver 160 mg/kg J- e, j 

SB-SO-31-XX Zinc 3900 mg/kg J- j 

TL-SE-13-XX Antimony 95 mg/kg J+ j, e 

TL-SE-13-XX Chromium 36 mg/kg J+ j 

TL-SE-13-XX Copper 4400 mg/kg J+ j 

TL-SE-13-XX Iron 22000 mg/kg J+ j 

TL-SE-13-XX Lead 1100 mg/kg J+ j 

TL-SE-13-XX Silver 160 mg/kg J j, e 

TL-SE-13-XX Vanadium 59 mg/kg J+ j 

WS-SO-01-XX Mercury 5.8 mg/kg J e, j 

WS-SO-33-XX Arsenic 450 mg/kg J- j 

WS-SO-33-XX Cadmium 11 mg/kg J- j 

WS-SO-33-XX Chromium 120 mg/kg J- j 

WS-SO-33-XX Copper 150 mg/kg J- j 

WS-SO-33-XX Iron 28000 mg/kg J- j 

WS-SO-33-XX Lead 3700 mg/kg J- j 

WS-SO-33-XX Nickel 65 mg/kg J- j 

WS-SO-33-XX Silver 13 mg/kg J- j 

WS-SO-33-XX Vanadium 53 mg/kg J- j 

WS-SO-33-XX Zinc 830 mg/kg 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
 

APPENDIX D 

DEVELOPER AND REFERENCE LABORATORY DATA
D-1

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

1 KP-SO-06-XX Reference Laboratory 8.1 J+ 1 J- 0.1 U 290 26 1,400 620 1 KP-SO-10-XX Reference Laboratory 6.1 J+ 1 J- 0.1 U 300 26 1,600 560 1 KP-SO-15-XX Reference Laboratory 6.3 J+ 1 J- 0.1 U 340 26 1,600 510 1 KP-SO-18-XX Reference Laboratory 6.7 J+ 1 J- 0.1 U 250 24 1,200 500 1 KP-SO-22-XX Reference Laboratory 8.3 J+ 1 J- 0.1 U 260 29 1,300 650 1 KP-SO-06-RI Rigaku, Inc. 289 85 866 198 37 3,882 358 1 KP-SO-10-RI Rigaku, Inc. 325 116 893 246 43 3,883 399 1 KP-SO-15-RI Rigaku, Inc. 303 101 913 227 40 3,880 357 1 KP-SO-18-RI Rigaku, Inc. 310 105 885 212 42 3,892 360 1 KP-SO-22-RI Rigaku, Inc. 366 124 957 212 41 3,968 359 2 KP-SO-07-XX Reference Laboratory 17 J+ 2 J- 0.1 U 170 48 990 1,200 2 KP-SO-13-XX Reference Laboratory 16 J+ 1 J- 0.045 U 180 52 980 1,200 2 KP-SO-20-XX Reference Laboratory 19 J+ 2 J- 0.1 U 160 46 910 1,300 2 KP-SO-24-XX Reference Laboratory 17 J+ 1 J- 0.1 U 160 49 900 1,100 2 KP-SO-27-XX Reference Laboratory 15 J+ 1 J- 0.05 U 170 45 970 1,200 2 KP-SO-29-XX Reference Laboratory 18 J+ 2 J- 0.1 U 150 42 870 1,200 2 KP-SO-32-XX Reference Laboratory 16 J+ 2 J- 0.045 U 180 50 970 1,200 2 KP-SO-07-RI Rigaku, Inc. 420 102 854 91 65 3,569 792 2 KP-SO-13-RI Rigaku, Inc. 510 102 971 81 64 3,526 747 2 KP-SO-20-RI Rigaku, Inc. 459 82 899 142 60 3,603 777 2 KP-SO-24-RI Rigaku, Inc. 467 98 908 89 62 3,637 804 2 KP-SO-27-RI Rigaku, Inc. 399 117 885 156 58 3,576 760 2 KP-SO-29-RI Rigaku, Inc. 447 108 871 91 51 3,537 789 2 KP-SO-32-RI Rigaku, Inc. 457 107 885 154 57 3,606 790 3 KP-SO-04-XX Reference Laboratory 94 J+ 3 0.046 U 180 200 1,300 5,800 3 KP-SO-16-XX Reference Laboratory 93 J+ 3 0.063 U 200 230 1,400 6,100 3 KP-SO-23-XX Reference Laboratory 86 J+ 3 0.048 U 180 190 1,300 5,300 3 KP-SO-26-XX Reference Laboratory 90 J+ 4 0.061 U 210 230 1,500 6,500 3 KP-SO-31-XX Reference Laboratory 88 28 0.1 U 140 200 1,100 5,700 3 KP-SO-04-RI Rigaku, Inc. 1,011 126 765 129 186 3,642 3,280 3 KP-SO-16-RI Rigaku, Inc. 1,106 145 779 74 183 3,584 3,259 3 KP-SO-23-RI Rigaku, Inc. 1,042 120 764 123 183 3,626 3,269 3 KP-SO-26-RI Rigaku, Inc. 1,125 104 777 137 192 3,639 3,392 3 KP-SO-31-RI Rigaku, Inc. 1,184 148 810 125 182 3,665 3,379 
D-2

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

1 KP-SO-06-XX Reference Laboratory 0.06 U 140 0.25 U 0.25 U 2 J 11 1 KP-SO-10-XX Reference Laboratory 0.03 U 150 0.22 U 0.25 U 2 J 12 1 KP-SO-15-XX Reference Laboratory 0.03 U 170 0.25 U 0.25 U 2 J 15 1 KP-SO-18-XX Reference Laboratory 0.02 U 120 0.25 U 0.25 U 2 J 11 1 KP-SO-22-XX Reference Laboratory 0.03 U 130 0.25 U 0.25 U 2 J 11 1 KP-SO-06-RI Rigaku, Inc. 71 122 16 302 19 36 1 KP-SO-10-RI Rigaku, Inc. 58 128 19 306 18 38 1 KP-SO-15-RI Rigaku, Inc. 62 127 14 301 21 34 1 KP-SO-18-RI Rigaku, Inc. 69 133 16 316 25 31 1 KP-SO-22-RI Rigaku, Inc. 70 121 16 321 19 45 2 KP-SO-07-XX Reference Laboratory 0.03 U 87 0.21 U 0.25 U 1 J 26 2 KP-SO-13-XX Reference Laboratory 0.04 U 90 0.25 U 0.25 U 1 J 24 2 KP-SO-20-XX Reference Laboratory 0.03 U 79 0.25 U 0.25 U 1 J 25 2 KP-SO-24-XX Reference Laboratory 0.02 U 78 0.25 U 0.25 U 1 J 22 2 KP-SO-27-XX Reference Laboratory 0.02 U 87 0.25 U 0.25 U 1 J 24 2 KP-SO-29-XX Reference Laboratory 0.01 U 73 0.25 U 0.25 U 1 J 22 2 KP-SO-32-XX Reference Laboratory 0.01 U 88 0.51 0.25 U 1 J 24 2 KP-SO-07-RI Rigaku, Inc. 68 94 15 290 25 40 2 KP-SO-13-RI Rigaku, Inc. 50 86 15 326 15 35 2 KP-SO-20-RI Rigaku, Inc. 62 94 17 310 24 57 2 KP-SO-24-RI Rigaku, Inc. 62 90 16 305 28 44 2 KP-SO-27-RI Rigaku, Inc. 66 90 15 301 18 41 2 KP-SO-29-RI Rigaku, Inc. 63 93 17 294 24 41 2 KP-SO-32-RI Rigaku, Inc. 64 96 18 308 22 47 3 KP-SO-04-XX Reference Laboratory 0.02 U 93 0.28 U 0.16 J 1 J 45 3 KP-SO-16-XX Reference Laboratory 0.02 U 100 0.25 U 0.16 J 1 J 47 3 KP-SO-23-XX Reference Laboratory 0.02 U 91 0.25 U 0.13 J 1 J 41 3 KP-SO-26-XX Reference Laboratory 0.01 U 110 0.22 U 0.17 J 1 J 52 3 KP-SO-31-XX Reference Laboratory 0.02 U 68 0.25 U 0.4 2 J 38 3 KP-SO-04-RI Rigaku, Inc. 61 81 17 260 25 57 3 KP-SO-16-RI Rigaku, Inc. 48 81 19 271 15 55 3 KP-SO-23-RI Rigaku, Inc. 59 78 18 262 18 53 3 KP-SO-26-RI Rigaku, Inc. 52 88 16 267 20 59 3 KP-SO-31-RI Rigaku, Inc. 42 82 20 273 14 58 
D-3

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

4 KP-SO-02-XX Reference Laboratory 410 10 0.1 6 780 1,700 18,000 4 KP-SO-03-XX Reference Laboratory 360 9 0.074 U 5 670 1,600 19,000 4 KP-SO-05-XX Reference Laboratory 410 12 0.13 U 6 780 2,000 24,000 4 KP-SO-09-XX Reference Laboratory 420 11 0.094 U 5 780 1,800 22,000 4 KP-SO-21-XX Reference Laboratory 370 10 0.098 U 5 700 1,700 19,000 4 KP-SO-02-RI Rigaku, Inc. 2,230 166 588 -8 539 3,679 10,300 4 KP-SO-03-RI Rigaku, Inc. 2,237 120 598 31 590 3,686 10,425 4 KP-SO-05-RI Rigaku, Inc. 2,056 140 578 -13 573 3,666 10,700 4 KP-SO-09-RI Rigaku, Inc. 2,034 136 581 7 545 3,637 10,389 4 KP-SO-21-RI Rigaku, Inc. 2,049 131 565 9 580 3,663 10,432 5 WS-SO-06-XX Reference Laboratory 1.3 U 48 1.9 120 50 28,000 110 5 WS-SO-08-XX Reference Laboratory 1.3 45 2 120 47 26,000 71 5 WS-SO-12-XX Reference Laboratory 1.3 UJ 43 1.8 110 45 25,000 65 5 WS-SO-17-XX Reference Laboratory 1.3 UJ 47 1.9 120 49 28,000 70 5 WS-SO-27-XX Reference Laboratory 1.3 UJ 49 2 120 51 28,000 72 5 WS-SO-30-XX Reference Laboratory 1.2 J- 51 2 130 53 29,000 81 5 WS-SO-35-XX Reference Laboratory 1.3 UJ 49 2 130 51 28,000 74 5 WS-SO-06-RI Rigaku, Inc. 147 75 600 113 42 15,860 6 5 WS-SO-08-RI Rigaku, Inc. 164 52 602 83 42 15,925 4 5 WS-SO-12-RI Rigaku, Inc. 135 66 587 65 50 15,982 -3 5 WS-SO-17-RI Rigaku, Inc. 162 50 613 115 38 15,770 16 5 WS-SO-27-RI Rigaku, Inc. 176 32 598 118 37 15,837 6 5 WS-SO-30-RI Rigaku, Inc. 168 69 601 89 39 15,943 6 5 WS-SO-35-RI Rigaku, Inc. 158 61 620 105 42 15,895 6 6 WS-SO-03-XX Reference Laboratory 8.9 J- 500 12 140 170 32,000 4,300 6 WS-SO-05-XX Reference Laboratory 8.6 J- 440 12 140 160 31,000 4,000 6 WS-SO-09-XX Reference Laboratory 7.1 J- 480 12 130 160 30,000 4,000 6 WS-SO-14-XX Reference Laboratory 8.4 J- 430 11 120 150 28,000 3,700 6 WS-SO-26-XX Reference Laboratory 7.6 J- 520 12 140 160 30,000 4,000 6 WS-SO-31-XX Reference Laboratory 7.2 J- 520 12 140 170 32,000 4,200 6 WS-SO-33-XX Reference Laboratory 6.9 J- 450 J- 11 J- 120 J- 150 J- 28,000 J- 3,700 6 WS-SO-03-RI Rigaku, Inc. 441 199 565 94 102 16,124 1,996 6 WS-SO-05-RI Rigaku, Inc. 445 230 579 98 94 16,250 2,026 6 WS-SO-09-RI Rigaku, Inc. 413 186 576 115 98 16,184 1,979 6 WS-SO-14-RI Rigaku, Inc. 466 240 566 132 98 16,132 1,974 6 WS-SO-26-RI Rigaku, Inc. 468 241 593 103 101 16,212 1,979 6 WS-SO-31-RI Rigaku, Inc. 479 211 578 129 97 16,183 1,967 6 WS-SO-33-RI Rigaku, Inc. 480 184 592 115 101 16,200 2,028 
D-4

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

4 KP-SO-02-XX Reference Laboratory 0.04 U 4 0.42 U 0.82 0 J 100 4 KP-SO-03-XX Reference Laboratory 0.04 U 3 0.25 U 0.73 0 J 92 4 KP-SO-05-XX Reference Laboratory 0.04 U 4 0.24 U 0.82 0 J 110 4 KP-SO-09-XX Reference Laboratory 0.05 U 3 0.25 U 0.84 0 J 110 4 KP-SO-21-XX Reference Laboratory 0.04 U 4 0.25 U 0.76 0 J 100 4 KP-SO-02-RI Rigaku, Inc. 54 32 20 212 28 91 4 KP-SO-03-RI Rigaku, Inc. 47 31 18 200 24 91 4 KP-SO-05-RI Rigaku, Inc. 52 33 20 198 21 91 4 KP-SO-09-RI Rigaku, Inc. 53 37 21 206 26 90 4 KP-SO-21-RI Rigaku, Inc. 44 33 21 203 25 95 5 WS-SO-06-XX Reference Laboratory 0.07 U 61 1.3 U 0.93 J 56 230 5 WS-SO-08-XX Reference Laboratory 0.06 U 58 1.3 U 0.86 J 52 220 5 WS-SO-12-XX Reference Laboratory 0.07 UJ 55 1.3 U 0.94 J 49 210 5 WS-SO-17-XX Reference Laboratory 0.07 UJ 59 1.3 U 0.89 J 56 230 5 WS-SO-27-XX Reference Laboratory 0.11 J- 61 1.3 U 0.9 J 57 230 5 WS-SO-30-XX Reference Laboratory 0.07 UJ 65 1.3 U 1 J 58 240 5 WS-SO-35-XX Reference Laboratory 0.07 UJ 62 1.3 U 1 J 57 240 5 WS-SO-06-RI Rigaku, Inc. 26 44 8 204 63 146 5 WS-SO-08-RI Rigaku, Inc. 28 39 9 208 77 146 5 WS-SO-12-RI Rigaku, Inc. 24 41 7 199 75 146 5 WS-SO-17-RI Rigaku, Inc. 29 38 7 207 74 149 5 WS-SO-27-RI Rigaku, Inc. 23 41 7 204 84 141 5 WS-SO-30-RI Rigaku, Inc. 23 44 7 210 57 140 5 WS-SO-35-RI Rigaku, Inc. 29 39 8 219 78 151 6 WS-SO-03-XX Reference Laboratory 0.86 J- 75 1.6 15 58 930 6 WS-SO-05-XX Reference Laboratory 0.76 J- 71 1.3 U 15 57 900 6 WS-SO-09-XX Reference Laboratory 0.89 J- 70 1.3 U 14 56 870 6 WS-SO-14-XX Reference Laboratory 0.74 J- 64 1.3 U 13 50 820 6 WS-SO-26-XX Reference Laboratory 0.83 J- 70 1.3 U 14 56 900 6 WS-SO-31-XX Reference Laboratory 0.85 J- 72 1.2 U 15 60 950 6 WS-SO-33-XX Reference Laboratory 0.87 J- 65 J- 1.3 U 13 J- 53 J- 830 J6 WS-SO-03-RI Rigaku, Inc. 23 45 9 188 74 399 6 WS-SO-05-RI Rigaku, Inc. 30 43 7 197 81 395 6 WS-SO-09-RI Rigaku, Inc. 31 49 6 193 57 418 6 WS-SO-14-RI Rigaku, Inc. 29 48 8 202 70 399 6 WS-SO-26-RI Rigaku, Inc. 26 47 10 199 69 396 6 WS-SO-31-RI Rigaku, Inc. 24 39 7 196 63 396 6 WS-SO-33-RI Rigaku, Inc. 30 40 7 198 66 406 
D-5

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

7 WS-SO-01-XX Reference Laboratory 41 J- 1900 47 100 590 32,000 18,007 WS-SO-04-XX Reference Laboratory 45 J- 2000 50 94 640 34,000 20,007 WS-SO-15-XX Reference Laboratory 48 J- 2300 56 82 720 37,000 24,007 WS-SO-22-XX Reference Laboratory 41 J- 1900 47 84 620 33,000 17,007 WS-SO-34-XX Reference Laboratory 45 J- 2000 50 91 660 36,000 22,007 WS-SO-01-RI Rigaku, Inc. 813 866 425 137 392 17,607 9,607 WS-SO-04-RI Rigaku, Inc. 877 828 427 112 396 17,625 9,657 WS-SO-15-RI Rigaku, Inc. 901 841 445 88 379 17,579 9,764 7 WS-SO-22-RI Rigaku, Inc. 952 848 434 120 378 17,542 9,554 7 WS-SO-34-RI Rigaku, Inc. 845 838 434 106 379 17,569 9,668 WS-SO-02-XX Reference Laboratory 130 J- 4200 98 49 1300 44,000 35,008 WS-SO-16-XX Reference Laboratory 110 J- 3900 91 59 1300 42,000 24,008 WS-SO-18-XX Reference Laboratory 130 J- 4100 95 63 1300 44,000 37,008 WS-SO-21-XX Reference Laboratory 120 J- 3900 90 43 1200 40,000 43,008 WS-SO-24-XX Reference Laboratory 97 J- 3600 81 54 1100 38,000 27,008 WS-SO-29-XX Reference Laboratory 120 J- 3800 90 51 1200 40,000 42,008 WS-SO-37-XX Reference Laboratory 120 J- 4100 95 63 1300 42,000 26,008 WS-SO-02-RI Rigaku, Inc. 389 1,541 338 129 744 20,249 17,438 WS-SO-16-RI Rigaku, Inc. 364 1,544 336 130 740 20,082 17,158 WS-SO-18-RI Rigaku, Inc. 522 1,558 326 180 735 19,895 17,248 WS-SO-21-RI Rigaku, Inc. 466 1,485 336 139 745 19,866 17,268 WS-SO-24-RI Rigaku, Inc. 309 1,548 312 158 731 20,151 17,208 WS-SO-29-RI Rigaku, Inc. 531 1,522 330 101 745 20,030 17,218 WS-SO-37-RI Rigaku, Inc. 568 1,564 317 129 734 20,159 17,319 WS-SO-13-XX Reference Laboratory 200 J- 5800 150 53 1800 47,000 45,009 WS-SO-19-XX Reference Laboratory 150 J- 5000 130 66 1500 39,000 24,009 WS-SO-28-XX Reference Laboratory 120 J- 4200 100 54 1200 33,000 30,009 WS-SO-32-XX Reference Laboratory 190 J- 5500 140 54 1700 44,000 30,009 WS-SO-36-XX Reference Laboratory 120 J- 3800 92 51 1100 30,000 45,009 WS-SO-13-RI Rigaku, Inc. 101 2,007 303 152 975 19,879 20,959 WS-SO-19-RI Rigaku, Inc. 139 2,004 304 152 966 20,134 20,929 WS-SO-28-RI Rigaku, Inc. 270 2,006 306 156 956 19,964 21,269 WS-SO-32-RI Rigaku, Inc. 304 2,028 308 147 957 20,163 20,969 WS-SO-36-RI Rigaku, Inc. 223 2,032 301 113 970 20,164 21,15
D-6

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

7 WS-SO-01-XX Reference Laboratory 5.8 J 66 1.3 U 69 J- 42 3,000 7 WS-SO-04-XX Reference Laboratory 6.5 62 1.3 U 76 J- 44 3,100 7 WS-SO-15-XX Reference Laboratory 5.8 58 1.3 U 90 J- 52 3,400 7 WS-SO-22-XX Reference Laboratory 4.8 57 1.3 U 72 J- 44 3,000 7 WS-SO-34-XX Reference Laboratory 5.4 60 1.3 U 78 J- 47 3,200 7 WS-SO-01-RI Rigaku, Inc. 22 46 14 146 60 1,501 7 WS-SO-04-RI Rigaku, Inc. 20 51 11 152 73 1,473 7 WS-SO-15-RI Rigaku, Inc. 19 46 10 154 71 1,473 7 WS-SO-22-RI Rigaku, Inc. 23 45 13 148 67 1,487 7 WS-SO-34-RI Rigaku, Inc. 22 47 12 146 60 1,484 8 WS-SO-02-XX Reference Laboratory 17 57 1.3 U 150 J- 36 6,000 8 WS-SO-16-XX Reference Laboratory 15 60 1.1 J 150 J- 35 5,700 8 WS-SO-18-XX Reference Laboratory 17 62 1.9 140 J- 36 5,900 8 WS-SO-21-XX Reference Laboratory 14 51 1.6 150 J- 33 5,500 8 WS-SO-24-XX Reference Laboratory 16 54 2.1 140 J- 30 5,200 8 WS-SO-29-XX Reference Laboratory 15 55 1.7 140 J- 33 5,500 8 WS-SO-37-XX Reference Laboratory 14 63 3 140 J- 34 5,800 8 WS-SO-02-RI Rigaku, Inc. 21 55 15 112 51 2,557 8 WS-SO-16-RI Rigaku, Inc. 17 57 18 116 67 2,536 8 WS-SO-18-RI Rigaku, Inc. 21 53 16 114 59 2,551 8 WS-SO-21-RI Rigaku, Inc. 27 58 17 119 58 2,512 8 WS-SO-24-RI Rigaku, Inc. 17 51 16 113 63 2,529 8 WS-SO-29-RI Rigaku, Inc. 16 51 17 113 61 2,544 8 WS-SO-37-RI Rigaku, Inc. 15 52 18 117 56 2,535 9 WS-SO-13-XX Reference Laboratory 11 75 3.7 170 J- 24 9,000 9 WS-SO-19-XX Reference Laboratory 12 74 3.7 160 J- 20 7,700 9 WS-SO-28-XX Reference Laboratory 11 59 2.3 130 J- 16 6,100 9 WS-SO-32-XX Reference Laboratory 11 73 3.7 190 J- 23 8,500 9 WS-SO-36-XX Reference Laboratory 13 55 1.7 120 J- 15 5,700 9 WS-SO-13-RI Rigaku, Inc. 20 65 21 109 50 3,978 9 WS-SO-19-RI Rigaku, Inc. 28 69 20 106 51 4,001 9 WS-SO-28-RI Rigaku, Inc. 17 62 20 105 54 3,938 9 WS-SO-32-RI Rigaku, Inc. 18 65 22 104 60 3,978 9 WS-SO-36-RI Rigaku, Inc. 23 71 20 106 56 4,005 
D-7

