United States Office of Research and EPA/540/R-06/005 

 Environmental Protection Development February 2006 

 Agency Washington, DC 20460 

Innovative Technology 

Verification Report 

XRF Technologies for Measuring 

Trace Elements in 

Soil and Sediment 

Rontec PicoTAX 

XRF Analyzer
EPA/540/R-06/005 

February 2006 

Innovative Technology 

Verification Report 

Rontec PicoTAX 

XRF Analyzer

Prepared by 

Tetra Tech EM Inc. 

Cincinnati, Ohio 45202-1072 

Contract No. 68-C-00-181 

Task Order No. 42 

Dr. Stephen Billets 

Characterization and Monitoring Branch 

Environmental Sciences Division 

Las Vegas, Nevada 89193-3478 

National Exposure Research Laboratory 

Office of Research and Development 

U.S. Environmental Protection Agency 
______________________________________________________________________________

 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 Rontec PicoTAX x-ray fluorescence (XRF) analyzer was demonstrated under the U.S. Environmental 

Protection Agency (EPA) Superfund Innovative Technology Evaluation (SITE) Program. The field 

portion of the demonstration was conducted in January 2005 at the Kennedy Athletic, Recreational and 

Social Park (KARS) at Kennedy Space Center on Merritt Island, Florida. The demonstration was 

designed to collect reliable performance and cost data for the PicoTAX analyzer and seven other 

commercially available XRF instruments for measuring trace elements in soil and sediment. The 

performance and cost data were evaluated to document the relative performance of each XRF instrument. 

This innovative technology verification report describes the objectives and the results of that evaluation 

and serves to verify the performance and cost of the PicoTAX analyzer. Separate reports have been 

prepared for the other XRF instruments that were evaluated as part of the demonstration. 

The objectives of the evaluation included determining each XRF instrument’s accuracy, precision, sample 

throughput, and tendency for matrix effects. To fulfill these objectives, the field demonstration 

incorporated the analysis of 326 prepared samples of soil and sediment that contained 13 target elements. 

The prepared samples included blends of environmental samples from nine different sample collection 

sites as well as spiked samples with certified element concentrations. Accuracy was assessed by 

comparing the XRF instrument’s results with data generated by a fixed laboratory (the reference 

laboratory). The reference laboratory performed element analysis using acid digestion and inductively 

coupled plasma – atomic emission spectrometry (ICP-AES), in accordance with EPA Method 

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

accordance with EPA Method 7471A. 

The PicoTAX is a transportable bench-top device that provides quantitative and semi-quantitative multielement microanalysis of soils and sediments using total reflection XRF spectroscopy. The spectrometer 

includes a 40-watt metal-ceramic x-ray tube excitation source and a thermoelectrically cooled silicon drift 

(Si Drift) x-ray detector. The PicoTAX is capable of detecting up to 75 elements from aluminum to 

yttrium and from palladium to uranium. 

The PicoTAX uses an internal standard for instrument calibration; thus, initial calibration is not required. 

A solution of internal standard that contains a project-specific element is added to each sample to 

establish response factors (determined by the software). Element quantitation is determined by 

comparing the response to the unknown element to the response of the internal standard with a known 

concentration. 

A laptop computer is used to monitor and control all aspects of PicoTAX system operation. Rontec’s 

Quantum software, which is loaded into the laptop computer, calibrates the instrument, handles 

measurement data and methods, controls all hardware functions, and provides statistical functions, 

reporting functions, and data and spectra export.

This report describes the results of the evaluation of the PicoTAX analyzer based on the data obtained 

during the demonstration. The method detection limits, accuracy, and precision of the instrument for each 

of the 13 target analytes are presented and discussed. The cost of element analysis using the PicoTAX 

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

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 
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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 .....................................................................40 

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

 6.4 Contact Information.........................................................................................................41 
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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 .....................................................56 

 7.6 Primary Objective 6 – Sample Throughput .....................................................................56 

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

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

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

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

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

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

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

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

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

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

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

 

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

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

APPENDICES

Appendix A: 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 Rontec PicoTAX XRF Analyzer Technical Specifications ..........................................................40 

7-1 Evaluation of Sensitivity – Method Detection Limits for Rontec PicoTAX ................................44 

7-2 Comparison of Mean PicoTAX MDLs to All-Instrument Mean MDLs and EPA 

 Method 6200 Data ........................................................................................................................46 

7-3 Evaluation of Accuracy – Relative Percent Differences versus Reference Laboratory Data 

 for the Rontec PicoTAX ...............................................................................................................48 

7-4 Summary of Correlation Evaluation for the PicoTAX .................................................................50 

7-5 Evaluation of Precision – Relative Standard Deviations for the Rontec PicoTAX ......................53 

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

 versus the PicoTAX and All Demonstration Instruments.............................................................54 

7-7 Effects of Interferent Elements on the RPDs (Accuracy) for Other Target Elements, Rontec 

 PicoTAX .......................................................................................................................................55 

7-8 Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Rontec PicoTAX .................57 

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

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

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

9-1 Summary of Rontec PicoTAX Performance – Primary Objectives..............................................66 

9-2 Summary of Rontec PicoTAX Performance – Secondary Objectives..........................................68
______________________________________________________________________________

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 Rontec PicoTAX XRF Analyzer Set Up for Benchtop Analysis..................................................39 

6-2 Quart Disks Drying on a Hot Plate ...............................................................................................41 

6-3 Rontec Technicians Recording Identification Numbers ...............................................................41 

7-1 Linear Correlation Plot for PicoTAX Showing High Correlation for Zinc ..................................49 

7-2 Linear Correlation Plot for PicoTAX Showing High Data Variability for Silver ........................51 

8-1 Comparison of Labor Requirements for the PicoTAX versus Other XRF Instruments ...............63 

9-1 Method Detection Limits (sensitivity), Accuracy, and Precision of the Rontec PicoTAX 

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

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
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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; Dr. Hagen Stosnach, Dr. Armin Gross and Ulrick Waldschläger of RÖNTEC AG in 

Germany, Paul Smith of RÖNTEC USA; and Dr. Jackie Quinn of the National Aeronautics and Space 

Administration (NASA), Kennedy Space Center (KSC). The demonstration team also acknowledges the 

field support of Michael Deliz of NASA KSC and Mark Speranza of Tetra Tech NUS, the consultant 

program manager for NASA. 
______________________________________________________________________________________

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 

Rontec PicoTAX XRF analyzer based on the results 

of the demonstration. 

1.1 Organization of this Report 

This report is organized to first present general 

information pertinent to the demonstration. This 

information is common to all eight ITVRs that were 

developed from the XRF demonstration. 

Specifically, this information includes an 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 

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 

Analytcal, 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 Brooker 

AXS AXS, 11/2005)

 RÖNTEC USA Rontec PicoTAX PicoTAX
__________________________________________________________________________________

2

evaluation (Chapter 7), a cost analysis (Chapter 8), 

and a summary of the demonstration results (Chapter 

9). References are provided in Chapter 10. 

A verification statement for the instrument is 

provided as Appendix A. Comments from the 

instrument developer on the demonstration and any 

exceptions to EPA’s evaluation are presented in 

Appendix B. Appendices C, D, and E contain the 

data validation summary report for the reference 

laboratory data and detailed evaluations of instrument 

versus reference laboratory results. 

1.2 Description of the SITE Program 

Performance verification of innovative environmental 

technologies is an integral part of EPA’s regulatory 

and research mission. The SITE Program was 

established by the EPA Office of Solid Waste and 

Emergency Response and ORD under the Superfund 

Amendments and Reauthorization Act of 1986. The 

overall goal of the SITE Program is to conduct 

performance verification studies and to promote 

acceptance of innovative technologies that may be 

used to achieve long-term protection of human health 

and the environment. The program is designed to 

meet three primary objectives: (1) identify and 

remove obstacles to development and commercial 

use of innovative technologies (2) demonstrate 

promising innovative technologies and gather reliable 

information on performance and cost to support site 

characterization and cleanup; and (3) maintain an 

outreach program to operate existing technologies 

and identify new opportunities for their use. 

Additional information on the SITE Program is 

available on the EPA ORD web site 

(www.epa.gov/ord/SITE). 

The intent of a SITE demonstration is to obtain 

representative, high-quality data on the performance 

and cost of one or more innovative technologies so 

that potential users can assess a technology’s 

suitability for a specific application. The SITE 

Program includes the following program elements: 

• Monitoring and Measurement Technology 

(MMT) Program – Evaluates technologies that 

sample, detect, monitor, or measure hazardous 

and toxic substances. These technologies are 

expected to provide better, faster, or more 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 
__________________________________________________________________________________

3

reports for each instrument (EPA 1996a, 1996b, 

1998a, 1998b, 1998c, and 1998d). In 2003, two XRF 

instruments were included in a demonstration of field 

methods for analysis of mercury in soil and sediment. 

Individual ITVRs were also prepared for each of 

these two instruments (EPA 2004a, 2004b). 

Although XRF spectrometry is now considered a 

mature technology for elemental analysis, 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). 
__________________________________________________________________________________

4

As illustrated in Figure 1-1, characteristic radiation 

arises when the energy from the x-ray source exceeds 

the absorption edge energy of inner-shell electrons, 

ejecting one or more electrons. The vacancies are 

filled by electrons that cascade in from the outer 

shells. The energy states of the electrons in the outer 

shells are higher than those of the inner-shell 

electrons, and the outer-shell electrons emit energy in 

the form of x-rays as they cascade down. The energy 

of this x-ray radiation is unique for each element. 

An XRF analyzer consists of three major 

components: (1) a source that generates x-rays (a 

radioisotope or x-ray tube); (2) a detector that 

converts x-rays emitted from the sample into 

measurable electronic signals; and (3) a data 

processing unit that records the emission or 

fluorescence energy signals and calculates the 

elemental concentrations in the sample. 

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. 
__________________________________________________________________________________

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). 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. Concentra-tions of cadmium that exceed 

37 mg/kg may result in adverse effects in humans. 

Typical detection limits for field-portable XRF 

instruments range from 10 to 50 mg/kg. Elevated 

concentrations of cadmium are associated with mine 

wastes and industrial facilities. Cadmium is 

successfully analyzed by both ICP-AES and 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 

therefore included in the study. Furthermore, iron is 
__________________________________________________________________________________

6

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 

ecological risk-based screening levels for soil. 
__________________________________________________________________________________

7

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. 
__________________________________________________________________________________

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 

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. 

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 
__________________________________________________________________________________ 

 16

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 

that might provide the developer’s field team any 

insight as to the nature or content of the sample. 
__________________________________________________________________________________

22

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 therefore included RPD comparisons 

between sample blends with high concentrations of 

iron (more than 50,000 ppm) and other sample 

blends. These RPD comparisons were performed 

for the specific target elements of interest (copper, 

chromium, and others) to assess chemical 

interferences from iron. Outliers and 

subpopulations in the RPD data sets for specific 

target elements, as identified through graphical 

means (probability plots and box plots), were also 

examined for potential interference effects. 

The software that is included with many XRF 

instruments can correct for chemical interferences. 

The results of this evaluation were intended to 

differentiate the instruments that incorporated 

effective software for addressing chemical 

interferences. 
________________________________________________________________________________

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 

that might bias the results. Since the matrices (soil 
__________________________________________________________________________________ 

32

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 PicoTAX XRF analyzer is manufactured by 

RÖNTEC AG, Berlin, Germany and distributed in 

the United States by RÖNTEC USA (Rontec). This 

chapter provides a technical description of the 

PicoTAX based on information obtained from Rontec 

and the observation of this analyzer during the field 

demonstration. This chapter also identifies a Rontec 

company contact, where additional technical 

information may be obtained. 

6.1 General Description 

The PicoTAX is a portable bench-top device that 

provides quantitative and semi-quantitative multielement microanalysis of soils and sediments using 

total reflection x-ray fluorescence spectroscopy. The 

spectrometer includes a 40-watt metal-ceramic x-ray 

tube excitation source and a thermoelectrically 

cooled silicon drift (Si Drift) x-ray detector. The 

PicoTAX is capable of detecting up to 75 elements 

from aluminum to yttrium and from palladium to 

uranium. 

The PicoTAX uses an internal standard for 

instrument calibration; thus, initial calibration is not 

required. A solution of internal standard that 

contains a project-specific element is added to each 

sample to establish response factors (determined by 

the software). Element quantitation is determined by 

comparing the response of the unknown element to 

the response of the internal standard with a known 

concentration. 

A laptop computer is used to monitor and control all 

aspects of PicoTAX system operation. Rontec’s 

Quantum software, which is loaded into the laptop 

computer, calibrates the instrument, handles 

measurement data and methods, controls all hardware 

functions, and provides statistical functions, reporting 

functions, and data and spectra export. 

Technical specifications for the PicoTAX are 

presented in Table 6-1. The PicoTAX is shown in 

the standard bench-top configuration in Figure 6-1. 

 

Figure 6-1. Rontec PicoTAX XRF analyzer set up 

for bench-top analysis. 

6.2 Instrument Operations during the 

Demonstration 

The PicoTAX spectrometer and accessories were 

shipped to the demonstration site from Rontec 

headquarters in Berlin, Germany in packaging that 

complied with international and customs regulations. 

A heavy-duty crate with an inner metal liner 

contained the instrument, necessary tools, and an 

analytical balance. According to Rontec, a smaller 

metal and wood box would typically be used for 

shipment within the United States. The tools and 

balance would typically be shipped separately. The 

total weight of the analyzer and accessories was 

approximately 45 kg. 

6.2.1 Set up and Calibration 

The PicoTAX was set on a vibration free bench and 

plugged into a 110-volt (V) electrical outlet. After 

connecting the instrument to an accompanying laptop 

personal computer (PC), the PicoTAX software was 

initialized. The XRF detector was allowed to warm 

up for 20 to 25 minutes and the optical path of the 

instrument was inspected. Sample preparation 

equipment consisted of the analytical balance, a 

mortar and pestle for sample grinding, test tube rack 

to hold sample tubes, and reagents for preparation 
__________________________________________________________________________________ 

 40

Table 6-1. Rontec PicoTAX XRF Analyzer Technical Specifications 

Weight: 37 kg. 

Dimensions: 420 x 590 x 300 mm. 

Excitation Source: 40W metal ceramic x-ray tube, Mo-target, air cooled. 

X-ray Optics: Ni/C multilayer, 17.5 keV, 80% reflectivity. 

Detector: XFlash Detector, 10 mm2, 160 eV FWHM. 

Signal Processing: Digital signal processing unit, data interchange, and control via RS232 

interface. 

Software: Modular Quantum software package for instrument control, spectra 

accumulation, calibration, and quantification. 

Element Range: Elements from aluminum to yttrium and from palladium to uranium 

(niobium to rhodium are not detectable). 

Sample Container: 30 mm quartz disk. 

Variants: PicoTAX Basic with single sample changer. 

 PicoTAX Automatic with automatic changer for 25 sample disks.

Power: 110-220 volts, 50 hertz, 180 watts. 

and analysis. The total time for setting up the XRF 

analyzer and sample preparation equipment was about 

30 minutes. 

Gallium was selected as the internal standard for this 

effort. The gallium internal standard solution was 

added to each sample to establish response factors and 

quantitatively determine the concentrations of 

elements in each sample. 

6.2.2 Demonstration Sample Processing 

Rontec provided a team of three technical staff 

members from their headquarters in Berlin, Germany 

to process samples. One staff member prepared 

samples for analysis, one operated the PicoTAX 

analyzer, and the third assisted with data management 

or other tasks. 

The typical daily routine for this demonstration 

involved analyzing 3 batches of 25 samples daily. Of 

the 25 samples in a batch, 22 were actual samples and 

the other 3 for QC and performance check samples. 

Thus, Rontec was able to analyze 66 samples in a 24-

hour period using an autosampler to assist in the 

analysis once operations were standardized. At the 

beginning of each day, Rontec reviewed the sample 

analysis completed during the previous night’s run. 

The quartz disks used to contain each sample in the 

autosampler were cleaned and reused. All samples 

were prepared and analyzed in accordance with the 

procedures listed in the PicoTAX instrument manual 

and application note that was available during the 

demonstration. 

The procedure for preparing soil samples for analysis 

is described briefly below but is provided in detail in 

their instrument manual and application note: 

• Approximately 150 milligrams (mg) of soil was 

finely ground to less than 75 microns. 

• An amount of approximately 25 mg of the finely 

ground soil sample was mixed with 2.5 milliliters 

of Triton X solution to form a soil suspension and 

then with 40 microliters of gallium standard 

solution to incorporate the internal standard. 

• Cleaned quartz disks were prepared for analytical 

use by adding a drop of silicon solution to the 

center of each disk and warming on a hot plate to 

about 60 °C for about 10 minutes. This 

procedural step leaves a surface residue of silicon 

that helps contain the soil suspension for XRF 

analysis. 

• Ten microliters of the soil suspension was 

dispensed on top of the silicon residue and the 

disks returned to the hot plate for an additional 10 

minutes to dry (Figure 6-2). The final samples for 

analysis contained circular soil residues on the 

quartz disks. 
__________________________________________________________________________________ 

 41

Figure 6-2. Quartz disks drying on a hot plate. 

• Cooled disks were placed into the autosampler 

tray, which feeds into the PicoTAX analyzer. 

Each disk was marked for identification and 

recorded on a log sheet (Figure 6-3). 

Figure 6-3. Rontec technicians recording 

identification numbers. 

An autosampler was used to allow overnight 

processing of samples through the PicoTAX 

analyzer. The autosampler had 25 slots for samples; 

thus, samples were analyzed in a batch of 25 samples 

that included 22 demonstration samples and 3 QC 

samples. Each sample was analyzed for 10 minutes 

for the demonstration, thus requiring over 4 hours to 

analyze each batch. After the analysis was complete, 

the software automatically calculated the element 

concentrations from raw data and provided the results 

in tabular format (text files or Microsoft Excel® data 

files). The quartz disks were cleaned and reused for 

this demonstration; however, disposable acrylic disks 

may also be used instead. 

6.3 General Demonstration Results 

The unique sample preparation required for the 

PicoTAX analyzer took about 5 minutes to complete 

and occupied one member of the field team 

essentially full time at the demonstration site. The 

analysis time in the XRF analyzer was set at 10 

minutes for the demonstration, although Rontec 

indicated that sufficient precision and accuracy could 

be obtained for soil and sediment samples using 

shorter analysis times. These factors limited the 

number of samples that could be processed to three 

batches of 22 samples (66 samples) per day once the 

instrument had been set up and overall efficiency had 

been optimized. 

The three-person Rontec field team completed the 

analysis of 260 samples during 5 full days at the 

demonstration site (Monday through Friday). 

Because some supplies did not arrive on Monday, 

and the team needed to catch an international flight 

on Saturday morning, the Rontec field team was 

allowed to take the remaining 66 samples in the 

demonstration sample set back to Germany for 

analysis. At the rate the Rontec field team was 

processing samples during the field demonstration, 

these remaining samples would have taken 1 full day 

to process. 

6.4 Contact Information 

In November 2005, Rontec was acquired by Bruker 

AXS Inc. Additional information on Rontec’s 

PicoTAX XRF analyzer is available from the 

following source: 

BRUKER AXS Inc. 

 5465 East Cheryl Parkway 

 Madison, WI 53711-5373, USA 

 Telephone: (800) 234-XRAY 

 Telephone: (608) 276-3000 

 Fax: (608) 276-3006 

 Email: info@bruker-axs.com 
__________________________________________________________________________________ 

 42

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_______________________________________________________________________________________

 43

Chapter 7 

Performance Evaluation 

As discussed in Chapter 6, Rontec analyzed 260 of the 

326 demonstration samples of soil and sediment at the 

field demonstration site between January 24 and 28, 

2005. Weather delayed Rontec’s arrival at the field 

demonstration on Monday, January 24, and further 

delayed the receipt of some supplies until Tuesday, 

January 25. In addition, Rontec’s detailed sample 

preparation process affected sample throughput during 

the field demonstration and the field team had to catch 

an international plane flight on Saturday morning, 

January 29. For these reasons, EPA allowed Rontec to 

analyze the remaining 66 samples the following week 

at Rontec’s Berlin laboratories. A complete set of 

electronic data for the PicoTAX in Excel spreadsheet 

format was delivered to Tetra Tech on March 3, 2005. 

Because data quality for antimony was anticipated to 

be poor due to the x-ray tube used in the demonstration 

(molybdenum), no data were reported for antimony by 

Rontec. Although results were reported for silver and 

cadmium, Rontec also anticipated poor accuracy and 

precision for these two elements because of the x-ray 

tube used. All the data provided by Rontec are 

tabulated and compared with the reference laboratory 

data and the ERA-certified spike concentrations in 

Appendix D. 

The PicoTAX data set was reviewed and evaluated in 

accordance with the primary and secondary objectives 

of the demonstration. The findings of the evaluation 

for each objective are presented below. 

7.1 Primary Objective 1 — Method Detection 

Limits

Samples were selected to calculate MDLs for each 

target element from the 12 potential MDL sample 

blends, as described in Section 4.2.1. The evaluation 

and selection of data for the MDL calculation also 

addressed results reported as “not detected” by Rontec. 

For many of the MDL blend results, element 

concentrations were below the statistical lower limits 

of detection (LLD) calculated by the PicoTAX’s 

instrument algorithms. Non-detect values were 

reported by Rontec as “<LLD” without additional 

clarification as to the concentration represented by the 

LLD. In selecting samples from among the 12 blends 

for the calculation of MDLs, blends where one or more 

of the seven replicates was reported as “<LLD” were 

generally not used. In essence, this meant that all 

seven replicates had to have detected concentrations, 

as reported by Rontec, to calculate an MDL for a 

blend. However, this approach produced very limited 

or no MDL results for a few elements, so blends for 

which at least six of the seven replicates were 

detections were included in the evaluation. In 

addition, the fourth replicate for MDL Blend 8 and the 

second replicate for MDL Blend 10 were removed 

from the evaluation because all results from these two 

replicates differed significantly from the results for the 

other replicates of the blend. These replicates may 

have been inadvertently switched with replicates from 

other blends. Iron was not included in the MDL 

evaluation, as was discussed in Section 4.2.1. 

The MDLs calculated for the PicoTAX are presented 

in Table 7-1. As shown, only a single MDL could be 

calculated for silver, and only three or fewer MDLs 

could be calculated for cadmium, mercury, and 

selenium. Eight or more MDLs could be calculated for 

the remaining target elements. Also shown in Table 7-

1 are the mean MDLs calculated for each target 

element, which are classified as follows: 

• Very low (1 to 20 ppm): selenium. 

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

vanadium. 

• Medium (50 to 100 ppm): mercury, nickel, and 

zinc. 

• High (greater than 100 ppm): cadmium, 

chromium, lead, and silver. 

Mean MDLs greater than 500 ppm were calculated for 

cadmium and silver; no other mean MDLs were above 

110 ppm. The MDLs for cadmium and silver were 

based on very limited data (one to two blends each) 

and are somewhat uncertain; however, these findings 

are in keeping with the developer’s prediction of poor 

performance for these elements. High biases in a few 

PicoTAX results produced some extremely high MDLs
_____________________________________________________________________________________________

44

Table 7-1. Evaluation of Sensitivity — Method Detection Limits for the Rontec PicoTAX1

 Antimony Arsenic Cadmium 

Matrix Blend No. 

Rontec 

MDL2

Rontec 

Conc.3

Ref. Lab 

Conc4

Rontec 

MDL2

Rontec 

Conc.3

Ref. Lab 

Conc. 4

Rontec 

MDL2

Rontec 

Conc.3

Ref. Lab 

Conc. 4

R

M

Soil 2 NA NA 17 NC ND 1.5 NC ND ND Soil 5 NA NA ND 38 59 47 NC ND 1.9 Soil 6 NA NA 8 NC 343 477 NC ND 12 Soil 85 NA NA 118 NC 3596 3,943 939 963 91 Soil 105 NA NA ND 19 43 39 NC ND 0.96 Soil 12 NA NA 62 NC 590 559 120 48 263 Soil 18 NA NA ND 12 19 9 NC ND ND Sediment 29 NA NA ND 15 12 10 NC ND ND Sediment 31 NA NA ND 7 6 11 NC ND ND Sediment 32 NA NA ND 21 34 31 NC ND ND Sediment 39 NA NA ND 22 18 14 NC ND ND Sediment 65 NA NA 11 55 287 250 NC ND 44 Mean Rontec MDL NC 23 529 

Copper Lead Mercury 

Matrix Blend No. 

Rontec 

MDL2

Rontec 

Conc.3

Ref. Lab 

Conc. 4

Rontec 

MDL2

Rontec 

Conc.3

Ref. Lab 

Conc. 4

Rontec 

MDL2

Rontec 

Conc.3

Ref. Lab 

Conc. 4

R

M

Soil 2 11 46 47 NC 1342 1,200 NC ND ND Soil 5 21 59 49 502 203 78 NC ND ND Soil 6 83 149 160 NC 4289 3,986 NC ND 0.83 Soil 85 NC 1249 1,243 NC 47306 33,429 NC ND 15 Soil 105 7 33 31 63 86 72 NC ND 0.14 Soil 12 NC 871 747 NC 5142 4,214 NC ND 1.8 Soil 18 40 56 50 60 19 17 153 46 56 Sediment 29 NC 1638 1,986 31 29 33 NC ND 0.24 Sediment 31 NC 683 1,514 44 36 51 NC ND ND Sediment 32 18 37 36 54 41 26 NC ND ND Sediment 39 36 95 94 49 47 27 NC ND ND Sediment 65 20 73 69 36 326 25 15 196 32 Mean PicoTAX MDL 29 105 84 
_____________________________________________________________________________________________

45

Table 7-1. Evaluation of Sensitivity — Method Detection Limits for the Rontec PicoTAX1 (Continu

Selenium Silver Vanadium 

Matrix Blend No. 

Rontec 

MDL2

Rontec 

Conc.3

Ref. Lab 

Conc. 4

Rontec 

MDL2

Rontec 

Conc.3

Ref. Lab 

Conc. 4

Rontec 

MDL2

Rontec 

Conc.3

Ref. Lab 

Conc. 4

R

M

Soil 2 NC ND ND NC ND ND NC ND 1.2 Soil 5 NC ND ND NC ND 0.93 42 63 55 Soil 6 NC ND ND NC ND 14 26 51 56 Soil 85 18 15 ND 539 1286 144 NC ND 34 Soil 105 NC ND ND NC ND ND 31 51 51 Soil 12 5 4 15 NC ND 38 33 42 45 Soil 18 NC ND ND NC ND ND 112 108 67 Sediment 29 NC ND ND NC ND ND 53 48 96 Sediment 31 NC ND ND NC ND 6.2 37 32 76 Sediment 32 NC ND 4.6 NC ND ND 57 67 57 Sediment 39 NC ND ND NC ND ND 34 32 38 Sediment 65 2 20 22 NC ND 41 15 18 31 Mean PicoTAX MDL 9 539 44 

Notes: 1 Detection limits and concentrations are in milligrams per kilogram (mg/kg), or parts per million (ppm). 2 MDLs calculated from the 12 MDL sample blends for the PicoTAX in this technology demonstration (in bold typeface 3 This column lists the mean concentration reported for this MDL sample blend by the PicoTAX. 4 This column lists the mean concentration reported for this MDL sample blend by the reference laboratory. 5 Only six replicates are included for this blend because one outlier replicate with extreme concentrations for all element6 To increase the number of calculated MDLs for this metal, this blend was included despite the fact that detections were 

developer for only six of the seven replicates. This mean concentration and the corresponding MDL were calculated udetected concentrations. 

Conc. Concentration. MDL Method detection limit. NA Results for this element were not provided by Rontec. NC The MDL was not calculated because reference laboratory concentrations exceeded five times the expected MD

50 ppm, depending on the element) or an insufficient number of detected concentrations were reported. 

ND One or more results for this blend were reported as “Not Detected.” Excepted as noted, blends with one or mo

by the XRF were not used for calculating the MDL for this element. 

Ref. Lab. Reference laboratory. 
__________________________________________________________________________________

46

in individual MDL sample blends for a number of 

other target elements. However, these extreme 

MDLs appeared to occur on a random and isolated 

basis, and no generalized trends in MDLs relative to 

sample medium (soil versus sediment) or blend could 

be discerned. 

The mean MDLs calculated for the PicoTAX are 

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

XRF instruments that participated in the 

demonstration and the mean MDLs derived from 

performance data presented in EPA Method 6200 

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

PicoTAX were lower than the available mean MDLs 

calculated from EPA Method 6200 data for all 

elements except lead. However, when compared 

with the results for all eight XRF instruments that 

participated in the demonstration, the PicoTAX 

exhibited high relative mean MDLs for nine of the 11 

target elements for which MDLs could be calculated. 

The only elements for which the PicoTAX had 

equivalent or lower MDLs were arsenic and 

selenium. 

7.2 Primary Objective 2 — Accuracy and 

 Comparability 

The number of demonstration sample blends that 

met the criteria for evaluation of accuracy, as 

described in Section 4.2.2, was low for silver (9 

samples) and cadmium (12 samples), but was 

greater than 20 for the remaining target elements. 

RPDs between the mean concentrations obtained 

from the PicoTAX and the reference laboratory 

were calculated for each blend that met the criteria. 

Table 7-3 presents the median RPDs for each target 

Table 7-2. Comparison of Mean PicoTAX MDLs to All-Instrument Mean MDLs 

 and EPA Method 6200 Data1 

Element 

PicoTAX

Mean MDLs2

All XRF 

Instrument 

Mean MDLs3

EPA Method 6200 

Mean Detection Limits4

Antimony NC 61 55 5

Arsenic 23 26 92 

Cadmium 529 70 NR 

Chromium 109 83 376 

Copper 29 23 171 

Lead 105 40 78 

Mercury 84 23 NR 

Nickel 78 50 100 5

Selenium 9 8 NR 

Silver 539 42 NR 

Vanadium 44 28 NR 

Zinc 73 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 this EPA 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. 

NC Not calculated; no XRF data reported for this metal. 

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

47

element, along with the number of RPD results used 

to calculate the median. These statistics are provided 

for all demonstration samples as well as for 

subpopulations grouped by medium (soil versus 

sediment) and concentration level (Levels 1 through 

4, as documented in Table 3-1). Additional summary 

statistics for the RPDs (minimum, maximum, and 

mean) are provided in Appendix E (Table E-1). 

Accuracy was classified as follows for the target 

elements based on the overall median RPDs: 

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

none. 

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

arsenic, chromium, copper, iron, lead, nickel, 

selenium, silver, vanadium, and zinc. 

• Fair (median RPD between 25 percent and 50 

percent): mercury. 

• Poor (median RPD greater than 50 percent): 

cadmium. 

The median RPD was used for this evaluation 

because it is less affected by extreme values than is 

the mean. (The initial evaluation of the RPD 

populations for the demonstration showed that they 

were generally right-skewed or lognormal.) Further, 

the classification of the elements based on accuracy 

generally stayed the same when the mean rather than 

the median RPD was used for the evaluation, 

although the means were somewhat higher for many 

elements (Table E-1). Review of the median RPDs 

revealed few trends with respect to media type (soil 

versus sediment) or concentration level. The most 

notable trends are summarized below: 

• Higher overall median RPDs were observed in 

sediment than in soil for nickel and silver. For 

silver, however, the limited number of sample 

blends available for evaluation and the high 

overall variability of the RPDs produce 

uncertainty in the accuracy evaluation. 

• High median RPDs in the soil matrices were 

observed in the Level 1 samples for cadmium 

(with concentrations between 50 and 500 ppm). 

The median RPDs of 157 percent at this 

concentration level (classified in the “poor” 

range) was much higher than those for higher 

concentration levels, where the median RPDs 

were in the “fair” to “good” ranges. Although 

the accuracy data set was limited for cadmium, 

the Level 1 RPDs appeared to be skewed high by 

the results for sample Blends 7 through 9 from 

the Wickes Smelter site, which contained high 

concentrations of other elements (such as lead, 

zinc, and iron). A smaller effect was seen for 

selenium, where the Level 1 median RPDs were 

elevated for both soil and sediment, but remained 

in the “fair” range. Review of individual RPDs 

in the selenium data set indicated that this trend 

appeared to be generalized rather than caused by 

limited data or extreme results from specific 

blends. 

• The best accuracy for mercury was observed in 

the Level 1 samples (with concentrations 

between 20 and 200 ppm) in both the soil and 

sediment matrices, where median RPDs were in 

the “good” range (the median RPDs for the other 

concentration levels were above 25 percent, 

falling in the “fair” range). These samples were 

generally characterized by very low 

concentrations of other elements, including 

elements adjacent to mercury in the periodic 

table such as cadmium and lead. 

As an additional basis for comparison, Table 7-3 

presents the overall average of the median RPDs for 

all eight XRF instruments. Complete summary 

statistics for the RPDs across all eight XRF 

instruments are included in Appendix E (Table E-1). 

Table 7-3 indicates that the median RPDs for the 

PicoTAX were equivalent to or below the allinstrument medians for 11 of the 12 elements 

compared. For arsenic, mercury, selenium, silver and 

zinc, the median RPDs for the PicoTAX were less 

than half the all-instrument medians. Only cadmium 

displayed a higher median RPD for the PicoTAX 

than for all eight instruments that participated in the 

demonstration. 

In addition to calculating RPDs, the evaluation of 

accuracy included preparing linear correlation plots 

of PicoTAX concentration values against the 

reference laboratory values. These plots are 

presented for the individual target elements in 

Figures E-1 through E-12 of Appendix E. The plots 

include a 45-degree line showing the “ideal” 

relationship between the PicoTAX data and the 

reference laboratory data, as well as a “best fit” linear 
________________________________________________________________________________________________

48

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

Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Sel

Matrix 

Sample Group Statistic Ref Lab 

ERA 

Spike 

Soil Level 1 Number 0 -- 15 4 28 16 5 16 7 22 

Median NC -- 20.7% 157.0% 20.7% 10.4% 20.5% 24.9% 19.3% 16.7% 

Level 2 Number 0 0 4 6 4 8 13 4 7 5 

Median NC NC 4.6% 49.6% 10.9% 10.0% 23.2% 16.3% 43.3% 21.6% 

Level 3 Number 0 0 4 2 2 2 13 8 2 6 

Median NC NC 8.7% 10.0% 14.4% 24.9% 12.0% 20.4% 38.9% 5.6% 

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

Median -- -- -- -- -- -- 2.4% 22.9% -- -- 

 All Soil Number 0 0 23 12 34 26 38 33 16 33 

Median NC NC 14.3% 83.2% 17.9% 11.5% 14.9% 21.6% 33.0% 12.2% 

Sediment Level 1 Number 0 0 17 0 21 8 3 16 2 18 

Median NC NC 12.9% NC 20.3% 5.6% 37.6% 30.0% 27.5% 34.9% 

Level 2 Number 0 0 4 0 3 4 19 4 4 6 

Median NC NC 8.6% NC 13.4% 17.2% 27.5% 10.9% 40.7% 29.4% 

 Level 3 Number 0 0 2 0 3 10 4 3 2 4 

Median NC NC 19.2% NC 25.0% 18.5% 31.1% 39.7% 31.7% 13.7% 

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

 Median -- -- -- -- -- -- 8.4% -- -- --  All Sediment Number 0 0 23 0 27 22 32 23 8 28 ` Median NC NC 12.9% NC 20.3% 15.4% 21.6% 25.5% 37.8% 29.4% All Samples Rontec Number 0 0 46 12 61 48 70 56 24 61 

 PicoTAX Median NC NC 13.4% 83.2% 18.1% 12.3% 17.3% 22.9% 33.0% 21.2% 

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

 Instruments Median 84.3% 70.6% 26.2% 16.7% 26.0% 16.2% 26.0% 21.5% 58.6% 25.4% 1

Notes: All median RPDs presented in this table are based on the population of absolute values of the individual RPDs. 

