Ok United States Environmental Protection ^^LmI Mm. Agency Innovative Technology Verification Report XRF Technologies for Measuring Trace Elements in Soil and Sediment Rigaku ZSX Mini II XRF Analyzer RESEARCH AND DEVELOPMENT ------- EPA/540/R-06/001 April 2006 www epa gov Innovative Technology Verification Report Rigaku ZSX Mini II XRF Analyzer Contract No. 68-C-00-181 Task Order No. 42 Prepared for Dr. Stephen Billets U.S. Environmental Protection Agency Office of Research and Development National Exposure Research Laboratory Environmental Sciences Division Characterization and Monitoring Branch Las Vegas, NV 89193-3478 Prepared by Tetra Tech EM Inc. Cincinnati, OH 45202-1072 Notice: Although this work was reviewed by EPA and approved for publication, it may not necessarily reflect official Agency policy Mention of trade names and commercial products does not constitute endorsement or recommendation for use. U.S. Environmental Protection Agency Office of Research and Development Washington, DC 20460 180cmt>06 RPT ~ 4/7/2006 ------- 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. u ------- 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 arc 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 strategics. 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 arc 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 arc 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 ill ------- Abstract The Rigaku ZSX Mini II (ZSX Mini II) XRF Services x-ray fluorescence (XRF) analyzer was demon- strated under the U.S. Environmental Protection Agency (EPA) Superfund Innovative Technology Evaluation (SITE) Program. The field portion of the demonstration was conducted in January 2005 at the Kennedy Athletic, Recreational and Social Park (KARS) at Kennedy Space Center on Merritt Island, Florida. The demonstration was designed to collect reliable performance and cost data for the ZSX Mini II analyzer and seven other commercially available XRF instruments for measuring trace elements in soil and sediment. The performance and cost data were evaluated to document the relative performance of each XRF instrument. This innovative technology verification report describes the objectives and the results of that evaluation and serves to verify the performance and cost of the ZSX Mini II analyzer. Separate reports have been prepared for the other XRF instruments that were evaluated as part of the demonstration. The objectives of the evaluation included determining each XRF instrument's accuracy, precision, sample throughput, and tendency for matrix effects. To fulfill these objectives, the field demonstration incorporated the analysis of 326 prepared samples of soil and sediment that contained 13 target elements. The prepared samples included blends of environmental samples from nine different sample collection sites as well as spiked samples with certified element concentrations. Accuracy was assessed by comparing the XRF instrument's results with data generated by a fixed laboratory (the reference laboratory). The reference laboratory performed element analysis using acid digestion and inductively coupled plasma - atomic emission spectrometry (ICP-AES), in accordance with EPA Method 3050B/6010B, and using cold vapor atomic absorption (CVAA) spectroscopy for mercury only, in accordance with EPA Method 7471 A. The ZSX Mini II is a "wavelength-dispersive" XRF analyzer that can analyze for elements ranging in mass from fluorine to uranium. The ZSX Mini II differentiates the x-ray energies emitted from a sample by dispersing the x-rays into different wavelength ranges using crystals. By contrast, more common "energy-dispersive" XRF analyzers differentiate between x-ray energies based on voltages measured by the detector. For some applications, wavelength-dispersive XRF analyzers can achieve high resolutions and very good sensitivity through the reduction of interelement interferences. Wavelength-dispersive XRFs have historically been large, laboratory-bound instruments with significant requirements for power and cooling. The ZSX Mini II is a smaller, transportable unit that can operate without additional cooling fluids on standard 110-volt circuits. The unit can employ an economical gas proportional counter as a detector rather than a diode detector with a multi-channel analyzer (common in energy-dispersive instruments) because wavelength resolution is achieved with the crystals. This report describes the results of the evaluation of the ZSX Mini II analyzer based on the data obtained during the demonstration. The method detection limits, accuracy, and precision of the instrument for each of the 13 target analytes arc presented and discussed. The cost of element analysis using the ZSX Mini II analyzer is compiled and compared to both fixed laboratory costs and average XRF instrument costs. IV ------- Contents Chapter Page Notice ii Foreword iii Abstract iv Acronyms, Abbreviations, and Symbols x Acknowledgements xiv 1.0 INTRODUCTION 1 1.1 Organization of this Report 1 1.2 Description of the SITE Program 2 1.3 Scope of the Demonstration 2 1.4 General Description ofXRF 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 Northcrn-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 Supcrfund Site 14 2.9 Wickcs 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 Homogcnization 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 v ------- Contents (Continued) Chapter Page 3.3 Demonstration Site and Logistics 20 3.3.1 Demonstration Site Selection 20 3.3.2 Demonstration Site Logistics 20 3.3.3 EPA Demonstration Team and Developer Field Team Responsibilities 21 3.3.4 Sample Management During the Field Demonstration 21 3.3.5 Data Management 22 4.0 EVALUATION DESIGN 23 4.1 Evaluation Objectives 23 4.2 Experimental Design 23 4.2.1 Primary Objective 1 - Method Detection Limits 24 4.2.2 Primary Objective 2 - Accuracy 25 4.2.3 Primary Objective 3 - Precision 26 4.2.4 Primary Objective 4 - Impact of Chemical and Spectral Interferences 27 4.2.5 Primary Objective 5 - Effects of Soil Characteristics 28 4.2.6 Primary Objective 6 - Sample Throughput 28 4.2.7 Primary Objective 7 - Technology Costs 28 4.2.8 Secondary Objective 1 - Training Requirements 28 4.2.9 Secondary Objective 2 - Health and Safety 29 4.2.10 Secondary Objective 3 - Portability 29 4.2.11 Secondary Objective 4 - Durability 29 4.2.12 Secondary Objective 5 - Availability 29 4.3 Deviations from the Demonstration Plan 29 5.0 REFERENCE LABORATORY 31 5.1 Selection of Reference Methods 31 5.2 Selection of Reference Laboratory 32 5.3 QA/QC Results for Reference Laboratory 33 5.3.1 Reference Laboratory Data Validation 33 5.3.2 Reference Laboratory Technical Systems Audit 34 5.3.3 Other Reference Laboratory Data Evaluations 34 5.4 Summary of Data Quality and Usability 36 6.0 TECHNOLOGY DESCRIPTION 39 6.1 General Description 39 6.2 Instrument Operations during the Demonstration 39 6.2.1 Setup and Calibration 39 6.2.2 Demonstration Sample Processing 41 6.3 General Demonstration Results 41 6.4 Contact Information 42 VI ------- Contents (Continued) Chapter Page 7.0 PERFORMANCE EVALUATION 43 7.1 Primary Objective 1 - Method Detection Limits 43 7.2 Primary Objective 2 - Accuracy and Comparability 46 7.3 Primary Objective 3 - Precision 51 7.4 Primary Objective 4 - Impact of Chemical and Spectral Interferences 52 7.5 Primary Objective 5 - Effects of Soil Characteristics 55 7.6 Primary Objective 6 - Sample Throughput 59 7.7 Primary Objective 7-Technology Cost 59 7.8 Secondary Objective 1 - Training Requirements 59 7.9 Secondary Objective 2 - Health and Safety 59 7.10 Secondary Objective 3 - Portability 60 7.11 Secondary Objective 4 - Durability 60 7.12 Secondary Objective 5 - Availability 60 8.0 ECONOMIC ANALYSIS 61 8.1 Equipment Costs 61 8.2 Supply Costs 61 8.3 Labor Costs 61 8.4 Comparison of XRF Analysis and Reference Laboratory Costs 62 9.0 SUMMARY OF TECHNOLOGY PERFORMANCE 65 10.0 REFERENCES 71 APPENDICES Appendix A: Appendix B: Appendix C: Appendix D: Appendix E: Verification Statement Developer Discussion Data Validation Summary Report Developer and Reference Laboratory Data Statistical Data Summaries vn ------- TABLES Contents (Continued) 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, Wickcs Smelter Site-Roaster Slag Pile 14 3-1 Concentration Levels for Target Elements in Soil and Sediment 18 3-2 Number of Environmental Sample Blends and Demonstration Samples 19 3-3 Number of Spiked Sample Blends and Demonstration Samples 19 4-1 Evaluation Objectives 24 5-1 Number of Validation Qualifiers 35 5-2 Percent Recovery for Reference Laboratory Results in Comparison to ERA Certified Spike Values for Blends 46 through 70 37 5-3 Precision of Reference Laboratory Results for Blends 1 through 70 38 6-1 Rigaku ZSX Mini II XRF Technical Specifications 40 7-1 Evaluation of Sensitivity - Method Detection Limits for the ZSX Mini II 44 7-2 Comparison of ZSX Mini MDLs to All-Instrument Mean MDLs and EPA Method 6200 Data 46 7-3 Evaluation of Accuracy - Relative Percent Differences versus Reference Laboratory Data for the ZSX Mini II 49 7-4 Summary of Correlation Evaluation for the ZSX Mini II 50 7-5 Evaluation of Precision - Relative Standard Deviations for the ZSX Mimi II 53 7-6 Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory versus the ZSX Mini II and All Demonstration Instruments 54 7-7 Effects of Interferent Elements on the RPDs (Accuracy) for Other Target Elements 56 7-8 Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Rigaku ZSX Mini II 57 8-1 Equipment Costs 61 8-2 Time Required to Complete Analytical Analysis 62 8-3 Comparison of XRF Technology and Reference Method Costs 64 9-1 Summary of Rigaku ZSX Mini II Performance - Primary Objectives 66 9-2 Summary of Rigaku ZSX Mini II Performance - Secondary Objectives 68 viii ------- FIGURES Contents (Continued) Page 1-1 The XRF Process 4 3-1 Bulk Sample Processing Diagram 16 3-2 K.ARS Park Recreation Building 20 3-3 Work Areas for the XRF Instalments in the Recreation Building 21 3-4 Visitors Day Presentation 21 3-5 Sample Storage Room 22 6-1 Rigaku ZSX Mini II XRF Analyzer Set Up for Bench-Top Analysis 39 6-2 Rigaku Technician Filling a Sample Cup For Analysis 41 6-3 Samples Placed into the 12-Position Sample Changer Awaiting Analysis 41 7-1 Linear Correlation Plot for Lead Showing High Correlation 48 7-2 Linear Correlation Plot for Silver Indicating Low Overall Correlation with the Reference Laboratory 51 8-1 Comparison of Activity Times for the ZSX Mini II versus Other XRF Instruments 63 9-1 Method Detection Limits (sensitivity), Accuracy, and Precision of the ZSX Mini II in Comparison to the Average of All Eight XRF Instruments 69 ix ------- Acronyms, Abbreviations, and Symbols MS Micrograms HA Micro-amps AC Alternating current ADC Analog to digital converter Ag Silver Am Amcricium 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 Fc Iron FPT Fundamental Parameters Technique FWHM Full width of peak at half maximum height GB Gigabyte Hg Mercury Hz Hertz ------- Acronyms, Abbreviations, and Symbols (Continued) ICP-AES Inductively coupled plasma-atomic emission spectrometry ICP-MS Inductively coupled plasma-mass spectrometry IR Infrared ITVR Innovative Technology Verification Report KARS Kennedy Athletic, Recreational and Social (Park) kcV Kiloclcctron 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 in A Milli-amps MB Megabyte MBq Mega Bccquercls MCA Multi-channel analyzer mCi Millicurics 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 XI ------- Acronyms, Abbreviations, and Symbols (Continued) p Phosphorus Pb Lead PC Personal computer PDA Personal digital assistant PCB Polychlorinated biphenyls Pd Palladium PE Performance evaluation PeT Pentaerythritol PPb Parts per billion PPm Parts per million Pu Plutonium QA Quality assurance QAPP Quality assurance project plan QC Quality control r2 Correlation coefficient RCRA Resource Conservation and Recovery Act Rh Riiodium 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 xii ------- Acronyms, Abbreviations, and Symbols (Continued) V Vanadium V Volts voc Volatile organic compound w Watts WDXRF Wavelength-dispersive XRF WRS Wilcoxon Rank Sum XRF X-ray fluorescence Zn Zinc Xlll ------- Acknowledgements This report was co-authorcd by Dr. Greg Swanson and Dr. Mark Colsman of Tetra Tech EM Inc. The authors acknowledge the advice and support of the following individuals in preparing this report: Dr. Stephen Billets and Mr. George Brilis of the U.S. Environmental Protection Agency's National Exposure Research Laboratory; Jose Brum and George Fischer of Rigaku, Inc.; and Dr. Jackie Quinn of the National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC). The demonstration team also acknowledges the field support of Michael Deliz of NASA KSC and Mark Speranza of Tetra Tech NUS, the consultant program manager for NASA. xiv ------- Chapter 1 Introduction The U.S. Environmental Protection Agency (EPA), Office of Research and Development (ORD) conducted a demonstration to evaluate the performance of innovative x-ray fluorescence (XRF) technologies for measuring trace elements in soil and sediment. The demonstration was conducted as part of the EPA Supcrfund 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 arc 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 Tabic 1-1. Participating Tech cost information, were then documented in an Innovative Technology Verification Report (ITVR) for each instrument. This ITVR documents EPA's evaluation of the Rigaku ZSX Mini II XRF analyzer based on the results of the demonstration. 1.1 Organization of this Report This report is organized to first present general information pertinent to the demonstration. This information is common to all eight ITVRs that were developed from the XRF demonstration. Specifically, this information includes an introduction (Chapter 1), the locations where the field samples were collected (Chapter 2), the field demonstration (Chapter 3), the evaluation design (Chapter 4), and the reference laboratory results (Chapter 5). The second part of this report provides information relevant to the specific instrument that is the subject of this ITVR. This information includes a description of the instrument (Chapter 6), a performance evaluation (Chapter 7), a cost analysis (Chapter 8), and a summary of the demonstration results (Chapter 9). nology Developers and Instruments 1 Developer Full Name Distributor in the Developer Short Instrument Full Instrument Short United States Name Name Name Elvatcch, Ltd. Xcalibur XRF Services Xcalibur ElvaX ElvaX lnnov-X Systems lnnov-X Systems Innov-X XT400 Series XT400 NITON Analyzers, A NITON Analyzers, A Niton XLt 700 Series XLt Division of Thermo Division of Thermo XLi 700 Series XLi Electron Corporation Electron Cornoration Oxford Instruments Oxford Instruments Oxford X-Mct 3000 TX X-Mct Analytical. Ltd. Analytical. Ltd. ED2000 ED2000 Rigaku, Inc. Rigaku, Inc. Rigaku ZSX Mini II ZSX Mini II RONTEC AG RONTEC USA Rontcc PicoTAX PicoTAX (acquired by Brukcr 1 AXS. 11/2005 1 ------- References are provided in Chapter 10. A verification statement for the instrument is provided as Appendix A. Comments from the instrument developer on the demonstration and any exceptions to EPA's evaluation are presented in Appendix B. Appendices C, D, and E contain the data validation summary report for the reference laboratory data and detailed evaluations of instrument versus reference laboratory results. 1.2 Description of the SITE Program Performance verification of innovative environmental technologies is an integral part of EPA's regulatory and research mission. The SITE Program was established by the EPA Office of Solid Waste and Emergency Response and ORD under the Superfund Amendments and Reauthorization Act of 1986. The overall goal of the SITE Program is to conduct performance verification studies and to promote acceptance of innovative technologies that may be used to achieve long-term protection of human health and the environment. The program is designed to meet three primary objectives: (1) identify and remove obstacles to development and commercial use of innovative technologies; (2) demonstrate promising innovative technologies and gather reliable information on performance and cost to support site characterization and cleanup; and (3) maintain an outreach program to operate existing technologies and identify new opportunities for their use. Additional information on the SITE Program is available on the EPA ORD web site (www.epa.gov/ord/SITE'). The intent of a SITE demonstration is to obtain representative, high-quality data on the performance and cost of one or more innovative technologies so that potential users can assess a technology's suitability for a specific application. The SITE Program includes the following program elements: • Monitoring and Measurement Technology (MMT) Program - Evaluates technologies that sample, detect, monitor, or measure hazardous and toxic substances. These technologies are expected to provide better, faster, or more cost- effective methods for producing real-time data during site characterization and remediation studies than can conventional technologies. • Remediation Technology Program - Demonstrates innovative treatment technologies to provide reliable data on performance, cost, and applicability for site cleanups. • Technology Transfer Program - Provides and disseminates technical information in the form of updates, brochures, and other publications that promote the SITE Program and the participating technologies. The demonstration of XRF instruments was conducted as part of the MMT Program, which is administered by the Environmental Sciences Division (ESD) of the National Exposure Research Laboratory (NERL) in Las Vegas, Nevada. Additional information on the NERL ESD is available on the EPA web site (www.epa.gov/nerlesdlA. Tetra Tech EM Inc. (Tetra Tech), an EPA contractor, provided comprehensive technical support to the demonstration. 1.3 Scope of the Demonstration Conventional analytical methods for measuring the concentrations of inorganic elements in soil and sediment are time-consuming and costly. For this reason, field-portable XRF instruments have been proposed as an alternative approach, particularly where rapid and cost-effective assessment of a site is a goal. The use of a field XRF instrument for elemental analysis allows field personnel to quickly assess the extent of contamination by target elements at a site. Furthermore, the near instantaneous data provided by field-portable XRF instruments can be used to quickly identify areas where there may be increased risks and allow development of a more focused and cost-effective sampling strategy for conventional laboratory analysis. EPA-sponsored demonstrations of XRF technologies have been under way for more than a decade. The first SITE MMT demonstration of XRF occurred in 1995, when six instruments were evaluated for their ability to analyze 10 target elements. The results of this demonstration were published in individual reports for each instrument (EPA 1996a, 1996b, 1998a, 1998b, 1998c, and 1998d). In 2003, two XRF instruments were included in a demonstration of field methods for analysis of mercury in soil and sediment. 2 ------- Individual ITVRs were also prepared for each of these two instruments (EPA 2004a, 2004b). Although XRF spectrometry is now considered a mature technology for elemental analysis, field- portable XRF instruments have evolved considerably over the past 10 years, and many of the instruments that were evaluated in the original demonstration arc 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 statc-of-thc- art instrumentation and its associated capabilities. During the demonstration, performance data regarding each field-portable XRF instrument were collected through analysis of a sample set that included a broad range of soil/sediment types and target clement 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 Mcrritt 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 7471 A. By assuming that the results from the reference laboratory were essentially "true" values, instrument accuracy was assessed by comparing the results obtained using the XRF instrument with the results from the reference laboratory. The data obtained using the XRF instrument were also assessed in other ways, in accordance with the objectives of the demonstration, to provide information on instrument precision, detection limits, and interferences. 1.4 General Description of XRF Technology XRF spectroscopy is an analytical technique that exposes a solid sample to an x-ray source. The x- rays from the source have the appropriate excitation energy that causes elements in the sample to emit characteristic x-rays. A qualitative elemental analysis is possible from the characteristic energy, or wavelength, of the fluorescent x-rays emitted. A quantitative elemental analysis is possible by counting the number (intensity) of x-rays at a given wavelength. Three electron shells arc generally involved in emissions of x-rays during XRF analysis of samples: the K, L, and M shells. Multiple-intensity peaks arc 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 arc the most energetic lines. K lines arc typically used for elements with atomic numbers from 11 to 46 (sodium to palladium), and L lines arc used for elements above atomic number 47 (silver). M-shcll emissions arc measurable only for metals with an atomic number greater than 57 (lanthanum). As illustrated in Figure 1-1, characteristic radiation arises when the energy from the x-ray source exceeds the absorption edge energy of inner-shell electrons, ejecting one or more electrons. The vacancies arc 3 ------- 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 well- considered sampling and analysis plan. Sample preparation and homogenization, instrument calibration, and laboratory confirmation analysis are all important aspects of an XRF sampling and analysis plan. EPA SW-846 Method 6200 provides additional guidance on sampling and analytical methodology for XRF analysis. 1.5 Properties of the Target Elements This section describes the target elements selected for the technology demonstration and the typical characteristics of each. Key criteria used in selecting the target elements included: • The frequency that the element is determined in environmental applications of XRF instruments. • The extent that the element poses an environmental consequence, such as a potential risk to human or environmental receptors. • The ability of XRF technology to achieve detection limits below typical remediation goals and risk assessment criteria. • The extent that the element may interfere with the analysis of other target elements. In considering these criteria, the critical target elements selected for this study were antimony, arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc. These 13 target elements are of significant concern for site cleanups and human health risk assessments because most are highly toxic or interfere with the analysis of other elements. The demonstration therefore focused on the analysis of these 13 elements in evaluating the various XRF instruments. 4 ------- 1.5.1 Antimony Naturally occurring antimony in surface soils is typically found at less than 1 to 4 milligrams per kilogram (mg/kg). Antimony is mobile in the environment and is bioavailable for uptake by plants; concentrations greater than 5 mg/kg are potentially phytotoxic, and concentrations above 31 mg/kg in soil may be hazardous to humans. Antimony may be found along with arsenic in mine wastes, at shooting ranges, and at industrial facilities. Typical detection limits for field-portable XRF instruments range from 10 to 40 mg/kg. Antimony is typically analyzed with success by ICP-AES; however, recovery of antimony in soil matrix spikes is often below quality control (QC) limits (50 percent or less) as a result of loss through volatilization during acid digestion. Therefore, results using ICP-AES may be lower than are obtained by XRF. 1.5.2 Arsenic Naturally occurring arsenic in surface soils typically ranges from 1 to 50 mg/kg; concentrations above 10 mg/kg arc 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 arc associated with mine wastes and industrial facilities. Arsenic is successfully analyzed by ICP-AES; however, spectral interferences between peaks for arsenic and lead can affect detection limits and accuracy in XRF analysis when the ratio of lead to arsenic is 10 to 1 or more. Risk-based screening levels and soil screening levels for arsenic may be lower than the detection limits of field-portable XRF instruments. 1.5.3 Cadmium Naturally occurring cadmium in surface soils typically ranges from 0.6 to 1.1 mg/kg; concentrations greater than 4 mg/kg are potentially phytotoxic. Concentrations of cadmium that exceed 37 mg/kg may result in adverse effects in humans. Typical detection limits for field-portable XRF instruments range from 10 to 50 mg/kg. Elevated concentrations of cadmium are associated with mine wastes and industrial facilities. Cadmium is successfully analyzed by both ICP-AES and field- portable XRF; however, action levels for cadmium may be lower than the detection limits of field- portable XRF instruments. 1.5.4 Chromium Naturally occurring chromium in surface soils typically ranges from 1 to 1,000 mg/kg; concentrations greater than 1 mg/kg are potentially phytotoxic, although specific phytotoxicity levels for naturally occurring chromium have not been documented. The variable oxidation states of chromium affect its behavior and toxicity. Concentrations of hexavalent chromium above 30 mg/kg and of trivalcnt 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 5 ------- therefore included in the study. Furthermore, iron is often used as a target reference element in XRF analysis. Naturally occurring iron in surface soils typically ranges from 7,000 to 550,000 mg/kg, with the iron content originating primarily from parent rock. Typical detection limits for field-portable XRF instruments are in the range of 10 to 60 mg/kg. Iron is easily analyzed by both ICP-AES and XRF; however, neither technique can distinguish among iron species in soil. Although iron in soil may pose few environmental consequences, high levels of iron may interfere with analyses of other elements in both techniques (ICP-AES and XRF). Spectral interference from iron is mitigated in ICP-AES analysis by applying inter-element correction factors, as required by the analytical method. Differences in analytical results between ICP-AES and XRF for other target elements are expected when concentrations of iron are high in the soil matrix. 1.5.7 Lead Naturally occurring lead in surface soils typically ranges from 2 to 200 mg/kg; concentrations greater than 50 mg/kg arc 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 arc expected when mercury levels are high. 1.5.9 Nickel Naturally occurring nickel in surface soils typically ranges from 5 to 500 mg/kg; a concentration of 30 mg/kg is potentially phytotoxic. Concentrations greater than 1,600 mg/kg may result in adverse health effects in humans. Typical detection limits for field- portable XRF instruments range from 10 to 60 mg/kg. Elevated concentrations of nickel are associated with mine wastes and industrial facilities. Nickel is a common environmental contaminant at metal processing sites. It is successfully analyzed by both ICP-AES and XRF with little interference; therefore, a strong correlation between the methods is expected. 1.5.10 Selenium Naturally occurring selenium in surface soils typically ranges from 0.1 to 2 mg/kg; concentrations greater than 1 mg/kg are potentially phytotoxic. Its toxicities are well documented for plants and livestock; however, it is also considered a trace nutrient. Concentrations above 390 mg/kg may result in adverse health effects in humans. Typical detection limits for field-portable XRF instruments range from 10 to 20 mg/kg. Most selenium is associated with sulfur or sulfide minerals, where concentrations can exceed 200 mg/kg. Selenium can be measured by both ICP-AES and XRF; however, detection limits using XRF usually exceed the 6 ------- ecological risk-based screening levels for soil. Analytical results for selenium using ICP-AES and XRF arc 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 arc 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 arc 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 arc 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. 7 ------- This page was left blank intentionally. 8 ------- 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 clement 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 uncontaminatcd (background) samples were collected at each site. A summary of the sample collection sites is presented in Table 2-1, which describes the types of metal- contaminated soils or sediments that were found at each site. This information is based on the historical data that were provided by the site owners or by the EPA remedial project managers. 2.1 Alton Steel Mill Site The Alton Steel Mill site (formerly the Laclede Steel site) is located at 5 Cut Street in Alton, Illinois. This 400-acrc 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 biphcnyls (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), semivolatilc 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. 9 ------- Tabic 2-1. Nature of Contamination in Soil and Sediment at Sample Collection Sites Sample Collection Site Source of Contamination Matrix Sitc-Spccific Metals of Concern for XRF Demonstration Sb As Cd Cr Cu Fe Pb HR Ni Se ar Zn 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 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, Memtt Island, FL Impacts to soil from historical facility operations and a former gun range. Soil X 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-nnle stretch of mountain creeks, including Aspen Creek, with heavy metals. Soil and Sediment X 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 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 X Sulphur Bank Mercury Mine Inactive mercury mine. Waste rock, tailings, and ore are distributed in piles throughout the property. Soil X 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 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 X X I Notes (in order of appearance in table): Sb: Antimony Cr: Chromium Pb: Lead Se: Selenium As: Arsenic Cu: Copper Hg: Mercury Ag: Silver Cd: Cadmium Fe: Iron Ni: Nickel Zn: Zinc Note: Vanadium was not a chemical of concern at any of the sites and so does not appear on the table. 