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

10 BN-SO-01-XX Reference Laboratory 1.3 UJ 38 0.94 120 32 24,000 63 10 BN-SO-10-XX Reference Laboratory 1.3 UJ 50 1.2 110 35 24,000 140 10 BN-SO-15-XX Reference Laboratory 1.3 UJ 34 0.82 110 29 22,000 56 10 BN-SO-18-XX Reference Laboratory 1.3 U 37 0.89 110 29 22,000 59 10 BN-SO-28-XX Reference Laboratory 1.5 35 0.87 100 28 22,000 58 10 BN-SO-31-XX Reference Laboratory 1.3 41 1 140 33 26,000 65 10 BN-SO-35-XX Reference Laboratory 1.4 37 0.98 120 30 23,000 60 10 BN-SO-01-RI Rigaku, Inc. 203 34 645 55 29 13,872 -17 10 BN-SO-10-RI Rigaku, Inc. 198 69 642 96 27 13,866 -15 10 BN-SO-15-RI Rigaku, Inc. 213 49 665 81 29 13,934 -21 10 BN-SO-18-RI Rigaku, Inc. 184 46 624 60 23 14,018 -14 10 BN-SO-28-RI Rigaku, Inc. 219 62 658 103 23 13,841 -11 10 BN-SO-31-RI Rigaku, Inc. 251 47 733 59 21 13,882 -10 10 BN-SO-35-RI Rigaku, Inc. 207 30 662 101 25 13,915 -11 11 BN-SO-02-XX Reference Laboratory 11 140 50 90 170 28,000 840 11 BN-SO-04-XX Reference Laboratory 9.1 120 42 79 140 24,000 700 11 BN-SO-17-XX Reference Laboratory 9.3 110 39 79 140 23,000 680 11 BN-SO-22-XX Reference Laboratory 7.3 98 34 65 110 20,000 590 11 BN-SO-27-XX Reference Laboratory 9.6 110 39 78 130 24,000 660 11 BN-SO-02-RI Rigaku, Inc. 241 75 640 125 92 13,783 303 11 BN-SO-04-RI Rigaku, Inc. 252 67 643 52 92 13,700 332 11 BN-SO-17-RI Rigaku, Inc. 252 77 648 69 95 13,691 310 11 BN-SO-22-RI Rigaku, Inc. 285 88 683 79 90 13,741 321 11 BN-SO-27-RI Rigaku, Inc. 288 76 663 45 94 13,692 318 12 BN-SO-03-XX Reference Laboratory 65 620 290 120 840 25,000 4,700 12 BN-SO-06-XX Reference Laboratory 60 600 280 94 810 24,000 4,500 12 BN-SO-08-XX Reference Laboratory 57 570 270 100 750 22,000 4,300 12 BN-SO-13-XX Reference Laboratory 65 320 150 98 410 17,000 2,400 12 BN-SO-20-XX Reference Laboratory 57 540 260 88 730 22,000 4,100 12 BN-SO-30-XX Reference Laboratory 64 630 300 100 860 26,000 4,800 12 BN-SO-34-XX Reference Laboratory 68 630 290 110 830 25,000 4,700 12 BN-SO-03-RI Rigaku, Inc. 538 315 672 146 488 14,067 2,193 12 BN-SO-06-RI Rigaku, Inc. 559 310 666 43 481 14,026 2,184 12 BN-SO-08-RI Rigaku, Inc. 558 298 674 100 495 13,942 2,185 12 BN-SO-13-RI Rigaku, Inc. 626 316 684 98 493 14,050 2,178 12 BN-SO-20-RI Rigaku, Inc. 523 301 662 77 516 13,973 2,147 12 BN-SO-30-RI Rigaku, Inc. 585 304 675 72 493 13,924 2,199 12 BN-SO-34-RI Rigaku, Inc. 563 296 660 93 489 14,105 2,176 
D-8

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

10 BN-SO-01-XX Reference Laboratory 0.13 63 1.3 U 1.3 UJ 55 92 10 BN-SO-10-XX Reference Laboratory 0.14 54 1.2 J 1.3 UJ 55 110 10 BN-SO-15-XX Reference Laboratory 0.15 58 1.3 U 1.3 UJ 49 89 10 BN-SO-18-XX Reference Laboratory 0.13 59 1.3 0.94 U 46 88 10 BN-SO-28-XX Reference Laboratory 0.16 54 1.3 U 0.77 U 48 81 10 BN-SO-31-XX Reference Laboratory 0.14 71 1.3 U 0.97 U 54 94 10 BN-SO-35-XX Reference Laboratory 0.15 63 1.2 J 0.85 U 50 87 10 BN-SO-01-RI Rigaku, Inc. 29 41 6 221 70 66 10 BN-SO-10-RI Rigaku, Inc. 23 44 7 221 73 72 10 BN-SO-15-RI Rigaku, Inc. 27 43 5 224 70 86 10 BN-SO-18-RI Rigaku, Inc. 25 49 5 224 54 63 10 BN-SO-28-RI Rigaku, Inc. 21 43 5 226 68 72 10 BN-SO-31-RI Rigaku, Inc. 25 41 7 241 71 87 10 BN-SO-35-RI Rigaku, Inc. 36 45 8 227 66 72 11 BN-SO-02-XX Reference Laboratory 0.37 54 4.3 7.6 60 470 11 BN-SO-04-XX Reference Laboratory 0.36 48 2.9 6.5 50 400 11 BN-SO-17-XX Reference Laboratory 0.39 47 2.7 6.3 49 390 11 BN-SO-22-XX Reference Laboratory 0.37 40 2.8 5.4 43 330 11 BN-SO-27-XX Reference Laboratory 0.38 46 3.7 6.1 52 380 11 BN-SO-02-RI Rigaku, Inc. 27 40 9 223 60 230 11 BN-SO-04-RI Rigaku, Inc. 30 45 7 223 58 220 11 BN-SO-17-RI Rigaku, Inc. 35 38 8 216 57 221 11 BN-SO-22-RI Rigaku, Inc. 23 41 6 236 77 232 11 BN-SO-27-RI Rigaku, Inc. 19 37 7 234 57 223 12 BN-SO-03-XX Reference Laboratory 1.6 100 17 42 48 2,300 12 BN-SO-06-XX Reference Laboratory 2 92 15 41 48 2,300 12 BN-SO-08-XX Reference Laboratory 2 94 14 38 39 2,200 12 BN-SO-13-XX Reference Laboratory 1.6 71 9.2 21 37 1,200 12 BN-SO-20-XX Reference Laboratory 1.6 84 14 37 44 2,100 12 BN-SO-30-XX Reference Laboratory 1.6 99 17 44 50 2,400 12 BN-SO-34-XX Reference Laboratory 2 100 17 42 49 2,300 12 BN-SO-03-RI Rigaku, Inc. 17 59 11 200 60 1,200 12 BN-SO-06-RI Rigaku, Inc. 22 55 11 197 54 1,212 12 BN-SO-08-RI Rigaku, Inc. 25 53 11 201 74 1,211 12 BN-SO-13-RI Rigaku, Inc. 20 59 11 208 63 1,218 12 BN-SO-20-RI Rigaku, Inc. 30 64 14 196 62 1,247 12 BN-SO-30-RI Rigaku, Inc. 34 58 11 212 64 1,213 12 BN-SO-34-RI Rigaku, Inc. 32 59 12 197 60 1,216 
D-9

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

13 BN-SO-07-XX Reference Laboratory 110 J- 990 J+ 520 82 1,400 23,000 6,900 13 BN-SO-16-XX Reference Laboratory 120 J- 1,100 J+ 570 86 1,500 25,000 8,100 13 BN-SO-21-XX Reference Laboratory 150 J- 1,300 J+ 660 110 1,700 30,000 8,900 13 BN-SO-25-XX Reference Laboratory 82 J- 700 J 370 J- 64 J- 930 J- 16,000 J- 5,400 13 BN-SO-33-XX Reference Laboratory 100 J- 1,100 640 100 1,600 27,000 8,000 13 BN-SO-07-RI Rigaku, Inc. 786 467 700 74 870 13,940 3,698 13 BN-SO-16-RI Rigaku, Inc. 871 475 741 101 875 14,102 3,735 13 BN-SO-21-RI Rigaku, Inc. 715 482 708 81 859 13,924 3,705 13 BN-SO-25-RI Rigaku, Inc. 805 500 722 59 895 13,960 3,730 13 BN-SO-33-RI Rigaku, Inc. 824 511 741 54 870 14,054 3,715 14 BN-SO-05-XX Reference Laboratory 160 J- 1,600 850 86 2,200 26,000 12,000 14 BN-SO-19-XX Reference Laboratory 150 J- 1,600 860 79 2,200 26,000 12,000 14 BN-SO-26-XX Reference Laboratory 150 J- 1,700 900 82 2,400 27,000 12,000 14 BN-SO-29-XX Reference Laboratory 150 J- 1,600 880 86 2,300 26,000 12,000 14 BN-SO-32-XX Reference Laboratory 160 J- 1,600 860 84 2,300 26,000 12,000 14 BN-SO-05-RI Rigaku, Inc. 800 705 695 86 1,336 14,228 5,477 14 BN-SO-19-RI Rigaku, Inc. 927 713 719 120 1,303 14,345 5,496 14 BN-SO-26-RI Rigaku, Inc. 967 711 729 79 1,326 14,305 5,559 14 BN-SO-29-RI Rigaku, Inc. 901 685 714 115 1,300 14,132 5,501 14 BN-SO-32-RI Rigaku, Inc. 894 695 719 81 1,314 14,401 5,584 15 CN-SO-01-XX Reference Laboratory 13 J- 13 21 190 700 38,000 1,200 15 CN-SO-04-XX Reference Laboratory 13 J- 11 21 200 680 37,000 1,200 15 CN-SO-08-XX Reference Laboratory 15 J- 15 25 210 740 43,000 1,300 15 CN-SO-10-XX Reference Laboratory 13 J- 13 22 200 760 39,000 1,200 15 CN-SO-11-XX Reference Laboratory 17 J- 16 30 240 860 47,000 1,600 15 CN-SO-01-RI Rigaku, Inc. 335 42 664 185 368 18,032 514 15 CN-SO-04-RI Rigaku, Inc. 323 17 635 205 405 18,122 513 15 CN-SO-08-RI Rigaku, Inc. 378 43 664 158 364 18,393 505 15 CN-SO-10-RI Rigaku, Inc. 341 35 641 188 383 18,522 531 15 CN-SO-11-RI Rigaku, Inc. 330 38 640 146 385 18,265 518 
D-10

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

13 BN-SO-07-XX Reference Laboratory 3.4 120 26 70 41 4,000 13 BN-SO-16-XX Reference Laboratory 3.4 130 29 77 44 4,400 13 BN-SO-21-XX Reference Laboratory 3.6 160 35 88 52 5,100 13 BN-SO-25-XX Reference Laboratory 3.8 88 J- 19 J- 48 J- 28 J- 2,900 J13 BN-SO-33-XX Reference Laboratory 4 150 34 81 48 5,100 13 BN-SO-07-RI Rigaku, Inc. 29 68 15 195 70 2,193 13 BN-SO-16-RI Rigaku, Inc. 34 70 16 207 60 2,187 13 BN-SO-21-RI Rigaku, Inc. 31 76 14 191 59 2,174 13 BN-SO-25-RI Rigaku, Inc. 29 74 17 190 64 2,204 13 BN-SO-33-RI Rigaku, Inc. 30 73 17 199 57 2,169 14 BN-SO-05-XX Reference Laboratory 5 160 48 110 39 6,700 14 BN-SO-19-XX Reference Laboratory 5 160 48 120 39 6,700 14 BN-SO-26-XX Reference Laboratory 5.4 160 49 120 40 7,000 14 BN-SO-29-XX Reference Laboratory 5.4 160 48 120 41 6,800 14 BN-SO-32-XX Reference Laboratory 5.4 160 48 120 39 6,700 14 BN-SO-05-RI Rigaku, Inc. 18 78 16 175 57 3,096 14 BN-SO-19-RI Rigaku, Inc. 21 80 19 177 56 3,077 14 BN-SO-26-RI Rigaku, Inc. 18 79 18 184 59 3,118 14 BN-SO-29-RI Rigaku, Inc. 25 80 20 178 63 3,074 14 BN-SO-32-RI Rigaku, Inc. 27 81 18 175 58 3,146 15 CN-SO-01-XX Reference Laboratory 0.13 240 2.2 12 21 3,100 15 CN-SO-04-XX Reference Laboratory 0.14 240 1.5 12 22 2,900 15 CN-SO-08-XX Reference Laboratory 0.16 280 1.3 U 15 26 3,200 15 CN-SO-10-XX Reference Laboratory 0.12 240 1.9 14 22 3,000 15 CN-SO-11-XX Reference Laboratory 0.15 320 1.3 U 16 27 3,500 15 CN-SO-01-RI Rigaku, Inc. 27 123 9 227 71 1,671 15 CN-SO-04-RI Rigaku, Inc. 32 122 7 228 75 1,628 15 CN-SO-08-RI Rigaku, Inc. 40 127 7 239 68 1,690 15 CN-SO-10-RI Rigaku, Inc. 37 126 7 232 70 1,658 15 CN-SO-11-RI Rigaku, Inc. 35 125 8 232 62 1,689 
D-11

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

16 AS-SO-02-XX Reference Laboratory 2.6 UJ 18 50 180 140 48,000 1,600 16 AS-SO-06-XX Reference Laboratory 2.4 UJ 19 52 190 130 52,000 1,600 16 AS-SO-10-XX Reference Laboratory 1.9 J- 18 48 180 110 45,000 1,400 16 AS-SO-11-XX Reference Laboratory 3.7 J- 22 63 230 150 52,000 2,100 16 AS-SO-13-XX Reference Laboratory 2.4 UJ 20 57 200 150 52,000 1,700 16 AS-SO-02-RI Rigaku, Inc. 247 7 518 147 62 18,017 607 16 AS-SO-06-RI Rigaku, Inc. 229 -13 523 105 56 17,814 636 16 AS-SO-10-RI Rigaku, Inc. 234 1 534 123 64 17,877 639 16 AS-SO-11-RI Rigaku, Inc. 259 -11 519 154 64 17,923 629 16 AS-SO-13-RI Rigaku, Inc. 226 8 515 135 66 18,167 646 17 AS-SO-01-XX Reference Laboratory 3.8 J- 26 100 420 250 100,000 3,200 17 AS-SO-04-XX Reference Laboratory 6.4 UJ 22 110 480 260 110,000 3,300 17 AS-SO-07-XX Reference Laboratory 3.6 J- 21 97 380 240 88,000 2,900 17 AS-SO-09-XX Reference Laboratory 2.6 UJ 25 J- 100 J- 390 J- 250 J- 94,000 J- 3,200 J17 AS-SO-12-XX Reference Laboratory 2.6 UJ 29 120 440 270 93,000 3,300 17 AS-SO-01-RI Rigaku, Inc. 169 -47 400 248 77 28,556 994 17 AS-SO-04-RI Rigaku, Inc. 140 -42 406 256 96 28,250 992 17 AS-SO-07-RI Rigaku, Inc. 142 -61 406 233 91 28,106 1,014 17 AS-SO-09-RI Rigaku, Inc. 154 -35 406 255 82 28,894 991 17 AS-SO-12-RI Rigaku, Inc. 115 -42 368 294 89 28,910 966 18 SB-SO-03-XX Reference Laboratory 1.2 UJ 9 0.51 U 150 48 38,000 18 18 SB-SO-06-XX Reference Laboratory 1.7 J- 8 0.51 U 140 44 35,000 16 18 SB-SO-14-XX Reference Laboratory 4.1 J- 9 0.51 U 150 46 37,000 17 18 SB-SO-38-XX Reference Laboratory 1.3 UJ 10 0.51 U 150 57 37,000 18 18 SB-SO-41-XX Reference Laboratory 1.3 UJ 9 0.51 U 160 58 40,000 19 18 SB-SO-47-XX Reference Laboratory 1.3 UJ 8 0.51 U 140 44 34,000 16 18 SB-SO-51-XX Reference Laboratory 1.3 UJ 9 0.51 U 160 50 40,000 18 18 SB-SO-03-RI Rigaku, Inc. 241 14 640 152 29 20,833 -46 18 SB-SO-06-RI Rigaku, Inc. 200 19 597 144 31 20,593 -54 18 SB-SO-14-RI Rigaku, Inc. 191 23 585 151 32 20,649 -51 18 SB-SO-38-RI Rigaku, Inc. 211 21 609 180 31 20,656 -63 18 SB-SO-41-RI Rigaku, Inc. 187 15 589 151 28 20,630 -41 18 SB-SO-47-RI Rigaku, Inc. 184 24 601 154 31 20,564 -39 18 SB-SO-51-RI Rigaku, Inc. 183 6 590 146 32 20,716 -55 
D-12

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

16 AS-SO-02-XX Reference Laboratory 0.76 91 2.6 U 4.5 42 3,300 16 AS-SO-06-XX Reference Laboratory 0.74 93 2.6 U 4.8 44 3,500 16 AS-SO-10-XX Reference Laboratory 0.78 84 1.1 U 4.4 42 3,000 16 AS-SO-11-XX Reference Laboratory 0.72 120 1.1 U 5.6 54 3,800 16 AS-SO-13-XX Reference Laboratory 0.79 100 3 5.2 50 3,800 16 AS-SO-02-RI Rigaku, Inc. 14 49 3 181 61 1,447 16 AS-SO-06-RI Rigaku, Inc. 15 40 3 181 56 1,475 16 AS-SO-10-RI Rigaku, Inc. 5 49 3 174 52 1,441 16 AS-SO-11-RI Rigaku, Inc. 14 49 1 179 63 1,457 16 AS-SO-13-RI Rigaku, Inc. 7 45 2 170 57 1,509 17 AS-SO-01-XX Reference Laboratory 1.4 180 2.6 U 9.3 66 6,900 17 AS-SO-04-XX Reference Laboratory 1.3 200 6.2 U 12 72 7,400 17 AS-SO-07-XX Reference Laboratory 1.4 160 2.7 8.9 63 6,300 17 AS-SO-09-XX Reference Laboratory 1.4 170 J- 2.6 U 9.6 J- 65 J- 6,800 J17 AS-SO-12-XX Reference Laboratory 1.4 190 2.6 U 3.2 73 7,500 17 AS-SO-01-RI Rigaku, Inc. -12 57 -4 135 70 2,628 17 AS-SO-04-RI Rigaku, Inc. -11 59 -2 133 57 2,696 17 AS-SO-07-RI Rigaku, Inc. -16 61 -3 135 56 2,725 17 AS-SO-09-RI Rigaku, Inc. -14 62 -2 135 52 2,602 17 AS-SO-12-RI Rigaku, Inc. -11 56 -1 123 62 2,698 18 SB-SO-03-XX Reference Laboratory 62 210 1.3 U 1.3 U 67 90 18 SB-SO-06-XX Reference Laboratory 55 200 1.3 U 1.3 U 63 82 18 SB-SO-14-XX Reference Laboratory 55 210 1.3 U 1.3 U 66 95 18 SB-SO-38-XX Reference Laboratory 56 210 1.3 U 1.3 U 68 91 18 SB-SO-41-XX Reference Laboratory 54 230 1.3 U 1.3 U 71 96 18 SB-SO-47-XX Reference Laboratory 58 200 1.3 U 1.3 U 62 82 18 SB-SO-51-XX Reference Laboratory 54 230 1.3 U 1.3 U 74 93 18 SB-SO-03-RI Rigaku, Inc. 48 107 6 216 117 63 18 SB-SO-06-RI Rigaku, Inc. 47 99 6 208 116 62 18 SB-SO-14-RI Rigaku, Inc. 37 98 4 199 110 63 18 SB-SO-38-RI Rigaku, Inc. 46 100 7 210 111 63 18 SB-SO-41-RI Rigaku, Inc. 45 100 5 204 113 62 18 SB-SO-47-RI Rigaku, Inc. 38 106 7 204 118 61 18 SB-SO-51-RI Rigaku, Inc. 48 97 7 209 148 63 
D-13

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

19 SB-SO-05-XX Reference Laboratory 1.6 J- 9 0.51 U 140 46 35,000 16 19 SB-SO-18-XX Reference Laboratory 1.2 UJ 10 0.51 U 150 46 38,000 17 19 SB-SO-30-XX Reference Laboratory 3.2 J- 7 0.51 U 94 27 22,000 10 19 SB-SO-40-XX Reference Laboratory 2.2 J- 9 0.51 U 120 40 33,000 15 19 SB-SO-53-XX Reference Laboratory 1.2 UJ 10 0.51 U 140 44 37,000 17 19 SB-SO-05-RI Rigaku, Inc. 212 4 608 158 24 20,004 -52 19 SB-SO-18-RI Rigaku, Inc. 209 16 605 137 25 19,723 -61 19 SB-SO-30-RI Rigaku, Inc. 231 21 618 161 30 19,809 -47 19 SB-SO-40-RI Rigaku, Inc. 236 -9 623 146 28 19,764 -40 19 SB-SO-53-RI Rigaku, Inc. 241 35 645 125 27 19,905 -50 20 SB-SO-08-XX Reference Laboratory 5.4 J- 13 0.51 U 120 39 32,000 17 20 SB-SO-11-XX Reference Laboratory 5.7 J- 13 0.51 U 140 46 36,000 20 20 SB-SO-21-XX Reference Laboratory 4.9 J 13 0.51 U 130 43 34,000 18 20 SB-SO-39-XX Reference Laboratory 4.7 J- 13 0.51 U 140 46 34,000 19 20 SB-SO-42-XX Reference Laboratory 4.6 J- 13 0.51 U 140 45 35,000 18 20 SB-SO-08-RI Rigaku, Inc. 172 27 581 117 28 18,535 -42 20 SB-SO-11-RI Rigaku, Inc. 179 11 600 123 30 18,371 -38 20 SB-SO-21-RI Rigaku, Inc. 192 4 578 135 78 19,571 -66 20 SB-SO-39-RI Rigaku, Inc. 194 11 586 135 24 18,504 -31 20 SB-SO-42-RI Rigaku, Inc. 183 7 578 112 28 18,441 -40 21 SB-SO-22-XX Reference Laboratory 10 J 18 0.51 U 120 37 29,000 22 21 SB-SO-25-XX Reference Laboratory 6.8 J+ 18 0.51 U 120 37 29,000 22 21 SB-SO-27-XX Reference Laboratory 6.7 J+ 18 0.51 U 120 37 29,000 22 21 SB-SO-35-XX Reference Laboratory 6 J+ 17 0.51 U 110 35 28,000 21 21 SB-SO-44-XX Reference Laboratory 6.8 J+ 18 0.51 U 120 37 29,000 22 21 SB-SO-22-RI Rigaku, Inc. 157 28 591 132 32 15,830 -39 21 SB-SO-25-RI Rigaku, Inc. 181 16 625 122 31 15,907 -35 21 SB-SO-27-RI Rigaku, Inc. 143 14 578 149 32 15,846 -39 21 SB-SO-35-RI Rigaku, Inc. 128 21 552 135 31 15,679 -51 21 SB-SO-44-RI Rigaku, Inc. 139 12 574 164 26 15,749 -57 
D-14