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

ERA Environmental Resource Associates, Inc. 

NC Not calculated; no XRF data provided for this element. 

Number Number of samples appropriate for accuracy evaluation. Ref Lab Reference laboratory (Shealy Environmental Services, Inc.) 

RPD Relative percent difference. 
__________________________________________________________________________________

49

equation (y = mx + b, where m is the slope of the line 

and b is the y-intercept of the line) and correlation 

coefficient (r2

) to help illustrate the “actual” relationship between the two methods. To be considered 

accurate, the correlation coefficient should be greater 

than 0.9, the slope (m) should be between 0.75 and 

1.25, and the y-intercept (b) should be relatively 

close to zero (that is, plus or minus the mean MDL in 

Table 7-1). Table 7-4 lists the results for these three 

correlation parameters and highlights in bold each 

target element that met all three accuracy criteria. 

This table shows that the results for chromium, iron, 

nickel, and zinc met all three of these criteria. The 

correlation plot for zinc is displayed in Figure 7-1 as 

an example of the correlations obtained for these 

elements. 

Figure 7-1. Linear correlation plot for PicoTAX 

 showing high correlation for zinc.

y = 1.07x - 21.19

R2 = 0.97

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

0 1000 2000 3000 4000 5000 6000 7000 8000

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)
______________________________________________________________________________________

50

Table 7-4. Summary of Correlation Evaluation for the PicoTAX 

Notes: 

1 A high bias was indicated for cadmium at low concentrations by the high relative y-intercept. 

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

concentrations in the demonstration samples. 

-- No bias observed. 

b Y-intercept of correlation line. 

m Slope of correlation line. 

r

2

 Correlation coefficient of correlation line. 

General observations from the correlation plots are as 

follows: 

• Consistent with the RPD evaluation and 

developer predictions, the correlation analysis 

showed a low degree of accuracy for cadmium 

and silver. However, these findings may have 

been affected by the limited availability of data in 

the various concentration ranges. Removal of the 

high outliers associated with complex Blends 8 

and 9 (Wickes Smelter slag) from the correlation 

analysis for cadmium improved the r2

 value to 

0.90 and lowered the y-intercept to near 0, 

producing a high correlation and eliminating the 

apparent positive bias at low concentrations. For 

silver, however, the low degree of correlation 

appeared to be due to a broader variability in the 

data rather than a few outliers. Figure 7-2 shows 

the correlation plot for silver. 

• Removal of a single outlier associated with the 

Alton Steel site (Blend 53) improved the 

correlation coefficient for selenium from 0.70 to 

0.90. 

• Mercury exhibited a high r2 value (0.99) but a 

slightly low bias (m = 0.73). Removing two 

extreme Level 4 concentrations (Blends 21 and 

22) from the plots produced a much poorer 

correlation coefficient (in the range of 0.81) and a 

lower bias (m = 0.58). 

Overall, the evaluations of accuracy showed an 

accept-able overall level of performance by the 

PicoTAX for the target elements. Correlations with 

the reference laboratory were generally high, and 

median RPDs were better for most elements in 

comparison to the average of all eight XRF 

instruments that participated in the demonstration. 

Factors such as Rontec’s rigorous sample preparation 

protocol and use of internal standards (Chapter 6) 

may have contributed to the high relative level of 

accuracy attained. However, the use of a 

molybdenum x-ray tube precluded the reporting of 

antimony results and produced low relative accuracy 

in the cadmium and silver results, consistent with 

Rontec’s predictions. 

Target Element m b r2

 Correlation Bias 

Arsenic 0.90 56 0.95 High -- 

Cadmium 0.78 272 0.62 Moderate High1

Chromium 1.04 27 0.95 High -- 

Copper 1.03 -33 0.86 Moderate -- 

Iron 1.02 4489 2 0.95 High -- 

Lead 1.42 -98 0.94 High High 

Mercury 0.73 -39 0.99 High Low 

Nickel 0.89 0.07 0.96 High -- 

Selenium 1.03 14 0.70 Moderate -- 

Silver 0.94 7.0 0.58 Moderate -- 

Vanadium 1.04 -11 0.89 Moderate -- 

Zinc 1.07 -21 0.97 High -- 
_______________________________________________________________________________________

51

Figure 7-2. Linear correlation plot for PicoTAX

 showing high data variability for silver.

y = 0.94x + 6.98

R2 = 0.58

0

50

100

150

200

250

300

350

400

450

0 50 100 150 200 250 300 350 400 450

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)

7.3 Primary Objective 3 — Precision 

As described in Section 4.2.3, the precision of the 

PicoTAX was evaluated by calculating RSDs for the 

replicate measurements from each sample blend. 

Median RSDs for the various concentration levels 

and media (soil and sediment), as well as for the 

demonstration sample set as a whole, are presented in 

Table 7-5. An expanded set of summary statistics for 

the RSDs (including minimum, maximum, and mean) 

is provided in Appendix E (Table E-2). 

The median RSDs calculated for the target elements 

ranged as high as 50.2 percent (silver). The ranges of 

median RSDs are further summarized below: 

• Very low (median RSD between 0 and 5 

percent): none. 

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

selenium. 

• Moderate (median RSD between 10 and 20 

percent): arsenic, copper, iron, lead, nickel, 

vanadium, and zinc. 

• High (median RSD greater than 20 percent): 

cadmium, chromium, mercury, and silver. 

The median RSDs for sediment were slightly larger 

for some target elements (such as arsenic, lead, and 

vanadium) than the median RSDs for soil. 

The level of precision observed may have been 

facilitated by the level of pre-processing 

(homogenizing, sieving, crushing, and drying) on the 

sample blends before the demonstration (Chapter 3). 

This observation is consistent with the previous SITE 

MMT program demonstration of XRF technologies 

that occurred in 1995 (EPA 1996a, 1996b, 1998a, 

1998b, 1998c, and 1998d). The high level of sample 

processing applied during both XRF technology 

demonstrations was necessary to minimize the effects 

of sample heterogeneity on the demonstration results 
__________________________________________________________________________________

52

and on comparability with the reference laboratories. 

During project design, site investigation teams that 

intend to compare XRF and laboratory data should 

similarly assess the need for sample processing steps 

to manage sample heterogeneity and improve data 

comparability. 

Over and above the pre-processing prior to the 

demonstration, Rontec performed an additional 

detailed preparation protocol during the demonstration to emulsify the samples, as described in 

Section 6.2.2. This level of additional sample 

preparation during the demonstration differentiated 

the PicoTAX from the other technology developers. 

(The other developers generally performed minimal 

additional sample preparation, consisting of only of 

transferring sample into analysis cups or pressing the 

samples into pellets.) 

Further review of the median RSDs in Table 7-5 

based on concentration range reveals slightly higher 

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

elements in Level 1 samples when compared with the 

rest of the data set. This effect was observed for 

multiple target elements in both soil and sediment, 

with large relative effects for arsenic, chromium, 

lead, mercury, and nickel in the sediment samples. 

This observation indicates that, to a minor extent, 

analytical precision for the PicoTAX may depend on 

concentration. 

As an additional comparison, Table 7-5 presents the 

overall average of the median RSDs for all eight XRF 

instruments that participated in the demonstration. 

Complete summary statistics for the RSDs across all 

eight XRF instruments are included in Table E-2. 

Table 7-5 indicates that the median RSDs for the 

PicoTAX were above the all-instrument medians for 

all 12 of the target elements compared. For 

cadmium, iron, mercury, and silver, the median RSDs 

for the PicoTAX were more than three times higher 

than the all-instrument medians. 

Table 7-6 presents median RSD statistics for the 

reference laboratory and compares these to the 

summary data for the PicoTAX. (Complete summary 

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

Table 7-6 indicates that the median RSDs for the 

PicoTAX were higher than the RSDs for the 

reference laboratory for all 12 target elements. For 

cadmium, mercury, and silver, the median RSDs for 

the PicoTAX were more than three times higher than 

the reference laboratory medians. Thus, the 

PicoTAX exhibited lower precision overall than 

either the reference laboratory or the other XRF 

instruments. The reduced precision of the PicoTAX 

relative to other XRF technologies may be a function 

of Rontec’s sample preparation process, in which a 

very small subsample (10 μL of a soil emulsion 

prepared using 0.15 grams of soil) is used for 

analysis (see Section 6.2.2). Despite the grinding and 

homogenizing protocols applied prior to the 

demonstration, the use of such a small aliquot of 

sample may have diminished the representativeness 

of the samples, reducing precision. 

7.4 Primary Objective 4 — Impact of 

Chemical and Spectral Interferences 

The RPD data from the accuracy evaluation were 

further processed to assess the effects of 

interferences. The RPD data for elements considered 

susceptible to interferences were grouped and 

compared based on the relative concentrations of 

potentially interfering elements. Of specific interest 

for the comparison were the potential effects of: 

• High concentrations of lead on the RPDs for 

arsenic. 

• High concentrations of nickel on the RPDs for 

copper (and vice versa). 

• High concentrations of zinc on RPDs for copper 

(and vice versa). 

The rationale and approach for evaluation of these 

interferents are described in Section 4.2.4. 

Interferent-to-element ratios were calculated using 

the mean concentrations the reference laboratory 

reported for each blend, classified as low (less than 

5X), moderate (5 to 10X), or high (greater than 10X). 

Table 7-7 presents median RPD data for arsenic, 

nickel, copper, and zinc that are grouped based on 

this classification scheme. Complete summary 

statistics are presented in Appendix E (Table E-4). 

The tables confirm significant interference effects of 

lead on arsenic. Specifically, as lead concentrations 

increased to greater than 10 times the arsenic 

concentration, the median RPD for arsenic increased 

from 12.9 percent (well within the “good” range 

defined in Section 7.2) to 43.0 percent (at the upper 

end of the “fair” range). Similar effects are observed 

for copper as an interferent for nickel; as copper 
_______________________________________________________________________________________________

53

Table 7-5. Evaluation of Precision — Relative Standard Deviations for the Rontec PicoTA

Matrix 

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

Soil Level 1 Number 0 15 4 28 16 5 16 7 22 

Median NC 13.8% 27.6% 26.3% 11.9% 19.2% 20.9% 25.2% 19.5% 

Level 2 Number 0 4 6 4 8 13 4 7 5 

Median NC 15.1% 31.5% 9.6% 16.7% 13.3% 12.6% 26.0% 11.6% 

Level 3 Number 0 4 2 2 2 13 8 2 6 

Median NC 12.7% 26.2% 3.7% 15.9% 17.9% 12.0% 33.8% 19.5% 

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

Median -- -- -- -- -- 15.7% 9.4% -- -- 

All Soil Number 0 23 12 34 26 38 33 16 33 

Median NC 14.3% 30.0% 22.1% 13.3% 16.6% 14.4% 25.6% 17.3% 

Sediment Level 1 Number 0 17 0 21 8 3 16 2 18 

Median NC 28.3% NC 32.5% 11.1% 20.3% 24.4% 55.8% 31.6% 

Level 2 Number 0 4 0 3 4 19 4 4 6 

Median NC 8.1% NC 9.9% 17.2% 14.0% 8.6% 29.8% 17.0% 

Level 3 Number 0 2 0 3 10 4 3 2 4 

Median NC 10.1% NC 7.2% 22.5% 16.0% 11.9% 12.9% 10.9% 

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

Median -- -- -- -- -- 17.5% -- -- -- 

All Sediment Number 0 23 0 27 22 32 23 8 28 

Median NC 18.8% NC 25.1% 16.2% 16.5% 21.3% 26.9% 18.8% 

All Samples PicoTAX Number 0 46 12 61 48 70 56 24 61 

Median NC 15.1% 30.0% 24.2% 15.2% 16.5% 14.5% 26.0% 18.5% 

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% 

Notes: -- No samples reported by the reference laboratory in this concentration range. 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 PicoTAX and Al

Matrix 

Sample 

Group Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Selenium 

Soil Ref. Lab Number 17 23 15 34 26 38 33 16 35 1

 Median 9.8% 12.4% 9.0% 10.6% 9.1% 8.7% 13.2% 6.6% 10.0% 7.1% Ref. Lab Number 7 24 10 26 21 31 22 10 27 1

Sediment

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

All Ref. Lab Number 24 47 25 60 47 69 55 26 62 2Samples Median 9.5% 9.5% 9.0% 8.4% 8.9% 8.5% 8.6% 6.6% 8.2% 7.4% 

PicoTAX Number 0 46 13 61 48 70 56 24 61 25 

All Samples Median NC 15.1% 31.0% 24.2% 15.2% 16.5% 14.5% 26.0% 18.5% 8.2% All All XRF Number 206 320 209 338 363 558 392 192 403 19Samples 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 samples appropriate for precision evaluation Ref. Lab Reference Laboratory 
_______________________________________________________________________________________________

55

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

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 29 7 10 42 5 14 39 1 8 35 2 11 

Median RPD of 

Target Element 2 12.9% 5.5% 43.0% 13.8% 42.2% 41.6% 11.1% 16.1% 14.4% 14.1% 6.6% 8.9% 

Median Interferent 

Concentration 89 9262 3434 123 871 1877 98 288 1906 177 4462 3015 

Median Target 

Element 

Concentration 135 1071 56 183 100 75 786 92 107 829 851 124 

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.
__________________________________________________________________________________

56 

concentrations increased to greater than 10 times the 

nickel concentration, the median RPD for nickel 

increased from 13.8 percent to 41.6 percent. 

Evaluation of the effects of nickel on copper, copper 

on zinc, and zinc on copper do not appear to show 

significant interferences. 

In presenting statistics for the raw RPDs as well as 

the absolute values of the RPDs, Table E-4 further 

shows that the interferences from lead appeared to 

produce an increasingly low bias in the arsenic data 

(as indicated by more positive raw RPDs). A similar 

trend was observed for the effect of copper on nickel.

7.5 Primary Objective 5 — Effects of Soil 

Characteristics 

The population of RPDs between the results obtained 

from the PicoTAX and the reference laboratory was 

further evaluated against sampling site and soil type. 

Separate sets of summary statistics were developed 

for the mean RPDs associated with each sampling 

site for comparison to the other sites and to the data 

set for all samples. The site-specific median RPDs 

are presented in Table 7-8, along with descriptions of 

soil or sediment type from observations during 

sampling at each site. Complete RPD summary 

statistics for each soil type (minimum, maximum, and 

mean) are presented in Table E-5 of Appendix E. 

Another perspective on the effects of soil type was 

developed by graphically assessing outliers and 

extreme values in the RPD data sets for each target 

element. This evaluation focused on correlating 

these extreme values with sample types or locations 

for multiple elements across the data set. Some 

outliers and extreme values are apparent in the 

correlation plots (Figures E-1 through E-12) and are 

further depicted for the various elements on box and 

whisker plots in Figure E-13. 

Review of Table 7-8 indicates that the median RPDs 

were highly variable and that trends or differences 

between sample sites were difficult to discern. 

Evaluations relative to sampling site were further 

complicated by the low numbers of samples for many 

target elements. (Table 7-8 indicates that only one to 

three samples were available from many sampling 

sites for evaluation of specific target elements.) High 

relative median RPDs for cadmium and nickel were 

observed in blends from the Wickes Smelter site. 

The median RPDs in these blends were 165 percent 

for cadmium and 50 percent for nickel, which were 

significantly higher than blends from other sampling 

sites for these two elements. The soil matrix from 

this site was described during the demonstration 

sample collection program (Chapter 2) as roaster 

slag, consisting of a black, fairly coarse sand and 

gravel material. This slag is an intermediate product 

in processing ore, wherein volatile sulfide materials 

are thermally removed, leaving concentrated heavy 

elements. Effects of the Wickes Smelter sample 

blends on XRF data quality were noted earlier for 

cadmium in the accuracy evaluation (Section 7.2). 

Review of the box and whiskers plot (Figure E-13) 

and the correlation plots from the accuracy evaluation 

revealed few other major trends in RPDs relative to 

sampling site. The outliers and extreme values 

apparent in Figure E-13 were broadly distributed 

between eight of the nine sampling sites. The Torch 

Lake site represented higher numbers of outliers 

relative to the other sampling sites. However, the 

evaluation found that sample matrix had a minor 

effect on the overall accuracy of the XRF data given 

that the ranges of RPDs observed for the target 

elements were very broad. The spread in the 

accuracy results is illustrated on the box and whiskers 

plot in Figure E-13. The plot shows that the broad 

overall distributions of RPDs precluded the 

identification of statistical outliers and extreme 

values for cadmium, mercury, and silver. Further data 

review indicated that the large spread in the RPD data 

for these metals was affected by high RPD values 

from the Wickes Smelter blends for cadmium, the 

Sulfur Bank mine blends for mercury, and a Ramsey 

Flats blend for silver. 

7.6 Primary Objective 6 — Sample 

Throughput 

The Rontec three-person field team was able to 

analyze all 326 demonstration samples in 4.5 days at 

the demonstration site and an equivalent of 1 

additional day in Berlin, Germany. Once the 

PicoTax instrument had been set up and operations 

had been streamlined, the Rontec field team was able 

to analye 66 samples (that is, three batches of 22 

samples) during an extended work day. This sample 

throughput was achieved by using different members 

of the field team to perform sample preparation and 

instrumental analysis and by loading one sample 

batch into the autosampler to run overnight. Without 

an extended work day, it was estimated that the
__________________________________________________________________________________

57 

Table 7-8. Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Rontec PicoTAX 

Matrix Site 

Matrix 

Description Statistic Antimony Arsenic Cadmium Chromium Copper 

Soil AS Fine to medium sand (steel Number -- 1 1 2 

processing) Median -- 181.4% 0.8% 10.8% 34.8

Soil BN Sandy loam, low organic (ore Number -- 7 5 7 

residuals) Median -- 5.5% 82.5% 17.9% 10.3

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

Median -- 17.6% 83.8% 90.1% 20.7

Soil & Number -- -- -- 4 Sediment 

KP Soil: Fine to medium quartz sand.

Sed.: Sandy loam, high organic. (Gun and skeet ranges) Median -- -- -- 16.3% 8.0

Sediment Number LV Clay/clay loam, salt crust (iron -- 11 1 11 

and other precipitates) Median -- 9.2% 6.1% 11.7% 6.4

Sediment Number RF Silty fine sand (tailings) -- 12 -- 12 1

Median -- 17.7% -- 22.2% 15.9

Soil Number SB Coarse sand and gravel (ore and -- 5 1 11 

waste rock) Median -- 20.7% 6.3% 39.8% 13.6

Sediment Number TL Silt and clay (slag-enriched) -- 2 -- 5 

Median -- 42.1% -- 20.3% 19.2

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

slag) Median -- 12.2% 165.3% 11.5% 4.2

 All Number -- 46 12 61 4

Median -- 13.4% 83.2% 18.1% 12.3
_____________________________________________________________________________________________

58 

Table 7-8. Effect of Soil Type on RPDs (Accuracy) of Target Elements, Rontec PicoTAX (Contin

Matrix Site 

Matrix 

Description Statistic Mercury Nickel Selenium Silver Va

Soil AS Fine to medium sand (steel Number -- 1 1 1 

processing) Median -- 74.6% 110.7% 19.3% 

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

residuals) Median 110.4% 10.6% 40.6% 5.6% 

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

Median 23.4% 21.6% 6.0% -- 

Number -- 3 -- -- 

Soil & Sediment 

KP Soil: Fine to medium quartz 

sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) Median -- 12.2% -- -- 

Sediment Number LV Clay/clay loam, salt crust (iron 4 11 5 1 

and other precipitates) Median 41.9% 10.2% 14.7% 34.5% 

Sediment Number RF Silty fine sand (tailings) 4 13 5 2 

Median 11.2% 36.7% 11.6% 89.7% 

Soil Number SB Coarse sand and gravel (ore and 11 11 3 -- 

waste rock) Median 43.3% 5.7% 9.6% -- 

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

Median 81.7% 30.1% 34.4% 33.8% 

Soil Number WS Coarse sand and gravel (roaster -- 7 1 2 

slag) Median -- 50.0% 4.8% 10.4% 

 All Number 24 61 25 9 

Median 33.0% 21.2% 11.6% 19.3% 

Notes: AS Alton Steel Mill Other Notes:  BN Burlington Northern railroad/ASARCO East. -- No samples reported by the reference laboratory 

 CN Naval Surface Warfare Center, Crane Division. Number Number of demonstration samples evalu KP KARS Park – Kennedy Space Center. RPD Relative percent difference (absolute va 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.
__________________________________________________________________________________

59 

Rontec field team could have only processed 44 

samples (that is, two batches of 22 samples) per day. 

This estimated sample throughput for a normal working 

day was lower than that observed for the other 

instruments that participated in the demonstration 

(average of 66 samples per day). The lower sample 

throughput was primarily the result of the long run time 

in the XRF spectrometer (10 minutes per sample). 

Rontec selected this instrument run time to provide the 

maximum analytical precision and accuracy for the 

demonstration. Rontec indicated that a reduction in 

analysis time of up to 50 percent could still provide data 

of sufficient accuracy and precision. If this claim is 

valid, then a sample throughput of 66 samples (3 

batches of 22 samples) per day could have been 

maintained with a normal 8-hour work day. 

A detailed discussion of the time required to complete 

the various steps of sample analysis using the PicoTAX 

is included as part of the labor cost analysis in Section 

8.3. 

7.7 Primary Objective 7 — Technology Costs 

The evaluations pertaining to this primary objective are 

described in Chapter 8, Economic Analysis. 

7.8 Secondary Objective 1 — Training 

Requirements

Technology users must be suitably trained to set up and 

operate the instrument to obtain the level of data quality 

required for specific projects. The amount of training 

required depends on the configuration and complexity 

of the instrument, along with the associated software. 

Rontec offers on-site training, on-line support, and 

telephone support to instrument users on an informal, as 

needed basis. Although Rontec provided three Ph.D.-

level scientists for the demonstration, plus an additional 

logistical support person, this level of expertise and 

staffing is not needed for analysis of soil and sediment 

samples. 

Two operating manuals are provided with the 

instrument, including an instrument manual and a 

software manual. The instrument manual provides the 

user with instructions for installing and operating the 

instrument, including packaging, transporting, and 

setup. The manual provides a descriptive summary of 

connections, control, and display elements, as well as 

the structural elements of the spectrometer. A section is 

also provided that discusses instrument maintenance, 

including adjusting the optical path, gain correction, and 

change out of the x-ray tube. The observer assessed 

that proper instrument setup and operation requires a 

chemist or technician with a basic knowledge of 

spectroscopy. 

The software manual provides a detailed description of 

the instrument operating system and Windows-based 

data management software. The software is operated 

from a notebook computer that is provided with the 

spectrometer. The manual includes instructions for 

installing software, starting the program, the user 

interface, spectral measurement, spectral evaluation, 

data export, and crystal orientation. This manual is 

detailed and thorough and is readily understandable for 

a technician-level analyst with basic computer and 

software skills along with an understanding of 

spectroscopy and RS-232 communications technology. 

On-line help is available to assist the analyst in 

operating the instrument and using the software. 

Processing soil and sediment samples entailed relatively 

simple procedures that could be performed by a field 

technician. In addition to the instrument manual, an 

application note was provided that listed instructions for 

analysis of soil and sediment samples. This document, 

although intended as a marketing document on the 

performance of XRF against traditional laboratory 

methodology, provided an excellent description of the 

sample preparation and analysis procedures required by 

the PicoTAX. The application note is available from 

the developer. 

7.9 Secondary Objective 2 — Health and Safety 

Included in the health and safety evaluation were the 

potential risks from: (1) potential radiation hazards 

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

reagents used in preparing and analyzing the samples. 

However, the evaluation did not include potential risks 

from exposure to site-specific hazardous materials, such 

as sample contaminants, or to physical safety hazards. 

These factors were excluded because of the wide and 

unpredictable range of sites and conditions that could be 

encountered in the field during an actual project 

application of the instrument. 

The PicoTAX spectrometer is enclosed within a 

cabinet; the x-ray tube is totally encased within the 

cabinet and emits no detectable radiation to the analyst 

or surrounding environment. Acetone (reagent grade) 
__________________________________________________________________________________

60 

was used to clean the quartz disks between uses. 

Acetone is extremely flammable, and the vapor may 

cause a flash fire. Inhalation of acetone fumes may 

irritate the respiratory tract. High concentrations of 

acetone fumes may cause coughing, dizziness, dullness, 

and headache. Higher concentrations can produce 

central nervous system depression, narcosis, and 

unconsciousness. However, the exposure to acetone 

during the disk cleaning process should be minimal as 

the quantities of acetone used are very small (a few 

drops). Further, exposure to acetone can be eliminated 

by using disposable acrylic disks that are available from 

Rontec. 

7.10 Secondary Objective 3 — Portability 

Portability depends on the size, weight, number of 

components, and power requirements of the instrument, 

and the reagents required. The size of the instrument, 

including physical dimensions and weight, is presented 

in Table 6-1. The number of components, power 

requirements, support structures, and reagent 

requirements are also listed in Table 6-1. Two 

distinctions were made during the demonstration 

regarding portability: 

(1) The instrument was considered fully portable if the 

dimensions were such that the instrument could be 

easily brought directly to the sample location by 

one person. 

(2) The instrument was considered transportable if the 

dimensions and power requirements were such that 

the instrument could be moved to a location near 

the sampling location, but required a larger and 

more stable environment (for example, a site trailer 

with AC power and stable conditions). 

Based on its dimensions and power requirements, the 

PicoTAX is defined as transportable. The PicoTAX 

Spectrometer is a bench-top unit that can be set on a 

table or bench in an office or mobile laboratory, or on 

the back of a truck bed, for field analysis. It is not 

capable of providing in situ analysis of soil. The 

instrument consists of a spectrometer, autosampler, 

sampler holders, and notebook PC that runs the 

operating system of the instrument and provides data 

analysis and management. There are two handles on 

each side of the instrument for ease in transporting. The 

PicoTAX is transported in a wood-lined metal box 

provided by the developer to protect the instrument 

from damage during shipment. Peripheral supplies for 

sample preparation are transported in separate 

shipments weighing less than 10 pounds. 

The PicoTAX spectrometer operates using a standard 

110 V AC power source. The notebook computer for 

the spectrometer also uses 110 V AC. Additionally, a 

balance was used to weigh sample material, and a hot 

plate was used to dry a suspension of each sample into a 

residue on a quartz disk. In total, therefore, four 

separate devices were required to complete the 

PicoTAX system, each needing 110 V AC power. 

7.11 Secondary Objective 4 — Durability 

Durability was evaluated by gathering information on 

the instrument’s warranty and the expected lifespan of 

the radioactive source or x-ray tube. The ability to 

upgrade software or hardware was also evaluated. 

Weather resistance was evaluated by examining the 

instrument for exposed electrical connections and 

openings that may allow water to penetrate (for portable 

instruments only). 

The PicoTAX system is constructed from impactresistant coated metal and molded plastic. The 

instrument is operational up to a maximum temperature 

of 40°C and 80 percent relative humidity (limited by the 

air cooling requirements of the detector). Because the 

spectrometer is intended for indoor use, it requires a 

stable operating environment and must be protected 

from weather. 

The metal ceramic x-ray tube is warranted for 2,500 

hours of operation; typically, Rontec tubes have a 

minimum lifespan of 10,000 operating hours. The 

entire instrument is warranted for 1 year for full 

coverage, and software is upgradeable for up to 2 years 

at no additional cost to the owner. Rontec provides 

product support as requested throughout the life of the 

instrument. 

7.12 Secondary Objective 5 — Availability 

Rontec is headquartered in Berlin, Germany, but also 

maintains an office in Carlisle, Massachusetts. The 

PicoTAX is available from the manufacturer for 

purchase only; no rental or long-term leasing options 

are currently available. In addition, no third party 

distributors for Rontec instrumentation were identified 

at the time of the demonstration. Rontec operates 

telephone and on-line support in both the U.S. and 

Europe. 
__________________________________________________________________________________

61 

Chapter 8 

Economic Analysis 

This chapter provides cost information for the Rontec 

PicoTAX XRF analyzer. Cost elements that were 

addressed included instrument purchase or rental, 

supplies, labor, and ancillary items. Sources of cost 

information included input from the technology 

developer and suppliers as well as observations 

during the field demonstration. Comparisons are 

provided to average costs for other XRF technologies 

and for conventional fixed-laboratory analysis to 

provide some perspective on the relative cost of using 

the PicoTAX. 

8.1 Equipment Costs 

Capital equipment costs include either purchase or 

rental of the PicoTAX and any ancillary equipment 

that is generally needed for sample analysis. (See 

Chapter 6 for a description of available accessories.) 

Information on purchase price and rental cost for the 

analyzer and accessories was obtained from Rontec. 

The PicoTAX used at the demonstration costs 

approximately $99,990 for the complete equipment 

package. The package includes a required 2 day 

training program for first time users, which 

separately costs $4,600. The package includes a 

cassette for 25 sample discs and Messjobebitor PCcontroller, which separately costs $15,440. 

The standard equipment package includes the metal 

ceramic x-ray tube. Purchased models include a 1-

year warranty on the x-ray tube. The x-ray tube is 

guaranteed for 2,500 hours. The lifespan of the x-ray 

tube is at least 5 years in normal usage. 

Rontec indicated that the PicoTAX is not available 

for rental. For comparison to the rental cost of other 

XRF instruments and for general evaluation 

purposes, an estimated rental cost was derived based 

on similar XRF technologies where both purchase 

and rental prices were available. 

The purchase price, rental cost, and shipping cost for 

the PicoTAX exceed the average costs for all XRF 

instruments that participated in the demonstration, as 

shown in Table 8-1. 

Table 8-1. Equipment Costs

Cost Element PicoTAX 

XRF 

Demonstration 

Average 1

Shipping $750 $410 

Capital Cost 

(Purchase)2

 $99,990 $54,300 

Weekly Rental $5,2003 $2,813 

Autosampler (for 

Overnight Analysis) 

 Included N/A 

Notes: 

1

 Average for all eight instruments in the 

demonstration 

2

 Capital cost includes cost for required instrument 

training 

3 Estimated rental cost. 

N/A Not available or not applicable for this 

comparison 

8.2 Supply Costs 

The supplies that were included in the cost estimate 

include sample containers, Mylar film, spatulas or 

scoops, wipes, and disposable gloves. The rate of 

consumption for these supplies was based on 

observations during the field demonstration. Unit 

prices for these supplies were based on price quotes 

from independent vendors of field equipment. 

Additional costs could include purchase of disposable 

acrylic discs rather than the quartz discs if the user 

wishes to eliminate disc cleaning efforts. 

The PicoTAX was operated for five days at the 

demonstration site, and two days in Berlin, to 

complete the analysis of all 326 samples. The 

supplies required to process samples were similar for 

all XRF instruments that participated in the 

demonstration and were estimated to cost about $245 

for 326 samples or $0.75 per sample. 

8.3 Labor Costs 

Labor costs were estimated based on the total time 

required by the field team to complete the analysis of 
__________________________________________________________________________________

62 

all 326 samples and the number of people in the field 

team, while making allowances for field team 

members that had responsibilities other than sample 

processing during the demonstration. For example, 

some developers sent sales representatives to the 

demonstration to communicate with visitors and 

provide outreach services; this type of staff time was 

not included in the labor cost analysis. 

While overall labor costs were based on the total time 

required to process samples, the time required to 

complete each definable activity was also measured 

during the field demonstration. These activities 

included: 

• Initial setup and calibration. 

• Sample preparation. 

• Sample analysis. 

• Daily shutdown and startup. 

• End of project packing. 

The estimated time required to complete each of 

these activities using the PicoTAX is listed in Table 

8-2. The “total processing time per sample” was 

calculated as the sum of all these activities assuming 

that the activities were conducted sequentially; 

therefore, it represents how much time it would take 

a single trained analyst to complete these activities. 

However, the “total processing time per sample” does 

not include activities that were less definable in terms 

of the amount of time taken, such as data 

management and procurement of supplies, and is 

therefore not a true total. 

The time to complete each activity using the 

PicoTAX is compared with the average of all XRF 

instruments in Table 8-2 and is compared with the 

range of all XRF instruments in Figure 8-1. In 

comparison to other XRF analyzers, the PicoTAX 

exhibited higher-than-average times except for daily 

shutdown and startup and end of project packing. 

Further, Rontec used a three-person team to operate 

the instrument during the field demonstration, 

whereas the field teams used by other developers 

included only one or two people. 

Table 8-2. Time Required to Complete Analytical 

Activities1

Activity PicoTAX Average2

Initial Setup and Calibration 90 54 

Sample Preparation 5.9 3.1 

Sample Analysis 12.5 6.7 

Daily Shutdown/Startup 0 10 

End of Project Packing 20 43 

Total Processing Time per 

Sample 18.7 10.0 

Notes: 

1

 All estimates are in minutes 

2

 Average for all eight XRF instruments in the 

demonstration 

The Rontec field team expended about 138 manhours to complete all sample processing activities 

during the field demonstration using the PicoTAX. 

This was significantly higher than the overall average 

of 69 hours for all instruments that participated in the 

demonstration. The primary reasons that labor hours 

were higher for the PicoTAX include: 

• The unique sample preparation protocol 

employed by Rontec, as described in Section 6.3, 

required substantial more time than the sample 

preparation procedures employed by other 

instruments. 

• The instrument run time of 10 minutes was 

longer than most other instruments. 

As noted by Rontec, however, the instrument run 

time could be reduced to 5 minutes without 

significantly affecting precision and accuracy. This 

would directly reduce the time required for sample 

analysis and significantly reduce the labor hours. 

Use of the autosampler saved significantly on the 

time required for sample analysis and the associated 

labor hours during the field demonstration. 

8.4 Comparison of XRF Analysis and 

Reference Laboratory Costs 

Two scenarios were evaluated to compare the cost for 

XRF analysis using the PicoTAX with the cost of 

fixed-laboratory analysis using the reference 

methods. Both scenarios assumed that 326 samples 

were to be analyzed, as in the field demonstration. 
__________________________________________________________________________________

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 PicoTAX versus other XRF instruments. 

The first scenario assumed that only one element was 

to be measured in a metal-specific project or 

application (for example, lead in soil, paint, or other 

solids) for comparison to laboratory per-metal unit 

costs. The second scenario assumed that 13 elements 

were to be analyzed, as in the field demonstration, for 

comparison to laboratory costs for a full suite of 

metals. However, Rontec did not report data for 

antimony during the field demonstration; thus, the 

second scenario includes only 12 elements for the 

PicoTAX. 

Typical unit costs for fixed-laboratory analysis using 

the reference methods were estimated using average 

costs from Tetra Tech’s basic ordering agreement 

with six national laboratories. These unit costs 

assume a standard turnaround time of 21 days and 

standard hard copy and electronic data deliverables 

that summarize results and raw analytical data. No 

costs were included for field labor that would be 

specifically associated with off-site fixed laboratory 

analysis, such as sample packaging and shipment. 

The cost for XRF analysis using the PicoTAX was 

based on equipment rental for 1 week, along with 

labor and supplies estimates established during the 

field demonstration. Sample preparation and sample 

analysis labor were estimated based on the observed 

division of responsibilities during the field 

demonstration, wherein Rontec utilized two people to 

prepare samples and one person to monitor the 

spectrometer and manage data on the laptop 

computer,. Additional sample preparation labor was 

added for drying, grinding, and homogenizing the 

samples (estimated at 10 minutes per sample) since 

these additional steps in sample preparation are 

required for XRF analysis but not for analysis in a 

fixed laboratory. A typical cost for managing 

investigation-derived waste (IDW), including general 

trash, personal protective equipment, wipes, and soil, 

was also added to the cost of XRF analysis because 

IDW costs are included in the unit cost for fixedlaboratory analysis. Since the cost for XRF analysis 

of one element or multiple elements does not vary 

significantly (all target elements are determined 

PicTAX 

Range for all eight XRF instruments 
__________________________________________________________________________________

64 

simultaneously when a sample is analyzed), the 

PicoTAX analysis cost was not adjusted for one 

element versus 12 elements. 