10 ------- Table 2-2. Historical Analytical Data, Alton Steel Mill Site Metal Maximum Concentration (m«/kg) Arsenic 80.3 Cadmium 97 Chromium 1,551 Lead 3,556 2.2 Burlington Northcrn-ASARCO Smelter Site The Burlington Northern (BN)-ASARCO Smelter site is located in the southwestern part of East Helena, Montana. The site was an active smelter for more than 100 years and closed in 2002. Most of the ore processed at the smelter was delivered on railroad cars. An area west of the plant site (the BN property) was used for temporary staging of ore cars and consists of numerous side tracks to the primary railroad line into the smelter. This site was selected to be included in the demonstration because it had not been remediated and contained several target elements in soil. At the request of EPA, the site owner collected samples of surface soil in this area in November 1997 and April 1998 and analyzed them for arsenic, cadmium, and lead; elevated concentrations were reported for all three metals. The site owner collected 24 samples of surface soil (16 in November 1997 and 8 in April 1998). The soils were found to contain up to 2,018 parts per million (ppm) arsenic, 876 ppm cadmium, and 43,907 ppm lead. One sample of contaminated soil and one sample of background soil were collected. The contaminated soil was a light brown sandy loam with low organic carbon content. The background soil was a medium brown sandy loam with slightly more organic material than the contaminated soil sample. Table 2- 3 presents the site owner's data for arsenic, cadmium, and lead (the maximum concentrations) from the 1997 and 1998 sampling events. Table 2-3. Historical Analytical Data, BN- ASARCO Smelter Site | Metal Maximum Concentration (ppm) | Arsenic 2,018 j Cadmium 876 1 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 Mcrritt 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 Mcrritt 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 bcrm 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 11 ------- 2.4 Leviathan Mine Site The Leviathan Mine site is an abandoned copper and sulfur mine located high on the eastern slopes of the Sierra Nevada Mountain range near the California- Nevada border. Development of the Leviathan Mine began in 1863, when copper sulfate was mined for use in the silver refineries of the Comstock Lode. Later, the underground mine was operated as a copper mine until a mass of sulfur was encountered. Mining stopped until about 1935, when sulfur was extracted for use in refining copper ore. In the 1950s, the mine was converted to an open-pit sulfur mine. Placement of excavated overburden and waste rock in nearby streams created acid mine drainage and environmental impacts in the 1950s. Environmental impacts noted at that time included large fish kills. Historical mining distributed waste rock around the mine site and created an open pit, adits, and solution cavities through mineralized rock. Oxygen in contact with the waste rock and mineralized rock in the adits oxidizes sulfur and sulfide minerals, generating acid. Water contacting the waste rock and flowing through the mineralized rock mobilizes the acid into the environment. The acid dissolves metals, including arsenic, copper, iron, and nickel, which creates conditions toxic to insects and fish in Leviathan, Aspen, and Bryant Creeks, downstream of the Leviathan Mine. Table 2-5 presents historical analytical data (the maximum concentrations) for the target elements detected at elevated concentrations in sediment samples collected along the three creeks. Four sediment and one soil sample were collected. One of the sediment samples was collected from the iron precipitate terraces formed from the acid mine drainage. The matrix of this sample appeared to be an orange silty clay loam. A second sediment sample was collected from the settling pond at the wastewater treatment system. The matrix of this sample was orange clay. A third sample was collected from the salt crust at the settling pond. This sample incorporated white crystalline material. One background sediment and one background soil sample were collected upstream of the mine. These samples consisted of light brown sandy loam. Table 2-5. Historical Analytical Data, Leviathan Mine Site Metal 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. 12 ------- Tabic 2-6. Historical Analytical Data, iN'SVVC 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 Supcrfund site in 1983. A large volume of tailings was deposited in a low- gradient reach of Silver Bow Creek in the Ramsay Flats area. Tailings at Ramsay Flats extend several hundred feet north of the Silver Bow Creek channel. About 18 inches of silty tailings overlie tcxturally stratified natural sediments that consist of low- pcrmcability 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 intcrlaycrcd 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 arc summarized in Tabic 2-7. 2.7 Sulphur Bank Mercury Mine Site The Sulphur Bank Mercury Mine (SBMM) is a 160- acrc 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 hydrothcrmal 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 arc 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. 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 13 ------- Table 2-8. Historical Analytical Data, Sulphur Bank Mercury Mine Site 1 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. Tabic 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 I Cadmium 70 Chromium 13 Copper 948 Iron 24,780 Lead 33,500 Nickel 7.3 Silver 83 Zinc 5,299 14 ------- Chapter 3 Field Demonstration The field demonstration required a sample set and a single location (the demonstration site) where all the technology developers could assemble to analyze the sample set under the oversight of the EPA/Tetra Tech field team. This chapter describes how the sample set was created, how the demonstration site was selected, and how the field demonstration was conducted. Additional detail regarding these topics is available in the Demonstration and Quality Assurance Project Plan (Tetra Tech 2005). 3.1 Bulk Sample Processing A set of samples that incorporated a variety of soil and sediment types and target clement 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 uncontaminatcd (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 incoiporating 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 Vibracorc or Ponar sediment sampler operated from a boat. Each 5-gallon bucket was ovcrpackcd 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. 15 ------- After each bulk sample had been sieved and crushed, the sample was mixed and homogenized using a Model T 50A Turbula shaker-mixer. This shaker was capable of handling up to 50 gallons (190 liters) of sample material; thus, this shaker could handle the complete volume of each bulk sample. Bulk samples of smaller volume were mixed and homogenized using a Model T 10B Turbula shaker-mixer that was capable of handling up to 10 gallons (38 liters). Aliquots from each homogenized bulk sample were then sampled and analyzed in triplicate for the 13 target elements using 1CP-AES and CVAA. If the relative percent difference between the highest and lowest result exceeded 10 percent for any element, the entire batch was returned to the shaker-mixer for additional homogenization. The entire processing scheme for the bulk samples is shown in Figure 3-1. Material was sieved through custom 1" screen to remove large material. Material cm shed using stainless steel hammer mill *— i L Package samples for distribution Figure 3-1. Bulk sample processing diagram. 16 ------- 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 En vironmental 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. 17 ------- Table 3-1. Concentration Levels for Target Elements in Soil and Sediment Analyte Level 1 Target Range (mg/kg) Level 2 Target Range (mg/kg) Level 3 Target Range (mg/kg) Level 4 Target Range (mg/kg) SOIL Antimony 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 I 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 18 ------- Tabic 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 Northcrn-ASARCO East Helena Site 5 29 1 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 Wickcs 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 Number of Number of Sampling Location Spiked Sample Blends Demonstration Samples Alton Steel Mill Site 1 3 Burlington Northcrn-ASARCO East 7 f. Helena Site Leviathan Mine Site 5 15 Naval Surface Warfare Center, Crane (1 Division Site z 0 Ramsey Flats—Silver Bow Creek Superfund Site 6 22 Sulphur Bank Mercury Mine Site 3 9 Torch Lake Superfund Site 4 12 Wickcs 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 19 ------- 3.3 Demonstration Site and Logistics The field demonstration occurred during the week of January 24, 2005. This section describes the selection of the demonstration site and the logistics of the field demonstration, including sample management. 3.3.1 Demonstration Site Selection The demonstration site was selected from among the list of sample collection sites to simulate a likely field deployment. The following criteria were used to assess which of the nine sample collection sites might best serve as the demonstration site: • Convenience and accessibility to participants in the demonstration. • Ease of access to the site, with a reasonably sized airport that can accommodate the travel schedules for the participants. • Program support and cooperation of the site owner. • Sufficient space and power to support developer testing. • Adequate conference room space to support a visitors day. • A temperate climate so that the demonstration could occur on schedule in January. After an extensive search for candidates, the site selected for the field demonstration was KARS Park, which is part of the Kennedy Space Center on Merritt Island, Florida. KARS Park was selected as the demonstration site for the following reasons: • Access and Site Owner Support — Representatives from NASA were willing to support the field demonstration by providing access to the site, assisting in logistical support during the demonstration, and hosting a visitors day. • Facilities Requirements and Feasibility — The recreation building was available and was of sufficient size to accommodate all the demonstration participants. Furthermore, the recreation building had adequate power to operate all the XRF instruments simultaneously and all the amenities to fully support the demonstration participants, as well as visitors, in reasonable comfort. • Ease of Access to the Site — The park, located about 45 minutes away from Orlando International Airport, was selected because of its easy accessibility by direct flight from many airports in the country. In addition, many hotels are located within 10 minutes of the site along the coast at Cocoa Beach, in a popular tourist area. Weather in this area of central Florida in January is dry and sunny, with pleasant daytime temperatures into the 70s (F) and cool nights. 3.3.2 Demonstration Site Logistics The field demonstration was held in the recreation building, which is just south of the gunnery range at KARS Park. Photographs of the KARS Park recreation building, where all the XRF instruments were set up and operated, are shown in Figures 3-2 and 3-3. A visitors day was held on January 26, 2005 when about 25 guests came to the site to hear about the demonstration and to observe the XRF instruments in operation. Visitors day presentations were conducted in a conference building adjacent to the recreation building at KARS Park (see Figure 3-4). Presenta- tions by NASA and EPA representatives were followed by a tour of the XRF instruments in the recreation building while demonstration samples were being analyzed. Figure 3-2. KARS Park recreation building. 20 ------- 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 21 ------- that might provide the developer's field team any insight as to the nature or content of the sample. Spiked samples were integrated with the environmental samples in a random manner so that the spiked samples could not be distinguished. The demonstration sample set was divided into 13 subsets, or batches, for tracking during the field demonstration. The samples provided to each developer's field team were randomly distributed in two fashions. First, the order of the jars within each batch was random, so that the sample order for a batch was different for each developer's field team. Second, the distribution of sample batches was random, so that each developer's field team received the sample batches in a different order. The observer provided the developer's field team with one batch of samples at a time. When the developer's field team reported that analysis of a batch was complete, the observer would reclaim all the unused sample material from that batch and then provide the next batch of samples for analysis. Chain-of-custody forms were used to document all sample transfers. When the analysis of all batches was complete, the observer assisted the developer's field team in cleanup of the work area and repackaging the instrument and any associated equipment. The members of the developer's field team were not allowed to take any part of the demonstration samples with them when they left the demonstration site. Samples that were not in the possession of the developer's field team during the demonstration were held in a secure storage room adjacent to the demonstration work area (see Figure 3-5). The storage room was closed and locked except when the observer retrieved samples from the room. Samples were stored at room temperature during the demonstration, in accordance with the quality assurance/quality control (QA/QC) requirements established for the project. Figure 3-5. Sample storage room. 3.3.5 Data Management Each of the developer's field teams was able to complete analysis of all 326 samples during the field demonstration (or during the subsequent week, in one case when the developer's field team arrived late at the demonstration site because of delays in international travel). The data produced by each developer's field team were submitted during or at the end of the field demonstration in a standard Microsoft Excel* spreadsheet. (The EPA/Tetra Tech field team had provided a template.) Since each instrument provided data in a different format, the developer's field team was responsible for reducing the data before they were submitted and for transferring the data into the Excel spreadsheet. The observer reviewed each data submittal for completeness, and the data were then uploaded into a master Excel spreadsheet on a laptop computer for temporary storage. Only the EPA/Tetra Tech field team had access to the master Excel spreadsheet during the field demonstration. Once the EPA/Tetra Tech field team returned to their offices, the demonstration data were transferred to an Microsoft Access* database for permanent storage. Each developer's data, as they existed in the Access database, were then provided to the developer for review. Any errors the developers identified were corrected, and the database was then finalized. All statistical analysis and data evaluation took place on this final database. 22 ------- 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 arc 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 arc listed in Table 4-1. These objectives were based on: • Input from MMT Program stakeholders, including developers and EPA staff. • General expectations of users of field measurement instruments. • The time available to complete the demonstration. • The capabilities of the instruments that the developers participating in the demonstration intended to highlight. 4.2 Experimental Design To address the first four primary objectives, each XRF instrument analyzed the demonstration sample set for the 13 target elements. The demonstration samples originated from multiple sampling locations across the country, as described in Chapter 2, to provide a diverse set of soil and sediment matrices. The demonstration sample set included both blended environmental samples and spiked background samples, as described in Chapter 3, to provide a wide range of concentrations and combinations of elements. When the field demonstration was completed, the results obtained using the XRF instruments were compared with data from a reference laboratory to evaluate the performance of each instrument in terms of accuracy and comparability (Primary Objective 2). The results for replicate samples were used to evaluate precision in various concentration ranges (Primary Objective 3) and the method detection limits (MDL) (Primary Objective 1). Each of these quantitative evaluations of instrument performance was carried out for each target element. The effect of chemical and spectral interferences and of soil characteristics (Primary Objectives 4 and 5) were evaluated to help explain extreme deviations or outliers observed in the XRF results when compared with the reference laboratory results. A second important comparison involved the average performance of all eight XRF instruments that participated in the demonstration. For the first three primary objectives (MDL, accuracy, precision), the performance of each individual instrument was compared to the overall average performance of all eight instruments. Where the result of the instrument under consideration was less than 10 percent different than the average result for all eight instruments, the result was considered "equivalent." A similar comparison was conducted with respect to cost (Primary Objective 7). These comparisons were intended to illustrate the performance of each XRF instrument in relation to its peers. 23 ------- The evaluation design for meeting each objective, including data analysis procedures, is discussed in more detail in the sections below. Where specific deviations from these procedures were necessary for the data set associated with specific instruments, these deviations are described as part of the performance evaluation in Chapter 7. 4.2.1 Primary Objective 1 — 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: where MDL - t(n-|,|-a=0 99)(s) MDL t n s = method detection limit = Student's t value for a 99 percent confidence level and a standard deviation estimate with n-1 degrees of freedom = number of samples = standard deviation. Table 4-1. Evaluation Objectives Objective 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. 1 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. 24 ------- Based on the data provided by the characterization laboratory before the demonstration, a total of 12 sample blends (seven for soil and five for sediment) were identified for use in the MDL determination. The demonstration approach specified the analysis of seven replicates for each of these sample blends by both the developer and the reference laboratory. It was predicted that these blends would allow the determination of a minimum of one MDL for soil and one MDL for sediment for each element, with the exception of iron. This prediction was based on the number of sample blends that contained concentrations less than 50 percent lower or higher than the lower limit of the Level 1 concentration range (from 20 to 50 ppm, depending on the element), as presented in Table 3-1. After the field demonstration, the data sets obtained by the developers and the reference laboratory for the MDL sample blends were reviewed to confirm that they were appropriate to use in calculating MDLs. The requirements of 40 CFR 136, Appendix B, were used as the basis for this evaluation. Specifically, the CFR states that samples to be used for MDL determinations should contain concentrations in the range of 1 to 5 times the predicted MDL. On this basis, and using a nominal predicted reporting limit of 50 ppm for the target elements based on past XRF performance and developer information, a concentration of 250 ppm (5 times the "predicted" nominal MDL) was used as a threshold in selecting samples to calculate the MDL. Thus, each of the 12 MDL blends that contained mean reference laboratory concentrations less than 250 ppm were used in calculating MDLs for a given target clement. 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 instalment 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-dctcct values in cither the XRF instrument or the reference laboratory analysis was excluded from the evaluation. 3. A blend was excluded from the evaluation when the average result from the reference laboratory was below a minimum concentration. The minimum concentration for exclusion from the accuracy assessment was identified as the lower limit of the lowest concentration range (Level 1 in Table 3-1), which is about 50 ppm for most elements. 4. The mean result for a blend obtained with the XRF instrument was compared with the corresponding mean result from the reference laboratory by calculating a relative percent difference (RPD). This comparison was carried out for each of the paired XRF and reference laboratory results included in the evaluation (up to 70 pairs) as follows: 25 ------- (Mr - Mn) 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: RSD = SD C x 100 where RSD = Relative standard deviation SD = Standard deviation C = Mean concentration. The standard deviation was calculated using the equation: SD = 1 " -1 *-1 ifc-cf 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. 26 ------- 2. A blend that exhibited one or more non-dctcct 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 Tabic 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 cither 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 XRT 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 Spectra/ Interferences The potential in the XRF analysis for spectral interference between adjacent elements on the periodic table was evaluated for the following clement 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 clement 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 arc absorbed or emitted by another clement within the sample, causing low or high bias. These interferences arc common in samples that contain high levels of iron, where low biases for copper and high biases for chromium can result. The evaluations for Primary Objective 4 included RPD comparisons between sample blends with high concentrations of iron (more than 50,000 ppm) and other sample blends. These RPD comparisons were performed for the specific target elements of interest (copper, chromium, and others) to assess chemical interferences from iron. Outliers and subpopulations in the RPD data sets for specific target elements, as identified through graphical means (probability plots and box plots), were also examined for potential interference effects. The software that is included with many XRF instruments can correct for chemical interferences. The results of this evaluation were therefore intended to differentiate the instruments that incorporated effective software for addressing chemical interferences. 27 ------- 4.2.5 Primary Objective 5 — Effects of Soil Characteristics The demonstration sample set included soil and sediment samples from nine locations across the U.S. and a corresponding variety of soil types and lithologies. The accuracy and precision statistics (RPD and RSD) were grouped by soil type (sample location) and the groups were compared to assess the effects of soil characteristics. Outliers and subpopulations in the RPD data sets, as identified through graphical means (correlation plots and box plots), were also examined for matrix effects. 4.2.6 Primary Objective 6 — Sample Throughput Sample throughput is a calculation of the total number of samples that can be analyzed in a specified time. The primary factors that affect sample throughput are the time required to prepare a sample for analysis, to conduct the analytical procedure for each sample, and to process and tabulate the resulting data. The time required to prepare and to analyze demonstration samples was recorded each day that demonstration samples were analyzed. Sample throughput can also be affected by the time required to set up and calibrate the instrument as well as the time required for quality control. The time required to perform these activities was also recorded during the field demonstration. An overall mean processing time per sample and an overall sample throughput rate was calculated based on the total time required to complete the analysis of the demonstration sample set from initial instrument setup through data reporting. The overall mean processing time per sample was then used as the primary basis for comparative evaluations. 4.2.7 Primary Objective 7 — Technology Costs The costs for analysis are an important factor in the evaluation and include the cost for the instrument, analytical supplies, and labor. The observer collected information on each of these costs during the field demonstration. Based on input from each technology developer and from distributors, the instrument cost was established for purchase of the equipment and for daily, weekly, and monthly rental. Some of the technologies are not yet widely available, and the developer has not established rental options. In these cases, an estimated weekly rental cost was derived for the summary cost evaluations based on the purchase price for the instrument and typical rental to purchase price ratios for similar instruments. The costs associated with leasing agreements were also specified in the report, if available. Analytical supplies include sample cups, spoons, x- ray film, 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. 28 ------- 4.2.9 Secondary Objective 2 — Health and Safety The health and safety requirements for operation of the instrument were identified, including any that arc 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 — A vailability The availability of the instrument from the developer, distributors, and rental agencies was documented. The availability of replacement parts and instrument- specific supplies was also noted. 4.3 Deviations from the Demonstration Plan Although the field demonstration and subsequent data evaluations generally followed the Demonstration and Quality Assurance Project Plan (Tctra Tech 2005), there were some deviations as new information was uncovered or as the procedures were reassessed while the plan was executed. These deviations arc 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 prc-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 clement 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 clement, and the "certified analysis" data set for a specific target clement was used as a supplement to the reference laboratory result when this criterion was exceeded. 3. Instrument accuracy and comparability in relation to the reference laboratory (Primary Objective 2) was originally planned to be assessed based on a combination of percent recovery (instrument result divided by reference laboratory result) and RPD. It was decided during the data analysis, however, that the RPD was a much better parameter for this assessment. Specifically, it was found that the mean or median of the absolute values of the RPD for each blend was a good discriminator of instrument performance for this objective. 4. Although this step was not described in the plan, some quantitative results for each instrument were compared with the overall average of all XRF instruments. Since there were eight instruments, it was believed that a comparison of 29 ------- this type did not violate EPA's agreement with the technology developers that one instrument would not be compared with another. Furthermore, this comparison provides an easy- to-understand basis for assessing instrument performance. 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 Rosncr outlier test was proposed in evaluating other matrix effects on XRF data quality (EPA 2000; Gilbert 1987). However, these statistical tests were not able to offer any substantive performance information over and above the evaluations based on RPDs and regression plots because of the limited sample numbers and scatter in the data. On this basis, the use of these two statistical tests was not further explored or presented. 30 ------- Chapter 5 Reference Laboratory As described in Chapter 4, a critical part of the evaluation was the comparison of the results obtained for the demonstration sample set by the XR.F 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, arc 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 (1CP-AES), in accordance with EPA SW-846 Method 3050B/601 OB, for all target elements except mercury • Cold vapor atomic absorption (CVAA) spectroscopy, in accordance with EPA SW-846 Method 7471 A, for mercury only Selection of these analytical methods for the demonstration was supported by the following additional considerations: (1) the methods arc widely available and widely used in current site characterizations, remedial investigations, risk assessments, and remedial actions; (2) substantial historical data arc available for these methods to document that their accuracy and precision arc 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 arc presented below. Element Analysis by ICP-AES. Method 601 OB (ICP-AES) was selected for 12 of the target elements because its demonstrated accuracy and precision meet the requirements of the XRF demonstration in the most cost-effective manner. The ICP-AES method is available at most environmental laboratories and substantial data exist to support the claim that the method is both accurate and precise enough to meet the objectives of the demonstration. Inductively coupled plasma-mass spectrometry (1CP- MS) was considered as a possible analytical technique; however, fewer data were available to support the claims of accuracy and precision. Furthermore, it was available in less than one-third of the laboratories solicited for this project. Finally, ICP-MS is a technique for analysis of trace elements and often requires serial dilutions to mitigate the effect of high concentrations of interfering ions or other matrix interferences. These dilutions can introduce the possibility of error and contaminants 31 ------- that might bias the results. Since the matrices (soil and sediment) for this demonstration are designed to contain high concentrations of elements and interfering ions, 1CP-AES was selected over 1CP-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 1CP-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 1CP-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 on- site laboratory technical systems audit (TSA). Each stage was evaluated by the project chemist and a procurement specialist. In Stage 1,12 analytical laboratories from across the U.S. were invited to bid by submitting extensive technical proposals. The technical proposals included: • A current statement of qualifications. • The laboratory quality assurance manual. • Standard operating procedures (SOP) (including sample receipt, laboratory information management, sample preparation, and analysis of elements). • Current instrument lists. • Results of recent analysis of performance evaluation samples and audits. • Method detection limit studies for the target elements. • Professional references, laboratory personnel experience, and unit prices. Nine of the 12 laboratories submitted formal written proposals. The proposals were scored based on technical merit and price, and a short list of five laboratories was identified. The scoring was weighed heavier for technical merit than for price. The five laboratories that received the highest score were advanced to stage 2. 32 ------- In stage 2, each of the laboratories was provided with a set of six samples to analyze. The samples consisted of three certified reference materials (one soil and two sediment samples) at custom spiking concentrations, as well as three pre-demonstration soil samples. The results received from each laboratory were reviewed and assessed. Scoring at this stage was based on precision (reproducibility of results for the three pre-demonstration samples), accuracy (comparison of results to certified values for the certified reference materials), and completeness of the data package (including the hard copy and electronic data deliverables). The two laboratories that received the highest score were advanced to stage 3. In stage 3, the two candidate laboratories were subjected to a thorough on-site TSA by the project chemist. The audit consisted of a direct comparison of the technical proposal to the actual laboratory procedures and conditions. The audit also tracked the pre-demonstration samples through the laboratory processes from sample receipt to results reporting. When the audit was conducted, the project chemist verified sample preparation and analysis for the three pre-demonstration samples. Each laboratory was scored on identical checklists. The reference laboratory was selected based on the highest overall score. The weights of the final scoring selection were as follows: Scoring Element 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, Shcaly Environmental Services, Inc. (Shcaly), of Caycc, 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, Shcaly analyzed all demonstration samples (both environmental and spiked samples) concurrently with the developers' analysis during the field demonstration. Shcaly analyzed the samples by ICP-AES using EPA SW-846 Method 3050B/6010B and by CVAA using EPA SW-846 Method 7471 A. 5.3 QA/QC Results for Reference Laboratory All data and QC results from the reference laboratory were reviewed in detail to determine that the reference laboratory data were of sufficiently high quality for the evaluation. Data validation of all reference laboratory results was the primary review tool that established the level of quality for the data set (Section 5.3.1). Additional reviews included the on-site TSA (Section 5.3.2) and other evaluations (Section 5.3.3). 