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

19 SB-SO-05-XX Reference Laboratory 540 200 1.3 U 1.3 U 61 80 19 SB-SO-18-XX Reference Laboratory 280 210 1.3 U 1.3 U 70 84 19 SB-SO-30-XX Reference Laboratory 290 120 1.3 J+ 1.3 U 43 50 19 SB-SO-40-XX Reference Laboratory 280 180 1.3 U 1.3 U 58 74 19 SB-SO-53-XX Reference Laboratory 270 200 1.3 U 1.3 U 64 81 19 SB-SO-05-RI Rigaku, Inc. 148 91 6 212 114 54 19 SB-SO-18-RI Rigaku, Inc. 134 99 4 212 98 62 19 SB-SO-30-RI Rigaku, Inc. 160 92 6 219 95 52 19 SB-SO-40-RI Rigaku, Inc. 160 95 5 218 107 61 19 SB-SO-53-RI Rigaku, Inc. 125 97 7 218 142 55 20 SB-SO-08-XX Reference Laboratory 730 180 1.3 U 1.3 U 57 70 20 SB-SO-11-XX Reference Laboratory 810 200 1.3 U 1.3 U 66 84 20 SB-SO-21-XX Reference Laboratory 740 190 1.3 U 1.3 U 58 75 20 SB-SO-39-XX Reference Laboratory 790 200 1.3 U 1.3 U 62 77 20 SB-SO-42-XX Reference Laboratory 740 200 1.3 U 1.3 U 65 78 20 SB-SO-08-RI Rigaku, Inc. 358 96 4 201 124 58 20 SB-SO-11-RI Rigaku, Inc. 345 93 4 202 141 61 20 SB-SO-21-RI Rigaku, Inc. 32 1,366 14 218 134 1,865 20 SB-SO-39-RI Rigaku, Inc. 346 91 5 212 118 56 20 SB-SO-42-RI Rigaku, Inc. 341 89 7 200 159 54 21 SB-SO-22-XX Reference Laboratory 3300 160 1.3 U 1.3 U 52 64 J21 SB-SO-25-XX Reference Laboratory 3000 160 1.3 U 1.3 U 54 63 21 SB-SO-27-XX Reference Laboratory 3100 170 1.3 U 1.3 U 54 65 21 SB-SO-35-XX Reference Laboratory 3100 160 1.3 U 1.3 U 50 62 21 SB-SO-44-XX Reference Laboratory 3000 170 1.3 U 1.3 U 53 64 21 SB-SO-22-RI Rigaku, Inc. 803 83 5 204 140 55 21 SB-SO-25-RI Rigaku, Inc. 787 85 7 209 125 53 21 SB-SO-27-RI Rigaku, Inc. 755 81 6 194 121 51 21 SB-SO-35-RI Rigaku, Inc. 773 90 6 196 121 55 21 SB-SO-44-RI Rigaku, Inc. 760 89 6 194 195 50 
D-15

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

22 SB-SO-23-XX Reference Laboratory 48 J- 37 0.1 U 21 7 4,500 36 22 SB-SO-28-XX Reference Laboratory 42 J- 36 0.1 U 21 7 4,400 36 22 SB-SO-32-XX Reference Laboratory 46 J- 40 0.1 U 23 7.6 4,900 40 22 SB-SO-43-XX Reference Laboratory 40 J- 35 0.1 U 20 6.7 4,200 34 22 SB-SO-48-XX Reference Laboratory 39 J- 36 0.1 U 21 6.9 4,500 36 22 SB-SO-23-RI Rigaku, Inc. 113 -6 703 77 11 4,597 -1 22 SB-SO-28-RI Rigaku, Inc. 89 -3 608 110 22 4,931 -4 22 SB-SO-32-RI Rigaku, Inc. 56 65 517 103 19 4,800 -1 22 SB-SO-43-RI Rigaku, Inc. 61 84 547 110 25 4,798 2 22 SB-SO-48-RI Rigaku, Inc. 56 84 538 76 21 4,797 -14 23 SB-SO-02-XX Reference Laboratory 44 J- 23 J- 0.5 U 130 43 35,000 22 J23 SB-SO-07-XX Reference Laboratory 45 J 22 0.5 U 120 38 35,000 23 23 SB-SO-10-XX Reference Laboratory 62 J 26 0.5 U 140 44 41,000 27 23 SB-SO-26-XX Reference Laboratory 61 J 30 0.5 U 160 50 46,000 31 23 SB-SO-50-XX Reference Laboratory 57 J 27 0.5 U 140 46 42,000 28 23 SB-SO-02-RI Rigaku, Inc. 182 16 571 117 32 21,148 -64 23 SB-SO-07-RI Rigaku, Inc. 230 20 600 125 26 21,733 -49 23 SB-SO-10-RI Rigaku, Inc. 198 17 569 146 24 21,449 -57 23 SB-SO-26-RI Rigaku, Inc. -47 -196 46 -124 -37 4,098 -234 23 SB-SO-50-RI Rigaku, Inc. 218 40 596 198 30 21,439 -50 24 SB-SO-01-XX Reference Laboratory 180 J 65 0.5 U 140 46 47,000 30 24 SB-SO-16-XX Reference Laboratory 170 J 64 0.5 U 140 45 47,000 30 24 SB-SO-24-XX Reference Laboratory 180 J 66 0.5 U 150 49 49,000 32 24 SB-SO-45-XX Reference Laboratory 180 J 63 0.5 U 140 45 47,000 30 24 SB-SO-52-XX Reference Laboratory 150 J 62 0.5 U 140 47 46,000 29 24 SB-SO-01-RI Rigaku, Inc. 260 36 604 140 28 22,448 -48 24 SB-SO-16-RI Rigaku, Inc. 235 42 578 178 22 22,611 -49 24 SB-SO-24-RI Rigaku, Inc. 233 42 596 171 28 22,572 -45 24 SB-SO-45-RI Rigaku, Inc. 216 23 558 129 28 22,432 -48 24 SB-SO-52-RI Rigaku, Inc. 245 29 564 129 26 22,574 -54 
D-16

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

22 SB-SO-23-XX Reference Laboratory 8500 26 0.22 J 0.26 UJ 13 8 22 SB-SO-28-XX Reference Laboratory 8800 26 0.26 U 0.26 UJ 13 8 22 SB-SO-32-XX Reference Laboratory 8900 28 0.36 0.1 UJ 14 9 22 SB-SO-43-XX Reference Laboratory 7600 24 0.26 U 0.26 UJ 13 8 22 SB-SO-48-XX Reference Laboratory 8200 25 0.26 U 0.1 UJ 13 8 22 SB-SO-23-RI Rigaku, Inc. 2,552 35 8 231 160 28 22 SB-SO-28-RI Rigaku, Inc. 2,712 39 8 209 196 32 22 SB-SO-32-RI Rigaku, Inc. 2,621 33 11 179 164 31 22 SB-SO-43-RI Rigaku, Inc. 2,651 36 7 184 322 29 22 SB-SO-48-RI Rigaku, Inc. 2,681 36 9 179 315 32 23 SB-SO-02-XX Reference Laboratory 130 J+ 180 1.2 U 1.2 UJ 59 88 23 SB-SO-07-XX Reference Laboratory 270 170 1.4 1.6 53 86 23 SB-SO-10-XX Reference Laboratory 220 200 2.8 1.8 59 100 23 SB-SO-26-XX Reference Laboratory 260 220 3.4 1.8 68 110 23 SB-SO-50-XX Reference Laboratory 200 200 2.9 1.8 61 100 23 SB-SO-02-RI Rigaku, Inc. 76 88 4 196 103 70 23 SB-SO-07-RI Rigaku, Inc. 75 94 4 206 111 66 23 SB-SO-10-RI Rigaku, Inc. 70 91 5 202 102 61 23 SB-SO-26-RI Rigaku, Inc. -88 2 -22 11 8 -9 23 SB-SO-50-RI Rigaku, Inc. 72 96 5 205 154 59 24 SB-SO-01-XX Reference Laboratory 400 190 1.8 2.3 65 95 24 SB-SO-16-XX Reference Laboratory 480 190 1.9 2.2 65 97 24 SB-SO-24-XX Reference Laboratory 420 200 2.5 2.3 67 95 24 SB-SO-45-XX Reference Laboratory 450 190 2.8 2.1 J- 63 93 24 SB-SO-52-XX Reference Laboratory 430 190 1.8 2.2 64 90 24 SB-SO-01-RI Rigaku, Inc. 105 83 4 208 107 60 24 SB-SO-16-RI Rigaku, Inc. 100 80 5 199 113 60 24 SB-SO-24-RI Rigaku, Inc. 108 81 6 205 112 59 24 SB-SO-45-RI Rigaku, Inc. 105 85 3 193 135 54 24 SB-SO-52-RI Rigaku, Inc. 111 86 5 202 135 59 
D-17

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

25 SB-SO-13-XX Reference Laboratory 430 J 160 1 U 140 46 61,000 36 25 SB-SO-19-XX Reference Laboratory 310 J 100 0.5 U 100 32 42,000 25 25 SB-SO-33-XX Reference Laboratory 350 J 110 0.5 U 100 33 45,000 28 25 SB-SO-37-XX Reference Laboratory 340 J 130 1 U 120 39 51,000 31 25 SB-SO-55-XX Reference Laboratory 340 J 120 0.5 U 120 37 49,000 29 25 SB-SO-13-RI Rigaku, Inc. 322 46 570 144 22 25,192 -54 25 SB-SO-19-RI Rigaku, Inc. 329 48 574 123 27 25,518 -58 25 SB-SO-33-RI Rigaku, Inc. 296 45 552 146 27 25,443 -52 25 SB-SO-37-RI Rigaku, Inc. 272 55 565 110 25 25,224 -60 25 SB-SO-55-RI Rigaku, Inc. 308 52 594 106 23 25,157 -53 26 SB-SO-12-XX Reference Laboratory 620 J 190 1 U 100 33 55,000 43 26 SB-SO-15-XX Reference Laboratory 600 J- 170 J- 1 U 91 J- 30 J- 51,000 J- 40 J26 SB-SO-17-XX Reference Laboratory 800 J+ 210 1 U 110 37 61,000 48 26 SB-SO-46-XX Reference Laboratory 740 J+ 190 1 U 120 35 57,000 47 26 SB-SO-54-XX Reference Laboratory 280 31 0.2 U 25 5.8 8,600 5 J26 SB-SO-12-RI Rigaku, Inc. 327 60 535 156 21 28,010 -60 26 SB-SO-15-RI Rigaku, Inc. 368 59 534 185 18 28,182 -59 26 SB-SO-17-RI Rigaku, Inc. 353 56 546 140 16 27,967 -62 26 SB-SO-46-RI Rigaku, Inc. 338 39 546 129 21 27,861 -61 26 SB-SO-54-RI Rigaku, Inc. 358 56 561 105 19 28,180 -62 27 KP-SE-08-XX Reference Laboratory 6.2 3 0.11 U 88 3.8 840 300 J27 KP-SE-11-XX Reference Laboratory 5.6 3 0.11 U 96 4.1 940 310 J27 KP-SE-17-XX Reference Laboratory 4.9 3 0.11 U 98 4.1 940 300 J27 KP-SE-25-XX Reference Laboratory 6 3 0.11 U 99 4.3 960 310 J27 KP-SE-30-XX Reference Laboratory 5.7 3 0.11 U 83 3.6 830 300 J27 KP-SE-08-RI Rigaku, Inc. 234 151 881 69 24 3,769 346 27 KP-SE-11-RI Rigaku, Inc. 184 119 787 88 22 3,754 357 27 KP-SE-17-RI Rigaku, Inc. 249 148 935 76 24 3,754 355 27 KP-SE-25-RI Rigaku, Inc. 250 161 940 65 21 3,743 343 27 KP-SE-30-RI Rigaku, Inc. 249 156 940 60 18 3,725 357 
D-18

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

25 SB-SO-13-XX Reference Laboratory 850 180 4.4 2.2 UJ 74 70 25 SB-SO-19-XX Reference Laboratory 740 120 2.5 1.8 51 51 25 SB-SO-33-XX Reference Laboratory 870 130 3 2 J 52 56 25 SB-SO-37-XX Reference Laboratory 790 150 2.5 U 2 UJ 63 58 25 SB-SO-55-XX Reference Laboratory 900 140 2.5 2.2 J 61 60 25 SB-SO-13-RI Rigaku, Inc. 161 72 3 203 121 52 25 SB-SO-19-RI Rigaku, Inc. 175 70 3 201 127 44 25 SB-SO-33-RI Rigaku, Inc. 161 72 2 201 102 44 25 SB-SO-37-RI Rigaku, Inc. 155 69 5 187 120 48 25 SB-SO-55-RI Rigaku, Inc. 160 73 3 209 157 46 26 SB-SO-12-XX Reference Laboratory 1,400 110 2.5 U 2.1 UJ 59 42 26 SB-SO-15-XX Reference Laboratory 1,100 100 J- 3.4 1.6 UJ 52 J- 36 J26 SB-SO-17-XX Reference Laboratory 1,200 120 2.8 2.3 UJ 60 42 26 SB-SO-46-XX Reference Laboratory 670 120 2.6 2.2 UJ 57 41 26 SB-SO-54-XX Reference Laboratory 560 20 0.5 U 0.5 UJ 11 6 26 SB-SO-12-RI Rigaku, Inc. 218 60 1 192 134 37 26 SB-SO-15-RI Rigaku, Inc. 225 59 2 198 123 36 26 SB-SO-17-RI Rigaku, Inc. 202 54 0 192 128 36 26 SB-SO-46-RI Rigaku, Inc. 227 53 2 200 154 37 26 SB-SO-54-RI Rigaku, Inc. 236 55 2 192 154 40 27 KP-SE-08-XX Reference Laboratory 0.09 U 42 0.27 U 0.27 UJ 4 5 27 KP-SE-11-XX Reference Laboratory 0.08 U 46 0.43 0.27 UJ 4 6 27 KP-SE-17-XX Reference Laboratory 0.08 U 47 0.27 U 0.27 UJ 4 5 27 KP-SE-25-XX Reference Laboratory 0.1 U 47 0.26 U 0.27 UJ 4 5 27 KP-SE-30-XX Reference Laboratory 0.1 U 39 0.24 U 0.27 UJ 4 5 27 KP-SE-08-RI Rigaku, Inc. 69 70 20 289 25 36 27 KP-SE-11-RI Rigaku, Inc. 78 69 18 260 22 32 27 KP-SE-17-RI Rigaku, Inc. 77 64 20 304 25 38 27 KP-SE-25-RI Rigaku, Inc. 74 65 20 303 21 33 27 KP-SE-30-RI Rigaku, Inc. 73 58 21 302 34 33 
D-19

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

28 KP-SE-01-XX Reference Laboratory 3.2 2 0.1 U 34 2.2 480 310 J28 KP-SE-12-XX Reference Laboratory 3.1 2 0.1 U 42 2.5 510 320 J28 KP-SE-14-XX Reference Laboratory 11 J- 2 0.1 U 46 J- 2.7 J+ 520 J- 680 J28 KP-SE-19-XX Reference Laboratory 3 2 0.1 U 44 2.3 510 330 28 KP-SE-28-XX Reference Laboratory 3.3 2 0.1 U 45 2.3 520 320 28 KP-SE-01-RI Rigaku, Inc. 301 126 974 33 23 3,454 352 28 KP-SE-12-RI Rigaku, Inc. 273 147 906 26 25 3,507 340 28 KP-SE-14-RI Rigaku, Inc. 306 143 957 67 19 3,392 321 28 KP-SE-19-RI Rigaku, Inc. 282 116 950 -3 16 3,396 329 28 KP-SE-28-RI Rigaku, Inc. 243 104 891 48 18 3,444 342 29 TL-SE-04-XX Reference Laboratory 1.2 U 10 0.5 U 62 1,900 42,000 32 29 TL-SE-10-XX Reference Laboratory 1.2 U 10 0.5 U 64 2,000 43,000 35 29 TL-SE-12-XX Reference Laboratory 1.2 U 10 0.5 U 66 2,100 44,000 34 29 TL-SE-15-XX Reference Laboratory 1.2 U 9 0.5 U 54 1,800 36,000 28 29 TL-SE-20-XX Reference Laboratory 1.2 U 10 0.5 U 64 2,000 42,000 32 29 TL-SE-24-XX Reference Laboratory 1.2 U 11 0.5 U 67 2,100 43,000 37 29 TL-SE-26-XX Reference Laboratory 1.2 U 10 0.5 U 62 2,000 40,000 34 29 TL-SE-04-RI Rigaku, Inc. 112 -31 478 54 923 21,259 -57 29 TL-SE-10-RI Rigaku, Inc. 119 -14 493 76 922 21,398 -68 29 TL-SE-12-RI Rigaku, Inc. 116 -25 481 65 909 21,337 -79 29 TL-SE-15-RI Rigaku, Inc. 114 -14 479 93 922 21,444 -55 29 TL-SE-20-RI Rigaku, Inc. 127 -24 483 74 942 21,349 -61 29 TL-SE-24-RI Rigaku, Inc. 147 -21 505 64 963 21,685 -62 29 TL-SE-26-RI Rigaku, Inc. 136 -16 510 77 930 21,391 -72 30 TL-SE-03-XX Reference Laboratory 2.5 U 9 1 U 91 1,600 63,000 12 30 TL-SE-19-XX Reference Laboratory 2.5 U 10 1 U 96 1,700 66,000 13 30 TL-SE-23-XX Reference Laboratory 2.5 U 9 1 U 92 1,600 64,000 12 30 TL-SE-25-XX Reference Laboratory 2.5 U 10 1 U 91 1,600 62,000 11 30 TL-SE-31-XX Reference Laboratory 2.5 U 10 1 U 110 1,800 74,000 13 30 TL-SE-03-RI Rigaku, Inc. 69 -37 383 83 689 29,357 -107 30 TL-SE-19-RI Rigaku, Inc. 71 -16 401 100 675 29,326 -93 30 TL-SE-23-RI Rigaku, Inc. 67 -42 417 118 678 29,328 -104 30 TL-SE-25-RI Rigaku, Inc. 62 -44 413 113 657 29,513 -101 30 TL-SE-31-RI Rigaku, Inc. 64 -26 393 91 682 29,358 -91 
D-20

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

28 KP-SE-01-XX Reference Laboratory 0.05 U 16 0.26 U 0.26 UJ 2 J 6 28 KP-SE-12-XX Reference Laboratory 0.06 U 20 0.26 U 0.26 UJ 2 J 8 28 KP-SE-14-XX Reference Laboratory 0.07 U 23 J- 0.26 U 0.26 UJ 3 J 7 28 KP-SE-19-XX Reference Laboratory 0.04 U 22 0.26 U 0.26 U 2 J 7 28 KP-SE-28-XX Reference Laboratory 0.06 U 22 0.26 U 0.26 U 2 J 6 28 KP-SE-01-RI Rigaku, Inc. 70 45 20 318 22 31 28 KP-SE-12-RI Rigaku, Inc. 60 44 17 308 30 55 28 KP-SE-14-RI Rigaku, Inc. 69 42 17 341 30 30 28 KP-SE-19-RI Rigaku, Inc. 66 46 20 316 20 35 28 KP-SE-28-RI Rigaku, Inc. 69 50 18 295 22 30 29 TL-SE-04-XX Reference Laboratory 0.26 J- 71 1.2 U 1.3 95 160 29 TL-SE-10-XX Reference Laboratory 0.19 J- 72 1.2 U 1.2 U 95 160 29 TL-SE-12-XX Reference Laboratory 0.22 J- 75 1.2 U 1.2 U 100 170 29 TL-SE-15-XX Reference Laboratory 0.28 J- 63 1.2 U 1 U 84 140 29 TL-SE-20-XX Reference Laboratory 0.26 J- 74 1.2 U 1.2 U 100 160 29 TL-SE-24-XX Reference Laboratory 0.26 J- 77 1.2 U 1.3 U 100 170 29 TL-SE-26-XX Reference Laboratory 0.24 J- 70 1.2 U 1.2 U 96 160 29 TL-SE-04-RI Rigaku, Inc. 10 44 1 166 136 93 29 TL-SE-10-RI Rigaku, Inc. 4 44 3 173 128 91 29 TL-SE-12-RI Rigaku, Inc. 7 43 -1 166 139 91 29 TL-SE-15-RI Rigaku, Inc. -1 45 1 161 140 93 29 TL-SE-20-RI Rigaku, Inc. 5 41 2 164 149 90 29 TL-SE-24-RI Rigaku, Inc. 16 41 1 183 148 99 29 TL-SE-26-RI Rigaku, Inc. 1 48 2 175 145 89 30 TL-SE-03-XX Reference Laboratory 0.32 J- 110 2.5 U 0.94 U 140 200 30 TL-SE-19-XX Reference Laboratory 0.32 J- 120 2.5 U 1.1 U 150 210 30 TL-SE-23-XX Reference Laboratory 0.41 J- 110 2.5 U 1.3 U 150 200 30 TL-SE-25-XX Reference Laboratory 0.44 J- 110 2.5 U 0.94 U 150 200 30 TL-SE-31-XX Reference Laboratory 0.57 J- 130 2.5 U 1.2 U 170 230 30 TL-SE-03-RI Rigaku, Inc. -17 50 -1 140 173 89 30 TL-SE-19-RI Rigaku, Inc. -7 51 -2 141 187 85 30 TL-SE-23-RI Rigaku, Inc. -7 48 -3 141 204 87 30 TL-SE-25-RI Rigaku, Inc. -10 49 -1 146 193 91 30 TL-SE-31-RI Rigaku, Inc. -8 54 0 139 192 89 
D-21