Table 8-3 summarizes the costs for the PicoTAX 

versus the cost for analysis in a fixed laboratory. 

This comparison shows that the PicoTAX compares 

favorably to a fixed laboratory in terms of overall 

cost when a large number of elements are to be 

determined. The PicoTAX compares unfavorably to 

a fixed laboratory when one element are to be 

determined. Use of the PicoTAX will likely produce 

additional cost savings, however, because analytical 

results will be available within a few hours after 

samples are collected, thereby expediting project 

decisions and reducing or eliminating the need for 

additional mobilizations. 

The total cost for the PicoTAX in the example 

scenario (326 samples) was estimated at $14,678, 

whether one or a number of elements was analyzed. 

This estimate compares with the average of $8,932 

for all XRF instruments that participated in the 

demonstration. However, it should be noted that 

bench-top instruments, such as the PicoTax, are 

known to cost more than hand-held instruments that 

were included in the calculation of the average cost 

for all XRF instruments. In comparison to other 

bench-top XRF instruments, the PicoTAX cost for 

the example scenario only slightly exceeded other 

instruments. 

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

Analytical Approach Quantity Item 

Unit 

Rate Total

 

PicoTAX (1 to 12 elements)

Shipping 1 Roundtrip $750 $750

Weekly Rental1 1 Week $5,2001 $5,200

Supplies 326 Sample $0.75 $245

Labor 192 Hours $43.75 $8,393

IDW N/A Each N/A $90

Total PicoTAX Analysis Cost (1 to 12 elements) $14,678

 

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 (12 elements) $63,896

Notes: 

1

 Estimated value as Rontec currently does not have a rental rate for the PicoTAX. 
__________________________________________________________________________________

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 Rontec PicoTAX XRF 

analyzer. The evaluation design incorporated 13 

target elements, 70 distinct sample blends, and a total 

of 326 samples. The blends included both soil and 

sediment samples from nine sampling locations. A 

rigorous program of sample preparation and 

characterization, reference laboratory analysis, 

QA/QC oversight, and data reduction supported the 

evaluation of XRF instrument performance. 

One important aspect of the demonstration was the 

sample blending and processing procedures 

(including drying, sieving, grinding, and 

homogenization) performed prior to the demonstration that significantly reduced uncertainties 

associated with the demonstration sample set. These 

procedures minimized the impacts of heterogeneity 

on method precision and on the comparability 

between XRF data and reference laboratory data. In 

like manner, project teams are encouraged to assess 

the effects of sampling uncertainty on data quality 

and to adopt appropriate sample preparation 

protocols before XRF is used for large-scale data 

collection, particularly if the project will involve 

comparisons to other methods (such as off-site 

laboratories). An initial pilot-scale method 

evaluation, carried out in cooperation with an 

instrument vendor, can yield site-specific standard 

operating procedures for sample preparation and 

analysis to ensure that the XRF method will meet 

data quality needs, such as accuracy and sensitivity 

requirements. A pilot study can also help the project 

team develop an initial understanding of the degree 

of correlation between field and laboratory data. This 

type of study is especially appropriate for sampling 

programs that will involve complex soil or sediment 

matrices with high concentrations of multiple 

elements because the demonstration found that XRF 

performance was more variable under these 

conditions. Initial pilot studies can also be used to 

develop site-specific calibrations, in accordance with 

EPA Method 6200, that adjust instrument algorithms 

to compensate for matrix effects. 

The findings of the evaluation of the PicoTAX for 

each primary and secondary objective of the 

technology demonstration are summarized in Tables 

9-1 and 9-2. The PicoTAX and the average 

performance of all eight instruments that participated 

in the XRF technology demonstration are compared 

in Figure 9-1. The comparison in Figure 9-1 

indicates that, when compared with the mean 

performance of all eight XRF instruments, the 

PicoTAX showed: 

• Equivalent or better MDLs for only two elements 

including arsenic and selenium (iron was not 

included in the MDL evaluation). 

• Equivalent or better accuracy (lower RPDs) for 

11 target elements (cadmium was the lone 

exception). 

• Equivalent or better precision (lower RSDs) for 

no target elements. 

As a transportable bench-top instrument that requires 

AC power, the PicoTAX must be operated in a 

mobile laboratory or other stable environment, and 

cannot be used for in situ soil analysis. Although 

good overall performance was observed for this 

instrument, the metal-ceramic x-ray tube used in this 

instrument produced poor results for cadmium and 

silver and precluded the reporting of any results for 

antimony (reducing the number of target elements 

from 13 to 12 for the PicoTAX). Moreover, a 

rigorous sample preparation protocol was applied by 

the developer during the demonstration to convert 

small aliquots of sample into emulsified residues on 

quartz disks for analysis. This on-site preparation 

protocol required additional equipment and space, 

reduced sample throughput, and may have also 

reduced analytical precision. 
________________________________________________________________________

66

Table 9-1. Summary of Rontec PicoTAX Performance – Primary Objectives 

Objective Performance Summary 

P1: Method 

Detection Limits 

• Low numbers of detections in the MDL blends produced limited data 

and therefore, uncertainty in the MDL calculations for cadmium, 

mercury, selenium, and silver. 

• Mean MDLs for the target elements ranged as follows: 

o MDLs of 1 to 20 ppm: selenium. 

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

o MDLs of 50 to 100 ppm: mercury, nickel, and zinc. 

o MDLs of greater than 100 ppm: cadmium, chromium, lead, and 

silver. (MDLs were greater than 500 ppm for cadmium and 

silver. Iron was not included in the MDL evaluation.) 

• The MDLs calculated for the PicoTAX were generally lower than 

reference MDL data from EPA Method 6200 (higher MDLs were 

observed only for lead). 

P2: Accuracy and 

Comparability 

• Median RPDs relative to reference laboratory data revealed the 

following, with lower RPDs indicating greater accuracy: 

o RPDs less than 10 percent: none. 

o RPDs of 10 to 25 percent: arsenic, chromium, copper, iron, 

lead, nickel, selenium, silver, vanadium, and zinc. 

o RPDs of 25 to 50 percent: mercury. 

o RPDs of greater than 50 percent: cadmium. 

• Correlation plots relative to reference laboratory data indicated: 

o High correlation coefficients (greater than 0.9) for seven of the 

12 target elements evaluated. However, the high correlation 

observed for one of these elements, mercury, was artificially 

improved by a few extreme concentrations. 

o Moderate correlation coefficients for cadmium, copper, 

selenium, silver, and vanadium. 

o High biases in the XRF data versus the lab data for cadmium 

and lead. A low bias was observed for mercury. 

• Significant uncertainty was introduced into the accuracy assessment for 

cadmium and silver because the low sensitivity of the instrument 

limited the sample blends available for evaluation. 

P3: Precision • Median RSDs for sample replicates were as follows, with lower RSDs 

indicating greater precision: 

o RSDs below 5 percent: none. 

o RSDs between 5 and 10 percent: selenium, 

o RSDs between 10 and 20 percent: arsenic, copper, iron, lead, 

nickel, vanadium, and zinc. 

o RSDs greater than 20 percent: cadmium, chromium, mercury, 

and silver. 

• RSDs were slightly higher (that is, precision was lower) in the lowest 

concentration sample blends for many of the target elements, indicating 

a slight concentration dependence for precision. 

• For all 12 of the target elements evaluated, median RSDs for the 

PicoTAX were higher than the RSDs for the reference laboratory data, 

indicating better precision for the reference laboratory. 
________________________________________________________________________

67

Table 9-1. Summary of Rontec PicoTAX Performance – Primary Objectives (continued) 

Objective Performance Summary 

P4: Effects of 

Sample 

Interferences 

• High relative concentrations (greater than 10X) of lead as an interfering 

element reduced accuracy for arsenic from “good” (median RPDs 

between 10 percent and 25 percent) to “fair” (median RPDs between 25 

and 50 percent). Further, the high concentrations of lead produced an 

increasingly low bias in arsenic results. 

• Similar effects (decreasing accuracy from good to fair, and an 

increasing negative bias) were observed for nickel in samples 

containing high concentrations of copper as an interferent. 

• Evaluation of high concentrations of nickel on copper, copper on zinc, 

and zinc on copper did not appear to show significant interference 

effects. 

P5: Effects of Soil 

Type 

• Low relative accuracy was observed for cadmium and nickel in blends 

of roaster slag from the Wickes Smelter site, which contained high 

overall element concentrations. 

• Slightly higher numbers of extreme RPDs were observed in blends from 

the Torch Lake site (copper, selenium, vanadium, zinc), the Sulfur Bank 

mine (mercury), and the Ramsey Flats site (silver). However, the 

evaluation found that sample matrix had a minor overall effect on 

accuracy for the PicoTAX. 

P6: Sample 

Throughput 

• Rontec’s rigorous sample preparation of protocol that included grinding 

the soil, creating a suspension, spiking internal standard, applying 

droplets of the suspension to a quartz disc, and then drying the disc to 

produce a thin residue for analysis took an average of 5.9 minutes per 

sample. 

• With an average instrument analysis time of 12.5 minutes per sample, 

the total sample processing time was 18.7 minutes per sample. 

• A maximum sample throughput of 66 samples per day (three batches of 

22 samples) was achieved during the demonstration by loading one 

sample batch into the autosampler to run overnight after sample 

preparation during the day. A more typical sample throughput was 

estimated to be 44 samples per day (two batches of 22 samples) for an 

8-hour work day. 

P7: Costs • Purchase cost is about $99,990 for the instrument as equipped in the 

demonstration (with autosampler, sample preparation equipment, and 

laptop PC). The purchase cost includes training. 

• The Rontec field team expended approximately 138 man-hours to 

complete the processing of the demonstration sample set (326 samples). 

In comparison, the average for all participating XRF instruments was 69 

man-hours. 

• By approximating a 1-week rental cost (based on similar bench-top 

instruments) and adding labor and shipping/supplies costs, a total 

project cost of $14,678 was estimated for a project the size of the 

demonstration. In comparison, the average project cost for all 

participating XRF instruments was $8,932 and for fixed-laboratory 

analysis of all 13 elements was $63,896. 
________________________________________________________________________

68

Table 9-2. Summary of Rontec PicoTAX Performance – Secondary Objectives 

Objective Performance Summary 

S1: Training 

Requirements 

• Field or laboratory technicians that have some familiarity with analytical 

chemistry and spectroscopy are qualified to operate the PicoTAX. 

• Rontec offers unlimited product support throughout the lifetime of the 

instrument, including on-line support and training as needed. Instrument 

purchase costs include a required 2-day training program ($4,600 

separately). 

• Detailed instrument and software manuals, as well as application notes, 

assist operators with soil analysis. 

S2: Health and 

Safety 

• The PicoTAX’s x-ray tube is totally encased and emits no detectable 

radiation outside of the instrument cabinet. 

• Acetone is used in the sample preparation process. This solvent is 

flammable and toxic, but exposure can be eliminated by using 

disposable acrylic disks. 

S3: Portability • Based on dimensions, weight, and power requirements, the PicoTAX is 

a transportable instrument and is designed to be used on a table top or 

possibly a truck bed. Required accessories for efficient sample 

processing include the autosampler, sample holders, a laptop, and 

sample preparation equipment. 

• The instrument and its laptop computer, along with an analytical balance 

and hotplate, require 110 volt AC power. 

S4: Durability • The PicoTAX’s x-ray tube is warranted for 2,500 hours, with an 

anticipated lifetime of 10,000 hours. 

• The instrument is fully warranted for 1 year, and software is upgradeable 

for 2 years at no cost. 

• The instrument is operational up to 40°C and 80 percent humidity. It 

requires a stable operating environment and protection from weather. 

S5: Availability • In November, 2005, Rontec was acquired by Bruker AXS Inc. with 

several world-wide offices, including Berlin, Germany and Madison, 

Wisconsin. 

• The PicoTAX is available for purchase only; no rental or long-term 

leasing options are currently available. 
______________________________________________________________________________ 

69 

Comparison of Mean MDLs: 

PicoTAX vs. All XRF Instruments

0

100

200

300

400

500

600

Arsenic

Cadmium

Chromium

Copper

Lead

Mercury

Nickel

Selenium

Silver

Vanadium

Zinc

Target Element

Mean MDL in 

Parts Per Millio

n

PicoTAX Mean MDL

All Instrument Mean MDL

Comparison of Median RPDs: 

PicoTAX vs. All XRF Instruments

0%

20%

40%

60%

80%

100%

Arsenic

Cadmium

Chromium

Copper

Iron

Lead

Mercury

Nickel

Selenium

Silver

Vanadium

Zinc

Target Element

Relative Percent 

Difference (RPD)

PicoTAX Median RPD

All Instrument Median RPD

Comparison of Median RSDs: 

PicoTAX vs. All XRF Instruments

0%

10%

20%

30%

40%

50%

60%

Arsenic

Cadmium

Chromium

Copper

Iron

Lead

Mercury

Nickel

Selenium

Silver

Vanadium

Zinc

Target Element

Relative Standard Deviatio

n

(RSD), Percent

PicoTAX Median RSD

All Instrument Median RSD

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

comparison to the average of all eight XRF instruments.
______________________________________________________________________________ 

70 

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______________________________________________________________________________ 

71 

Chapter 10 

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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 XMET® 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 costeffective technologies. The program assists and informs those involved in designing, distributing, permitting, and 

purchasing environmental technologies. This document summarizes the results of a demonstration of the Rontec 

PicoTAX hand-held x-ray fluorescence (XRF) analyzer for the analysis of 12 target elements in soil and sediment, 

including arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc. 

(One other target element for the demonstration, antimony, could not be analyzed by the PicoTAX.) 

PROGRAM OPERATION 

Under the SITE MMT Program, with the full participation of the technology developers, EPA evaluates and 

documents the performance of innovative technologies by developing demonstration plans, conducting field tests, 

collecting and analyzing demonstration data, and preparing reports. The technologies are evaluated under rigorous 

quality assurance protocols to produce well-documented data of known quality. EPA’s National Exposure 

Research Laboratory, which demonstrates field sampling, monitoring, and measurement technologies, selected 

Tetra Tech EM Inc. as the verification organization to assist in field testing technologies for measuring trace 

elements in soil and sediment using XRF technology. 

DEMONSTRATION DESCRIPTION 

The field demonstration of eight XRF instruments to measure trace elements in soil and sediment was conducted 

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

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

instrument, including the PicoTAX, during the field demonstration. These samples were derived from 70 different 

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

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

blends were also spiked to further adjust and refine the concentration ranges of the target elements. Between three 

TECHNOLOGY TYPE: X-ray Fluorescence (XRF) Analyzer 

APPLICATION: MEASUREMENT OF TRACE ELEMENTS IN SOIL AND SEDIMENT 

TECHNOLOGY NAME: PicoTAX XRF Analyzer 

COMPANY: Rontec 

ADDRESS: 90 Martin Street 

 Carlisle, MA 01741 

Telephone: (800) 875-1578 

Fax: (978) 266-2900 

Email: psmith@RONTECusa.com

Internet: www.RONTEC.com
A-2 

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 SW846 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 Rontec PicoTAX XRF analyzer. 

More detailed discussion can be found in the Innovative Technology Verification Report – XRF Technologies for

Measuring Trace Elements in Soil and Sediment: Rontec PicoTAX XRF Analyzer (EPA/540/R-06/005). 

TECHNOLOGY DESCRIPTION 

XRF spectroscopy is an analytical technique that exposes a sample (soil, alloy metal, filters, other solids, and thin 

samples) to an x-ray source. The x-rays from the source have the appropriate excitation energy that causes 

elements in the sample to emit characteristic x-rays. A qualitative elemental analysis is possible from the 

characteristic energy, or wavelength, of the fluorescent x-rays emitted. A quantitative elemental analysis is 

possible from the number (intensity) of x-rays at a given wavelength. 

The PicoTAX is a portable bench-top device that provides quantitative and semi-quantitative multi-element 

microanalysis of soils and sediments using total reflection XRF spectroscopy. The spectrometer includes a 40-watt 

metal-ceramic tube excitation source and a thermoelectrically cooled, silicon drift detector. The XRF analyzer is 

capable of detecting up to 75 elements from aluminum (atomic number [Z] = 13) to yttrium (Z = 39) and from 

palladium (Z = 46) to uranium (Z = 92). According to Rontec, the molybdenum tube source used for the 

demonstration displays poor performance for antimony, cadmium, and silver. (Although Rontec proceeded to 

report data for cadmium and silver, the demonstration confirmed poor overall performance for these metals.) 

The PicoTAX uses an internal standard for instrument calibration, thus an initial calibration is not required. A 

solution of an internal standard element (gallium was selected for the demonstration) is added to each sample to 

establish response factors (determined by the software). Element quantitation is determined by comparing the 

response of the unknown elements to the response of the internal standard that has a known concentration. The 

PicoTAX analysis method requires a rigorous sample preparation protocol that involves grinding a small soil 

aliquot (150 mg), emulsifying it, spiking the internal standard, applying drops of the emulsion to quartz disks, and 

drying the disks to create a uniform film. The dried disks are loaded on the instrument’s autosampler in batches of 

25 samples. 

VERIFICATION OF PERFORMANCE 

Method Detection Limit (MDL): MDLs were calculated using seven replicate analyses from each of 12 lowconcentration sample blends, according to the procedure described in Title 40 Code of Federal Regulations (CFR) 

Part 136, Appendix B, Revision 1.11. A mean MDL was further calculated for each element. The ranges into 

which the mean MDLs fell for the PicoTAX are listed below. 

Relative Sensitivity Mean MDL Target Elements 

High 1 – 20 ppm Selenium. 

Moderate 20 – 50 ppm Arsenic, Copper, and Vanadium. 

Low 50 – 100 ppm Mercury, Nickel, and Zinc. 

Very Low > 100 ppm Cadmium, Chromium, Lead, and Silver. 

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 PicoTAX results with the reference laboratory 

data. Accuracy was assessed by calculating the absolute relative percent difference (RPD) between the mean XRF 

and the mean reference laboratory concentration for each blend. Accuracy of the PicoTAX was classified from 

high to very low for the various target elements, as indicated in the table below, based on the overall median RPDs 

for the demonstration. 

Relative Accuracy Median RPD Target Elements 

High 0% - 10% None. 

Moderate 10% - 25% Arsenic, Chromium, Copper, Iron, Lead, Nickel, Selenium, Silver, 

Vanadium, and Zinc. 

Low 25% - 50% Mercury. 

Very Low > 50% Cadmium. 

Accuracy was also assessed through correlation plots between the mean PicoTAX and mean reference laboratory 

concentrations for the various sample blends. Correlation coefficients (r2

) for linear regression analysis of the plots 

are summarized below, along with any significant biases apparent from the plots in the XRF data versus the 

reference laboratory data. 

Arsenic 

Cadmium 

Chromium 

Copper 

Iron 

Lead 

Mercury 

Nickel 

Selenium 

Silver 

Vanadium 

Zinc 

Correlation 0.95 0.62 0.95 0.86 0.95 0.94 0.99 0.96 0.70 0.58 0.89 0.97 

Bias -- High -- -- -- High Low -- -- -- -- -- 

Notes: -- = No significant bias 

Precision: Replicates were analyzed for all sample blends. Precision was evaluated by calculating the standard 

deviation of the replicates, dividing by the average concentration of the replicates, and multiplying by 100 percent 

to yield the relative standard deviation (RSD) for each blend. Precision of the PicoTAX was classified from high to 

very low for each target element, as indicated in the table below, based on the overall median RSDs. These results 

indicated a lower level of precision in the PicoTAX data than in the reference laboratory data for all 12 of the target 

elements. 

Relative Precision Median RSD Target Elements 

High 0% - 5% None. 

Moderate 5% - 10% Selenium. 

Low 10% - 20% Arsenic, Copper, Iron, Lead, Nickel, Vanadium and Zinc. 

Very Low > 20% Cadmium, Chromium, Mercury, and Silver. 

Effects of Interferences: The RPDs from the evaluation of accuracy were further grouped and compared for a few 

elements of concern (arsenic, nickel, copper, and zinc) based on the relative concentrations of potentially 

interfering elements. Accuracy for arsenic was reduced from “moderate” (median RPDs of 10 percent to 25 

percent) to “low” (median RPDs between 25 and 50 percent) by high relative concentrations of lead (greater than 

10X the arsenic concentration). Similarly, accuracy for nickel was reduced from “moderate” to “low” by high 

relative concentrations of copper. Low biases were produced in both the arsenic and nickel results by these 

interferences. 

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

sampling site and soil type. This evaluation found high outlier RPD values, indicating low relative accuracy, for 

cadmium and nickel in blends of roaster slag from the Wickes Smelter site. These blends contained high overall 

element concentrations. Extreme RPDs were also observed in other blends of mining wastes from the Sulfur Bank 

Mercury Mine (mercury), the Ramsey Flats site (silver), and the Torch Lake site (multiple elements). However, the 

evaluation found that sample matrix had a minor overall effect on accuracy for the PicoTAX. 
A-4 

Sample Throughput: The total processing time per sample was estimated at 18.7 minutes, which included 5.9 

minutes of sample preparation and 12.5 minutes of instrument analysis time. On this basis, a sample throughput of 

44 samples per 8-hour work day was estimated with the use of the instrument’s autosampler. As noted above, 

however, the sample blends had undergone rigorous pre-processing before the demonstration. Sample throughput 

would have decreased if these sample preparation steps (grinding, drying, sieving) had been performed during the 

demonstration; these steps can add from 10 minutes to 2 hours to the sample processing time. 

Costs: A cost assessment identified a purchase cost of $99,990 for the PicoTAX as equipped for the 

demonstration. Using a hypothetical rental cost approximated from similar types of instruments, a total cost of 

$14,678 (with a labor cost of $8,393 at $43.75/hr) was estimated for a project similar to the demonstration (326 

samples of soil and sediment). In comparison, the project cost averaged $8,932 for all eight XRF instruments 

participating in the demonstration and $63,896 for fixed-laboratory analysis of all 13 target elements. 

Skills and Training Required: Field or laboratory technicians that have some familiarity with analytical 

chemistry and spectroscopy are qualified to operate the PicoTAX. Rontec offers product support as required 

throughout the lifetime of the instrument, including on-line support and training. A mandatory 2-day introductory 

training course is included in the instrument purchase cost. Detailed instrument and software manuals, as well as 

application notes, assist operators with soil analysis. 

Health and Safety Aspects: The PicoTAX’s x-ray tube is totally encased and emits no detectable radiation outside 

of the instrument cabinet. Acetone is used to clean the quartz disks in the sample preparation process, but use of 

acetone can be eliminated by using disposable acrylic disks. 

Portability: Based on dimensions (42 X 59 X 30 centimeters) and weight (28 kilograms), the PicoTAX is a 

transportable instrument, designed to be used on a table top or possibly a truck bed. Required accessories for 

efficient sample processing include the autosampler, sample holders, a laptop, and sample preparation equipment. 

The instrument and its laptop computer, along with an analytical balance and hotplate for sample preparation, 

require 110 volt AC power. 

Durability: The PicoTAX’s x-ray tube is warranted for 2,500 hours, with an anticipated lifetime of 10,000 hours. 

The instrument is fully warranted for 1 year, and software is upgradeable for 2 years at no cost. The instrument is 

operational up to 40°C and 80 percent humidity. It requires a stable operating environment and protection from 

weather. 

Availability: Rontec maintains offices in Berlin, Germany, and Carlisle, Massachusetts. There are currently no 

third-party distributors in the U.S. The PicoTAX is available for purchase only; no rental or long-term leasing 

options are currently available. 

RELATIVE PERFORMANCE 

The performance of the PicoTAX relative to the average of all eight XRF instruments that participated in the 

demonstration is shown below: 

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

Sensitivity Same о о о о о о о Same о о о

Accuracy ● о ● ● ● Same ● ● ● ● ● ●

Precision о о о о о о о о о о о о

Key: ● Better о Worse NC No MDL Calculated 

NOTICE: Verifications are based on an evaluation of technology performance under specific, predetermined criteria 

and the appropriate quality assurance procedures. EPA makes no expressed or implied warranties as to the 

performance of the technology and does not certify that a technology will always operate as verified. The end user is 

solely responsible for complying with any and all applicable federal, state, and local requirements.
 

APPENDIX B 

DEVELOPER DISCUSSION 
B-1 

DEVELOPER DISCUSSION 

1. Recent Technological Improvements 

1.1 Introduction 

The results of the EPA SITE demonstration measurements have shown several benefits of the PicoTAX 

TXRF spectrometer but also some analytical restrictions which desire technical improvements. The 

following sections discuss the objectives of the performance evaluation and how the performance could be 

improved. 

1.2 Method Detection Limits 

In addition to counting statistics and instrument sensitivity, the major limiting factor for MDLs is the 

reproducibility of measurement results when analysing elements close to the expected MDL. 

In TXRF analysis the small analysed sample amount restricts the reproducibility because small 

inhomogeneities of element distribution will have a large influence. In addition, the detector of the 

PicoTAX TXRF spectrometer is equipped with an active area of 10 mm2

, while the average sample area is 

about 30 – 40 mm2

. Thus, the complete sample is not taken into account for data acquisition. 

Two recent developments have improved the performance of the PicoTAX TXRF spectrometer and 

increased the quality of MDLs. First, the line focus X-ray tube was replaced by a micro focus tube. The 

improvement of excitation intensity can be estimated to be approximately 60 %. In addition, a 30 mm2

detector was introduced recently. This led to an average increase of signal intensity of 200 %. As a second 

positive effect, the new detector influences the overall counting statistics by increasing the actually 

analyzed sample area by a factor of three. 

To evaluate the benefits of these technical improvements for the MDLs, the reproducibility measurements 

of 12 soil and sediment samples were repeated. The sample preparation and measurement conditions were 

exactly the same as during the first measurement campaign. A summary of the results is given in Table 1; 

the complete data set can be found at the end of this chapter (Table 4). As the quality of measurement 

results for the elements antimony, cadmium and silver is poor in general, the MDLs for these elements are 

displayed in parentheses and are approximate. 
B-2 

Table 1. Comparison of Old PicoTAX-, new PicoTAX- and All XRF 

 Instrument Mean-MDLs. All Values are Given in mg/kg. 

 

 

Element 

PicoTAX 

Mean MDLs 

Old Values 

PicoTAX 

Mean MDLs 

New Values 

All XRF 

Instrument 

Mean MDLs 

Antimony NC (167) 61 

Arsenic 23 15 26 

Cadmium 529 (329) 70 

Chromium 109 30 83 

Copper 29 9 23 

Lead 105 37 40 

Mercury 84 16 23 

Nickel 78 28 50 

Selenium 9 7 8 

Silver 539 (58) 42 

Vanadium 44 37 28 

Zinc 73 39 38 

It is obvious that the application of the recent technology enhancements lead to a distinct improvement of 

the MDLs for some elements up to a factor of 3 to 4. 

1.3 Accuracy and comparability 

The larger detector area will certainly improve the accuracy of the PicoTAX. For a detailed evaluation of 

the improvements, the analysis of the complete set of 326 samples would be necessary. Therefore, only a 

qualitative assessment of the improvements can be provided at this point. Since for a detailed evaluation of 

accuracy and comparability the complete set of 326 samples would have to be analyzed, only an 

assessment of possible improvements by the recent technology enhancements is possible. Due to the larger 

detected sample area, samples with inhomogeneous element distribution will deliver more accurate results. 

The enhanced MDL will allow the analysis of elements in concentrations which were not detectable with 

the original equipment. 

The quality of measurement results for the elements antimony, cadmium and silver can not be improved 

significantly by the introduction of a micro focus tube and a larger detector. As mentioned in the previous 

sections, the detection of these elements is limited to the L-lines when applying a Mo tube. In soil and 

sediment samples, these lines are completely overlapped by the K-lines of the matrix elements calcium 

and potassium. A technical solution can be an alternative excitation source. Recently, initial measurements 

with a W-anode tube have been performed successfully. Figure 1 shows a TXRF spectra of a soil sample, 

containing 64 mg/kg of Cd. A commercially available system with W-excitation is planned to be released 

mid-2006. 
B-3 

 

Figure 1. TXRF spectra of a soil sample analysed with W-excitation. 

1.4 Precision 

The precision defined by the Relative Standard Deviation (RSD) can be assessed on the RSD values of the 

repetitive MDL measurements. A comparison of the ranges of median RSDs according to the 

classification described in chapter 7.3 is summarized in Table 2. The corresponding data set is given in 

Table 5 at the end of this chapter. 

Table 2. Comparison of Old and New RSD Values for the PicoTAX TXRF Spectrometer 

 Old values New values 

Arsenic Moderate Moderate 

Cadmium High High 

Chromium High High 

Copper Moderate Low 

Iron Moderate Low 

Lead Moderate Moderate 

Mercury High High 

Nickel Moderate Moderate 

Selenium Low Low 

Silver High High 

Vanadium Moderate Moderate 

Zinc Moderate Moderate 

 
B-4 

Although numerical enhancements are visible, a step into better classification ranges could just be 

achieved for the elements copper and iron. 

2. Analysis of Digested Soils and Sediments 

In contrast to common XRF systems, the application of TXRF spectroscopy is capable for trace element 

analysis in liquids. For an assessment of this laboratory based analysis, two samples from the EPA SITE 

program were analysed after microwave digestion. Microwave digestion was performed according to the 

EPA Method 3051; 10 μl of Ga solution (Merck, 1 g/L) were added to 1 ml of the digested solution for 

internal standardisation. After the resulting solution was thoroughly homogenized, an aliquot of 10 μL was 

transferred onto a quartz glass sample carrier and dried on a heating plate. TXRF analysis was performed 

with the same instrument as described in chapter 6.0 by applying measurement times of 600 seconds. The 

results of the measurements are summarized in Table 3. 

Table 3. Comparison of Reference Laboratory Values and PicoTAX Results of Microwave 

Digested Samples. All values in mg/kg. 

Sample CN-SO-03 KP-SO-02 

Element EPA values PicoTAX values EPA values PicoTAX values 

Arsenic 120 106 1.2 1.0 

Cadmium 88 Not detected Not detected Not detected 

Chromium 18 17 350 329 

Copper 100 76 31 26 

Iron 20,000 20,611 1,400 1,592 

Lead 180 179 580 588 

Mercury 42 Not detected 0.91 Not detected 

Nickel 110 74 150 167 

Selenium 52 41 Not detected Not detected 

Silver 130 Not detected 0.059 Not detected 

Vanadium 36 27 1.7 Not detected 

Zinc 78 69 15 10 

Barium Not analysed 95 Not analysed Not detected 

Bromine Not analysed 1.0 Not analysed 3.0 

Calcium Not analysed 2 854 Not analysed 217 

Manganese Not analysed 227 Not analysed 33 

Potassium Not analysed 1 961 Not analysed 23 

Rubidium Not analysed 39 Not analysed 3 

Strontium Not analysed 65 Not analysed Not detected 

Thorium Not analysed 65 Not analysed Not detected 

Titanium Not analysed 391 Not analysed 20 

Yttrium Not analysed 22 Not analysed Not detected 

Obviously, all values obtained after analysis of microwave digested samples show accuracies which can 

be classified either as “very good” or “good”. As digestion of the samples has no influence on the matrix 

composition, antimony, cadmium and silver could still not be analysed. The analysis of mercury after 

microwave digestion is not possible due to the volatility of this element. 

No MDL or RPD evaluation was performed for digested samples. But because one of the major limiting 

influences on these factors can be found in the sample inhomogeneity, values with increased quality can 

be expected. 
B-5 

Table 4. Evaluation of Sensitivity – Method Detection Limits for the Röntec PicoTAX (30 mm2 detec

Antimony Arsenic Cadmium 

Rontec Rontec 

Ref. 

Lab Rontec Rontec 

Ref. 

Lab Rontec Rontec Ref. Lab Ronte

Matrix Sample No. MDL Conc Conc MDL Conc Conc MDL Conc Conc MDL Soil AS-SO-01 NC NA ND 4 3 24 NC NA 62 NC Soil BN-SO-01 NC NA 140 NC 1632 1900 607 1399 1000 29 Soil KP-SO-01 27 207 270 NC NA 8 NC NA 0,1 5 Soil KP-SO-02 NC NA 6 6 4 1 NC NA ND 85 Soil SB-SO-02 NC NA ND 9 22 10 NC NA ND NC Soil SB-SO-03 NC NA 17 24 62 30 NC NA ND 11 Soil WS-SO-02 NC NA 110 NC 10808 6300 NC NA 170 33 Soil CN-SO-01 205 127 16 11 145 100 51 47 72 7 Sediment TL-SE-02 NC NA 2 5 18 10 NC NA ND 25 Sediment RF-SE-02 NC NA 2 57 277 220 NC NA 11 12 Sediment LV-SE-01 NC NA ND NC 767 800 NC NA ND 50 Sediment LV-SE-02 NC NA ND 3 59 31 NC NA ND 40 Mean Rontec MDL 167 15 329 30 
B-6 

Table 4. Evaluation of Sensitivity – Method Detection Limits for the Röntec PicoTAX (30 mm2 detector) – 

Copper Lead Mercury 

Rontec Rontec 

Ref. 

Lab Rontec Rontec 

Ref. 

Lab Rontec Rontec Ref. Lab Ronte

Matrix Sample No. MDL Conc Conc MDL Conc Conc MDL Conc Conc MDL Soil AS-SO-01 12 87 180 NC 1404 1900 NC NA 3 84 Soil BN-SO-01 NC 2384 3000 NC 12797 12000 NC NA 6 46 Soil KP-SO-01 NC 516 780 NC 18253 22000 NC NA 7 NC Soil KP-SO-02 7 20 31 32 615 580 NC NA 1 40 Soil SB-SO-02 4 41 52 24 5 22 45 25 66 39 Soil SB-SO-03 4 8 7 42 12 35 NC 4843 1900 3 Soil WS-SO-02 NC 3101 1900 NC 105085 50000 1 0,3 13 31 Soil CN-SO-01 11 78 86 87 126 150 10 15 41 10 Sediment TL-SE-02 NC 1601 2000 44 13 15 NC NA 1 13 Sediment RF-SE-02 NC 1396 1700 NC 707 700 10 15 6 16 Sediment LV-SE-01 14 36 46 23 9 30 NC NA 18 9 Sediment LV-SE-02 13 20 28 10 33 70 NC NA 22 15 Mean Rontec MDL 9 37 16 28 
B-7 

Table 4. Evaluation of Sensitivity – Method Detection Limits for the Röntec PicoTAX (30 mm2 detector) – 

Selenium Silver Vanadium 

Rontec Rontec 

Ref. 

Lab Rontec Rontec 

Ref. 