5.3.1 Reference Laboratory Data Validation After all demonstration samples had been analyzed, reference data from Shcaly 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 (Tctra 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. 33 ------- 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 clement analysis practices (including sample preparation) for 12 elements by EPA Methods 3050B and 601 OB and for total mercury by EPA Method 7471 A. All decision- making personnel for Shealy were present during the TSA, including the laboratory director, QA officer, director of inorganics analysis, and the inorganics laboratory supervisor. Project-specific requirements were reviewed with the Shealy project team as were all the QA criteria and reporting requirements in the demonstration plan. It was specifically noted that the demonstration samples would be dried, ground, and sieved before they were submitted to the laboratory, and that the samples would be received with no preservation required (specifically, no chemical preservation and no ice). The results of the performance audit were also reviewed. No findings or nonconformances that would adversely affect data quality were noted. Only two minor observations were noted; these related to the revision dates of two SOPs. Both observations were discussed at the debriefing meeting held at the laboratory after the TSA. Written responses to each of the observations were not required; however, the laboratory resolved these issues before the project was awarded. The auditor concluded that Shealy complied with the demonstration plan and its own SOPs, and that data generated at the laboratory should be of sufficient and known quality to be used as a reference for the XRF demonstration. 5.3.3 Other Reference Laboratory Data Evaluations The data validation indicated that all results from the reference laboratory were valid and usable for comparison to XRF data, and the pre-demonstration TSA indicated that the laboratory could fully comply with the requirements of the demonstration plan for producing data of high quality. However, the reference laboratory data were evaluated in other ways to support the claim that reference laboratory data are of high quality. These evaluations included the (1) assessment of accuracy based on ERA- certified spike values, (2) assessment of precision based on replicate measurements within the same sample blend, and (3) comparison of reference laboratory data to the initial characterization data that was obtained when the blends were prepared. Each of these evaluations is briefly discussed in the following paragraphs. Blends 46 through 70 of the demonstration sample set consisted of certified spiked samples that were used to assess the accuracy of the reference laboratory data. The summary statistics from 34 ------- comparing the "certified values" for the spiked samples with the reference laboratory results arc shown in Table 5-2. The target for percent recovery was 75 to 125 percent. The mean percent recoveries for 12 of the 13 target elements were well within this accuracy goal. Only the mean recovery for antimony was outside the goal (26.8 percent). The low mean percent recovery for antimony supported the recommendation made by the project team to conduct a secondary comparison of XRF data to ERA- ccrtificd 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. Tabic 5-1. Number of Validation Qualifiers Number and Percentage of Qualified Results per QC type 1 Method Blank MS/iMSD 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 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. ' 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 arc 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 Pcrccnts for individual elements arc calculated based on 326 results per element. Total pcrccnts at the bottom of the table arc calculated based on the total number of results for all elements (4,238). 35 ------- All blends (1 through 70) were prepared and delivered with multiple replicates. To assess precision, percent RSDs were calculated for the replicate sample results submitted by the reference laboratory for each of the 70 blends. Table 5-3 presents the summary statistics for the reference laboratory data for each of the 13 target elements. These summary statistics indicate good precision in that the median percent RSD was less than 10 percent for 11 out of 13 target elements (and the median RSD for the other two elements was just above 10 percent). Thus, this evaluation further supports the conclusion that the reference data set is of high quality. ARDL, in Mount Vernon, Illinois, was selected as the characterization laboratory to prepare environmental samples for the demonstration. As part of its work, ARDL analyzed several samples of each blend to evaluate whether the concentrations of the target elements and the homogeneity of the blends were suitable for the demonstration. ARDL analyzed the samples using the same methods as the reference laboratory; however, the data from the characterization laboratory were not validated and were not intended to be equivalent to the reference laboratory data. Rather, the intent was to use the results obtained by the characterization laboratory as an additional quality control check on the results from the reference laboratory. A review of the ARDL characterization data in comparison to the reference laboratory data indicated that ARDL obtained lower recoveries of several elements. When expressed as a percent of the average reference laboratory result (percent recovery), the median ARDL result was below the lower QC limit of 75 percent recovery for three elements — chromium, nickel, and selenium. This discrepancy between data from the reference laboratory and ARDL was determined to have no significant impact on reference laboratory data quality for three reasons: (1) the ARDL data were obtained on a rapid turnaround basis to evaluate homogeneity — accuracy was not a specific goal, (2) the ARDL data were not validated, and (3) all other quality measurement for the reference laboratory data indicated a high level of quality. 5.4 Summary of Data Quality and Usability A significant effort was undertaken to ensure that data of high quality were obtained as the reference data for this demonstration. The reference laboratory data set was deemed valid, usable, and of high quality based on the following: • Comprehensive selection process for the reference laboratory, with multiple levels of evaluation. • No data were rejected during data validation and few data qualifiers were added. • The observations noted during the reference laboratory audit were only minor in nature; no major findings or non-conformances were documented. • Acceptable accuracy (except for antimony, as discussed in Section 5.3.3) of reference laboratory results in comparison to spiked certified values. • Acceptable precision for the replicate samples in the demonstration sample set. Based on the quality indications listed above, the reference laboratory data were used in the evaluation of XRF demonstration data. A second comparison was made between XRF data and certified values for antimony (in Blends 46 through 70) to address the low bias exhibited for antimony in the reference laboratory data. 36 ------- Tabic 5-2. Percent Recovery for Reference Laboratory Results in Comparison to ERA Certified Spike Values for Blends 46 through 70 Statistic Sb As Cd Cr Cu Pe Pb Hg Ni Sc Ag V Zn Number of %R values 16 14 20 12 20 NC 12 15 16 23 20 15 10 Minimum %R 12.0 65.3 78.3 75.3 51.7 NC 1.4 81.1 77.0 2.2 32.4 58.5 0.0 Maximum %R 36.1 113.3 112.8 108.6 134.3 NC 97.2 243.8 1 16.2 114.2 100.0 103.7 95.2 Mean %R' 26.8 88.7 90.0 94.3 92.1 NC 81.1 117.3 93.8 89.9 78.1 90.4 90.6 Median %R' 28.3 90.1 87.3 97.3 91.3 NC 88.0 93.3 91.7 93.3 84.4 95.0 91.3 Notes: 'Values shown in bold fall outside the 75 to 125 percent acceptance criterion for percent recovery. ERA = Environmental Resource Associates, Inc. NC = Not calculated. %R = Percent recovery. Source of certified values: Environmental Resource Associates, Inc. Sb Antimony As Arsenic Cd Cadmium Cr Chromium Cu Copper Fc Iron Pb Lead Hg Mercury Ni Nickel Sc Selenium Ag Silver V Vanadium Zn Zinc 37 ------- Tabic 5-3. Precision of Reference Laboratory Results for Blends 1 through 70 Statistic Sb As Cd Cr Cu Fe Pb Hg Ni Sc Ag V Zn Number of %RSDs 43 69 43 69 70 70 69 62 68 35 44 69 70 Minimum %RSD 1.90 0.00 0.91 1.43 0.00 1.55 0.00 0.00 0.00 0.00 1.02 0.00 0.99 Maximum %RSD 78.99 139.85 40.95 136.99 45.73 46.22 150.03 152.59 44.88 37.30 54.21 43.52 48.68 Mean %RSD' 17.29 13.79 12.13 11.87 10.62 10.56 14.52 16.93 10.28 13.24 12.87 9.80 10.94 Median %RSD" 11.99 10.01 9.36 8.29 8.66 8.55 9.17 7.74 8.12 9.93 8.89 8.34 7.54 Notes: 'Values shown in bold fall outside precision criterion of less than or equal to 25 %RSD. %RSD = Percent relative standard deviation. Based on the three to seven replicate samples included in Blends 1 through 70. Sb Antimony As Arsenic Cd Cadmium Cr Chromium Cu Copper Fc Iron Pb Lead Hg Mercury Ni Nickel Se Selenium Ag Silver V Vanadium Zn Zinc 38 ------- Chapter 6 Technology Description The ZSX Mini II XRF analyzer is manufactured by Rigaku, Inc. This chapter provides a technical description of the ZSX Mini II based on information obtained from Rigaku and observation of this analyzer during the field demonstration. This section also identifies a Rigaku company contact, where additional technical information may be obtained. 6.1 General Description The ZSX Mini II is a wavelength-dispersive XRF analyzer that operates differently from an energy- dispersive XRF analyzer. Wavelength-dispersive XRF analyzers differentiate the x-ray energies emitted from a sample by dispersing the x-rays into different wavelength ranges using crystals. Conversely, energy-dispersive XRF analyzers differentiate between x-ray energies emitted based on the voltages measured by the detector. For some applications, wavelength-dispersive XRF analyzers can achieve high resolutions and good sensitivity. For example, laboratory-grade wavelength-dispersive XRF analyzers have resolved significant concentrations of arsenic and lead in many sample matrixes that pose challenges to energy-dispersive instruments. Wavelength-dispersive XRFs have historically been large, laboratory-bound instruments with significant requirements for power and cooling. The ZSX Mini II, however, is a smaller, transportable unit that can operate without additional cooling fluids on standard 110-volt circuits. The unit can employ an economical gas proportional counter as a detector rather than a diode detector with a multi-channel analyzer (used by energy-dispersive analyzers) because wavelength resolution is achieved with the crystals. The ZSX Mini II is shown in a benchtop configuration in Figure 6-1. Technical specifications for the ZSX Mini II are presented in Table 6-1. Figure 6-1. Rigaku ZSX Mini II XRF analyzer set up for bench-top analysis. 6.2 Instrument Operations during the Demonstration The ZSX Mini II and accessories were shipped by a professional freight service to the demonstration site in two wooden shipping crates with styrofoam padding. The ZSX Mini II is transportable; however, a sturdy table is required for bench-top configuration because it weighs approximately 260 pounds (120 kg). Peripheral equipment included the 12-position sample changer; a vacuum pump used to evacuate the sample chamber to reduce formation of oxides in the sample matrix; and a personal computer (PC) loaded with Microsoft Windows XP" and the ZSX Mini II calibration and operational software. 6.2.1 Setup and Calibration Rigaku assembled the ZSX Mini II and initialized the application software in about 1.5 hours. An experienced technician can set up the analyzer in 1 to 2 hours; an inexperienced technician may need 2 to 3 39 ------- Table 6-1. Rigaku ZSX Mini II XRF Technical Specifications Weight: 260 pounds (120 kg). 1 Dimensions: 570 millimeters (mm) wide, 500 mm deep, 250 mm high 1 Excitation Source: 50-Watt, 40-kilovolt (kV), 1.25-milli-amp, air-cooled end- window x-ray tube (with palladium or rhodium as an anode material). X-ray Optics: Analyzing crystals for x-ray dispersion include lithium fluoride (LiF), pentaerythritol (PeT), and thallium acid phthalate (TAP) operating on a revolving changer. Optional crystals include RX35 and germanium. Detector: Scintillation detector for analysis of titanium through uranium. Can be equipped with a gas proportional counter for light elements, requiring management of argon/methane carrier gas. Optional vacuum or helium environments for enhanced performance in analyzing light elements. Signal Processing: Digital signal processing unit. Software: Windows XP-based, multi-function software package for instrument control, spectra accumulation, calibration, and quantification (includes fundamental parameters methods). Element Range: From fluorine to uranium. Operating Environment: Temperature: 15 to 28 °C; less than 75 percent relative humidity (non-condensing). Sample Container: 25-mm plastic sample cups with polypropylene windows. Variants: ZSX Mini II with single sample changer. (Sample spinner is available.) ZSX Mini II with 12-position sample changer. ZSX Mini II can be adapted to accommodate oversize or irregular objects. 1 Power: AC single phase 110 Volts, 10 Amps, 50/60 Hertz hours for setup. A factory-new XRF analyzer may take 4 to 6 hours to uncrate, set up, and initialize all computer software. The Rigaku XRF analyzer software was observed to be self-explanatory in terms of analyzer start up. Menus guided the user through turning on the x-ray tube and initializing the XRF spectrometer optics and detector. The 13 individual elements, their characteristic energy wavelengths for monitoring, and the units of measure were selected using the software. The ZSX Mini II can be calibrated using the fundamental parameters procedure or empirically using reference standards and sitc-specific calibration materials. The ZSX Mini II used the factory calibration for this demonstration and verified the results using a calibration reference material provided by the U.S. Geological Survey. After the analyzer was set up at the demonstration site, the stored calibration curve information was used to calibrate the instrument, and known reference materials were analyzed to verify that the calibration curve was loaded. A single empirical calibration curve was used for all analysis during the demonstration. Other quality control samples used during the demonstration included a silicon dioxide blank and other standard reference materials as calibration verification checks. 40 ------- 6.2.2 Demonstration Sample Processing Rigaku sent a two-man team to the demonstration site to process the demonstration samples using the ZSX Mini II. The field team including an instrument applications specialist, who operated the instrument and reduced the data, and a sales representative, who served as the sample preparation technician. Sample preparation by Rigaku for this demonstration involved assembling the polypropylene sample cups; attaching a snap ring to support a Mylar" film across one end, filling the cup with the sample, and attaching a Teflon " film across the other end (see Figure 6-2). The Teflon5 film was perforated to allow venting and minimize rupture of the sample when a vacuum was applied during analysis. A unique sample identification (ID) number was marked in permanent marker on the Teflon8 film for sample identification. The sequence of events for each sample batch involved: • Loading a batch of 12 sample cups into the 12- position sample changer and placing it into the XRF analyzer (see Figure 6-3). • Starting the XRF analysis included sequential readings of wavelength and the intensity of the characteristic fluorescence produced by each sample. The intensity of the fluorescence at the characteristic wavelength for each element was converted to milligrams per kilogram based on the calibration. Figure 6-2. Rigaku technician filling a sample cup for analysis. • Reviewing the data after the sample batch had been analyzed and verifying the sample ID numbers. • Downloading data for each sample batch onto a Microsoft Excel8 spreadsheet. • Transferring the daily results from the ZSX Mini II data processor to a USB portable storage device for transfer to the demonstration oversight team. Each day, the results from the previous day were transferred to the Tetra Tech demonstration team via a USB portable storage drive. Figure 6.3. Samples placed into the 12-position sample changer awaiting analysis. 6.3 General Demonstration Results Rigaku analyzed all 326 soil and sediment samples in 4 days using the ZSX Mini II wavelength-dispersive XRF analyzer. Rigaku was able to prepare, analyze, and report 80 to 90 samples in a 12-hour day during the demonstration. (Rigaku had expected to analyze about 120 to 150 samples each day.) Data processing for the demonstration samples was completed within the ZSX Mini II data processor that is part of the XRF analyzer. The ZSX Mini II data processor stopped acquiring data several times during the demonstration, which required re-analysis of 41 ------- entire sample batches. Data acquisition issues continued to plague the analyzer even after the ZSX Mini II computer had been replaced, new application names for each batch had been created and saved, and smaller batch sizes run. The computer issue was random, except that it always stopped while the instrument was analyzing for vanadium. It was unclear whether the issue was related to hardware or software. 6.4 Contact Information Additional information on Rigaku's ZSX Mini II XRF analyzer is available from the following source: Mr. Jose Brum Rigaku Inc. 14 Ruth Circle Haverhill, Massachusetts 01832 Telephone: (978) 374-7725 Email: ibrum@RigakuMSC.com 42 ------- Chapter 7 Performance Evaluation As discussed in Chapter 6, Rigaku analyzed all 326 demonstration samples of soil and sediment at the field demonstration site between January 24 and 27, 2005. A complete set of electronic data in Microsoft Excel® spreadsheet format was delivered to the EPA and Tctra Tcch field team before Rigaku demobilized from the site on January 28, 2005. All data Rigaku provided at the close of the demonstration arc tabulated and compared with the reference laboratory data and the ERA-certificd spike concentrations, as applicable, in Appendix D. The data set for the ZSX Mini II was reviewed and evaluated in accordance with the primary and secondary objectives of the demonstration. The findings of the evaluation for each objective arc presented below. 7.1 Primary Objective 1 — Method Detection Limits Samples were selected to calculate MDLs for each target element from the 12 potential MDL sample blends, as described in Section 4.2.1. Rigaku reported the instrument response for each target clement in each sample; the instrument response — whether positive or negative — was used to calculate the MDL. The MDLs calculated for the ZSX Mini II arc presented in Table 7-1. As shown, the data for the MDL blends allowed between eight and 12 individual MDLs to be calculated for each target element. (Iron was not included in the MDL evaluation, as was discussed in Section 4.2.1.) The mean MDLs in Table 7-1 arc classified as follows: • Very low (1 to 20 ppm): copper, mercury, nickel, selenium, and zinc. • Low (20 to 50 ppm): arsenic, lead, silver, and vanadium. • Medium (50 to 100 ppm)' antimony, cadmium, and chromium. • High (greater than 100 ppm): none. Instrument response remained fairly consistent, with very few extreme values, for the target elements in the "very low" and "low" categories. No trends could be discerned in terms of sample matrix (soil versus sediment) or blend. For antimony and cadmium, however, the MDLs may be inflated by analytical results that were biased high. For the 12 MDL sample blends, the ZSX Mini II measured concentrations of antimony that ranged from 124 ppm to 565 ppm with a mean of 283 ppm, while the reference laboratory reported seven non-dctcct concentrations and a maximum concentration of 118 ppm. Similarly, the ZSX Mini II measured concentrations of cadmium that ranged from 328 ppm to 896 ppm with a mean of 609 ppm, while the reference laboratory reported six non-dctcct concentrations and a maximum concentration of 91 ppm. It is possible that a systematic high bias in the ZSX Mini II was a cause of the high MDLs for antimony and cadmium. (The correlation plots in Section 7.2 below also indicated positive biases at low concentrations for these and other target elements.) The mean MDL for chromium (61 ppm) appears to reasonably represent true instrument sensitivity for this element because the concentrations reported from the ZSX Mini II for the detection limit blends did not illustrate any major discrepancies when compared to the results from the reference laboratory. 43 ------- Tabic 7-1. Evaluation of Sensitivity — Method Detection Limits for the ZSX Mini II1 Antimony Arsenic Cadmium Chromium Calc. ZSX Mini Rcf. Lab Calc. ZSX Mini Rcf. Lab Calc. ZSX Mini Rcf. Lab Calc. ZSX Mini Ref. Lab Matrix Blend No. MDL2 Cone.3 Cone4 MDL2 Cone.3 Cone.4 MDL2 Cone.3 Cone.4 MDL2 Cone.3 Cone.4 Soil 2 111 451 17 34 102 1.5 118 896 ND 107 115 167 Soil 5 43 159 ND 45 58 47 34 603 1.9 62 98 121 Soil 6 77 456 8 NC 213 477 35 578 12 46 112 133 Soil 8 306 450 118 NC 1,537 3,943 32 328 91 78 138 55 Soil 10 66 211 ND 44 48 39 109 661 0.96 67 79 116 Soil 12 105 565 62 NC 306 559 NC 671 263 99 90 101 Soil 18 65 200 ND 20 17 9 60 601 ND 38 154 150 Sediment 29 41 124 ND 20 -21 10 41 490 ND 39 72 63 Sediment 31 43 170 ND 40 -11 11 30 534 ND 56 105 133 Sediment 32 40 191 ND 22 34 31 62 618 ND 30 70 75 Sediment 39 45 208 ND 61 13 14 41 645 ND 44 81 102 Sediment 65 92 205 11 NC 181 250 62 681 44 NC 200 303 Mean 86 36 57 61 Copper Lead Mercury Nickel Calc. ZSX Mini Rcf. Lab Calc. ZSX Mini Rcf. Lab Calc. ZSX Mini Rcf. Lab Calc. ZSX Mini Rcf. Lab Matrix Blend No. MDL2 Cone.3 Cone.4 MDL2 Cone.3 Cone.4 MDL2 Cone.3 Cone.4 MDL2 Cone.3 Cone.4 Soil 2 15 60 47 NC 780 1,200 18 62 ND 10 92 83 Soil 5 13 42 49 17 6 78 8 26 ND 7 41 60 Soil 6 9 99 160 NC 1,993 3,986 11 27 0.83 13 44 70 Soil 8 NC 739 1,243 NC 17,262 33,429 13 19 15 9 54 57 Soil 10 10 25 31 13 -14 72 15 27 0.14 9 44 60 Soil 12 NC 494 747 NC 2,180 4,214 21 26 1.8 10 58 91 Soil 18 5 30 50 26 -50 17 15 44 56 13 101 213 Sediment 29 NC 930 1,986 27 -65 33 17 6 0.24 8 44 72 Sediment 31 NC 708 1,514 22 -56 51 27 15 ND 11 98 196 Sediment 32 11 27 36 20 -38 26 7 32 ND 6 75 174 Sediment 39 13 68 94 20 -29 27 31 48 ND 11 99 202 Sediment 65 8 56 69 19 -22 25 21 58 32 25 134 214 Mean 11 21 17 11 Draft Final 44 October 14, 2005 ------- Tabic 7-1. Evaluation of Sensitivity — Method Detection Limits for the ZSX Mini II1 (Continued) Selenium Silver Vanadium Zinc Calc. 7.SX Mini Rcf. Lab Calc. 7.SX Mini Ref. Lab Calc. ZSX Mini Rcf. Lab Calc. Z.SX Mini Rcf. Lab Matrix Blend No. MDL2 Cone.3 Cone.4 MDL2 Cone.3 Cone4 MDL2 Cone.3 Cone.4 MDL2 Conc.J Cone.4 Soil 2 4 16 ND 37 305 ND 14 22 1.2 22 44 24 Soil 5 3 8 ND 20 207 0.93 29 73 55 12 146 229 Soil 6 4 8 ND 15 196 14 24 69 56 NC 401 886 Soil 8 4 17 ND 8 115 144 16 59 34 NC 2,538 5.657 Soil 10 3 6 ND 22 226 ND 21 67 51 29 74 92 Soil 12 4 11 15 19 201 38 19 62 45 NC 1,217 2,114 Soil 18 3 6 ND 17 207 ND 41 1 19 67 2 63 90 Sediment 29 4 1 ND 24 170 ND 22 141 96 10 92 160 Sediment 31 3 2 ND 9 188 6.2 17 122 76 9 71 137 Sediment 32 4 7 4.6 18 215 ND 12 85 57 33 58 69 Sediment 39 8 10 ND 27 217 ND 15 55 38 12 90 137 Sediment 65 6 16 22 30 226 41 15 51 31 NC 1,125 1,843 Mean 4 21 20 16 Notes: ' Detection limits and concentrations arc milligrams per kilogram (mg/kg), or parts per million (ppm). Cells that appear in bold typeface show MDLs calculated for the ZSX Mini II from the 12 MDL sample blends in this technology demonstration. 3 This column lists the mean concentration reported for this MDL sample blend by the ZSX Mini II. 4 This column lists the mean concentration reported for this MDL sample blend by the reference laboratory. Calc. Calculated. Cone. Concentration. MDL Method detection limit. NC The MDL was not calculated because reference laboratory concentrations exceeded five times the expected MDL range (approximately 50 ppm, depending on the element) or an insufficient number of detected concentrations were reported. ND One or more results for this blend were reported as "Not Detected." Blends with one or more ND result as reported by the XRF were not used for calculating the MDL for this clement. Rcf. Lab. Reference laboratory. Draft Final 45 October 14, 2005 ------- The mean MDLs calculated for the ZSX Mini II are compared in Table 7-2 with the mean MDLs for all eight XRF instruments that participated in the demonstration and with the mean MDLs derived from performance data presented in EPA Method 6200 (EPA 1998e). As shown, the mean MDLs for the ZSX Mini II are generally lower than were calculated from EPA Method 6200 data. The exception is antimony where, as noted above, high bias for the ZSX Mini II data appears to have produced a mean MDL that is higher than the available Method 6200 data. When compared with the all-instrument mean MDLs, the ZSX Mini II exhibited high relative mean MDLs for antimony and arsenic. Mean MDLs for the ZSX Mini II were less than one-half the all-instrument means for copper, nickel, selenium, silver, and zinc. 7.2 Primary Objective 2 — Accuracy and Comparability The number of demonstration sample blends that met the criteria for evaluation of accuracy, as described in Section 4.2.2, were adequate for all the target elements and ranged from 24 (mercury) to 70 (iron). RPDs between the mean concentrations obtained from the ZSX Mini II and the reference laboratory were calculated for each blend that met the criteria for an element. Table 7-3 presents the median RPDs, along with the number of RPD results used to calculate the median, for each target element. These statistics are provided for the demonstration as a whole, as well as for subpopulations grouped by medium (soil versus sediment) and concentration level (Levels 1 through 4, as documented in Table 3-1). Additional summary statistics for the RPDs (minimum, maximum, and mean) are provided in Appendix E (Table E-l). Table 7-2. Comparison of ZSX Mini II MDLs to All-Instrument Mean MDLs and EPA Method 6200 Data1 ZSX Mini II All XRF Instrument EPA Method 6200 Element Mean MDLs2 Mean MDLs3 Mean Detection Limits4 Antimony 86 61 55 s Arsenic 36 26 92 Cadmium 57 70 NR Chromium 61 83 376 Copper 11 23 171 Lead 21 40 78 Mercury 17 23 NR Nickel 11 50 O O Ui Selenium 4 8 NR Silver 21 42 NR Vanadium 20 28 NR Zinc 16 38 89 Notes: 1 Detection limits are in units of milligrams per kilogram (mg/kg), or parts per million (ppm). The mean MDLs calculated for this technology demonstration, as presented in Table 7-1. 3 The mean MDLs calculated for all eight XRF instruments that participated in the technology demonstration. 4 Mean values calculated from Table 4 of Method 6200 (EPA 1998e, www.epa.gov/sw-846'). 5 Only one value reported. EPA U.S. Environmental Protection Agency. MDL Method detection limit. NR Not reported; no MDLs reported for this element. 46 ------- Accuracy was classified as follows for the target elements based on the overall median RPDs. • Very good: (median RPD less than 10 percent): none. • Good (median RPD between 10 and 25 percent): none. • Fair (median RPD between 25 percent and 50 percent), arsenic, chromium, copper, silver, vanadium, and zinc. • Poor (median RPD greater than 50 percent): antimony, cadmium, iron, lead, mercury, nickel, and selenium. The highest overall median RPD of 101 percent was calculated for selenium. The median RPD was used for this evaluation because it is less affected by extreme values than is the mean. (The initial evaluation of the RPD populations showed that they were right-skewed or lognormal.) However, the classification of the elements based on accuracy generally stayed the same when the mean rather than the median RPD was used for the evaluation (Tabic E-l). The ability to evaluate the classification by medium (soil versus sediment) or by concentration range is limited by the variability of the data set. The only significant difference or trend noted in terms of sample matrix or concentration levels were low relative median RPDs in the Level 1 concentration samples when compared with the higher concentration levels. This effect was observed for a majority of the target elements (10 of 13) in soil and a smaller number (four) in sediment. For many target elements (arsenic, chromium, copper, iron, lead, selenium, and zinc), the effect was significant with median RPDs falling into the "good" to "very good" categories as compared with generally "poor" accuracy in the higher concentration levels. This observation implies that the ZSX Mini 11 may provide greater accuracy for less complex sample matrixes that contain lower concentrations of target elements. The developer may need to further refine instrument calibration and quantitation algorithms to better analyze samples that contain high concentrations of multiple target elements. Section 5.3.3 indicated that reference laboratory data for antimony were consistently biased low when compared with the ERA-ccrtified spike concentrations. This effect may be caused by volatilization of the antimony compounds used for spiking, resulting in loss of antimony during the sample digestion process at the reference laboratory. Therefore, Table 7-3 includes a second accuracy evaluation for antimony, comparing the results from the ZSX Mini II with the ERA-ccrtificd values. However, use of these values did not improve the RPDs for antimony. As an additional comparison, Table 7-3 overall average of the median RPDs for all eight XRF instruments. Complete summary statistics for the RPDs across all eight XRF instruments arc included in Appendix E (Table E-l). Table 7-3 indicates that the median RPDs for the ZSX Mini II were well above the all-instrument medians for 12 of the 13 target elements (vanadium was the only exception). These observations included the RPDs for antimony calculated versus the ERA-ccrtificd spike values, which were significantly lower than the RPDs versus the reference laboratory data for many of the other XRF instruments participating in the demonstration. In addition to calculating RPDs, the evaluation of accuracy included preparing linear correlation plots of ZSX Mini II concentration values against the reference laboratory values. These plots arc presented for the individual target elements in Figures E-l through E-l 3 of Appendix E. The plots include a 45-degrce line that shows the "ideal" relationship between the ZSX Mini II data and the reference laboratory data, as well as a "best fit" linear equation (y = mx + b, where m is the slope of the line and b is the y-intcrccpt 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-intcrccpt (b) should be relatively close to zero (that is, plus or minus the mean MDL in Tabic 7-1). Tabic 7-4 lists the results for these three correlation parameters and indicates that no target elements met all three accuracy criteria. 