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

31 TL-SE-01-XX Reference Laboratory 1.2 UJ 9 0.5 U 110 1,400 19,000 48 J31 TL-SE-11-XX Reference Laboratory 1.2 UJ 15 0.5 U 140 1,600 28,000 54 J31 TL-SE-14-XX Reference Laboratory 1.2 UJ 10 0.27 J 110 1,500 18,000 50 J31 TL-SE-18-XX Reference Laboratory 1.2 UJ 10 0.5 U 150 1,300 24,000 46 J31 TL-SE-22-XX Reference Laboratory 1.2 UJ 11 0.5 U 150 1,700 26,000 54 J31 TL-SE-27-XX Reference Laboratory 1.2 UJ 10 0.28 J 130 1,500 19,000 51 J31 TL-SE-29-XX Reference Laboratory 1.2 UJ 11 0.22 J 140 1,600 23,000 51 J31 TL-SE-01-RI Rigaku, Inc. 184 6 549 96 697 17,602 -55 31 TL-SE-11-RI Rigaku, Inc. 144 -26 522 83 708 18,031 -61 31 TL-SE-14-RI Rigaku, Inc. 182 -12 544 110 713 18,509 -48 31 TL-SE-18-RI Rigaku, Inc. 164 6 526 88 726 18,075 -54 31 TL-SE-22-RI Rigaku, Inc. 167 -15 533 110 724 18,371 -47 31 TL-SE-27-RI Rigaku, Inc. 170 -24 537 134 689 18,594 -64 31 TL-SE-29-RI Rigaku, Inc. 176 -15 529 117 703 18,315 -62 32 LV-SE-02-XX Reference Laboratory 1.3 UJ 28 0.51 U 72 33 23,000 20 J32 LV-SE-10-XX Reference Laboratory 1.3 UJ 34 0.51 U 84 42 28,000 25 J32 LV-SE-22-XX Reference Laboratory 1.3 UJ 30 0.51 U 69 33 23,000 22 J32 LV-SE-25-XX Reference Laboratory 1.3 UJ 31 0.51 U 74 36 25,000 23 J32 LV-SE-31-XX Reference Laboratory 1.3 UJ 32 0.51 U 78 36 25,000 49 J32 LV-SE-35-XX Reference Laboratory 1.3 UJ 31 J- 0.51 U 74 J- 35 24,000 J- 22 J32 LV-SE-50-XX Reference Laboratory 2.5 U 29 1 U 74 34 24,000 24 J32 LV-SE-02-RI Rigaku, Inc. 182 25 601 71 29 15,603 -30 32 LV-SE-10-RI Rigaku, Inc. 182 37 615 65 24 15,490 -29 32 LV-SE-22-RI Rigaku, Inc. 189 32 622 76 28 15,618 -45 32 LV-SE-25-RI Rigaku, Inc. 213 44 653 88 29 15,568 -39 32 LV-SE-31-RI Rigaku, Inc. 201 31 624 60 22 15,786 -39 32 LV-SE-35-RI Rigaku, Inc. 195 42 619 69 24 15,585 -36 32 LV-SE-50-RI Rigaku, Inc. 177 28 591 60 31 15,658 -44 33 LV-SE-12-XX Reference Laboratory 2.6 U 190 1 U 55 34 72,000 19 J33 LV-SE-26-XX Reference Laboratory 2.6 U 220 1 U 64 39 83,000 25 J33 LV-SE-33-XX Reference Laboratory 2.6 U 170 1 U 52 31 66,000 21 J33 LV-SE-39-XX Reference Laboratory 2.6 U 190 1 U 58 35 74,000 22 J33 LV-SE-42-XX Reference Laboratory 2.7 U 170 1.1 U 50 30 65,000 22 J33 LV-SE-12-RI Rigaku, Inc. 277 29 545 154 16 35,880 -88 33 LV-SE-26-RI Rigaku, Inc. 302 47 544 96 15 35,793 -72 33 LV-SE-33-RI Rigaku, Inc. 275 25 539 96 18 35,182 -83 33 LV-SE-39-RI Rigaku, Inc. 303 33 529 101 14 35,840 -78 33 LV-SE-42-RI Rigaku, Inc. 238 42 499 125 15 36,267 -81 
D-22

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

31 TL-SE-01-XX Reference Laboratory 0.07 U 180 1.2 U 5.7 J- 75 130 31 TL-SE-11-XX Reference Laboratory 0.02 U 210 1.2 U 5.5 J- 85 140 31 TL-SE-14-XX Reference Laboratory 0.08 U 180 1.2 U 5.7 J- 73 140 31 TL-SE-18-XX Reference Laboratory 0.03 U 190 1.2 U 6.3 J- 70 120 31 TL-SE-22-XX Reference Laboratory 0.08 U 210 1.2 U 6.5 J- 80 150 31 TL-SE-27-XX Reference Laboratory 0.02 U 200 1.2 U 7.8 J- 67 140 31 TL-SE-29-XX Reference Laboratory 0.08 U 200 1.2 U 5.9 J- 80 140 31 TL-SE-01-RI Rigaku, Inc. 10 94 2 184 116 72 31 TL-SE-11-RI Rigaku, Inc. 16 99 1 190 119 70 31 TL-SE-14-RI Rigaku, Inc. 14 103 2 186 127 72 31 TL-SE-18-RI Rigaku, Inc. 5 94 2 188 123 67 31 TL-SE-22-RI Rigaku, Inc. 27 103 2 189 117 72 31 TL-SE-27-RI Rigaku, Inc. 8 98 4 191 131 67 31 TL-SE-29-RI Rigaku, Inc. 27 98 1 185 123 74 32 LV-SE-02-XX Reference Laboratory 0.02 U 160 3.8 1.3 UJ 53 65 32 LV-SE-10-XX Reference Laboratory 0.02 U 200 4.7 1.3 UJ 66 77 32 LV-SE-22-XX Reference Laboratory 1.1 170 5.2 1.3 UJ 51 66 32 LV-SE-25-XX Reference Laboratory 1 170 5.1 1.3 UJ 56 70 32 LV-SE-31-XX Reference Laboratory 1 180 5.1 1.3 UJ 58 70 32 LV-SE-35-XX Reference Laboratory 1.4 170 J- 5 1.3 UJ 55 J- 67 J32 LV-SE-50-XX Reference Laboratory 1.2 170 3.3 2.5 U 57 65 32 LV-SE-02-RI Rigaku, Inc. 34 75 7 216 82 51 32 LV-SE-10-RI Rigaku, Inc. 31 75 6 213 83 55 32 LV-SE-22-RI Rigaku, Inc. 32 75 8 218 87 53 32 LV-SE-25-RI Rigaku, Inc. 31 74 7 225 87 79 32 LV-SE-31-RI Rigaku, Inc. 35 74 5 209 84 53 32 LV-SE-35-RI Rigaku, Inc. 28 73 9 216 80 63 32 LV-SE-50-RI Rigaku, Inc. 30 79 8 209 92 49 33 LV-SE-12-XX Reference Laboratory 5.6 71 3 2.6 U 72 66 33 LV-SE-26-XX Reference Laboratory 6 83 6.1 2.6 U 86 75 33 LV-SE-33-XX Reference Laboratory 6.8 66 2.8 2.6 U 67 59 33 LV-SE-39-XX Reference Laboratory 8 74 5.1 2.6 U 74 66 33 LV-SE-42-XX Reference Laboratory 4.3 67 3.4 2.7 U 64 57 33 LV-SE-12-RI Rigaku, Inc. 5 41 2 182 88 44 33 LV-SE-26-RI Rigaku, Inc. 3 39 1 188 104 42 33 LV-SE-33-RI Rigaku, Inc. 6 38 0 192 103 49 33 LV-SE-39-RI Rigaku, Inc. 2 44 2 184 92 42 33 LV-SE-42-RI Rigaku, Inc. 3 33 2 166 93 42 
D-23

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

34 LV-SE-09-XX Reference Laboratory 6.7 U 450 2.7 U 48 34 150,000 14 J34 LV-SE-19-XX Reference Laboratory 6.7 U 500 2.7 U 55 37 160,000 17 J34 LV-SE-27-XX Reference Laboratory 6.7 U 530 2.7 U 56 39 180,000 16 J34 LV-SE-36-XX Reference Laboratory 6.7 U 550 2.7 U 60 40 180,000 21 J34 LV-SE-38-XX Reference Laboratory 6.7 U 480 2.7 U 52 36 160,000 15 J34 LV-SE-09-RI Rigaku, Inc. 169 63 392 173 6 66,112 -122 34 LV-SE-19-RI Rigaku, Inc. 177 31 383 176 7 66,611 -122 34 LV-SE-27-RI Rigaku, Inc. 255 37 400 169 2 65,189 -130 34 LV-SE-36-RI Rigaku, Inc. 204 60 375 207 4 66,642 -118 34 LV-SE-38-RI Rigaku, Inc. -30 -59 274 55 -15 41,849 -172 35 LV-SE-07-XX Reference Laboratory 6.7 UJ 780 2.7 U 57 48 200,000 11 35 LV-SE-18-XX Reference Laboratory 6.7 UJ 800 2.7 U 61 49 210,000 11 35 LV-SE-23-XX Reference Laboratory 6.6 UJ 660 2.6 U 53 40 170,000 8 35 LV-SE-45-XX Reference Laboratory 6.7 UJ 650 2.7 U 50 40 170,000 8 35 LV-SE-48-XX Reference Laboratory 6.6 UJ 680 2.6 U 52 42 180,000 9 35 LV-SE-07-RI Rigaku, Inc. 191 73 332 217 0 85,976 -147 35 LV-SE-18-RI Rigaku, Inc. 144 91 336 200 1 84,794 -138 35 LV-SE-23-RI Rigaku, Inc. 147 87 328 234 1 86,198 -150 35 LV-SE-45-RI Rigaku, Inc. 242 65 349 226 4 85,141 -143 35 LV-SE-48-RI Rigaku, Inc. 117 96 312 210 -1 86,120 -142 36 LV-SE-01-XX Reference Laboratory 1.5 UJ 6 0.76 4 18 1,100 17 36 LV-SE-14-XX Reference Laboratory 1.5 UJ 5 0.74 4 16 980 14 36 LV-SE-21-XX Reference Laboratory 1.5 UJ 7 0.84 4 19 970 18 36 LV-SE-24-XX Reference Laboratory 1.5 UJ 5 0.68 4 15 840 14 36 LV-SE-32-XX Reference Laboratory 1.4 UJ 6 0.87 4 16 860 14 36 LV-SE-01-RI Rigaku, Inc. 44 -15 473 -74 6 3,040 -80 36 LV-SE-14-RI Rigaku, Inc. 38 1 481 -45 1 3,040 -80 36 LV-SE-21-RI Rigaku, Inc. 43 -20 487 -52 -1 3,057 -82 36 LV-SE-24-RI Rigaku, Inc. 42 -36 477 -61 -2 3,067 -83 36 LV-SE-32-RI Rigaku, Inc. 42 -30 479 -61 1 3,055 -82 
D-24

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

34 LV-SE-09-XX Reference Laboratory 6 55 6.7 U 6.7 U 100 51 J 34 LV-SE-19-XX Reference Laboratory 7.2 65 5.9 J 6.7 U 110 55 J 34 LV-SE-27-XX Reference Laboratory 11 64 6.7 U 6.7 U 120 58 J 34 LV-SE-36-XX Reference Laboratory 8.5 70 11 6.7 U 120 60 J 34 LV-SE-38-XX Reference Laboratory 7.9 75 6.7 U 6.7 U 100 54 J 34 LV-SE-09-RI Rigaku, Inc. -23 25 -5 133 117 27 34 LV-SE-19-RI Rigaku, Inc. -16 26 -5 138 112 22 34 LV-SE-27-RI Rigaku, Inc. -18 19 -4 137 117 33 34 LV-SE-36-RI Rigaku, Inc. -20 20 -5 132 117 30 34 LV-SE-38-RI Rigaku, Inc. -56 13 -13 96 70 9 35 LV-SE-07-XX Reference Laboratory 5.5 58 10 6.7 U 130 24 J 35 LV-SE-18-XX Reference Laboratory 5.4 60 12 6.7 U 140 52 J 35 LV-SE-23-XX Reference Laboratory 5 50 J 9.6 6.6 U 120 18 J 35 LV-SE-45-XX Reference Laboratory 5.6 50 J 8.2 6.7 U 120 19 J 35 LV-SE-48-XX Reference Laboratory 7.3 50 J 7.6 6.6 U 120 30 J 35 LV-SE-07-RI Rigaku, Inc. -29 18 -5 128 139 18 35 LV-SE-18-RI Rigaku, Inc. -31 19 -7 120 138 15 35 LV-SE-23-RI Rigaku, Inc. -32 18 -6 125 148 12 35 LV-SE-45-RI Rigaku, Inc. -27 19 -6 128 138 15 35 LV-SE-48-RI Rigaku, Inc. -35 16 -7 122 139 10 36 LV-SE-01-XX Reference Laboratory 0.1 U 49 1.5 U 1.5 U 2 J 14 J 36 LV-SE-14-XX Reference Laboratory 0.06 U 46 1.5 U 1.5 U 1 J 12 J 36 LV-SE-21-XX Reference Laboratory 0.05 U 49 1.5 U 1.5 U 2 J 14 J 36 LV-SE-24-XX Reference Laboratory 0.05 U 44 1.5 U 1.5 U 1 J 12 J 36 LV-SE-32-XX Reference Laboratory 0.05 U 47 1.4 U 1.4 U 1 J 19 36 LV-SE-01-RI Rigaku, Inc. -3 26 -1 165 3 14 36 LV-SE-14-RI Rigaku, Inc. -6 25 1 164 11 8 36 LV-SE-21-RI Rigaku, Inc. -1 28 0 171 13 11 36 LV-SE-24-RI Rigaku, Inc. 2 27 1 170 5 12 36 LV-SE-32-RI Rigaku, Inc. 1 28 0 169 10 8 
D-25

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

37 LV-SE-08-XX Reference Laboratory 1.3 UJ 30 0.52 U 54 23 23,000 55 37 LV-SE-16-XX Reference Laboratory 1.3 UJ 29 0.52 U 53 22 22,000 53 37 LV-SE-28-XX Reference Laboratory 1.3 UJ 31 0.52 U 59 25 25,000 59 37 LV-SE-30-XX Reference Laboratory 1.3 UJ 30 0.52 U 58 25 24,000 58 37 LV-SE-47-XX Reference Laboratory 1.3 UJ 31 0.52 U 56 23 23,000 57 37 LV-SE-08-RI Rigaku, Inc. 184 46 595 42 23 16,577 6 37 LV-SE-16-RI Rigaku, Inc. 185 36 628 112 19 16,504 -13 37 LV-SE-28-RI Rigaku, Inc. 211 4 651 64 25 16,469 -7 37 LV-SE-30-RI Rigaku, Inc. 180 34 607 76 23 16,750 -6 37 LV-SE-47-RI Rigaku, Inc. 165 34 576 33 25 16,509 -12 38 LV-SE-11-XX Reference Laboratory 1.4 UJ 150 6.6 120 270 42,000 7 38 LV-SE-29-XX Reference Laboratory 1.4 UJ 150 6.3 120 260 42,000 7 J+ 38 LV-SE-44-XX Reference Laboratory 1.4 U 140 6.1 120 250 40,000 8 38 LV-SE-46-XX Reference Laboratory 0.88 U 110 5 92 200 32,000 6 38 LV-SE-52-XX Reference Laboratory 1.4 U 160 6.8 130 280 44,000 8 38 LV-SE-11-RI Rigaku, Inc. 193 55 551 79 144 22,687 -68 38 LV-SE-29-RI Rigaku, Inc. 230 71 582 146 154 22,583 -70 38 LV-SE-44-RI Rigaku, Inc. 201 40 556 118 143 22,794 -75 38 LV-SE-46-RI Rigaku, Inc. 179 49 549 108 137 22,493 -68 38 LV-SE-52-RI Rigaku, Inc. 220 81 573 129 140 22,459 -68 39 RF-SE-07-XX Reference Laboratory 1.3 U 12 0.5 U 92 81 17,000 24 39 RF-SE-12-XX Reference Laboratory 1.2 U 14 0.5 U 100 110 20,000 25 39 RF-SE-23-XX Reference Laboratory 0.25 U 0 U 0.1 U 0 U 0.2 U 4 J 0 U 39 RF-SE-36-XX Reference Laboratory 1.2 U 12 0.5 U 91 82 17,000 22 39 RF-SE-42-XX Reference Laboratory 1.3 UJ 14 0.56 110 95 19,000 28 39 RF-SE-45-XX Reference Laboratory 1.3 UJ 15 0.52 U 110 100 21,000 33 39 RF-SE-53-XX Reference Laboratory 1.3 UJ 14 0.57 U 110 95 19,000 28 39 RF-SE-07-RI Rigaku, Inc. 202 28 666 79 68 13,796 -38 39 RF-SE-12-RI Rigaku, Inc. 202 15 627 106 75 14,275 -26 39 RF-SE-23-RI Rigaku, Inc. 216 11 641 71 69 13,770 -26 39 RF-SE-36-RI Rigaku, Inc. 191 33 648 77 60 13,504 -21 39 RF-SE-42-RI Rigaku, Inc. 193 24 651 91 66 13,628 -24 39 RF-SE-45-RI Rigaku, Inc. 222 -2 632 64 68 13,658 -29 39 RF-SE-53-RI Rigaku, Inc. 228 -23 651 81 69 13,779 -37 
D-26

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

37 LV-SE-08-XX Reference Laboratory 5.2 110 4.8 1.3 U 44 61 37 LV-SE-16-XX Reference Laboratory 5.4 110 5 1.3 U 42 59 37 LV-SE-28-XX Reference Laboratory 5.4 120 5.8 1.3 U 48 65 37 LV-SE-30-XX Reference Laboratory 6.3 120 5.6 1.3 U 48 66 37 LV-SE-47-XX Reference Laboratory 4.9 120 4.2 1.3 U 45 65 37 LV-SE-08-RI Rigaku, Inc. 31 70 9 206 85 64 37 LV-SE-16-RI Rigaku, Inc. 36 72 8 217 89 53 37 LV-SE-28-RI Rigaku, Inc. 37 68 9 215 86 55 37 LV-SE-30-RI Rigaku, Inc. 24 74 9 208 87 60 37 LV-SE-47-RI Rigaku, Inc. 34 69 7 201 86 54 38 LV-SE-11-XX Reference Laboratory 2.8 870 1.3 U 1.4 U 35 200 38 LV-SE-29-XX Reference Laboratory 1.5 J- 860 1.2 U 1.4 U 35 200 38 LV-SE-44-XX Reference Laboratory 1.5 830 1.4 U 1.4 U 34 190 38 LV-SE-46-XX Reference Laboratory 1.4 660 0.88 U 0.88 U 27 150 38 LV-SE-52-XX Reference Laboratory 21 910 1.4 U 1.4 U 38 210 38 LV-SE-11-RI Rigaku, Inc. 15 347 3 192 50 104 38 LV-SE-29-RI Rigaku, Inc. 2 353 2 195 42 106 38 LV-SE-44-RI Rigaku, Inc. 12 363 1 190 42 104 38 LV-SE-46-RI Rigaku, Inc. 9 357 3 188 43 110 38 LV-SE-52-RI Rigaku, Inc. 9 353 4 198 45 107 39 RF-SE-07-XX Reference Laboratory 0.09 U 180 1.3 U 1.3 U 34 130 39 RF-SE-12-XX Reference Laboratory 0.1 U 210 1.2 U 1.2 U 38 140 39 RF-SE-23-XX Reference Laboratory 2.4 2 U 0.25 U 0.37 3 U 1 U 39 RF-SE-36-XX Reference Laboratory 0.08 U 180 1 U 1.2 U 34 120 39 RF-SE-42-XX Reference Laboratory 0.08 U 210 1.3 U 1.3 U 40 140 39 RF-SE-45-XX Reference Laboratory 0.08 U 220 1.3 U 1.3 U 43 150 39 RF-SE-53-XX Reference Laboratory 0.08 U 210 1.3 U 1.3 U 40 140 39 RF-SE-07-RI Rigaku, Inc. 47 94 8 230 59 95 39 RF-SE-12-RI Rigaku, Inc. 47 102 8 218 59 96 39 RF-SE-23-RI Rigaku, Inc. 52 97 13 206 52 88 39 RF-SE-36-RI Rigaku, Inc. 39 99 7 226 59 88 39 RF-SE-42-RI Rigaku, Inc. 36 99 8 220 55 88 39 RF-SE-45-RI Rigaku, Inc. 53 96 11 212 46 92 39 RF-SE-53-RI Rigaku, Inc. 66 103 12 210 56 86 
D-27