Lab Rontec Rontec Ref. Lab Ronte

Matrix Sample No. MDL Conc Conc MDL Conc Conc MDL Conc Conc MDL Soil AS-SO-01 NC NA 3 NC NA 4 17 59 53 NC Soil BN-SO-01 6 35 52 NC NA 150 30 71 44 NC Soil KP-SO-01 9 14 0,2 NC NA 1 NC NA 0,4 13 Soil KP-SO-02 NC NA ND NC NA 0,1 6 5 2 16 Soil SB-SO-02 NC NA 2 NC NA ND 13 140 66 80 Soil SB-SO-03 NC NA ND NC NA 0,2 44 136 9 NC Soil WS-SO-02 17 99 3,6 NC NA 230 NC NA 24 NC Soil CN-SO-01 7 40 41 58 71 100 42 68 30 63 Sediment TL-SE-02 1 1 ND NC NA 2 97 30 140 19 Sediment RF-SE-02 NC 1 ND NC NA 11 20 53 43 NC Sediment LV-SE-01 NC 2 14 NC NA ND 67 141 150 72 Sediment LV-SE-02 4 2 4 NC NA ND 34 171 46 13 Mean Rontec MDL 7 58 37 39 
B-8 

Table 5. Evaluation of Precision – Relative Standard Deviations for the Röntec PicoTAX (30 mm2 d

 AS-SO-01 

BN-SO01 CN-SO- 01 KP-SO-02 SB-SO-02 SB-SO-03 WS-SO- 02 LV-SE-01 LV-SE-02 

Antimony NC NC NC NC NC NC 8.3 1) NC NC Arsenic 45.6 3.5 2.4 50.0 13.5 12.4 12.5 9.4 1.8 Cadmium NC 13.8 100.9 NC NC NC 42.7 NC NC Chromium 48.6 12.5 80.1 8.8 42.2 7.7 38.5 22.5 35.0 Copper 4.4 3.5 4.5 10.3 3.2 14.9 8.4 12.0 20.3 Iron 3.4 4.1 11.3 13.3 2.0 8.1 15.6 2.7 6.0 Lead 3.2 2.8 21.9 1.7 (137.9) 2) (111.6) 2) 8.4 78.9 9.1 Mercury NC NC 21.3 NC 58.0 14.3 36.9 NC NC Nickel 55.1 14.7 3.8 9.0 6.5 6.3 23.7 13.8 5.3 Selenium NC 5.2 5.4 NC NC NC 20.3 NC (63.8) 2) Silver NC NC 89.8 NC NC NC NC NC NC Vanadium 9.4 13.4 20.0 (34.3) 2) 2.9 10.2 NC 15.2 6.3 Zinc 13.0 2.0 24.0 65.6 21.6 NC 10.1 16.7 5.5 

1) Sample with extraordinary element distribution (Sb ~ 2000 μg/kg, K and Ca ~ 3000 resp. 4000 mg/kg) 2) Element concentration close to or below the MDL. 
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 RESULTS ...............................................................................................C-3 

3.1 Holding Time.................................................................................................................................C-3 

3.2 Calibration.....................................................................................................................................C-3 

3.3 Laboratory Blanks.........................................................................................................................C-4 

3.4 Laboratory Control Samples .........................................................................................................C-5 

3.5 Matrix Spike Samples ...................................................................................................................C-5 

3.6 Serial Dilution Results ..................................................................................................................C-5 

3.7 ICP Interference Check Samples ..................................................................................................C-6 

3.8 Target Analyte Identification and Quantitation ............................................................................C-6 

3.9 Quantitation Limit Verification.....................................................................................................C-6

4.0 PRECISION, ACCURACY, REPRESENTATIVENESS, COMPLETENESS, AND 

COMPARABILITY EVALUATION SUMMARY .....................................................................C-6

4.1 Precision........................................................................................................................................C-7 

4.2 Accuracy .......................................................................................................................................C-7 

4.3 Representativeness ........................................................................................................................C-7 

4.4 Completeness ................................................................................................................................C-7 

4.5 Comparability................................................................................................................................C-7

5.0 CONCLUSIONS FOR DATA QUALITY AND DATA USABILITY .......................................C-8 

6.0 REFERENCES..............................................................................................................................C-8 

APPENDIX

DATA VALIDATION REPORTS
 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 
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laboratory and all participating technology vendors. As such, 326 prepared soil/sediment samples were 

delivered to Shealy for the measurement of total metals. The analytical program included the following 

analyses and methods: 

• Total metal for 22 analytes by inductively coupled plasma atomic emission spectroscopy 

(ICP-AES) according to EPA Methods 3050B/6010B (EPA 1996) 

• Total mercury by cold vapor atomic absorption spectroscopy (CVAA) according to EPA 

Method 7471A (EPA 1996) 

3.0 DATA VALIDATION RESULTS 

The parameters listed in Section 2.0 were evaluated during cursory review and full validation of analytical 

reports for all methods, as applicable. Each of the validation components discussed in this section is 

summarized as follows: 

• Acceptable – All criteria were met and no data were qualified on that basis 

• Acceptable with qualification – Most criteria were met, but at least one data point was 

qualified as estimated because of issues related to the review component 

Since no data were rejected, all data were determined to be either acceptable or acceptable with 

qualification. Sections 3.1 through 3.9 discuss each review component and the results of each. Tables 

that summarize the data validation findings follow Section 6.0 of this DVSR. Only qualified data are 

included in the tables. No reference laboratory data were rejected during the validation process. As such, 

all results are acceptable with the qualification noted in the sections that follow. 

3.1 Holding Time 

Acceptable. The technical holding times were defined as the maximum time allowable between sample 

collection and, as applicable, sample extraction, preparation, or analysis. The holding times used for 

validation purposes were recommended in the specific analytical methods (EPA 1996) and were specified 

in the QAPP (Tetra Tech 2005). 

Because the soil and sediment samples were prepared prior to submission to the reference laboratory, and 

because the preparation included drying to remove moisture, no chemical or physical (for example ice) 

preservation was required. The holding time for sample digestion was 180 days for the ICP-AES 

analyses and 28 days for mercury. All sample digestions and analyses were conducted within the 

specified holding times. No data were qualified based on holding time exceedances. This fact contributes 

to the high technical quality of the reference data. 

3.2 Calibration 

Acceptable. Laboratory instrument calibration requirements were established to ensure that analytical 

instruments could produce acceptable qualitative and quantitative data for all target analytes. Initial 

calibration demonstrates that the instrument is capable of acceptable performance at the beginning of an 

analytical run, while producing a linear curve. Continuing calibration demonstrates that the instrument is 

capable of repeating the performance established during the initial calibration (EPA 1996). 
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For total metal analyses (ICP-AES and CVAA), initial calibration review included evaluating criteria for 

the curve’s correlation coefficient and initial calibration verification (ICV) percent recoveries. The ICV 

percent recoveries verify that the analytical system is operating within the established calibration criteria 

at the beginning of an analytical run. The continuing calibration review included evaluation of the criteria 

for continuing calibration verification (CCV) percent recoveries. The CCV percent recoveries verify that 

the analytical system is operating within the established calibration throughout the analytical run. 

All ICV and CCV percent recoveries associated with the reference data were within acceptable limits of 

90 to 110 percent. As such, no data were qualified or rejected because of calibration exceedances. This 

fact contributes to the high technical quality of the data. 

3.3 Laboratory Blanks 

Acceptable with qualification. No field blanks were required by the QAPP, since samples were prepared 

after collection and before submission to the reference laboratory. However, laboratory blanks were 

prepared and analyzed to evaluate the existence and magnitude of contamination resulting from 

laboratory activities. Blanks prepared and analyzed in the laboratory consisted of calibration and 

preparation blanks. If a problem with any blank existed, all associated data were carefully evaluated to 

assess whether the sample data were affected. At a minimum, calibration blanks were analyzed for every 

10 analyses conducted on each instrument. Preparation blanks were prepared at a frequency of one per 

preparation batch per matrix or every 20 samples, whichever is greater (EPA 1996). 

When laboratory blank contamination was identified, sample results were compared to the practical 

quantitation limit (PQL) and the maximum blank value as required by the validation guidelines (EPA 

2004). Most of the blank detections were positive results (i.e. greater than the method detection limit 

[MDL]), but less than the PQL. In these instances, if associated sample results were also less than the 

PQL, they were qualified as undetected (U); with the comment code “b.” In these same instances, if the 

associated sample results were greater than the PQL, the reviewer used professional judgment to 

determine if the sample results were adversely affected. If so, then the results were qualified as estimated 

with the potential for being biased high (J+). If not, then no qualification was required. 

In a few cases, the maximum blank value exceeded the PQL. In these cases, all associated sample results 

less than the PQL were qualified as undetected (U) with the comment code “b.” In cases where the 

associated sample results were greater than the PQL, but less than the blank concentration, the results 

were also qualified as undetected (U); with the comment code “b.” If the associated sample results were 

greater than both the PQL and the blank value, the reviewer used professional judgment to determine if 

sample results were adversely affected. If so, then the results were qualified as estimated with the 

potential for being biased high (J+); with the comment code “b.” Sample results significantly above the 

blank were not qualified. 

In addition to laboratory blank contamination, negative drift greater than the magnitude of the PQL was 

observed in some laboratory blanks. Associated sample data were qualified as undetected (U) if the 

results were less than the PQL. Professional judgement was used to determine if the negative drift 

adversely affected associated sample results greater than the PQL. If so, then sample results were 

qualified as estimated with the potential for being biased low (J-) due to the negative drift of the 

instrument baseline; with the comment code “b.” 

Of all target analyte data, 2.6 percent of the data was qualified as undetected because of laboratory blank 

contamination (U, b), and less than 1 percent of the data was qualified as estimated (either J+, b or J-, b). 

The low occurrence of results affected by blank contamination indicates that the general quality of the 
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. 
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5.0 CONCLUSIONS FOR DATA QUALITY AND DATA USABILITY 

Although some qualifiers were added to the data, a final review of the data set with respect to the data quality 

parameters discussed in Section 4.0 indicates that the data are of overall good quality. No analytical data were 

rejected. The data quality is generally consistent with project objectives for producing data of suitable quality 

for comparison to XRF data. All supporting documentation and data are available upon request, including 

cursory review and full validation reports as well as the electronic database that contains sample results. 

6.0 REFERENCES 

Tetra Tech EM, Inc. (Tetra Tech). 2005. “Demonstration and Quality Assurance Project Plan, XRF 

Technologies for Measuring Trace Elements in Soil and Sediment.” March. 

U.S. Environmental Protection Agency (EPA). 1996. “Test Methods for Evaluating Solid Waste”, Third 

Edition (SW-846). With promulgated revisions. December. 

EPA. 2004. “USEPA Contract Laboratory Program National Functional Guidelines For Inorganic Data 

Review”. October.
 

TABLES 
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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) 
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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) 

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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) 

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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 

 
TABLE 5: DATA QUALIFICATIONS: SERIAL DILUTION EXCEEDANCES (Continued) 

 

C-27 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Comment 

Code 

LV-SO-34-XX Antimony 870 mg/kg J- j 

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 
TABLE 5: DATA QUALIFICATIONS: SERIAL DILUTION EXCEEDANCES (Continued) 

 

C-28 

Sample ID Analyte Result Unit 

Validation 

Qualifier 

Comment 

Code 

SB-SO-15-XX Iron 51000 mg/kg J- j 

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, RONTEC Pico Tax and Reference Laboratory 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe P

1 KP-SO-06-XX Reference Laboratory 8.1 J+ 1 J- 0.1 U 290 26 1,400 621 KP-SO-10-XX Reference Laboratory 6.1 J+ 1 J- 0.1 U 300 26 1,600 561 KP-SO-15-XX Reference Laboratory 6.3 J+ 1 J- 0.1 U 340 26 1,600 51 KP-SO-18-XX Reference Laboratory 6.7 J+ 1 J- 0.1 U 250 24 1,200 501 KP-SO-22-XX Reference Laboratory 8.3 J+ 1 J- 0.1 U 260 29 1,300 651 KP-SO-06-RU RONTEC USA Inc. n.d. <LLD <LLD 314 32 1,764 781 KP-SO-10-RU RONTEC USA Inc. n.d. <LLD <LLD 352 31 1,912 671 KP-SO-15-RU RONTEC USA Inc. n.d. 0 <LLD 368 29 2,037 601 KP-SO-18-RU RONTEC USA Inc. n.d. <LLD <LLD 282 20 1,567 501 KP-SO-22-RU RONTEC USA Inc. n.d. 0 <LLD 287 24 1,661 652 KP-SO-07-XX Reference Laboratory 17 J+ 2 J- 0.1 U 170 48 990 1,202 KP-SO-13-XX Reference Laboratory 16 J+ 1 J- 0.045 U 180 52 980 1,202 KP-SO-20-XX Reference Laboratory 19 J+ 2 J- 0.1 U 160 46 910 1,302 KP-SO-24-XX Reference Laboratory 17 J+ 1 J- 0.1 U 160 49 900 1,102 KP-SO-27-XX Reference Laboratory 15 J+ 1 J- 0.05 U 170 45 970 1,202 KP-SO-29-XX Reference Laboratory 18 J+ 2 J- 0.1 U 150 42 870 1,202 KP-SO-32-XX Reference Laboratory 16 J+ 2 J- 0.045 U 180 50 970 1,202 KP-SO-07-RU RONTEC USA Inc. n.d. <LLD <LLD 209 40 1,318 1,12 KP-SO-13-RU RONTEC USA Inc. n.d. <LLD <LLD 178 44 1,109 1,502 KP-SO-20-RU RONTEC USA Inc. n.d. <LLD <LLD 267 49 1,620 1,322 KP-SO-24-RU RONTEC USA Inc. n.d. <LLD <LLD 204 48 1,973 1,092 KP-SO-27-RU RONTEC USA Inc. n.d. <LLD <LLD 269 50 1,632 1,452 KP-SO-29-RU RONTEC USA Inc. n.d. 0 <LLD 220 45 1,373 1,532 KP-SO-32-RU RONTEC USA Inc. n.d. <LLD <LLD 261 43 1,790 1,363 KP-SO-04-XX Reference Laboratory 94 J+ 3 0.046 U 180 200 1,300 5,803 KP-SO-16-XX Reference Laboratory 93 J+ 3 0.063 U 200 230 1,400 6,103 KP-SO-23-XX Reference Laboratory 86 J+ 3 0.048 U 180 190 1,300 5,303 KP-SO-26-XX Reference Laboratory 90 J+ 4 0.061 U 210 230 1,500 6,503 KP-SO-31-XX Reference Laboratory 88 28 0.1 U 140 200 1,100 5,703 KP-SO-04-RU RONTEC USA Inc. n.d. 8 48 158 220 1,484 9,683 KP-SO-16-RU RONTEC USA Inc. n.d. 3 60 190 199 1,781 6,643 KP-SO-23-RU RONTEC USA Inc. n.d. 4 218 159 213 1,581 6,903 KP-SO-26-RU RONTEC USA Inc. n.d. 2 102 136 177 1,150 5,933 KP-SO-31-RU RONTEC USA Inc. n.d. 5 177 205 190 1,598 5,66
D-2 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

1 KP-SO-06-XX Reference Laboratory 140 0.25 U 0.25 U 2 J 11 1 KP-SO-10-XX Reference Laboratory 150 0.22 U 0.25 U 2 J 12 1 KP-SO-15-XX Reference Laboratory 170 0.25 U 0.25 U 2 J 15 1 KP-SO-18-XX Reference Laboratory 120 0.25 U 0.25 U 2 J 11 1 KP-SO-22-XX Reference Laboratory 130 0.25 U 0.25 U 2 J 11 1 KP-SO-06-RU RONTEC USA Inc. 160 <LLD <LLD <LLD 11 1 KP-SO-10-RU RONTEC USA Inc. 180 <LLD <LLD <LLD 9 1 KP-SO-15-RU RONTEC USA Inc. 174 <LLD <LLD <LLD 15 1 KP-SO-18-RU RONTEC USA Inc. 133 <LLD <LLD <LLD 11 1 KP-SO-22-RU RONTEC USA Inc. 139 <LLD 29 2 9 2 KP-SO-07-XX Reference Laboratory 87 0.21 U 0.25 U 1 J 26 2 KP-SO-13-XX Reference Laboratory 90 0.25 U 0.25 U 1 J 24 2 KP-SO-20-XX Reference Laboratory 79 0.25 U 0.25 U 1 J 25 2 KP-SO-24-XX Reference Laboratory 78 0.25 U 0.25 U 1 J 22 2 KP-SO-27-XX Reference Laboratory 87 0.25 U 0.25 U 1 J 24 2 KP-SO-29-XX Reference Laboratory 73 0.25 U 0.25 U 1 J 22 2 KP-SO-32-XX Reference Laboratory 88 0.51 0.25 U 1 J 24 2 KP-SO-07-RU RONTEC USA Inc. 104 <LLD <LLD <LLD 19 2 KP-SO-13-RU RONTEC USA Inc. 91 <LLD <LLD <LLD 17 2 KP-SO-20-RU RONTEC USA Inc. 126 <LLD <LLD <LLD 21 2 KP-SO-24-RU RONTEC USA Inc. 98 <LLD <LLD <LLD 18 2 KP-SO-27-RU RONTEC USA Inc. 129 <LLD 43 <LLD 18 2 KP-SO-29-RU RONTEC USA Inc. 105 <LLD 25 <LLD 22 2 KP-SO-32-RU RONTEC USA Inc. 127 <LLD <LLD <LLD 18 3 KP-SO-04-XX Reference Laboratory 93 0.28 U 0.16 J 1 J 45 3 KP-SO-16-XX Reference Laboratory 100 0.25 U 0.16 J 1 J 47 3 KP-SO-23-XX Reference Laboratory 91 0.25 U 0.13 J 1 J 41 3 KP-SO-26-XX Reference Laboratory 110 0.22 U 0.17 J 1 J 52 3 KP-SO-31-XX Reference Laboratory 68 0.25 U 0.4 2 J 38 3 KP-SO-04-RU RONTEC USA Inc. 77 <LLD 28 <LLD 43 3 KP-SO-16-RU RONTEC USA Inc. 89 <LLD 130 <LLD 49 3 KP-SO-23-RU RONTEC USA Inc. 77 <LLD 55 <LLD 57 3 KP-SO-26-RU RONTEC USA Inc. 71 <LLD 77 <LLD 35 3 KP-SO-31-RU RONTEC USA Inc. 97 <LLD 133 <LLD 39 
D-3 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

4 KP-SO-02-XX Reference Laboratory 410 10 0.1 6 780 1,700 18,4 KP-SO-03-XX Reference Laboratory 360 9 0.074 U 5 670 1,600 19,4 KP-SO-05-XX Reference Laboratory 410 12 0.13 U 6 780 2,000 24,4 KP-SO-09-XX Reference Laboratory 420 11 0.094 U 5 780 1,800 22,4 KP-SO-21-XX Reference Laboratory 370 10 0.098 U 5 700 1,700 19,4 KP-SO-02-RU RONTEC USA Inc. n.d. 28 149 <LLD 834 2,343 27,4 KP-SO-03-RU RONTEC USA Inc. n.d. 32 91 <LLD 1,232 2,184 32,4 KP-SO-05-RU RONTEC USA Inc. n.d. 35 205 <LLD 686 1,081 20,4 KP-SO-09-RU RONTEC USA Inc. n.d. 20 901 <LLD 685 2,628 25,4 KP-SO-21-RU RONTEC USA Inc. n.d. 29 885 2 708 1,851 21,5 WS-SO-06-XX Reference Laboratory 1.3 U 48 1.9 120 50 28,000 5 WS-SO-08-XX Reference Laboratory 1.3 45 2 120 47 26,000 5 WS-SO-12-XX Reference Laboratory 1.3 UJ 43 1.8 110 45 25,000 5 WS-SO-17-XX Reference Laboratory 1.3 UJ 47 1.9 120 49 28,000 5 WS-SO-27-XX Reference Laboratory 1.3 UJ 49 2 120 51 28,000 5 WS-SO-30-XX Reference Laboratory 1.2 J- 51 2 130 53 29,000 5 WS-SO-35-XX Reference Laboratory 1.3 UJ 49 2 130 51 28,000 5 WS-SO-06-RU RONTEC USA Inc. n.d. 50 <LLD 130 52 32,525 5 WS-SO-08-RU RONTEC USA Inc. n.d. 49 <LLD 132 60 32,178 5 WS-SO-12-RU RONTEC USA Inc. n.d. 48 <LLD 204 58 30,859 5 WS-SO-17-RU RONTEC USA Inc. n.d. 62 <LLD 111 56 27,017 5 WS-SO-27-RU RONTEC USA Inc. n.d. 52 <LLD 125 55 30,405 5 WS-SO-30-RU RONTEC USA Inc. n.d. 73 <LLD 148 56 29,626 5 WS-SO-35-RU RONTEC USA Inc. n.d. 78 <LLD 166 73 44,622 6 WS-SO-03-XX Reference Laboratory 8.9 J- 500 12 140 170 32,000 4,6 WS-SO-05-XX Reference Laboratory 8.6 J- 440 12 140 160 31,000 4,6 WS-SO-09-XX Reference Laboratory 7.1 J- 480 12 130 160 30,000 4,6 WS-SO-14-XX Reference Laboratory 8.4 J- 430 11 120 150 28,000 3,6 WS-SO-26-XX Reference Laboratory 7.6 J- 520 12 140 160 30,000 4,6 WS-SO-31-XX Reference Laboratory 7.2 J- 520 12 140 170 32,000 4,6 WS-SO-33-XX Reference Laboratory 6.9 J- 450 J- 11 J- 120 J- 150 J- 28,000 J- 3,6 WS-SO-03-RU RONTEC USA Inc. n.d. 402 <LLD 94 203 32,172 4,6 WS-SO-05-RU RONTEC USA Inc. n.d. 418 <LLD 109 139 29,831 4,6 WS-SO-09-RU RONTEC USA Inc. n.d. 281 <LLD 119 137 30,539 3,6 WS-SO-14-RU RONTEC USA Inc. n.d. 282 <LLD 123 152 31,519 5,6 WS-SO-26-RU RONTEC USA Inc. n.d. 334 <LLD 100 118 26,067 3,6 WS-SO-31-RU RONTEC USA Inc. n.d. 336 <LLD 131 148 33,898 4,6 WS-SO-33-RU RONTEC USA Inc. n.d. 351 <LLD 101 148 33,397 3,
D-4 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

4 KP-SO-02-XX Reference Laboratory 4 0.42 U 0.82 0 J 100 4 KP-SO-03-XX Reference Laboratory 3 0.25 U 0.73 0 J 92 4 KP-SO-05-XX Reference Laboratory 4 0.24 U 0.82 0 J 110 4 KP-SO-09-XX Reference Laboratory 3 0.25 U 0.84 0 J 110 4 KP-SO-21-XX Reference Laboratory 4 0.25 U 0.76 0 J 100 4 KP-SO-02-RU RONTEC USA Inc. 2 9 113 <LLD 128 4 KP-SO-03-RU RONTEC USA Inc. 3 14 83 <LLD 146 4 KP-SO-05-RU RONTEC USA Inc. 5 4 181 <LLD 112 4 KP-SO-09-RU RONTEC USA Inc. <LLD 11 154 <LLD 101 4 KP-SO-21-RU RONTEC USA Inc. <LLD 11 240 6 103 5 WS-SO-06-XX Reference Laboratory 61 1.3 U 0.93 J 56 230 5 WS-SO-08-XX Reference Laboratory 58 1.3 U 0.86 J 52 220 5 WS-SO-12-XX Reference Laboratory 55 1.3 U 0.94 J 49 210 5 WS-SO-17-XX Reference Laboratory 59 1.3 U 0.89 J 56 230 5 WS-SO-27-XX Reference Laboratory 61 1.3 U 0.9 J 57 230 5 WS-SO-30-XX Reference Laboratory 65 1.3 U 1 J 58 240 5 WS-SO-35-XX Reference Laboratory 62 1.3 U 1 J 57 240 5 WS-SO-06-RU RONTEC USA Inc. 41 <LLD <LLD 65 266 5 WS-SO-08-RU RONTEC USA Inc. 38 <LLD <LLD 66 254 5 WS-SO-12-RU RONTEC USA Inc. 51 <LLD <LLD 59 248 5 WS-SO-17-RU RONTEC USA Inc. 36 <LLD <LLD 45 249 5 WS-SO-27-RU RONTEC USA Inc. 39 <LLD <LLD 57 245 5 WS-SO-30-RU RONTEC USA Inc. 58 <LLD <LLD 61 296 5 WS-SO-35-RU RONTEC USA Inc. 64 <LLD <LLD 89 358 6 WS-SO-03-XX Reference Laboratory 75 1.6 15 58 930 6 WS-SO-05-XX Reference Laboratory 71 1.3 U 15 57 900 6 WS-SO-09-XX Reference Laboratory 70 1.3 U 14 56 870 6 WS-SO-14-XX Reference Laboratory 64 1.3 U 13 50 820 6 WS-SO-26-XX Reference Laboratory 70 1.3 U 14 56 900 6 WS-SO-31-XX Reference Laboratory 72 1.2 U 15 60 950 6 WS-SO-33-XX Reference Laboratory 65 J- 1.3 U 13 J- 53 J- 830 J6 WS-SO-03-RU RONTEC USA Inc. 32 <LLD <LLD 58 784 6 WS-SO-05-RU RONTEC USA Inc. 40 <LLD <LLD 54 809 6 WS-SO-09-RU RONTEC USA Inc. 45 <LLD <LLD 50 669 6 WS-SO-14-RU RONTEC USA Inc. 42 <LLD <LLD 44 817 6 WS-SO-26-RU RONTEC USA Inc. 36 <LLD <LLD 38 623 6 WS-SO-31-RU RONTEC USA Inc. 63 <LLD <LLD 53 848 6 WS-SO-33-RU RONTEC USA Inc. 35 <LLD <LLD 63 729 
D-5 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe P

7 WS-SO-01-XX Reference Laboratory 41 J- 1900 47 100 590 32,000 18,07 WS-SO-04-XX Reference Laboratory 45 J- 2000 50 94 640 34,000 20,07 WS-SO-15-XX Reference Laboratory 48 J- 2300 56 82 720 37,000 24,07 WS-SO-22-XX Reference Laboratory 41 J- 1900 47 84 620 33,000 17,07 WS-SO-34-XX Reference Laboratory 45 J- 2000 50 91 660 36,000 22,07 WS-SO-01-RU RONTEC USA Inc. n.d. 1,907 346 107 793 38,275 25,27 WS-SO-04-RU RONTEC USA Inc. n.d. 1,890 432 127 755 36,058 25,97 WS-SO-15-RU RONTEC USA Inc. n.d. 1,496 161 34 477 30,305 19,87 WS-SO-22-RU RONTEC USA Inc. n.d. 1,553 399 59 559 32,206 21,07 WS-SO-34-RU RONTEC USA Inc. n.d. 2,095 365 75 693 40,750 25,98 WS-SO-02-XX Reference Laboratory 130 J- 4200 98 49 1300 44,000 35,08 WS-SO-16-XX Reference Laboratory 110 J- 3900 91 59 1300 42,000 24,08 WS-SO-18-XX Reference Laboratory 130 J- 4100 95 63 1300 44,000 37,08 WS-SO-21-XX Reference Laboratory 120 J- 3900 90 43 1200 40,000 43,08 WS-SO-24-XX Reference Laboratory 97 J- 3600 81 54 1100 38,000 27,08 WS-SO-29-XX Reference Laboratory 120 J- 3800 90 51 1200 40,000 42,08 WS-SO-37-XX Reference Laboratory 120 J- 4100 95 63 1300 42,000 26,08 WS-SO-02-RU RONTEC USA Inc. n.d. 3,327 803 26 1,424 43,729 48,98 WS-SO-16-RU RONTEC USA Inc. n.d. 3,670 827 54 1,217 40,476 47,68 WS-SO-18-RU RONTEC USA Inc. n.d. 3,343 998 24 1,151 35,927 45,58 WS-SO-21-RU RONTEC USA Inc. n.d. 76 <LLD 63 76 20,751 2,48 WS-SO-24-RU RONTEC USA Inc. n.d. 3,722 740 52 1,246 40,749 47,48 WS-SO-29-RU RONTEC USA Inc. n.d. 3,884 1,502 145 1,329 45,579 49,38 WS-SO-37-RU RONTEC USA Inc. n.d. 3,633 905 34 1,128 38,835 44,89 WS-SO-13-XX Reference Laboratory 200 J- 5800 150 53 1800 47,000 45,09 WS-SO-19-XX Reference Laboratory 150 J- 5000 130 66 1500 39,000 24,09 WS-SO-28-XX Reference Laboratory 120 J- 4200 100 54 1200 33,000 30,09 WS-SO-32-XX Reference Laboratory 190 J- 5500 140 54 1700 44,000 30,09 WS-SO-36-XX Reference Laboratory 120 J- 3800 92 51 1100 30,000 45,09 WS-SO-13-RU RONTEC USA Inc. n.d. 5,274 1,552 22 1,488 38,933 60,99 WS-SO-19-RU RONTEC USA Inc. n.d. 4,034 1,100 51 1,424 33,213 57,29 WS-SO-28-RU RONTEC USA Inc. n.d. 6,204 1,201 24 1,713 47,171 69,09 WS-SO-32-RU RONTEC USA Inc. n.d. 4,168 1,571 39 1,406 35,036 54,89 WS-SO-36-RU RONTEC USA Inc. n.d. 5,987 1,645 28 1,734 53,791 65,2
D-6 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

7 WS-SO-01-XX Reference Laboratory 66 1.3 U 69 J- 42 3,000 7 WS-SO-04-XX Reference Laboratory 62 1.3 U 76 J- 44 3,100 7 WS-SO-15-XX Reference Laboratory 58 1.3 U 90 J- 52 3,400 7 WS-SO-22-XX Reference Laboratory 57 1.3 U 72 J- 44 3,000 7 WS-SO-34-XX Reference Laboratory 60 1.3 U 78 J- 47 3,200 7 WS-SO-01-RU RONTEC USA Inc. 33 <LLD <LLD 26 3,696 7 WS-SO-04-RU RONTEC USA Inc. 40 <LLD <LLD 27 3,189 7 WS-SO-15-RU RONTEC USA Inc. 22 7 <LLD 14 2,629 7 WS-SO-22-RU RONTEC USA Inc. 35 4 107 12 3,620 7 WS-SO-34-RU RONTEC USA Inc. 28 <LLD <LLD 43 3,296 8 WS-SO-02-XX Reference Laboratory 57 1.3 U 150 J- 36 6,000 8 WS-SO-16-XX Reference Laboratory 60 1.1 J 150 J- 35 5,700 8 WS-SO-18-XX Reference Laboratory 62 1.9 140 J- 36 5,900 8 WS-SO-21-XX Reference Laboratory 51 1.6 150 J- 33 5,500 8 WS-SO-24-XX Reference Laboratory 54 2.1 140 J- 30 5,200 8 WS-SO-29-XX Reference Laboratory 55 1.7 140 J- 33 5,500 8 WS-SO-37-XX Reference Laboratory 63 3 140 J- 34 5,800 8 WS-SO-02-RU RONTEC USA Inc. 15 14 37 8 6,365 8 WS-SO-16-RU RONTEC USA Inc. 32 13 88 <LLD 5,526 8 WS-SO-18-RU RONTEC USA Inc. 20 18 98 5 5,486 8 WS-SO-21-RU RONTEC USA Inc. 298 256 <LLD 222 2,325 8 WS-SO-24-RU RONTEC USA Inc. 35 24 64 3 5,855 8 WS-SO-29-RU RONTEC USA Inc. 58 16 451 9 5,455 8 WS-SO-37-RU RONTEC USA Inc. 25 8 30 10 4,967 9 WS-SO-13-XX Reference Laboratory 75 3.7 170 J- 24 9,000 9 WS-SO-19-XX Reference Laboratory 74 3.7 160 J- 20 7,700 9 WS-SO-28-XX Reference Laboratory 59 2.3 130 J- 16 6,100 9 WS-SO-32-XX Reference Laboratory 73 3.7 190 J- 23 8,500 9 WS-SO-36-XX Reference Laboratory 55 1.7 120 J- 15 5,700 9 WS-SO-13-RU RONTEC USA Inc. 40 14 149 5 8,204 9 WS-SO-19-RU RONTEC USA Inc. 29 33 199 <LLD 7,055 9 WS-SO-28-RU RONTEC USA Inc. 35 29 212 <LLD 9,125 9 WS-SO-32-RU RONTEC USA Inc. 30 20 217 <LLD 7,130 9 WS-SO-36-RU RONTEC USA Inc. 65 10 65 7 9,334 
D-7 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

10 BN-SO-01-XX Reference Laboratory 1.3 UJ 38 0.94 120 32 24,000 10 BN-SO-10-XX Reference Laboratory 1.3 UJ 50 1.2 110 35 24,000 10 BN-SO-15-XX Reference Laboratory 1.3 UJ 34 0.82 110 29 22,000 10 BN-SO-18-XX Reference Laboratory 1.3 U 37 0.89 110 29 22,000 10 BN-SO-28-XX Reference Laboratory 1.5 35 0.87 100 28 22,000 10 BN-SO-31-XX Reference Laboratory 1.3 41 1 140 33 26,000 10 BN-SO-35-XX Reference Laboratory 1.4 37 0.98 120 30 23,000 10 BN-SO-01-RU RONTEC USA Inc. n.d. 45 <LLD 166 36 27,190 10 BN-SO-10-RU RONTEC USA Inc. n.d. 3,042 494 741 113 26,768 10 BN-SO-15-RU RONTEC USA Inc. n.d. 53 <LLD 127 35 30,747 10 BN-SO-18-RU RONTEC USA Inc. n.d. 41 <LLD 157 32 25,640 10 BN-SO-28-RU RONTEC USA Inc. n.d. 42 <LLD 97 29 24,685 10 BN-SO-31-RU RONTEC USA Inc. n.d. 40 <LLD 126 32 25,015 10 BN-SO-35-RU RONTEC USA Inc. n.d. 38 <LLD 102 32 24,168 11 BN-SO-02-XX Reference Laboratory 11 140 50 90 170 28,000 11 BN-SO-04-XX Reference Laboratory 9.1 120 42 79 140 24,000 11 BN-SO-17-XX Reference Laboratory 9.3 110 39 79 140 23,000 11 BN-SO-22-XX Reference Laboratory 7.3 98 34 65 110 20,000 11 BN-SO-27-XX Reference Laboratory 9.6 110 39 78 130 24,000 11 BN-SO-02-RU RONTEC USA Inc. n.d. 112 <LLD 71 160 27,648 11 BN-SO-04-RU RONTEC USA Inc. n.d. 132 <LLD 88 163 34,057 1,11 BN-SO-17-RU RONTEC USA Inc. n.d. 126 <LLD 60 179 31,054 11 BN-SO-22-RU RONTEC USA Inc. n.d. 99 <LLD 65 115 20,222 11 BN-SO-27-RU RONTEC USA Inc. n.d. 126 <LLD 203 161 26,812 12 BN-SO-03-XX Reference Laboratory 65 620 290 120 840 25,000 4,12 BN-SO-06-XX Reference Laboratory 60 600 280 94 810 24,000 4,12 BN-SO-08-XX Reference Laboratory 57 570 270 100 750 22,000 4,12 BN-SO-13-XX Reference Laboratory 65 320 150 98 410 17,000 2,12 BN-SO-20-XX Reference Laboratory 57 540 260 88 730 22,000 4,12 BN-SO-30-XX Reference Laboratory 64 630 300 100 860 26,000 4,12 BN-SO-34-XX Reference Laboratory 68 630 290 110 830 25,000 4,12 BN-SO-03-RU RONTEC USA Inc. n.d. 642 46 126 989 32,118 5,12 BN-SO-06-RU RONTEC USA Inc. n.d. 490 65 107 764 28,845 4,12 BN-SO-08-RU RONTEC USA Inc. n.d. 751 43 121 1,103 36,069 6,12 BN-SO-13-RU RONTEC USA Inc. n.d. 506 42 156 755 30,263 4,12 BN-SO-20-RU RONTEC USA Inc. n.d. 583 46 128 767 23,249 4,12 BN-SO-30-RU RONTEC USA Inc. n.d. 572 30 74 886 23,876 4,12 BN-SO-34-RU RONTEC USA Inc. n.d. 586 63 130 833 28,817 4,
D-8 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