47 ------- Figure 7-1: Linear correlation plot for lead indicating low instrument bias. ¦ Rigaku ZSX Mini 45 Degrees — — Linear (Rigaku ZSX Mini) 40000 35000 0 5000 10000 15000 20000 25000 30000 35000 40000 Reference Laboratory (ppm) ? 30000 s. Q. £ 25000 X | 20000 2 X (3 15000 S .1 10000 5000 The correlation coefficients for arsenic, chromium, copper, iron, lead, mercury, nickel, selenium, and zinc were greater than 0.9, indicating a consistent instrument response to differences in concentration. However, the slopes (m) for each of these target elements were between 0.27 and 0.59, indicating a consistent low bias. Furthermore, only copper had a y-intercept that was less than the detection limit. A correlation plot for lead is presented in Figure 7-1 as an example of representative instrument performance for this group of target elements. Overall correlation of the ZSX Mini II data with the reference laboratory was low for antimony, cadmium, silver, and vanadium. High intercepts combined with low slopes for cadmium and vanadium actually meant that a significant positive bias changed to a significant negative bias as concentrations increased for these elements. The correlation coefficients for antimony and silver were 0.1 or less, indicating that the instrument response essentially did not correlate with the reference laboratory data. On this basis, it appears that the ZSX Mini II does not provide accurate data for antimony and silver, in that its data cannot be correlated with other reference methods. The correlation plot for silver is presented in Figure 7-2 as an example. 48 ------- Tabic 7-3. Evaluation of Accuracy — Relative Percent Differences Versus Reference Laboratory Data for the ZSX Mini II Sample Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Selenium Silver Vanadium Zinc Matriv Croup Statistic RcrUib ERA Spike Soil Level 1 Number 8 1 8 7 23 16 5 4 7 23 4 3 12 19 Median 161 2% 84 9% 14 0% 116 1% 21.0% 32.2% 93 3% 84.1% 24.3% 50.0% 77 6% 91 9% 57.8% 27 2% Level 2 Number 5 1 4 7 4 8 13 4 6 5 5 3 4 6 Median 32.1% 84.8% 74 4% 21 4% 60 4% 49.3% 48 6% 68.9% 106.6% 60.6% 102.3% 45 1% 21.7% 58 7% Level 3 Number 4 3 4 2 2 2 13 8 2 6 4 7 4 9 Median 28 8% 108 3% 82 4% 49.7% 80 5% 33.0% 60 3% 65.1% 112 1% 74 1% 105 9% 37 0% 36 8% 65 2% Level 4 Number Median -- -- -- -- -- -- 7 70 8% 5 64.5% -- -- -- -- -- -- All Soil Number 17 5 16 16 29 26 38 21 15 34 13 13 20 34 Median 116.8% 96 1% 71 3% 49 7% 29.3% 40 0% 58 5% 66 7% 78 3% 57 7% 101 5% 40.4% 31 4% 50.4% Sediment Level 1 Number 4 4 8 3 7 8 3 6 2 18 5 5 6 18 Median 174 4% 101.7% 47.3% 123.3% 9.3% 26.7% 122 4% 82 0% 67 5% 62 0% 89.6% 112.6% 39.2% 39.6% Level 2 Number 4 4 3 4 3 4 19 4 4 6 4 4 8 5 Median 79.9% 83.3% 47 7% 65.0% 52 7% 39.7% 33 4% 70 3% 87.1% 57.1% 108.4% 36.3% 20.9% 59 4% Level 3 Number 3 3 2 3 3 10 4 3 3 4 3 3 3 4 Median 20 6% 116 2% 29 1% 20 9% 52 2% 71.4% 42 7% 54 7% 71.4% 66.0% 109.1% 34.0% 41.4% 68 3% Level 4 Number Median -- -- -- -- -- -- 6 70 5% -- -- — -- -- -- -- All Sediment Number II 11 13 10 13 22 32 13 9 28 12 12 17 27 Median 84 3% 108 9% 45 5% 65 0% 43 7% 40 0% 38 0% 71.4% 71.4% 63 1% 103 2% 65 4% 35 5% 48.6% All Samples ZSX Mini Number 28 16 29 26 42 48 70 34 24 62 25 25 37 61 Median 92 2% 102 2% 49 2% 60 9% 37 2% 40 0% 52 4% 66.8% 74.2% 60.4% 101 5% 45.1% 35 2% 48 6% All Samples All XRF Number 206 110 320 209 338 363 558 392 192 403 195 177 218 471 Instruments Median 84.3% 70.6% 26 2% 16.7% 26 0% 16 2% 26.0% 21 5% 58.6% 25.4% 16 7% 28 7% 38.3% 19 4% Notes. All median RPDs presented in this tabic arc absolute values. -- No samples reported by the reference laboratory in this concentration range ERA Environmental Resource Associates, Inc NC Not calculated. Number Number of samples appropriate for accuracy evaluation Rcf Reference laboratory (Shcaly Environmental Services, Inc.). RPI) Relative percent difference. 49 ------- Table 7-4. Summary of Correlation Evaluation for the ZSX Mini II Target Element m b r2 Correlation Bias Antimony (vs. Reference Lab) 0.51 296 0.11 Low Indeterminate ' Antimony (vs. ERA Certified Value) 0.02 258 0 None Indeterminate ' Arsenic 0.45 32 0.90 High Low Cadmium 0.42 573 0.82 Moderate Variable 2 Chromium 0.43 63 0.95 High Low 1 Copper 0.59 5 0.95 High Low Iron 0.38 5610 3 0.93 High Low Lead 0.54 92 0.99 High Low Mercury 0.30 29 0.98 High Low Nickel 0.42 32 0.93 High Low Selenium 0.27 8 0.97 High Low Silver 0.04 198 0.01 None Indeterminate 1 Vanadium 0.56 53 0.73 Moderate Variable2 1 Zinc 0.47 47 0.97 High Low | Notes i 7 3 b m -) The bias for this element is indeterminate because of the lack of correlation observed with the reference laboratory data. The bias for this element tended to be high at low concentrations (because of a high intercept) and low at high concentrations (because of a low slope). Overall correlation with the reference laboratory was moderate to low for this element. For iron, no MDL was calculated and the high intercept value was the result of the extreme range of concentrations in the demonstration samples. Y-intercept of correlation line. Slope of correlation line. Correlation coefficient of correlation line. 50 ------- Figure 7-2. Linear correlation plot for Rigaku indicating low overall correlation with the reference laboratory for silver. 450 400 350 = 300 X 250 X 200 a 3 t '50 ae 100 50 ¦ Rigaku ZSX Mini 45 Degrees — — Linear (Rigaku ZSX Mini) 1 £ ^ ¦ tr-m- p rf—¦— m ¦ y = 0.04x + 197.88 R2 = 0.01 1 ¦ / ¦ ¦ 50 100 150 200 250 300 Reference Laboratory (ppm) 350 400 450 In conclusion, the demonstration found potential issues with accuracy for the ZSX Mini II. Median RPDs tended to be higher than the other XRF technologies demonstrated, remaining in the "fair" to "poor" range for all target elements. The correlation plots further showed that, although satisfactory correlations with reference laboratory data were obtained for many of the target elements, a significant and consistent low bias was observed (thus producing the high RPDs). The correlation analysis indicated biases that varied from high to low as concentrations increased for some elements, and further showed very poor overall agreement of the ZSX Mini II data with the reference laboratory data for both antimony and silver. The developer indicates that poor performance is expected for antimony, silver, and cadmium because the instrument does not have a primary beam filter to remove interference lines from the x-ray tube (Appendix B). For the remaining target elements, it is possible that a refined, project-specific instrument calibration could have improved the comparability of the data from the ZSX Mini II with that of the reference laboratory. 7.3 Primary Objective 3 — Precision As described in Section 4.2.3, the precision of the ZSX Mini II data set was evaluated by calculating RSDs for the replicate measurements from each sample blend. Median RSDs for the various concentration levels and media (soil and sediment) are presented in Table 7-5. The table also presents the median RSDs for the demonstration data set as a whole for the ZSX Mini II. Additional summary statistics for the RSDs (including minimum, maximum, and mean) are provided in Appendix E (Table E-2). The RSD calculation found a high level of precision for the ZSX Mini II across all target elements. Median RSDs for the demonstration data ranged only as high as 14.7 percent (chromium). The ranges into which the median RSDs fell are summarized below: 51 ------- • Very low (median RSD between 0 and 5 percent): cadmium, copper, iron, lead, mercury, nickel, selenium, silver, and zinc. • Low (median RSD between 5 and 10 percent): antimony and vanadium. • Moderate (median RSD between 10 and 20 percent): arsenic and chromium. • High (median RSD greater than 20 percent): none. No differences were observed between the RSDs for soil and sediment. Use of the mean as opposed to the median RSDs (Table E-2) indicated a similarly high level of precision in the results from the ZSX Mini II for all elements except mercury. The high overall level of precision may have been facilitated by the level of processing (homogenizing, sieving, crushing, and drying) performed on the sample blends before the demonstration (Chapter 3). This observation is consistent with the previous SITE MMT Program demonstration of XRF technologies that occurred in 1995 (EPA 1996a, 1996b, 1998a, 1998b, 1998c, and 1998d). The high level of sample processing applied during both XRF technology demonstrations was necessary to minimize the effects of sample heterogeneity on the demonstration results and on comparability with the reference laboratories. During project design, site investigation teams that intend to compare XRF and laboratory data should similarly assess the need for sample processing steps to manage sample heterogeneity and improve data comparability. Further review of the median RSDs in Table 7-5 based on concentration range reveals slightly higher RSDs (in other words, lower precision) for the target elements in Level 1 samples when compared with the rest of the data set. This effect was greatest for arsenic, chromium, and vanadium, where the median RSDs increased to between 10 and 20 percent in Level 1 blends. This observation indicates that, to a minor extent, analytical precision for the ZSX Mini 11 is concentration-dependent. Furthermore, precision shows the opposite trend from accuracy in that accuracy is higher at low concentrations for many target elements (Section 7.2), while precision is lower. Even for the Level 1 samples, however, the effect of concentration on precision was small; the mean RSDs for the target elements remained relatively good, with the highest RSD at 17.8 percent (for chromium in sediment). As an additional comparison, Table 7-5 also presents the median RSDs calculated for all XRF instruments that participated in the demonstration. Additional summary statistics for the RSDs calculated across all XRF instruments combined are included in Table E- 2. Table 7-5 indicates that the median RSDs for the ZSX Mini II were equivalent to or below the all- instrument medians for all elements except arsenic and chromium, for which slightly higher median RSDs were observed. Table 7-6 presents median RSD statistics for the reference laboratory and compares these to the summary data for the ZSX Mini II. These reference laboratory median RSD statistics were calculated using the same blends as were used in the RSD statistics for the ZSX Mini II. (Additional summary statistics are provided in Table E-3 of Appendix E.) Table 7-6 indicates that the median RSDs for the ZSX Mini II were equivalent to or lower than the reference laboratory RSDs for 12 of 13 target elements. (Only the RSD for chromium was slightly higher for the ZSX Mini II.) Thus, the ZSX Mini II exhibited slightly better precision overall than the reference laboratory. In comparison to the median RSDs for the ZSX Mini II, Table 7-6 shows that the median RSDs for all XRF instruments participating in the demonstration were lower than the reference laboratory RSDs for 11 out of the 13 target elements (the exceptions were chromium and vanadium). 7.4 Primary Objective 4 — Impact of Chemical and Spectral Interferences The RPD data from the accuracy evaluation were further processed to assess the effects of interferences. The RPD data for elements considered susceptible to interferences were grouped and compared based on the relative concentrations of potentially interfering elements. Of specific interest for the comparison were the potential effects of: • High concentrations of lead on the RPDs for arsenic, • High concentrations of nickel on the RPDs for copper (and vice versa), and • High concentrations of zinc on RPDs for copper (and vice versa). 52 ------- Table 7-5. Evaluation of Precision — Relative Standard Deviations for the ZSX Mini II Sample Matrix Group Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Mcrcurv Nickel Selenium Silver Vanadium Zinc Soil Level 1 Number 8 8 7 23 16 5 4 7 23 4 3 12 19 Median 6.2% 13.0% 1.8% 14 8% 4.5% 1 0% 7.5% 9.6% 4 7% 7 9% 2 5% 12 3% 4 2% Level 2 Number 5 4 7 4 8 13 4 6 5 5 3 4 6 Median 6.9% 3 2% 2 2% 4 3% 1 9% 0 5% 2.1% 5 2% 2 3% 3.2% 2 0% 5 5% 1.4% Level 3 Number 4 4 2 2 2 13 8 2 6 4 7 4 9 Median 4 9% 1 7% 1.1% 2.7% 0.6% 0.6% 1 8% 2.4% 1 3% 1 9% 2.4% 5 2% 1.0% Level 4 Number Median -- -- -- -- 7 0 7% 5 0.8% -- -- -- -- -- -- All Soil Number 17 16 16 29 26 38 21 15 34 13 13 20 34 Median 6 3% 6.1% 1 8% 13.0% 3 4% 0 6% 1.8% 5 3% 3.9% 3.2% 2 4% 1 1.1% 2 1% Sediment Level 1 Number 4 8 3 7 8 3 6 2 18 5 4 6 18 Median 1 1 0% 15 8% 1 2% 17.8% 3 4% 0.4% 4 0% 7.6% 4 0% 10.8% 1 4% 4.4% 4 S% Level 2 Number 4 3 4 3 4 19 4 4 6 4 4 8 18 Median 5 5% 1 1.2% 1 9% 9.1% 2 1% 0.7% 2.3% 7 3% 5 2% 7.2% 1 3% 4 7% 2 8% Level 3 Number 3 2 3 3 10 4 3 3 4 3 3 3 4 Median 7 2% 9.9% 3 0% 18.2% 1 7% 1 1% 2 6% 3 6% 1 6% 3.1% 4 1% 4.7% 2.2% Level 4 Number -- -- -- -- -- 6 -- -- -- -- - -- -- All Sediment Median Number 11 13 10 13 22 0.7% 32 13 9 28 12 1 1 17 27 Median 7 2% 14.4% 1 3% 17.8% 2 1% 0.7% 2 6% 4 5% 3 7% 7.6% 1 5% 4.7% 3.6% All Samples ZSX Mini Number 28 29 26 42 48 70 34 24 62 25 24 37 61 Median 6 4% 10 1% 1 6% 14 7% 2.3% 0.6% 2 0% 4 9% 3.7% 3 9% 2.4% 5 9% 2.5% All Samples All XRF Number 206 320 209 338 363 558 392 192 403 195 177 218 471 Instruments Median 6.1% 8.2% 3.6% 12.1% 5 1% 2 2% 4 9% 6 8% 7.0% 4 5% 5.2% 8 5% 5.3% Notes: No samples reported by the reference laboratory in this concentration ranges. Number Number of samples appropriate for precision evaluation RSD Relative standard deviation 53 ------- Tabic 7-6. Evaluation of Precision - Relative Standard Deviations for the Reference Laboratory versus the ZSX Mini II and All Demonstration Instruments Matrix Sample Group Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Selenium Silver Vanadium Zinc Soil Ref Lab Number Median 17 9.8% 23 12.4% 15 9.0% 34 10.6% 26 9.1% 38 8.7% 33 13.2% 16 6.6% 35 10.0% 13 7.1% 13 7.5% 21 6.6% 35 9.1% Sediment RefLab Number Median 7 9.1% 24 9.2% 10 8.2% 26 7.5% 21 8.9% 31 8.1% 22 7.4% 10 6.9% 27 7.3% 12 7.6% 10 6.6% 17 8.1% 27 6.9% All Samples Ref Lab Number Median 24 9.5% 47 9.5% 25 9.0% 60 8.4% 47 8.9% 69 8.5% 55 8.6% 26 6.6% 62 8.2% 25 7.4% 23 7.1% 38 7.2% 62 7.4% All Samples ZSX Mini Number Median 28 6.4% 29 10.1% 26 1.6% 42 14.7% 48 2.3% 70 0.6% 34 2.0% 24 4.9% 62 3.7% 25 3.9% 24 2.4% 37 5.9% 61 2.5% All Samples All XRF Instruments Number Median 206 6.1% 320 8.2% 209 3.6% 338 12.1% 363 5.1% 558 2.2% 392 4.9% 192 6.8% 403 7.0% 195 4 5% 177 5.2% 218 8.5% 471 5.3% Notes: Number Number of demonstration samples evaluated. Ref. Lab. Reference laboratory. XRF X-ray fluorescence 54 ------- Intcrfcrcnt-to-clcmcnt ratios were calculated using the mean concentrations reported for each blend by the reference laboratory, classified as low (less than 5X), moderate (5 to 10X), or high (greater than 10X). Tabic 7-7 presents median RPD data for arsenic, nickel, copper, and zinc that arc grouped based on this classification scheme. Additional summary statistics arc presented in Appendix E (Tabic E-4). The table indicates that the median RPD for arsenic was lower (that is, accuracy was higher) at the higher lcad-to-arscnic ratios than at the low or moderate lcad-to-arscnic ratios. Typically, the opposite trend is expected1 high lead concentrations will tend to cause a high bias and thereby reduce accuracy in XRF measurements of arsenic. However, Section 7.2 listed arsenic among the elements for which the ZSX Mini II results were consistently biased low (Figure E-2). Thus, any high bias caused by the effects of lead may have offset the inherent low bias in the instrument (for example, from calibration or quantitation protocols) to produce results closer to the reference laboratory. Similar effects were indicated in the other intcrferent/clcmcnt pairs in that median RPDs remained equivalent or declined slightly as intcrfcrcnt concentrations increased. Overall, therefore, the low accuracy of the ZSX Mini II data set appears to have complicated the evaluation of intcrclcmcnt interferences, and may mask the effects of such interferences. 7.5 Primary Objective 5 — Effects of Soil Characteristics The population of RPDs between the ZSX Mini II results and the reference laboratory results were further evaluated against sampling site and soil type. Separate sets of summary statistics were developed for the mean RPDs associated with each sampling site for comparison to the other sites and to the demonstration data set as a whole. The site-specific median RPDs arc 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) arc presented in Appendix E (Table E-5). Another perspective on the effects of soil type was developed by graphically assessing outliers and extreme values in the mean RPD data sets for the target elements. This evaluation focused on correlating these values with sample types or locations for multiple elements across the data set. Outliers and extreme values arc apparent in the correlation plots (Figures E-l through E-13) and arc further depicted for the various elements on box and whisker plots in Figure E-14. Review of Tabic 7-8 indicates that the median RPDs were highly variable and that trends or differences between sample sites were difficult to discern. For many target elements, evaluations relative to sampling site were further complicated by the low numbers of samples (Table 7-8 indicates that only 1 to 3 samples were available from many sampling sites for evaluation of specific target elements.) The degree of variation in RPDs for the target elements was greatest in the samples from KARS Park, where the median RPDs ranged from 11.8 percent (nickel) to 153 percent (antimony). Other sample sites for which the range of RPDs across the different target elements was greater than 100 percent included: Alton Steel, Burlington Northern, Sulphur Bank, and Torch Lake. The smallest RPD range was observed for the Ramsey Flats site, where a minimum RPD of 29.7 percent was noted for vanadium and a maximum RPD of 78.5 percent was calculated for lead. These observations indicate that the relatively low accuracy and consistently low bias of the Rigaku data may have masked any effects of soil type on the results. Review of the box and whiskers plot (Figure E-14) and the correlation plots from the accuracy evaluation revealed no other general trends in RPDs relative to sampling site. The high outliers and extreme values apparent in Figure E-14 were distributed among the KARS Park, Alton Steel, Sulphur Bank, and Leviathan Mine sites. However, the plots further demonstrate that sample matrix appeared to have little overall effect on the accuracy of the XRF data. Figure E-14 shows the broad overall distributions of RPDs for many elements such that relatively few high outliers or extreme values could be identified. The identification of high statistical outliers or extreme values was precluded for eight of the target elements, including antimony, cadmium, chromium, lead, mercury, selenium, silver, and vanadium. 55 ------- Tabic 7-7. Effects of Intcrfcrcnt Elements on the RPDs (Accuracy) for Other Target Elements' Parameter Lead Effects on Arsenic Copper EfTects on Nickel Nickel Effects on Copper Zinc Effects on Copper Copper Effects on Zinc Interferent/ <5 o 1 >10 <5 LA 1 © >10 <5 5-10 >10 <5 5-10 >10 <5 5-10 >10 Element Ratio Number of Samples 15 7 7 43 5 14 39 1 8 35 2 11 48 3 10 Median RPD of Target Element2 45.5% 76.5% 16.3% 62.7% 55.3% 53.3% 46.1% 31.1% 30.1% 40.2% 44.1% 31.0% 53.0% 38.4% 46.2% Median Interferent Concentration 173 3716 1390 62 700 1017 80 203 963 92 2190 1430 73 676 1301 Median Target Element Concentration 92 487 93 99 88 60 565 57 70 567 532 77 410 88 78 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 ------- Table 7-8. Effect of Soil Type on the RPDs (Accuracy) for Target Elements, Rigaku ZSX Mini II Matrix Site Matrix Description Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Soil AS Fine to medium sand (steel processing) Number — — 3 2 3 3 3 Median -- — 116.1% 43 4% 74.3% 94.0% 104.1% Soil BN Sandy loam, low organic (ore residuals) Number 4 6 5 4 6 7 5 Median 146 1% 64.4% 26.8% 51.4% 40.0% 52.7% 73.5% Soil CN Sandy loam (burn pit residue) Number 2 1 2 1 3 3 2 Median 87 4% 3.3% 93.1% 16 5% 31.0% 51.3% 90.0% Soil & Sediment KP Soil: Fine to medium quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) Number 2 — — 3 2 6 6 Median 153.4% 37.0% 19.8% 105 0% 42.8% Sediment LV Clay/clay loam, salt crust (iron and other precipitates) Number 4 3 5 7 4 12 2 Median 33.7% 82.3% 36.4% 62.9% 40.9% 39.4% 43.6% Sediment RF Silty fine sand (tailings) Number 5 10 5 6 13 13 8 Median 75.6% 40.2% 65.4% 42.2% 31.1% 35.2% 78.5% Soil SB Coarse sand and gravel (ore and waste rock) Number 5 2 1 10 4 12 — Median 54.1% 92 1% 42.2% 7.8% 46.9% 59.7% — Sediment TL Silt and clay (slag-enriched) Number 3 1 2 2 7 7 2 Median 90 6% 56.8% 82.7% 14 1% 72.5% 35.4% 78.9% Soil WS Coarse sand and gravel (roaster slag) Number 3 6 3 7 6 7 6 Median 116.8% 79.3% 112.8% 29.3% 44.1% 60.3% 57.6% All Number Median 28 29 26 42 48 70 34 92.2% 49.2% 60.9% 37.2% 40.0% 52.4% 66.8% 57 ------- Tabic 7-8. Effect of Soil Type on RPDs (Accuracy) of Target Elements, Rigaku ZSX Mini II (Continued) Matrix Site Matrix Description Statistic Mercury Nickel Selenium Silver Vanadium Zinc Soil AS Fine to medium sand (steel processing) Number — 3 1 1 1 3 Median — 71.3% 97.5% 40.4% 13.7% 81.4% Soil BN Sandy loam, low organic (ore residuals) Number 1 6 4 4 4 7 Median 39.9% 62.0% 96.2% 42.8% 26.6% 54.6% Soil CN Sandy loam (burn pit residue) Number 2 3 2 2 1 3 Median 42.1% 71.5% 87.9% 91.0% 26.5% 56.1% Soil & Sediment 1CP Soil: Fine to medium quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) Number — 3 — — — 2 Median 11.8% 17.2% Sediment LV Clay/clay loam, salt crust (iron and other precipitates) Number 4 11 5 4 9 9 Median 52.8% 65.5% 100.3% 34.7% 19.8% 17.4% Sediment RF Silty fine sand (tailings) Number 5 13 5 5 3 13 Median 59.0% 55.9% 97.6% 64.0% 29.7% 48.4% Soil SB Coarse sand and gravel (ore and waste rock) Number 10 10 3 1 9 10 Median 112.1% 65.3% 106.6% 38.3% 60.9% 36.2% Sediment TL Silt and clay (slag-enriched) Number 2 6 4 4 7 7 Median 128.8% 66.8% 120.3% 58.8% 41.0% 63.9% Soil WS Coarse sand and gravel (roaster slag) Number — 7 1 4 3 7 Median — 37.6% 101.5% 48.3% 27.6% 60.1% All Number 24 62 25 25 37 61 Median 74.2% 60.4% 101.5% 45.1% 35.2% 48.6% Notes: Other Notes: AS Alton Steel Mill — BN Burlington Northern railroad/ASARCO East. Number CN Naval Surface Warfare Center, Crane Division. RPD KP KARS Park - Kennedy Space Center. LV Leviathan Mine/Aspen Creek. RF Ramsey Flats - Silver Bow Creek. SB Sulphur Bank Mercury Mine. TL Torch Lake Superfund Site. WS Wickes Smelter Site. No samples reported by the reference laboratory in this concentration range. Number of demonstration samples evaluated. Relative percent difference. 58 ------- 7.6 Primary Objective 6 — Sample Throughput The Rigaku two-person field team was able to analyze all 326 demonstration samples in 4 days at the demonstration site. Once the ZSX Mini 11 instrument had been set up and operations had been streamlined, the Rigaku field team was able to analyze a maximum of 107 samples during an extended work day. This sample throughput was achieved by using different members of the field team to perform sample preparation and instrumental analysis and by using the autosamplcr to process samples through the XRF spectrometer. Without an extended work day, and taking into account instrument set-up and demobilization time, it was estimated that the Rigaku field team would have averaged about 69 samples per day .This estimated sample throughput for a normal working day was similar to that observed for the other instruments that participated in the demonstration (average of 66 samples per day). A detailed discussion of the time required to complete the various steps of sample analysis using the ZSX Mini II is included as part of the labor cost analysis in Section 8.3. 7.7 Primary Objective 7 — Technology Costs The evaluations pertaining to this primary objective arc fully described in Chapter 8, Economic Analysis. 7.8 Secondary Objective 1 — Training Requirements The instrument operator must be suitably trained to set up and operate the instrument to obtain the level of data quality required for specific projects. The amount of training required depends on the configuration and complexity of the instrument along with the associated software. Most developers have established standard training programs. Rigaku recommends that the operator have a high school diploma and basic operational training. Field or laboratory technicians arc generally qualified to operate this instrument. The Rigaku staff member who operated the instrument during the demonstration held a B.S. degree in chemistry, with several years of experience in operation of the ZSX Mini II. Rigaku recommends that operators complete at least the training Rigaku offers for instrument users. When an instrument is purchased, a Rigaku service engineer will set it up and provide basic instruction on operation and safety. After about a week, a Rigaku application specialist will come to the site where the instrument will be used to provide a 3-day comprehensive training course adapted for the user's specific application. Additional 3-day training classes arc offered for SI,800. Participants arc encouraged to bring samples to class to analyze as part of the hands-on exercise for the training. A built-in modem allows a support technician to operate and troublcshoot the instrument from a remote location. In addition to the general instrument operational instruction and training, the operator and data manager must be familiar with using a personal computer (PC) to acquire and manage analytical data obtained from the instrument. Rigaku provides a copy of its instrument software with each instrument purchase. The software allows direct transfer to analytical results from the instrument to the PC, thereby minimizing the potential for lost data. 7.9 Secondary Objective 2 — Health and Safety Included in the health and safety evaluation were the potential risks from. (1) potential radiation hazards from the instrument itself, and (2) exposure to any reagents used in preparing and analyzing the samples. However, the evaluation did not include potential risks from exposure to sitc-spccific hazardous materials, such as sample contaminants, or to physical safety hazards. These factors were excluded because of the wide and unpredictable range of sites and conditions that could be encountered in the field during an actual project application of the instrument. The ZSX Mini II contains an x-ray tube that is positioned to deliver x-rays into a lead-shielded scaling sample chamber. Each instrument is equipped with a sample chamber lock, and large lights indicate when x-rays arc being generated. The instrument will not operate if the lock is not latched. The sample chamber lock, lead-shielded sample chamber, and safety lights arc designed to minimize possible exposure to the x-ray radiation. 59 ------- The second potential source of risk to XRF instrument operators is exposure to reagent chemicals used in sample preparation. However, for the ZSX Mini II, there are no risks from this source because no chemical reagents are required for sample preparation. The sample chamber may be placed in a vacuum or purged with inert gas such as helium in some applications (for example, to improve data quality for lighter elements). As an inert gas, helium is relatively harmless, as long as users apply standard safety procedures for management and use of high- pressure gas cylinders. The risks from exposure to radiation or to helium are likewise minimal when the instrument is operated according to the manufacturer's recommendations. 7.10 Secondary Objective 3 — Portability Portability depends on the size, weight, number of components, and power requirements of the instrument, and the reagent required. The size of the instrument, including physical dimensions and weight, is presented in Table 6-1. The number of components, power requirements, support structures, and reagent requirements arc also listed in Table 6-1. Two distinctions were made during the demonstration regarding portability: (1) The instrument was considered fully portable if the dimensions were such that the instrument could be easily brought directly to the sample location by one person. (2) The instrument was considered transportable if the dimensions and power requirements were such that the instrument could be moved to a location near the sampling location, but required a larger and more stable environment (for example, a site trailer with AC power and stable conditions). Based on the dimensions and power requirements, the ZSX Mini 11 is defined as transportable. It is capable of being transported to a field trailer or other fixed location with the required power supply and a stable weatherproof environment. 7.11 Secondary Objective 4 — Durability Durability was evaluated by gathering information on the instrument's warranty and the expected lifespan of the radioactive source or x-ray tube. The ability to upgrade software or hardware also was evaluated. Weather resistance was evaluated by examining the instrument for exposed electrical connections and openings that may allow water to penetrate (for portable instruments only). Rigaku provides a 12-month limited warranty on parts and labor. Additional warranties, optional extended warranties, and service contracts vary by country. Since x-ray tube sources are new to the world of portable instrumentation, no clear data have been obtained on the useful life that can be assumed. Rigaku indicated that the lifespan of an x-ray tube in the ZSX Mini II can be as high as 10,000 hours of operation. Rigaku is continually upgrading both the instrument and software to enhance environmental analysis. It is expected that Rigaku will continue to provide upgrades to instruments and software as long as there is a market for improved technologies. The ZSX Mini II instrument is made with hard-tool plastic that is durable and impact-resistant under nearly all field applications. The instrument is not weatherproof and must be located in a stable environment. 7.12 Secondary Objective 5 — Availability Rigaku LLC was founded in 1931 and has six salespersons in the U.S. and many more worldwide. Rigaku provides product support for all instruments through service contracts tailored to the client's needs. A network of 35 service representatives provides service and customer support for instrument owners. The ZSX Mini II is available for lease or for long- term rental on a case-specific basis. The ZSX Mini II is not available from third-party vendors for lease or rental. 60 ------- Chapter 8 Economic Analysis Tabic 8-1. Equipment Costs Cost Element ZSX Mini II XRF Demonstration Average * Shipping S500 S410 Capital Cost (Purchase) $82,500 S54,300 Weekly Rental S4,300 S2,813 Autosamplcr (for Overnight Analysis) Included N/A This chapter provides cost information for the Rigaku ZSX Mini II XRF analyzer. Cost elements that were addressed included instrument purchase or rental, supplies, labor, and ancillary items. Sources of cost information included input from the technology developer and suppliers as well as observations during the field demonstration. Comparisons arc provided to average costs for other XRF technologies and for conventional fixed-laboratory analysis to provide some perspective on the relative cost of using the ZSX Mini II instrument. 