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

40 RF-SE-03-XX Reference Laboratory 1.2 UJ 27 1.3 93 200 17,000 88 40 RF-SE-28-XX Reference Laboratory 1.2 UJ 31 1.5 100 220 18,000 99 40 RF-SE-38-XX Reference Laboratory 1.2 UJ 27 1.2 90 190 16,000 83 40 RF-SE-49-XX Reference Laboratory 1.2 UJ 31 1.5 100 220 18,000 97 40 RF-SE-55-XX Reference Laboratory 1.2 UJ 24 1.1 91 180 15,000 75 40 RF-SE-03-RI Rigaku, Inc. 200 60 661 117 152 13,154 13 40 RF-SE-28-RI Rigaku, Inc. 236 36 669 97 157 13,234 11 40 RF-SE-38-RI Rigaku, Inc. 210 44 655 81 154 13,164 6 40 RF-SE-49-RI Rigaku, Inc. 240 5 669 71 151 13,062 9 40 RF-SE-55-RI Rigaku, Inc. 231 44 677 113 160 13,209 13 41 RF-SE-06-XX Reference Laboratory 1.3 UJ 70 3.6 90 490 20,000 230 41 RF-SE-13-XX Reference Laboratory 1.3 UJ 76 3.7 92 530 21,000 230 41 RF-SE-27-XX Reference Laboratory 1.3 UJ 64 3.1 78 440 18,000 200 41 RF-SE-31-XX Reference Laboratory 1.3 UJ 39 1.8 63 250 12,000 120 41 RF-SE-58-XX Reference Laboratory 1.3 UJ 71 3.6 89 500 21,000 230 41 RF-SE-06-RI Rigaku, Inc. 208 57 648 89 341 13,637 74 41 RF-SE-13-RI Rigaku, Inc. 232 42 654 65 329 13,248 82 41 RF-SE-27-RI Rigaku, Inc. 220 70 640 54 340 13,557 79 41 RF-SE-31-RI Rigaku, Inc. 225 62 659 94 347 13,482 75 41 RF-SE-58-RI Rigaku, Inc. 222 58 644 94 329 13,362 69 42 RF-SE-02-XX Reference Laboratory 1.3 UJ 110 5.4 93 740 24,000 330 42 RF-SE-22-XX Reference Laboratory 1.3 UJ 99 4.7 84 670 22,000 300 42 RF-SE-25-XX Reference Laboratory 1.3 UJ 88 4 78 580 19,000 270 42 RF-SE-30-XX Reference Laboratory 1.3 UJ 89 4.3 78 610 21,000 290 42 RF-SE-57-XX Reference Laboratory 1.3 UJ 89 4.5 79 610 21,000 300 42 RF-SE-02-RI Rigaku, Inc. 208 73 623 81 435 13,697 119 42 RF-SE-22-RI Rigaku, Inc. 214 72 619 91 439 13,627 103 42 RF-SE-25-RI Rigaku, Inc. 221 64 653 109 425 13,476 110 42 RF-SE-30-RI Rigaku, Inc. 224 66 637 102 420 13,501 110 42 RF-SE-57-RI Rigaku, Inc. 217 56 620 69 426 13,633 114 
D-28

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

40 RF-SE-03-XX Reference Laboratory 0.48 150 1.2 U 1.2 U 40 300 40 RF-SE-28-XX Reference Laboratory 0.57 160 1.2 U 1.2 U 44 320 40 RF-SE-38-XX Reference Laboratory 0.41 140 1.2 U 1.2 U 39 300 40 RF-SE-49-XX Reference Laboratory 0.43 170 1.2 U 1.2 U 43 330 40 RF-SE-55-XX Reference Laboratory 0.42 140 1.2 U 1.2 U 35 280 40 RF-SE-03-RI Rigaku, Inc. 36 89 7 227 56 190 40 RF-SE-28-RI Rigaku, Inc. 33 83 12 217 59 191 40 RF-SE-38-RI Rigaku, Inc. 33 89 8 228 62 193 40 RF-SE-49-RI Rigaku, Inc. 51 85 12 218 59 182 40 RF-SE-55-RI Rigaku, Inc. 38 82 9 239 60 187 41 RF-SE-06-XX Reference Laboratory 1.1 150 1.3 U 1.3 U 44 740 41 RF-SE-13-XX Reference Laboratory 1.2 160 1.3 U 1.3 45 790 41 RF-SE-27-XX Reference Laboratory 1.2 130 1.3 U 1.3 U 39 670 41 RF-SE-31-XX Reference Laboratory 1.1 86 1.3 U 1.3 U 28 420 41 RF-SE-58-XX Reference Laboratory 1.2 150 1.3 U 1.3 U 46 770 41 RF-SE-06-RI Rigaku, Inc. 33 81 9 220 64 405 41 RF-SE-13-RI Rigaku, Inc. 36 83 13 216 61 383 41 RF-SE-27-RI Rigaku, Inc. 30 80 11 209 55 417 41 RF-SE-31-RI Rigaku, Inc. 39 78 6 230 58 399 41 RF-SE-58-RI Rigaku, Inc. 38 86 7 227 52 385 42 RF-SE-02-XX Reference Laboratory 1.6 180 1.3 U 2.7 50 1,100 42 RF-SE-22-XX Reference Laboratory 1.7 160 1.3 U 2.3 44 990 42 RF-SE-25-XX Reference Laboratory 1.5 140 1.5 1.7 40 890 42 RF-SE-30-XX Reference Laboratory 1.5 150 1.3 U 1.9 44 960 42 RF-SE-57-XX Reference Laboratory 1.5 150 2 2.2 44 1,000 42 RF-SE-02-RI Rigaku, Inc. 39 82 7 220 54 504 42 RF-SE-22-RI Rigaku, Inc. 31 88 13 206 61 494 42 RF-SE-25-RI Rigaku, Inc. 29 83 13 213 58 482 42 RF-SE-30-RI Rigaku, Inc. 27 84 13 212 49 468 42 RF-SE-57-RI Rigaku, Inc. 34 82 7 216 58 482 
D-29

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

43 RF-SE-15-XX Reference Laboratory 1.3 UJ 120 6.2 72 820 23,000 390 43 RF-SE-24-XX Reference Laboratory 1.3 UJ 130 J+ 6.5 J+ 74 J+ 860 J+ 24,000 J+ 410 J+ 43 RF-SE-32-XX Reference Laboratory 1.3 UJ 120 5.1 64 770 20,000 330 43 RF-SE-43-XX Reference Laboratory 1.3 UJ 130 5.7 68 840 22,000 350 43 RF-SE-59-XX Reference Laboratory 1.3 UJ 140 5.9 73 890 23,000 380 43 RF-SE-15-RI Rigaku, Inc. 209 95 598 142 566 14,112 160 43 RF-SE-24-RI Rigaku, Inc. 209 80 608 99 579 14,375 163 43 RF-SE-32-RI Rigaku, Inc. 218 76 624 48 582 14,256 161 43 RF-SE-43-RI Rigaku, Inc. 228 80 653 48 555 14,218 166 43 RF-SE-59-RI Rigaku, Inc. 229 84 617 74 552 14,169 166 44 RF-SE-05-XX Reference Laboratory 4.1 J+ 160 9.1 69 1,000 26,000 450 44 RF-SE-26-XX Reference Laboratory 2.2 J+ 140 8.4 64 990 23,000 440 44 RF-SE-39-XX Reference Laboratory 2.9 J+ 160 9.3 73 1,100 26,000 490 44 RF-SE-44-XX Reference Laboratory 2.7 J+ 140 8.2 64 970 24,000 420 44 RF-SE-56-XX Reference Laboratory 3.5 J+ 180 9.6 75 1200 27,000 490 44 RF-SE-05-RI Rigaku, Inc. 260 95 638 83 716 14,924 187 44 RF-SE-26-RI Rigaku, Inc. 229 114 657 86 693 14,916 193 44 RF-SE-39-RI Rigaku, Inc. 243 86 617 50 693 14,579 174 44 RF-SE-44-RI Rigaku, Inc. 211 112 610 129 701 14,778 176 44 RF-SE-56-RI Rigaku, Inc. 273 84 658 94 697 14,768 183 45 RF-SE-04-XX Reference Laboratory 3.2 J+ 230 12 42 1,500 27,000 730 45 RF-SE-14-XX Reference Laboratory 4.4 J+ 260 12 47 1,700 30,000 800 45 RF-SE-19-XX Reference Laboratory 3.7 J+ 250 13 48 1,700 30,000 800 45 RF-SE-34-XX Reference Laboratory 2.9 J+ 210 10 39 1,400 24,000 660 45 RF-SE-52-XX Reference Laboratory 3.4 J+ 220 11 42 1,500 26,000 720 45 RF-SE-04-RI Rigaku, Inc. 252 119 611 65 947 15,229 327 45 RF-SE-14-RI Rigaku, Inc. 207 160 604 64 956 15,099 331 45 RF-SE-19-RI Rigaku, Inc. 212 154 591 91 946 15,270 326 45 RF-SE-34-RI Rigaku, Inc. 274 127 627 23 933 15,283 310 45 RF-SE-52-RI Rigaku, Inc. 220 148 600 109 952 15,259 316 
D-30

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

43 RF-SE-15-XX Reference Laboratory 2.6 160 1.4 3.6 45 1,300 43 RF-SE-24-XX Reference Laboratory 2.3 170 J+ 1.3 U 3.8 J+ 46 J+ 1,400 J43 RF-SE-32-XX Reference Laboratory 2.8 140 1.3 U 4.2 36 1,100 43 RF-SE-43-XX Reference Laboratory 2.7 150 1.3 U 4 40 1,200 43 RF-SE-59-XX Reference Laboratory 0.09 U 160 1.3 U 4.5 42 1,300 43 RF-SE-15-RI Rigaku, Inc. 22 90 12 202 64 637 43 RF-SE-24-RI Rigaku, Inc. 21 96 11 202 68 665 43 RF-SE-32-RI Rigaku, Inc. 27 85 6 209 58 649 43 RF-SE-43-RI Rigaku, Inc. 14 89 12 208 64 639 43 RF-SE-59-RI Rigaku, Inc. 39 84 8 213 62 627 44 RF-SE-05-XX Reference Laboratory 2.6 150 3.1 7.4 J- 48 1,800 44 RF-SE-26-XX Reference Laboratory 2.5 140 2.8 7.2 J- 42 1,700 44 RF-SE-39-XX Reference Laboratory 2.2 150 2.6 8.2 J- 49 1,900 44 RF-SE-44-XX Reference Laboratory 2.3 140 2.4 7.2 J- 44 1,600 44 RF-SE-56-XX Reference Laboratory 2.2 160 1.8 8.3 J- 51 1,900 44 RF-SE-05-RI Rigaku, Inc. 32 80 7 223 61 833 44 RF-SE-26-RI Rigaku, Inc. 15 76 12 211 64 837 44 RF-SE-39-RI Rigaku, Inc. 25 76 7 220 57 802 44 RF-SE-44-RI Rigaku, Inc. 18 77 11 207 62 796 44 RF-SE-56-RI Rigaku, Inc. 35 73 7 220 67 809 45 RF-SE-04-XX Reference Laboratory 4.2 130 2.8 12 J- 46 2,400 45 RF-SE-14-XX Reference Laboratory 4.7 140 3 13 J- 51 2,600 45 RF-SE-19-XX Reference Laboratory 3.9 140 4.1 14 J- 52 2,700 45 RF-SE-34-XX Reference Laboratory 4.5 120 1.9 10 J- 42 2,200 45 RF-SE-52-XX Reference Laboratory 4.1 130 2 11 J- 47 2,300 45 RF-SE-04-RI Rigaku, Inc. 37 76 6 207 55 1,083 45 RF-SE-14-RI Rigaku, Inc. 3 75 12 204 52 1,066 45 RF-SE-19-RI Rigaku, Inc. -3 88 12 202 66 1,080 45 RF-SE-34-RI Rigaku, Inc. 26 81 6 218 56 1,030 45 RF-SE-52-RI Rigaku, Inc. 8 77 12 206 66 1,078 
D-31

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe P

46 BN-SO-11-XX Reference Laboratory 4 J- 2,900 720 820 120 23,000 546 BN-SO-14-XX Reference Laboratory 3.5 J- 2,800 690 800 120 22,000 546 BN-SO-23-XX Reference Laboratory 1.2 UJ 2,800 700 800 120 23,000 546 BN-SO-11-RI Rigaku, Inc. 176 1,404 899 408 93 13,667 -346 BN-SO-14-RI Rigaku, Inc. 168 1,371 880 442 88 13,694 -246 BN-SO-23-RI Rigaku, Inc. 152 1,306 837 376 86 13,626 -347 BN-SO-09-XX Reference Laboratory 750 J- 97 2,700 2,900 100 22,000 4,7047 BN-SO-12-XX Reference Laboratory 750 J- 89 2,600 2,800 96 21,000 4,5047 BN-SO-24-XX Reference Laboratory 810 J- 97 2,900 3,000 100 23,000 4,9047 BN-SO-09-RI Rigaku, Inc. 763 63 1,506 1,080 69 12,828 2,1347 BN-SO-12-RI Rigaku, Inc. 769 89 1,534 1,034 74 12,772 2,2047 BN-SO-24-RI Rigaku, Inc. 699 89 1,516 1,089 70 12,869 2,1848 SB-SO-09-XX Reference Laboratory 1.3 UJ 9 0.51 U 130 120 35,000 148 SB-SO-20-XX Reference Laboratory 1.3 UJ 11 0.51 U 170 150 44,000 248 SB-SO-31-XX Reference Laboratory 1.3 UJ 8 J- 0.51 U 140 130 38,000 248 SB-SO-09-RI Rigaku, Inc. 169 0 563 137 78 19,548 -648 SB-SO-20-RI Rigaku, Inc. 231 23 686 130 27 18,103 -448 SB-SO-31-RI Rigaku, Inc. 202 7 601 147 87 19,821 -549 SB-SO-29-XX Reference Laboratory 1.2 U 9 0.5 U 140 130 41,000 149 SB-SO-36-XX Reference Laboratory 1.2 U 8 0.5 U 120 100 33,000 149 SB-SO-56-XX Reference Laboratory 1.2 U 10 0.5 U 150 140 42,000 249 SB-SO-29-RI Rigaku, Inc. 223 0 606 159 75 19,982 -549 SB-SO-36-RI Rigaku, Inc. 215 10 589 142 81 20,196 -549 SB-SO-56-RI Rigaku, Inc. 207 3 596 117 76 20,017 -550 SB-SO-04-XX Reference Laboratory 940 13 2,800 2,800 100 38,000 250 SB-SO-34-XX Reference Laboratory 980 12 2,500 2,500 91 34,000 150 SB-SO-49-XX Reference Laboratory 700 12 2,500 2,400 89 33,000 150 SB-SO-04-RI Rigaku, Inc. 323 18 1,717 1,224 70 18,689 -450 SB-SO-34-RI Rigaku, Inc. 321 31 1,676 1,253 68 18,682 -350 SB-SO-49-RI Rigaku, Inc. 302 8 1,688 1,288 68 18,764 -4
D-32

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

46 BN-SO-11-XX Reference Laboratory 24 J- 2,900 140 140 J- 150 3,900 46 BN-SO-14-XX Reference Laboratory 26 2,800 130 140 J- 150 3,800 46 BN-SO-23-XX Reference Laboratory 31 2,800 130 130 J- 150 3,800 46 BN-SO-11-RI Rigaku, Inc. 40 1,353 44 225 113 2,044 46 BN-SO-14-RI Rigaku, Inc. 45 1,339 44 215 124 2,080 46 BN-SO-23-RI Rigaku, Inc. 37 1,315 41 209 111 1,981 47 BN-SO-09-XX Reference Laboratory 0.39 1,500 290 100 J- 340 81 47 BN-SO-12-XX Reference Laboratory 0.34 1,400 290 210 J- 310 74 47 BN-SO-24-XX Reference Laboratory 0.37 1,600 300 140 J- 350 81 47 BN-SO-09-RI Rigaku, Inc. 17 639 87 214 199 59 47 BN-SO-12-RI Rigaku, Inc. 23 641 83 215 185 63 47 BN-SO-24-RI Rigaku, Inc. 19 625 84 224 183 58 48 SB-SO-09-XX Reference Laboratory 30 2900 26 160 J- 120 3,600 48 SB-SO-20-XX Reference Laboratory 10 3700 30 140 J- 160 4,500 48 SB-SO-31-XX Reference Laboratory 32 3200 J- 28 J- 160 J- 140 3,900 J48 SB-SO-09-RI Rigaku, Inc. 24 1,331 11 224 147 1,850 48 SB-SO-20-RI Rigaku, Inc. 346 94 4 233 121 59 48 SB-SO-31-RI Rigaku, Inc. 32 1,348 13 221 148 1,871 49 SB-SO-29-XX Reference Laboratory 7.9 J 200 160 1.2 UJ 400 3,900 49 SB-SO-36-XX Reference Laboratory 36 160 130 1.2 UJ 320 3,200 49 SB-SO-56-XX Reference Laboratory 9 210 160 1.2 UJ 410 4,100 49 SB-SO-29-RI Rigaku, Inc. 39 104 46 216 246 1,952 49 SB-SO-36-RI Rigaku, Inc. 36 106 44 207 248 1,958 49 SB-SO-56-RI Rigaku, Inc. 37 103 47 206 272 1,935 50 SB-SO-04-XX Reference Laboratory 40 3,300 390 1.3 UJ 58 86 50 SB-SO-34-XX Reference Laboratory 36 3,000 360 1.3 UJ 52 77 50 SB-SO-49-XX Reference Laboratory 36 2,800 330 1.2 UJ 52 72 50 SB-SO-04-RI Rigaku, Inc. 41 1,363 103 219 97 58 50 SB-SO-34-RI Rigaku, Inc. 37 1,359 104 219 88 53 50 SB-SO-49-RI Rigaku, Inc. 40 1,350 105 205 119 51 
D-33

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

51 WS-SO-07-XX Reference Laboratory 3.8 53 1.9 640 4,400 25,000 1,700 51 WS-SO-11-XX Reference Laboratory 1.2 U 46 1.4 570 3,900 19,000 1,500 51 WS-SO-25-XX Reference Laboratory 1.2 U 59 3.1 730 4,900 24,000 1,900 51 WS-SO-07-RI Rigaku, Inc. 299 54 575 357 3,374 15,153 1,017 51 WS-SO-11-RI Rigaku, Inc. 251 57 564 391 3,324 15,055 1,011 51 WS-SO-25-RI Rigaku, Inc. 308 54 579 347 3,364 15,226 984 52 WS-SO-10-XX Reference Laboratory 1.3 U 83 1.8 67 76 19,000 1,900 52 WS-SO-20-XX Reference Laboratory 1.3 U 100 1.9 81 90 23,000 2,300 52 WS-SO-23-XX Reference Laboratory 1.3 U 110 2.1 82 96 23,000 2,500 52 WS-SO-10-RI Rigaku, Inc. 339 80 571 89 86 15,292 1,369 52 WS-SO-20-RI Rigaku, Inc. 340 93 568 86 70 15,252 1,375 52 WS-SO-23-RI Rigaku, Inc. 317 118 562 134 77 15,199 1,426 53 AS-SO-03-XX Reference Laboratory 1.2 U 14 1,300 33 6,200 15,000 160 53 AS-SO-05-XX Reference Laboratory 1.2 U 9 900 23 4,500 11,000 110 53 AS-SO-08-XX Reference Laboratory 1.2 U 10 930 24 4,600 11,000 120 53 AS-SO-03-RI Rigaku, Inc. 160 38 1,091 62 3,421 10,202 41 53 AS-SO-05-RI Rigaku, Inc. 157 21 1,130 76 3,439 10,199 52 53 AS-SO-08-RI Rigaku, Inc. 154 8 1,085 47 3,447 10,116 30 54 LV-SO-03-XX Reference Laboratory 1.6 42 590 600 130 24,000 94 54 LV-SO-40-XX Reference Laboratory 2.7 42 580 590 130 24,000 92 54 LV-SO-49-XX Reference Laboratory 7.4 43 600 610 130 25,000 98 54 LV-SO-03-RI Rigaku, Inc. 199 39 808 318 92 18,230 14 54 LV-SO-40-RI Rigaku, Inc. 191 36 810 308 96 18,375 -8 54 LV-SO-49-RI Rigaku, Inc. 194 32 824 313 94 18,292 3 55 LV-SO-04-XX Reference Laboratory 860 120 2,400 2,300 98 22,000 4,000 55 LV-SO-34-XX Reference Laboratory 870 J- 110 J- 2,300 J- 2,200 J- 87 20,000 J- 3,700 55 LV-SO-37-XX Reference Laboratory 590 84 1,700 1,600 66 16,000 2,800 55 LV-SO-04-RI Rigaku, Inc. 819 102 1,482 1,135 70 17,094 2,288 55 LV-SO-34-RI Rigaku, Inc. 720 83 1,472 1,094 78 16,931 2,192 55 LV-SO-37-RI Rigaku, Inc. 778 94 1,473 1,137 75 17,016 2,264 
D-34

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

51 WS-SO-07-XX Reference Laboratory 0.26 260 1.2 U 400 J- 48 180 51 WS-SO-11-XX Reference Laboratory 0.27 240 1.2 U 340 J- 43 160 51 WS-SO-25-XX Reference Laboratory 0.25 300 1.2 U 450 J- 54 200 51 WS-SO-07-RI Rigaku, Inc. 19 173 5 216 83 135 51 WS-SO-11-RI Rigaku, Inc. 28 170 6 208 68 134 51 WS-SO-25-RI Rigaku, Inc. 16 165 7 219 71 136 52 WS-SO-10-XX Reference Laboratory 0.06 U 290 280 1.3 UJ 260 1,900 52 WS-SO-20-XX Reference Laboratory 0.06 U 350 340 1.3 UJ 320 2,300 52 WS-SO-23-XX Reference Laboratory 0.05 U 380 360 1.3 UJ 330 2,500 52 WS-SO-10-RI Rigaku, Inc. 29 198 108 200 214 1,421 52 WS-SO-20-RI Rigaku, Inc. 29 205 104 191 212 1,418 52 WS-SO-23-RI Rigaku, Inc. 27 207 108 195 212 1,452 53 AS-SO-03-XX Reference Laboratory 3.7 J- 520 200 480 J- 29 350 53 AS-SO-05-XX Reference Laboratory 2.5 J- 370 140 330 J- 23 250 53 AS-SO-08-XX Reference Laboratory 2.5 J- 380 140 280 J- 23 260 53 AS-SO-03-RI Rigaku, Inc. 29 226 55 239 65 183 53 AS-SO-05-RI Rigaku, Inc. 34 233 55 248 55 186 53 AS-SO-08-RI Rigaku, Inc. 33 221 55 237 54 182 54 LV-SO-03-XX Reference Laboratory 48 J- 2,000 120 210 J- 120 3,700 54 LV-SO-40-XX Reference Laboratory 46 J- 1,900 120 210 J- 120 3,700 54 LV-SO-49-XX Reference Laboratory 52 J- 2,000 120 220 J- 120 3,800 54 LV-SO-03-RI Rigaku, Inc. 49 991 39 214 136 2,161 54 LV-SO-40-RI Rigaku, Inc. 50 1,007 39 209 145 2,133 54 LV-SO-49-RI Rigaku, Inc. 52 989 41 212 149 2,120 55 LV-SO-04-XX Reference Laboratory 130 J- 2,000 230 1.2 UJ 260 53 55 LV-SO-34-XX Reference Laboratory 130 J- 1,900 J- 220 J- 1.2 UJ 230 J- 48 J55 LV-SO-37-XX Reference Laboratory 130 J- 1,400 170 1.2 U 180 37 55 LV-SO-04-RI Rigaku, Inc. 89 995 71 201 212 51 55 LV-SO-34-RI Rigaku, Inc. 87 974 73 196 198 50 55 LV-SO-37-RI Rigaku, Inc. 87 993 74 196 222 51 
D-35