10 BN-SO-01-XX Reference Laboratory 63 1.3 U 1.3 UJ 55 92 10 BN-SO-10-XX Reference Laboratory 54 1.2 J 1.3 UJ 55 110 10 BN-SO-15-XX Reference Laboratory 58 1.3 U 1.3 UJ 49 89 10 BN-SO-18-XX Reference Laboratory 59 1.3 0.94 U 46 88 10 BN-SO-28-XX Reference Laboratory 54 1.3 U 0.77 U 48 81 10 BN-SO-31-XX Reference Laboratory 71 1.3 U 0.97 U 54 94 10 BN-SO-35-XX Reference Laboratory 63 1.2 J 0.85 U 50 87 10 BN-SO-01-RU RONTEC USA Inc. 51 <LLD <LLD 51 115 10 BN-SO-10-RU RONTEC USA Inc. 2,982 135 20 139 4,299 10 BN-SO-15-RU RONTEC USA Inc. 60 <LLD <LLD 67 120 10 BN-SO-18-RU RONTEC USA Inc. 59 <LLD <LLD 42 100 10 BN-SO-28-RU RONTEC USA Inc. 45 <LLD 53 55 103 10 BN-SO-31-RU RONTEC USA Inc. 45 <LLD <LLD 51 124 10 BN-SO-35-RU RONTEC USA Inc. 46 <LLD <LLD 41 118 11 BN-SO-02-XX Reference Laboratory 54 4.3 7.6 60 470 11 BN-SO-04-XX Reference Laboratory 48 2.9 6.5 50 400 11 BN-SO-17-XX Reference Laboratory 47 2.7 6.3 49 390 11 BN-SO-22-XX Reference Laboratory 40 2.8 5.4 43 330 11 BN-SO-27-XX Reference Laboratory 46 3.7 6.1 52 380 11 BN-SO-02-RU RONTEC USA Inc. 43 <LLD <LLD 38 469 11 BN-SO-04-RU RONTEC USA Inc. 54 <LLD <LLD 74 525 11 BN-SO-17-RU RONTEC USA Inc. 31 <LLD <LLD 63 498 11 BN-SO-22-RU RONTEC USA Inc. 26 <LLD <LLD 38 384 11 BN-SO-27-RU RONTEC USA Inc. 62 <LLD <LLD 59 481 12 BN-SO-03-XX Reference Laboratory 100 17 42 48 2,300 12 BN-SO-06-XX Reference Laboratory 92 15 41 48 2,300 12 BN-SO-08-XX Reference Laboratory 94 14 38 39 2,200 12 BN-SO-13-XX Reference Laboratory 71 9.2 21 37 1,200 12 BN-SO-20-XX Reference Laboratory 84 14 37 44 2,100 12 BN-SO-30-XX Reference Laboratory 99 17 44 50 2,400 12 BN-SO-34-XX Reference Laboratory 100 17 42 49 2,300 12 BN-SO-03-RU RONTEC USA Inc. 134 6 <LLD 36 2,842 12 BN-SO-06-RU RONTEC USA Inc. 67 1 <LLD 50 2,358 12 BN-SO-08-RU RONTEC USA Inc. 86 5 <LLD 51 3,458 12 BN-SO-13-RU RONTEC USA Inc. 127 6 <LLD 46 2,296 12 BN-SO-20-RU RONTEC USA Inc. 69 4 <LLD 26 2,476 12 BN-SO-30-RU RONTEC USA Inc. 52 5 <LLD 33 2,602 12 BN-SO-34-RU RONTEC USA Inc. 78 4 <LLD 54 2,735 
D-9 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

13 BN-SO-07-XX Reference Laboratory 110 J- 990 J+ 520 82 1,400 23,000 13 BN-SO-16-XX Reference Laboratory 120 J- 1,100 J+ 570 86 1,500 25,000 13 BN-SO-21-XX Reference Laboratory 150 J- 1,300 J+ 660 110 1,700 30,000 13 BN-SO-25-XX Reference Laboratory 82 J- 700 J 370 J- 64 J- 930 J- 16,000 J- 13 BN-SO-33-XX Reference Laboratory 100 J- 1,100 640 100 1,600 27,000 13 BN-SO-07-RU RONTEC USA Inc. n.d. 978 181 74 1,699 30,616 13 BN-SO-16-RU RONTEC USA Inc. n.d. 1,106 254 84 1,641 35,714 13 BN-SO-21-RU RONTEC USA Inc. n.d. 1,380 292 137 2,236 35,315 113 BN-SO-25-RU RONTEC USA Inc. n.d. 938 263 99 1,509 26,293 13 BN-SO-33-RU RONTEC USA Inc. n.d. 952 158 135 1,461 28,501 14 BN-SO-05-XX Reference Laboratory 160 J- 1,600 850 86 2,200 26,000 114 BN-SO-19-XX Reference Laboratory 150 J- 1,600 860 79 2,200 26,000 114 BN-SO-26-XX Reference Laboratory 150 J- 1,700 900 82 2,400 27,000 114 BN-SO-29-XX Reference Laboratory 150 J- 1,600 880 86 2,300 26,000 114 BN-SO-32-XX Reference Laboratory 160 J- 1,600 860 84 2,300 26,000 114 BN-SO-05-RU RONTEC USA Inc. n.d. 1,700 615 105 2,998 34,577 114 BN-SO-19-RU RONTEC USA Inc. n.d. 1,472 640 38 2,301 27,347 114 BN-SO-26-RU RONTEC USA Inc. n.d. 1,451 764 88 2,252 28,547 114 BN-SO-29-RU RONTEC USA Inc. n.d. 1,593 1,125 44 2,246 27,404 114 BN-SO-32-RU RONTEC USA Inc. n.d. 1,584 539 38 2,660 35,560 115 CN-SO-01-XX Reference Laboratory 13 J- 13 21 190 700 38,000 15 CN-SO-04-XX Reference Laboratory 13 J- 11 21 200 680 37,000 15 CN-SO-08-XX Reference Laboratory 15 J- 15 25 210 740 43,000 15 CN-SO-10-XX Reference Laboratory 13 J- 13 22 200 760 39,000 15 CN-SO-11-XX Reference Laboratory 17 J- 16 30 240 860 47,000 15 CN-SO-01-RU RONTEC USA Inc. n.d. 6 <LLD 397 391 27,736 15 CN-SO-04-RU RONTEC USA Inc. n.d. 9 <LLD 284 647 38,159 15 CN-SO-08-RU RONTEC USA Inc. n.d. 3 <LLD 352 508 47,045 15 CN-SO-10-RU RONTEC USA Inc. n.d. 5 <LLD 343 694 50,623 15 CN-SO-11-RU RONTEC USA Inc. n.d. 6 <LLD 359 615 45,485 
D-10 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

13 BN-SO-07-XX Reference Laboratory 120 26 70 41 4,000 13 BN-SO-16-XX Reference Laboratory 130 29 77 44 4,400 13 BN-SO-21-XX Reference Laboratory 160 35 88 52 5,100 13 BN-SO-25-XX Reference Laboratory 88 J- 19 J- 48 J- 28 J- 2,900 J13 BN-SO-33-XX Reference Laboratory 150 34 81 48 5,100 13 BN-SO-07-RU RONTEC USA Inc. 87 12 <LLD 29 4,783 13 BN-SO-16-RU RONTEC USA Inc. 91 13 <LLD 65 5,688 13 BN-SO-21-RU RONTEC USA Inc. 112 15 <LLD 33 7,118 13 BN-SO-25-RU RONTEC USA Inc. 98 9 <LLD 30 5,010 13 BN-SO-33-RU RONTEC USA Inc. 87 13 <LLD 25 4,611 14 BN-SO-05-XX Reference Laboratory 160 48 110 39 6,700 14 BN-SO-19-XX Reference Laboratory 160 48 120 39 6,700 14 BN-SO-26-XX Reference Laboratory 160 49 120 40 7,000 14 BN-SO-29-XX Reference Laboratory 160 48 120 41 6,800 14 BN-SO-32-XX Reference Laboratory 160 48 120 39 6,700 14 BN-SO-05-RU RONTEC USA Inc. 93 24 <LLD 23 8,850 14 BN-SO-19-RU RONTEC USA Inc. 87 21 <LLD 24 7,024 14 BN-SO-26-RU RONTEC USA Inc. 66 18 108 34 6,757 14 BN-SO-29-RU RONTEC USA Inc. 125 22 75 14 7,871 14 BN-SO-32-RU RONTEC USA Inc. 115 21 <LLD 39 7,875 15 CN-SO-01-XX Reference Laboratory 240 2.2 12 21 3,100 15 CN-SO-04-XX Reference Laboratory 240 1.5 12 22 2,900 15 CN-SO-08-XX Reference Laboratory 280 1.3 U 15 26 3,200 15 CN-SO-10-XX Reference Laboratory 240 1.9 14 22 3,000 15 CN-SO-11-XX Reference Laboratory 320 1.3 U 16 27 3,500 15 CN-SO-01-RU RONTEC USA Inc. 169 <LLD <LLD 15 2,793 15 CN-SO-04-RU RONTEC USA Inc. 192 <LLD <LLD 26 3,673 15 CN-SO-08-RU RONTEC USA Inc. 237 <LLD <LLD 19 3,949 15 CN-SO-10-RU RONTEC USA Inc. 226 <LLD <LLD 10 4,458 15 CN-SO-11-RU RONTEC USA Inc. 230 <LLD <LLD 15 3,866 
D-11 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

16 AS-SO-02-XX Reference Laboratory 2.6 UJ 18 50 180 140 48,000 1,616 AS-SO-06-XX Reference Laboratory 2.4 UJ 19 52 190 130 52,000 1,616 AS-SO-10-XX Reference Laboratory 1.9 J- 18 48 180 110 45,000 1,416 AS-SO-11-XX Reference Laboratory 3.7 J- 22 63 230 150 52,000 2,116 AS-SO-13-XX Reference Laboratory 2.4 UJ 20 57 200 150 52,000 1,716 AS-SO-02-RU RONTEC USA Inc. n.d. 6 <LLD 171 95 41,649 1,816 AS-SO-06-RU RONTEC USA Inc. n.d. 3 14 223 121 31,662 1,916 AS-SO-10-RU RONTEC USA Inc. n.d. 3 <LLD 234 149 61,654 2,416 AS-SO-11-RU RONTEC USA Inc. n.d. 4 <LLD 273 151 69,371 2,116 AS-SO-13-RU RONTEC USA Inc. n.d. 4 <LLD 178 105 44,658 2,017 AS-SO-01-XX Reference Laboratory 3.8 J- 26 100 420 250 100,000 3,217 AS-SO-04-XX Reference Laboratory 6.4 UJ 22 110 480 260 110,000 3,317 AS-SO-07-XX Reference Laboratory 3.6 J- 21 97 380 240 88,000 2,917 AS-SO-09-XX Reference Laboratory 2.6 UJ 25 J- 100 J- 390 J- 250 J- 94,000 J- 3,217 AS-SO-12-XX Reference Laboratory 2.6 UJ 29 120 440 270 93,000 3,317 AS-SO-01-RU RONTEC USA Inc. n.d. 1 152 355 163 55,703 4,017 AS-SO-04-RU RONTEC USA Inc. n.d. 3 188 339 177 59,143 4,017 AS-SO-07-RU RONTEC USA Inc. n.d. 1 <LLD 626 183 104,786 3,817 AS-SO-09-RU RONTEC USA Inc. n.d. 1 <LLD 338 171 91,767 3,517 AS-SO-12-RU RONTEC USA Inc. n.d. 1 35 723 199 91,093 4,418 SB-SO-03-XX Reference Laboratory 1.2 UJ 9 0.51 U 150 48 38,000 18 SB-SO-06-XX Reference Laboratory 1.7 J- 8 0.51 U 140 44 35,000 18 SB-SO-14-XX Reference Laboratory 4.1 J- 9 0.51 U 150 46 37,000 18 SB-SO-38-XX Reference Laboratory 1.3 UJ 10 0.51 U 150 57 37,000 18 SB-SO-41-XX Reference Laboratory 1.3 UJ 9 0.51 U 160 58 40,000 18 SB-SO-47-XX Reference Laboratory 1.3 UJ 8 0.51 U 140 44 34,000 18 SB-SO-51-XX Reference Laboratory 1.3 UJ 9 0.51 U 160 50 40,000 18 SB-SO-03-RU RONTEC USA Inc. n.d. 17 <LLD 206 49 43,686 18 SB-SO-06-RU RONTEC USA Inc. n.d. 18 21 194 47 45,687 18 SB-SO-14-RU RONTEC USA Inc. n.d. 18 <LLD 223 51 45,684 18 SB-SO-38-RU RONTEC USA Inc. n.d. 13 <LLD 228 45 37,030 18 SB-SO-41-RU RONTEC USA Inc. n.d. 18 <LLD 233 59 52,708 18 SB-SO-47-RU RONTEC USA Inc. n.d. 25 <LLD 438 82 55,521 18 SB-SO-51-RU RONTEC USA Inc. n.d. 22 <LLD 260 62 57,083 
D-12 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

16 AS-SO-02-XX Reference Laboratory 91 2.6 U 4.5 42 3,300 16 AS-SO-06-XX Reference Laboratory 93 2.6 U 4.8 44 3,500 16 AS-SO-10-XX Reference Laboratory 84 1.1 U 4.4 42 3,000 16 AS-SO-11-XX Reference Laboratory 120 1.1 U 5.6 54 3,800 16 AS-SO-13-XX Reference Laboratory 100 3 5.2 50 3,800 16 AS-SO-02-RU RONTEC USA Inc. <LLD 81 <LLD 50 3,367 16 AS-SO-06-RU RONTEC USA Inc. <LLD 46 <LLD 40 3,334 16 AS-SO-10-RU RONTEC USA Inc. <LLD 95 <LLD 39 5,103 16 AS-SO-11-RU RONTEC USA Inc. <LLD 105 <LLD 33 4,747 16 AS-SO-13-RU RONTEC USA Inc. <LLD 87 <LLD 39 3,751 17 AS-SO-01-XX Reference Laboratory 180 2.6 U 9.3 66 6,900 17 AS-SO-04-XX Reference Laboratory 200 6.2 U 12 72 7,400 17 AS-SO-07-XX Reference Laboratory 160 2.7 8.9 63 6,300 17 AS-SO-09-XX Reference Laboratory 170 J- 2.6 U 9.6 J- 65 J- 6,800 J17 AS-SO-12-XX Reference Laboratory 190 2.6 U 3.2 73 7,500 17 AS-SO-01-RU RONTEC USA Inc. <LLD 81 199 55 7,605 17 AS-SO-04-RU RONTEC USA Inc. <LLD 86 239 45 7,598 17 AS-SO-07-RU RONTEC USA Inc. <LLD 129 <LLD 12 9,169 17 AS-SO-09-RU RONTEC USA Inc. <LLD 101 <LLD 25 7,149 17 AS-SO-12-RU RONTEC USA Inc. <LLD 108 <LLD 30 8,832 18 SB-SO-03-XX Reference Laboratory 210 1.3 U 1.3 U 67 90 18 SB-SO-06-XX Reference Laboratory 200 1.3 U 1.3 U 63 82 18 SB-SO-14-XX Reference Laboratory 210 1.3 U 1.3 U 66 95 18 SB-SO-38-XX Reference Laboratory 210 1.3 U 1.3 U 68 91 18 SB-SO-41-XX Reference Laboratory 230 1.3 U 1.3 U 71 96 18 SB-SO-47-XX Reference Laboratory 200 1.3 U 1.3 U 62 82 18 SB-SO-51-XX Reference Laboratory 230 1.3 U 1.3 U 74 93 18 SB-SO-03-RU RONTEC USA Inc. 209 <LLD <LLD 85 114 18 SB-SO-06-RU RONTEC USA Inc. 192 <LLD <LLD 111 114 18 SB-SO-14-RU RONTEC USA Inc. 177 <LLD <LLD 78 116 18 SB-SO-38-RU RONTEC USA Inc. 165 <LLD <LLD 56 107 18 SB-SO-41-RU RONTEC USA Inc. 271 <LLD <LLD 132 140 18 SB-SO-47-RU RONTEC USA Inc. 254 <LLD <LLD 146 142 18 SB-SO-51-RU RONTEC USA Inc. 257 <LLD <LLD 148 141 
D-13 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

19 SB-SO-05-XX Reference Laboratory 1.6 J- 9 0.51 U 140 46 35,000 19 SB-SO-18-XX Reference Laboratory 1.2 UJ 10 0.51 U 150 46 38,000 19 SB-SO-30-XX Reference Laboratory 3.2 J- 7 0.51 U 94 27 22,000 19 SB-SO-40-XX Reference Laboratory 2.2 J- 9 0.51 U 120 40 33,000 19 SB-SO-53-XX Reference Laboratory 1.2 UJ 10 0.51 U 140 44 37,000 19 SB-SO-05-RU RONTEC USA Inc. n.d. 22 <LLD 176 42 40,162 19 SB-SO-18-RU RONTEC USA Inc. n.d. 19 <LLD 204 49 43,287 19 SB-SO-30-RU RONTEC USA Inc. n.d. 13 <LLD 120 31 28,889 19 SB-SO-40-RU RONTEC USA Inc. n.d. 21 <LLD 227 51 44,833 19 SB-SO-53-RU RONTEC USA Inc. n.d. 14 <LLD 142 37 31,242 20 SB-SO-08-XX Reference Laboratory 5.4 J- 13 0.51 U 120 39 32,000 20 SB-SO-11-XX Reference Laboratory 5.7 J- 13 0.51 U 140 46 36,000 20 SB-SO-21-XX Reference Laboratory 4.9 J 13 0.51 U 130 43 34,000 20 SB-SO-39-XX Reference Laboratory 4.7 J- 13 0.51 U 140 46 34,000 20 SB-SO-42-XX Reference Laboratory 4.6 J- 13 0.51 U 140 45 35,000 20 SB-SO-08-RU RONTEC USA Inc. n.d. 27 <LLD 195 50 47,131 20 SB-SO-11-RU RONTEC USA Inc. n.d. 24 <LLD 246 45 41,552 20 SB-SO-21-RU RONTEC USA Inc. n.d. 19 <LLD 156 34 30,321 20 SB-SO-39-RU RONTEC USA Inc. n.d. 25 <LLD 174 45 40,830 20 SB-SO-42-RU RONTEC USA Inc. n.d. 29 <LLD 232 63 49,786 21 SB-SO-22-XX Reference Laboratory 10 J 18 0.51 U 120 37 29,000 21 SB-SO-25-XX Reference Laboratory 6.8 J+ 18 0.51 U 120 37 29,000 21 SB-SO-27-XX Reference Laboratory 6.7 J+ 18 0.51 U 120 37 29,000 21 SB-SO-35-XX Reference Laboratory 6 J+ 17 0.51 U 110 35 28,000 21 SB-SO-44-XX Reference Laboratory 6.8 J+ 18 0.51 U 120 37 29,000 21 SB-SO-22-RU RONTEC USA Inc. n.d. 29 <LLD 173 30 29,418 21 SB-SO-25-RU RONTEC USA Inc. n.d. 24 <LLD 163 29 26,599 21 SB-SO-27-RU RONTEC USA Inc. n.d. 21 <LLD 107 28 25,354 21 SB-SO-35-RU RONTEC USA Inc. n.d. 27 <LLD 365 40 33,860 21 SB-SO-44-RU RONTEC USA Inc. n.d. 31 <LLD 206 46 41,728 
D-14 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

19 SB-SO-05-XX Reference Laboratory 200 1.3 U 1.3 U 61 80 19 SB-SO-18-XX Reference Laboratory 210 1.3 U 1.3 U 70 84 19 SB-SO-30-XX Reference Laboratory 120 1.3 J+ 1.3 U 43 50 19 SB-SO-40-XX Reference Laboratory 180 1.3 U 1.3 U 58 74 19 SB-SO-53-XX Reference Laboratory 200 1.3 U 1.3 U 64 81 19 SB-SO-05-RU RONTEC USA Inc. 180 <LLD <LLD 76 93 19 SB-SO-18-RU RONTEC USA Inc. 178 <LLD <LLD 76 102 19 SB-SO-30-RU RONTEC USA Inc. 141 <LLD <LLD 82 77 19 SB-SO-40-RU RONTEC USA Inc. 225 <LLD <LLD 98 117 19 SB-SO-53-RU RONTEC USA Inc. 136 <LLD <LLD 65 76 20 SB-SO-08-XX Reference Laboratory 180 1.3 U 1.3 U 57 70 20 SB-SO-11-XX Reference Laboratory 200 1.3 U 1.3 U 66 84 20 SB-SO-21-XX Reference Laboratory 190 1.3 U 1.3 U 58 75 20 SB-SO-39-XX Reference Laboratory 200 1.3 U 1.3 U 62 77 20 SB-SO-42-XX Reference Laboratory 200 1.3 U 1.3 U 65 78 20 SB-SO-08-RU RONTEC USA Inc. 214 <LLD <LLD 125 107 20 SB-SO-11-RU RONTEC USA Inc. 208 <LLD <LLD 107 117 20 SB-SO-21-RU RONTEC USA Inc. 232 <LLD <LLD 65 72 20 SB-SO-39-RU RONTEC USA Inc. 177 <LLD <LLD 53 99 20 SB-SO-42-RU RONTEC USA Inc. 226 <LLD <LLD 128 134 21 SB-SO-22-XX Reference Laboratory 160 1.3 U 1.3 U 52 64 J21 SB-SO-25-XX Reference Laboratory 160 1.3 U 1.3 U 54 63 21 SB-SO-27-XX Reference Laboratory 170 1.3 U 1.3 U 54 65 21 SB-SO-35-XX Reference Laboratory 160 1.3 U 1.3 U 50 62 21 SB-SO-44-XX Reference Laboratory 170 1.3 U 1.3 U 53 64 21 SB-SO-22-RU RONTEC USA Inc. 146 <LLD <LLD 72 67 21 SB-SO-25-RU RONTEC USA Inc. 122 <LLD <LLD 84 62 21 SB-SO-27-RU RONTEC USA Inc. 136 <LLD <LLD 78 56 21 SB-SO-35-RU RONTEC USA Inc. 216 <LLD <LLD 50 79 21 SB-SO-44-RU RONTEC USA Inc. 235 <LLD <LLD 109 97 
D-15 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

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-RU RONTEC USA Inc. n.d. 72 <LLD 93 11 7,298 60 22 SB-SO-28-RU RONTEC USA Inc. n.d. 37 <LLD 28 7 3,460 29 22 SB-SO-32-RU RONTEC USA Inc. n.d. 60 <LLD 97 14 6,026 40 22 SB-SO-43-RU RONTEC USA Inc. n.d. 52 <LLD 84 11 5,353 39 22 SB-SO-48-RU RONTEC USA Inc. n.d. 61 <LLD 70 10 5,512 41 23 SB-SO-02-XX Reference Laboratory 44 J- 23 J- 0.5 U 130 43 35,000 22 23 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-RU RONTEC USA Inc. n.d. 34 <LLD 186 47 43,933 23 23 SB-SO-07-RU RONTEC USA Inc. n.d. 45 <LLD 186 53 48,139 33 23 SB-SO-10-RU RONTEC USA Inc. n.d. 33 17 153 40 38,473 16 23 SB-SO-26-RU RONTEC USA Inc. n.d. 31 <LLD 296 36 34,334 22 23 SB-SO-50-RU RONTEC USA Inc. n.d. 50 <LLD 865 60 59,622 17 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-RU RONTEC USA Inc. n.d. 86 <LLD 205 51 59,634 20 24 SB-SO-16-RU RONTEC USA Inc. n.d. 71 <LLD 194 42 43,135 14 24 SB-SO-24-RU RONTEC USA Inc. n.d. 75 <LLD 136 40 40,606 18 24 SB-SO-45-RU RONTEC USA Inc. n.d. 85 <LLD 170 53 52,600 20 24 SB-SO-52-RU RONTEC USA Inc. n.d. 77 <LLD 159 43 47,037 19 
D-16 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

22 SB-SO-23-XX Reference Laboratory 26 0.22 J 0.26 UJ 13 8 22 SB-SO-28-XX Reference Laboratory 26 0.26 U 0.26 UJ 13 8 22 SB-SO-32-XX Reference Laboratory 28 0.36 0.1 UJ 14 9 22 SB-SO-43-XX Reference Laboratory 24 0.26 U 0.26 UJ 13 8 22 SB-SO-48-XX Reference Laboratory 25 0.26 U 0.1 UJ 13 8 22 SB-SO-23-RU RONTEC USA Inc. 14 <LLD <LLD 130 <LLD 22 SB-SO-28-RU RONTEC USA Inc. 14 <LLD <LLD 70 25 22 SB-SO-32-RU RONTEC USA Inc. 37 <LLD <LLD 67 46 22 SB-SO-43-RU RONTEC USA Inc. 17 <LLD <LLD 126 11 22 SB-SO-48-RU RONTEC USA Inc. 16 <LLD <LLD 167 <LLD 23 SB-SO-02-XX Reference Laboratory 180 1.2 U 1.2 UJ 59 88 23 SB-SO-07-XX Reference Laboratory 170 1.4 1.6 53 86 23 SB-SO-10-XX Reference Laboratory 200 2.8 1.8 59 100 23 SB-SO-26-XX Reference Laboratory 220 3.4 1.8 68 110 23 SB-SO-50-XX Reference Laboratory 200 2.9 1.8 61 100 23 SB-SO-02-RU RONTEC USA Inc. 182 <LLD <LLD 105 112 23 SB-SO-07-RU RONTEC USA Inc. 181 <LLD <LLD 81 132 23 SB-SO-10-RU RONTEC USA Inc. 157 <LLD <LLD 86 98 23 SB-SO-26-RU RONTEC USA Inc. 153 <LLD <LLD 94 101 23 SB-SO-50-RU RONTEC USA Inc. 232 <LLD <LLD 137 152 24 SB-SO-01-XX Reference Laboratory 190 1.8 2.3 65 95 24 SB-SO-16-XX Reference Laboratory 190 1.9 2.2 65 97 24 SB-SO-24-XX Reference Laboratory 200 2.5 2.3 67 95 24 SB-SO-45-XX Reference Laboratory 190 2.8 2.1 J- 63 93 24 SB-SO-52-XX Reference Laboratory 190 1.8 2.2 64 90 24 SB-SO-01-RU RONTEC USA Inc. 157 <LLD <LLD 90 120 24 SB-SO-16-RU RONTEC USA Inc. 166 <LLD <LLD 104 94 24 SB-SO-24-RU RONTEC USA Inc. 143 <LLD <LLD 73 92 24 SB-SO-45-RU RONTEC USA Inc. 181 <LLD <LLD 105 125 24 SB-SO-52-RU RONTEC USA Inc. 167 <LLD <LLD 105 109 
D-17 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

25 SB-SO-13-XX Reference Laboratory 430 J 160 1 U 140 46 61,000 25 SB-SO-19-XX Reference Laboratory 310 J 100 0.5 U 100 32 42,000 25 SB-SO-33-XX Reference Laboratory 350 J 110 0.5 U 100 33 45,000 25 SB-SO-37-XX Reference Laboratory 340 J 130 1 U 120 39 51,000 25 SB-SO-55-XX Reference Laboratory 340 J 120 0.5 U 120 37 49,000 25 SB-SO-13-RU RONTEC USA Inc. n.d. 152 <LLD 146 39 53,366 25 SB-SO-19-RU RONTEC USA Inc. n.d. 104 <LLD 96 30 38,031 25 SB-SO-33-RU RONTEC USA Inc. n.d. 140 <LLD 381 50 54,289 25 SB-SO-37-RU RONTEC USA Inc. n.d. 145 <LLD 250 49 58,186 25 SB-SO-55-RU RONTEC USA Inc. n.d. 133 <LLD 174 41 49,892 26 SB-SO-12-XX Reference Laboratory 620 J 190 1 U 100 33 55,000 26 SB-SO-15-XX Reference Laboratory 600 J- 170 J- 1 U 91 J- 30 J- 51,000 J- 26 SB-SO-17-XX Reference Laboratory 800 J+ 210 1 U 110 37 61,000 26 SB-SO-46-XX Reference Laboratory 740 J+ 190 1 U 120 35 57,000 26 SB-SO-54-XX Reference Laboratory 280 31 0.2 U 25 5.8 8,600 26 SB-SO-12-RU RONTEC USA Inc. n.d. 217 <LLD 153 42 61,880 26 SB-SO-15-RU RONTEC USA Inc. n.d. 174 <LLD 136 40 49,739 26 SB-SO-17-RU RONTEC USA Inc. n.d. 161 <LLD 93 35 43,888 26 SB-SO-46-RU RONTEC USA Inc. n.d. 190 <LLD 92 35 53,422 26 SB-SO-54-RU RONTEC USA Inc. n.d. 210 <LLD 119 38 58,068 27 KP-SE-08-XX Reference Laboratory 6.2 3 0.11 U 88 3.8 840 327 KP-SE-11-XX Reference Laboratory 5.6 3 0.11 U 96 4.1 940 327 KP-SE-17-XX Reference Laboratory 4.9 3 0.11 U 98 4.1 940 327 KP-SE-25-XX Reference Laboratory 6 3 0.11 U 99 4.3 960 327 KP-SE-30-XX Reference Laboratory 5.7 3 0.11 U 83 3.6 830 327 KP-SE-08-RU RONTEC USA Inc. n.d. 1 <LLD 133 5 1,371 427 KP-SE-11-RU RONTEC USA Inc. n.d. 3 <LLD 110 5 1,235 327 KP-SE-17-RU RONTEC USA Inc. n.d. <LLD <LLD 96 6 1,304 427 KP-SE-25-RU RONTEC USA Inc. n.d. <LLD <LLD 110 5 1,180 427 KP-SE-30-RU RONTEC USA Inc. n.d. <LLD <LLD 130 5 1,509 4
D-18 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

25 SB-SO-13-XX Reference Laboratory 180 4.4 2.2 UJ 74 70 25 SB-SO-19-XX Reference Laboratory 120 2.5 1.8 51 51 25 SB-SO-33-XX Reference Laboratory 130 3 2 J 52 56 25 SB-SO-37-XX Reference Laboratory 150 2.5 U 2 UJ 63 58 25 SB-SO-55-XX Reference Laboratory 140 2.5 2.2 J 61 60 25 SB-SO-13-RU RONTEC USA Inc. 138 <LLD <LLD 107 98 25 SB-SO-19-RU RONTEC USA Inc. 114 <LLD <LLD 73 57 25 SB-SO-33-RU RONTEC USA Inc. 429 35 <LLD 57 86 25 SB-SO-37-RU RONTEC USA Inc. 152 <LLD <LLD 52 99 25 SB-SO-55-RU RONTEC USA Inc. 122 <LLD <LLD 66 80 26 SB-SO-12-XX Reference Laboratory 110 2.5 U 2.1 UJ 59 42 26 SB-SO-15-XX Reference Laboratory 100 J- 3.4 1.6 UJ 52 J- 36 J26 SB-SO-17-XX Reference Laboratory 120 2.8 2.3 UJ 60 42 26 SB-SO-46-XX Reference Laboratory 120 2.6 2.2 UJ 57 41 26 SB-SO-54-XX Reference Laboratory 20 0.5 U 0.5 UJ 11 6 26 SB-SO-12-RU RONTEC USA Inc. 125 <LLD <LLD 99 131 26 SB-SO-15-RU RONTEC USA Inc. 87 <LLD <LLD 53 100 26 SB-SO-17-RU RONTEC USA Inc. 81 <LLD <LLD 57 47 26 SB-SO-46-RU RONTEC USA Inc. 89 <LLD <LLD 80 67 26 SB-SO-54-RU RONTEC USA Inc. 84 <LLD <LLD 65 61 27 KP-SE-08-XX Reference Laboratory 42 0.27 U 0.27 UJ 4 5 27 KP-SE-11-XX Reference Laboratory 46 0.43 0.27 UJ 4 6 27 KP-SE-17-XX Reference Laboratory 47 0.27 U 0.27 UJ 4 5 27 KP-SE-25-XX Reference Laboratory 47 0.26 U 0.27 UJ 4 5 27 KP-SE-30-XX Reference Laboratory 39 0.24 U 0.27 UJ 4 5 27 KP-SE-08-RU RONTEC USA Inc. 61 <LLD <LLD <LLD 7 27 KP-SE-11-RU RONTEC USA Inc. 47 <LLD <LLD 2 7 27 KP-SE-17-RU RONTEC USA Inc. 45 <LLD <LLD <LLD 7 27 KP-SE-25-RU RONTEC USA Inc. 50 <LLD <LLD <LLD 7 27 KP-SE-30-RU RONTEC USA Inc. 63 <LLD <LLD 3 7 
D-19 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

28 KP-SE-01-XX Reference Laboratory 3.2 2 0.1 U 34 2.2 480 28 KP-SE-12-XX Reference Laboratory 3.1 2 0.1 U 42 2.5 510 28 KP-SE-14-XX Reference Laboratory 11 J- 2 0.1 U 46 J- 2.7 J+ 520 J- 28 KP-SE-19-XX Reference Laboratory 3 2 0.1 U 44 2.3 510 28 KP-SE-28-XX Reference Laboratory 3.3 2 0.1 U 45 2.3 520 28 KP-SE-01-RU RONTEC USA Inc. n.d. 2 <LLD 46 3 1,038 28 KP-SE-12-RU RONTEC USA Inc. n.d. <LLD <LLD 41 2 1,245 28 KP-SE-14-RU RONTEC USA Inc. n.d. <LLD <LLD 48 2 954 28 KP-SE-19-RU RONTEC USA Inc. n.d. 1 <LLD 39 3 881 28 KP-SE-28-RU RONTEC USA Inc. n.d. <LLD <LLD 50 2 713 29 TL-SE-04-XX Reference Laboratory 1.2 U 10 0.5 U 62 1,900 42,000 29 TL-SE-10-XX Reference Laboratory 1.2 U 10 0.5 U 64 2,000 43,000 29 TL-SE-12-XX Reference Laboratory 1.2 U 10 0.5 U 66 2,100 44,000 29 TL-SE-15-XX Reference Laboratory 1.2 U 9 0.5 U 54 1,800 36,000 29 TL-SE-20-XX Reference Laboratory 1.2 U 10 0.5 U 64 2,000 42,000 29 TL-SE-24-XX Reference Laboratory 1.2 U 11 0.5 U 67 2,100 43,000 29 TL-SE-26-XX Reference Laboratory 1.2 U 10 0.5 U 62 2,000 40,000 29 TL-SE-04-RU RONTEC USA Inc. n.d. 12 <LLD 54 1,888 47,319 29 TL-SE-10-RU RONTEC USA Inc. n.d. 8 <LLD 45 1,002 31,807 29 TL-SE-12-RU RONTEC USA Inc. n.d. 10 <LLD 30 1,235 27,621 29 TL-SE-15-RU RONTEC USA Inc. n.d. 8 10 29 829 25,442 29 TL-SE-20-RU RONTEC USA Inc. n.d. 15 <LLD 57 2,549 50,279 29 TL-SE-24-RU RONTEC USA Inc. n.d. 21 <LLD 56 2,120 53,443 29 TL-SE-26-RU RONTEC USA Inc. n.d. 13 <LLD 55 1,842 49,680 30 TL-SE-03-XX Reference Laboratory 2.5 U 9 1 U 91 1,600 63,000 30 TL-SE-19-XX Reference Laboratory 2.5 U 10 1 U 96 1,700 66,000 30 TL-SE-23-XX Reference Laboratory 2.5 U 9 1 U 92 1,600 64,000 30 TL-SE-25-XX Reference Laboratory 2.5 U 10 1 U 91 1,600 62,000 30 TL-SE-31-XX Reference Laboratory 2.5 U 10 1 U 110 1,800 74,000 30 TL-SE-03-RU RONTEC USA Inc. n.d. 7 <LLD 62 1,061 48,412 30 TL-SE-19-RU RONTEC USA Inc. n.d. 18 <LLD 76 1,746 75,114 30 TL-SE-23-RU RONTEC USA Inc. n.d. 12 555 85 1,775 75,899 30 TL-SE-25-RU RONTEC USA Inc. n.d. 13 <LLD 84 1,891 74,691 30 TL-SE-31-RU RONTEC USA Inc. n.d. 13 <LLD 85 1,857 80,869 
D-20 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