8.1 Equipment Costs Capital equipment costs include either purchase or rental of the ZSX Mini II and any ancillary equipment that is generally needed for sample analysis. (See Chapter 6 for a description of available accessories.) Information on purchase price for the analyzer and accessories was obtained from Rigaku. The ZSX Mini II instrument costs between S80,000 and S85,000, depending on the configuration. The cost includes peripherals such as the x-ray spectrometer, 12-postion sample changer, vacuum pump, and personal computer loaded with the appropriate operational software. At the time of the demonstration, Rigaku indicated that models arc not available for rental. However, long-term lease programs arc available through Rigaku. For evaluation and comparison purposes later in this chapter, an estimated rental cost was derived based on similar XRF technologies where both purchase and rental prices were available. Purchased models include a 1-year parts and labor warranty. The lifespan of the x-ray tube is about 4 to 5 years for normal usage. The purchase price and shipping cost for the ZSX Mini II exceed the average costs for all XRF instruments that participated in the demonstration, as shown in Table 8-1. Notes: * Average for all eight demonstration vendors N/A Not available or not applicable for this comparison 8.2 Supply Costs The supplies that were included in the cost estimate include sample containers, Mylar® film, spatulas or scoops, wipes, and disposable gloves. The rate of consumption for these supplies was based on observations during the field demonstration. Unit prices for these supplies were based on price quotes from independent vendors of field equipment. Additional costs include purchase of helium or P-10 (argon/methane) gas if an oxygcn-frcc environment is best suited for the analysis. The ZSX Mini II was operated for 4 days to complete the analysis of the demonstration sample set (326 samples) during the field demonstration. The supplies required to process samples were similar for all XRF instruments that participated in the demonstration and were estimated to cost about S250 for 326 samples or SO.75 per sample. 8.3 Labor Costs Labor costs were estimated based on the total time required by the field team to complete the analysis of all 326 samples and the number of people in the field team, while making allowances for field team members that had responsibilities other than sample 61 ------- processing during the demonstration. For example, some developers sent sales representatives to the demonstration to communicate with visitors and provide outreach services; this type of staff time was not included in the labor cost analysis. While overall labor costs were based on the total time required to process samples, the time required to complete each definable activity was also measured during the field demonstration. These activities included: • Initial setup and calibration • Sample preparation • Sample analysis • Daily shutdown and startup • End of project packing The estimated time required to complete each of these activities using the ZSX Mini II is listed in Table 8-2. The "total processing time per sample" was calculated as the sum of all these activities assuming that the activities were conducted sequentially; therefore, it represents how much time it would take a single trained analyst to complete these activities. However, the "total processing time per sample" does not include activities that were less definable in terms of the amount of time taken, such as data management and procurement of supplies, and is therefore not a true total. The time to complete all sample analysis using the ZSX Mini 11 is compared with the average of all XRF instruments in Table 8-2 and is compared with the range of all XRF instruments in Figure 8-1. In comparison to other XRF analyzers, the ZSX Mini II exhibited higher-than-average times for initial setup and calibration and for end of project packing. The ZSX Mini II exhibited lower-than-average times for sample preparation, sample analysis, daily shutdown and startup, and total processing time per sample. Table 8-2. Time Required to Complete Analytical Activities' Activity ZSX Mini II Average2 1 Initial Setup and Calibration 90 54 Sample Preparation 2.2 3.1 Sample Analysis 5.7 6.7 Daily Shutdown/Startup 0 10 1 End of Project Packing 147 43 Total Processing Time per Sample 8.6 10.0 Notes: 1 All estimates are in minutes " Average for all eight XRF instruments in the demonstration The Rigaku field team expended about 67 labor hours to complete all sample processing activities during the field demonstration using the ZSX Mini II. This was similar to the overall average of 69 labor hours for all instruments that participated in the demonstration. 8.4 Comparison of XRF Analysis and Reference Laboratory Costs Two scenarios were evaluated to compare the cost for XRF analysis using the ZSX Mini II with the cost of fixed-laboratory analysis using the reference methods. Both scenarios assumed that 326 samples were to be analyzed, as in the field demonstration. The first scenario assumed that only one element was to be measured in a metal-specific project or application (for example, lead in soil, paint, or other solids) for comparison to laboratory per-metal unit costs. The second scenario assumed that 13 elements were to be analyzed, as in the field demonstration, for comparison to laboratory costs for a full suite of metals. 62 ------- Initial Set up and Calibration Sample Preparation Sample Analysis Total Processing Time Daily Shut Down/Start Up End of project packing 0 ZSX Mini II | Range for all eight XRF instruments Figure 8-1. Comparison of activity times for the ZSX Mini II versus other XRF instruments. Typical unit costs for fixed-laboratory analysis using the reference methods were estimated using information on average cost from Tetra Tech's basic ordering agreement with six national laboratories. These unit costs assume a standard turnaround time of 21 days and standard hard copy and electronic data deliverables that summarize results and raw analytical data. No costs were included for field labor that would be specifically associated with off- site fixed laboratory analysis, such as sample packaging and shipment. The cost for XRF analysis using the ZSX Mini II was based on equipment rental for 1 week, along with labor and supplies estimates established during the field demonstration. As noted previously, the estimate used a hypothetical rental rate for the ZSX Mini II based on a survey of rental versus purchase costs of other XRF instruments. Labor costs were estimated based on the number of people in the field team and the time spent during the field demonstration to complete the analysis of the 326 demonstration samples. Labor costs were added for drying, grinding, and homogenizing the samples (estimated at 10 minutes per sample) since these additional steps in sample preparation are required for XRF analysis but not for analysis in a fixed laboratory. A typical cost for managing investigation-derived waste (IDW), including general trash, personal protective equipment, wipes, and soil, was also added to the cost of XRF analysis because IDW costs are included in the unit cost for fixed- laboratory analysis. The IDW management cost was fixed, based on the average IDW disposal cost per instrument during the demonstration, because IDW generation did not vary significantly between instruments during the demonstration. Since the cost for XRF analysis of one element or multiple elements does not vary significantly (all target elements are determined simultaneously when a sample is analyzed), the ZSX Mini II analysis cost was not adjusted for one element versus 13 elements. Table 8-3 summarizes the costs for the ZSX Mini II versus the cost for analysis in a fixed laboratory. This comparison shows that the ZSX Mini II 63 ------- compares favorably to a fixed laboratory in terms of overall cost when a large number of elements are to be determined. The ZSX Mini II compares unfavorably to a fixed laboratory when one element is to be determined. Use of the ZSX Mini II will likely produce additional cost savings because analytical results will be available within a few hours after samples are collected, thereby expediting project decisions and reducing or eliminating the need for additional mobilizations. The total cost for the ZSX Mini II in the example scenario (326 samples) was estimated at S10,421. This estimate compares with the average of S8,932 for all XRF instruments that participated in the demonstration. However, it should be noted that bench-top instruments, such as the ZSX Mini II, typically cost more than the hand-held instruments that were included in the average cost for all XRF instruments. In comparison to other bench-top XRF instruments, the cost of the ZSX Mini II for the example scenario was similar. Table 8-3. Comparison of XRF Technology and Reference Method Costs Analytical Approach Quantity Item Unit Rate Total ZSX Mini 11 (1 to 13 elements) Shipping 1 Roundtrip S500 S500 Weekly Rental' 1 Week S4,300' S4,300 Supplies 326 Sample S0.75 S245 Labor 54 Hours S43.75 S5,286 IDW N/A N/A N/A S90 Total ZSX Mini 11 Analysis Cost (1 to 13 elements) SI 0,421 Fixed Laboratory (1 clement) (EPA Method 6010, ICP-AES) 326 Sample S21 S6,846 Total Fixed Laboratory Costs (1 element) $6,846 Fixed Laboratory (13 elements) Mercury (EPA Method 7471, CVAA) 326 Sample S36 SI 1,736 All other Elements (EPA Method 6010, ICP-AES) 326 Sample SI 60 S52,160 Total Fixed Laboratory Costs (13 elements) §63,896 Notes: 1 Estimated value as Rigaku currently does not have a rental rate for the ZSX Mini II. 64 ------- Chapter 9 Summary of Technology Performance The preceding chapters of this report document that the evaluation design succeeded in providing detailed performance data for the Rigaku ZSX Mini II XRF analyzer. The evaluation design incoiporatcd 13 target elements, 70 distinct sample blends, and a total of 326 samples. The blends included both soil and sediment samples from nine sampling locations. A rigorous program of sample preparation and characterization, reference laboratory analysis, QA/QC oversight, and data reduction supported the evaluation of XRF instrument performance. One important aspect of the demonstration was the sample blending and processing procedures (including drying, sieving, grinding, and homogenization) that significantly reduced uncertainties associated with the demonstration sample set. These procedures minimized the impacts of heterogeneity on method precision and on the comparability between XRF data and reference laboratory data. In like manner, project teams arc 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 arid analysis to ensure that the XRF method will meet data quality needs, such as accuracy and sensitivity requirements. A pilot study can also help the project team develop an initial understanding of the degree of correlation between field and laboratory data. This type of study is especially appropriate for sampling programs that will involve complex soil or sediment matrices with high concentrations of multiple elements because the demonstration found that XRF performance was more variable under these conditions. Initial pilot studies can also be used to develop site-specific calibrations, in accordance with EPA Method 6200, that adjust instrument algorithms to compensate for matrix effects. The findings of the evaluation of the ZSX Mini II analyzer for each primary and secondary objective arc summarized in Tables 9-1 and 9-2. The ZSX Mini II and the combined performance of all eight instruments that participated in the XRF technology evaluation program arc compared in Figure 9-1. The comparison in Figure 9-1 indicates that, when compared with the mean performance of all eight XRF instruments, the ZSX Mini II showed: • Equivalent or better MDLs for all target elements except antimony and arsenic (iron was not included in the MDL evaluation). • Equivalent or poorer accuracy (RPDs) for 12 of the 13 target elements (vanadium was the exception). When RPDs for antimony were calculated versus sample spike levels rather than reference laboratory data (which may be biased low), accuracy for antmony remained low relative to the program as whole. • Equivalent or better precision (RSDs) for 11 of the 13 target elements (arsenic and chromium were the exceptions). Bench-top instruments, such as the ZSX Mini II, typically provide improved MDLs in comparison to portable instruments, and so the better than average performance in this area was expected. As a bench- top instrument, however, the ZSX Mini 11 is not fully portable and requires a stable operating environment. The reasons for the poorer than average accuracy for most elements arc not known with any certainty but may relate to the algorithms employed to quantify target elements or to inadequate calibration. 65 ------- Table 9-1. Summary of Rigaku ZSX Mini II Performance - Primary Objectives Objective Performance Summary PI: Method Detection Limits • Mean MDLs for the target elements ranged as follows: o MDLs of 1 to 20 ppm: copper, mercury, nickel, selenium, and zinc. o MDLs of 20 to 50 ppm: arsenic, lead, silver, and vanadium, o MDLs of 50 to 100 ppm: antimony, cadmium, and chromium, o MDLs greater than 100 ppm: none. (Iron was not included in the MDL evaluation.) • The MDLs for antimony and cadmium may be inflated by high biases in the XRF results in some of the MDL sample blends. • No significant differences were noted between MDLs for soil and sediment, or among different sample blends. • For all the target elements except antimony, the MDLs calculated were lower than reference MDL data from EPA Method 6200. P2: Accuracy and Comparability • Median RPDs between the ZSX Mini II and reference laboratory data revealed the following, with lower RPDs indicating greater accuracy: o RPDs less than 25 percent: none. o RPDs of 25 to 50 percent: arsenic, chromium, copper, silver, vanadium, and zinc. o RPDs greater than 50 percent: antimony, cadmium, iron, lead, mercury, nickel, and selenium. • Data review indicated that the reference laboratory results for some spiked demonstration samples may be biased low for antimony due to the volatility of the spiking compounds used. However, unlike a number of other instruments in the XRF technology demonstration, high RPDs for antimony were not improved for the ZSX Mini II when calculated relative to certified spike values rather than reference laboratory results. • Lower RPDs (that is, higher accuracy) were noted in low concentration samples versus higher concentration samples for multiple target elements in both soil and sediment. • Correlation plots relative to reference laboratory data indicated: o Significant negative biases for most of the target elements (or, for cadmium and vanadium, biases that change from high to low as concentrations increase). o Poor to no correlation with the reference laboratory results for antimony and silver. P3: Precision • Median RSDs were good for all elements, as follows: o RSDs of 0 to 5 percent: cadmium, copper, iron, mercury, nickel, selenium, silver, and zinc, o RSDs of 5 to 10 percent: antimony and vanadium, o RSDs of 10 to 20 percent: arsenic and chromium. • In contrast to accuracy, the precision of the ZSX Mini II improved slightly as concentration increased. • Median RSDs for the ZSX Mini II for all elements except chromium were equivalent to or lower than the RSDs calculated for the reference laboratory data, indicating slightly better precision for the XRF instrument. 66 ------- Tabic 9-1. Summary of Rigaku ZSX Mini II Performance - Primary Objectives (continued) Objective Performance Summarv P4: Effects of Sample Interferences • High relative concentrations of lead appeared to slightly improve accuracy for arsenic, reducing the instrument's negative bias. Median RPDs for arsenic decreased from 45.5 percent to 16.3 percent as the concentration of lead increased. • Overall, significant interference effects could not be determined because of the low accuracy of the XRF data. P5: Effects of Soil Type • The degree of variation in RPDs for the target elements was greatest in the samples from KARS Park, a former gun range, where the median RPDs ranged from 11.8 percent (nickel) to 153 percent (antimony). Other sample sites for which the range of RPDs across the different target elements was greater than 100 percent included: Alton Steel, Burlington Northern, Sulphur Bank, and Torch Lake. • The high outliers and extreme values were distributed among the KARS Park, Alton Steel, Sulphur Bank, and Leviathan Mine sites. However, the evaluation found that sample matrix had little overall effect on accuracy for the ZSX Mini II, given the broad overall ranges of RPDs observed. P6: Sample Throughput • With an average sample preparation time of 2.2 minutes and an instrument analysis time of 5.7 minutes per sample, the total sample processing time was 8.6 minutes per sample. • A maximum sample throughput of 107 samples was achieved during the field demonstration on one extended work day. A typical average sample throughput was estimated to be 69 samples per day for an 8- hour work day. P7: Costs • Instrument purchase cost was about S82,500. This cost included an optional autosamplcr, vacuum pump, and personal computer. According to the developer, short-term and long-term leases arc available, but no rates were provided. • The Rigaku field team expended approximately 67 labor hours to complete the processing of the demonstration sample set (326 samples). In comparison, the average for all participating XRF instruments was 69 labor hours. • By approximating a 1-wcck rental cost (based on similar XRF instruments) and adding labor and shipping/supplies costs, a total project cost of SI 0,421 was estimated for a project the size of the demonstration using the ZSX Mini II. In comparison, the average project cost for all participating XRF instruments was S8,932 and the cost for fixed-laboratory analysis of all 13 elements was S63,896. 67 ------- Table 9-2. Summary of Rigaku ZSX Mini II Performance - Secondary Objectives Objective Performance Summary SI: Training Requirements • Field or laboratory technicians with a high school diploma and basic operational training are generally qualified to operate the ZSX Mini II. • Rigaku offers free instrument setup for purchasers, followed by customized training that generally lasts about 3 days. • The ZSX Mini II comes equipped with a modem that allows qualified technicians to remotely troubleshoot the instrument and guide operators. S2: Health and Safety • The ZSX Mini II is equipped with safety measures to minimize possible exposure to emissions from the x-ray tube. The instrument cannot be operated if these safety measures are disabled. • Users of the ZSX Mini II should be able to safely manage high pressure gas cylinders (helium) if an inert atmosphere is desired for sample analysis. S3: Portability • Based on dimensions, weight, and power requirements, the ZSX Mini II is a transportable (as opposed to fully portable) instrument. It is best used in a field trailer or other fixed location. S4: Durability • The ZSX Mini II has a 12-month limited warranty for parts and labor. Additional optional warranties and service contracts are available, depending on the country where the instrument is purchased and used. • The average lifespan of an x-ray tube in the ZSX Mini II is anticipated to be 10,000 hours (7 years) • The ZSX Mini II is encased in durable hard-tool plastic but is not weatherproof. It must be used in a stable, sheltered environment. S5: Availability • Rigaku maintains offices in the U.S. and Europe for its XRF division, with 10 sales representatives distributed across North America and Europe. A world-wide network of 35 service representatives provides service and customer support. • The ZSX Mini II is available for short-term rental or long-term lease. Rates vary and arc project-specific. The instrument is not available from third-party vendors. 68 ------- Comparison of Mean MDLs: ZSX Mini II vs. All Developers ¦ ZSX Mini II Mean MDL D All Developer Mean MDL ~: rfT-rfT-JP ^ j? J" ^ o0 V s/ ~/ ' Target Metal ¦5 i! 18.0% 16.0% 14.0% 12.0% 10.0% 8.0% 6.0% 4.0% 2.0% 0.0% Comparison of Median RSDs: ED2000 vs. All Developers ¦ ZSX Mini II Median RSD ~ All Developer Median RSD m v t> Target Metal Figure 9-1. Method detection limits (sensitivity), accuracy, and precision of the ZSX Mini II in comparison to the average of all eight XRF instruments. 69 ------- This page was left blank intentionally. 70 ------- Chapter 10 References Gilbert, R.O. 1987. Statistical Methods for Environmental Pollution Monitoring. Van Nostrand Rcinhold, New York. Tctra Tech EM Inc. 2005. Demonstration and Quality Assurance Plan. Prepared for U.S. Environmental Protection Agency, Supcrfund Innovative Technology Evaluation Program. March. U.S. Environmental Protection Agency (EPA). 1996a. 77V Spectrace TN 9000 and TN Pb Field Portable X-ray Fluorescence Analyzers. EPA/600/R-97/145. March. EPA. 1996b. Field Portable X-ray Fluorescence Analyzer HNU Systems SEFA-P. EPA/600/R-97/144. March. EPA. 1996c. Test Methods for Evaluating Solid Waste. Physical/Chemical Methods (SIV- 846). December. EPA. 1998a. Environmental Technology Verification Report; Field Portable X-ray Fluorescence Analyzer. Metorex X-Met 920-MP. EPA/600/R-97/151. March. EPA. 1998b. Environmental Technology Verification Report; Field Portable X-ray Fluorescence Analyzer. Niton XL Spectrum Analyzer. EPA/600/R-97/150. March. EPA. 1998c. Scitect MAP Spectrum Analyzer Field Portable X-Ray Fluorescence Analyzers. EPA/600/R-97/147. March. EPA. 1998d. Metorex X-MET 920-P and 940 Field Portable X-ray Fluorescence Analyzers. EPA/600/R-97/146. March. EPA. 1998c. EPA Method 6200. from "Test Methods for Evaluating Solid Waste. Physical/Chemical Methods (SW-S46), Update IVA. December. EPA. 2000. Guidance for Data Quality Assessment: Practical Methods for Data Analysis. EPA QA/G-9 QA00 Update. EPA/600/R-96/084. July. EPA. 2004a. Innovative Technology Verification Report. Field Measurement Technology<• for Mercury in Soil and Sediment - Metorex's X-MET® 2000 X-Ray Fluorescence Technology. EPA/600/R-03/149. May. EPA. 2004b. Innovative Technology> Verification Report: Field Measurement Technology for Mercury in Soil and Sediment - Niton's XLi/XLt 700 Series X-Ray Fluorescence Analyzers. EPA/600/R-03/148. May. EPA. 2004c. USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review. Final. OSWER 9240.1-45. EPA 540-R-04-004. October. 71 ------- APPENDIX A VERIFICATION STATEMENT ------- United States Environmental Protection Agency Office of Research and Development Washington, DC 20460 oEPA SITE Monitoring and Measurement Technology Program Verification Statement TECHNOLOGY TYPE: X-ray Fluorescence (XRF) Analyzer APPLICATION. MEASUREMENT OF TRACE ELEMENTS IN SOIL AND SEDIMENT TECHNOLOGY NAME: ZSX Mini II COMPANY: Rigaku Incorporated ADDRESS: 9009 New Trails Drive The Woodlands, TX 77381-5209 PHONE: 281-363-1033 WEB SITE: www.r12akumsc.com/xrf E-MAIL: info(S),ri2akumsc.com VERIFICATION PROGRAM DESCRIPTION The U.S. Environmental Protection Agency (EPA) created the Supcrfund Innovative Technology Evaluation (SITE) Monitoring and Measurement Technology (MMT) Program to facilitate deployment of innovative technologies through performance verification and information dissemination. The goal of this program is to further environmental protection by substantially accelerating the acceptance and use of improved and cost-effective technologies. The program assists and informs those involved in designing, distributing, permitting, and purchasing environmental technologies. This document summarizes the results of a demonstration of the Rigaku Incorporated ZSX Mini II bench-top x-ray fluorescence (XRF) analyzer for the analysis of 13 target elements in soil and sediment, including antimony, arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc. PROGRAM OPERATION Under the SITE MMT Program, with the full participation of the technology developers, EPA evaluates and documents the performance of innovative technologies by developing demonstration plans, conducting field tests, collecting and analyzing demonstration data, and preparing reports. The technologies arc 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 Tctra Tech EM Inc. as the verification organization to assist in field testing technologies for measuring trace elements in soil and sediment using XRF technology. DEMONSTRATION DESCRIPTION The field demonstration of eight XRF technologies to measure trace elements in soil and sediment was conducted from January 24 through 28, 2005, at the Kennedy Athletic, Recreational and Social (KARS) Park, which is part of the Kennedy Space Center on Mcrritt Island, Florida. A total of 326 samples were analyzed by each XRF technology developer, including Rigaku, during the field demonstration. These samples were derived from 70 different blends and spiked blends of soil and sediment collected from nine sites across the U.S. The sample blends were thoroughly dried, sieved, crushed, mixed, and characterized before they were used for the demonstration. Some blends were also A-l ------- spiked to further adjust and refine the concentration ranges of the target elements. Between three and seven replicate samples of each blend were included in the demonstration sample set and analyzed by the technology developers during the field demonstration. Shealy Environmental Services, Inc. (Shealy), of Cayce, South Carolina, was selected as the reference laboratory to generate comparative data in evaluation of XRF instrument performance. Shealy analyzed all demonstration samples (both environmental and spiked) concurrently with the developers during the field demonstration. The samples were analyzed by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) using EPA SW-846 Method 3050B/6010B and by Cold Vapor Atomic Absorption Spectroscopy (CVAA) using EPA SW-846 Method 7471A (mercury only). This verification statement provides a summary of the evaluation results for the Rigaku ZSX Mini II XRF instrument. More detailed discussion can be found in the Innovative Technology Verification Report - XRF Technologies for Measuring Trace Elements in Soil and Sediment: Rigaku ZSX Mini II XRF Analyzer (EPA/540/R-06/001). TECHNOLOGY DESCRIPTION XRF spectroscopy is an analytical technique that exposes a sample (soil, alloy metal, filters, other solids, and thin samples) to an x-ray source. The x-rays from the source have the appropriate excitation energy that causes elements in the sample to emit characteristic x-rays. A qualitative elemental analysis is possible from the characteristic energy, or wavelength, of the fluorescent x-rays emitted. A quantitative elemental analysis is possible from the number (intensity) of x-rays at a given wavelength. The ZSX Mini II differs from the other XRF technologies evaluated in the SITE MMT demonstration in that it is a "wavelength-dispersive" XRF analyzer. Wavelength-dispersive XRF analyzers differentiate the x-ray energies emitted from a sample by dispersing them into different wavelength ranges using crystals. The other seven technologies participating in the demonstration were "energy-dispersive" XRF analyzers that differentiate x-ray energies based on voltages measured by the detector. Wavelength dispersive XRFs have historically been large, laboratory-bound instruments with significant requirements for power and cooling. The ZSX Mini II is a smaller, transportable unit that can operate at room temperature on standard 110-volt circuits. The ZSX Mini II has a sample chamber that can: accommodate up to 12 samples, be adapted for irregularly-shaped objects, operate under vacuum or helium environments (enhancing performance for light elements), and spin samples during analysis (with an available spinner accessory). Up to five types of analyzing crystals are available for x-ray dispersion, including lithium fluoride, pentaerythritol, thallium acid phthalate, RX35, and germanium. Multiple crystals can be used for a single analysis using a revolving changer. In contrast to energy-dispersive instruments, the unit employs an economical gas proportional counter as a detector rather than a diode array/multi-channel analyzer detector because wavelength resolution is achieved with the crystals. VERIFICATION OF PERFORMANCE Method Detection Limit: MDLs were calculated using seven replicate analyses from each of 12 low-concentration sample blends, according to the procedure described in Title 40 Code of Federal Regulations (CFR) Part 136, Appendix B, Revision 1.11. A mean MDL was further calculated for each target element. The ranges into which the mean MDLs fell for the ZSX Mini II are listed below (lower MDL values indicate better sensitivity). Relative Sensitivity Mean MDL Target Elements High 1 - 20 ppm Copper, Mercury, Nickel, Selenium, and Zinc. Moderate 20 - 50 ppm Arsenic, Lead, Silver, and Vanadium. Low 50- 100 ppm Antimony, Cadmium, and Chromium. Very Low > 100 ppm None. Notes: ppm = Parts per million. Iron was not included in the MDL evaluation. A-2 ------- Accuracy: Accuracy was evaluated based on the agreement of the XRF results with the reference laboratory data. Accuracy was assessed by calculating the absolute relative percent difference (RPD) between the mean XRF and the mean reference laboratory concentration for each blend. Accuracy of the ZSX Mini II was classified from high to very low for the various target elements, as indicated in the table below, based on the overall median RPDs calculated for the demonstration. Relative Accuracy Median RPD Target Elements High 0%- 10% None Moderate 10% - 25% None. Low 25% - 50% Arsenic. Chromium, Copper, Silver, Vanadium, and Zinc. Very Low > 50% Antimony*. Cadmium, Iron, Lead, Mercury, Nickel, and Selenium. * Calculation of RPDs versus sample spike concentrations rather than reference laboratory results (due to potential low bias in the reference laboratory results for antimony) failed to improve accuracy. Accuracy was also assessed through correlation plots between the mean ZSX Mini II and mean reference laboratory concentrations for the various sample blends. Correlation coefficients (r2) for linear regression analysis of the plots arc summarized below, along with any significant biases apparent from the plots in the XRF data versus the reference laboratory data. * s' o J? Arsenic V 3 U u Copper Iron fj Mercury Nickel 3 e id Silver 3 '"V J3 3 > U s Correlation 0 11 0.90 0.82 0.95 0 95 0 93 0.99 0 98 0 93 0 97 001 0.73 0 97 Bias Indct Low Var Low Low Low Low Low Low Low Indet Var Low Notes. Indet = Indeterminate due to low correlation. Var = Bias varies from high to low as concentration increases. * Correlation did not improve when compared to sample spike concentrations as opposed to reference laboratory data Precision: Replicates were analyzed for all sample blends. Precision was evaluated by calculating the standard deviation of the replicates, dividing by the average concentration of the replicates, and multiplying by 100 percent to yield the relative standard deviation (RSD) for each blend. Precision of the ZSX Mini II was classified from high to very low for each target element, as indicated in the table below, based on the overall median RSDs. The calculated