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe P

56 CN-SO-03-XX Reference Laboratory 22 87 63 17 72 15,000 130 56 CN-SO-06-XX Reference Laboratory 20 91 64 18 74 16,000 130 56 CN-SO-07-XX Reference Laboratory 20 90 63 19 72 17,000 130 56 CN-SO-03-RI Rigaku, Inc. 193 104 638 62 68 12,600 52 56 CN-SO-06-RI Rigaku, Inc. 194 72 677 30 62 12,004 43 56 CN-SO-07-RI Rigaku, Inc. 205 101 668 52 71 12,449 46 57 CN-SO-02-XX Reference Laboratory 230 19 820 290 140 22,000 490 57 CN-SO-05-XX Reference Laboratory 130 6 630 26 160 23,000 25 57 CN-SO-09-XX Reference Laboratory 120 6 580 21 140 19,000 23 57 CN-SO-02-RI Rigaku, Inc. 190 44 858 42 112 12,591 -19 57 CN-SO-05-RI Rigaku, Inc. 169 46 825 13 112 12,750 -26 57 CN-SO-09-RI Rigaku, Inc. 186 10 828 64 98 12,514 -29 58 LV-SE-06-XX Reference Laboratory 30 23 160 540 30 18,000 1,600 58 LV-SE-13-XX Reference Laboratory 31 24 160 540 30 18,000 1,600 58 LV-SE-41-XX Reference Laboratory 30 21 150 480 26 16,000 1,500 58 LV-SE-06-RI Rigaku, Inc. 310 -8 652 299 22 14,762 996 58 LV-SE-13-RI Rigaku, Inc. 367 3 668 301 30 14,849 1,013 58 LV-SE-41-RI Rigaku, Inc. 430 1 662 309 23 14,832 1,008 59 LV-SE-05-XX Reference Laboratory 92 20 440 840 39 16,000 14 59 LV-SE-20-XX Reference Laboratory 140 J+ 31 680 1,400 60 22,000 21 59 LV-SE-43-XX Reference Laboratory 160 J+ 24 550 1,100 47 19,000 17 59 LV-SE-05-RI Rigaku, Inc. 225 30 857 558 43 15,135 -18 59 LV-SE-20-RI Rigaku, Inc. 205 36 836 475 32 15,081 -30 59 LV-SE-43-RI Rigaku, Inc. 203 15 879 473 38 15,079 -22 60 LV-SE-15-XX Reference Laboratory 290 J+ 32 1,300 83 2,300 22,000 18 60 LV-SE-17-XX Reference Laboratory 280 J+ 31 1,300 79 2,200 21,000 17 60 LV-SE-51-XX Reference Laboratory 210 J+ 26 1,100 72 2,000 19,000 15 60 LV-SE-15-RI Rigaku, Inc. 221 19 1,106 91 1,291 14,724 -32 60 LV-SE-17-RI Rigaku, Inc. 194 13 1,044 67 1,312 14,853 -43 60 LV-SE-51-RI Rigaku, Inc. 221 2 1,122 50 1,302 14,751 -34 
D-36

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

56 CN-SO-03-XX Reference Laboratory 34 J- 74 36 90 30 58 56 CN-SO-06-XX Reference Laboratory 40 J- 76 38 94 32 59 56 CN-SO-07-XX Reference Laboratory 36 J- 75 37 91 33 58 56 CN-SO-03-RI Rigaku, Inc. 43 69 18 226 69 55 56 CN-SO-06-RI Rigaku, Inc. 52 73 20 228 56 55 56 CN-SO-07-RI Rigaku, Inc. 38 66 19 230 59 65 57 CN-SO-02-XX Reference Laboratory 270 J- 530 190 68 160 1,900 57 CN-SO-05-XX Reference Laboratory 280 J- 360 190 78 160 2,200 57 CN-SO-09-XX Reference Laboratory 260 J- 330 170 74 140 2,100 57 CN-SO-02-RI Rigaku, Inc. 140 183 55 216 117 1,159 57 CN-SO-05-RI Rigaku, Inc. 134 186 51 205 117 1,191 57 CN-SO-09-RI Rigaku, Inc. 136 187 51 211 119 1,135 58 LV-SE-06-XX Reference Laboratory 610 J- 360 160 110 480 52 58 LV-SE-13-XX Reference Laboratory 640 J- 360 160 110 470 51 58 LV-SE-41-XX Reference Laboratory 610 J- 320 150 99 420 46 58 LV-SE-06-RI Rigaku, Inc. 290 210 57 212 311 53 58 LV-SE-13-RI Rigaku, Inc. 288 211 55 211 309 54 58 LV-SE-41-RI Rigaku, Inc. 303 208 57 216 336 52 59 LV-SE-05-XX Reference Laboratory 2.6 J- 400 340 49 340 1,800 59 LV-SE-20-XX Reference Laboratory 2.8 660 500 75 J- 530 2,800 59 LV-SE-43-XX Reference Laboratory 2.8 530 420 60 J- 430 2,300 59 LV-SE-05-RI Rigaku, Inc. 31 271 120 216 308 1,216 59 LV-SE-20-RI Rigaku, Inc. 33 263 123 221 270 1,196 59 LV-SE-43-RI Rigaku, Inc. 33 269 127 222 276 1,211 60 LV-SE-15-XX Reference Laboratory 500 230 92 300 J- 180 62 60 LV-SE-17-XX Reference Laboratory 490 220 89 200 J- 170 58 60 LV-SE-51-XX Reference Laboratory 470 200 76 250 J- 160 54 60 LV-SE-15-RI Rigaku, Inc. 241 115 27 250 147 71 60 LV-SE-17-RI Rigaku, Inc. 234 110 25 234 137 56 60 LV-SE-51-RI Rigaku, Inc. 252 106 31 246 134 54 
D-37

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

61 TL-SE-05-XX Reference Laboratory 100 J+ 34 0.34 J 40 4,900 24,000 1,200 61 TL-SE-09-XX Reference Laboratory 100 J+ 33 0.24 J 39 4,800 23,000 1,200 61 TL-SE-13-XX Reference Laboratory 95 J+ 31 0.45 J 36 J+ 4,400 J+ 22,000 J+ 1,100 61 TL-SE-05-RI Rigaku, Inc. 248 -27 542 84 2,111 15,461 454 61 TL-SE-09-RI Rigaku, Inc. 260 9 540 57 2,112 15,340 461 61 TL-SE-13-RI Rigaku, Inc. 275 17 545 35 2,152 15,446 474 62 TL-SE-06-XX Reference Laboratory 1.2 U 86 350 34 2000 22,000 1,700 62 TL-SE-17-XX Reference Laboratory 1.2 U 85 340 33 2100 21,000 1,700 62 TL-SE-28-XX Reference Laboratory 1.2 U 89 360 34 2100 22,000 1,700 62 TL-SE-06-RI Rigaku, Inc. 241 55 675 31 1,119 15,139 783 62 TL-SE-17-RI Rigaku, Inc. 268 51 687 52 1,129 15,114 809 62 TL-SE-28-RI Rigaku, Inc. 301 39 693 19 1,180 15,217 824 63 TL-SE-07-XX Reference Laboratory 30 11 48 66 2200 37,000 13 63 TL-SE-21-XX Reference Laboratory 33 13 51 73 2300 44,000 15 63 TL-SE-30-XX Reference Laboratory 31 11 47 64 2200 36,000 14 63 TL-SE-07-RI Rigaku, Inc. 184 -32 514 71 1,084 27,719 -85 63 TL-SE-21-RI Rigaku, Inc. 169 -43 490 88 1,076 28,311 -90 63 TL-SE-30-RI Rigaku, Inc. 158 -36 467 65 1,051 27,607 -81 64 TL-SE-02-XX Reference Laboratory 77 15 160 64 3,100 32,000 12 64 TL-SE-08-XX Reference Laboratory 66 10 180 74 3,200 45,000 11 64 TL-SE-16-XX Reference Laboratory 73 15 170 69 3,100 38,000 13 64 TL-SE-02-RI Rigaku, Inc. 181 -33 516 113 1,422 27,920 -93 64 TL-SE-08-RI Rigaku, Inc. 176 -15 510 89 1,466 28,667 -87 64 TL-SE-16-RI Rigaku, Inc. 174 -16 518 55 1,463 28,379 -97 
D-38

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

61 TL-SE-05-XX Reference Laboratory 980 54 130 180 J- 66 100 61 TL-SE-09-XX Reference Laboratory 820 53 130 170 J- 63 100 61 TL-SE-13-XX Reference Laboratory 990 49 120 160 J 59 J+ 96 61 TL-SE-05-RI Rigaku, Inc. 325 39 34 195 117 58 61 TL-SE-09-RI Rigaku, Inc. 308 38 29 193 115 58 61 TL-SE-13-RI Rigaku, Inc. 304 38 32 197 113 64 62 TL-SE-06-XX Reference Laboratory 2.2 44 45 56 78 83 62 TL-SE-17-XX Reference Laboratory 2.6 43 44 56 78 81 62 TL-SE-28-XX Reference Laboratory 2.8 44 45 57 81 83 62 TL-SE-06-RI Rigaku, Inc. 13 38 18 198 110 63 62 TL-SE-17-RI Rigaku, Inc. 14 39 15 193 116 57 62 TL-SE-28-RI Rigaku, Inc. 20 34 17 196 111 57 63 TL-SE-07-XX Reference Laboratory 40 94 120 63 110 160 63 TL-SE-21-XX Reference Laboratory 120 100 140 67 120 170 63 TL-SE-30-XX Reference Laboratory 100 93 120 62 100 160 63 TL-SE-07-RI Rigaku, Inc. 5 46 32 175 193 78 63 TL-SE-21-RI Rigaku, Inc. 16 48 33 169 192 78 63 TL-SE-30-RI Rigaku, Inc. 4 48 28 158 178 74 64 TL-SE-02-XX Reference Laboratory 400 99 44 120 110 160 64 TL-SE-08-XX Reference Laboratory 350 100 39 130 120 170 64 TL-SE-16-XX Reference Laboratory 420 100 44 120 110 160 64 TL-SE-02-RI Rigaku, Inc. 44 48 8 165 174 81 64 TL-SE-08-RI Rigaku, Inc. 42 47 10 162 178 83 64 TL-SE-16-RI Rigaku, Inc. 51 53 11 166 163 74 
D-39

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

65 RF-SE-01-XX Reference Laboratory 12 230 40 280 63 14,000 22 65 RF-SE-09-XX Reference Laboratory 10 260 45 310 71 16,000 26 65 RF-SE-11-XX Reference Laboratory 11 240 43 300 72 15,000 25 65 RF-SE-17-XX Reference Laboratory 11 250 43 300 67 15,000 26 65 RF-SE-29-XX Reference Laboratory 13 280 49 330 75 17,000 26 65 RF-SE-37-XX Reference Laboratory 11 260 45 320 72 16,000 27 65 RF-SE-50-XX Reference Laboratory 8.9 230 40 280 65 14,000 23 65 RF-SE-01-RI Rigaku, Inc. 190 192 661 176 56 12,047 -18 65 RF-SE-09-RI Rigaku, Inc. 182 171 711 163 61 11,379 -14 65 RF-SE-11-RI Rigaku, Inc. 183 164 663 173 59 11,335 -16 65 RF-SE-17-RI Rigaku, Inc. 230 209 685 195 55 11,264 -21 65 RF-SE-29-RI Rigaku, Inc. 229 203 665 276 54 11,433 -28 65 RF-SE-37-RI Rigaku, Inc. 176 155 678 183 55 11,488 -27 65 RF-SE-50-RI Rigaku, Inc. 248 174 702 236 55 10,934 -30 66 RF-SE-08-XX Reference Laboratory 14 460 67 510 1,800 18,000 580 66 RF-SE-10-XX Reference Laboratory 12 400 58 440 1,500 16,000 510 66 RF-SE-33-XX Reference Laboratory 13 440 64 490 1,700 18,000 570 66 RF-SE-08-RI Rigaku, Inc. 241 269 662 308 1,327 12,503 295 66 RF-SE-10-RI Rigaku, Inc. 225 273 647 258 1,318 12,340 299 66 RF-SE-33-RI Rigaku, Inc. 242 257 658 272 1,258 12,280 284 67 RF-SE-16-XX Reference Laboratory 85 J- 72 J- 310 J- 820 J- 73 J- 16,000 J- 24 J67 RF-SE-41-XX Reference Laboratory 100 82 360 950 85 18,000 25 67 RF-SE-48-XX Reference Laboratory 100 87 380 1,000 90 19,000 27 67 RF-SE-16-RI Rigaku, Inc. 215 24 755 686 65 11,960 -21 67 RF-SE-41-RI Rigaku, Inc. 178 49 787 475 66 12,153 -25 67 RF-SE-48-RI Rigaku, Inc. 238 40 801 616 63 11,987 -27 
D-40

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

65 RF-SE-01-XX Reference Laboratory 47 200 21 37 29 1,700 65 RF-SE-09-XX Reference Laboratory 45 220 23 42 32 1,900 65 RF-SE-11-XX Reference Laboratory 52 210 20 40 29 1,800 65 RF-SE-17-XX Reference Laboratory 20 210 22 40 30 1,800 65 RF-SE-29-XX Reference Laboratory 20 240 26 44 35 2,100 65 RF-SE-37-XX Reference Laboratory 22 220 23 44 32 1,900 65 RF-SE-50-XX Reference Laboratory 19 200 20 38 29 1,700 65 RF-SE-01-RI Rigaku, Inc. 53 149 16 229 56 1,239 65 RF-SE-09-RI Rigaku, Inc. 54 132 16 241 54 1,127 65 RF-SE-11-RI Rigaku, Inc. 54 131 13 231 53 1,113 65 RF-SE-17-RI Rigaku, Inc. 64 131 18 214 50 1,112 65 RF-SE-29-RI Rigaku, Inc. 71 131 18 215 50 1,117 65 RF-SE-37-RI Rigaku, Inc. 54 139 15 228 54 1,123 65 RF-SE-50-RI Rigaku, Inc. 59 125 17 223 41 1,041 66 RF-SE-08-XX Reference Laboratory 29 250 42 0.39 U 120 120 66 RF-SE-10-XX Reference Laboratory 27 220 39 0.34 U 100 110 66 RF-SE-33-XX Reference Laboratory 28 240 41 0.33 U 120 130 66 RF-SE-08-RI Rigaku, Inc. 65 147 20 216 98 83 66 RF-SE-10-RI Rigaku, Inc. 60 141 20 221 90 84 66 RF-SE-33-RI Rigaku, Inc. 64 129 19 222 92 86 67 RF-SE-16-XX Reference Laboratory 260 1,700 J- 1.2 U 130 J- 32 J- 760 J67 RF-SE-41-XX Reference Laboratory 230 1,900 1.2 U 140 39 830 67 RF-SE-48-XX Reference Laboratory 250 2,000 2.2 150 40 880 67 RF-SE-16-RI Rigaku, Inc. 183 941 13 214 56 441 67 RF-SE-41-RI Rigaku, Inc. 170 956 7 228 48 455 67 RF-SE-48-RI Rigaku, Inc. 185 922 14 218 54 442 
D-41

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 

68 RF-SE-18-XX Reference Laboratory 320 810 770 950 78 16,000 860 68 RF-SE-35-XX Reference Laboratory 300 740 700 860 70 15,000 780 68 RF-SE-54-XX Reference Laboratory 320 880 840 1,000 86 18,000 920 68 RF-SE-18-RI Rigaku, Inc. 246 619 957 631 57 11,434 457 68 RF-SE-35-RI Rigaku, Inc. 283 432 946 383 57 11,390 448 68 RF-SE-54-RI Rigaku, Inc. 235 609 945 633 57 11,492 460 69 RF-SE-20-XX Reference Laboratory 550 1300 540 94 93 20,000 28 69 RF-SE-46-XX Reference Laboratory 270 590 240 44 40 8,900 13 69 RF-SE-51-XX Reference Laboratory 480 1100 450 77 77 17,000 23 69 RF-SE-20-RI Rigaku, Inc. 238 811 803 91 54 12,122 -16 69 RF-SE-46-RI Rigaku, Inc. 238 804 814 48 57 12,343 -15 69 RF-SE-51-RI Rigaku, Inc. 233 817 807 33 62 12,212 -8 70 RF-SE-21-XX Reference Laboratory 1.3 U 62 1,700 76 1,000 16,000 2,100 70 RF-SE-40-XX Reference Laboratory 1.3 U 70 1,900 85 1,100 18,000 2,400 70 RF-SE-47-XX Reference Laboratory 1.3 U 72 1,900 90 1,200 19,000 2,400 70 RF-SE-21-RI Rigaku, Inc. 201 158 1,368 41 734 11,906 1,311 70 RF-SE-40-RI Rigaku, Inc. 442 58 1,407 89 759 11,948 1,356 70 RF-SE-47-RI Rigaku, Inc. 196 154 1,326 71 713 12,192 1,268 
D-42

Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Hg Ni Se Ag V Zn 

68 RF-SE-18-XX Reference Laboratory 600 390 140 140 390 120 68 RF-SE-35-XX Reference Laboratory 650 350 140 150 340 110 68 RF-SE-54-XX Reference Laboratory 670 420 160 180 410 120 68 RF-SE-18-RI Rigaku, Inc. 327 205 49 215 232 96 68 RF-SE-35-RI Rigaku, Inc. 384 202 54 231 246 89 68 RF-SE-54-RI Rigaku, Inc. 334 201 48 216 237 77 69 RF-SE-20-XX Reference Laboratory 0.48 1,400 380 59 36 1,400 69 RF-SE-46-XX Reference Laboratory 0.45 650 170 26 16 650 69 RF-SE-51-XX Reference Laboratory 0.48 1,200 320 48 30 1,200 69 RF-SE-20-RI Rigaku, Inc. 53 636 92 207 52 655 69 RF-SE-46-RI Rigaku, Inc. 53 634 93 211 48 698 69 RF-SE-51-RI Rigaku, Inc. 48 638 92 205 51 671 70 RF-SE-21-XX Reference Laboratory 320 220 440 120 130 100 70 RF-SE-40-XX Reference Laboratory 280 250 480 100 150 120 70 RF-SE-47-XX Reference Laboratory 320 250 510 120 150 120 70 RF-SE-21-RI Rigaku, Inc. 29 113 124 216 98 72 70 RF-SE-40-RI Rigaku, Inc. 210 127 150 232 105 83 70 RF-SE-47-RI Rigaku, Inc. 38 108 125 211 116 75 

Notes: All concentrations reported in milligrams per kilogram (mg/kg), or parts per million (ppm). Sample results for which “0” or no value was reported were considered nondetections as reported by Xcalibur. Reference laboratory data qualifiers were as follows: J Estimated concentration. J+ Concentration is considered estimated and biased high. J- Concentration is considered estimated and biased low. U Analyte is not detected; the associated concentration value is the sample reporting limit.
APPENDIX E 

STATISTICAL DATA SUMMARIES
E-1

Figure E-2: Linear Correlation Plot for Arsenic

y = 0.45x + 31.89

R2 = 0.90

0

500

1000

1500

2000

2500

3000

0 500 1000 1500 2000 2500 3000

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)

 

Figure E-1: Linear Correlation Plot for Antimony

y = 0.51x + 296.46

R2 = 0.11

y = 0.02x + 258.07

R2 = 0.00

0

500

1000

1500

2000

2500

0 500 1000 1500 2000 2500 3000 3500

Reference Laboratoy or Certified Value (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini vs Reference Laboratory

Rigaku ZSX Mini vs Certified Value

45 Degrees

Linear (Rigaku ZSX Mini vs Reference

Laboratory)

Linear (Rigaku ZSX Mini vs Certified Value)
E-2

Figure E-4: Linear Correlation Plot for Chromium

y = 0.43x + 63.40

R2 = 0.95

0

500

1000

1500

2000

2500

3000

3500

0 500 1000 1500 2000 2500 3000 3500

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)

Figure E-3: Linear Correlation Plot for Cadmium

y = 0.42x + 572.79

R2 = 0.82

0

500

1000

1500

2000

2500

3000

0 500 1000 1500 2000 2500 3000

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)
E-3

Figure E-5: Linear Correlation Plot for Copper

y = 0.59x + 5.09

R2 = 0.95

0

1000

2000

3000

4000

5000

6000

0 1000 2000 3000 4000 5000 6000

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)

Figure E-6: Linear Correlation Plot for Iron

y = 0.38x + 5609.63

R2 = 0.93

0

20000

40000

60000

80000

100000

120000

140000

160000

180000

200000

0 20000 40000 60000 80000 100000 120000 140000 160000 180000 200000

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)
E-4

Figure E-7: Linear Correlation Plot for Lead

y = 0.54x - 92.44

R2 = 0.99

0

5000

10000

15000

20000

25000

30000

35000

40000

0 5000 10000 15000 20000 25000 30000 35000 40000

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)

Figure E-8: Linear Correlation Plot for Mercury

y = 0.30x + 29.42

R2 = 0.98

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

0 1000 2000 3000 4000 5000 6000 7000 8000 9000

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)
E-5

Figure E-9: Linear Correlation Plot for Nickel

y = 0.42x + 31.83

R2 = 0.93

0

500

1000

1500

2000

2500

3000

3500

0 500 1000 1500 2000 2500 3000 3500

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)

Figure E-10: Linear Correlation Plot for Selenium

y = 0.27x + 8.15

R2 = 0.97

0

100

200

300

400

500

600

0 100 200 300 400 500 600

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)
E-6

Figure E-11: Linear Correlation Plot for Silver

y = 0.04x + 197.88

R2 = 0.01

0

50

100

150

200

250

300

350

400

450

0 50 100 150 200 250 300 350 400 450

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)

Figure E-12: Linear Correlation Plot for Vanadium

y = 0.56x + 53.20

R2 = 0.73

0

50

100

150

200

250

300

350

400

450

500

0 50 100 150 200 250 300 350 400 450 500

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)
E-7

Figure E-13: Linear Correlation Plot for Zinc

y = 0.47x + 47.43

R2 = 0.97

0

1000

2000

3000

4000

5000

6000

7000

8000

0 1000 2000 3000 4000 5000 6000 7000 8000

Reference Laboratory (ppm)

Rigaku ZSX Mini XRF (ppm)