28 KP-SE-01-XX Reference Laboratory 16 0.26 U 0.26 UJ 2 J 6 28 KP-SE-12-XX Reference Laboratory 20 0.26 U 0.26 UJ 2 J 8 28 KP-SE-14-XX Reference Laboratory 23 J- 0.26 U 0.26 UJ 3 J 7 28 KP-SE-19-XX Reference Laboratory 22 0.26 U 0.26 U 2 J 7 28 KP-SE-28-XX Reference Laboratory 22 0.26 U 0.26 U 2 J 6 28 KP-SE-01-RU RONTEC USA Inc. 20 <LLD <LLD 4 23 28 KP-SE-12-RU RONTEC USA Inc. 22 <LLD <LLD 23 9 28 KP-SE-14-RU RONTEC USA Inc. 21 <LLD <LLD <LLD 8 28 KP-SE-19-RU RONTEC USA Inc. 17 <LLD <LLD <LLD 6 28 KP-SE-28-RU RONTEC USA Inc. 23 <LLD <LLD <LLD 7 29 TL-SE-04-XX Reference Laboratory 71 1.2 U 1.3 95 160 29 TL-SE-10-XX Reference Laboratory 72 1.2 U 1.2 U 95 160 29 TL-SE-12-XX Reference Laboratory 75 1.2 U 1.2 U 100 170 29 TL-SE-15-XX Reference Laboratory 63 1.2 U 1 U 84 140 29 TL-SE-20-XX Reference Laboratory 74 1.2 U 1.2 U 100 160 29 TL-SE-24-XX Reference Laboratory 77 1.2 U 1.3 U 100 170 29 TL-SE-26-XX Reference Laboratory 70 1.2 U 1.2 U 96 160 29 TL-SE-04-RU RONTEC USA Inc. 54 <LLD <LLD 60 186 29 TL-SE-10-RU RONTEC USA Inc. 33 <LLD <LLD 36 111 29 TL-SE-12-RU RONTEC USA Inc. 94 <LLD <LLD 37 119 29 TL-SE-15-RU RONTEC USA Inc. 30 <LLD <LLD 27 97 29 TL-SE-20-RU RONTEC USA Inc. 82 <LLD <LLD 77 187 29 TL-SE-24-RU RONTEC USA Inc. 61 <LLD <LLD 54 221 29 TL-SE-26-RU RONTEC USA Inc. 56 <LLD <LLD 46 187 30 TL-SE-03-XX Reference Laboratory 110 2.5 U 0.94 U 140 200 30 TL-SE-19-XX Reference Laboratory 120 2.5 U 1.1 U 150 210 30 TL-SE-23-XX Reference Laboratory 110 2.5 U 1.3 U 150 200 30 TL-SE-25-XX Reference Laboratory 110 2.5 U 0.94 U 150 200 30 TL-SE-31-XX Reference Laboratory 130 2.5 U 1.2 U 170 230 30 TL-SE-03-RU RONTEC USA Inc. 63 <LLD <LLD 49 133 30 TL-SE-19-RU RONTEC USA Inc. 93 <LLD <LLD 109 307 30 TL-SE-23-RU RONTEC USA Inc. 99 <LLD 93 93 222 30 TL-SE-25-RU RONTEC USA Inc. 92 <LLD <LLD 77 219 30 TL-SE-31-RU RONTEC USA Inc. 101 <LLD <LLD 118 236 
D-21 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

31 TL-SE-01-XX Reference Laboratory 1.2 UJ 9 0.5 U 110 1,400 19,000 431 TL-SE-11-XX Reference Laboratory 1.2 UJ 15 0.5 U 140 1,600 28,000 531 TL-SE-14-XX Reference Laboratory 1.2 UJ 10 0.27 J 110 1,500 18,000 531 TL-SE-18-XX Reference Laboratory 1.2 UJ 10 0.5 U 150 1,300 24,000 431 TL-SE-22-XX Reference Laboratory 1.2 UJ 11 0.5 U 150 1,700 26,000 531 TL-SE-27-XX Reference Laboratory 1.2 UJ 10 0.28 J 130 1,500 19,000 531 TL-SE-29-XX Reference Laboratory 1.2 UJ 11 0.22 J 140 1,600 23,000 531 TL-SE-01-RU RONTEC USA Inc. n.d. 7 <LLD 104 1,007 35,595 531 TL-SE-11-RU RONTEC USA Inc. n.d. 5 <LLD 80 674 23,745 331 TL-SE-14-RU RONTEC USA Inc. n.d. 4 <LLD 55 344 11,035 131 TL-SE-18-RU RONTEC USA Inc. n.d. 4 <LLD 61 560 14,856 231 TL-SE-22-RU RONTEC USA Inc. n.d. 11 <LLD 167 783 31,767 431 TL-SE-27-RU RONTEC USA Inc. n.d. 6 <LLD 89 713 22,219 331 TL-SE-29-RU RONTEC USA Inc. n.d. 8 <LLD 129 700 22,100 432 LV-SE-02-XX Reference Laboratory 1.3 UJ 28 0.51 U 72 33 23,000 232 LV-SE-10-XX Reference Laboratory 1.3 UJ 34 0.51 U 84 42 28,000 232 LV-SE-22-XX Reference Laboratory 1.3 UJ 30 0.51 U 69 33 23,000 232 LV-SE-25-XX Reference Laboratory 1.3 UJ 31 0.51 U 74 36 25,000 232 LV-SE-31-XX Reference Laboratory 1.3 UJ 32 0.51 U 78 36 25,000 432 LV-SE-35-XX Reference Laboratory 1.3 UJ 31 J- 0.51 U 74 J- 35 24,000 J- 232 LV-SE-50-XX Reference Laboratory 2.5 U 29 1 U 74 34 24,000 232 LV-SE-02-RU RONTEC USA Inc. n.d. 25 <LLD 83 36 34,858 532 LV-SE-10-RU RONTEC USA Inc. n.d. 44 <LLD 168 47 36,427 332 LV-SE-22-RU RONTEC USA Inc. n.d. 30 <LLD 128 42 32,042 332 LV-SE-25-RU RONTEC USA Inc. n.d. 39 <LLD 59 31 31,844 232 LV-SE-31-RU RONTEC USA Inc. n.d. 29 <LLD 79 35 28,942 532 LV-SE-35-RU RONTEC USA Inc. n.d. 38 <LLD 81 34 26,193 232 LV-SE-50-RU RONTEC USA Inc. n.d. 31 <LLD 73 34 36,500 733 LV-SE-12-XX Reference Laboratory 2.6 U 190 1 U 55 34 72,000 133 LV-SE-26-XX Reference Laboratory 2.6 U 220 1 U 64 39 83,000 233 LV-SE-33-XX Reference Laboratory 2.6 U 170 1 U 52 31 66,000 233 LV-SE-39-XX Reference Laboratory 2.6 U 190 1 U 58 35 74,000 233 LV-SE-42-XX Reference Laboratory 2.7 U 170 1.1 U 50 30 65,000 233 LV-SE-12-RU RONTEC USA Inc. n.d. 247 <LLD 89 44 103,600 133 LV-SE-26-RU RONTEC USA Inc. n.d. 201 <LLD 95 43 84,371 133 LV-SE-33-RU RONTEC USA Inc. n.d. 185 <LLD 59 35 71,708 233 LV-SE-39-RU RONTEC USA Inc. n.d. 191 <LLD 75 30 72,280 433 LV-SE-42-RU RONTEC USA Inc. n.d. 145 <LLD 54 31 62,867 13
D-22 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

31 TL-SE-01-XX Reference Laboratory 180 1.2 U 5.7 J- 75 130 31 TL-SE-11-XX Reference Laboratory 210 1.2 U 5.5 J- 85 140 31 TL-SE-14-XX Reference Laboratory 180 1.2 U 5.7 J- 73 140 31 TL-SE-18-XX Reference Laboratory 190 1.2 U 6.3 J- 70 120 31 TL-SE-22-XX Reference Laboratory 210 1.2 U 6.5 J- 80 150 31 TL-SE-27-XX Reference Laboratory 200 1.2 U 7.8 J- 67 140 31 TL-SE-29-XX Reference Laboratory 200 1.2 U 5.9 J- 80 140 31 TL-SE-01-RU RONTEC USA Inc. 113 <LLD <LLD 49 126 31 TL-SE-11-RU RONTEC USA Inc. 80 <LLD <LLD 34 76 31 TL-SE-14-RU RONTEC USA Inc. 57 <LLD <LLD 18 48 31 TL-SE-18-RU RONTEC USA Inc. 92 <LLD <LLD 22 52 31 TL-SE-22-RU RONTEC USA Inc. 216 <LLD <LLD 47 102 31 TL-SE-27-RU RONTEC USA Inc. 215 <LLD <LLD 27 87 31 TL-SE-29-RU RONTEC USA Inc. 121 <LLD <LLD 29 93 32 LV-SE-02-XX Reference Laboratory 160 3.8 1.3 UJ 53 65 32 LV-SE-10-XX Reference Laboratory 200 4.7 1.3 UJ 66 77 32 LV-SE-22-XX Reference Laboratory 170 5.2 1.3 UJ 51 66 32 LV-SE-25-XX Reference Laboratory 170 5.1 1.3 UJ 56 70 32 LV-SE-31-XX Reference Laboratory 180 5.1 1.3 UJ 58 70 32 LV-SE-35-XX Reference Laboratory 170 J- 5 1.3 UJ 55 J- 67 J32 LV-SE-50-XX Reference Laboratory 170 3.3 2.5 U 57 65 32 LV-SE-02-RU RONTEC USA Inc. 110 <LLD <LLD 84 88 32 LV-SE-10-RU RONTEC USA Inc. 129 1 <LLD 57 86 32 LV-SE-22-RU RONTEC USA Inc. 137 1 <LLD 80 88 32 LV-SE-25-RU RONTEC USA Inc. 119 0 <LLD 42 76 32 LV-SE-31-RU RONTEC USA Inc. 123 1 <LLD 64 74 32 LV-SE-35-RU RONTEC USA Inc. 86 2 <LLD 53 70 32 LV-SE-50-RU RONTEC USA Inc. 83 2 <LLD 91 92 33 LV-SE-12-XX Reference Laboratory 71 3 2.6 U 72 66 33 LV-SE-26-XX Reference Laboratory 83 6.1 2.6 U 86 75 33 LV-SE-33-XX Reference Laboratory 66 2.8 2.6 U 67 59 33 LV-SE-39-XX Reference Laboratory 74 5.1 2.6 U 74 66 33 LV-SE-42-XX Reference Laboratory 67 3.4 2.7 U 64 57 33 LV-SE-12-RU RONTEC USA Inc. 92 <LLD <LLD 64 104 33 LV-SE-26-RU RONTEC USA Inc. 67 <LLD <LLD 66 88 33 LV-SE-33-RU RONTEC USA Inc. 37 1 <LLD 38 77 33 LV-SE-39-RU RONTEC USA Inc. 53 2 <LLD 59 71 33 LV-SE-42-RU RONTEC USA Inc. 74 3 <LLD 85 71 
D-23 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

34 LV-SE-09-XX Reference Laboratory 6.7 U 450 2.7 U 48 34 150,000 34 LV-SE-19-XX Reference Laboratory 6.7 U 500 2.7 U 55 37 160,000 34 LV-SE-27-XX Reference Laboratory 6.7 U 530 2.7 U 56 39 180,000 34 LV-SE-36-XX Reference Laboratory 6.7 U 550 2.7 U 60 40 180,000 34 LV-SE-38-XX Reference Laboratory 6.7 U 480 2.7 U 52 36 160,000 34 LV-SE-09-RU RONTEC USA Inc. n.d. 595 <LLD 50 37 200,522 34 LV-SE-19-RU RONTEC USA Inc. n.d. 541 <LLD 26 33 181,384 <L34 LV-SE-27-RU RONTEC USA Inc. n.d. 424 <LLD 35 29 150,539 34 LV-SE-36-RU RONTEC USA Inc. n.d. 455 <LLD 54 34 150,866 34 LV-SE-38-RU RONTEC USA Inc. n.d. 505 <LLD 94 36 164,068 35 LV-SE-07-XX Reference Laboratory 6.7 UJ 780 2.7 U 57 48 200,000 35 LV-SE-18-XX Reference Laboratory 6.7 UJ 800 2.7 U 61 49 210,000 35 LV-SE-23-XX Reference Laboratory 6.6 UJ 660 2.6 U 53 40 170,000 35 LV-SE-45-XX Reference Laboratory 6.7 UJ 650 2.7 U 50 40 170,000 35 LV-SE-48-XX Reference Laboratory 6.6 UJ 680 2.6 U 52 42 180,000 35 LV-SE-07-RU RONTEC USA Inc. n.d. 825 <LLD 50 44 253,402 <L35 LV-SE-18-RU RONTEC USA Inc. n.d. 775 <LLD 44 56 202,701 <L35 LV-SE-23-RU RONTEC USA Inc. n.d. 772 <LLD 37 40 228,099 <L35 LV-SE-45-RU RONTEC USA Inc. n.d. 667 <LLD 134 33 179,984 35 LV-SE-48-RU RONTEC USA Inc. n.d. 653 <LLD 142 29 168,659 36 LV-SE-01-XX Reference Laboratory 1.5 UJ 6 0.76 4 18 1,100 36 LV-SE-14-XX Reference Laboratory 1.5 UJ 5 0.74 4 16 980 36 LV-SE-21-XX Reference Laboratory 1.5 UJ 7 0.84 4 19 970 36 LV-SE-24-XX Reference Laboratory 1.5 UJ 5 0.68 4 15 840 36 LV-SE-32-XX Reference Laboratory 1.4 UJ 6 0.87 4 16 860 36 LV-SE-01-RU RONTEC USA Inc. n.d. <LLD 1,404 <LLD 7 730 36 LV-SE-14-RU RONTEC USA Inc. n.d. 1 372 4 10 673 36 LV-SE-21-RU RONTEC USA Inc. n.d. <LLD 1,197 <LLD 12 672 36 LV-SE-24-RU RONTEC USA Inc. n.d. 3 927 <LLD 14 797 36 LV-SE-32-RU RONTEC USA Inc. n.d. 2 <LLD <LLD 8 436 
D-24 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

34 LV-SE-09-XX Reference Laboratory 55 6.7 U 6.7 U 100 51 J 34 LV-SE-19-XX Reference Laboratory 65 5.9 J 6.7 U 110 55 J 34 LV-SE-27-XX Reference Laboratory 64 6.7 U 6.7 U 120 58 J 34 LV-SE-36-XX Reference Laboratory 70 11 6.7 U 120 60 J 34 LV-SE-38-XX Reference Laboratory 75 6.7 U 6.7 U 100 54 J 34 LV-SE-09-RU RONTEC USA Inc. 160 <LLD <LLD 79 88 34 LV-SE-19-RU RONTEC USA Inc. 61 1 <LLD 89 78 34 LV-SE-27-RU RONTEC USA Inc. 54 <LLD <LLD 40 86 34 LV-SE-36-RU RONTEC USA Inc. 45 2 <LLD 40 68 34 LV-SE-38-RU RONTEC USA Inc. 23 4 <LLD 30 76 35 LV-SE-07-XX Reference Laboratory 58 10 6.7 U 130 24 J 35 LV-SE-18-XX Reference Laboratory 60 12 6.7 U 140 52 J 35 LV-SE-23-XX Reference Laboratory 50 J 9.6 6.6 U 120 18 J 35 LV-SE-45-XX Reference Laboratory 50 J 8.2 6.7 U 120 19 J 35 LV-SE-48-XX Reference Laboratory 50 J 7.6 6.6 U 120 30 J 35 LV-SE-07-RU RONTEC USA Inc. 70 2 <LLD 116 48 35 LV-SE-18-RU RONTEC USA Inc. 46 5 <LLD 72 41 35 LV-SE-23-RU RONTEC USA Inc. 54 2 <LLD 64 45 35 LV-SE-45-RU RONTEC USA Inc. 25 3 <LLD 62 35 35 LV-SE-48-RU RONTEC USA Inc. 19 2 450 64 29 36 LV-SE-01-XX Reference Laboratory 49 1.5 U 1.5 U 2 J 14 J 36 LV-SE-14-XX Reference Laboratory 46 1.5 U 1.5 U 1 J 12 J 36 LV-SE-21-XX Reference Laboratory 49 1.5 U 1.5 U 2 J 14 J 36 LV-SE-24-XX Reference Laboratory 44 1.5 U 1.5 U 1 J 12 J 36 LV-SE-32-XX Reference Laboratory 47 1.4 U 1.4 U 1 J 19 36 LV-SE-01-RU RONTEC USA Inc. 44 <LLD 514 <LLD 7 36 LV-SE-14-RU RONTEC USA Inc. 39 <LLD 193 3 8 36 LV-SE-21-RU RONTEC USA Inc. 40 <LLD 428 <LLD 13 36 LV-SE-24-RU RONTEC USA Inc. 38 <LLD 400 <LLD 8 36 LV-SE-32-RU RONTEC USA Inc. 32 <LLD <LLD 3 6 
D-25 

Appendix D: Analytical Data Summary, RONTEC Pico Tax 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-RU RONTEC USA Inc. n.d. 42 <LLD 51 27 39,625 109 37 LV-SE-16-RU RONTEC USA Inc. n.d. 33 <LLD 85 35 32,967 102 37 LV-SE-28-RU RONTEC USA Inc. n.d. 27 <LLD 62 25 278 94 37 LV-SE-30-RU RONTEC USA Inc. n.d. 39 <LLD 49 22 22,219 54 37 LV-SE-47-RU RONTEC USA Inc. n.d. 28 <LLD 54 26 26,058 103 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 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-RU RONTEC USA Inc. n.d. 147 <LLD 74 254 47,660 11 38 LV-SE-29-RU RONTEC USA Inc. n.d. 138 <LLD 125 237 39,654 4 38 LV-SE-44-RU RONTEC USA Inc. n.d. 151 <LLD 110 276 46,297 25 38 LV-SE-46-RU RONTEC USA Inc. n.d. 117 <LLD 98 220 38,544 34 38 LV-SE-52-RU RONTEC USA Inc. n.d. 149 <LLD 112 282 49,693 29 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 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-RU RONTEC USA Inc. n.d. 21 <LLD 90 104 22,218 37 39 RF-SE-12-RU RONTEC USA Inc. n.d. 27 <LLD 145 103 24,091 28 39 RF-SE-23-RU RONTEC USA Inc. n.d. 5 <LLD 83 82 20,014 76 39 RF-SE-36-RU RONTEC USA Inc. n.d. 21 <LLD 111 112 27,871 55 39 RF-SE-42-RU RONTEC USA Inc. n.d. 16 <LLD 85 84 21,471 38 39 RF-SE-45-RU RONTEC USA Inc. n.d. 20 <LLD 91 92 22,497 51 39 RF-SE-53-RU RONTEC USA Inc. n.d. 15 <LLD 72 88 20,362 47 
D-26 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

37 LV-SE-08-XX Reference Laboratory 110 4.8 1.3 U 44 61 37 LV-SE-16-XX Reference Laboratory 110 5 1.3 U 42 59 37 LV-SE-28-XX Reference Laboratory 120 5.8 1.3 U 48 65 37 LV-SE-30-XX Reference Laboratory 120 5.6 1.3 U 48 66 37 LV-SE-47-XX Reference Laboratory 120 4.2 1.3 U 45 65 37 LV-SE-08-RU RONTEC USA Inc. 100 1 <LLD 57 100 37 LV-SE-16-RU RONTEC USA Inc. 120 2 <LLD 56 90 37 LV-SE-28-RU RONTEC USA Inc. 104 1 <LLD 45 63 37 LV-SE-30-RU RONTEC USA Inc. 90 2 <LLD 39 64 37 LV-SE-47-RU RONTEC USA Inc. 84 2 134 48 70 38 LV-SE-11-XX Reference Laboratory 870 1.3 U 1.4 U 35 200 38 LV-SE-29-XX Reference Laboratory 860 1.2 U 1.4 U 35 200 38 LV-SE-44-XX Reference Laboratory 830 1.4 U 1.4 U 34 190 38 LV-SE-46-XX Reference Laboratory 660 0.88 U 0.88 U 27 150 38 LV-SE-52-XX Reference Laboratory 910 1.4 U 1.4 U 38 210 38 LV-SE-11-RU RONTEC USA Inc. 883 <LLD <LLD 18 206 38 LV-SE-29-RU RONTEC USA Inc. 821 <LLD <LLD 17 184 38 LV-SE-44-RU RONTEC USA Inc. 946 1 <LLD 29 227 38 LV-SE-46-RU RONTEC USA Inc. 772 <LLD <LLD 24 177 38 LV-SE-52-RU RONTEC USA Inc. 952 <LLD 423 31 228 39 RF-SE-07-XX Reference Laboratory 180 1.3 U 1.3 U 34 130 39 RF-SE-12-XX Reference Laboratory 210 1.2 U 1.2 U 38 140 39 RF-SE-23-XX Reference Laboratory 2 U 0.25 U 0.37 3 U 1 U 39 RF-SE-36-XX Reference Laboratory 180 1 U 1.2 U 34 120 39 RF-SE-42-XX Reference Laboratory 210 1.3 U 1.3 U 40 140 39 RF-SE-45-XX Reference Laboratory 220 1.3 U 1.3 U 43 150 39 RF-SE-53-XX Reference Laboratory 210 1.3 U 1.3 U 40 140 39 RF-SE-07-RU RONTEC USA Inc. 137 2 <LLD 15 141 39 RF-SE-12-RU RONTEC USA Inc. 175 <LLD <LLD 33 123 39 RF-SE-23-RU RONTEC USA Inc. 120 <LLD 28 27 114 39 RF-SE-36-RU RONTEC USA Inc. 170 <LLD 38 41 207 39 RF-SE-42-RU RONTEC USA Inc. 132 <LLD <LLD 27 122 39 RF-SE-45-RU RONTEC USA Inc. 100 <LLD <LLD 49 140 39 RF-SE-53-RU RONTEC USA Inc. 140 <LLD 59 30 119 
D-27 

Appendix D: Analytical Data Summary, RONTEC Pico Tax 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 17,000 840 RF-SE-28-XX Reference Laboratory 1.2 UJ 31 1.5 100 220 18,000 940 RF-SE-38-XX Reference Laboratory 1.2 UJ 27 1.2 90 190 16,000 840 RF-SE-49-XX Reference Laboratory 1.2 UJ 31 1.5 100 220 18,000 940 RF-SE-55-XX Reference Laboratory 1.2 UJ 24 1.1 91 180 15,000 740 RF-SE-03-RU RONTEC USA Inc. n.d. 21 <LLD 86 185 22,413 1440 RF-SE-28-RU RONTEC USA Inc. n.d. 19 <LLD 82 174 16,154 1140 RF-SE-38-RU RONTEC USA Inc. n.d. 44 <LLD 171 219 26,782 940 RF-SE-49-RU RONTEC USA Inc. n.d. 28 <LLD 79 185 19,425 1140 RF-SE-55-RU RONTEC USA Inc. n.d. 26 <LLD 83 202 20,676 1741 RF-SE-06-XX Reference Laboratory 1.3 UJ 70 3.6 90 490 20,000 2341 RF-SE-13-XX Reference Laboratory 1.3 UJ 76 3.7 92 530 21,000 2341 RF-SE-27-XX Reference Laboratory 1.3 UJ 64 3.1 78 440 18,000 2041 RF-SE-31-XX Reference Laboratory 1.3 UJ 39 1.8 63 250 12,000 1241 RF-SE-58-XX Reference Laboratory 1.3 UJ 71 3.6 89 500 21,000 2341 RF-SE-06-RU RONTEC USA Inc. n.d. 52 <LLD 76 397 18,911 2741 RF-SE-13-RU RONTEC USA Inc. n.d. 93 <LLD 150 373 20,401 2341 RF-SE-27-RU RONTEC USA Inc. n.d. 90 <LLD 78 531 24,575 2541 RF-SE-31-RU RONTEC USA Inc. n.d. 79 <LLD 97 389 23,439 2441 RF-SE-58-RU RONTEC USA Inc. n.d. 50 <LLD 60 404 21,685 2842 RF-SE-02-XX Reference Laboratory 1.3 UJ 110 5.4 93 740 24,000 3342 RF-SE-22-XX Reference Laboratory 1.3 UJ 99 4.7 84 670 22,000 3042 RF-SE-25-XX Reference Laboratory 1.3 UJ 88 4 78 580 19,000 2742 RF-SE-30-XX Reference Laboratory 1.3 UJ 89 4.3 78 610 21,000 2942 RF-SE-57-XX Reference Laboratory 1.3 UJ 89 4.5 79 610 21,000 3042 RF-SE-02-RU RONTEC USA Inc. n.d. 75 <LLD 56 543 19,787 3442 RF-SE-22-RU RONTEC USA Inc. n.d. 83 <LLD 66 510 23,425 3442 RF-SE-25-RU RONTEC USA Inc. n.d. 83 <LLD 53 539 24,307 2542 RF-SE-30-RU RONTEC USA Inc. n.d. 68 <LLD 92 546 22,093 3642 RF-SE-57-RU RONTEC USA Inc. n.d. 74 <LLD 54 530 21,034 36
D-28 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

40 RF-SE-03-XX Reference Laboratory 150 1.2 U 1.2 U 40 300 40 RF-SE-28-XX Reference Laboratory 160 1.2 U 1.2 U 44 320 40 RF-SE-38-XX Reference Laboratory 140 1.2 U 1.2 U 39 300 40 RF-SE-49-XX Reference Laboratory 170 1.2 U 1.2 U 43 330 40 RF-SE-55-XX Reference Laboratory 140 1.2 U 1.2 U 35 280 40 RF-SE-03-RU RONTEC USA Inc. 108 <LLD <LLD 37 415 40 RF-SE-28-RU RONTEC USA Inc. 138 <LLD 221 42 190 40 RF-SE-38-RU RONTEC USA Inc. 108 <LLD 36 50 304 40 RF-SE-49-RU RONTEC USA Inc. 115 <LLD <LLD 30 259 40 RF-SE-55-RU RONTEC USA Inc. 95 <LLD <LLD 50 241 41 RF-SE-06-XX Reference Laboratory 150 1.3 U 1.3 U 44 740 41 RF-SE-13-XX Reference Laboratory 160 1.3 U 1.3 45 790 41 RF-SE-27-XX Reference Laboratory 130 1.3 U 1.3 U 39 670 41 RF-SE-31-XX Reference Laboratory 86 1.3 U 1.3 U 28 420 41 RF-SE-58-XX Reference Laboratory 150 1.3 U 1.3 U 46 770 41 RF-SE-06-RU RONTEC USA Inc. 78 <LLD <LLD 33 616 41 RF-SE-13-RU RONTEC USA Inc. 82 <LLD <LLD 35 579 41 RF-SE-27-RU RONTEC USA Inc. 150 <LLD <LLD 29 790 41 RF-SE-31-RU RONTEC USA Inc. 85 <LLD <LLD 24 731 41 RF-SE-58-RU RONTEC USA Inc. 77 <LLD 120 55 631 42 RF-SE-02-XX Reference Laboratory 180 1.3 U 2.7 50 1,100 42 RF-SE-22-XX Reference Laboratory 160 1.3 U 2.3 44 990 42 RF-SE-25-XX Reference Laboratory 140 1.5 1.7 40 890 42 RF-SE-30-XX Reference Laboratory 150 1.3 U 1.9 44 960 42 RF-SE-57-XX Reference Laboratory 150 2 2.2 44 1,000 42 RF-SE-02-RU RONTEC USA Inc. 67 <LLD <LLD 35 770 42 RF-SE-22-RU RONTEC USA Inc. 70 <LLD <LLD 37 831 42 RF-SE-25-RU RONTEC USA Inc. 80 <LLD <LLD 31 717 42 RF-SE-30-RU RONTEC USA Inc. 90 <LLD <LLD 52 937 42 RF-SE-57-RU RONTEC USA Inc. 71 <LLD 23 46 800 
D-29 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe P

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 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-RU RONTEC USA Inc. n.d. 174 <LLD 89 889 26,090 465 43 RF-SE-24-RU RONTEC USA Inc. n.d. 122 <LLD 69 686 25,855 488 43 RF-SE-32-RU RONTEC USA Inc. n.d. 167 <LLD 80 862 28,931 435 43 RF-SE-43-RU RONTEC USA Inc. n.d. 123 <LLD 51 744 26,941 494 43 RF-SE-59-RU RONTEC USA Inc. n.d. 140 <LLD 37 747 29,784 521 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-RU RONTEC USA Inc. n.d. 163 <LLD 56 945 23,076 458 44 RF-SE-26-RU RONTEC USA Inc. n.d. 218 <LLD 101 1,847 25,154 783 44 RF-SE-39-RU RONTEC USA Inc. n.d. 304 <LLD 56 1,520 34,504 583 44 RF-SE-44-RU RONTEC USA Inc. n.d. 180 <LLD 46 1,060 27,517 505 44 RF-SE-56-RU RONTEC USA Inc. n.d. 135 <LLD 409 976 40,100 629 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-RU RONTEC USA Inc. n.d. 227 <LLD 25 1,163 23,502 680 45 RF-SE-14-RU RONTEC USA Inc. n.d. 216 <LLD 32 1,183 23,637 739 45 RF-SE-19-RU RONTEC USA Inc. n.d. 265 <LLD 47 1,205 27,027 704 45 RF-SE-34-RU RONTEC USA Inc. n.d. 246 <LLD 29 1,398 28,603 757 45 RF-SE-52-RU RONTEC USA Inc. n.d. 197 <LLD 34 1,296 26,306 832 
D-30 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

43 RF-SE-15-XX Reference Laboratory 160 1.4 3.6 45 1,300 43 RF-SE-24-XX Reference Laboratory 170 J+ 1.3 U 3.8 J+ 46 J+ 1,400 J43 RF-SE-32-XX Reference Laboratory 140 1.3 U 4.2 36 1,100 43 RF-SE-43-XX Reference Laboratory 150 1.3 U 4 40 1,200 43 RF-SE-59-XX Reference Laboratory 160 1.3 U 4.5 42 1,300 43 RF-SE-15-RU RONTEC USA Inc. 110 <LLD <LLD 41 1,034 43 RF-SE-24-RU RONTEC USA Inc. 68 <LLD <LLD 41 1,170 43 RF-SE-32-RU RONTEC USA Inc. 171 <LLD 18 35 1,123 43 RF-SE-43-RU RONTEC USA Inc. 82 <LLD <LLD 54 981 43 RF-SE-59-RU RONTEC USA Inc. 67 <LLD 39 51 1,067 44 RF-SE-05-XX Reference Laboratory 150 3.1 7.4 J- 48 1,800 44 RF-SE-26-XX Reference Laboratory 140 2.8 7.2 J- 42 1,700 44 RF-SE-39-XX Reference Laboratory 150 2.6 8.2 J- 49 1,900 44 RF-SE-44-XX Reference Laboratory 140 2.4 7.2 J- 44 1,600 44 RF-SE-56-XX Reference Laboratory 160 1.8 8.3 J- 51 1,900 44 RF-SE-05-RU RONTEC USA Inc. 49 <LLD <LLD 21 1,179 44 RF-SE-26-RU RONTEC USA Inc. 158 <LLD 128 67 1,997 44 RF-SE-39-RU RONTEC USA Inc. 116 <LLD <LLD 43 1,810 44 RF-SE-44-RU RONTEC USA Inc. 72 <LLD <LLD 51 1,945 44 RF-SE-56-RU RONTEC USA Inc. 100 <LLD <LLD 95 1,738 45 RF-SE-04-XX Reference Laboratory 130 2.8 12 J- 46 2,400 45 RF-SE-14-XX Reference Laboratory 140 3 13 J- 51 2,600 45 RF-SE-19-XX Reference Laboratory 140 4.1 14 J- 52 2,700 45 RF-SE-34-XX Reference Laboratory 120 1.9 10 J- 42 2,200 45 RF-SE-52-XX Reference Laboratory 130 2 11 J- 47 2,300 45 RF-SE-04-RU RONTEC USA Inc. 61 <LLD <LLD 35 1,518 45 RF-SE-14-RU RONTEC USA Inc. 49 <LLD <LLD 35 1,823 45 RF-SE-19-RU RONTEC USA Inc. 62 <LLD 40 40 1,917 45 RF-SE-34-RU RONTEC USA Inc. 77 <LLD <LLD 44 2,250 45 RF-SE-52-RU RONTEC USA Inc. 71 <LLD <LLD 55 1,953 
D-31 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

46 BN-SO-11-XX Reference Laboratory 4 J- 2,900 720 820 120 23,000 46 BN-SO-14-XX Reference Laboratory 3.5 J- 2,800 690 800 120 22,000 46 BN-SO-23-XX Reference Laboratory 1.2 UJ 2,800 700 800 120 23,000 46 BN-SO-11-RU RONTEC USA Inc. n.d. 47 <LLD 137 32 28,672 46 BN-SO-14-RU RONTEC USA Inc. n.d. 3,318 188 806 124 28,671 46 BN-SO-23-RU RONTEC USA Inc. n.d. 2,830 385 651 106 21,762 47 BN-SO-09-XX Reference Laboratory 750 J- 97 2,700 2,900 100 22,000 447 BN-SO-12-XX Reference Laboratory 750 J- 89 2,600 2,800 96 21,000 447 BN-SO-24-XX Reference Laboratory 810 J- 97 2,900 3,000 100 23,000 447 BN-SO-09-RU RONTEC USA Inc. n.d. 54 2,656 2,479 98 26,685 547 BN-SO-12-RU RONTEC USA Inc. n.d. 64 3,791 2,485 96 24,218 547 BN-SO-24-RU RONTEC USA Inc. n.d. 54 2,962 2,302 93 21,118 448 SB-SO-09-XX Reference Laboratory 1.3 UJ 9 0.51 U 130 120 35,000 48 SB-SO-20-XX Reference Laboratory 1.3 UJ 11 0.51 U 170 150 44,000 48 SB-SO-31-XX Reference Laboratory 1.3 UJ 8 J- 0.51 U 140 130 38,000 48 SB-SO-09-RU RONTEC USA Inc. n.d. 19 <LLD 165 141 47,351 48 SB-SO-20-RU RONTEC USA Inc. n.d. 12 21 189 123 34,051 48 SB-SO-31-RU RONTEC USA Inc. n.d. 11 <LLD 118 83 26,680 49 SB-SO-29-XX Reference Laboratory 1.2 U 9 0.5 U 140 130 41,000 49 SB-SO-36-XX Reference Laboratory 1.2 U 8 0.5 U 120 100 33,000 49 SB-SO-56-XX Reference Laboratory 1.2 U 10 0.5 U 150 140 42,000 49 SB-SO-29-RU RONTEC USA Inc. n.d. 14 <LLD 532 124 45,006 49 SB-SO-36-RU RONTEC USA Inc. n.d. 14 <LLD 187 142 44,131 49 SB-SO-56-RU RONTEC USA Inc. n.d. 10 <LLD 115 108 31,211 50 SB-SO-04-XX Reference Laboratory 940 13 2,800 2,800 100 38,000 50 SB-SO-34-XX Reference Laboratory 980 12 2,500 2,500 91 34,000 50 SB-SO-49-XX Reference Laboratory 700 12 2,500 2,400 89 33,000 50 SB-SO-04-RU RONTEC USA Inc. n.d. 15 1,666 2,868 102 45,051 50 SB-SO-34-RU RONTEC USA Inc. n.d. 24 2,357 2,945 122 43,034 50 SB-SO-49-RU RONTEC USA Inc. n.d. 15 3,301 2,767 100 37,444 
D-32 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