RSDs indicated a higher level of precision in the ZSX Mini II than in the reference laboratory data for all target elements except arsenic and chromium. Relative Precision Median RSD Target Elements High 0% - 5% Cadmium, Copper, Iron, Lead, Mercury, Nickel, Selenium, Silver, and Zinc Moderate 5%- 10% Antimony and Vanadium. Low 10%-20% Arsenic and Chromium. Very Low > 20% None. Effects of Interferences: The RPDs from the evaluation of accuracy were further grouped and compared for a few elements of concern (arsenic, nickel, copper, and zinc) based on the relative concentrations of potentially interfering elements. This evaluation found that high relative lead concentrations (more than 10X), a potential intcrfcrcnt for arsenic, actually improved the apparent accuracy for arsenic results in the ZSX Mini II data set (decreasing the median RPDs for arsenic from 45 percent to 16 percent) by counteracting the inherently low instrument bias. Similar but smaller effects were observed on nickel, copper, and zinc results for other interfering elements. Effects of Soil Characteristics: The RPDs from the evaluation of accuracy were also further evaluated in terms of sampling site and soil type. This evaluation found high variability in RPD values for multiple target elements in sandy soil from the K.ARS Park site, a former gun range. Extreme RPD ranges and A-3 ------- high RPD outliers were also observed on a more limited basis in blends from other sampling sites; however, sample matrix had little overall effect on accuracy for the ZSX Mini II, given the broad overall ranges of RPDs observed. Sample Throughput: The total processing time per sample was estimated at 8.6 minutes, which included 2.2 minutes of sample preparation and 5.7 minutes of instrument analysis time. A sample throughput of 69 samples per 8-hour work day was estimated with the use of the instrument's autosampler. As noted above, however, the sample blends had undergone rigorous pre-processing before the demonstration. Sample throughput would have decreased if these sample preparation steps (grinding, drying, sieving) had been performed during the demonstration; these steps can add from 10 minutes to 2 hours to the sample processing time. Costs: A cost assessment identified a purchase cost of S82,500 plus S500 shipping for the ZSX Mini II. Using a hypothetical rental cost approximated from similar types of instruments, a total cost of S 10,421 (with a labor cost of $5,286 at S43.75/hr) associated with sample preparation and analysis was estimated for a project similar to the demonstration (326 samples of soil and sediment). In comparison, the project cost averaged S8,932 for all eight XRF instruments participating in the demonstration and $63,896 for fixed-laboratory analysis of all samples for the 13 target elements. Skills and training required: Field or laboratory technicians with a high school diploma are generally qualified to operate the ZSX Mini II. Rigaku offers free training for instrument purchasers that generally lasts about 3 days, and the instrument is equipped with a modem for remote troubleshooting. Health and Safety Aspects: The ZSX Mini II is equipped with safety measures to minimize possible exposure to emissions from the x-ray tube. The instrument cannot be operated if these safety measures are disabled. Users of the ZSX Mini II must be able to safely manage high-pressure gas cylinders (if inert atmosphere analysis is desired). Portability: Based on dimensions, weight, and power requirements, the ZSX Mini II is a transportable (as opposed to fully portable) instrument. It is best used in a field trailer or other fixed location with the required power supply and a stable, weatherproof environment. Durability: The ZSX Mini II is encased in durable hard-tool plastic but is not weatherproof. Rigaku offers a 12-month limited warranty for parts and labor. The average lifespan of the x-ray tube source is estimated at 10,000 hours or 7 years. Availability: New instruments are available from the Rigaku offices in The Woodlands, Texas, and London. Customers are supported by world-wide network of 10 sales and 35 service representatives. RELATIVE PERFORMANCE ZSX Mini II overall performance relative to the XRF demonstration as a whole (all 8 instruments) is as follows: Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Selenium Silver Vanadium Zinc Sensitivity O O • • • • • • • • • • • Accuracy O O O O 0 O O O O O O • O Precision Same o • O • • • • • • • • • Key: • Better 0 Worse NOTICE: Verifications are based on an evaluation of technology performance under specific, predetermined criteria and the appropriate quality assurance procedures. EPA makes no expressed or implied warranties as to the performance of the technology and does not certify that a technology will always operate as verified. The end user is solely responsible for complying with any and all applicable federal, state, and local requirements. A-4 ------- APPENDIX B DEVELOPER DISCUSSION ------- DEVELOPER DISCUSSION Although we did not match well with the unknowns certified results, our instrument tracked well with the assayed numbers. In other words, as they went up or down in concentration, so did we. From our point of view the test went well; the ZSX Mini II demonstrated better sensitivity and repeatability versus all other instruments. The ZSX Mini II has proven to be excellent for analysis of heavy elements such as Cu, Fe, Ti, or Zr. Elements such as Ag, Cd and Sb were our worst performers for the reason that the ZSX Mini II does not have a Primary Beam Filter. These elements are not possible at low concentrations on the ZSX Mini II due to either sensitivity or interference from tube lines. The lack of finite standard concentration values was of prime concern for us in this test. The supplied reference materials had a range for the element concentrations, not exact values. We are curious as to how the other vendors obtained more accurate results as the ZSX Mini II always out performs all these instruments in regular competitions. Perhaps we missed some information on this setup? One of the categories was on portability of the unit. The notation concerning how many people it takes to move the unit indicates that the ZSX Mini II is not field portable. The definition of "field portable" is relative. Its portability is shown in the fact that it was shipped to this site, set up and the tests run in a short period of time. It is not an instrument that is hand carried but definitely portable within the definition of portable for this application and is readily placed in a van, or other smaller vehicles. This is not possible with the larger, full power XRF systems. For the item where the Mini II was noted as requiring facilities like a stable platform, gas, electricity and temperature controlled environment. Other systems at the site also required many of these facilities while still others needed acids, fume hoods, hot plates, etc. Rigaku feels that we participated in this test with the intent of simulating a field situation. Although the samples were ground - this would not necessarily be found in the field - they were run as loose powders as would be expected in a remote environment. Our main concern is the method on which we had based our calibrations. The fact that we were poor only in the accuracy aspect relates to improper concentration values of the calibration reference materials. As stated earlier, the Mini II is produced for just such tests and has a proven track record for such analyses. We thank you for allowing us to participate in this exercise and look forward to any further experiments you may have in the future. B-l ------- APPENDIX C DATA VALIDATION SUMMARY REPORT ------- Contents Chapter Page Acronyms, Abbreviations, and Symbols iii 1.0 INTRODUCTION C-l 2.0 VALIDATION METHODOLOGY C-1 3.0 DATA VALIDATION C-3 3.1 Holding Time C-3 3.2 Calibration C-3 3.3 Laboratory Blanks C-4 3.4 Laboratory Control Samples C-5 3.5 Matrix Spike Samples C-5 3.6 Serial Dilution Results C-5 3.7 ICP Interference Check Samples C-6 3.8 Target Analyte Identification and Quantitation C-6 3.9 Quantitation Limit Verification C-6 4.0 PRECISION, ACCURACY, REPRESENTATIVENESS, COMPLETENESS, AND COMPARABILITY EVALUATION SUMMARY C-6 4.1 Precision C-l 4.2 Accuracy C-l 4.3 Representativeness C-l 4.4 Completeness C-l 4.5 Comparability C-l 5.0 CONCLUSIONS FOR DATA QUALITY AND DATA USABILITY C-8 6.0 REFERENCES C-8 APPENDIX DATA VALIDATION REPORTS l ------- 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 Shcaly Shcaly Environmental Services. Inc. SITE Supcrfund Innovative Technology Evaluation Tctra Tcch Tctra Tcch EM Inc. XRF X-ray fluorescence 11 ------- 1.0 INTRODUCTION This data validation summary report (DVSR) summarizes the reference laboratory quality control (QC) data gathered during the x-ray fluorescence (XRF) technologies demonstration conducted under the U.S. Environmental Protection Agency (EPA) Superfund Innovative Technology Evaluation (SITE) program. The reference laboratory was procured following the federal acquisition regulations (FAR) and an extensive selection process. Shealy Environmental Services, Inc. (Shealy), of Cayce, South Carolina, was selected as the reference laboratory for this project. Thirteen target analytes were measured in reference samples and include antimony, arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc. The laboratory reported results for 22 metals at the request of EPA; however, for the purposes of meeting project objectives, only the data validation for the 13 target analytes is summarized in this document. The objective of the validation is to determine the validity of the reference data, as well as its usability in meeting the primary objective of comparing reference data to XRF data generated during the demonstration. Shealy provided the data to Tetra Tech EM Inc. (Tetra Tech) in electronic and hardcopy formats; a total of 13 sample delivery groups (SDG) contain all the data for this project. The DVSR consists of seven sections, including this introduction. Section 2.0 presents the data validation methodology. Section 3.0 presents the results of the reference laboratory data validation. Section 4.0 summarizes the precision, accuracy, representativeness, completeness, and comparability (PARCC) evaluation. Section 5.0 presents conclusions about the overall evaluation of the reference data. Section 6.0 lists the references used to prepare this DVSR. Tables are presented following Section 6.0. 2.0 VALIDATION METHODOLOGY Data validation is the systematic process for reviewing and qualifying data against a set of criteria to ensure that the reference data are adequate for the intended use. The data validation process assesses acceptability of the data by evaluating the critical indicator parameters of PARCC. The laboratory analytical data were validated according to the procedures outlined in the following documents: • "USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review" (EPA 2004). hereinafter referred to as the "EPA guidance." • "Demonstration and Quality Assurance Project Plan, XRF Technologies for Measuring Trace Elements in Soil and Sediment" (Tetra Tech 2005). hereinafter referred to as "the QAPP." Data validation occurred in the following two stages: (1) a cursory review of analytical reports and quality assurance and quality control (QA/QC) information for 100 percent of the reference data and (2) full validation of analytical reports, QA/QC information, and associated raw data for 10 percent of the reference data as required by the QAPP (Tetra Tech 2005). QA/QC criteria were reviewed in accordance with EPA guidance (EPA 2004) and the QAPP (Tetra Tech 2005). The cursory review for total metals consisted of evaluating the following requirements, as applicable: • Holding times C-l ------- • Initial and continuing calibrations • Laboratory blank results • Laboratory control sample (LCS) and laboratory control sample duplicates (LCSD) results • Matrix spike (MS) and matrix spike duplicate (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 analytc 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 arc 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 analytc identification and quantitation • Assigning qualifiers to affected data when QA/QC criteria were not achieved • Reviewing and summarizing implications of the frequency and severity of qualifiers in the validated data Prior to the XRF demonstration, soil and sediment samples were collected from nine locations across the U.S. and then blended, dried, sieved, and homogenized in the characterization laboratory to produce a set of 326 reference samples. Each of these samples were subsequently analyzed by both the reference C-2 ------- laboratory and all participating technology vendors. As such, 326 prepared soil/sediment samples were delivered to Shealy for the measurement of total metals. The analytical program included the following analyses and methods: • Total metal for 22 analytes by inductively coupled plasma atomic emission spectroscopy (ICP-AES) according to EPA Methods 3050B/6010B (EPA 1996) • Total mercury by cold vapor atomic absorption spectroscopy (CVAA) according to EPA Method 7471A CEPA 1996) 3.0 DATA VALIDATION RESULTS The parameters listed in Section 2.0 were evaluated during cursory review and full validation of analytical reports for all methods, as applicable. Each of the validation components discussed in this section is summarized as follows: • Acceptable - All criteria were met and no data were qualified on that basis • Acceptable with qualification - Most criteria were met, but at least one data point was qualified as estimated because of issues related to the review component Since no data were rejected, all data were determined to be either acceptable or acceptable with qualification. Sections 3.1 through 3.9 discuss each review component and the results of each. Tables that summarize the data validation findings follow Section 6.0 of this DVSR. Only qualified data are included in the tables. No reference laboratory data were rejected during the validation process. As such, all results are acceptable with the qualification noted in the sections that follow. 3.1 Holding Time Acceptable. The technical holding times were defined as the maximum time allowable between sample collection and, as applicable, sample extraction, preparation, or analysis. The holding times used for validation purposes were recommended in the specific analytical methods (EPA 1996) and were specified in the QAPP (Tetra Tech 2005). Because the soil and sediment samples were prepared prior to submission to the reference laboratory, and because the preparation included drying to remove moisture, no chemical or physical (for example ice) preservation was required. The holding time for sample digestion was 180 days for the ICP-AES analyses and 28 days for mercury. All sample digestions and analyses were conducted within the specified holding times. No data were qualified based on holding time exceedances. This fact contributes to the high technical quality of the reference data. 3.2 Calibration Acceptable. Laboratory instrument calibration requirements were established to ensure that analytical instruments could produce acceptable qualitative and quantitative data for all target analytes. Initial calibration demonstrates that the instrument is capable of acceptable performance at the beginning of an analytical run, while producing a linear curve. Continuing calibration demonstrates that the instrument is capable of repeating the performance established during the initial calibration (EPA 1996). C-3 ------- For total metal analyses (1CP-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 cxccedanccs. 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 1996V 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"). iMost 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 analytc 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 (cither J+, b or J-, b). The low occurrence of results affected by blank contamination indicates that the general quality of the C-4 ------- analytical data was not significantly compromised by blank contamination. Table 3 provides all results that were qualified based on laboratory blanks. 3.4 Laboratory Control Samples Acceptable. LCSs and LCSDs were prepared and analyzed with each batch of 20 or fewer samples of the same matrix. All percent recoveries were within the QC limits of 80 to 120 percent; all relative percent differences (RPD) between the LCD and LCSD values were less than the criterion of 20 percent. No data were qualified or rejected on the basis of LCS/LCSD results. This fact contributes to the high technical quality of the data. 3.5 Matrix Spike Samples Acceptable with qualification. MS and 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 cither 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-5 ------- 3.7 ICP Interference Check Samples Acceptable. ICP results for each ICS were evaluated. The ICS verifies the validity of the laboratory's inter-element and background correction factors. High levels of certain elements (including aluminum, calcium, iron, and magnesium) can affect sample results if the intcr-clemcnt 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 arc used to quantify the analyte concentration in the sample digest. Sample digest concentrations arc 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. Shcaly 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 analytcs 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 2005V 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 analytcs in some samples, dilutions were required. However, the required PQLs for the reference laboratory were high enough that even with dilution and moisture content factors applied, the reporting limits did not exceed those of the XRF instruments. This allows for effective comparison of results between the reference laboratory and XRF instruments. 4.0 PRECISION, ACCURACY, REPRESENTATIVENESS, COMPLETENESS, AND COMPARABILITY EVALUATION SUMMARY All analytical data were reviewed for PARCC parameters to validate reference data. The following sections discuss the overall data quality, including the PARCC parameters, as determined by the data validation. C-6 ------- 4.1 Precision Precision is a measure of the reproducibility of an experimental value without considering a true or referenced value. The primary indicators of precision were the MS/MSD RPD and LCS/LCSD RPD between the duplicate results. Precision criteria of less than 20 percent RPD for LCS/LCSD and 25 percent for MS/MSD were generally met for all duplicate pairs. No data were qualified based on duplicate precision of MS/MSD or LCS/LCSD pairs that were not already qualified for other reasons. Such low occurrence of laboratory precision problems supports the validity, usability, and defensibility of the data. 4.2 Accuracy Accuracy assesses the proximity of an experimental value to a true or referenced value. The primary accuracy indicators were the recoveries of MS and LCS spikes. Accuracy is expressed as percent recovery. Overall, about 8 percent of the data was qualified as estimated and no data were rejected because of accuracy problems. The low frequency of accuracy problems supports the validity, usability, and defensibility of the data. 4.3 Representativeness Representativeness refers to how well sample data accurately reflect true environmental conditions. The QAPP was carefully designed to ensure that actual environmental samples be collected by choosing representative sites across the US from which sample material was collected. The blending and homogenization was executed according to the approved QAPP (Tetra Tech 2005). 4.4 Completeness Completeness is defined as the percentage of measurements that are considered to be valid. The validity of sample results is evaluated through the data validation process. Sample results that are rejected and any missing analyses are considered incomplete. Data that are qualified as estimated (J) or undetected estimated (UJ) are considered valid and usable. Data qualified as rejected (R) are considered unusable for all purposes. Since no data were rejected in this data set, a completeness of 100 percent was achieved. A total of 4,238 target analyte results were evaluated. The completeness goal stated in the QAPP (Tetra Tech 2005) was 90 percent. 4.5 Comparability Comparability is a qualitative parameter that expresses the confidence with which one data set may be compared to another. Widely-accepted SW-846 methods were used for this project. It is recognized that direct comparison of the reference laboratory data (using 1CP-AES and CVAA techniques) to the XRF measurements may result in discrepancies due to differences in the preparation and measurement techniques; however, the reference laboratory data is expected to provide an acceptable basis for comparison to XRF measurement results in accordance with the project objectives. Comparability of the data was also achieved by producing full data packages, by using a homogenous matrix, standard quantitation limits, standardized data validation procedures, and by evaluating the PARCC parameters uniformly. In addition, the use of specified and well-documented analyses, approved laboratories, and the standardized process of data review and validation have resulted in a high degree of comparability for the data. C-7 ------- 5.0 CONCLUSIONS FOR DATA QUALITY AND DATA USABILITY Although some qualifiers were added to the data, a final review of the data set with respect to the data quality parameters discussed in Section 4.0 indicates that the data arc 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 arc available upon request, including cursory review and full validation reports as well as the electronic database that contains sample results. 6.0 REFERENCES Tctra Tech EM, Inc. (Tctra Tech). 2005. "Demonstration and Quality Assurance Project Plan, XRF Technologies for Measuring Trace Elements in Soil and Sediment."' March. U.S. Environmental Protection Agency (EPA). 1996. "Test Methods for Evaluating Solid Waste", Third Edition (SW-846). With promulgated revisions. December. EPA. 2004. "USEPA Contract Laboratory Program National Functional Guidelines For Inorganic Data Review". October. C-8 ------- TABLES ------- TABLE 1: DATA VALIDATION QUALIFIERS AND COMMENT CODES Qualifier Definition No Qualifier Indicates that the data arc 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 arc unusable (compound may or may not be present). Resampling and rcanalysis 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 c 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 Internal standard criteria exceeded (not applicable to this data set) Other qualification (will be specified in report) C-9 ------- TABLE 2: QC CRITERIA Parameter Method QC Check Frequency Criterion Corrective Action Reference Method Target Metals 3050B/6010B Method and One per Less than the 1. Check calculations (12 ICP metals and 7471A instrument blanks analytical batch reporting limit 2. Assess and eliminate source of and Hg) of 20 or less contamination 3. Reanalyze blank 4. Inform Tetra Tech project manager 5. Flag affected results MS/MSD One per analytical batch of 20 or less 75 to 125 percent recovery RPD < 25 1. Check calculations 2. Check LCS/LCSD and digest duplicate results to determine whether they meet criterion 3. Inform Tetra Tech project manager 4. Flag affected results LCS/LCSD One per analytical batch of 20 or less 80 to 120 percent recovery RPD < 20 1. Check calculations 2. Check instrument operating conditions and adjust as necessary 3. Check MS/MSD and digest duplicate results to determine whether they meet criterion 4. Inform Tetra Tech project manager 5. Rcdigest and reanalyze the entire batch of samples 6. Flag affected results Performance One per Within acceptance 1. Evaluated by Tetra Tech QA chemist audit samples analytical batch of 20 or less limits 2. Inform laboratory and recommend changes 3. Flag affected results Percent moisture Laboratory duplicates One per analytical batch of 20 or less RPD < 20 1. Check calculations 2. Reanalyze sample batch 3. Inform Tetra Tech project manager 4. Flag affected results C-10 ------- TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION Sample ID Analytc 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, c AS-SO-IO-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, c 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 C-ll ------- TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION (Continued) Sample ID Analyte Result Unit Validation Qualifier Comment Code KP-SO-IO-XX Arsenic 0.7 mg/kg J- b KP-SO-IO-XX Mercury 0.028 mg/kg U b KP-SO-IO-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 C-12 ------- TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION (Continued) Sample ID Analvtc 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, c 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, c SB-SO-18-XX Antimony 1.2 mg/kg UJ b, c SB-SO-30-XX Selenium 1.3 mg/kg J+ b SB-SO-32-XX Silver 0.1 mg/kg UJ b, c SB-SO-37-XX Silver 2 mg/kg UJ b SB-SO-46-XX Silver 2.2 mg/kg UJ b. c SB-SO-48-XX Silver 0.1 mg/kg UJ b, c SB-SO-53-XX Antimony 1.2 mg/kg UJ b, c 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 C-13 ------- TABLE 3: DATA QUALIFICATION: LABORATORY METHOD BLANK CONTAMINATION (Continued) 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-IO-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 exceedanccs 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-14 ------- TABLE 4: DATA QUALIFICATION'S': MATRIX SPIKE RECOVERY EXCEEDANCES Sample ID Analvtc Result Unit Validation Qualifier Validation Code AS-SO-Ol-XX Antimony 3.8 mg/kg J- c AS-SO-02-XX Antimony <2.6 mg/kg UJ c AS-SO-03-XX Mercury 3.7 mg/kg J- c 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 - c AS-SO-05-XX Silver 330 mg/kg J- c AS-SO-06-XX Antimony 2.4 mg/kg UJ b. c AS-SO-07-XX Antimony 3.6 mg/kg J- e AS-SO-08-XX Mercury 2.5 mg/kg J- c AS-SO-08-XX Silver 280 mg/kg J- e AS-SO-09-XX Antimony <2.6 mg/kg UJ c AS-SO-IO-XX Antimony 1.9 mg/kg J - c AS-SO-11-XX Antimony 3.7 mg/kg J- c AS-SO-12-XX Antimony <2.6 mg/kg UJ c AS-SO-13-XX Antimony 2.4 mg/kg UJ b, c BN-SO-Ol-XX Antimony <1.3 mg/kg UJ c BN-SO-Ol-XX Silver <1.3 mg/kg UJ c BN-SO-05-XX Antimony 160 mg/kg J- c BN-SO-07-XX Antimony 110 mg/kg J- c BN-SO-07-XX Silver 990 mg/kg J+ c BN-SO-09-XX Antimony 750 mg/kg J- c BN-SO-09-XX Silver 100 mg/kg J- c BN-SO-IO-XX Antimony <1.3 mg/kg UJ c BN-SO-IO-XX Silver <1.3 mg/kg UJ c BN-SO-11-XX Antimony 4 mg/kg J- c BN-SO-11-XX Silver 140 mg/kg J- c 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 c BN-SO-16-XX Antimony 120 mg/kg J- c BN-SO-16-XX Arsenic 1100 mg/kg J+ c BN-SO-19-XX Antimony 150 mg/kg J- c BN-SO-21-XX Antimony 150 mg/kg J- c C-15 ------- TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) Sample ID Analyte Result Unit Validation Qualifier Validation Code BN-SO-21-XX Arsenic 1300 mg/kg J+ c 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, i BN-SO-25-XX Arsenic 700 mg/kg J e, i 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-Ol-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- c CN-SO-05-XX Mercury 280 mg/kg J- e CN-SO-06-XX Mercury 40 mg/kg J- c 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-IO-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 c KP-SE-14-XX Lead 680 mg/kg J- e, i 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 C-16 ------- TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) Sample ID Analvtc Result Unit Validation Qualifier Validation Code KP-SE-30-XX Silver <0.27 mg/kg UJ c K.P-SO-04-XX Antimony 94 mg/kg J+ e K.P-SO-06-XX Antimony 8.1 mg/kg J+ e K.P-SO-07-XX Antimony 17 mg/kg J+ c KP-SO-IO-XX Antimony 6.1 mg/kg J+ c KLP-SO-13-XX Antimony 16 mg/kg J+ c ICP-SO-15-XX Antimony 6.3 mg/kg J+ c KP-SO-16-XX Antimony 93 mg/kg Jt e KP-SO-18-XX Antimony 6.7 mg/kg J+ c KP-SO-20-XX Antimony 19 mg/kg J+ c KP-SO-22-XX Antimony 8.3 mg/kg J+ c KP-SO-23-XX Antimony 86 mg/kg J+ c KP-SO-24-XX Antimony 17 mg/kg J+ c K.P-SO-26-XX Antimony 90 mg/kg J+ c KP-SO-27-XX Antimony 15 mg/kg J+ c KP-SO-29-XX Antimony 18 mg/kg J+ c KP-SO-32-XX Antimony 16 mg/kg J+ e LV-SE-01-XX Antimony <1.5 mg/kg UJ c LV-SE-02-XX Antimony <1.3 mg/kg UJ c LV-SE-02-XX Lead 20 mg/kg J- c LV-SE-02-XX Silver <1.3 mg/kg UJ c LV-SE-05-XX Mercury 2.6 mg/kg J- c LV-SE-06-XX Mercury 610 mg/kg J- c LV-SE-07-XX Antimony <6.7 mg/kg UJ c LV-SE-08-XX Antimony <1.3 mg/kg UJ e LV-SE-09-XX Lead 14 mg/kg J- c LV-SE-10-XX Antimony <1.3 mg/kg UJ c 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 c LV-SE-12-XX Lead 19 mg/kg J- c LV-SE-I3-XX Mercury 640 mg/kg J- c LV-SE-14-XX Antimony <1.5 mg/kg UJ c LV-SE-15-XX Antimony 290 mg/kg J+ c LV-SE-15-XX Silver 300 mg/kg J- e LV-SE-16-XX Antimony <1.3 mg/kg UJ c LV-SE-17-XX Antimony 280 mg/kg J+ c C-17 ------- TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) 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 c LV-SE-25-XX Antimony <1.3 mg/kg UJ e LV-SE-25-XX Lead 23 mg/kg J- c 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- c 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- c LV-SE-43-XX Antimony 160 mg/kg J+ c 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 C-18 ------- TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) Sample ID Analvtc Result Unit Validation Qualifier Validation Code LV-SE-48-XX Antimony <6.6 mg/kg UJ c LV-SE-50-XX Lead 24 mg/kg J- e LV-SE-51-XX Antimony 210 mg/kg J + c LV-SE-51-XX Silver 250 mg/kg J- c LV-SO-03-XX Mercury 48 mg/kg J- c LV-SO-03-XX Silver 210 mg/kg J- c LV-SO-04-XX Mercury 130 mg/kg J- c LV-SO-04-XX Silver <1.2 mg/kg UJ c LV-SO-34-XX Mercury 130 mg/kg J- c LV-SO-34-XX Silver <1.2 mg/kg UJ c LV-SO-37-XX Mercury 130 mg/kg J- c LV-SO-40-XX Mercury 46 mg/kg J- c LV-SO-40-XX Silver 210 mg/kg J- c LV-SO-49-XX Mercury 52 mg/kg J- c LV-SO-49-XX Silver 220 mg/kg J- c RF-SE-02-XX Antimony <1.3 mg/kg UJ c RF-SE-03-XX Antimony <1.2 mg/kg UJ c RF-SE-04-XX Antimony 3.2 mg/kg J+ c RF-SE-04-XX Silver 12 mg/kg J- c RF-SE-05-XX Antimony 4.1 mg/kg J+ c RF-SE-05-XX Silver 7.4 mg/kg J- c RF-SE-06-XX Antimony <1.3 mg/kg UJ c RF-SE-13-XX Antimony <1.3 mg/kg UJ c RF-SE-14-XX Antimony 4.4 mg/kg J+ c RF-SE-14-XX Silver 13 mg/kg J- c RF-SE-15-XX Antimony <1.3 mg/kg UJ c RF-SE-19-XX Antimony 3.7 mg/kg J+ c RF-SE-19-XX Silver 14 mg/kg J- c RF-SE-22-XX Antimony <1.3 mg/kg UJ c RF-SE-24-XX Antimony <1.3 mg/kg UJ c RF-SE-25-XX Antimony <1.3 mg/kg UJ c RF-SE-26-XX Antimony 2.2 mg/kg J+ c RF-SE-26-XX Silver 7.2 mg/kg J- c RF-SE-27-XX Antimony <1.3 mg/kg UJ c RF-SE-28-XX Antimony <1.2 mg/kg UJ c RF-SE-30-XX Antimony <1.3 mg/kg UJ c RF-SE-31-XX Antimony <1.3 mg/kg UJ c C-19 ------- TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) 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-Ol-XX Antimony 180 mg/kg J e SB-SO-02-XX Antimony 44 mg/kg J- c, i 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 C-20 ------- TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) Sample ID Analvtc Result Unit Validation Qualifier Validation Code SB-S0-15-XX Antimony 600 mg/kg J- i, c 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, c SB-SO-19-XX Antimony 310 mg/kg J c SB-SO-20-XX Antimony <1.3 mg/kg UJ c SB-SO-20-XX Silver 140 mg/kg J- c SB-SO-21-XX Antimony 4.9 mg/kg J c SB-SO-22-XX Antimony 10 mg/kg J C, j SB-SO-23-XX Antimony 48 mg/kg J- c SB-SO-23-XX Silver <0.26 mg/kg UJ c SB-SO-24-XX Antimony 180 mg/kg J c SB-SO-25-XX Antimony 6.8 mg/kg J+ c SB-SO-26-XX Antimony 61 mg/kg J c SB-SO-27-XX Antimony 6.7 mg/kg J+ c SB-SO-28-XX Antimony 42 mg/kg J- c SB-SO-28-XX Silver <0.26 mg/kg UJ e SB-SO-29-XX Silver <1.2 mg/kg UJ c SB-SO-30-XX Antimony 3.2 mg/kg J- c SB-SO-31-XX Antimony <1.3 mg/kg UJ c SB-SO-31-XX Silver 160 mg/kg J- c,.i SB-SO-32-XX Antimony 46 mg/kg J- c SB-SO-32-XX Silver 0.1 mg/kg UJ b, c SB-SO-33-XX Antimony 350 mg/kg J c SB-SO-33-XX Silver 2 mg/kg J c SB-SO-34-XX Silver <1.3 mg/kg UJ c SB-SO-35-XX Antimony 6 mg/kg J+ c 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- c SB-SO-40-XX Antimony 2.2 mg/kg J- e SB-SO-41-XX Antimony <1.3 mg/kg UJ c SB-SO-42-XX Antimony 4.6 mg/kg J- c SB-SO-43-XX Antimony 40 mg/kg J- c SB-SO-43-XX Silver <0.26 mg/kg UJ c C-21 ------- TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) Sample ID Analyte Result Unit Validation Qualifier Validation Code SB-SO-44-XX Antimony 6.8 mg/ku J+ e SB-SO-45-XX Antimony 180 mfi/kg J e SB-SO-45-XX Silver 2.1 mg/kg J- e SB-SO-46-XX Antimony 740 trig/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+ i, e TL-SE-13-XX Silver 160 mg/kg J i.