Rigaku ZSX Mini

45 Degrees

Linear (Rigaku ZSX Mini)
E-8

Box Plot for Relative Percent Difference (RPD)

Rigaku ZSX Mini II

Median; Box: 25%-75%; Whisker: Non-Outlier Range

 Median 

 25%-75% 

 Non-Outlier Range 

 Outliers

 Extremes

35-LV

17-AS

27-KP

28-KP

17-AS

48-SB

65-RF

20-SB

Sb-RL

Sb-CV

As

Cd

Cr

Cu

Fe

Pb

Hg

Ni

Se

Ag

V

Zn

-20%

0%

20%

40%

60%

80%

100%

120%

140%

160%

180%

200%

Mean RPD Values Between the ZSX Mini II

and the Reference Laboratory

and Certified Values

2-KP

1-KP,2-KP

3-KP

8-WS,9-WS

34-LV

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, Rigaku ZSX Mini II Data Set. 
E-9

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the R

Conc Antimony 

Matrix Range Statistic Ref Lab ERA Spike Arsenic Cadmium Chromium Copper Iron Lead Soil Level 1 Number 8 1 8 7 23 16 5 4 

Minimum 28.3% 84.9% 1.0% 85.3% 2.0% 7.6% 6.1% 43.1% Maximum 181.5% 84.9% 98.1% 165.0% 88.7% 97.9% 116.7% 104.1% 

 Mean 142.1% 84.9% 32.7% 126.8% 27.5% 38.9% 75.9% 78.9%  Median 161.2% 84.9% 14.0% 116.1% 21.0% 32.2% 93.3% 84.1%  Level 2 Number 5 1 4 7 4 8 13 4  Minimum 12.7% 84.8% 58.5% 5.5% 55.7% 27.0% 12.8% 42.4%  Maximum 150.7% 84.8% 79.1% 36.4% 65.5% 65.0% 53.7% 90.7%  Mean 70.4% 84.8% 71.6% 23.2% 60.5% 47.1% 40.0% 67.7%  Median 32.1% 84.8% 74.4% 21.4% 60.4% 49.3% 48.6% 68.9%  Level 3 Number 4 3 4 2 2 2 13 8  Minimum 0.1% 96.1% 70.2% 42.2% 68.7% 27.0% 49.8% 43.6% 

Maximum 93.9% 162.0% 87.8% 57.1% 92.4% 39.0% 75.6% 104.9% 

 Mean 37.9% 122.1% 80.7% 49.7% 80.5% 33.0% 60.9% 65.2%  Median 28.8% 108.3% 82.4% 49.7% 80.5% 33.0% 60.3% 65.1% 

Level 4 Number -- -- -- -- -- -- 7 5 

Minimum -- -- -- -- -- -- 49.6% 49.2% Maximum -- -- -- -- -- -- 109.1% 73.9% Mean -- -- -- -- -- -- 76.3% 64.4% Median -- -- -- -- -- -- 70.8% 64.5% 

All Soil Number 17 5 16 16 29 26 38 21 

 Minimum 0.1% 84.8% 1.0% 5.5% 2.0% 7.6% 6.1% 42.4% 

Maximum 181.5% 162.0% 98.1% 165.0% 92.4% 97.9% 116.7% 104.9% 

 Mean 96.5% 107.2% 54.4% 71.9% 35.7% 41.0% 58.6% 68.1%  Median 116.8% 96.1% 71.3% 49.7% 29.3% 40.0% 58.5% 66.7% 
E-10

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the R(Continued) 

Conc 

Matrix Range Statistic Nickel Selenium Silver Vanadium ZincSoil Level 1 Number 23 4 3 12 19 

Minimum 1.0% 57.9% 63.9% 13.7% 0.3% Maximum 101.3% 101.5% 96.7% 91.1% 138.0% Mean 45.1% 78.6% 84.2% 48.6% 35.6% Median 50.0% 77.6% 91.9% 57.8% 27.2% 

Level 2 Number 5 5 3 4 6 

Minimum 44.4% 97.5% 40.4% 1.0% 43.8% Maximum 74.7% 110.8% 85.3% 26.5% 81.4% Mean 60.3% 103.5% 56.9% 17.7% 61.4% Median 60.6% 102.3% 45.1% 21.7% 58.7% 

Level 3 Number 6 4 7 4 9 

Minimum 56.6% 95.8% 0.9% 6.0% 54.3% Maximum 111.8% 110.4% 59.6% 55.4% 104.2% Mean 77.2% 104.5% 33.7% 33.7% 72.0% Median 74.1% 105.9% 37.0% 36.8% 65.2% 

Level 4 Number -- -- -- -- -- 

Minimum -- -- -- -- -- Maximum -- -- -- -- -- Mean -- -- -- -- -- Median -- -- -- -- -- 

All Soil Number 34 13 13 20 34 

Minimum 1.0% 57.9% 0.9% 1.0% 0.3% Maximum 111.8% 110.8% 96.7% 91.1% 138.0% Mean 53.0% 96.2% 50.7% 39.4% 49.8% Median 57.7% 101.5% 40.4% 31.4% 50.4% 
E-11

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the R(Continued) 

Conc Antimony 

Matrix Range Statistic Ref Lab ERA Spike Arsenic Cadmium Chromium Copper Iron LeaSediment Level 1 Number 4 4 8 3 7 8 3 6 

Minimum 138.0% 25.1% 10.2% 100.7% 0.4% 19.9% 105.0% 14.5Maximum 179.7% 134.7% 82.3% 164.9% 119.8% 55.0% 148.5% 91.3Mean 166.6% 90.8% 47.5% 129.7% 32.5% 29.6% 125.3% 62.7Median 174.4% 101.7% 47.3% 123.3% 9.3% 26.7% 122.4% 82.0

 Level 2 Number 4 4 3 4 3 4 19 4  Minimum 47.1% 35.3% 32.0% 42.5% 40.7% 38.4% 15.7% 60.9 Maximum 90.6% 108.9% 158.7% 76.2% 52.9% 40.2% 44.7% 86.4

Mean 74.4% 77.7% 79.5% 62.2% 48.8% 39.5% 32.5% 72.0

 Median 79.9% 83.3% 47.7% 65.0% 52.7% 39.7% 33.4% 70.3

Level 3 Number 3 3 2 3 3 10 4 3 

 Minimum 20.3% 111.7% 20.6% 12.3% 43.7% 24.7% 30.0% 43.6 Maximum 58.7% 134.0% 37.7% 29.2% 75.7% 84.2% 57.1% 71.4 Mean 33.2% 120.6% 29.1% 20.8% 57.2% 62.9% 43.1% 56.6 Median 20.6% 116.2% 29.1% 20.9% 52.2% 71.4% 42.7% 54.7 Level 4 Number -- -- -- -- -- -- 6 -- 

Minimum -- -- -- -- -- -- 55.6% -- Maximum -- -- -- -- -- -- 92.1% -- Mean -- -- -- -- -- -- 71.5% -- Median -- -- -- -- -- -- 70.5% -- 

All Sediment Number 11 11 13 10 13 22 32 13 

 Minimum 20.3% 25.1% 10.2% 12.3% 0.4% 19.9% 15.7% 14.5

Maximum 179.7% 134.7% 158.7% 164.9% 119.8% 84.2% 148.5% 91.3Mean 96.7% 94.2% 52.1% 70.0% 42.0% 46.6% 49.9% 64.1

 Median 84.3% 108.9% 45.5% 65.0% 43.7% 40.0% 38.0% 71.4
E-12

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the R(Continued) 

Conc 

Matrix Range Statistic Nickel Selenium Silver Vanadium ZincSediment Level 1 Number 18 5 5 6 18 

Minimum 31.3% 30.1% 89.3% 27.7% 4.1% Maximum 104.7% 127.1% 138.9% 59.0% 80.9% Mean 64.2% 83.8% 116.2% 41.1% 41.4% Median 62.0% 89.6% 112.6% 39.2% 39.6% 

Level 2 Number 6 4 4 8 5 

Minimum 45.9% 94.0% 13.7% 3.1% 46.5% Maximum 69.5% 121.3% 66.8% 52.1% 68.1% Mean 57.3% 108.0% 38.3% 24.7% 58.2% Median 57.1% 108.4% 36.3% 20.9% 59.4% 

Level 3 Number 4 3 3 3 4 

Minimum 52.0% 103.6% 2.6% 35.5% 48.4% Maximum 79.8% 112.9% 64.0% 45.8% 78.3% Mean 66.0% 108.5% 33.5% 40.9% 65.8% Median 66.0% 109.1% 34.0% 41.4% 68.3% 

Level 4 Number -- -- -- -- -- 

Minimum -- -- -- -- -- Maximum -- -- -- -- -- Mean -- -- -- -- -- Median -- -- -- -- -- 

All Sediment Number 28 12 12 17 27 

Minimum 31.3% 30.1% 2.6% 3.1% 4.1% Maximum 104.7% 127.1% 138.9% 59.0% 80.9% Mean 63.0% 98.1% 69.6% 33.4% 48.1% Median 63.1% 103.2% 65.4% 35.5% 48.6% 
E-13

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the R(Continued) 

Conc Antimony 

Matrix Range Statistic Ref Lab ERA Spike Arsenic Cadmium Chromium Copper Iron All ZSX Mini II Number 28 16 29 26 42 48 70 34 Samples Minimum 0.1% 25.1% 1.0% 5.5% 0.4% 7.6% 6.1% 14

Maximum 181.5% 162.0% 158.7% 165.0% 119.8% 97.9% 148.5% 10Mean 96.6% 98.2% 53.4% 71.1% 37.7% 43.5% 54.6% 66Median 92.2% 102.2% 49.2% 60.9% 37.2% 40.0% 52.4% 66

All All Instruments Number 206 110 320 209 338 363 558 Samples Minimum 0.1% 0.1% 0.2% 0.1% 0.1% 0.2% 0.0% 

Maximum 181.5% 162.0% 182.8% 168.1% 151.7% 111.1% 190.1% 1Mean 80.6% 62.7% 36.6% 29.6% 30.8% 24.6% 35.4% Median 84.3% 70.6% 26.2% 16.7% 26.0% 16.2% 26.0% 2

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the R

(Continued) 

Conc 

Matrix Range Statistic Nickel Selenium Silver Vanadium ZincAll ZSX Mini II Number 62 25 25 37 61 Samples Minimum 1.0% 30.1% 0.9% 1.0% 0.3% 

Maximum 111.8% 127.1% 138.9% 91.1% 138.0% Mean 57.5% 97.1% 59.8% 36.7% 49.0% Median 60.4% 101.5% 45.1% 35.2% 48.6% 

All All Instruments Number 403 195 177 218 471 Samples Minimum 0.3% 0.0% 0.0% 0.1% 0.0% 

Maximum 146.5% 127.1% 129.7% 129.5% 138.0% Mean 31.0% 32.0% 36.0% 42.2% 26.3% Median 25.4% 16.7% 28.7% 38.3% 19.4% 

Notes: All RPDs presented in this table are absolute values. -- No samples reported by the reference laboratory in this concentration range. Number Number of demonstration samples evConc Concentration. Ref Lab Reference laboratory (Shealy Environ

ERA Environmental Resource Associates, Inc .RPD Relative percent difference.
E-14

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Mimi 

Conc 

Matrix Range Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead MercuSoil Level 1 Number 8 8 7 23 16 5 4 7 

Minimum 3.4% 3.4% 0.9% 6.2% 1.6% 0.5% 3.6% 1.4% Maximum 41.4% 20.1% 4.1% 29.5% 50.5% 2.5% 26.3% 136.8% Mean 12.9% 13.2% 2.2% 15.7% 7.7% 1.2% 11.2% 26.2% 

 Median 6.2% 13.0% 1.8% 14.8% 4.5% 1.0% 7.5% 9.6%  Level 2 Number 5 4 7 4 8 13 4 6 

Minimum 6.3% 1.6% 0.4% 1.6% 0.8% 0.2% 1.7% 2.2% Maximum 7.3% 11.4% 3.6% 8.1% 4.3% 2.5% 2.6% 49.8% Mean 6.9% 4.9% 2.0% 4.6% 2.1% 0.6% 2.1% 12.8% Median 6.9% 3.2% 2.2% 4.3% 1.9% 0.5% 2.1% 5.2% 

 Level 3 Number 4 4 2 2 2 13 8 2 

Minimum 3.7% 0.7% 0.9% 2.6% 0.4% 0.2% 0.4% 2.3% Maximum 6.5% 3.7% 1.2% 2.7% 0.8% 43.2% 2.2% 2.6% Mean 5.0% 1.9% 1.1% 2.7% 0.6% 4.3% 1.6% 2.4% Median 4.9% 1.7% 1.1% 2.7% 0.6% 0.6% 1.8% 2.4% 

Level 4 Number -- -- -- -- -- 7 5 -- 

Minimum -- -- -- -- -- 0.4% 0.5% -- Maximum -- -- -- -- -- 1.3% 1.4% -- Mean -- -- -- -- -- 0.8% 0.9% -- Median -- -- -- -- -- 0.7% 0.8% -- 

All Soil Number 17 16 16 29 26 38 21 15 

Minimum 3.4% 0.7% 0.4% 1.6% 0.4% 0.2% 0.4% 1.4% Maximum 41.4% 20.1% 4.1% 29.5% 50.5% 43.2% 26.3% 136.8% Mean 9.3% 8.3% 2.0% 13.2% 5.5% 2.0% 3.3% 17.7% Median 6.3% 6.1% 1.8% 13.0% 3.4% 0.6% 1.8% 5.3% 
E-15

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Mimi 

Conc 

Matrix Range Statistic Nickel Selenium Silver Vanadium ZincSoil Level 1 Number 23 4 3 12 19 

Minimum 1.4% 3.9% 2.4% 9.7% 0.9% Maximum 164.2% 49.2% 3.4% 22.4% 192.9% Mean 11.6% 17.2% 2.8% 13.6% 14.3% Median 4.7% 7.9% 2.5% 12.3% 4.2% 

Level 2 Number 5 5 3 4 6 

Minimum 1.1% 0.1% 0.9% 1.1% 0.8% Maximum 2.7% 4.6% 3.5% 11.1% 2.4% Mean 2.1% 2.8% 2.1% 5.8% 1.5% Median 2.3% 3.2% 2.0% 5.5% 1.4% 

Level 3 Number 6 4 7 4 9 

Minimum 0.5% 1.2% 1.2% 0.4% 0.6% Maximum 77.8% 2.3% 2.8% 5.8% 82.5% Mean 13.9% 1.8% 2.3% 4.1% 10.2% Median 1.3% 1.9% 2.4% 5.2% 1.0% 

Level 4 Number -- -- -- -- -- 

Minimum -- -- -- -- -- Maximum -- -- -- -- -- Mean -- -- -- -- -- Median -- -- -- -- -- 

All Soil Number 34 13 13 20 34 

Minimum 0.5% 0.1% 0.9% 0.4% 0.6% Maximum 164.2% 49.2% 3.5% 22.4% 192.9% Mean 10.6% 6.9% 2.3% 10.2% 10.9% Median 3.9% 3.2% 2.4% 11.1% 2.1% 
E-16

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Mini (Continued) 

Conc 

Matrix Range Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead MerSediment Level 1 Number 4 8 3 7 8 3 6 2 

Minimum 3.9% 8.8% 0.8% 6.1% 0.6% 0.4% 1.6% 3.8Maximum 16.3% 46.2% 1.2% 22.0% 7.1% 1.4% 6.2% 11.Mean 10.5% 19.4% 1.1% 17.1% 3.8% 0.7% 3.8% 7.6Median 11.0% 15.8% 1.2% 17.8% 3.4% 0.4% 4.0% 7.6

 Level 2 Number 4 3 4 3 4 19 4 4 

Minimum 2.0% 3.2% 0.7% 1.8% 1.3% 0.2% 1.4% 3.6Maximum 14.4% 15.8% 3.0% 20.5% 3.1% 2.9% 2.6% 110Mean 6.8% 10.0% 1.9% 10.5% 2.2% 0.9% 2.2% 32.Median 5.5% 11.2% 1.9% 9.1% 2.1% 0.7% 2.3% 7.3

Level 3 Number 3 2 3 3 10 4 3 3 

Minimum 1.2% 0.8% 0.7% 9.7% 0.8% 0.5% 0.9% 2.7Maximum 10.0% 19.0% 3.7% 26.2% 2.9% 1.4% 3.3% 9.0Mean 6.1% 9.9% 2.5% 18.0% 1.7% 1.0% 2.3% 5.1Median 7.2% 9.9% 3.0% 18.2% 1.7% 1.1% 2.6% 3.6

 Level 4 Number -- -- -- -- -- 6 -- -

Minimum -- -- -- -- -- 0.3% -- -Maximum -- -- -- -- -- 17.8% -- -Mean -- -- -- -- -- 3.5% -- -Median -- -- -- -- -- 0.7% -- -

All Sediment Number 11 13 10 13 22 32 13 9 

Minimum 1.2% 0.8% 0.7% 1.8% 0.6% 0.2% 0.9% 2.7Maximum 16.3% 46.2% 3.7% 26.2% 7.1% 17.8% 6.2% 110Mean 8.0% 15.8% 1.8% 15.8% 2.6% 1.4% 3.0% 17.Median 7.2% 14.4% 1.3% 17.8% 2.1% 0.7% 2.6% 4.5
E-17

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Mini (Continued) 

Conc 

Matrix Range Statistic Nickel Selenium Silver Vanadium ZincSediment Level 1 Number 18 5 4 6 18 

Minimum 1.8% 2.5% 1.2% 1.7% 1.8% Maximum 25.5% 12.6% 5.2% 7.4% 18.4% Mean 5.7% 9.4% 2.3% 4.3% 6.1% Median 4.0% 10.8% 1.4% 4.4% 4.8% 

Level 2 Number 6 4 4 8 18 

Minimum 0.7% 2.0% 0.9% 3.1% 1.8% Maximum 8.4% 7.6% 3.3% 19.2% 3.6% Mean 4.5% 6.0% 1.7% 6.8% 2.7% Median 5.2% 7.2% 1.3% 4.7% 2.8% 

Level 3 Number 4 3 3 3 4 

Minimum 0.3% 0.9% 3.6% 2.8% 0.8% Maximum 1.8% 11.2% 5.0% 7.1% 5.2% Mean 1.3% 5.0% 4.2% 4.9% 2.6% Median 1.6% 3.1% 4.1% 4.7% 2.2% 

Level 4 Number -- -- -- -- -- 

Minimum -- -- -- -- -- Maximum -- -- -- -- -- Mean -- -- -- -- -- Median -- -- -- -- -- 

All Sediment Number 28 12 11 17 27 

Minimum 0.3% 0.9% 0.9% 1.7% 0.8% Maximum 25.5% 12.6% 5.2% 19.2% 18.4% Mean 4.8% 7.2% 2.6% 5.6% 5.0% Median 3.7% 7.6% 1.5% 4.7% 3.6% 
E-18

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Mini (Continued) 

Conc 

Matrix Range Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead MAll Samples ZSX Mini II Number 28 29 26 42 48 70 34 

Minimum 1.2% 0.7% 0.4% 1.6% 0.4% 0.2% 0.4% 

 Maximum 41.4% 46.2% 4.1% 29.5% 50.5% 43.2% 26.3% 1

Mean 8.8% 11.6% 1.9% 14.0% 4.1% 1.7% 3.2% Median 6.4% 10.1% 1.6% 14.7% 2.3% 0.6% 2.0% 

All Samples All Instruments Number 206 320 209 338 363 558 392 

Minimum 0.5% 0.2% 0.4% 0.6% 0.1% 0.1% 0.2% Maximum 97.7% 71.7% 92.8% 116.3% 58.3% 101.8% 115.6% 1Mean 8.9% 11.2% 8.2% 15.9% 7.5% 5.2% 9.3% 

 Median 6.1% 8.2% 3.6% 12.1% 5.1% 2.2% 4.9% 

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Mini (Continued) 

Conc 

Matrix Range Statistic Nickel Selenium Silver Vanadium ZincAll Samples ZSX Mini II Number 62 25 24 37 61 

Minimum 0.3% 0.1% 0.9% 0.4% 0.6% Maximum 164.2% 49.2% 5.2% 22.4% 192.9% Mean 8.0% 7.0% 2.5% 8.1% 8.3% Median 3.7% 3.9% 2.4% 5.9% 2.5% 

All Samples All Instruments Number 403 195 177 218 471 

Minimum 0.3% 0.1% 0.6% 0.4% 0.1% Maximum 164.2% 98.8% 125.3% 86.1% 192.9% Mean 10.8% 7.2% 10.3% 12.5% 8.0% Median 7.0% 4.5% 5.2% 8.5% 5.3% 

Notes: -- No samples reported by the reference laboratory in this concentration range. Number Number of demonstration samples evaluated. RSD Relative standard deviation 
E-19

Table E-3. Evaluation of Precision - Relative Standard Deviations Calculated for the Reference Laboratory 

Matrix Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel All Soil Number 17 23 15 34 26 38 33 16 35  Minimum 3.6% 1.4% 0.9% 1.4% 0.0% 1.6% 0.0% 0.0% 0.0%  Maximum 38.0% 45.8% 21.4% 137.0% 21.0% 46.2% 150.0% 50.7% 44.9%  Mean 14.3% 11.7% 11.1% 14.3% 10.1% 10.2% 17.6% 13.8% 11.4%  Median 9.8% 12.4% 9.0% 10.6% 9.1% 8.7% 13.2% 6.6% 10.0% All Sediment Number 7 24 10 26 21 31 22 10 27  Minimum 2.9% 2.4% 2.9% 4.6% 1.8% 2.7% 0.0% 2.8% 0.6%  Maximum 33.6% 36.7% 37.5% 35.5% 38.8% 37.5% 41.1% 48.0% 35.8%  Mean 14.4% 10.7% 11.4% 9.8% 9.7% 9.9% 11.6% 14.3% 9.4%  Median 9.1% 9.2% 8.2% 7.5% 8.9% 8.1% 7.4% 6.9% 7.3% All Number 24 47 25 60 47 69 55 26 62  Minimum 2.9% 1.4% 0.9% 1.4% 0.0% 1.6% 0.0% 0.0% 0.0%  Maximum 38.0% 45.8% 37.5% 137.0% 38.8% 46.2% 150.0% 50.7% 44.9%  Mean 14.3% 11.2% 11.2% 12.4% 9.9% 10.1% 15.2% 14.0% 10.6%  Median 9.5% 9.5% 9.0% 8.4% 8.9% 8.5% 8.6% 6.6% 8.2% 
E-20