46 BN-SO-11-XX Reference Laboratory 2,900 140 140 J- 150 3,900 46 BN-SO-14-XX Reference Laboratory 2,800 130 140 J- 150 3,800 46 BN-SO-23-XX Reference Laboratory 2,800 130 130 J- 150 3,800 46 BN-SO-11-RU RONTEC USA Inc. 63 <LLD <LLD 61 112 46 BN-SO-14-RU RONTEC USA Inc. 2,924 153 <LLD 127 4,272 46 BN-SO-23-RU RONTEC USA Inc. 2,986 117 109 117 4,229 47 BN-SO-09-XX Reference Laboratory 1,500 290 100 J- 340 81 47 BN-SO-12-XX Reference Laboratory 1,400 290 210 J- 310 74 47 BN-SO-24-XX Reference Laboratory 1,600 300 140 J- 350 81 47 BN-SO-09-RU RONTEC USA Inc. 1,399 285 106 275 96 47 BN-SO-12-RU RONTEC USA Inc. 1,594 297 203 291 86 47 BN-SO-24-RU RONTEC USA Inc. 1,464 267 116 234 83 48 SB-SO-09-XX Reference Laboratory 2900 26 160 J- 120 3,600 48 SB-SO-20-XX Reference Laboratory 3700 30 140 J- 160 4,500 48 SB-SO-31-XX Reference Laboratory 3200 J- 28 J- 160 J- 140 3,900 J48 SB-SO-09-RU RONTEC USA Inc. 2,958 34 <LLD 154 3,871 48 SB-SO-20-RU RONTEC USA Inc. 3,188 25 <LLD 115 4,241 48 SB-SO-31-RU RONTEC USA Inc. 1,984 20 <LLD 73 2,629 49 SB-SO-29-XX Reference Laboratory 200 160 1.2 UJ 400 3,900 49 SB-SO-36-XX Reference Laboratory 160 130 1.2 UJ 320 3,200 49 SB-SO-56-XX Reference Laboratory 210 160 1.2 UJ 410 4,100 49 SB-SO-29-RU RONTEC USA Inc. 195 189 <LLD 406 3,793 49 SB-SO-36-RU RONTEC USA Inc. 202 183 <LLD 373 4,730 49 SB-SO-56-RU RONTEC USA Inc. 156 124 <LLD 304 3,965 50 SB-SO-04-XX Reference Laboratory 3,300 390 1.3 UJ 58 86 50 SB-SO-34-XX Reference Laboratory 3,000 360 1.3 UJ 52 77 50 SB-SO-49-XX Reference Laboratory 2,800 330 1.2 UJ 52 72 50 SB-SO-04-RU RONTEC USA Inc. 2,524 457 <LLD 86 103 50 SB-SO-34-RU RONTEC USA Inc. 3,632 432 <LLD 43 109 50 SB-SO-49-RU RONTEC USA Inc. 3,447 397 <LLD 88 108 
D-33 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

51 WS-SO-07-XX Reference Laboratory 3.8 53 1.9 640 4,400 25,000 151 WS-SO-11-XX Reference Laboratory 1.2 U 46 1.4 570 3,900 19,000 151 WS-SO-25-XX Reference Laboratory 1.2 U 59 3.1 730 4,900 24,000 151 WS-SO-07-RU RONTEC USA Inc. n.d. 48 <LLD 631 4,546 29,751 251 WS-SO-11-RU RONTEC USA Inc. n.d. 47 <LLD 632 5,153 24,951 251 WS-SO-25-RU RONTEC USA Inc. n.d. 68 <LLD 668 5,506 28,037 252 WS-SO-10-XX Reference Laboratory 1.3 U 83 1.8 67 76 19,000 152 WS-SO-20-XX Reference Laboratory 1.3 U 100 1.9 81 90 23,000 252 WS-SO-23-XX Reference Laboratory 1.3 U 110 2.1 82 96 23,000 252 WS-SO-10-RU RONTEC USA Inc. n.d. 66 <LLD 103 89 29,399 252 WS-SO-20-RU RONTEC USA Inc. n.d. 2,876 927 35 966 33,229 3952 WS-SO-23-RU RONTEC USA Inc. n.d. 69 <LLD 66 89 27,609 253 AS-SO-03-XX Reference Laboratory 1.2 U 14 1,300 33 6,200 15,000 53 AS-SO-05-XX Reference Laboratory 1.2 U 9 900 23 4,500 11,000 53 AS-SO-08-XX Reference Laboratory 1.2 U 10 930 24 4,600 11,000 53 AS-SO-03-RU RONTEC USA Inc. n.d. 10 1,282 34 8,590 22,713 53 AS-SO-05-RU RONTEC USA Inc. n.d. 10 1,202 47 7,844 22,911 53 AS-SO-08-RU RONTEC USA Inc. n.d. 6 672 23 5,491 20,294 54 LV-SO-03-XX Reference Laboratory 1.6 42 590 600 130 24,000 54 LV-SO-40-XX Reference Laboratory 2.7 42 580 590 130 24,000 54 LV-SO-49-XX Reference Laboratory 7.4 43 600 610 130 25,000 54 LV-SO-03-RU RONTEC USA Inc. n.d. 41 <LLD 581 124 34,151 54 LV-SO-40-RU RONTEC USA Inc. n.d. 54 <LLD 680 121 31,441 54 LV-SO-49-RU RONTEC USA Inc. n.d. 52 <LLD 763 119 37,325 55 LV-SO-04-XX Reference Laboratory 860 120 2,400 2,300 98 22,000 455 LV-SO-34-XX Reference Laboratory 870 J- 110 J- 2,300 J- 2,200 J- 87 20,000 J- 355 LV-SO-37-XX Reference Laboratory 590 84 1,700 1,600 66 16,000 255 LV-SO-04-RU RONTEC USA Inc. n.d. 174 1,990 2,673 121 41,565 555 LV-SO-34-RU RONTEC USA Inc. n.d. 133 2,795 2,927 103 31,759 555 LV-SO-37-RU RONTEC USA Inc. n.d. 107 2,019 2,633 94 30,341 4
D-34 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

51 WS-SO-07-XX Reference Laboratory 260 1.2 U 400 J- 48 180 51 WS-SO-11-XX Reference Laboratory 240 1.2 U 340 J- 43 160 51 WS-SO-25-XX Reference Laboratory 300 1.2 U 450 J- 54 200 51 WS-SO-07-RU RONTEC USA Inc. 211 <LLD <LLD 46 188 51 WS-SO-11-RU RONTEC USA Inc. 260 <LLD 188 37 206 51 WS-SO-25-RU RONTEC USA Inc. 281 <LLD 77 34 252 52 WS-SO-10-XX Reference Laboratory 290 280 1.3 UJ 260 1,900 52 WS-SO-20-XX Reference Laboratory 350 340 1.3 UJ 320 2,300 52 WS-SO-23-XX Reference Laboratory 380 360 1.3 UJ 330 2,500 52 WS-SO-10-RU RONTEC USA Inc. 327 320 <LLD 279 2,392 52 WS-SO-20-RU RONTEC USA Inc. 21 11 30 12 4,425 52 WS-SO-23-RU RONTEC USA Inc. 296 303 <LLD 280 2,229 53 AS-SO-03-XX Reference Laboratory 520 200 480 J- 29 350 53 AS-SO-05-XX Reference Laboratory 370 140 330 J- 23 250 53 AS-SO-08-XX Reference Laboratory 380 140 280 J- 23 260 53 AS-SO-03-RU RONTEC USA Inc. 206 655 415 59 454 53 AS-SO-05-RU RONTEC USA Inc. 207 597 409 42 447 53 AS-SO-08-RU RONTEC USA Inc. 168 417 75 45 334 54 LV-SO-03-XX Reference Laboratory 2,000 120 210 J- 120 3,700 54 LV-SO-40-XX Reference Laboratory 1,900 120 210 J- 120 3,700 54 LV-SO-49-XX Reference Laboratory 2,000 120 220 J- 120 3,800 54 LV-SO-03-RU RONTEC USA Inc. 2,124 120 53 105 4,380 54 LV-SO-40-RU RONTEC USA Inc. 2,344 129 <LLD 126 4,819 54 LV-SO-49-RU RONTEC USA Inc. 1,100 137 <LLD 130 2,171 55 LV-SO-04-XX Reference Laboratory 2,000 230 1.2 UJ 260 53 55 LV-SO-34-XX Reference Laboratory 1,900 J- 220 J- 1.2 UJ 230 J- 48 J55 LV-SO-37-XX Reference Laboratory 1,400 170 1.2 U 180 37 55 LV-SO-04-RU RONTEC USA Inc. 2,235 293 <LLD 277 85 55 LV-SO-34-RU RONTEC USA Inc. 2,136 270 <LLD 294 67 55 LV-SO-37-RU RONTEC USA Inc. 1,496 257 <LLD 287 64 
D-35 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

56 CN-SO-03-XX Reference Laboratory 22 87 63 17 72 15,000 56 CN-SO-06-XX Reference Laboratory 20 91 64 18 74 16,000 56 CN-SO-07-XX Reference Laboratory 20 90 63 19 72 17,000 56 CN-SO-03-RU RONTEC USA Inc. n.d. 109 <LLD 24 92 23,426 56 CN-SO-06-RU RONTEC USA Inc. n.d. 106 17 11 92 16,552 56 CN-SO-07-RU RONTEC USA Inc. n.d. 105 <LLD 10 85 19,147 57 CN-SO-02-XX Reference Laboratory 230 19 820 290 140 22,000 457 CN-SO-05-XX Reference Laboratory 130 6 630 26 160 23,000 57 CN-SO-09-XX Reference Laboratory 120 6 580 21 140 19,000 57 CN-SO-02-RU RONTEC USA Inc. n.d. 10 238 27 145 24,617 57 CN-SO-05-RU RONTEC USA Inc. n.d. 11 415 31 204 25,341 57 CN-SO-09-RU RONTEC USA Inc. n.d. 11 179 13 158 35,028 58 LV-SE-06-XX Reference Laboratory 30 23 160 540 30 18,000 1,58 LV-SE-13-XX Reference Laboratory 31 24 160 540 30 18,000 1,58 LV-SE-41-XX Reference Laboratory 30 21 150 480 26 16,000 1,58 LV-SE-06-RU RONTEC USA Inc. n.d. 96 <LLD 527 34 33,642 2,58 LV-SE-13-RU RONTEC USA Inc. n.d. 52 <LLD 542 34 33,065 2,58 LV-SE-41-RU RONTEC USA Inc. n.d. 40 <LLD 715 37 27,720 2,59 LV-SE-05-XX Reference Laboratory 92 20 440 840 39 16,000 59 LV-SE-20-XX Reference Laboratory 140 J+ 31 680 1,400 60 22,000 59 LV-SE-43-XX Reference Laboratory 160 J+ 24 550 1,100 47 19,000 59 LV-SE-05-RU RONTEC USA Inc. n.d. 33 197 1,193 53 37,411 59 LV-SE-20-RU RONTEC USA Inc. n.d. 27 111 1,059 52 35,911 59 LV-SE-43-RU RONTEC USA Inc. n.d. 14 <LLD 1,210 45 26,671 60 LV-SE-15-XX Reference Laboratory 290 J+ 32 1,300 83 2,300 22,000 60 LV-SE-17-XX Reference Laboratory 280 J+ 31 1,300 79 2,200 21,000 60 LV-SE-51-XX Reference Laboratory 210 J+ 26 1,100 72 2,000 19,000 60 LV-SE-15-RU RONTEC USA Inc. n.d. 47 779 48 2,108 28,157 60 LV-SE-17-RU RONTEC USA Inc. n.d. 51 855 118 2,373 34,264 60 LV-SE-51-RU RONTEC USA Inc. n.d. 27 <LLD 61 1,656 27,276 61 TL-SE-05-XX Reference Laboratory 100 J+ 34 0.34 J 40 4,900 24,000 1,61 TL-SE-09-XX Reference Laboratory 100 J+ 33 0.24 J 39 4,800 23,000 1,61 TL-SE-13-XX Reference Laboratory 95 J+ 31 0.45 J 36 J+ 4,400 J+ 22,000 J+ 1,61 TL-SE-05-RU RONTEC USA Inc. n.d. 74 66 52 2,515 31,161 2,61 TL-SE-09-RU RONTEC USA Inc. n.d. 25 <LLD 16 2,351 13,275 61 TL-SE-13-RU RONTEC USA Inc. n.d. 30 <LLD 22 2,322 18,679 
D-36 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

56 CN-SO-03-XX Reference Laboratory 74 36 90 30 58 56 CN-SO-06-XX Reference Laboratory 76 38 94 32 59 56 CN-SO-07-XX Reference Laboratory 75 37 91 33 58 56 CN-SO-03-RU RONTEC USA Inc. 92 40 <LLD 51 79 56 CN-SO-06-RU RONTEC USA Inc. 100 38 47 35 76 56 CN-SO-07-RU RONTEC USA Inc. 86 39 <LLD 33 75 57 CN-SO-02-XX Reference Laboratory 530 190 68 160 1,900 57 CN-SO-05-XX Reference Laboratory 360 190 78 160 2,200 57 CN-SO-09-XX Reference Laboratory 330 170 74 140 2,100 57 CN-SO-02-RU RONTEC USA Inc. 311 160 <LLD 113 2,121 57 CN-SO-05-RU RONTEC USA Inc. 344 180 <LLD 133 2,312 57 CN-SO-09-RU RONTEC USA Inc. 328 174 <LLD 151 2,237 58 LV-SE-06-XX Reference Laboratory 360 160 110 480 52 58 LV-SE-13-XX Reference Laboratory 360 160 110 470 51 58 LV-SE-41-XX Reference Laboratory 320 150 99 420 46 58 LV-SE-06-RU RONTEC USA Inc. 389 180 <LLD 479 83 58 LV-SE-13-RU RONTEC USA Inc. 369 189 <LLD 483 79 58 LV-SE-41-RU RONTEC USA Inc. 338 176 <LLD 597 70 59 LV-SE-05-XX Reference Laboratory 400 340 49 340 1,800 59 LV-SE-20-XX Reference Laboratory 660 500 75 J- 530 2,800 59 LV-SE-43-XX Reference Laboratory 530 420 60 J- 430 2,300 59 LV-SE-05-RU RONTEC USA Inc. 471 496 90 484 2,112 59 LV-SE-20-RU RONTEC USA Inc. 537 466 <LLD 441 2,481 59 LV-SE-43-RU RONTEC USA Inc. 463 414 <LLD 489 2,256 60 LV-SE-15-XX Reference Laboratory 230 92 300 J- 180 62 60 LV-SE-17-XX Reference Laboratory 220 89 200 J- 170 58 60 LV-SE-51-XX Reference Laboratory 200 76 250 J- 160 54 60 LV-SE-15-RU RONTEC USA Inc. 158 72 204 129 61 60 LV-SE-17-RU RONTEC USA Inc. 190 76 365 166 77 60 LV-SE-51-RU RONTEC USA Inc. 136 68 494 161 67 61 TL-SE-05-XX Reference Laboratory 54 130 180 J- 66 100 61 TL-SE-09-XX Reference Laboratory 53 130 170 J- 63 100 61 TL-SE-13-XX Reference Laboratory 49 120 160 J 59 J+ 96 61 TL-SE-05-RU RONTEC USA Inc. 37 43 <LLD 44 81 61 TL-SE-09-RU RONTEC USA Inc. 13 59 <LLD 6 40 61 TL-SE-13-RU RONTEC USA Inc. 20 60 <LLD 18 50 
D-37 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe P

62 TL-SE-06-XX Reference Laboratory 1.2 U 86 350 34 2000 22,000 1,762 TL-SE-17-XX Reference Laboratory 1.2 U 85 340 33 2100 21,000 1,762 TL-SE-28-XX Reference Laboratory 1.2 U 89 360 34 2100 22,000 1,762 TL-SE-06-RU RONTEC USA Inc. n.d. 19 <LLD 60 2,613 66,310 62 TL-SE-17-RU RONTEC USA Inc. n.d. 46 <LLD 42 939 36,870 1,362 TL-SE-28-RU RONTEC USA Inc. n.d. 80 <LLD 46 2,140 37,399 2,163 TL-SE-07-XX Reference Laboratory 30 11 48 66 2200 37,000 63 TL-SE-21-XX Reference Laboratory 33 13 51 73 2300 44,000 63 TL-SE-30-XX Reference Laboratory 31 11 47 64 2200 36,000 63 TL-SE-07-RU RONTEC USA Inc. n.d. 23 23 62 3,699 72,976 <LL63 TL-SE-21-RU RONTEC USA Inc. n.d. 17 <LLD 50 2,435 62,156 63 TL-SE-30-RU RONTEC USA Inc. n.d. 17 <LLD 63 2,534 69,874 64 TL-SE-02-XX Reference Laboratory 77 15 160 64 3,100 32,000 64 TL-SE-08-XX Reference Laboratory 66 10 180 74 3,200 45,000 64 TL-SE-16-XX Reference Laboratory 73 15 170 69 3,100 38,000 64 TL-SE-02-RU RONTEC USA Inc. n.d. 21 <LLD 44 3,085 65,681 64 TL-SE-08-RU RONTEC USA Inc. n.d. 24 <LLD 90 4,183 75,135 64 TL-SE-16-RU RONTEC USA Inc. n.d. 12 16 39 1,689 40,259 65 RF-SE-01-XX Reference Laboratory 12 230 40 280 63 14,000 65 RF-SE-09-XX Reference Laboratory 10 260 45 310 71 16,000 65 RF-SE-11-XX Reference Laboratory 11 240 43 300 72 15,000 65 RF-SE-17-XX Reference Laboratory 11 250 43 300 67 15,000 65 RF-SE-29-XX Reference Laboratory 13 280 49 330 75 17,000 65 RF-SE-37-XX Reference Laboratory 11 260 45 320 72 16,000 65 RF-SE-50-XX Reference Laboratory 8.9 230 40 280 65 14,000 65 RF-SE-01-RU RONTEC USA Inc. n.d. 304 <LLD 335 77 1,573 65 RF-SE-09-RU RONTEC USA Inc. n.d. 276 <LLD 400 78 19,246 65 RF-SE-11-RU RONTEC USA Inc. n.d. 305 <LLD 370 72 16,797 <LL65 RF-SE-17-RU RONTEC USA Inc. n.d. 274 <LLD 323 70 18,068 65 RF-SE-29-RU RONTEC USA Inc. n.d. 297 <LLD 319 63 18,387 65 RF-SE-37-RU RONTEC USA Inc. n.d. 260 <LLD 301 82 17,706 65 RF-SE-50-RU RONTEC USA Inc. n.d. 296 <LLD 333 72 23,497 
D-38 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

62 TL-SE-06-XX Reference Laboratory 44 45 56 78 83 62 TL-SE-17-XX Reference Laboratory 43 44 56 78 81 62 TL-SE-28-XX Reference Laboratory 44 45 57 81 83 62 TL-SE-06-RU RONTEC USA Inc. 77 160 <LLD 73 175 62 TL-SE-17-RU RONTEC USA Inc. 33 24 <LLD 55 99 62 TL-SE-28-RU RONTEC USA Inc. 36 41 <LLD 59 91 63 TL-SE-07-XX Reference Laboratory 94 120 63 110 160 63 TL-SE-21-XX Reference Laboratory 100 140 67 120 170 63 TL-SE-30-XX Reference Laboratory 93 120 62 100 160 63 TL-SE-07-RU RONTEC USA Inc. 82 89 30 59 190 63 TL-SE-21-RU RONTEC USA Inc. 75 152 85 85 159 63 TL-SE-30-RU RONTEC USA Inc. 81 156 62 69 182 64 TL-SE-02-XX Reference Laboratory 99 44 120 110 160 64 TL-SE-08-XX Reference Laboratory 100 39 130 120 170 64 TL-SE-16-XX Reference Laboratory 100 44 120 110 160 64 TL-SE-02-RU RONTEC USA Inc. 77 47 33 97 165 64 TL-SE-08-RU RONTEC USA Inc. 88 77 67 69 213 64 TL-SE-16-RU RONTEC USA Inc. 46 28 101 51 102 65 RF-SE-01-XX Reference Laboratory 200 21 37 29 1,700 65 RF-SE-09-XX Reference Laboratory 220 23 42 32 1,900 65 RF-SE-11-XX Reference Laboratory 210 20 40 29 1,800 65 RF-SE-17-XX Reference Laboratory 210 22 40 30 1,800 65 RF-SE-29-XX Reference Laboratory 240 26 44 35 2,100 65 RF-SE-37-XX Reference Laboratory 220 23 44 32 1,900 65 RF-SE-50-XX Reference Laboratory 200 20 38 29 1,700 65 RF-SE-01-RU RONTEC USA Inc. 175 20 55 14 1,573 65 RF-SE-09-RU RONTEC USA Inc. 113 20 <LLD 17 996 65 RF-SE-11-RU RONTEC USA Inc. 140 20 <LLD 16 1,309 65 RF-SE-17-RU RONTEC USA Inc. 99 18 <LLD 27 935 65 RF-SE-29-RU RONTEC USA Inc. 161 20 <LLD 15 1,473 65 RF-SE-37-RU RONTEC USA Inc. 115 20 <LLD 14 1,000 65 RF-SE-50-RU RONTEC USA Inc. 164 20 231 20 1,704 
D-39 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Sb As Cd Cr Cu Fe 

66 RF-SE-08-XX Reference Laboratory 14 460 67 510 1,800 18,000 566 RF-SE-10-XX Reference Laboratory 12 400 58 440 1,500 16,000 566 RF-SE-33-XX Reference Laboratory 13 440 64 490 1,700 18,000 566 RF-SE-08-RU RONTEC USA Inc. n.d. 601 <LLD 615 1,204 22,179 666 RF-SE-10-RU RONTEC USA Inc. n.d. 660 <LLD 736 1,347 26,903 666 RF-SE-33-RU RONTEC USA Inc. n.d. 656 <LLD 633 1,628 29,358 667 RF-SE-16-XX Reference Laboratory 85 J- 72 J- 310 J- 820 J- 73 J- 16,000 J- 67 RF-SE-41-XX Reference Laboratory 100 82 360 950 85 18,000 67 RF-SE-48-XX Reference Laboratory 100 87 380 1,000 90 19,000 67 RF-SE-16-RU RONTEC USA Inc. n.d. 112 <LLD 1,246 84 23,391 67 RF-SE-41-RU RONTEC USA Inc. n.d. 99 <LLD 1,606 213 24,704 67 RF-SE-48-RU RONTEC USA Inc. n.d. 109 <LLD 1,082 85 31,425 68 RF-SE-18-XX Reference Laboratory 320 810 770 950 78 16,000 868 RF-SE-35-XX Reference Laboratory 300 740 700 860 70 15,000 768 RF-SE-54-XX Reference Laboratory 320 880 840 1,000 86 18,000 968 RF-SE-18-RU RONTEC USA Inc. n.d. 1,162 <LLD 1,244 87 24,728 968 RF-SE-35-RU RONTEC USA Inc. n.d. 1,239 <LLD 1,261 109 34,720 968 RF-SE-54-RU RONTEC USA Inc. n.d. 906 <LLD 1,109 79 19,404 1,169 RF-SE-20-XX Reference Laboratory 550 1300 540 94 93 20,000 69 RF-SE-46-XX Reference Laboratory 270 590 240 44 40 8,900 69 RF-SE-51-XX Reference Laboratory 480 1100 450 77 77 17,000 69 RF-SE-20-RU RONTEC USA Inc. n.d. 876 <LLD 104 87 20,301 69 RF-SE-46-RU RONTEC USA Inc. n.d. 956 <LLD 88 78 18,922 69 RF-SE-51-RU RONTEC USA Inc. n.d. 932 1,001 79 79 21,808 70 RF-SE-21-XX Reference Laboratory 1.3 U 62 1,700 76 1,000 16,000 2,170 RF-SE-40-XX Reference Laboratory 1.3 U 70 1,900 85 1,100 18,000 2,470 RF-SE-47-XX Reference Laboratory 1.3 U 72 1,900 90 1,200 19,000 2,470 RF-SE-21-RU RONTEC USA Inc. n.d. 45 <LLD 76 743 23,337 2,570 RF-SE-40-RU RONTEC USA Inc. n.d. 37 1,756 89 896 23,550 2,870 RF-SE-47-RU RONTEC USA Inc. n.d. 18 2,056 146 1,176 27,209 3,1
D-40 

Appendix D: Analytical Data Summary, RONTEC Pico Tax and Reference Laboratory (Continued) 

Blend 

No. Sample ID Source of Data Ni Se Ag V Zn 

66 RF-SE-08-XX Reference Laboratory 250 42 0.39 U 120 120 66 RF-SE-10-XX Reference Laboratory 220 39 0.34 U 100 110 66 RF-SE-33-XX Reference Laboratory 240 41 0.33 U 120 130 66 RF-SE-08-RU RONTEC USA Inc. 113 40 35 132 124 66 RF-SE-10-RU RONTEC USA Inc. 136 44 44 142 130 66 RF-SE-33-RU RONTEC USA Inc. 160 44 <LLD 128 140 67 RF-SE-16-XX Reference Laboratory 1,700 J- 1.2 U 130 J- 32 J- 760 J67 RF-SE-41-XX Reference Laboratory 1,900 1.2 U 140 39 830 67 RF-SE-48-XX Reference Laboratory 2,000 2.2 150 40 880 67 RF-SE-16-RU RONTEC USA Inc. 1,037 <LLD 60 21 588 67 RF-SE-41-RU RONTEC USA Inc. 1,768 <LLD 26 17 731 67 RF-SE-48-RU RONTEC USA Inc. 1,569 <LLD 28 47 715 68 RF-SE-18-XX Reference Laboratory 390 140 140 390 120 68 RF-SE-35-XX Reference Laboratory 350 140 150 340 110 68 RF-SE-54-XX Reference Laboratory 420 160 180 410 120 68 RF-SE-18-RU RONTEC USA Inc. 263 186 <LLD 486 130 68 RF-SE-35-RU RONTEC USA Inc. 277 210 63 533 159 68 RF-SE-54-RU RONTEC USA Inc. 324 159 254 437 104 69 RF-SE-20-XX Reference Laboratory 1,400 380 59 36 1,400 69 RF-SE-46-XX Reference Laboratory 650 170 26 16 650 69 RF-SE-51-XX Reference Laboratory 1,200 320 48 30 1,200 69 RF-SE-20-RU RONTEC USA Inc. 770 324 <LLD 23 731 69 RF-SE-46-RU RONTEC USA Inc. 999 342 20 26 907 69 RF-SE-51-RU RONTEC USA Inc. 901 329 130 17 876 70 RF-SE-21-XX Reference Laboratory 220 440 120 130 100 70 RF-SE-40-XX Reference Laboratory 250 480 100 150 120 70 RF-SE-47-XX Reference Laboratory 250 510 120 150 120 70 RF-SE-21-RU RONTEC USA Inc. 167 434 51 152 94 70 RF-SE-40-RU RONTEC USA Inc. 179 490 378 156 126 70 RF-SE-47-RU RONTEC USA Inc. 338 509 237 203 161 

Notes: All concentrations reported in milligrams per kilogram (mg/kg), or parts per million (ppm). <LLC Reported by RONTEC as less than the instrument’s statistical lower limit of detection (LLD). J Estimated concentration. J+ Concentration is considered estimated and biased high. J- Concentration is considered estimated and biased low. n.d. Not detectable by instrument. U Analyte is not detected; the associated concentration value is the sample reporting limit. 
 

 

APPENDIX E 

STATISTICAL DATA SUMMARIES
 

E-1 

Figure E-1: Linear Correlation Plot for Arsenic

y = 0.90x + 56.55

R2 = 0.95

0

1000

2000

3000

4000

5000

6000

0 1000 2000 3000 4000 5000 6000

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)

Figure E-2: Linear Correlation Plot for Cadmium

y = 0.78x + 272.24

R2 = 0.62

0

500

1000

1500

2000

2500

3000

3500

0 500 1000 1500 2000 2500 3000

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)
 

E-2 

Figure E-3: Linear Correlation Plot for Chromium

y = 1.04x + 27.17

R2 = 0.95

0

500

1000

1500

2000

2500

3000

3500

0 500 1000 1500 2000 2500 3000 3500

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)

Figure E-4: Linear Correlation Plot for Copper

y = 1.03x - 33.94

R2 = 0.86

0

1000

2000

3000

4000

5000

6000

7000

8000

0 1000 2000 3000 4000 5000 6000

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)
 

E-3 

Figure E-5: Linear Correlation Plot for Iron

y = 1.02x + 4489.75

R2 = 0.95

0

50000

100000

150000

200000

250000

0 20000 40000 60000 80000 100000 120000 140000 160000 180000 200000

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)

Figure E-6: Linear Correlation Plot for Lead

y = 1.42x - 98.03

R2 = 0.94

0

10000

20000

30000

40000

50000

60000

70000

0 5000 10000 15000 20000 25000 30000 35000 40000

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)
 

E-4 

Figure E-7: Linear Correlation Plot for Mercury

y = 0.73x - 39.22

R2 = 0.99

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

0 1000 2000 3000 4000 5000 6000 7000 8000 9000

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)

Figure E-8: Linear Correlation Plot for Nickel

y = 0.89x + 0.07

R2 = 0.96

0

500

1000

1500

2000

2500

3000

3500

0 500 1000 1500 2000 2500 3000 3500

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)
 

E-5 

Figure E-9: Linear Correlation Plot for Selenium

y = 1.03x + 13.73

R2 = 0.70

0

100

200

300

400

500

600

700

800

900

1000

0 100 200 300 400 500 600

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)

Figure E-10: Linear Correlation Plot for Silver

y = 0.94x + 6.98

R2 = 0.58

0

50

100

150

200

250

300

350

400

450

0 50 100 150 200 250 300 350 400 450

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)
 

E-6 

Figure E-11: Linear Correlation Plot for Vanadium

y = 1.04x - 10.65

R2 = 0.89

0

100

200

300

400

500

600

0 50 100 150 200 250 300 350 400 450 500

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)

Figure E-12: Linear Correlation Plot for Zinc

y = 1.07x - 21.19

R2 = 0.97

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

0 1000 2000 3000 4000 5000 6000 7000 8000

Reference Laboratory (ppm)

RONTEC PicoTAX XRF (ppm)

RONTEC PicoTAX

45 Degrees

Linear (RONTEC PicoTAX)
 

E-7 

Box Plot for Relative Percent Difference (RPD)

Rontec PicoTAX

Median; Box: 25%-75%; Whisker: Non-Outlier Range

 Median 

 25%-75% 

 Non-Outlier Range 

 Outliers

 Extremes

58-LV

70-RF

17-AS

23-SB

57-CN

67-RF

31-TL

61-TL

62-TL

5-WS

48-SB

57-CN

62-TL

53-AS

61-TL

61-TL

61-TL

26-SB

As Cd Cr Cu Fe Pb Hg Ni Se Ag V Zn

Target Element

-20%

0%

20%

40%

60%

80%

100%

120%

140%

160%

180%

200%

Mean RPD Values Between the PicoTAX

and the Reference Laboratory

Notes: 

The “box” in each box plot presents the range of RPD values that lie between the 25th and 75th percentiles (that is, the 

“quartiles”) of the full RPD population for each element. In essence, the box displays the “interquartile range” of RPD 

values. The square data point within each box represents the median RPD for the population. The “whiskers” emanating 

from the top and bottom of each box represent the largest and smallest data points, respectively, that are within 1.5 times 

the interquartile range. Values outside the whiskers are identified as outliers and extremes. 

Some of the more significant extremes and outliers are labeled with the associated Blend numbers and sample site 

abbreviations (see the footnotes of Table E-5 for definitions). Also refer to Appendix D for the sampling site associated 

with each Blend number. 

Figure E-13. Box and Whisker Plot for Mean RPD Values Showing Outliers and Extremes for Target 

 Elements, Rontec PicoTAX Data Set. 
E-8 

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for th

 PicoTAX 

 Conc Antimony Arsenic Cadmium Chromium Copper Iron LeaMatrix Range Statistic Ref Lab ERA Spike Soil Level 1 Number 0 0 15 4 28 16 5 16 

Minimum NC NC 2.7% 138.5% 2.5% 1.0% 13.6% 9.1

Maximum NC NC 181.4% 168.1% 130.1% 34.8% 48.6% 122.