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 C-22 ------- TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) Sample ID Analytc 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- c 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- c TL-SE-29-XX Antimony <1.2 mg/kg UJ c TL-SE-29-XX Lead 51 mg/kg J- c TL-SE-29-XX Silver 5.9 mg/kg J - c WS-SO-Ol-XX Antimony 41 mg/kg J. c WS-SO-Ol-XX Mercury 5.8 mg/kg J c, i WS-SO-Ol-XX Silver 69 mg/kg J- c WS-SO-02-XX Antimony 130 mg/kg J- c WS-SO-02-XX Silver 150 mg/kg J- c WS-SO-03-XX Antimony 8.9 mg/kg J- c WS-SO-03-XX Mercury 0.86 mg/kg J- c WS-SO-04-XX Antimony 45 mg/kg J- c WS-SO-04-XX Silver 76 mg/kg J - c WS-SO-05-XX Antimony 8.6 mg/kg J- c WS-SO-05-XX Silver 0.76 mg/kg J- c WS-SO-07-XX Silver 400 mg/kg J- c WS-SO-09-XX Antimony 7.1 mg/kg J- e WS-SO-09-XX Mercury 0.89 mg/kg J_ e WS-SO-IO-XX Silver <1.3 mg/kg UJ c WS-SO-11-XX Silver 340 mg/kg J- c WS-SO-12-XX Antimony <1.3 mg/kg UJ c WS-SO-12-XX Mercury 0.068 mg/kg UJ b, e WS-SO-13-XX Antimony 200 mg/kg J- c WS-SO-13-XX Silver 170 mg/kg J- e WS-SO-14-XX Antimony 8.4 mg/kg J- c WS-SO-14-XX Mercury 0.74 mg/kg J- c WS-SO-15-XX Antimony 48 mg/kg J- c WS-SO-15-XX Silver 90 mg/kg J- c WS-SO-16-XX Antimony 110 mg/kg J- c WS-SO-16-XX Silver 150 mg/kg J- c WS-SO-17-XX Antimony <1.3 mg/kg UJ c WS-SO-17-XX Mercury 0.069 mg/kg UJ b, c WS-SO-18-XX Antimony 130 mg/kg J- c C-23 ------- TABLE 4: DATA QUALIFICATION: MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) 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- c WS-SO-24-XX Silver 140 mg/kg J- c 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- c 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- c 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, c WS-SO-36-XX Antimony 120 mg/kg J- e WS-SO-36-XX Silver 120 mg/kg J- c WS-SO-37-XX Antimony 120 mg/kg J- c WS-SO-37-XX Silver 140 mg/kg J- e C-24 ------- TABLE 4: DATA QUALIFICATION': MATRIX SPIKE RECOVERY EXCEEDANCES (Continued) Notes. < = Less than mg/kg = Milligram per kilogram b = Data were qualified based on blank contamination c = Data were additionally qualified based on matrix spike/matrix spike duplicate excecdances j = Data were additionally qualified based on serial dilution cxcccdanccs J = Result is estimated and biased could not be determined J+ = Result is estimated and potentially biased high J- = Result is estimated and potentially biased low UJ = Result is undetected at estimated quantitation limit C-25 ------- TABLE 5: DATA QUALIFICATION: SERIAL DILUTION EXCEEDANCES Sample ID Analyte Result Unit Validation Qualifier Comment Code AS-SO-09-XX Arsenic 25 trig/kg J- i AS-SO-09-XX Cadmium 100 mg/kg J- i AS-SO-09-XX Chromium 390 mg/kg J- i AS-SO-09-XX Copper 250 mg/kg J- i AS-SO-09-XX Iron 94000 mg/kg J- i AS-SO-09-XX Lead 3200 mg/kg J- i AS-SO-09-XX Nickel 170 mg/kg J- i AS-SO-09-XX Silver 9.6 mg/kg J- i AS-SO-09-XX Vanadium 65 mg/kg J- i AS-SO-09-XX Zinc 6800 mg/kg J- BN-SO-11-XX Mercury 24 mg/kg J- i BN-SO-25-XX Antimony 82 mg/kg J- e, i BN-SO-25-XX Arsenic 700 mg/kg J e,.j BN-SO-25-XX Cadmium 370 mg/kg J- i BN-SO-25-XX Chromium 64 mg/kg J- i BN-SO-25-XX Copper 930 mg/kg J- BN-SO-25-XX Iron 16000 mg/kg J- BN-SO-25-XX Lead 5400 mg/kg J- i BN-SO-25-XX Nickel 88 mg/kg J- BN-SO-25-XX Selenium 19 mg/kg J- BN-SO-25-XX Silver 48 mg/kg J- BN-SO-25-XX Vanadium 28 mg/kg J- BN-SO-25-XX Zinc 2900 mg/kg J - KP-SE-14-XX Antimony 11 mg/kg J- KP-SE-14-XX Chromium 46 mg/kg J- KP-SE-14-XX Copper 2.7 mg/kg J + i KP-SE-14-XX Iron 520 mg/kg J- i KP-SE-14-XX Lead 680 mg/kg J- e, i KP-SE-14-XX Nickel 23 mg/kg J- i LV-SE-29-XX Lead 7.2 mg/kg J + i LV-SE-29-XX Mercury 1.5 mg/kg J- i LV-SE-35-XX Arsenic 31 mg/kg J- i LV-SE-35-XX Chromium 74 mg/kg J- i LV-SE-35-XX Iron 24000 mg/kg J- i LV-SE-35-XX Nickel 170 mg/kg J- i LV-SE-35-XX Vanadium 55 mg/kg J- i LV-SE-35-XX Zinc 67 mg/kg J- i LV-SO-34-XX Antimony 870 mg/kg J- i C-26 ------- TABLE 5: DATA QUALIFICATIONS: SERIAL DILUTION EXCEEDANCES (Continued) Sample ID Analvte Result Unit Validation Qualifier Comment Code LV-SO-34-XX Arsenic 110 mg/kg j~ i LV-SO-34-XX Cadmium 2300 mg/kg j. i LV-SO-34-XX Chromium 2200 mg/kg j- i LV-SO-34-XX Iron 20000 mg/kg J. .i LV-SO-34-XX Lead 3700 mg/kg J. i LV-SO-34-XX Nickel 1900 mg/kg j. .i LV-SO-34-XX Selenium 220 mg/kg j- .i LV-SO-34-XX Vanadium 230 mg/kg J- i LV-SO-34-XX Zinc 48 mg/kg j. .i RF-SE-16-XX Antimony 85 mg/kg J. i RF-SE-16-XX Arsenic 72 mg/kg j- .i RF-SE-16-XX Cadmium 310 mg/kg j. i RF-SE-16-XX Chromium 820 mg/kg j- i RF-SE-16-XX Copper 73 mg/kg J— i RF-SE-16-XX Iron 16000 mg/kg j- i RF-SE-16-XX Lead 24 mg/kg J- i RF-SE-16-XX Nickel 1700 mg/kg J- i RF-SE-16-XX Silver 130 mg/kg J- i RF-SE-16-XX V anadium 32 mg/kg j. i RF-SE-16-XX Zinc 760 mg/kg j- i RF-SE-24-XX Arsenic 130 mg/kg J+ i RF-SE-24-XX Cadmium 6.5 mg/kg J+ i RF-SE-24-XX Chromium 74 mg/kg J+ i RF-SE-24-XX Copper 860 mg/kg J+ i RF-SE-24-XX Iron 24000 mg/kg J+ i RF-SE-24-XX Lead 410 mg/kg J+ i RF-SE-24-XX Nickel 170 mg/kg J+ i RF-SE-24-XX Silver 3.8 mg/kg J+ i RF-SE-24-XX Vanadium 46 mg/kg J+ j RF-SE-24-XX Zinc 1400 mg/kg J. i SB-SO-02-XX Antimony 44 mg/kg J - c,j SB-SO-02-XX Arsenic 23 mg/kg j. i SB-SO-02-XX Lead 22 mg/kg J- i SB-SO-02-XX Mercury 130 mg/kg J+ i SB-SO-15-XX Antimony 600 mg/kg J- j,c SB-SO-15-XX Arsenic 170 mg/kg J- i SB-SO-15-XX Chromium 91 mg/kg J- .i SB-SO-15-XX Copper 30 mg/kg J- i SB-SO-15-XX Iron 51000 mg/kg J- .i C-27 ------- TABLE 5: DATA QUALIFICATIONS: SERIAL DILUTION EXCEEDANCES (Continued) Sample ID Analyte Result Unit Validation Qualifier Comment Code SB-SO-15-XX Lead 40 mg/kfi J- i SB-SO-15-XX Nickel 100 mg/kg J- i SB-SO-15-XX Vanadium 52 mg/kg J- i SB-SO-15-XX Zinc 36 mg/kg J- i SB-SO-22-XX Antimony 10 mg/kg J e, i SB-SO-22-XX Zinc 64 mg/kg J- i SB-SO-31-XX Arsenic 8 mg/kg J- i SB-SO-31-XX Nickel 3200 mg/kg J- i SB-SO-31-XX Selenium 28 mg/kg J_ j SB-SO-31-XX Silver 160 mg/kg J- e, i SB-SO-31-XX Zinc 3900 mg/kg J- i TL-SE-13-XX Antimony 95 mg/kg J + i,e TL-SE-13-XX Chromium 36 mg/kg J + j TL-SE-13-XX Copper 4400 mg/kg J + i TL-SE-13-XX Iron 22000 mg/kg J + i TL-SE-13-XX Lead 1100 mg/kg J + i TL-SE-13-XX Silver 160 mg/kg J i, e TL-SE-13-XX Vanadium 59 mg/kg J + i WS-SO-Ol-XX Mercury 5.8 mg/kg J e, i WS-SO-33-XX Arsenic 450 mg/kg J- i WS-SO-33-XX Cadmium 11 mg/kg J- i WS-SO-33-XX Chromium 120 mg/kg J- i WS-SO-33-XX Copper 150 mg/kg J_ i WS-SO-33-XX Iron 28000 mg/kg J- i WS-SO-33-XX Lead 3700 . mg/kg J- i WS-SO-33-XX Nickel 65 mg/kg J- i WS-SO-33-XX Silver 13 mg/kg J_ i WS-SO-33-XX Vanadium 53 mg/kg J- i ' WS-SO-33-XX Zinc 830 mg/kg J" i Notes: mg/kg e j J J+ J- Milligram per kilogram Data were additionally qualified based on matrix spike/matrix spike duplicate exceedances Data were qualified based on serial dilution exceedances Result is estimated and biased could not be determined Result is estimated and potentially biased high Result is estimated and potentially biased low C-28 ------- APPENDIX D DEVELOPER AND REFERENCE LABORATORY DATA ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 1 KP-SO-06-XX Reference Laboratory 8 1 J+ 1 J- 0.1 U 290 26 1,400 620 1 KP-SO-IO-XX Reference Laboratory 6.1 J+ 1 J- 0.1 U 300 26 1,600 560 1 KP-SO-15-XX Reference Laboratory 6.3 J+ 1 J- 0 1 U 340 26 1,600 510 I KP-SO-18-XX Reference Laboratory 6.7 J+ l J- 0 1 U 250 24 1,200 500 1 KP-SO-22-XX Reference Laboratory 8 3 J+ 1 J- 0 1 U 260 29 1,300 650 1 KP-SO-06-RI Rigaku, Inc. 289 85 866 198 37 3,882 358 I KP-SO-IO-RI Rigaku, Inc. 325 116 893 246 43 3,883 399 I KP-SO-15-RI Rignku,Inc. 303 101 913 227 40 3,880 357 I KP-SO-18-R1 Rigaku,Inc 310 105 885 212 42 3,892 360 ] KP-SO-22-RI Rigaku,Inc 366 124 957 212 41 3,968 359 2 KP-SO-07-XX Reference Laboratory 17 J+ 2 J- 0 1 U 170 48 990 1,200 2 KP-SO-13-XX Reference Laboratory 16 J+ 1 J - 0.045 U 180 52 980 1,200 2 KP-SO-20-XX Reference Laboratory 19 J+ 2 J- 0.1 U 160 46 910 1,300 2 KP-SO-24-XX Reference Laboratory 17 J+ 1 J- 0.1 U 160 49 900 1,100 2 KP-SO-27-XX Reference Laboratory 15 J+ 1 J- 0.05 U 170 45 970 1,200 2 KP-SO-29-XX Reference Laboratory 18 J+ 2 J - 0.1 U 150 42 870 1,200 2 KP-SO-32-XX Reference Laboratory 16 J+ 2 J- 0.045 U 180 50 970 1,200 2 KP-SO-07-R1 Rigaku, Inc. 420 102 854 91 65 3,569 792 2 KP-SO-I3-RI Rigaku,Inc 510 102 971 81 64 3,526 747 2 KP-SO-20-RI Rigaku,Inc 459 82 899 142 60 3,603 777 2 KP-SO-24-R1 Rigaku, Inc 467 98 908 89 62 3,637 804 2 KP-SO-27-R1 Rigaku, Inc. 399 117 885 156 58 3,576 760 2 KP-SO-29-R1 Rigaku, Inc. 447 108 871 91 51 3,537 789 2 KP-SO-32-R1 Rigaku, Inc. 457 107 885 154 57 3,606 790 3 KP-SO-04-XX Reference Laboratory 94 J+ 3 0 046 U 180 200 1,300 5,800 3 KP-SO-16-XX Reference Laboratory 93 J+ 3 0 063 U 200 230 1,400 6,100 3 KP-SO-23-XX Reference Laboratory 86 J+ 3 0 048 U 180 190 1,300 5,300 3 KP-SO-26-XX Reference Laboratory 90 J+ 4 0.061 U 210 230 1,500 6,500 3 KP-SO-31-XX Reference Laboratory 88 28 0 1 U 140 200 1,100 5,700 3 KP-SO-04-RI Rigaku,Inc 1,011 126 765 129 186 3,642 3,280 3 KP-SO-I6-R1 Rigaku,Inc 1,106 145 779 74 183 3,584 3,259 3 KP-SO-23-RI Rigaku,Inc 1,042 120 764 123 183 3,626 3,269 3 KP-SO-26-RI Rigaku,Inc 1,125 104 777 137 192 3,639 3,392 3 KP-SO-31 -Rl Rigaku, Inc. 1,184 148 810 125 182 3,665 3,379 D-l ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Hp Ni Se AS V Zn 1 KP-SO-06-XX Rcfcicnce Laboiatory 0 06 U 140 0 25 U 0 25 U 2 J 11 1 KP-SO-IO-XX Reference Laboratory 0.03 U 150 0.22 U 0 25 U 2 J 12 I KP-SO-I5-XX Reference Laboiatory 0.03 U 170 0 25 U 0 25 U 2 J 15 1 KP-SO-1S-XX Reference Laboratoiy 0 02 U 120 0 25 U 0.25 U 2 J II l KP-SO-22-XX Rcfcicnce Laboratory 0 03 U 130 0 25 U 0 25 U 2 J 11 I KP-SO-06-RI Rigaku. Inc 71 122 16 302 19 36 I KP-SO-IO-RI Rigaku. Inc 58 128 19 306 18 38 I KP-SO-I5-RI Rigaku, Inc. 62 127 14 301 21 34 I KP-SO-18-RI Rigaku. Inc 69 133 16 316 25 31 I KP-SO-22-RI Rigaku, Inc 70 121 16 321 19 45 2 KP-SO-07-XX Reference Laboiatoiy 0 03 U 87 0 21 U 0 25 U 1 J 26 2 KP-SO-I3-XX Rcfcicnce Laboiatoiy 0 04 U 90 0.25 U 0 25 U 1 J 24 2 KP-SO-20-XX Reference Laboiatoiy 0 03 U 79 0.25 U 0 25 U 1 J 25 2 K P-SO-24-XX Rcfcicnce Laboiatoiy 0 02 U 78 0.25 U 0 25 U 1 J 22 2 KP-SO-27-XX Rcfcicnce Laboratoiy 0 02 U 87 0.25 U 0 25 U 1 J 24 2 KP-SO-29-XX Rcfcicnce Laboratory 001 U 73 0 25 U 0 25 U 1 J 22 2 KP-SO-32-XX Rcfcicnce Laboratoiy 001 U SS 051 0 25 U 1 J 24 2 KP-SO-07-R1 Rigaku, Inc 68 94 15 290 25 40 2 KP-SO-I3-R1 Rigaku. Inc 50 86 15 326 15 35 2 KP-SO-20-RI Rigaku. Inc 62 94 17 310 24 57 2 KP-SO-24-R1 Rigaku, Inc 62 90 16 305 28 44 2 KP-SO-27-RI Rigaku. Inc 66 90 15 301 18 41 2 KP-SO-29-RI Rigaku. Inc 63 93 17 294 24 41 2 KP-SO-32-RI Rigaku. Inc 64 96 18 30S 22 47 3 KP-SO-04-XX Reference Laboratoiy 0 02 U 93 0 28 U 0 16 J 1 J 45 3 KP-SO-16-XX Reference Laboratory 0 02 U 100 0 25 U 0 16 J 1 J 47 3 KP-SO-23-XX Reference Laboratory 0 02 U 91 0 25 U 0 13 J 1 J 41 3 KP-SO-26-XX Reference Laboratory 0 01 U 110 0 22 U 0 17 J 1 J 52 3 KP-SO-31 -XX Reference Laboratory 0 02 U 6S 0 25 U 04 2 J 38 3 KP-SO-04-RI Rigaku. Inc. 61 81 17 260 25 57 3 KP-SO-I6-RI Rigaku.Inc 48 81 19 271 15 55 3 KP-SO-23-RI Rigaku. Inc. 59 78 18 262 18 53 3 KP-SO-26-R1 Rigaku, Inc. 52 S8 16 267 20 59 3 KP-SO-3 l-RI Rigaku, Inc. 42 82 20 273 14 58 D-2 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 4 KP-SO-02-XX Reference Laboratory 410 10 0.1 6 780 1,700 18,000 4 KP-SO-03-XX Reference Laboratory 360 9 0.074 U 5 670 1,600 19,000 4 KP-SO-05-XX Reference Laboratory 410 12 0 13 U 6 780 2,000 24,000 4 KP-SO-09-XX Reference Laboratory 420 11 0 094 U 5 780 1,800 22,000 4 KP-SO-2I-XX Reference Laboratory 370 10 0.098 U 5 700 1,700 19,000 4 KP-SO-02-RI Rigaku, Inc. 2,230 166 588 -8 539 3,679 10,300 4 KP-SO-03-RI Rigaku, inc. 2,237 120 598 31 590 3,686 10.425 4 KP-SO-05-RI Rigaku, Inc 2,056 140 578 -13 573 3,666 10,700 4 KP-SO-09-RI Rigaku, Inc 2,034 136 581 7 545 3,637 10,389 4 KP-SO-2I-RI Rigaku, Inc 2,049 131 565 9 580 3,663 10,432 5 VVS-SO-06-XX Reference Laboratory 1 3 U 48 1 9 120 50 28,000 110 5 WS-SO-08-XX Reference Laboratory 1.3 45 2 120 47 26,000 71 5 WS-SO-I2-XX Reference Laboratory 1 3 UJ 43 1.8 110 45 25,000 65 5 WS-SO-I7-XX Reference Laboratory 1 3 UJ 47 1.9 120 49 28,000 70 5 VVS-SO-27-XX Reference Laboratory 1 3 UJ 49 2 120 51 28,000 72 5 VVS-SO-30-XX Reference Laboratory 1 2 J - 51 2 130 53 29,000 81 5 WS-SO-35-XX Reference Laboratory 1.3 UJ 49 2 130 51 28,000 74 5 WS-SO-06-RI Rigaku, Inc. 147 75 600 113 42 15,860 6 5 WS-SO-08-RI Rigaku, Inc. 164 52 602 83 42 15,925 4 5 WS-SO-12-RI Rigaku, Inc. 135 66 587 65 50 15,982 -3 5 WS-SO-17-RI Rigaku, Inc 162 50 613 115 38 15,770 16 5 VVS-SO-27-RI Rigaku,Inc 176 32 598 118 37 15,837 6 5 WS-SO-30-RI Rigaku, Inc 168 69 601 89 39 15,943 6 5 WS-SO-35-RI Rigaku, Inc. 158 61 620 105 42 15,895 6 6 VVS-SO-03-XX Reference Laboratory 8.9 J- 500 12 140 170 32,000 4,300 6 VVS-SO-05-XX Reference Laboratory 8 6 J- 440 12 140 160 31,000 4,000 6 WS-SO-09-XX Reference Laboratory 7 1 J- 480 12 130 160 30,000 4,000 6 WS-SO-I4-XX Reference Laboratory 8 4 J - 430 11 120 150 28,000 3,700 6 WS-SO-26-XX Reference Laboratory 7.6 J- 520 12 140 160 30,000 4,000 6 WS-SO-3I-XX Reference Laboratory 7.2 J- 520 12 140 170 32,000 4,200 6 VVS-SO-33-XX Reference Laboratory 6 9 J- 450 J- II J- 120 J- 150 J- 28,000 J- 3,700 J- 6 VVS-SO-03-RI Rigaku,Inc 441 199 565 94 102 16,124 1,996 6 WS-SO-05-RI Rigaku, Inc 445 230 579 98 94 16,250 2,026 6 WS-SO-09-RI Rigaku, Inc. 413 186 576 115 98 16,184 1,979 6 WS-SO-I4-RI Rigaku, Inc 466 240 566 132 98 16,132 1,974 6 WS-SO-26-R1 Rigaku, Inc. 468 241 593 103 101 16,212 1,979 6 VVS-SO-3I-RI Rigaku, Inc. 479 211 578 129 97 16,183 1,967 6 WS-SO-33-RI Rigaku, Inc. 480 184 592 115 101 16,200 2,028 D-3 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data 1-lK Nl Se ar V Zn 4 KP-SO-02-XX Reference Laboiatory 0 04 U 4 0 42 U 0.82 0 J 100 4 KP-SO-03-XX Rcfcicnee Laboiatory 0 04 U 3 0 25 U 0 73 0 J 92 4 KP-SO-05-XX Reference Laboratory 0 04 U 4 0 24 U 0 82 0 J 110 4 KP-SO-09-XX Reference Laboratory 0.05 U 3 0 25 U 0 84 0 J 110 4 KP-SO-2I-XX Reference Laboiatory 0 04 U 4 0 25 U 0 76 0 J 100 4 KP-SO-02-RI Rigaku,Inc 54 32 20 212 28 91 4 KP-SO-03-RI Rigaku,Inc 47 31 18 200 24 91 4 KP-SO-05-RI Rigaku,Inc 52 33 20 198 21 91 4 KP-SO-09-RI Rigaku,Inc 53 37 21 206 26 90 4 KP-SO-21 -Rl Rigaku, Inc 44 33 21 203 25 95 5 WS-SO-06-XX Refciencc Laboratory 0 07 U 61 1 3 U 0 93 J 56 230 5 WS-SO-OS-XX Reference Laboratory 0 06 U 58 1 3 U 0 86 J 52 220 5 WS-SO-12-XX Reference Laboratory 0 07 UJ 55 1.3 U 0 94 J 49 210 5 WS-SO-17-XX Reference Laboratory 0 07 UJ 59 1 3 U 0 89 J 56 230 5 WS-SO-27-XX Reference Laboratory Oil J- 61 1 3 U 09 J 57 230 5 WS-SO-30-XX Reference Laboratory 0 07 UJ 65 1 3 U 1 J 58 240 5 WS-SO-35-XX Reference Laboiatory 0.07 UJ 62 1 3 U 1 J 57 240 5 WS-SO-06-RI Rigaku, Inc. 26 44 8 204 63 146 5 WS-SO-08-RI Rigaku. Inc 28 39 9 208 77 146 5 WS-SO-12-RI Rigaku. Inc. 24 41 7 199 75 146 5 WS-SO- 17-RI Rigaku, Inc 29 38 7 207 74 149 5 WS-SO-27-R1 Rigaku. Inc 23 41 7 204 84 141 5 WS-SO-30-RI Rigaku. Inc 23 44 7 210 57 140 5 WS-SO-35-R1 Rigaku, Inc 29 39 8 219 78 151 6 WS-SO-03-XX Reference Laboratoiy 0 86 J- 75 1 6 15 58 930 6 WS-SO-05-XX Reference Laboratory 0.76 J- 71 1 3 U 15 57 900 6 WS-SO-09-XX Reference Laboratory 0 89 J- 70 1 3 U 14 56 870 6 WS-SO- 14-XX Reference Laboratory 0 74 J- 64 1 3 U 13 50 820 6 WS-SO-26-XX Refciencc Laboratoiy 0 83 J- 70 1.3 U 14 56 900 6 WS-SO-31 -XX Reference Laboratory 0 85 J- 72 1 2 U 15 60 950 6 WS-SO-33-XX Reference Laboratory 0 87 J- 65 J- 1.3 U 13 J- 53 J- 830 J- 6 WS-SO-03-RI Rigaku. Inc. 23 45 9 188 74 399 6 WS-SO-05-RI Rigaku,Inc 30 43 7 197 81 395 6 WS-SO-09-RI Rigaku. Inc. 31 49 6 193 57 418 6 WS-SO-14-RI Rigaku,Inc 29 48 8 202 70 399 6 WS-SO-26-R1 Rigaku. Inc. 26 47 10 199 69 396 6 WS-SO-3 l-RI Rigaku. Inc 24 39 7 196 63 396 6 WS-SO-33-R1 Rigaku. Inc. 30 40 7 198 66 406 D-4 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 7 WS-SO-Ol-XX Reference Laboratory 41 J- 1900 47 100 590 32,000 18,000 7 WS-SO-04-XX Reference Laboratory 45 J- 2000 50 94 640 34,000 20,000 7 WS-SO-15-XX Reference Laboratory 48 J- 2300 56 82 720 37,000 24,000 7 VVS-SO-22-XX Reference Laboratory 41 J- 1900 47 84 620 33,000 17,000 7 WS-SO-34-XX Reference Laboratory 45 J- 2000 50 91 660 36,000 22,000 7 WS-SO-OI-RI Rigaku, Inc. 813 866 425 137 392 17,607 9,601 7 WS-SO-04-RI Rigaku, Inc. 877 828 427 112 396 17,625 9,652 7 WS-SO-15-RI Rigaku, Inc 901 841 445 88 379 17,579 9,764 7 WS-SO-22-RI Rigaku, Inc 952 848 434 120 378 17,542 9,554 7 WS-SO-34-RI Rigaku, Inc. 845 838 434 106 379 17,569 9,666 8 WS-SO-02-XX Reference Laboratory 130 J- 4200 98 49 1300 44,000 35,000 8 WS-SO-I6-XX Reference Laboratory 110 J- 3900 91 59 1300 42,000 24,000 8 WS-SO-I8-XX Reference Laboratory 130 J- 4100 95 63 1300 44,000 37,000 8 WS-SO-21 -XX Reference Laboratory 120 J- 3900 90 43 1200 40,000 43,000 8 WS-SO-24-XX Reference Laboratory 97 J- 3600 81 54 1100 38,000 27,000 8 WS-SO-29-XX Reference Laboratory 120 J- 3800 90 51 1200 40,000 42,000 8 WS-SO-37-XX Reference Laboratory 120 J - 4100 95 63 1300 42,000 26,000 8 WS-SO-02-RI Rigaku, Inc. 389 1,541 338 129 744 20,249 17,432 8 WS-SO-I6-RI Rigaku, Inc. 364 1,544 336 130 740 20,082 17,151 8 WS-SO-I8-RI Rigaku, Inc. 522 1,558 326 180 735 19,895 17,246 8 WS-SO-21-RI Rigaku, Inc 466 1,485 336 139 745 19,866 17,269 8 WS-SO-24-RI Rigaku, Inc 309 1,548 312 158 731 20,151 17,209 8 VVS-SO-29-RI Rigaku, Inc. 531 1,522 330 101 745 20,030 17,210 8 WS-SO-37-RI Rigaku, Inc 568 1,564 317 129 734 20,159 17,313 9 WS-SO-I3-XX Reference Laboratory 200 J- 5800 150 53 1800 47,000 45,000 9 WS-SO-I9-XX Reference Laboratory 150 J- 5000 130 66 1500 39,000 24,000 9 WS-SO-28-XX Reference Laboratory 120 J- 4200 100 54 1200 33,000 30,000 9 WS-SO-32-XX Reference Laboratory 190 J- 5500 140 54 1700 44,000 30,000 9 WS-SO-36-XX Reference Laboratory 120 J- 3800 92 51 1100 30,000 45,000 9 WS-SO-I3-RI Rigaku, Inc. 101 2,007 303 152 975 19,879 20,959 9 WS-SO-I9-RI Rigaku, Inc. 139 2,004 304 152 966 20,134 20,926 9 WS-SO-28-R1 Rigaku, Inc 270 2,006 306 156 956 19,964 21,260 9 WS-SO-32-RI Rigaku, Inc 304 2,028 308 147 957 20,163 20,967 9 WS-SO-36-RI Rigaku, Inc 223 2,032 301 113 970 20,164 21,151 D-5 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data us Nl Sc Ar V Zn 7 WS-SO-OI-XX Reference Laboratoiy 5 8 J 66 1 3 U 69 J- 42 3,000 7 WS-SO-04-XX Reference Laboiatory 6 5 62 1.3 U 76 J- 44 3.100 7 WS-SO-I5-XX Rcfeience Labotatory 5 S 58 1 3 U 90 J- 52 3,400 7 WS-SO-22-XX Refcience Laboratory 48 57 1 3 U 72 J- 44 3.000 7 WS-SO-34-XX Reference Laboiatory 54 60 1 3 U 78 J- 47 3,200 7 WS-SO-OI-RI Rigaku. Inc 22 46 14 146 60 1,501 7 WS-SO-04-RI Rigaku. Inc. 20 51 11 152 73 1.473 7 WS-SO-15-RI Rigaku, Inc. 19 46 10 154 71 1,473 7 WS-SO-22-RI Rigaku. Inc. 23 45 13 I4S 67 I.4S7 7 WS-SO-34-RI Rigaku. Inc 22 47 12 146 60 1.484 8 WS-SO-02-XX Reference Laboratory 17 57 1.3 U 150 J- 36 6.000 8 WS-SO-16-XX Reference Laboratoiy 15 60 1.1 J 150 J- 35 5,700 S WS-SO-IS-XX Reference Laboratoiy 17 62 1.9 140 J - 36 5.900 8 NVS-SO-21 -XX Reference Laboratoiy 14 51 1.6 150 J- 33 5,500 8 WS-SO-24-XX Reference Laboratoiy 16 54 2 1 140 J- 30 5,200 8 WS-SO-29-XX Reference Laboratory 15 55 1 7 140 J- 33 5.500 8 WS-SO-37-XX Reference Laboiatory 14 63 3 140 J- 34 5.800 8 WS-SO-02-RI Rigaku, Inc 21 55 15 112 51 2.557 S WS-SO-I6-RI Rigaku. Inc 17 57 18 116 67 2,536 S WS-SO-IS-RI Rigaku. Inc. 21 53 16 114 59 2,551 S WS-SO-21 -Rl Rigaku, Inc. 27 58 17 119 58 2,512 S WS-SO-24-RI Rigaku. Inc. 17 51 16 113 63 2.529 8 WS-SO-29-RI Rigaku. Inc 16 51 17 113 61 2,544 8 WS-SO-37-RI Rigaku. Inc. 15 52 IS 117 56 2.535 9 WS-SO-I3-XX Reference Laboratoiy 11 75 3.7 170 J- 24 9.000 9 WS-SO-19-XX Reference Laboiatoiy 12 74 3.7 160 J- 20 7,700 9 WS-SO-28-XX Reference Laboratoiy 11 59 2 3 130 J- 16 6,100 9 WS-SO-32-XX Rcfeience Laboratoiy 1 1 73 3 7 190 J- 23 8,500 9 WS-SO-36-XX Reference Laboratoiy 13 55 1 7 120 J- 15 5,700 9 WS-SO-I3-RI Rigaku. Inc 20 65 21 109 50 3,97S 9 WS-SO-19-RI Rigaku. Inc 28 69 20 106 51 4.001 9 WS-SO-28-RI Rigaku. Inc 17 62 20 105 54 3,938 9 WS-SO-32-RI Rigaku, Inc IS 65 22 104 60 3.978 9 WS-SO-36-RI Rigaku. Inc 23 71 20 106 56 4,005 D-6 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 10 BN-SO-OI -XX Reference Laboratory 1 3 UJ 38 0.94 120 32 24,000 63 10 BN-SO-10-XX Reference Laboratory 1 3 UJ 50 1.2 110 35 24,000 140 10 BN-SO-I5-XX Reference Laboratory 1 3 UJ 34 0.82 110 29 22,000 56 10 BN-SO-I8-XX Reference Laboratory 1 3 U 37 0 89 1 10 29 22,000 59 10 BN-SO-28-XX Reference Laboratory 1 5 35 0 87 100 28 22,000 58 10 BN-SO-31 -XX Reference Laboratory 1 3 41 1 140 33 26,000 65 10 BN-SO-35-XX Reference Laboratory 1.4 37 0.98 120 30 23,000 60 10 BN-SO-OI-Rl Rigaku, Inc. 203 34 645 55 29 13,872 -17 10 BN-SO-10-RI Rigaku, Inc 198 69 642 96 27 13,866 -15 10 BN-SO-15-RI Rigaku, Inc 213 49 665 81 29 13,934 -21 10 BN-SO-18-RI Rigaku, Inc 184 46 624 60 23 14,018 -14 10 BN-SO-28-R1 Rigaku, Inc 219 62 658 103 23 13,841 -11 10 BN-SO-3 l-RI Rigaku, Inc 251 47 733 59 21 13,882 -10 10 BN-SO-35-RI Rigaku, Inc. 207 30 662 101 25 13,915 -11 II BN-SO-02-XX Reference Laboratory 11 140 50 90 170 28,000 840 II BN-SO-04-XX Reference Laboratory 9 1 120 42 79 140 24,000 700 11 BN-SO-17-XX Reference Laboratory 9.3 110 39 79 140 23,000 680 11 BN-SO-22-XX Reference Laboratory 7.3 98 34 65 110 20,000 590 11 BN-SO-27-XX Reference Laboratory 9.6 110 39 78 130 24,000 660 II BN-SO-02-RI Rigaku, Inc 241 75 640 125 92 13,783 303 11 BN-SO-04-RI Rigaku, Inc 252 67 643 52 92 13,700 332 11 BN-SO-I7-RI Rigaku, Inc. 252 77 648 69 95 13,691 310 11 BN-SO-22-RI Rigaku, Inc. 285 88 683 79 90 13,741 321 11 BN-SO-27-RI Rigaku, Inc. 288 76 663 45 94 13,692 318 12 BN-SO-03-XX Reference Laboratory 65 620 290 120 840 25,000 4,700 12 BN-SO-06-XX Reference Laboratory 60 600 280 94 810 24,000 4,500 12 BN-SO-08-XX Reference Laboratory 57 570 270 100 750 22,000 4,300 12 BN-SO-13-XX Reference Laboratory 65 320 150 98 410 17,000 2,400 12 BN-SO-20-XX Reference Laboratory 57 540 260 88 730 22,000 4,100 12 BN-SO-30-XX Reference Laboratory 64 630 300 100 860 26,000 4,800 12 BN-SO-34-XX Reference Laboratory 68 630 290 110 830 25,000 4,700 12 BN-SO-03-RI Rigaku,Inc 538 315 672 146 488 14,067 2,193 12 BN-SO-06-RI Rigaku, inc. 559 310 666 43 481 14,026 2,184 12 BN-SO-08-RI Rigaku, Inc. 558 298 674 100 495 13,942 2,185 12 BN-SO-I3-RI Rigaku, Inc 626 316 684 98 493 14,050 2,178 12 BN-SO-20-RI Rigaku, Inc 523 301 662 77 516 13,973 2,147 12 BN-SO-30-RI Rigaku, Inc. 585 304 675 72 493 13,924 2,199 12 BN-SO-34-RI Rigaku, Inc 563 296 660 93 489 14.105 2,176 D-7 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No Sample ID Source of Data Mr Ni Sc Ag V Zn 10 BN-SO-OI -XX Rcfcicncc Laboratory 0 13 63 1 3 U 1 3 UJ 55 92 10 BN-SO-10-XX Rcfcicncc Laboiatory 0 14 54 1 2 J 1 3 UJ 55 110 10 BN-SO-15-XX Rcfcicncc Laboratory 0 15 58 1 3 U 1 3 UJ 49 89 10 BN-SO-1 S-XX Rcfcicncc Laboratory 0 13 59 1 3 0.94 U 46 88 10 BN-SO-28-XX Rcfcicncc Laboiatory 0 16 54 1 3 U 0 77 U 48 81 10 BN-SO-31 -XX Rcfcicncc Laboratory 0.14 71 1 3 U 0 97 U 54 94 10 BN-SO-35-XX Reference Laboratory 0.15 63 1 2 J 0 85 U 50 87 10 BN-SO-OI-Rl Rigaku. Inc 29 41 6 221 70 66 10 BN-SO-IO-RI Rigaku,Inc 23 44 7 221 73 72 10 BN-SO-I5-RI Rigaku.Inc 27 43 5 224 70 86 10 BN-SO-18-RI Rigaku. Inc 25 49 5 224 54 63 10 BN-SO-28-RI Rigaku. Inc 21 43 5 226 68 72 10 BN-SO-3 1 -Rl Rigaku.Inc 25 41 7 241 71 87 10 BN-SO-35-RI Rigaku. Inc 36 45 8 227 66 72 11 BN-SO-02-XX Rcfcicncc Laboratory 0 37 54 4 3 7 6 60 . 470 11 BN-SO-04-XX Reference Laboratory 0 36 48 2 9 65 50 400 11 BN-SO-17-XX Reference Laboratory 0 39 47 27 63 49 390 11 BN-SO-22-XX Rcfcicncc Laboiatory 0 37 40 2 8 54 43 330 11 BN-SO-27-XX Rcfcicncc Laboratory 0 38 46 3 7 6 1 52 380 11 BN-SO-02-RI Rigaku. inc 27 40 9 223 60 230 11 BN-SO-04-RI Rigaku. Inc 30 45 7 223 58 220 11 BN-SO-17-RI Rigaku, Inc 35 38 8 216 57 221 11 BN-SO-22-RI Rigaku. Inc 23 41 6 236 77 232 11 BN-SO-27-RI Rigaku, Inc 19 37 7 234 57 223 12 BN-SO-03-XX Rcfcicncc Laboratory 1.6 100 17 42 48 2.300 12 BN-SO-06-XX Reference Laboratory 2 92 15 41 48 2,300 12 BN-SO-08-XX Reference Laboratory 2 94 14 38 39 2.200 12 BN-SO-13-XX Reference Laboratory 1 6 71 92 21 37 1,200 12 I3N-SO-20-XX Reference Laboratory 1.6 84 14 37 44 2,100 12 BN-SO-30-XX Reference Laboratory 1 6 99 17 44 50 2.400 12 BN-SO-34-XX Reference Laboratory 2 100 17 42 49 2,300 12 I3N-SO-03-RI Rigaku. Inc. 17 59 1 1 200 60 1,200 12 I3N-SO-06-RI Rigaku. Inc. 22 55 1 1 197 54 1,212 12 I3N-SO-08-RI Rigaku, Inc. 25 53 1 1 201 74 1.21 1 12 I3N-SO-13-RI Rigaku. Inc. 20 59 1 1 208 63 1,218 12 BN-SO-20-RI Rigaku. Inc. 30 64 14 196 62 1,247 12 I3N-SO-30-RI Rigaku. Inc. 34 58 1 1 212 64 1,213 12 I3N-SO-34-RI Rigaku, Inc 32 59 12 197 60 1,216 D-8 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 13 BN-SO-07-XX Reference Laboratory 110 J- 990 J+ 520 82 1,400 23,000 6,900 13 BN-SO-I6-XX Reference Laboratory 120 J- 1,100 J+ 570 86 1,500 25,000 8,100 13 13N-SO-21 -XX Reference Laboratory 150 J- 1,300 J+ 660 110 1,700 30,000 8,900 13 BN-SO-25-XX Reference Laboratory 82 J- 700 J 370 J- 64 J- 930 J- 16,000 J- 5,400 J- 13 BN-SO-33-XX Reference Laboratory 100 J- 1,100 640 100 1,600 27,000 8,000 13 BN-SO-07-RI Rigaku, Inc 786 467 700 74 870 13.940 3,698 13 BN-SO-16-R1 Rigaku,Inc 871 475 741 101 875 14,102 3,735 13 BN-SO-21-R1 Rigaku,Inc 715 482 708 81 859 13,924 3,705 13 BN-SO-25-R1 Rigaku, Inc 805 500 722 59 895 13,960 3,730 13 BN-SO-33-RI Rigaku, Inc 824 511 741 54 870 14,054 3,715 14 BN-SO-05-XX Reference Laboratory 160 J- 1,600 850 86 2,200 26,000 12,000 14 BN-SO-19-XX Reference Laboratory 150 J- 1,600 860 79 2,200 26,000 12,000 14 BN-SO-26-XX Reference Laboratory 150 J- 1,700 900 82 2,400 27,000 12,000 14 BN-SO-29-XX Reference Laboratory 150 J- 1,600 880 86 2,300 26,000 12,000 14 BN-SO-32-XX Reference Laboratory 160 J- 1,600 860 84 2.300 26,000 12,000 14 BN-SO-05-R1 Rigaku, Inc. 800 705 695 86 1,336 14,228 5,477 14 BN-SO-19-R1 Rigaku,Inc 927 713 719 120 1,303 14,345 5,496 14 BN-SO-26-RI Rigaku, Inc. 967 711 729 79 1,326 14,305 5,559 14 BN-SO-29-RI Rigaku, Inc. 901 685 714 115 1,300 14,132 5,501 14 BN-SO-32-R1 Rigaku, Inc. 894 695 719 81 1,314 14,401 5,584 15 CN-SO-Ol-XX Reference Laboratory 13 J- 13 21 190 700 38,000 1,200 15 CN-SO-04-XX Reference Laboratory 13 J- 11 21 200 680 37,000 1,200 15 CN-SO-08-XX Reference Laboratory 15 J- 15 25 210 740 43,000 1,300 15 CN-SO-IO-XX Reference Laboratory 13 J- 13 22 200 760 39,000 1,200 15 CN-SO-11-XX Reference Laboratory 17 J- 16 30 240 860 47,000 1.600 15 CN-SO-OI -Rl Rigaku,Inc 335 42 664 185 368 18,032 514 15 CN-SO-04-RI Rigaku,Inc 323 17 635 205 405 18,122 513 15 CN-SO-08-RI Rigaku, Inc. 378 43 664 158 364 18,393 505 15 CN-SO-IO-RI Rigaku, Inc. 341 35 641 188 383 18,522 531 15 CN-SO-I l-Rl Rigaku, Inc 330 38 640 146 385 18,265 518 D-9 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Mr Nl Se Ag V Zn 13 BN-SO-07-XX Reference Laboiatory 34 120 26 70 41 4.000 13 BN-SO-I6-XX Reference Laboiatory 34 130 29 77 44 4,400 13 BN-SO-21-XX Kcfcicncc Laboratory 3 6 160 35 88 52 5.100 13 BN-SO-25-XX Rcfcicncc Laboiatory 3 8 88 J- 19 J- 4S J- 28 J- 2,900 J- 13 BN-SO-33-XX Reference Laboratory 4 150 34 81 48 5,100 13 BN-SO-07-RI Rigaku, Inc. 29 68 15 195 70 2,193 13 BN-SO-I6-RI Rigaku, Inc 34 70 16 207 60 2,187 13 BN-SO-2I-RI Rigaku, lnc 31 76 14 191 59 2,174 13 BN-SO-25-R1 Rigaku. Inc 29 74 17 190 64 2,204 13 BN-SO-33-R1 Rigaku,lnc 30 73 17 199 57 2,169 14 BN-SO-05-XX Reference Laboratory 5 160 48 110 39 6.700 14 BN-SO-19-XX Reference Laboratory 5 160 48 120 39 6.700 14 BN-SO-26-XX Reference Laboratory 5 4 160 49 120 40 7,000 14 BN-SO-29-XX Reference Laboratory 54 160 48 120 41 6.800 14 BN-SO-32-XX Reference Laboratory 54 160 48 120 39 6.700 14 BN-SO-05-RI Rigaku, Inc. 18 78 16 175 57 3.096 14 BN-SO-I9-RI Rigaku, Inc. 21 80 19 177 56 3,077 14 BN-SO-26-R1 Rigaku, Inc. 18 79 18 184 59 3,118 14 BN-SO-29-R1 Rigaku, Inc 25 80 20 178 63 3,074 14 BN-SO-32-R1 Rigaku, Inc 27 81 18 175 58 3.146 15 CN-SO-Ol -XX Reference Laboratory 0 13 240 2.2 12 21 3,100 15 CN-SO-04-XX Reference Laboratory 0 14 240 1.5 12 22 2.900 15 CN-SO-08-XX Rcfcicncc Laboratory 0 16 280 1 3 U 15 26 3,200 15 CN-SO-IO-XX Reference Laboratory 0 12 240 1 9 14 22 3,000 15 CN-SO-11 -XX Reference Laboratory 0 15 320 1 3 U 16 27 3,500 15 CN-SO-Ol-Rl Rigaku. Inc. 27 123 9 227 71 1,671 15 CN-SO-04-RI Rigaku, Inc. 32 122 7 228 75 1,628 15 CN-SO-08-RI Rigaku.Inc 40 127 7 239 68 1.690 15 CN-SO-IO-RI Rigaku, Inc 37 126 7 232 70 1.658 15 CN-SO-11 -Rl Rigaku. Inc 35 125 8 232 62 1,689 D-10 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 16 AS-SO-02-XX Reference Laboratory 2 6 UJ 18 50 180 140 48,000 1,600 16 AS-SO-06-XX Reference Laboratory 2.4 UJ 19 52 190 130 52,000 1,600 16 AS-SO-IO-XX Reference Laboratory 1 9 J- 18 48 180 110 45,000 1,400 16 AS-SO-I l-XX Reference Laboratory 3.7 J- 22 63 230 150 52,000 2,100 16 AS-SO-I3-XX Reference Laboratory 2.4 UJ 20 57 200 150 52,000 1,700 16 AS-SO-02-RI Rigaku, Inc 247 7 518 147 62 18,017 607 16 AS-SO-06-R1 Rigaku, Inc. 229 -13 523 105 56 17,814 636 16 AS-SO-IO-RI Rigaku, Inc. 234 1 534 123 64 17,877 639 16 AS-SO-1 l-RI Rigaku, Inc. 259 -11 519 154 64 17,923 629 16 AS-SO-13-RI Rigaku, Inc. 226 8 515 135 66 18,167 646 17 AS-SO-OI-XX Reference Laboratory 3 8 J- 26 100 420 250 100,000 3,200 17 AS-SO-04-XX Reference Laboratory 6.4 UJ 22 110 480 260 110,000 3,300 17 AS-SO-07-XX Reference Laboratory 3.6 J - 21 97 380 240 88,000 2,900 17 AS-SO-09-XX Reference Laboratory 2.6 UJ 25 J- 100 J- 390 J- 250 J- 94,000 J- 3,200 J- 17 AS-SO-12-XX Reference Laboratory 2.6 UJ 29 120 440 270 93,000 3,300 17 AS-SO-OI-RI Rigaku, Inc. 169 -47 400 248 77 28,556 994 17 AS-SO-04-RI Rigaku, Inc. 140 -42 406 256 96 28,250 992 17 AS-SO-07-R1 Rigaku, Inc. 142 -61 406 233 91 28,106 1,014 17 AS-SO-09-RI Rigaku, Inc 154 -35 406 255 82 28,894 991 17 AS-SO-I2-RI Rigaku, Inc. 115 -42 368 294 89 28,910 966 18 SB-SO-03-XX Reference Laboratory 1 2 UJ 9 051 U 150 48 38,000 18 18 SB-SO-06-XX Reference Laboratory 1.7 J- 8 0.51 U 140 44 35,000 16 18 SB-SO-I4-XX Reference Laboratory 4.1 J- 9 0.51 U 150 46 37,000 17 18 SB-SO-38-XX Reference Laboratory 1.3 UJ 10 0.51 U 150 57 37,000 18 18 SB-SO-41-XX Reference Laboratory 1 3 UJ 9 051 U 160 58 40,000 19 18 SB-SO-47-XX Reference Laboratory 1 3 UJ 8 051 U 140 44 34,000 16 18 SB-SO-5I-XX Reference Laboratory 1.3 UJ 9 0.51 U 160 50 40,000 18 18 SB-SO-03-RI Rigaku, Inc. 241 14 640 152 29 20,833 -46 18 SB-SO-06-RI Rigaku, Inc. 200 19 597 144 31 20,593 -54 18 SB-SO-14-R1 Rigaku, Inc 191 23 585 151 32 20,649 -51 18 SB-SO-38-RI Rigaku, Inc 211 21 609 180 31 20,656 -63 18 SB-SO-4I-RI Rigaku, Inc 187 15 589 151 28 20,630 -41 18 SB-SO-47-RI Rigaku, Inc. 184 24 601 154 31 20,564 -39 18 SB-SO-5I-RI Rigaku, Inc. 183 6 590 146 32 20,716 -55 D-l 1 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No Sample ID Source of Data l-lK Nl Sc Ar V Zn 16 AS-SO-02-XX Rcfeicncc Laboratory 0 76 91 2 6 U 4 5 42 3.300 16 AS-SO-06-XX Reference Laboratory 0 74 93 2 6 U 4 S 44 3.500 16 AS-SO-IO-XX Reference Laboratory 0 78 84 1 1 U 44 42 3.000 16 AS-SO-I l-XX Rcfciencc Laboiatory 0 72 120 1 1 U 5 6 54 3,S00 16 AS-SO-I3-XX Rcfeicncc Laboratory 0 79 100 3 5 2 50 3.S00 16 AS-SO-02-RI