Table E-3. Evaluation of Precision - Relative Standard Deviations Calculated for the Reference Laboratory (Continued) 

Matrix Statistic Vanadium ZincAll Soil Number 21 35 

Minimum 0.0% 1.0% Maximum 18.1% 46.5% 

Mean 8.4% 10.4% 

Median 6.6% 9.1% 

All Sediment Number 17 27 

Minimum 2.2% 1.4% Maximum 21.9% 35.8% Mean 8.4% 8.9% Median 8.1% 6.9% 

All Number 38 62 

Minimum 0.0% 1.0% Maximum 21.9% 46.5% Mean 8.4% 9.8% Median 7.2% 7.4% 

Notes: Number Number of demonstration samples evaluated. RSD Relative standard deviation 
E-21

Table E-4. Evaluation of the Effects of Interferent Elements on RPDs (Accuracy) of Other Target Elements1 

Parameter Statistic Lead Effects on Arsenic Copper Effects on Nickel Nickel Effects on CoInterferent/Element Ratio <5 5 - 10 >10 <5 5 - 10 >10 <5 5 - 10 Number of Samples 15 7 7 43 5 14 39 1 RPD of Target Element2 Minimum -3.3% 40.7% -57.9% -56.5% 44.6% 1.0% 7.6% 31.1% 

Maximum 158.7% 87.8% 82.1% 111.8% 66.4% 78.8% 97.9% 31.1% Mean 54.2% 71.1% 15.1% 57.7% 56.4% 47.8% 46.3% 31.1% Median 45.5% 76.5% 11.7% 62.7% 55.3% 53.3% 46.1% 31.1% 

RPD of Target Element Minimum 3.3% 40.7% 1.0% 7.9% 44.6% 1.0% 7.6% 31.1%  (Absolute Value)2 Maximum 158.7% 87.8% 82.1% 111.8% 66.4% 78.8% 97.9% 31.1% 

Mean 54.7% 71.1% 32.9% 60.8% 56.4% 47.8% 46.3% 31.1% Median 45.5% 76.5% 16.3% 62.7% 55.3% 53.3% 46.1% 31.1% 

Interferent Minimum 47 317 805 1 494 385 33 203  Concentration Range Maximum 455 21053 9647 735 1301 3436 355 203 

Mean 206 7435 2654 98 754 1398 94 203 Median 173 3716 1390 62 700 1017 80 203 

Target Element Minimum 49 77 48 18 58 38 30 57  Concentration Range Maximum 1361 2016 844 1357 139 226 3436 57 

Mean 264 762 192 273 92 81 724 57 Median 92 487 93 99 88 60 565 57 
E-22

Table E-4. Evaluation of the Effects of Interferent Elements on RPDs (Accuracy) of Other Target Elements1 (Continued) 

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 

Parameter Statistic Zinc Effects on Copper Copper Effects on ZincInterferent/Element Ratio <5 5 - 10 >10 <5 5 - 10 >10 Number of Samples 35 2 11 48 3 10 RPD of Target Element Minimum 7.6% 40.9% 12.0% -138.0% 11.2% -4.1% 

Maximum 84.2% 47.4% 97.9% 104.2% 80.9% 72.3% Mean 44.1% 44.1% 41.7% 42.3% 43.5% 44.4% Median 40.2% 44.1% 31.0% 50.2% 38.4% 46.2% 

RPD of Target Element Minimum 7.6% 40.9% 12.0% 0.3% 11.2% 4.1%  (Absolute Value) Maximum 84.2% 47.4% 97.9% 138.0% 80.9% 72.3% 

Mean 44.1% 44.1% 41.7% 50.2% 43.5% 45.2% Median 40.2% 44.1% 31.0% 53.0% 38.4% 46.2% 

Interferent Minimum 51 401 446 16 565 708  Concentration Range Maximum 3102 3980 2670 1316 735 3436 

Mean 509 2190 1487 218 659 1682 Median 92 2190 1430 73 676 1301 

Target Element Minimum 30 99 56 37 77 59  Concentration Range Maximum 3436 965 107 3980 92 184 

Mean 771 532 76 827 86 90 Median 567 532 77 410 88 78 
E-23

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements 

 Antimony Arsenic 

 Matrix Reference Laboratory Certified Value Reference LaboratorMatrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS 

Number -- -- -- -- -- -- Minimum -- -- -- -- -- -- Maximum -- -- -- -- -- -- 

Soil 

Mean -- -- -- -- -- -- 

AS Fine to medium sand 

(steel processing) 

Median -- -- -- -- -- -- 

Soil Number 4 4 1 1 6 6 

Minimum -160.3% 3.5% 108.3% 108.3% 16.3% 16.3% Maximum 3.5% 160.3% 108.3% 108.3% 79.1% 79.1% Mean -112.2% 114.0% 108.3% 108.3% 56.2% 56.2% 

BN Sandy loam, low 

organic (ore residuals) 

Median -146.1% 146.1% 108.3% 108.3% 64.4% 64.4% 

Soil Number 2 2 2 2 1 1 

Minimum -162.1% 12.7% -84.9% 84.8% -3.3% 3.3% Maximum -12.7% 162.1% 84.8% 84.9% -3.3% 3.3% Mean -87.4% 87.4% 0.0% 84.9% -3.3% 3.3% 

CN Sandy loam (burn pit 

residue) 

Median -87.4% 87.4% 0.0% 84.9% -3.3% 3.3% 

Soil & Number 2 2 -- -- -- -- Sediment Minimum -169.5% 137.3% -- -- -- -- 

Maximum -137.3% 169.5% -- -- -- -- Mean -153.4% 153.4% -- -- -- -- 

KP Soil: Fine to medium 

quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) Median -153.4% 153.4% -- -- -- -- 

Sediment Number 4 4 4 4 3 3 

Minimum -169.6% 0.1% -84.4% 81.3% 11.7% 11.7% Maximum 20.3% 169.6% 116.2% 116.2% 158.7% 158.7% Mean -49.1% 59.3% 52.3% 94.5% 84.2% 84.2% 

LV Clay/clay loam, salt 

crust (iron and other precipitate) 

Median -23.5% 33.7% 88.7% 90.2% 82.3% 82.3% 

Sediment Number 5 5 5 5 10 10 

Minimum -179.7% 20.6% -134.7% 35.3% -57.9% 10.2% Maximum 58.7% 179.7% 134.0% 134.7% 49.2% 57.9% Mean -71.0% 102.7% 5.5% 106.9% 26.3% 37.9% 

RF Silty fine sand (tailings) 

Median -75.6% 75.6% 35.3% 118.9% 36.6% 40.2% 
E-24

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Antimony Arsenic 

 Matrix Reference Laboratory Certified Value Reference Laboratory 

Matrix Site Description Statistic RPD

RPD ABS Val RPD RPD ABS Val RPD

RPD ABS Val 

Soil SB Number 5 5 1 1 2 2 

Minimum -181.5% 14.8% 162.0% 162.0% 86.1% 86.1% Maximum 93.9% 181.5% 162.0% 162.0% 98.1% 98.1% Mean -10.2% 75.3% 162.0% 162.0% 92.1% 92.1% 

Coarse sand and gravel (ore and waste rock) 

Median 14.8% 54.1% 162.0% 162.0% 92.1% 92.1% 

Sediment TL Number 3 3 3 3 1 1 

Minimum -138.0% 84.3% 25.1% 25.1% 56.8% 56.8% Maximum -84.3% 138.0% 108.9% 108.9% 56.8% 56.8% Mean -104.3% 104.3% 73.1% 73.1% 56.8% 56.8% 

Silt and clay (slagenriched) 

Median -90.6% 90.6% 85.4% 85.4% 56.8% 56.8% 

Soil WS Number 3 3 -- -- 6 6 

Minimum -180.9% 28.3% -- -- -4.5% 1.0% Maximum -28.3% 180.9% -- -- 87.8% 87.8% Mean -108.7% 108.7% -- -- 54.3% 55.8% Median -116.8% 116.8% -- -- 79.3% 79.3% 

Coarse sand and gravel (roaster slag) 

 All Number 28 28 16 16 29 29 

Minimum -181.5% 0.1% -134.7% 25.1% -57.9% 1.0% Maximum 93.9% 181.5% 162.0% 162.0% 158.7% 158.7% Mean -77.6% 96.6% 45.4% 98.2% 48.8% 53.4% Median -87.4% 92.2% 85.1% 102.2% 47.7% 49.2% 
E-25

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Chromium Copper Iron

 Matrix Reference Laboratory Reference Laboratory Reference Laborato

Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD 

Number 2 2 3 3 3 3 Minimum 38.3% 38.3% 39.0% 39.0% 19.2% 19.2% Maximum 48.5% 48.5% 97.9% 97.9% 109.1% 109.1

Soil 

Mean 43.4% 43.4% 70.4% 70.4% 74.1% 74.1% 

AS Fine to medium sand (steel 

processing) 

Median 43.4% 43.4% 74.3% 74.3% 94.0% 94.0% 

Soil Number 4 4 6 6 7 7 

Minimum -14.2% 14.2% 29.7% 29.7% 48.6% 48.6% Maximum 92.4% 92.4% 53.6% 53.6% 58.9% 58.9% Mean 45.2% 52.3% 40.7% 40.7% 52.5% 52.5% 

BN Sandy loam, low organic 

(ore residuals) 

Median 51.4% 51.4% 40.0% 40.0% 52.7% 52.7% 

Soil Number 1 1 3 3 3 3 

Minimum 16.5% 16.5% 7.6% 7.6% 25.7% 25.7% Maximum 16.5% 16.5% 65.0% 65.0% 76.3% 76.3% Mean 16.5% 16.5% 34.5% 34.5% 51.1% 51.1% 

CN Sandy loam (burn pit 

residue) 

Median 16.5% 16.5% 31.0% 31.0% 51.3% 51.3% 

Soil & Number 3 3 2 2 6 6 Sediment Minimum 27.1% 27.1% 12.5% 12.5% -148.5% 70.3% 

Maximum 43.0% 43.0% 27.0% 27.0% -70.3% 148.5

Mean 35.7% 35.7% 19.8% 19.8% -107.4% 107.4

KP Soil: Fine to medium 

quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) 

Median 37.0% 37.0% 19.8% 19.8% -105.0% 105.0

Sediment Number 7 7 4 4 12 12 

Minimum -119.8% 0.4% 11.9% 11.9% -105.0% 12.8% Maximum 75.7% 119.8% 55.0% 55.0% 92.1% 105.0Mean 8.7% 62.6% 37.2% 37.2% 31.3% 48.8% 

LV Clay/clay loam, salt crust 

(iron and other precipitate) 

Median 52.7% 62.9% 40.9% 40.9% 33.7% 39.4% 

Sediment Number 6 6 13 13 13 13 

Minimum -9.3% 0.9% 19.9% 19.9% 22.3% 22.3% Maximum 52.9% 52.9% 48.9% 48.9% 57.1% 57.1% Mean 29.9% 33.3% 31.8% 31.8% 37.0% 37.0% 

RF Silty fine sand (tailings) 

Median 42.2% 42.2% 31.1% 31.1% 35.2% 35.2% 
E-26

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Chromium Copper Iron

 Matrix Reference Laboratory Reference Laboratory Reference Laboratory

Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABSoil SB Number 10 10 4 4 12 12 

Minimum -46.3% 2.0% 30.6% 30.6% -6.1% 6.1% Maximum 68.7% 68.7% 70.2% 70.2% 75.6% 75.6% Mean -1.1% 17.5% 48.6% 48.6% 55.9% 56.9% 

Coarse sand and gravel (ore and waste rock) 

Median -3.8% 7.8% 46.9% 46.9% 59.7% 59.7% 

Sediment TL Number 2 2 7 7 7 7 

Minimum -5.0% 5.0% 57.6% 57.6% 20.7% 20.7% Maximum 23.3% 23.3% 84.2% 84.2% 76.5% 76.5% Mean 9.1% 14.1% 72.3% 72.3% 42.7% 42.7% 

Silt and clay (slagenriched) 

Median 9.1% 14.1% 72.5% 72.5% 35.4% 35.4% 

Soil WS Number 7 7 6 6 7 7 

Minimum -88.7% 16.8% 12.0% 12.0% 34.8% 34.8% Maximum 55.7% 88.7% 50.8% 50.8% 69.5% 69.5% Mean -19.0% 45.7% 38.1% 38.1% 55.1% 55.1% 

Coarse sand and gravel (roaster slag) 

Median -22.0% 29.3% 44.1% 44.1% 60.3% 60.3% 

All Number 42 42 48 48 70 70 

Minimum -119.8% 0.4% 7.6% 7.6% -148.5% 6.1% Maximum 92.4% 119.8% 97.9% 97.9% 109.1% 148.5% Mean 12.0% 37.7% 43.5% 43.5% 33.0% 54.6% Median 16.7% 37.2% 40.0% 40.0% 46.6% 52.4% 
E-27

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

 Lead Mercury Nickel

 Matrix Reference Laboratory Reference Laboratory Reference Laboratory

Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD A

Number 3 3 -- -- 3 3 Minimum 90.7% 90.7% -- -- 60.6% 60.6% Maximum 104.9% 104.9% -- -- 101.3% 101.3% 

Soil 

Mean 99.9% 99.9% -- -- 77.7% 77.7% 

AS Fine to medium sand (steel 

processing) 

Median 104.1% 104.1% -- -- 71.3% 71.3% 

Soil Number 5 5 1 1 6 6 

Minimum 63.6% 63.6% -39.9% 39.9% 31.7% 31.7% Maximum 74.7% 74.7% -39.9% 39.9% 81.0% 81.0% Mean 70.5% 70.5% -39.9% 39.9% 58.9% 58.9% 

BN Sandy loam, low organic 

(ore residuals) 

Median 73.5% 73.5% -39.9% 39.9% 62.0% 62.0% 

Soil Number 2 2 2 2 3 3 

Minimum 86.3% 86.3% -18.8% 18.8% 7.9% 7.9% Maximum 93.6% 93.6% 65.4% 65.4% 74.7% 74.7% Mean 90.0% 90.0% 23.3% 42.1% 51.4% 51.4% 

CN Sandy loam (burn pit 

residue) 

Median 90.0% 90.0% 23.3% 42.1% 71.5% 71.5% 

Soil & Number 6 6 -- -- 3 3 Sediment Minimum -14.5% 14.5% -- -- -10.0% 10.0% 

Maximum 64.5% 64.5% -- -- 11.9% 11.9% Mean 34.4% 39.3% -- -- 4.6% 11.2% 

KP Soil: Fine to medium 

quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) 

Median 42.8% 42.8% -- -- 11.8% 11.8% 

Sediment Number 2 2 4 4 11 11 

Minimum 43.6% 43.6% -3.6% 3.6% 48.8% 48.8% Maximum 43.6% 43.6% 71.4% 71.4% 104.7% 104.7% Mean 43.6% 43.6% 43.4% 45.1% 70.4% 70.4% 

LV Clay/clay loam, salt crust 

(iron and other precipitate) 

Median 43.6% 43.6% 52.8% 52.8% 65.5% 65.5% 

Sediment Number 8 8 5 5 13 13 

Minimum 54.7% 54.7% -77.0% 31.8% 45.9% 45.9% Maximum 91.3% 91.3% 107.2% 107.2% 69.5% 69.5% Mean 75.3% 75.3% 12.6% 66.6% 57.8% 57.8% 

RF Silty fine sand (tailings) 

Median 78.5% 78.5% 31.8% 59.0% 55.9% 55.9% 
E-28

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Lead Mercury Nickel

 Matrix Reference Laboratory Reference Laboratory Reference Laboratory

Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABSoil SB Number -- -- 10 10 10 10 

Minimum -- -- -139.3% 5.3% -56.5% 50.0% Maximum -- -- 134.7% 139.3% 111.8% 111.8% Mean -- -- 65.7% 94.6% 58.4% 69.7% 

Coarse sand and gravel (ore and waste rock) 

Median -- -- 97.8% 112.1% 65.3% 65.3% 

Sediment TL Number 2 2 2 2 6 6 

Minimum 71.4% 71.4% 99.4% 99.4% 31.3% 31.3% Maximum 86.4% 86.4% 158.1% 158.1% 78.8% 78.8% Mean 78.9% 78.9% 128.8% 128.8% 60.0% 60.0% 

Silt and clay (slagenriched) 

Median 78.9% 78.9% 128.8% 128.8% 66.8% 66.8% 

Soil WS Number 6 6 -- -- 7 7 

Minimum 46.5% 46.5% -- -- 1.0% 1.0% Maximum 70.7% 70.7% -- -- 50.4% 50.4% Mean 58.1% 58.1% -- -- 29.8% 29.8% 

Coarse sand and gravel (roaster slag) 

Median 57.6% 57.6% -- -- 37.6% 37.6% 

All Number 34 34 24 24 62 62 

Minimum -14.5% 14.5% -139.3% 3.6% -56.5% 1.0% Maximum 104.9% 104.9% 158.1% 158.1% 111.8% 111.8% Mean 65.7% 66.6% 48.2% 76.7% 55.4% 57.5% Median 66.8% 66.8% 66.2% 74.2% 60.4% 60.4% 
E-29

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Selenium Silver Vanadium Z

 Matrix 

Reference Laboratory Reference Laboratory Reference Laboratory R

Matrix Site Description Statistic RPD

RPD ABS Val RPD RPD ABS Val RPD RPD ABS Val R

Number 1 1 1 1 1 1 3 Minimum 97.5% 97.5% 40.4% 40.4% 13.7% 13.7% 4Maximum 97.5% 97.5% 40.4% 40.4% 13.7% 13.7% 8

Soil 

Mean 97.5% 97.5% 40.4% 40.4% 13.7% 13.7% 7

AS Fine to medium sand 

(steel processing) 

Median 97.5% 97.5% 40.4% 40.4% 13.7% 13.7% 8

Soil Number 4 4 4 4 4 4 7 

Minimum 57.9% 57.9% -91.9% 36.8% -27.6% 19.6% 2Maximum 110.4% 110.4% -36.8% 91.9% 55.4% 55.4% 7Mean 90.2% 90.2% -53.6% 53.6% 8.4% 32.1% 5

BN Sandy loam, low 

organic (ore residuals) 

Median 96.2% 96.2% -42.8% 42.8% 3.0% 26.6% 5

Soil Number 2 2 2 2 1 1 3 

Minimum 65.0% 65.0% -96.7% 85.3% 26.5% 26.5% 0Maximum 110.8% 110.8% -85.3% 96.7% 26.5% 26.5% 6Mean 87.9% 87.9% -91.0% 91.0% 26.5% 26.5% 3

CN Sandy loam (burn pit 

residue) 

Median 87.9% 87.9% -91.0% 91.0% 26.5% 26.5% 5

Soil & Number -- -- -- -- -- -- 2 Sediment Minimum -- -- -- -- -- -- -

Maximum -- -- -- -- -- -- 1Mean -- -- -- -- -- -- -

KP Soil: Fine to medium 

quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) Median -- -- -- -- -- -- -

Sediment Number 5 5 4 4 9 9 9 

Minimum 94.0% 94.0% -112.6% 0.9% -40.3% 3.1% -Maximum 109.1% 109.1% 2.6% 112.6% 41.4% 41.4% 6Mean 100.4% 100.4% -44.0% 45.7% 1.0% 22.5% 2

LV Clay/clay loam, salt 

crust (iron and other precipitate) 

Median 100.3% 100.3% -33.0% 34.7% 3.1% 19.8% 1

Sediment Number 5 5 5 5 3 3 1

Minimum 30.1% 30.1% -138.9% 34.0% 19.2% 19.2% 2Maximum 112.9% 112.9% -34.0% 138.9% 45.8% 45.8% 7Mean 82.7% 82.7% -82.2% 82.2% 31.6% 31.6% 5

RF Silty fine sand 

(tailings) 

Median 97.6% 97.6% -64.0% 64.0% 29.7% 29.7% 4
E-30

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Selenium Silver Vanadium 

 Matrix Reference Laboratory Reference Laboratory Reference Laboratory 

Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Soil SB Number 3 3 1 1 9 9 

Minimum 101.5% 101.5% -38.3% 38.3% -91.1% 1.0% Maximum 110.3% 110.3% -38.3% 38.3% 38.3% 91.1% Mean 106.1% 106.1% -38.3% 38.3% -48.3% 57.0% 

Coarse sand and gravel (ore and waste rock) 

Median 106.6% 106.6% -38.3% 38.3% -60.9% 60.9% 

Sediment TL Number 4 4 4 4 7 7 

Minimum 89.6% 89.6% -110.6% 13.7% -59.0% 22.0% Maximum 127.1% 127.1% -13.7% 110.6% -22.0% 59.0% Mean 114.3% 114.3% -60.5% 60.5% -42.0% 42.0% 

Silt and clay (slag-enriched) 

Median 120.3% 120.3% -58.8% 58.8% -41.0% 41.0% 

Soil WS Number 1 1 4 4 3 3 

Minimum 101.5% 101.5% -63.9% 22.8% -27.6% 20.7% Maximum 101.5% 101.5% 59.6% 63.9% 35.2% 35.2% Mean 101.5% 101.5% 13.9% 45.8% -4.4% 27.8% 

Coarse sand and gravel (roaster slag) 

Median 101.5% 101.5% 29.9% 48.3% -20.7% 27.6% 

All Number 25 25 25 25 37 37 

Minimum 30.1% 30.1% -138.9% 0.9% -91.1% 1.0% 

Maximum 127.1% 127.1% 59.6% 138.9% 55.4% 91.1% Mean 97.1% 97.1% -46.7% 59.8% -15.2% 36.7% 

Median 101.5% 101.5% -44.3% 45.1% -20.7% 35.2% 

Notes: Difference is the mean of all RPDs minus the mean site RPD (absolute values). AS Alton Steel Mill RF Ramsey Flats – Silver Bow Creek BN Burlington Northern Railroad/ASARCO East SB Sulfur Bank Mercury Mine CN Naval Surface Warfare Center, Crane Division TL Torch Lake Superfund Site KP KARS Park – Kennedy Space Center WS Wickes Smelter Site LV Leviathan Mine/Aspen Creek Other Notes: -- No samples reported by the reference laboratory in this concentration range. Number Number of demonstration samples evaluated. RPD Relative Percent Difference (raw value). RPD ABS Val Relative Percent Difference (absolute value).