 Mean NC NC 32.9% 155.2% 32.0% 11.6% 23.9% 43.1 Median NC NC 20.7% 157.0% 20.7% 10.4% 20.5% 24.9 Level 2 Number 0 0 4 6 4 8 13 4 

Minimum NC NC 3.1% 0.8% 0.5% 0.5% 8.7% 2.2

 Maximum NC NC 32.6% 84.2% 29.8% 26.8% 56.5% 25.7

Mean NC NC 11.2% 45.7% 13.0% 11.0% 26.0% 15.1

 Median NC NC 4.6% 49.6% 10.9% 10.0% 23.2% 16.3 Level 3 Number 0 0 4 2 2 2 13 8  Minimum NC NC 5.5% 6.3% 10.8% 14.1% 3.0% 7.3 Maximum NC NC 12.2% 13.7% 17.9% 35.6% 25.5% 42.2 Mean NC NC 8.7% 10.0% 14.4% 24.9% 12.0% 20.2 Median NC NC 8.7% 10.0% 14.4% 24.9% 12.0% 20.4 Level 4 Number -- -- -- -- -- -- 7 5 

Minimum -- -- -- -- -- -- 0.0% 15.3Maximum -- -- -- -- -- -- 18.6% 55.4Mean -- -- -- -- -- -- 5.9% 28.7Median -- -- -- -- -- -- 2.4% 22.9

 All Soil Number 0 0 23 12 34 26 38 16 

Minimum NC NC 2.7% 0.8% 0.5% 0.5% 0.0% 11.2

 Maximum NC NC 181.4% 168.1% 130.1% 35.6% 56.5% 70.9

Mean NC NC 25.0% 76.2% 28.8% 12.4% 17.2% 33.7

 Median NC NC 14.3% 83.2% 17.9% 11.5% 14.9% 30.0
E-9 

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for 

 PicoTAX (Continued) 

 Conc Nickel Selenium Silver Vanadium Zinc Matrix Range Statistic Soil Level 1 Number 22 4 0 13 20 

Minimum 1.0% 5.2% NC 0.1% 0.0% Maximum 62.8% 80.8% NC 68.7% 83.3% Mean 22.7% 42.3% NC 30.0% 25.4% Median 16.7% 41.5% NC 29.2% 21.0% 

 Level 2 Number 5 5 0 4 6 

Minimum 6.2% 1.3% NC 0.2% 3.4% Maximum 74.6% 110.7% NC 20.7% 23.6% Mean 26.7% 27.1% NC 14.0% 12.0% Median 21.6% 6.9% NC 17.5% 11.3% 

 Level 3 Number 6 4 4 4 9  Minimum 0.9% 3.7% 5.6% 4.3% 0.9%  Maximum 18.6% 27.7% 19.3% 24.7% 23.4% 

Mean 7.5% 13.4% 11.4% 14.8% 10.5% 

Median 5.6% 11.1% 10.4% 15.2% 10.9% 

 Level 4 Number -- -- -- -- --  Minimum -- -- -- -- --  Maximum -- -- -- -- --  Mean -- -- -- -- --  Median -- -- -- -- --  All Soil Number 33 13 4 21 35  Minimum 0.9% 1.3% 5.6% 0.1% 0.0%  Maximum 74.6% 110.7% 19.3% 68.7% 83.3% 

Mean 20.6% 27.5% 11.4% 24.0% 19.3% Median 12.2% 6.9% 10.4% 20.7% 16.0% 
E-10 

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for 

 PicoTAX (Continued) 

 Conc Antimony Arsenic Cadmium Chromium Copper Iron LMatrix Range Statistic Ref Lab ERA Spike Sediment Level 1 Number 0 0 17 0 21 8 3 

Minimum NC NC 1.2% NC 3.0% 0.7% 35.8% 0

 Maximum NC NC 93.5% NC 63.8% 42.5% 62.2% 18

Mean NC NC 24.0% NC 19.8% 11.4% 45.2% 10Median NC NC 12.9% NC 20.3% 5.6% 37.6% 10

 Level 2 Number 0 0 4 0 3 4 19  Minimum NC NC 0.4% NC 11.6% 6.2% 2.7% 0 Maximum NC NC 38.4% NC 31.8% 18.7% 73.5% 18

Mean NC NC 14.0% NC 18.9% 14.8% 28.6% 10

 Median NC NC 8.6% NC 13.4% 17.2% 27.5% 10 Level 3 Number 0 0 2 0 3 10 4 

Minimum NC NC 7.9% NC 3.6% 0.4% 6.0% 21

 Maximum NC NC 30.6% NC 34.7% 75.7% 54.7% 39

Mean NC NC 19.2% NC 21.1% 24.5% 30.7% 33

 Median NC NC 19.2% NC 25.0% 18.5% 31.1% 39 Level 4 Number -- -- -- -- -- -- 6  Minimum -- -- -- -- -- -- 1.5% 

Maximum -- -- -- -- -- -- 10.5% 

 Mean -- -- -- -- -- -- 6.9%  Median -- -- -- -- -- -- 8.4%  All Sediment Number 0 0 23 0 27 22 32  Minimum NC NC 0.4% NC 3.0% 0.4% 1.5% 0 Maximum NC NC 93.5% NC 63.8% 75.7% 73.5% 70

Mean NC NC 21.9% NC 19.9% 18.0% 26.3% 29

 Median NC NC 12.9% NC 20.3% 15.4% 21.6% 25
E-11 

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for 

 PicoTAX (Continued) 

 Conc Nickel Selenium Silver Vanadium Zinc Matrix Range Statistic Sediment Level 1 Number 18 5 1 6 19 

Minimum 4.0% 4.8% 8.5% 15.0% 1.0% Maximum 77.2% 50.7% 8.5% 94.3% 53.9% Mean 35.5% 20.5% 8.5% 49.5% 19.2% Median 34.9% 17.4% 8.5% 45.0% 11.6% 

 Level 2 Number 6 4 2 8 5 

Minimum 5.1% 4.4% 59.1% 11.4% 1.3% Maximum 53.8% 81.0% 114.6% 66.0% 25.5% Mean 27.7% 30.8% 86.9% 37.7% 16.3% Median 29.4% 18.9% 86.9% 43.8% 19.4% 

 Level 3 Number 4 3 2 3 4 

Minimum 5.7% 0.2% 34.5% 8.4% 0.7% Maximum 24.6% 13.4% 64.8% 24.3% 35.7% 

 Mean 14.4% 7.5% 49.7% 15.2% 16.1%  Median 13.7% 8.8% 49.7% 12.9% 14.0%  Level 4 Number -- -- -- -- -- 

Minimum -- -- -- -- -- Maximum -- -- -- -- -- Mean -- -- -- -- -- Median -- -- -- -- -- 

 All Sediment Number 28 12 5 17 28 

Minimum 4.0% 0.2% 8.5% 8.4% 0.7% Maximum 77.2% 81.0% 114.6% 94.3% 53.9% Mean 30.8% 20.7% 56.3% 37.9% 18.2% Median 29.4% 14.1% 59.1% 24.3% 16.2% 
E-12 

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for 

 PicoTAX (Continued) 

 Conc Antimony Arsenic Cadmium Chromium Copper Iron Matrix Range Statistic Ref Lab ERA Spike All Rontec Number 0 0 46 12 61 48 70 Samples PicoTAX Minimum NC NC 0.4% 0.8% 0.5% 0.4% 0.0% 

Maximum NC NC 181.4% 168.1% 130.1% 75.7% 73.5% 

Mean NC NC 23.4% 76.2% 24.8% 15.0% 21.4% 

Median NC NC 13.4% 83.2% 18.1% 12.3% 17.3% 

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% Mean 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% 

Table E-1. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for 

 PicoTAX (Continued) 

 Conc Nickel Selenium Silver Vanadium Zinc Matrix Range Statistic All Rontec Number 61 25 9 38 63 Samples PicoTAX Minimum 0.9% 0.2% 5.6% 0.1% 0.0% 

Maximum 77.2% 110.7% 114.6% 94.3% 83.3% Mean 25.3% 24.2% 36.4% 30.2% 18.8% Median 21.2% 11.6% 19.3% 22.9% 16.0% 

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% 
E-13 

Notes: All RPDs presented in this table are absolute values. -- No samples reported by the reference laboratory in this concentration range. Conc Concentration. ERA Environmental Resouce Associstes, Inc. NC Not calculated due to lack of XRF data. Number Number of demonstration samples evaluated. Ref Lab Reference laboratory (Shealy Environmental Services, Inc.). RPD Relative percent difference. SRF X-ray fluorescence. 
E-14 

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX 

 Conc Matrix Range Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Soil Low Number 0 15 4 28 16 5 16 

Minimum NC 2.0% 17.4% 11.8% 0.1% 10.6% 2.2% Maximum NC 71.7% 31.0% 89.0% 25.9% 29.4% 78.7% Mean NC 18.2% 25.9% 34.8% 12.1% 19.9% 24.3% Median NC 13.8% 27.6% 26.3% 11.9% 19.2% 20.9% 

 Medium Number 0 4 6 4 8 13 4 

Minimum NC 6.5% 20.1% 3.3% 8.9% 4.4% 11.7% Maximum NC 17.3% 48.5% 15.1% 28.2% 20.5% 25.5% Mean NC 13.5% 33.4% 9.4% 17.0% 13.2% 15.6% Median NC 15.1% 31.5% 9.6% 16.7% 13.3% 12.6% 

 High Number 0 4 2 2 2 13 8 

Minimum NC 6.1% 18.7% 3.1% 9.6% 8.5% 1.7% Maximum NC 19.6% 33.6% 4.3% 22.1% 29.1% 23.0% Mean NC 12.8% 26.2% 3.7% 15.9% 17.3% 11.7% Median NC 12.7% 26.2% 3.7% 15.9% 17.9% 12.0% 

 Very High Number -- -- -- -- -- 7 5 

Minimum -- -- -- -- -- 8.4% 3.8% Maximum -- -- -- -- -- 30.9% 18.6% Mean -- -- -- -- -- 18.9% 10.7% Median -- -- -- -- -- 15.7% 9.4% 

 All Soil Number 0 23 12 34 26 38 33 

Minimum NC 2.0% 17.4% 3.1% 0.1% 4.4% 1.7% Maximum NC 71.7% 48.5% 89.0% 28.2% 30.9% 78.7% Mean NC 16.5% 29.7% 30.0% 13.9% 16.5% 18.1% Median NC 14.3% 30.0% 22.1% 13.3% 16.6% 14.4% 
E-15 

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Contin

 Conc Matrix Range Statistic Nickel Selenium Silver Vanadium Zinc Soil Low Number 22 4 0 13 20 

Minimum 7.8% 1.4% NC 14.7% 2.5% Maximum 70.0% 27.4% NC 51.0% 42.0% Mean 22.7% 14.6% NC 26.9% 15.7% Median 19.5% 14.9% NC 27.1% 15.5% 

 Medium Number 5 5 0 4 6 

Minimum 5.0% 5.9% NC 6.0% 4.3% Maximum 14.4% 22.3% NC 35.7% 20.1% Mean 10.3% 15.1% NC 16.9% 12.2% Median 11.6% 18.9% NC 12.9% 13.8% 

 High Number 6 4 4 4 9 

Minimum 1.5% 3.7% 37.6% 0.4% 0.7% Maximum 35.8% 7.0% 125.3% 14.5% 37.4% Mean 17.8% 5.6% 66.4% 7.2% 15.1% Median 19.5% 6.0% 51.4% 7.0% 12.0% 

 Very High Number -- -- -- -- -- 

Minimum -- -- -- -- -- Maximum -- -- -- -- -- Mean -- -- -- -- -- Median -- -- -- -- -- 

 All Soil Number 33 13 4 21 35 

Minimum 1.5% 1.4% 37.6% 0.4% 0.7% Maximum 70.0% 27.4% 125.3% 51.0% 42.0% Mean 19.9% 12.0% 66.4% 21.3% 14.9% Median 17.3% 7.0% 51.4% 18.2% 14.7% 
E-16 

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Contin

 Conc Matrix Range Statistic Antimony Arsenic Cadmium Chromium Copper Iron LSediment Low Number 0 17 0 21 8 3 

Minimum NC 6.4% NC 12.2% 6.1% 9.7% 4

Maximum NC 63.1% NC 116.3% 58.3% 20.6% 11

Mean NC 28.9% NC 35.8% 17.0% 16.9% 28Median NC 28.3% NC 32.5% 11.1% 20.3% 24

 Medium Number 0 4 0 3 4 19 

Minimum NC 5.2% NC 9.9% 2.7% 6.4% 4Maximum NC 13.5% NC 17.6% 31.3% 61.7% 75

Mean NC 8.7% NC 12.5% 17.1% 21.3% 24

Median NC 8.1% NC 9.9% 17.2% 14.0% 8

 High Number 0 2 0 3 10 4 

Minimum NC 4.5% NC 6.9% 4.3% 8.2% 11Maximum NC 15.8% NC 20.4% 45.5% 29.9% 93

Mean NC 10.1% NC 11.5% 24.6% 17.5% 38

Median NC 10.1% NC 7.2% 22.5% 16.0% 11

 Very High Number -- -- -- -- -- 6 

Minimum -- -- -- -- -- 11.2% 

Maximum -- -- -- -- -- 29.4% Mean -- -- -- -- -- 18.0% Median -- -- -- -- -- 17.5% 

 All Sediment Number 0 23 0 27 22 32 

Minimum NC 4.5% NC 6.9% 2.7% 6.4% 4Maximum NC 63.1% NC 116.3% 58.3% 61.7% 11

Mean NC 23.8% NC 30.5% 20.5% 19.8% 28Median NC 18.8% NC 25.1% 16.2% 16.5% 21
E-17 

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Contin

 Conc Matrix Range Statistic Nickel Selenium Silver Vanadium Zinc Sediment Low Number 18 5 1 6 19 

Minimum 5.1% 3.8% 46.5% 15.3% 6.2% 

Maximum 77.6% 98.8% 46.5% 86.1% 38.5% Mean 31.6% 32.6% 46.5% 37.7% 21.6% 

Median 31.6% 5.6% 46.5% 31.0% 21.7% 

 Medium Number 6 4 2 8 5 

Minimum 7.0% 3.6% 50.2% 5.4% 6.9% Maximum 41.9% 28.1% 50.2% 47.6% 13.1% Mean 19.2% 15.8% 50.2% 24.4% 10.6% Median 17.0% 15.8% 50.2% 24.4% 11.2% 

 High Number 4 3 2 3 4 

Minimum 8.2% 2.8% 41.0% 5.6% 8.1% 

Maximum 25.9% 9.0% 73.9% 12.9% 24.2% 

Mean 14.0% 6.7% 57.4% 9.5% 16.3% 

Median 10.9% 8.2% 57.4% 9.9% 16.4% 

 Very High Number -- -- -- -- -- 

Minimum -- -- -- -- -- 

Maximum -- -- -- -- -- Mean -- -- -- -- -- 

Median -- -- -- -- -- 

 All Sediment Number 28 12 5 17 28 

Minimum 5.1% 2.8% 41.0% 5.4% 6.2% Maximum 77.6% 98.8% 73.9% 86.1% 38.5% Mean 26.4% 20.5% 52.4% 26.5% 18.8% 

Median 18.8% 8.6% 50.2% 27.0% 15.5% 
E-18 

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Contin

Conc 

Matrix Range Statistic Antimony Arsenic Cadmium Chromium Copper Iron All All Number 0 46 12 61 48 70 

Minimum NC 2.0% 17.4% 3.1% 0.1% 4.4% Maximum NC 71.7% 48.5% 116.3% 58.3% 61.7% Mean NC 20.1% 29.7% 30.2% 16.9% 18.0% Median NC 15.1% 30.0% 24.2% 15.2% 16.5% 

All Samples All Instruments Number 421 498 440 492 531 560 

Minimum 0.5% 1.1% 1.3% 1.0% 0.3% 0.1% Maximum 23.2% 33.6% 29.5% 36.4% 32.8% 20.9% Mean 8.5% 9.1% 7.2% 12.1% 9.6% 3.5% Median 11.0% 11.5% 6.0% 15.6% 7.3% 2.2% 

Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rontec PicoTAX (Contin

Conc 

Matrix Range Statistic Nickel Selenium Silver Vanadium Zinc All All Number 61 25 9 38 63 

Minimum 1.5% 1.4% 37.6% 0.4% 0.7% Maximum 77.6% 98.8% 125.3% 86.1% 42.0% Mean 22.9% 16.1% 58.6% 23.6% 16.7% Median 18.5% 8.2% 50.2% 19.8% 14.7% 

All Samples All Instruments Number 509 433 441 462 535 

Minimum 1.6% 0.3% 1.5% 0.9% 0.1% Maximum 28.1% 18.5% 24.8% 24.3% 19.3% Mean 10.9% 5.9% 9.0% 8.8% 6.6% Median 8.4% 10.6% 12.9% 11.4% 5.8% 

Notes: -- No samples reported by the reference laboratory in this concentration range. Conc Concentration. NC Not calculated due to lack of XRF data. Number Number of demonstration samples evaluated. RSD Relative standard deviation. XRF X-ray fluorescence. 
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 All Soil Number 17 23 15 34 26 38 33 

Minimum 3.6% 1.4% 0.9% 1.4% 0.0% 1.6% 0.0% Maximum 38.0% 45.8% 21.4% 137.0% 21.0% 46.2% 150.0% Mean 14.3% 11.7% 11.1% 14.3% 10.1% 10.2% 17.6% Median 9.8% 12.4% 9.0% 10.6% 9.1% 8.7% 13.2% 

All Sediment Number 7 24 10 26 21 31 22 

Minimum 2.9% 2.4% 2.9% 4.6% 1.8% 2.7% 0.0% 

 Maximum 33.6% 36.7% 37.5% 35.5% 38.8% 37.5% 41.1% 

Mean 14.4% 10.7% 11.4% 9.8% 9.7% 9.9% 11.6% Median 9.1% 9.2% 8.2% 7.5% 8.9% 8.1% 7.4% 

All Samples Number 24 47 25 60 47 69 55 

Minimum 2.9% 1.4% 0.9% 1.4% 0.0% 1.6% 0.0% Maximum 38.0% 45.8% 37.5% 137.0% 38.8% 46.2% 150.0% Mean 14.3% 11.2% 11.2% 12.4% 9.9% 10.1% 15.2% Median 9.5% 9.5% 9.0% 8.4% 8.9% 8.5% 8.6% 

Table E-3. Evaluation of Precision - Relative Standard Deviations Calculated for the Reference Laboratory (C

Matrix Statistic Selenium Silver Vanadium Zinc All Soil Number 13 13 21 35 

Minimum 0.0% 2.3% 0.0% 1.0% 

Maximum 22.7% 37.1% 18.1% 46.5% 

Mean 8.9% 12.4% 8.4% 10.4% Median 7.1% 7.5% 6.6% 9.1% 

All Sediment Number 12 10 17 27 

Minimum 1.3% 1.0% 2.2% 1.4% 

Maximum 37.3% 21.3% 21.9% 35.8% 

Mean 10.0% 9.4% 8.4% 8.9% Median 7.6% 6.6% 8.1% 6.9% 

All Samples Number 25 23 38 62 

Minimum 0.0% 1.0% 0.0% 1.0% 

Maximum 37.3% 37.1% 21.9% 46.5% 

Mean 9.4% 11.1% 8.4% 9.8% Median 7.4% 7.1% 7.2% 7.4% 
E-20 

Table E-4. Evaluation of the Effects of Interferent Elements on RPDs (Accuracy) of Other Target Elements 1

Parameter Statistic Lead Effects on Arsenic Copper Effects on Nickel Nickel EfInterferent/Element Ratio <5 5 - 10 >10 <5 5 - 10 >10 <5 Number of Samples 29 7 10 42 5 14 39 RPD of Target Element2 Minimum -41.9% -5.5% -93.5% -29.2% 4.4% 6.2% -35.6% 

Maximum 21.4% 32.6% 181.4% 69.4% 53.8% 77.2% 75.7% Mean -13.4% 4.1% 25.3% 11.2% 36.8% 43.6% 3.2% Median -12.6% -2.7% 24.6% 8.3% 42.2% 41.6% -0.5% 

RPD of Target Element Minimum 0.4% 2.7% 3.5% 0.9% 4.4% 6.2% 0.4%  (Absolute Value)2 Maximum 41.9% 32.6% 181.4% 69.4% 53.8% 77.2% 75.7% 

Mean 15.8% 8.9% 55.7% 17.8% 36.8% 43.6% 14.8% Median 12.9% 5.5% 43.0% 13.8% 42.2% 41.6% 11.1% 

Interferent Minimum ND 865 1108 ND 683 655 ND  Concentration Range Maximum 1030 61480 23605 938 1393 7308 875 

Mean 221 19418 6276 216 1000 2481 144 Median 89 9262 3434 123 871 1877 98 

Target Element Minimum 25 119 1 42 88 23 56  Concentration Range Maximum 2065 5133 1788 3201 136 251 7308 

Mean 302 1701 323 526 110 94 1209 Median 135 1071 56 183 100 75 786 
E-21 

Table E-4. Evaluation of the Effects of Interferent Elements on RPDs (Accuracy) of Other Target Elements 1 (

Parameter Statistic Zinc Effects on Copper Copper Effects on Zinc Interferent/Element Ratio <5 5 - 10 >10 <5 5 - 10 >10 Number of Samples 35 2 11 50 3 10 RPD of Target Element2 Minimum -35.6% -6.2% -42.5% -83.3% -14.0% -38.6% 

Maximum 75.7% 7.1% 34.8% 35.7% -7.1% 53.9% Mean 1.5% 0.4% -1.1% -11.1% -10.8% -2.0% Median -0.5% 0.4% -1.0% -12.0% -11.4% -8.5% 

RPD of Target Element Minimum 0.4% 6.2% 1.0% 0.0% 7.1% 1.2%  (Absolute Value)2 Maximum 75.7% 7.1% 42.5% 83.3% 14.0% 53.9% 

Mean 15.9% 6.6% 13.6% 18.4% 10.8% 23.2% Median 14.1% 6.6% 8.9% 16.8% 11.4% 17.2% 

Interferent Minimum 45 754 678 ND 829 683  Concentration Range Maximum 7675 8170 8071 2491 1666 7308 

Mean 1084 4462 3143 468 1144 2830 Median 177 4462 3015 169 938 2221 

Target Element Minimum 56 149 73 45 118 57  Concentration Range Maximum 7308 1553 382 8170 223 411 

Mean 1280 851 144 1674 156 158 Median 829 851 124 674 127 145 

Notes: 1. Concentrations are reported in units of milligrams per kilogram (mg/kg), or parts per million (ppm). 2. Table presents statistics for raw (unmodified) RPDs as well as absolute value RPDs. < Less than. > Greater than. RPD Relative percent difference. NC Not calculated due to lack of XRF data. ND Nondetect. XRF X-ray fluorescence.
E-22 

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements 

Antimony Arsenic 

 Matrix Reference Laboratory Certified Value Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Va

Number -- -- -- -- 1 1 Minimum -- -- -- -- 181.4% 181.4% Maximum -- -- -- -- 181.4% 181.4% 

Soil 

Mean -- -- -- -- 181.4% 181.4% 

AS Fine to medium sand 

(steel processing) 

Median -- -- -- -- 181.4% 181.4% 

Soil Number -- -- -- -- 7 7 

Minimum -- -- -- -- -10.2% 2.7% Maximum -- -- -- -- 49.0% 49.0% Mean -- -- -- -- 3.3% 11.8% 

BN Sandy loam, low 

organic (ore residuals) 

Median -- -- -- -- -3.1% 5.5% 

Soil Number -- -- -- -- 1 1 

Minimum -- -- -- -- -17.6% 17.6% Maximum -- -- -- -- -17.6% 17.6% Mean -- -- -- -- -17.6% 17.6% 

CN Sandy loam (burn pit 

residue) 

Median -- -- -- -- -17.6% 17.6% 

Soil & Number -- -- -- -- -- -- Sediment Minimum -- -- -- -- -- -- 

Maximum -- -- -- -- -- -- Mean -- -- -- -- -- -- 

KP Soil: Fine to medium 

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

Sediment Number -- -- -- -- 11 11 

Minimum -- -- -- -- -93.5% 0.4% Maximum -- -- -- -- 1.6% 93.5% Mean -- -- -- -- -17.6% 18.1% 

LV Clay/clay loam, salt 

crust (iron and other precipitate) 

Median -- -- -- -- -9.2% 9.2% 

Sediment Number -- -- -- -- 12 12 

Minimum -- -- -- -- -38.4% 1.4% Maximum -- -- -- -- 68.4% 68.4% Mean -- -- -- -- -5.0% 21.8% 

RF Silty fine sand (tailings) 

Median -- -- -- -- -12.7% 17.7% 
E-23 

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 ABS Va

Number 2 2 3 3 3 3 Minimum -12.1% 9.6% -35.6% 8.9% -56.2% 0.0% Maximum -9.6% 12.1% 34.8% 35.6% 18.6% 56.2% 

Soil 

Mean -10.8% 10.8% 2.7% 26.5% -12.5% 24.9% 

AS Fine to medium sand 

(steel processing) 

Median -10.8% 10.8% 8.9% 34.8% 0.0% 18.6% 

Soil Number 7 7 6 6 7 7 

Minimum -21.8% 10.2% -18.1% 3.5% -25.5% 8.7% Maximum 28.6% 28.6% 3.9% 18.1% -8.7% 25.5% Mean -1.6% 17.8% -7.8% 10.2% -16.0% 16.0% 

BN Sandy loam, low 

organic (ore residuals) 

Median -10.9% 17.9% -10.3% 10.3% -15.8% 15.8% 

Soil Number 2 2 3 3 3 3 

Minimum -50.0% 50.0% -20.7% 14.0% -28.2% 2.4% Maximum 130.1% 130.1% 26.8% 26.8% -2.4% 28.2% Mean 40.1% 90.1% -2.6% 20.5% -17.1% 17.1% 

CN Sandy loam (burn pit 

residue) 

Median 40.1% 90.1% -14.0% 20.7% -20.8% 20.8% 

Soil & Number 4 4 2 2 6 6 Sediment Minimum -31.5% 7.1% -11.1% 5.0% -62.2% 13.6% 

Maximum 7.1% 31.5% 5.0% 11.1% -13.6% 62.2% Mean -14.3% 17.8% -3.1% 8.0% -33.2% 33.2% 

KP Soil: Fine to medium 

quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) Median -16.3% 16.3% -3.1% 8.0% -30.3% 30.3% 

Sediment Number 11 11 4 4 12 12 

Minimum -39.2% 3.0% -23.4% 0.7% -57.9% 2.1% Maximum 11.4% 39.2% 7.0% 23.4% 35.8% 57.9% Mean -12.6% 16.0% -2.8% 9.2% -22.3% 28.2% 

LV Clay/clay loam, salt 

crust (iron and other precipitate) 

Median -11.7% 11.7% 2.5% 6.4% -19.0% 30.7% 

Sediment Number 12 12 13 13 13 13 

Minimum -63.8% 5.5% -42.5% 1.2% -46.7% 3.4% Maximum 24.8% 63.8% 22.1% 42.5% 6.0% 46.7% Mean -15.9% 22.1% -0.7% 14.6% -22.3% 23.2% 

RF Silty fine sand (tailings) 

Median -16.5% 22.2% 4.6% 15.9% -20.5% 20.5% 
E-24 

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Mercury Nickel Selenium 

 Matrix Reference Laboratory Reference Laboratory Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS V

Number -- -- 1 1 1 1 Minimum -- -- 74.6% 74.6% -110.7% 110.7% Maximum -- -- 74.6% 74.6% -110.7% 110.7% 

Soil 

Mean -- -- 74.6% 74.6% -110.7% 110.7% 

AS Fine to medium sand 

(steel processing) 

Median -- -- 74.6% 74.6% -110.7% 110.7% 

Soil Number 1 1 6 6 4 4 

Minimum 110.4% 110.4% -4.2% 0.9% -1.3% 1.3% Maximum 110.4% 110.4% 48.9% 48.9% 80.8% 80.8% Mean 110.4% 110.4% 16.3% 17.7% 40.2% 40.8% 

BN Sandy loam, low 

organic (ore residuals) 

Median 110.4% 110.4% 10.6% 10.6% 40.6% 40.6% 

Soil Number 2 2 3 3 2 2 

Minimum 16.2% 16.2% -21.2% 21.2% -5.2% 5.2% Maximum 30.7% 30.7% 22.4% 22.4% 6.7% 6.7% Mean 23.4% 23.4% 7.6% 21.7% 0.8% 6.0% 

CN Sandy loam (burn pit 

residue) 

Median 23.4% 23.4% 21.6% 21.6% 0.8% 6.0% 

Soil & Number -- -- 3 3 -- -- Sediment Minimum -- -- -29.2% 10.1% -- -- 

Maximum -- -- 12.2% 29.2% -- -- Mean -- -- -9.0% 17.1% -- -- 

KP Soil: Fine to medium 

quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) Median -- -- -10.1% 12.2% -- -- 

Sediment Number 4 4 11 11 5 5 

Minimum 11.7% 11.7% -10.2% 4.0% -27.7% 6.9% Maximum 53.5% 53.5% 43.0% 43.0% 17.4% 27.7% Mean 37.3% 37.3% 10.0% 14.5% -8.2% 15.1% 

LV Clay/clay loam, salt 

crust (iron and other precipitate) 

Median 41.9% 41.9% 7.8% 10.2% -8.8% 14.7% 

Sediment Number 4 4 13 13 5 5 

Minimum -0.4% 0.4% 5.1% 5.1% -23.1% 0.2% Maximum 27.9% 27.9% 69.4% 69.4% 11.6% 23.1% Mean 12.5% 12.7% 38.5% 38.5% -6.0% 10.6% 

RF Silty fine sand (tailings) 

Median 11.2% 11.2% 36.7% 36.7% -4.8% 11.6% 
E-25 

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Vanadium Zinc 

 Matrix Reference Laboratory Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val 

Number 1 1 3 3 Minimum 68.7% 68.7% -35.7% 14.5% Maximum 68.7% 68.7% -14.5% 35.7% 

Soil 

Mean 68.7% 68.7% -21.9% 21.9% 

AS Fine to medium sand 

(steel processing) 

Median 68.7% 68.7% -15.4% 15.4% 

Soil Number 4 4 7 7 

Minimum -6.5% 0.1% -23.6% 10.3% Maximum 22.3% 22.3% -10.3% 23.6% Mean 9.1% 12.3% -17.2% 17.2% 

BN Sandy loam, low 

organic (ore residuals) 

Median 10.2% 13.5% -17.9% 17.9% 

Soil Number 1 1 3 3 

Minimum 14.5% 14.5% -27.3% 7.3% Maximum 14.5% 14.5% -7.3% 27.3% Mean 14.5% 14.5% -17.4% 17.4% 

CN Sandy loam (burn pit 

residue) 

Median 14.5% 14.5% -17.6% 17.6% 

Soil & Number -- -- 2 2 Sediment Minimum -- -- -14.0% 0.0% 

Maximum -- -- 0.0% 14.0% Mean -- -- -7.0% 7.0% 

KP Soil: Fine to medium 

quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) Median -- -- -7.0% 7.0% 

Sediment Number 9 9 10 10 

Minimum -24.7% 0.2% -44.0% 0.7% Maximum 66.0% 66.0% 0.7% 44.0% Mean 8.8% 22.9% -20.9% 21.0% 

LV Clay/clay loam, salt 

crust (iron and other precipitate) 

Median -0.2% 15.0% -19.0% 19.0% 

Sediment Number 3 3 13 13 

Minimum -24.3% 16.7% -11.6% 1.0% Maximum -16.7% 24.3% 35.7% 35.7% Mean -19.4% 19.4% 9.3% 14.3% 

RF Silty fine sand (tailings) 

Median -17.2% 17.2% 8.2% 11.6% 
E-26 

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 VaSoil Number -- -- -- -- 5 5 

Minimum -- -- -- -- -41.9% 8.4% Maximum -- -- -- -- -8.4% 41.9% Mean -- -- -- -- -26.0% 26.0% 

SB Coarse sand and gravel 

(ore and waste rock) 

Median -- -- -- -- -20.7% 20.7% 

Sediment Number -- -- -- -- 2 2 

Minimum -- -- -- -- -27.4% 27.4% Maximum -- -- -- -- 56.8% 56.8% Mean -- -- -- -- 14.7% 42.1% 

TL Silt and clay (slagenriched) 

Median -- -- -- -- 14.7% 42.1% 

Soil Number -- -- -- -- 7 7 

Minimum -- -- -- -- -21.3% 3.5% Maximum -- -- -- -- 37.0% 37.0% Mean -- -- -- -- 8.7% 17.3% 

WS Coarse sand and gravel 

(roaster slag) 

Median -- -- -- -- 9.2% 12.2% 

 All Number -- -- -- -- 46 46 

Minimum -- -- -- -- -93.5% 0.4% Maximum -- -- -- -- 181.4% 181.4% Mean -- -- -- -- -2.3% 23.4% Median -- -- -- -- -6.8% 13.4% 
E-27 

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 ABS VaSoil Number 11 11 4 4 12 12 

Minimum -83.8% 6.9% -14.5% 1.0% -25.5% 2.3% Maximum -6.9% 83.8% 14.3% 14.5% 7.9% 25.5% Mean -40.8% 40.8% -3.5% 10.7% -11.1% 12.4% 

SB Coarse sand and gravel 

(ore and waste rock) 

Median -39.8% 39.8% -7.0% 13.6% -12.6% 12.6% 

Sediment Number 5 5 7 7 7 7 

Minimum 15.0% 15.0% -25.6% 0.4% -73.5% 1.5% Maximum 30.4% 30.4% 75.7% 75.7% 8.9% 73.5% Mean 22.7% 22.7% 21.0% 28.5% -24.7% 27.7% 

TL Silt and clay (slagenriched) 

Median 20.3% 20.3% 8.5% 19.2% -7.6% 8.9% 

Soil Number 7 7 6 6 7 7 

Minimum -17.8% 0.5% -14.1% 0.5% -27.3% 1.3% Maximum 51.8% 51.8% 7.1% 14.1% 1.3% 27.3% Mean 7.3% 16.0% -2.9% 5.2% -10.9% 11.2% 

WS Coarse sand and gravel 

(roaster slag) 

Median 0.5% 11.5% -1.8% 4.2% -7.6% 7.6% 

 All Number 61 61 48 48 70 70 

Minimum -83.8% 0.5% -42.5% 0.4% -73.5% 0.0% Maximum 130.1% 130.1% 75.7% 75.7% 35.8% 73.5% Mean -10.2% 24.8% 0.9% 15.0% -19.1% 21.4% Median -11.2% 18.1% -0.6% 12.3% -16.4% 17.3% 
E-28 

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Mercury Nickel Selenium 

 Matrix Reference Laboratory Reference Laboratory Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS VSoil Number 11 11 11 11 3 3 

Minimum -94.0% 4.7% -28.1% 1.0% -17.4% 5.5% Maximum 73.0% 94.0% 18.6% 28.1% 5.5% 17.4% Mean 23.0% 41.0% 0.3% 9.1% -7.2% 10.8% 

SB Coarse sand and gravel 

(ore and waste rock) 

Median 28.7% 43.3% 1.0% 5.7% -9.6% 9.6% 

Sediment Number 2 2 6 6 4 4 

Minimum 47.7% 47.7% 18.8% 18.8% -50.7% 4.4% Maximum 115.8% 115.8% 77.2% 77.2% 81.0% 81.0% Mean 81.7% 81.7% 36.4% 36.4% 1.9% 38.5% 

TL Silt and clay (slagenriched) 

Median 81.7% 81.7% 30.1% 30.1% -11.2% 34.4% 

Soil Number -- -- 7 7 1 1 

Minimum -- -- 6.2% 6.2% 4.8% 4.8% Maximum -- -- 62.8% 62.8% 4.8% 4.8% Mean -- -- 37.9% 37.9% 4.8% 4.8% 

WS Coarse sand and gravel 

(roaster slag) 

Median -- -- 50.0% 50.0% 4.8% 4.8% 

 All Number 24 24 61 61 25 25 

Minimum -94.0% 0.4% -29.2% 0.9% -110.7% 0.2% Maximum 115.8% 115.8% 77.2% 77.2% 81.0% 110.7% Mean 32.2% 40.5% 20.7% 25.3% -1.1% 24.2% Median 29.7% 33.0% 18.8% 21.2% -4.8% 11.6% 
E-29 

Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) 

Vanadium Zinc 

 Matrix Reference Laboratory Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val Soil Number 10 10 11 11 

Minimum -50.4% 4.3% -83.3% 10.9% Maximum 20.7% 50.4% 11.1% 83.3% Mean -26.7% 31.7% -25.7% 27.8% 

SB Coarse sand and gravel 

(ore and waste rock) 

Median -33.7% 33.7% -22.9% 22.9% 

Sediment Number 7 7 7 7 

Minimum 23.5% 23.5% -38.6% 1.2% Maximum 94.3% 94.3% 53.9% 53.9% Mean 57.8% 57.8% 7.5% 22.8% 

TL Silt and clay (slagenriched) 

Median 52.4% 52.4% 1.2% 7.9% 

Soil Number 3 3 7 7 

Minimum -13.9% 7.9% -18.0% 0.9% Maximum 8.2% 13.9% 16.0% 18.0% Mean 0.7% 10.0% -5.3% 10.1% 

WS Coarse sand and gravel 

(roaster slag) 

Median 7.9% 8.2% -4.5% 9.9% 

 All Number 38 38 63 63 

Minimum -50.4% 0.1% -83.3% 0.0% Maximum 94.3% 94.3% 53.9% 83.3% Mean 7.3% 30.2% -9.7% 18.8% Median 2.1% 22.9% -11.5% 16.0% 

Site Abbreviations: Other Notes: AS Alton Steel Mill -- No samples reported by the referBN Burlington Northern Railroad/ASARCO East concentration range. CN Naval Surface Warfare Center, Crane Division Number Number of demonstration sampleKP KARS Park – Kennedy Space Center RPD Relative percent difference (unmLV Leviathan Mine/Aspen Creek RPD Abs Val Relative percent difference (absoRF Ramsey Flats – Silver Bow Creek SB Sulfur Bank Mercury Mine TL Torch Lake Superfund Site WS Wickes Smelter Site