Rigaku.Inc 14 49 3 181 61 1.447 16 AS-SO-06-RI Rigaku. Inc 15 40 3 ISI 56 1.475 16 AS-SO-IO-RI Rigaku. Inc 5 49 3 174 52 1.441 16 AS-SO-11-RI Rigaku.Inc 14 49 1 179 63 1.457 16 AS-SO-I3-RI Rigaku.Inc 7 45 2 170 57 1,509 17 AS-SO-Ol-XX Refcicncc Laboratory 1 4 ISO 2 6 U 93 66 6.900 17 AS-SO-04-XX Reference Laboratoiy 1 3 200 6 2 U 12 72 7.400 17 AS-SO-07-XX Rcfeicncc Laboratory 1 4 160 2 7 89 63 6.300 17 AS-SO-09-XX Rcfeicncc Laboiatory 1 4 170 J- 2 6 U 9 6 J - 65 J- 6,800 J- 17 AS-SO-I 2-XX Rcfciencc Laboiatory 1 4 190 2 6 U 3 2 73 7,500 17 AS-SO-OI-R1 Rigaku. Inc -12 57 -4 135 70 2.628 17 AS-SO-04-RI Rignku. Inc -11 59 _2 133 57 2,696 17 AS-SO-07-RI Rigaku. Inc -16 61 -3 135 56 2,725 17 AS-SO-09-R1 Rigaku, Inc -14 62 .2 135 52 2,602 17 AS-SO-12-R1 Rigaku. Inc -1 1 56 -1 123 62 2.698 18 SI3-SO-03-XX Refcicncc Laboratoiy 62 210 1 3 U 1 3 U 67 90 18 SI3-SO-06-XX Reference Laboratoiy 55 200 1 3 U 1 3 U 63 82 18 SI3-SO-I4-XX Reference Laboratory 55 210 1 3 U 1 3 U 66 95 18 S13-SO-38-XX Reference Laboratoiy 56 210 1 3 U 1 3 U 68 91 18 SI3-SO-41 -XX Refcicncc Laboiatory 54 230 1 3 U 1 3 U 71 96 IS S13-SO-47-XX Reference Laboratory 58 200 1 3 U 1 3 U 62 82 18 SI3-SO-51 -XX Rcfciencc Laboratoiy 54 230 1 3 U 1 3 U 74 93 18 SI3-SO-03-RI Rigaku. Inc 48 107 6 216 117 63 IS SI3-SO-06-RI Rigaku, Inc. 47 99 6 208 116 62 IS SI3-SO-I4-RI Rigaku. Inc. 37 98 4 199 110 63 IS SI3-SO-38-RI Rigaku, Inc. 46 100 7 210 1 11 63 IS SI3-SO-41 -R1 Rigaku. Inc. 45 100 5 204 113 62 IS SI3-SO-47-RI Rigaku, Inc. 38 106 7 204 118 61 IS SI3-SO-51 -Rl Rigaku, Inc 48 97 7 209 148 63 D-12 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 19 SB-SO-05-XX Reference Laboratory 1 6 J- 9 0.51 U 140 46 35,000 16 19 SB-SO-18-XX Reference Laboratory 1.2 UJ 10 0.51 U 150 46 38,000 17 19 SB-SO-30-XX Reference Laboratory 3.2 J - 7 0.51 U 94 27 22,000 10 19 SB-SO-40-XX Reference Laboratory 2.2 J - 9 051 U 120 40 33,000 15 19 SB-SO-53-XX Reference Laboratory 1.2 UJ 10 0.51 U 140 44 37,000 17 19 SB-SO-05-RI Rigaku, Inc 212 4 608 158 24 20,004 -52 19 SB-SO-I8-RI Rigaku, Inc. 209 16 605 137 25 19,723 -61 19 SB-SO-30-RI Rtgaku, Inc. 231 21 618 161 30 19,809 -47 19 SB-SO-40-RI Rigaku, Inc. 236 -9 623 146 28 19,764 -40 19 SB-SO-53-R1 Rigaku, Inc. 241 35 645 125 27 19,905 -50 20 SB-SO-08-XX Reference Laboratory 5.4 J- 13 0.51 U 120 39 32,000 17 20 SB-SO-11 -XX Reference Laboratory 5 7 J- 13 0.51 U 140 46 36,000 20 20 SB-SO-2I-XX Reference Laboratory 4.9 J 13 0.51 U 130 43 34,000 18 20 SB-SO-39-XX Reference Laboratory 4 7 J- 13 051 U 140 46 34,000 19 20 SB-SO-42-XX Reference Laboratory 4.6 J- 13 051 U 140 45 35,000 18 20 SB-SO-08-RI Rigaku, Inc 172 27 581 117 28 18,535 -42 20 SB-SO-11-R1 Rigaku, Inc. 179 11 600 123 30 18,371 -38 20 SB-SO-21-RI Rigaku,Inc 192 4 578 135 78 19,571 -66 20 SB-SO-39-RI Rigaku, Inc 194 II 586 135 24 18,504 -31 20 SB-SO-42-R1 Rigaku, Inc. 183 7 578 112 28 18,441 -40 21 SB-SO-22-XX Reference Laboratory 10 J 18 0.51 U 120 37 29,000 22 21 SB-SO-25-XX Reference Laboratory 6.8 J+ 18 0.51 U 120 37 29,000 22 21 SB-SO-27-XX Reference Laboratory 6.7 J+ 18 051 U 120 37 29,000 22 21 SB-SO-35-XX Reference Laboratory 6 J+ 17 051 U 110 35 28,000 21 21 SB-SO-44-XX Reference Laboratory 6 8 J+ 18 051 U 120 37 29,000 22 21 SB-SO-22-RI Rigaku,Inc 157 28 591 132 32 15,830 -39 21 SB-SO-25-R1 Rigaku, Inc 181 16 625 122 31 15,907 -35 21 SB-SO-27-RI Rigaku, Inc. 143 14 578 149 32 15,846 -39 21 SB-SO-35-RI Rigaku, Inc. 128 21 552 135 31 15,679 -51 21 SB-SO-44-RI Rigaku, Inc. 139 12 574 164 26 15,749 -57 D-13 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No Sample ID Source of Data "k Ni Sc As V Zn 19 SB-SO-05-XX Reference Laboiatory 540 200 1 3 U 1 3 U 61 80 19 SB-SO-I8-XX Rcfcicncc Laboratory 280 210 1 3 U 1.3 U 70 84 19 SB-SO-30-XX Rcfcicncc Lnboiatory 290 120 1 3 J+ 1 3 U 43 50 19 S13-SO-40-XX Reference Laboratory 280 180 1.3 U 1 3 U 58 74 19 SI3-SO-53-XX Rcfcicncc Laboiatory 270 200 1 3 U 1 3 U 64 81 19 SB-SO-05-R1 Rigaku, Inc I4S 91 6 212 114 54 19 SB-SO-1S-R1 Rigaku. Inc 134 99 4 212 98 62 19 SI3-SO-30-R1 Rigaku. Inc 160 92 6 219 95 52 19 SI3-SO-40-RI Rigaku, Inc 160 95 5 218 107 61 19 SB-SO-53-RI Rigaku.Inc 125 97 7 218 142 55 20 SI3-SO-OS-XX Reference Laboratory 730 180 1 3 U 1 3 U 57 70 20 SI3-SO-11 -XX Reference Laboratory 810 200 1 3 U 1 3 IJ 66 84 20 SI3-SO-21 -XX Reference Laboiatoiy 740 190 1 3 U 1 3 U 58 75 20 SI3-SO-39-XX Reference Laboiatory 790 200 1 3 U 1 3 U 62 77 20 SI3-SO-42-XX Rcfcicncc Laboratoiy 740 200 1 3 U 1 3 U 65 78 20 SB-SO-08-RI Rigaku. Inc. 358 96 4 201 124 58 20 SI3-SO-11-RI Rigaku. Inc 345 93 4 202 141 61 20 S13-SO-21-R1 Rigaku.Inc 32 1.366 14 218 134 I.S65 20 SI3-SO-39-RI Rigaku.Inc 346 91 5 212 118 56 20 SB-SO-42-R1 Rigaku. Inc 341 89 7 200 159 54 21 SB-SO-22-XX Reference Laboratoiy 3300 160 1 3 U 1.3 U 52 64 J- 21 SB-SO-25-XX Reference Laboiatory 3000 160 1 3 U 1 3 U 54 63 21 SB-SO-27-XX Rcfcicncc Laboiatoiy 3100 170 1 3 U 1 3 U 54 65 21 SB-SO-35-XX Rcfcicncc Laboratoiy 3100 160 1.3 U 1 3 U 50 62 21 SB-SO-44-XX Rcfcicncc Laboiatoiy 3000 170 1 3 U 1.3 U 53 64 21 SI3-SO-22-RI Rigaku. Inc 803 83 5 204 140 55 2! SB-SO-25-RI Rigaku,Inc 787 85 7 209 125 53 21 SB-SO-27-RI Rigaku,Inc 755 SI 6 194 121 51 21 SB-SO-35-RI Rigaku, Inc 773 90 6 196 121 55 21 SB-SO-44-RI Rigaku, Inc. 760 89 6 194 195 50 D-14 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 22 SB-SO-23-XX Rcfcicncc Laboratory 48 J- 37 0.1 u 21 7 4,500 36 22 SB-SO-28-XX Reference Laboratory 42 1- 36 0.1 u 21 7 4,400 36 22 SB-SO-32-XX Reference Laboratory 46 J- 40 0 1 u 23 76 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-R1 Rigaku, Inc 113 -6 703 77 11 4,597 -1 22 SB-SO-28-R1 Rigaku, Inc 89 -3 608 110 22 4,931 -4 22 SB-SO-32-RI Rigaku,Inc 56 65 517 103 19 4,800 -1 22 SB-SO-43-RI Rigaku,Inc 61 84 547 110 25 4,798 2 22 SB-SO-48-RI Rigaku, Inc. 56 84 538 76 21 4,797 -14 23 SB-SO-02-XX Reference Laboratory 44 J- 23 J- 0 5 U 130 43 35,000 22 J- 23 SB-SO-07-XX Reference Laboratory 45 J 22 05 U 120 38 35,000 23 23 SB-SO-IO-XX Reference Laboratory 62 J 26 0.5 U 140 44 41,000 27 23 SB-SO-26-XX Reference Laboratory 61 J 30 0.5 U 160 50 46,000 31 23 SB-SO-50-XX Reference Laboratory 57 J 27 0.5 U 140 46 42,000 28 23 SB-SO-02-RI Rigaku, Inc. 182 16 571 117 32 21,148 -64 23 SB-SO-07-RI Rigaku, Inc. 230 20 600 125 26 21,733 -49 23 SB-SO-IO-RI Rigaku, Inc. 198 17 569 146 24 21,449 -57 23 SB-SO-26-R1 Rigaku, Inc. -47 -196 46 -124 -37 4,098 -234 23 SB-SO-50-RI Rigaku. Inc. 218 40 596 198 30 21,439 -50 24 SB-SO-OI-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 05 U 140 45 47,000 30 24 SB-SO-52-XX Rcfciencc Laboratory 150 J 62 0 5 U 140 47 46,000 29 24 SB-SO-OI-RI Rigaku, Inc. 260 36 604 140 28 22,448 -48 24 SB-SO-16-RI Rigaku, Inc. 235 42 578 178 22 22,611 -49 24 SB-SO-24-R1 Rigaku, Inc 233 42 596 171 28 22,572 -45 24 SB-SO-45-RI Rigaku, Inc 216 23 558 129 28 22,432 -48 24 SB-SO-52-RI Rigaku, Inc. 245 29 564 129 26 22,574 -54 D-15 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Mr Nl Sc Ak V Zn 22 SB-SO-23-XX Reference Laboiatory S500 26 0 22 J 0 26 UJ 13 s 22 SB-SO-28-XX Kcference Laboratory 8S00 26 0 26 U 0 26 UJ 13 s 22 SB-SO-32-XX Rcfcicncc Laboratory S900 28 0 36 0.1 UJ 14 9 22 SI3-SO-43-XX Rcfcicncc Laboratory 7600 24 0 26 U 0 26 UJ 13 8 22 SI3-SO-4S-XX Reference Laboratory S200 25 0 26 U 0 1 UJ 13 S 22 SB-SO-23-RI Rigaku.Inc 2,552 35 8 231 160 2S 22 SB-SO-2S-R1 Rigaku, Inc 2.712 39 S 209 196 32 22 S13-SO-32-R1 Rigaku, Inc 2.621 33 11 179 164 31 22 SB-SO-43-RI Rigaku, Inc. 2.651 36 7 IS4 322 29 22 SI3-SO-48-RI Rigaku,Inc. 2,681 36 9 179 315 32 23 SB-SO-02-XX Reference Laboratoiy 130 J+ ISO 1.2 U 1 2 UJ 59 SS 23 SB-SO-07-XX Rcfcicncc Laboratoiy 270 170 1 4 1.6 53 S6 23 SB-SO-IO-XX Reference Laboratory 220 200 2 8 1.8 59 100 23 SB-SO-26-XX Reference Laboratoiy 260 220 3 4 I.S 68 110 23 SB-SO-50-XX Rcfcicncc Laboratoiy 200 200 2 9 1 S 61 100 23 SB-SO-02-RI Rigaku. Inc 76 SS 4 196 103 70 23 SB-SO-07-RI Rigaku,Inc 75 94 4 206 111 66 23 SB-SO-IO-RI Rigaku, Inc 70 91 5 202 102 61 23 SB-SO-26-RI Rigaku. Inc -88 2 -22 11 8 -9 23 SB-SO-50-RI Rigaku, Inc 72 96 5 205 154 59 24 SB-SO-OI-XX Reference Laboiatory 400 190 I.S 2 3 65 95 24 SB-SO-I6-XX Rcfcicncc Laboratory 480 190 1 9 2 2 65 97 24 SB-SO-24-XX Reference Laboiatory 420 200 2 5 2 3 67 95 24 SB-SO-45-XX Rcfcicncc Laboiatory 450 190 2 S 2 1 J- 63 93 24 SB-SO-52-XX Rcfcicncc Laboratory 430 190 1 8 2 2 64 90 24 SB-SO-OI-R1 Rigaku, Inc 105 S3 4 208 107 60 24 SB-SO-16-R1 Rigaku. Inc. 100 80 5 199 113 60 24 SB-SO-24-R] Rigaku,Inc. 108 SI 6 205 112 59 24 SB-SO-45-RI Rigaku. Inc. 105 85 3 193 135 54 24 SH-SO-52-RI Rigaku. Inc 11 1 86 5 202 135 59 D-16 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 25 SB-SO-I3-XX Reference Laboratory 430 J 160 I U 140 46 61,000 36 25 SB-SO-19-XX Reference Laboratory 310 J 100 05 U 100 32 42,000 25 25 SB-SO-33-XX Reference Laboratory 350 J 110 0.5 U 100 33 45,000 28 25 SB-SO-37-XX Reference Laboratory 340 J 130 1 U 120 39 51,000 31 25 SB-SO-55-XX Reference Laboratory 340 J 120 0.5 U 120 37 49,000 29 25 SB-SO-I3-R1 Rigaku,Inc 322 46 570 144 22 25,192 -54 25 SB-SO-I9-RI Rigaku,Inc 329 48 574 123 27 25,518 -58 25 SB-SO-33-RI Rigaku,Inc 296 45 552 146 27 25,443 -52 25 SB-SO-37-RI Rigaku, Inc. 272 55 565 110 25 25,224 -60 25 SB-SO-55-RI Rigaku, Inc. 308 52 594 106 23 25,157 -53 26 SB-SO-I2-XX Reference Laboratory 620 J 190 1 U 100 33 55,000 43 26 SB-SO-15-XX Reference Laboratory 600 J- 170 J- 1 U 91 J- 30 J- 51,000 J- 40 J- 26 SB-SO-17-XX Reference Laboratory 800 J+ 210 1 U 110 37 61,000 48 26 SB-SO-46-XX Reference Laboratory 740 J+ 190 1 U 120 35 57,000 47 26 SB-SO-54-XX Reference Laboratory 280 31 0.2 U 25 5 8 8,600 5 J- 26 SB-SO-I2-RI Rigaku, Inc. 327 60 535 156 21 28,010 -60 26 SB-SO-15-RI Rigaku,Inc 368 59 534 185 18 28,182 -59 26 SB-SO-17-RI Rigaku,Inc 353 56 546 140 16 27,967 -62 26 SB-SO-46-RI Rigaku, Inc 338 39 546 129 21 27,861 -61 26 SB-SO-54-RI Rigaku,Inc 358 56 561 105 19 28,180 -62 27 KP-SE-08-XX Reference Laboratory 6.2 3 0.11 U 88 3 8 840 300 J- 27 KP-SE-11-XX Reference Laboratory 5.6 3 0.11 U 96 4 1 940 310 J- 27 KP-SE-17-XX Reference Laboratory 49 3 0 11 U 98 4.1 940 300 J- 27 KP-SE-25-XX Reference Laboratory 6 3 0 11 U 99 4.3 960 310 J- 27 KP-SE-30-XX Reference Laboratory 5.7 3 0.11 U 83 3.6 830 300 J- 27 KP-SE-08-RI Rigaku, Inc. 234 151 881 69 24 3,769 346 27 KP-SE-I l-RI Rigaku, Inc. 184 119 787 88 22 3,754 357 27 KP-SE-I7-RI Rigaku, Inc 249 148 935 76 24 3,754 355 27 K.P-SE-25-R1 Rigaku,Inc 250 161 940 65 21 3,743 343 27 K.P-SE-30-RI Rigaku,Inc 249 156 940 60 18 3,725 357 D-17 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No Sample ID Source of Data Mr Ni Se AS V Zn 25 SI3-SO-I3-XX Reference Laboratory 850 ISO 4 4 2 2 UJ 74 70 25 SB-SO-I9-XX Reference Laboratory 740 120 2 5 I.S 51 51 25 SI3-SO-33-XX Refeicnce Laboiatory 870 130 3 2 J 52 56 25 SI3-SO-37-XX Reference Laboiatory 790 150 2 5 U 2 UJ 63 58 25 SI3-SO-55-XX Reference Laboiatory 900 140 2 5 22 J 61 60 25 SB-SO-I3-RI Rigaku, Inc 161 72 3 203 121 52 25 S13-SO-19-K1 Rigaku, Inc 175 70 3 201 127 44 25 SI3-SO-33-KI Rigaku, Inc. 161 72 2 201 102 44 25 SI3-SO-37-RI Rigaku, Inc. 155 69 5 187 120 4S 25 SI3-SO-55-RI Riuaku, Inc. 160 73 3 209 157 46 26 SB-SO-I2-XX Reference Laboratoiy 1,400 110 2 5 U 2 1 UJ 59 42 26 S13-SO-15-XX Reference Laboratory 1,100 100 J- 3 4 1 6 UJ 52 J- 36 J- 26 S13-SO-17-XX Refeicnce Laboiatory 1,200 120 2 8 2.3 UJ 60 42 26 SB-SO-46-XX Reference Laboiatory 670 120 2 6 2 2 UJ 57 41 26 S13-SO-54-XX Reference Laboratoiy 560 20 0 5 U 0.5 UJ 11 6 26 SB-SO-I2-RI Rigaku, Inc 218 60 1 192 134 37 26 SB-SO-15-RI Rigaku. Inc 225 59 2 198 123 36 26 SI3-SO-I7-RI Rigaku. Inc 202 54 0 192 128 36 26 SI3-SO-46-RI Rigaku. Inc 227 53 2 200 154 37 26 SI3-SO-54-RI Rigaku, Inc 236 55 2 192 154 40 27 KP-SC-OS-XX Reference Laboratory 0 09 U 42 0 27 U 0 27 UJ 4 5 27 KP-SIM 1-XX Reference Laboratory 0.08 U 46 0 43 0 27 UJ 4 6 27 KP-SII-I7-XX Reference Laboratoiy 0.08 U 47 0 27 U 0 27 UJ 4 5 27 KP-SI--25-XX Reference Laboratory 0.1 U 47 0 26 U 0 27 UJ 4 5 27 KP-SI--30-XX Rcfcicnce Laboratoiy 0.1 U 39 0 24 U 0 27 UJ 4 5 27 KP-SI--08-RI Rigaku, Inc 69 70 20 289 25 36 27 KP-SI--I l-Rl Rigaku. Inc 78 69 18 260 22 32 27 KP-SIM7-RI Rigaku. Inc 77 64 20 304 25 38 27 KP-SII-25-RI Rigaku. Inc. 74 65 20 303 21 33 27 K P-SII-30-R1 Rigaku. Inc 73 58 21 302 34 33 D-18 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 28 KP-SE-OI-XX Reference Laboratory 3.2 2 0.1 U 34 2 2 480 310 J- 28 K.P-SE-I2-XX Reference Laboratory 3.1 2 0.1 U 42 2 5 510 320 J- 28 K.P-SE-I4-XX Reference Laboratory 11 J- 2 0.1 U 46 J- 2 7 J+ 520 J- 680 J- 28 K.P-SE-I9-XX Reference Laboratory 3 2 0.1 U 44 2.3 510 330 28 K.P-SE-28-XX Reference Laboratory 3.3 2 0.1 U 45 2 3 520 320 28 KP-SII-01 -Rl Rigaku, Inc 301 126 974 33 23 3,454 352 28 KP-SE-I2-RI Rigaku,Inc 273 147 906 26 25 3,507 340 28 KP-SE-I4-RI Rigaku, Inc 306 143 957 67 19 3,392 321 28 KP-SE-I9-R1 Rigaku,Inc 282 116 950 -3 16 3,396 329 28 KP-SE-28-R1 Rigaku,Inc 243 104 891 48 18 3,444 342 29 TL-SE-04-XX Reference Laboratory 1.2 U 10 0.5 U 62 1,900 42,000 32 29 TL-SII-I0-XX Reference Laboratory 1.2 U 10 0.5 U 64 2,000 43,000 35 29 TL-SE-I2-XX Reference Laboratory 1.2 U 10 0.5 U 66 2,100 44,000 34 29 TL-SE-I5-XX Reference Laboratory 1.2 U 9 05 U 54 1,800 36,000 28 29 TL-SE-20-XX Reference Laboratory 1.2 U 10 0.5 U 64 2,000 42,000 32 29 TL-SE-24-XX Reference Laboratory 1 2 U 11 0.5 U 67 2,100 43,000 37 29 TL-SE-26-XX Reference Laboratory 1 2 U 10 0.5 U 62 2,000 40,000 34 29 TL-SE-04-RI Rigaku,Inc 112 -31 478 54 923 21,259 -57 29 TL-SE-10-RI Rigaku, Inc. 119 -14 493 76 922 21,398 -68 29 TL-SE-12-RI Rigaku, Inc. 116 -25 481 65 909 21,337 -79 29 TL-SE-15-RI Rigaku, Inc. 114 -14 479 93 922 21,444 -55 29 TL-S1I-20-RI Rigaku, Inc. 127 -24 483 74 942 21,349 -61 29 TL-SE-24-RI Rigaku,Inc 147 -21 505 64 963 21,685 -62 29 TL-SE-26-RI Rigaku,Inc 136 -16 510 77 930 21,391 -72 30 TL-SE-03-XX Reference Laboratory 2 5 U 9 1 U 91 1,600 63,000 12 30 TL-SE-I9-XX Reference Laboratory 2.5 U 10 1 U 96 1,700 66,000 13 30 TL-SE-23-XX Reference Laboratory 2.5 U 9 1 U 92 1,600 64,000 12 30 TL-SE-25-XX Reference Laboratory 2.5 U 10 1 U 91 1,600 62,000 II 30 TL-SE-3I-XX Reference Laboratory 2 5 U 10 1 U 110 1,800 74,000 13 30 TL-SE-03-RI Rigaku, Inc. 69 -37 383 83 689 29,357 -107 30 TL-SE-19-RI Rigaku, Inc. 71 -16 401 100 675 29,326 -93 30 TL-SE-23-RI Rigaku,Inc 67 -42 417 118 678 29,328 -104 30 TL-SE-25-RI Rigaku,Inc 62 -44 413 113 657 29,513 -101 30 TL-SE-3I-RI Rigaku,Inc 64 -26 393 91 682 29,358 -91 D-19 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Mr Ni Se Ar V Zn 28 KP-SE-01 -XX Reference Labointory 0 05 U 16 0 26 U 0 26 UJ 2 J 6 28 KP-SE-I2-XX Reference Laboiatoiy 0 06 U 20 0 26 U 0 26 UJ 2 J S 2S KP-SE-14-XX Reference Laboratory 0 07 U 23 J- 0.26 U 0.26 UJ 3 J 7 28 K.P-SE-I9-XX Reference Labotatory 0.04 U 22 0 26 U 0 26 U 2 J 7 28 KP-S E-28-XX Reference Laboratory 0 06 U 22 0 26 U 0 26 U 2 J 6 28 KP-SE-01 -Rl Rigaku, Inc 70 45 20 318 22 31 28 KP-SE-I2-RI Rigaku. Inc 60 44 17 308 30 55 28 KP-SE-I4-RI Rigaku. Inc. 69 42 17 341 30 30 28 KP-SE-I9-RI Rigaku, Inc. 66 46 20 316 20 35 28 KP-SE-28-RI Rigaku, Inc. 69 50 18 295 22 30 29 TL-SE-04-XX Reference Laboratory 0 26 J- 71 1 2 U 1 3 95 160 29 TL-SE-I0-XX Reference Laboratoiy 0 19 J- 72 1 2 U 1 2 U 95 160 29 TL-SE-I2-XX Rcfcicncc Laboratoiy 0 22 J- 75 1 2 U 1 2 U 100 170 29 TL-SE-15-XX Reference Laboratoiy 0 28 J- 63 1 2 U 1 U 84 140 29 TL-SE-20-XX Reference Laboiatoiy 0 26 J- 74 1 2 U 1.2 U 100 160 29 TL-SE-24-XX Reference Laboiatoiy 0 26 J- 77 1 2 U 1.3 U 100 170 29 TL-SE-26-XX Reference Laboratory 0 24 J- 70 1 2 U 1.2 U 96 160 29 TL-SE-04-RI Rigaku, Inc 10 44 1 166 136 93 29 TL-SE-I0-RI Rigaku, Inc 4 44 3 173 128 91 29 TL-SE-I2-R1 Rigaku, Inc 7 43 -1 166 139 91 29 TL-SE-15-RI Rigaku, Inc -1 45 1 161 140 93 29 TL-SE-20-RI Rigaku, Inc 5 41 2 164 149 90 29 TL-SE-24-RI Rigaku,Inc 16 41 1 183 148 99 29 TL-SE-26-R1 Rigaku,Inc 1 48 2 175 145 89 30 TL-SE-03-XX Reference Laboratory 0 32 J- 110 2.5 U 0 94 U 140 200 30 TL-SE- 19-XX Reference Laboratory 0 32 J- 120 2.5 U 1 1 U 150 210 30 TL-SE-23-XX Reference Laboratory 0 41 J - 110 2.5 U 1 3 U 150 200 30 TL-SE-25-XX Reference Laboratory 0 44 J- 1 10 2.5 U 0 94 U 150 200 30 TL-SE-31 -XX Reference Laboratory 0 57 J- 130 2 5 U 1 2 U 170 230 30 TL-SE-03-RI Rigaku, Inc. -17 50 -1 140 173 89 30 TL-SE-I9-RI Rigaku, Inc. -7 51 -2 141 187 85 30 TL-SE-23-RI Rigaku, Inc. -7 48 -3 141 204 87 30 TL-SE-25-RI Rigaku, Inc. -10 49 -1 146 193 91 30 TL-SE-3 l-RI Rigaku, Inc -8 54 0 139 192 89 D-20 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 31 TL-SE-01-XX Reference Laboratory 1 2 UJ 9 05 U 110 1,400 19,000 48 J- 31 TL-SE-I l-XX Reference Laboratory 1 2 UJ 15 0.5 U 140 1,600 28,000 54 J- 31 TL-SE-I4-XX Reference Laboratory 1 2 UJ 10 0.27 J 110 1,500 18,000 50 J- 31 TL-SE-I8-XX Reference Laboratory 1.2 UJ 10 0.5 U 150 1,300 24,000 46 J- 31 TL-SE-22-XX Reference Laboratory 1.2 UJ 11 0.5 U 150 1,700 26,000 54 J- 31 TL-SE-27-XX Reference Laboratory 1.2 UJ 10 0.28 J 130 1,500 19,000 51 J- 31 TL-SE-29-XX Reference Laboratory 1.2 UJ 11 0.22 J 140 1,600 23,000 51 J- 31 TL-SE-OI-RI Rigaku, Inc. 184 6 549 96 697 17,602 -55 31 TL-SE-I l-RI Rigaku, Inc. 144 -26 522 83 708 18,031 -61 31 TL-SE-I4-RI Rigaku, Inc. 182 -12 544 110 713 18,509 -48 31 TL-SE-I8-RI Rigaku, Inc 164 6 526 88 726 18,075 -54 31 TL-SE-22-R1 Rigaku, Inc 167 -15 533 110 724 18,371 -47 31 TL-SE-27-RI Rigaku, Inc. 170 -24 537 134 689 18,594 -64 31 TL-SE-29-RI Rigaku, Inc 176 -15 529 117 703 18,315 -62 32 LV-SE-02-XX Reference Laboratory 1.3 UJ 28 051 U 72 33 23,000 20 J- 32 LV-SE-IO-XX Reference Laboratory 1.3 UJ 34 051 U 84 42 28,000 25 J- 32 LV-SE-22-XX Reference Laboratory 1.3 UJ 30 051 U 69 33 23,000 22 J- 32 LV-SE-25-XX Reference Laboratory 1.3 UJ 31 051 u 74 36 25,000 23 J- 32 LV-SE-31-XX Reference Laboratory 1 3 UJ 32 0.51 u 78 36 25,000 49 J- 32 LV-SE-35-XX Reference Laboratory 1 3 UJ 31 J- 0.51 u 74 J- 35 24,000 J- 22 J- 32 LV-SE-50-XX Reference Laboratory 2 5 U 29 1 u 74 34 24,000 24 J- 32 LV-SE-02-RI Rigaku, Inc 182 25 601 71 29 15,603 -30 32 LV-SE-I0-R1 Rigaku, Inc. 182 37 615 65 24 15,490 -29 32 LV-SE-22-RI Rigaku,Inc 189 32 622 76 28 15,618 -45 32 LV-SE-25-RI Rigaku, Inc 213 44 653 88 29 15,568 -39 32 LV-SE-31-RI Rigaku, Inc. 201 31 624 60 22 15,786 -39 32 LV-SE-35-RI Rigaku, Inc. 195 42 619 69 24 15,585 -36 32 LV-SE-50-RI Rigaku, Inc. 177 28 591 60 31 15,658 -44 33 LV-SE-12-XX Reference Laboratory 26 U 190 1 u 55 34 72,000 19 J- 33 LV-SE-26-XX Reference Laboratory 2.6 U 220 1 u 64 39 83,000 25 J- 33 LV-SE-33-XX Reference Laboratory 2.6 U 170 1 u 52 31 66,000 21 J- 33 LV-SE-39-XX Reference Laboratory 2.6 U 190 1 u 58 35 74,000 22 J - 33 LV-SE-42-XX Reference Laboratory 2 7 U 170 1.1 u 50 30 65,000 22 J- 33 LV-SE-12-R1 Rigaku, Inc. 277 29 545 154 16 35,880 -88 33 LV-SE-26-RI Rigaku, Inc. 302 47 544 96 15 35,793 -72 33 LV-SE-33-RI Rigaku,Inc 275 25 539 96 18 35,182 -83 33 LV-SE-39-RI Rigaku,Inc 303 33 529 101 14 35,840 -78 33 LV-SE-42-R1 Rigaku, Inc 238 42 499 125 15 36,267 -81 D-21 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Dala Ms Ni Se Ag V Zn 31 TL-S11-01-XX Reference Laboratory 0 07 U 180 1.2 U 5 7 J- 75 130 31 TL-SIM 1-XX Reference Laboratory 0.02 U 210 1 2 U 5 5 J- 85 140 31 TL-SIM 4-XX Reference Labointory 0.08 U 180 1 2 U 5 7 J- 73 140 31 TL-SIM S-XX Refeicnce Laboiatory 0 03 U 190 1 2 U 6.3 J- 70 120 31 TL-SE-22-XX Reference Laboratory 0.0S U 210 1 2 U 6 5 J- 80 150 31 TL-SE-27-XX Reference Laboiatory 0.02 U 200 1 2 U 7 8 J- 67 140 31 TL-Sli-29-XX Reference Laboratory 0 08 U 200 1 2 U 5 9 J- SO 140 31 TL-SE-OI-RI Rigaku, Inc. 10 94 2 184 116 72 31 TL-SIM l-RI Rigaku, inc. 16 99 1 190 119 70 31 TL-SIM4-RI Rigaku, Inc 14 103 2 186 127 72 31 TL-SIM 8-RI Rigaku, Inc 5 94 2 188 123 67 31 TL-S11-22-R1 Rigaku, Inc 27 103 2 189 117 72 31 TL-S1I-27-RI Rigaku, Inc 8 98 4 191 131 67 31 "1" L-SII-29-RI Rigaku, Inc 27 98 1 185 123 74 32 LV-SL-02-XX Refeicnce Laboratory 0.02 U 160 3 8 1 3 UJ 53 65 32 LV-SIMO-XX Reference Laboratory 0.02 U 200 4 7 1 3 UJ 66 77 32 LV-SI--22-XX Reference Labointory 1 1 170 5 2 1 3 UJ 51 66 32 LV-SE-25-XX Reference Laboratory 1 170 5 1 1 3 UJ 56 70 32 LV-SE-31 -XX Refeicnce Labointory 1 180 5 1 1 3 UJ 58 70 32 LV-SE-35-XX Reference Laboratory 1 4 170 J- 5 1 3 UJ 55 J- 67 J- 32 LV-SE-50-XX Refeicnce Laboiatory 1 2 170 3.3 2 5 U 57 65 32 LV-SE-02-RI Rigaku, Inc. 34 75 7 216 82 51 32 LV-S1M0-R1 Rigaku. Inc 31 75 6 213 83 55 32 LV-SL-22-R1 Rigaku, Inc. 32 75 8 21S 87 53 32 LV-SI--25-RI Rigaku, Inc 31 74 7 225 87 79 32 LV-SL-31 -R1 Rigaku. Inc 35 74 5 209 S4 53 32 LV-SI--35-RI Rigaku, Inc 28 73 9 216 80 63 32 LV-SI--50-RI Rigaku.Inc 30 79 8 209 92 49 33 LV-SIM2-XX Reference Laboratory 5 6 71 3 26 U 72 66 33 LV-SI--26-XX Reference Laboratory 6 83 6 1 26 U 86 75 33 LV-SL-33-XX Reference Laboiatory 6 8 66 2.8 2.6 U 67 59 33 LV-SE-39-XX Reference Laboratory 8 74 5 1 26 U 74 66 33 LV-SI-X2-XX Reference Laboratory 43 67 3 4 2 7 U 64 57 33 LV-SIM2-RI Rigaku. Inc 5 41 2 182 88 44 33 LV-SE-26-RI Rigaku, Inc 3 39 1 188 104 42 33 LV-SE-33-RI Rigaku, Inc 6 38 0 192 103 49 33 LV-SE-39-RI Rigaku, Inc 2 44 2 184 92 42 33 LV-SE-42-RI Rigaku, Inc 3 33 2 166 93 42 D-22 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 34 LV-SE-09-XX Reference Laboratory 67 U 450 2.7 U 48 34 150,000 14 J- 34 LV-SE-I9-XX Reference Laboratory 6.7 U 500 2 7 U 55 37 160,000 17 J- 34 LV-SE-27-XX Reference Laboratory 6.7 U 530 2 7 U 56 39 180,000 16 J- 34 LV-SE-36-XX Reference Laboratory 6.7 U 550 27 U 60 40 180,000 21 J- 34 LV-SE-38-XX Reference Laboratory 67 U 480 2.7 U 52 36 160,000 15 J- 34 LV-SE-09-RI Rigaku, Inc. 169 63 392 173 6 66,112 -122 34 LV-SE-I9-RI Rigaku, Inc. 177 31 383 176 7 66,611 -122 34 LV-SE-27-R1 Rigaku, Inc. 255 37 400 169 2 65,189 -130 34 LV-SE-36-R1 Rigaku, Inc. 204 60 375 207 4 66,642 -118 34 LV-SE-38-RI Rigaku, Inc -30 -59 274 55 -15 41,849 -172 35 LV-SE-07-XX Reference Laboratory 6.7 UJ 780 2.7 U 57 48 200,000 11 35 LV-SE-18-XX Reference Laboratory 6.7 UJ 800 2.7 U 61 49 210,000 11 35 LV-SE-23-XX Reference Laboratory 6.6 UJ 660 2.6 U 53 40 170,000 8 35 LV-SE-45-XX Reference Laboratory 6.7 UJ 650 2.7 U 50 40 170,000 8 35 LV-SE-48-XX Reference Laboratory 6.6 UJ 680 2.6 U 52 42 180,000 9 35 LV-SE-07-R1 Rigaku, Inc. 191 73 332 217 0 85,976 -147 35 LV-SE-18-R1 Rigaku, Inc. 144 91 336 200 1 84,794 -138 35 LV-SE-23-RI Rigaku, Inc. 147 87 328 234 1 86,198 -150 35 LV-SE-45-RI Rigaku, Inc 242 65 349 226 4 85,141 -143 35 LV-SE-48-RI Rigaku, Inc 117 96 312 210 -1 86,120 -142 36 LV-SE-OI -XX Reference Laboratory 1.5 UJ 6 0.76 4 18 1,100 17 36 LV-SE-I4-XX Reference Laboratory 1.5 UJ 5 0.74 4 16 980 14 36 LV-SE-2I-XX Reference Laboratory 1.5 UJ 7 0 84 4 19 970 18 36 LV-SE-24-XX Reference Laboratory 1 5 UJ 5 0 68 4 15 840 14 36 LV-SE-32-XX Reference Laboratory 1 4 UJ 6 0 87 4 16 860 14 36 LV-SE-OI-Rl Rigaku, Inc 44 -15 473 -74 6 3,040 -80 36 LV-SE-I4-RI Rigaku, Inc. 38 1 481 -45 1 3,040 -80 36 LV-SE-2I-RI Rigaku, Inc. 43 -20 487 -52 -1 3,057 -82 36 LV-SE-24-R1 Rigaku, Inc 42 -36 477 -61 -2 3,067 -83 36 LV-SE-32-RI Rigaku, Inc. 42 -30 479 -61 1 3,055 -82 D-23 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data i-iR Ni Se As V Zn 34 LV-SE-09-XX Reference Laboiatory 6 55 67 U 6 7 U 100 51 J 34 LV-SE-I9-XX Rcfeicncc Lahorntory 7 2 65 5 9 J 6 7 U 110 55 J 34 LV-SE-27-XX Reference Laboratory 1 1 64 67 U 6.7 U 120 58 J 34 LV-SE-36-XX Reference Laboiatory 8 5 70 11 67 U 120 60 J 34 LV-SE-38-XX Reference Laboratory 79 75 6 7 U 67 U 100 54 J 34 LV-SE-09-RI Rigaku, Inc -23 25 -5 133 117 27 34 LV-SIM9-RI Rigaku. Inc -16 26 -5 138 112 22 34 LV-SE-27-RI Rigaku, Inc -18 19 -4 137 117 33 34 LV-SE-36-RI Rigaku, Inc -20 20 -5 132 117 30 34 LV-SE-38-R1 Rigaku, Inc -56 13 -13 96 70 9 35 LV-SE-07-XX Reference Laboratory 5 5 5S 10 67 U 130 24 J 35 LV-SE-I8-XX Reference Laboratory 5 4 60 12 6 7 U 140 52 J 35 LV-SE-23-XX Refeience Laboratory 5 50 J 9 6 6 6 U 120 18 J 35 LV-SE-45-XX Rcfeicncc Laboratory 5 6 50 J 8 2 6 7 U 120 19 J 35 LV-SE-48-XX Reference Laboratory 73 50 J 76 66 U 120 30 J 35 LV-SE-07-R1 Rigaku, Inc. -29 18 -5 128 139 18 35 LV-SE-18-RI Rigaku, Inc -31 19 -7 120 138 15 35 LV-SE-23-RI Rigaku, Inc. -32 18 -6 125 148 12 35 LV-SE-45-RI Rigaku, Inc. -27 19 -6 128 138 15 35 LV-SE-48-RI Rigaku.Inc -35 16 -7 122 139 10 36 LV-SE-OI-XX Reference Laboratory 0 1 U 49 1 5 U 1.5 U 2 J 14 J 36 LV-SE-I4-XX Reference Laboratory 0 06 U 46 1 5 U 1.5 U 1 J 12 J 36 LV-SE-2I-XX Reference Laboratory 0 05 U 49 1 5 U 1.5 U 2 J 14 J 36 LV-SE-24-XX Reference Laboratory 0 05 U 44 1 5 U 1 5 U 1 J 12 J 36 LV-SE-32-XX Reference Laboiatory 0 05 U 47 1 4 U 1 4 U 1 J 19 36 LV-SE-OI-RI Rigaku. Inc. -3 26 -1 165 3 14 36 LV-SE-I4-R1 Rigaku, Inc. -6 25 1 164 II 8 36 LV-SE-2I-R1 Rigaku,Inc -1 28 0 171 13 11 36 LV-SE-24-RI Rigaku, Inc 2 27 1 170 5 12 36 LV-SE-32-RI Rigaku,Inc 1 28 0 169 10 8 D-24 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 37 LV-SE-08-XX Reference Laboratory 1 3 UJ 30 0 52 U 54 23 23,000 55 37 LV-SE-I6-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-R1 Rigaku, Inc. 184 46 595 42 23 16,577 6 37 LV-SIM6-R1 Rigaku, Inc. 185 36 628 112 19 16,504 -13 37 LV-SE-28-RI Rigaku,Inc 211 4 651 64 25 16,469 -7 37 LV-SE-30-RI Rigaku,Inc 180 34 607 76 23 16,750 -6 37 LV-SE-47-RI Rigaku,Inc 165 34 576 33 25 16,509 -12 38 LV-SE-I l-XX Reference Laboratory 1 4 UJ 150 6.6 120 270 42,000 7 38 LV-SE-29-XX Reference Laboratory 1 4 UJ 150 6 3 120 260 42,000 7 J+ 38 LV-SE-44-XX Reference Laboratory 1 4 U 140 6.1 120 250 40,000 8 38 LV-SE-46-XX Reference Laboratory 0.88 U 110 5 92 200 32,000 6 38 LV-SE-52-XX Reference Laboratory 1.4 U 160 68 130 280 44,000 8 38 LV-SE-11-RI Rigaku, Inc. 193 55 551 79 144 22,687 -68 38 LV-SE-29-RI Rigaku,Inc 230 71 582 146 154 22,583 -70 38 LV-SE-44-RI Rigaku.Inc 201 40 556 118 143 22,794 -75 38 LV-SE-46-R1 Rigaku,Inc 179 49 549 108 137 22,493 -68 38 LV-SE-52-R1 Rigaku, Inc 220 81 573 129 140 22,459 -68 39 RF-SE-07-XX Reference Laboratory 1 3 U 12 0 5 U 92 81 17,000 24 39 RF-SE-I2-XX Reference Laboratory 1.2 U 14 0 5 U 100 110 20,000 25 39 RF-SE-23-XX Reference Laboratory 0.25 U 0 U 0.1 U 0 U 0.2 U 4 J 0 U 39 RF-SE-36-XX Reference Laboratory 1.2 U 12 O LTl c 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-R1 Rigaku, Inc. 202 28 666 79 68 13,796 -38 39 RF-SE-I2-RI Rigaku,Inc. 202 15 627 106 75 14,275 -26 39 RF-SE-23-RI Rigaku,Inc 216 11 641 71 69 13,770 -26 39 RF-SE-36-RI Rigaku,Inc 191 33 648 77 60 13,504 -21 39 RF-SE-42-RI Rigaku,Inc. 193 24 651 91 66 13,628 -24 39 RF-SE-45-RI Rigaku,Inc. 222 -2 632 64 68 13,658 -29 39 RF-SE-53-RI Rigaku, Inc. 228 -23 651 81 69 13,779 -37 D-25 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No Sample ID Source of Data Mr Ni Se Ar V Zn 37 LV-SG-08-XX Rcfcicncc Laboialory 5 2 110 4.8 1.3 U 44 61 37 LV-SK-I6-XX Reference Laboratory 5 4 110 5 1 3 U 42 59 37 LV-SG-28-XX Reference Laboratory 54 120 5 8 1 3 U 4S 65 37 LV-SII-30-XX Rcfcicncc Laboratory 6 3 120 5 6 1.3 U 4S 66 37 LV-SG-47-XX Rcfcicncc Laboratoiy 4 9 120 4.2 1 3 U 45 65 37 LV-SG-OS-RI Rigaku. Inc. 31 70 9 206 85 64 37 I.V-SIM6-RI Rigaku, Inc. 36 72 8 217 89 53 37 LV-SI--28-RI Rigaku, Inc 37 68 9 215 S6 55 37 LV-SIE-30-RI Rigaku,Inc 24 74 9 208 87 60 37 LV-SI:-47-RI Rigaku.Inc 34 69 7 201 86 54 38 LV-SIM l-XX Reference Laboratory 2.8 870 1 3 U 1 4 u 35 200 38 LV-SK-29-XX Rcfcicncc Laboratory 1.5 J- 860 1 2 U 1 4 u 35 200 38 LV-SI--44-XX Reference Laboratory 1.5 S30 1 4 U 1 4 u 34 190 38 LV-SI--46-XX Reference Laboratory 1.4 660 0 88 U OSS u 27 150 38 LV-Sli-52-XX Reference Laboratory 21 910 1 4 U 1 4 u 38 210 38 LV-SI--I l-RI Rigaku. Inc 15 347 3 192 50 104 38 LV-SC-29-RI Rigaku, Inc 2 353 2 195 42 106 38 LV-SI--44-RI Rigaku. Inc 12 363 1 190 42 104 38 LV-SI:-46-RI Rigaku, Inc 9 357 3 IS8 43 1 10 38 LV-SI--52-RI Rigaku, Inc 9 353 4 198 45 107 39 RF-SE-07-XX Reference Laboratory 0.09 U 180 1.3 U 1.3 u 34 130 39 RF-SI--I2-XX Reference Laboratoiy 0 1 U 210 1 2 U 1.2 u 38 140 39 RF-SE-23-XX Reference Laboratory 24 2 U 0 25 U 0.37 3 U 1 U 39 R1--SF-36-XX Rcfcicncc Laboratory 0 08 U 180 1 U 1.2 u 34 120 39 RF-SF-42-XX Reference Laboratory 0 08 U 210 1 3 U 1.3 u 40 140 39 RF-SF-45-XX Reference Laboratory 0 08 U 220 1 3 U 1 3 u 43 150 39 RF-SI;-53-XX Reference Laboratoiy 0 08 U 210 1 3 U 1 3 u 40 140 39 RF-SI--07-R1 Rigaku, Inc 47 94 8 230 59 95 39 RI--SK-12-R1 Rigaku. Inc. 47 102 8 218 59 96 39 R lr-Sli-23-R1 Rigaku, Inc 52 97 13 206 52 88 39 RI--SI--36-RI Rigaku.Inc 39 99 7 226 59 88 39 RF-SI--42-RI Rigaku.Inc 36 99 S 220 55 88 39 RI--SII-45-R1 Rigaku,Inc 53 96 11 212 46 92 39 RT-SII-53-RI Rigaku,Inc 66 103 12 210 56 S6 D-26 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 40 RF-SB-03-XX Reference Laboratory 1.2 UJ 27 1.3 93 200 17,000 88 40 RF-SE-28-XX Reference Laboratory 1.2 UJ 31 1.5 100 220 18,000 99 40 RF-SE-38-XX Reference Laboratory 1 2 UJ 27 1 2 90 190 16.000 83 40 RF-SE-49-XX Reference Laboratory 1 2 UJ 31 1 5 100 220 18,000 97 40 RF-SE-55-XX Reference Laboratory 1.2 UJ 24 1.1 91 180 15,000 75 40 RF-SE-03-RI Rigaku, Inc. 200 60 661 117 152 13,154 13 40 RF-SE-28-RI Rigaku, Inc. 236 36 669 97 157 13,234 11 40 RF-SE-38-RI Rigaku, lnc 210 44 655 81 154 13,164 6 40 RF-SE-49-R1 Rigaku, lnc 240 5 669 71 151 13,062 9 40 RF-SE-55-RI Rigaku, lnc 231 44 677 113 160 13,209 13 41 RF-SE-06-XX Reference Laboratory 1 3 UJ 70 3.6 90 490 20,000 230 41 RF-SE-13-XX Reference Laboratory 1 3 UJ 76 3.7 92 530 21,000 230 41 RF-SE-27-XX Reference Laboratory 1.3 UJ 64 3.1 78 440 18,000 200 41 RF-SE-31-XX Reference Laboratory 1.3 UJ 39 1.8 63 250 12,000 120 41 RF-SE-58-XX Reference Laboratory 1.3 UJ 71 3.6 89 500 21,000 230 41 RF-SE-06-RI Rigaku, Inc. 208 57 648 89 341 13,637 74 41 RF-SE-13-RI Rigaku, Inc. 232 42 654 65 329 13,248 82 41 RF-SE-27-R1 Rigaku, Inc. 220 70 640 54 340 13,557 79 41 RF-SE-3I-RI Rigaku, lnc 225 62 659 94 347 13,482 75 41 RF-SE-58-RI Rigaku. lnc 222 58 644 94 329 13,362 69 42 RF-SE-02-XX Reference Laboratory 1.3 UJ 110 5.4 93 740 24,000 330 42 RF-SE-22-XX Reference Laboratory 1.3 UJ 99 4.7 84 670 22,000 300 42 RF-SE-25-XX Reference Laboratory 1.3 UJ 88 4 78 580 19,000 270 42 RF-SE-30-XX Reference Laboratory 1.3 UJ 89 4.3 78 610 21,000 290 42 RF-SE-57-XX Reference Laboratory 1 3 UJ 89 45 79 610 21,000 300 42 RF-SE-02-RI Rigaku, Inc. 208 73 623 81 435 13,697 119 42 RF-SE-22-R1 Rigaku, Inc. 214 72 619 91 439 13,627 103 42 RF-SE-25-RI Rtgaku, Inc. 221 64 653 109 425 13,476 110 42 RF-SE-30-RI Rigaku,lnc 224 66 637 102 420 13,501 110 42 RF-SE-57-RI Rigaku,lnc 217 56 620 69 426 13,633 114 D-27 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Mr Ni Se As V Zn 40 RF-SE-03-XX Reference Laboratory 0 48 150 1 2 U 1 2 U 40 300 40 RF-SE-28-XX Rcfcicncc Laboiatoiy 0 57 160 1 2 U 1.2 U 44 320 40 RF-SE-3S-XX Reference Laboiatoiy 041 140 1.2 U 1 2 U 39 300 40 RF-SE-49-XX Reference Laboratory 0.43 170 1 2 U 1 2 U 43 330 40 RF-SE-55-XX Rcfcicncc Laboiatory 0 42 140 1 2 U 1 2 U 35 280 40 RF-SE-03-RI Rigaku, hie 36 89 7 227 56 190 40 RF-SIE-28-RI Rigaku. hie 33 83 12 217 59 191 40 RF-SE-38-RI Rigaku. hie 33 S9 8 228 62 193 40 RI--SE-49-RI Rigaku. Inc 51 S5 12 218 59 182 40 RF-SE-55-RI Rigaku. Inc 38 82 9 239 60 187 41 RF-SE-06-XX Reference Laboratory 1 1 150 1 3 U 1 3 U 44 740 41 RF-SE-13-XX Reference Laboiatoiy 1 2 160 1 3 U 1 3 45 790 41 RF-SE-27-XX Reference Laboiatory 1 2 130 1 3 U 1 3 U 39 670 41 RF-SIE-31 -XX Rcfcicncc Laboiatory 1 1 86 1 3 U 1.3 U 2S 420 41 RF-SE-58-XX Rcfcicncc Laboiatoiy 1 2 150 1 3 U 1.3 U 46 770 41 RI--SE-06-R1 Rigaku. Inc 33 81 9 220 64 405 41 RI--SE-13-RI Rigaku, Inc 36 83 13 216 61 383 41 RF-SE-27-R1 Rigaku. Inc 30 80 11 209 55 417 41 RF-SE-3I-R1 Rigaku, Inc 39 78 6 230 58 399 41 RF-SE-58-RI Rigaku, Inc 38 86 7 227 52 385 42 RE-SE-02-XX Reference Laboiatory 1 6 180 1 3 U 2 7 50 1.100 42 RF-SE-22-XX Reference Laboiatoiy 1 7 160 1 3 U 2 3 44 990 42 RF-SE-25-XX Reference Laboiatory 1 5 140 1 5 1 7 40 890 42 RF-SE-30-XX Reference Laboiatory 1 5 150 1 3 U 1.9 44 960 42 RF-SE-57-XX Reference Laboratory 1 5 150 2 2.2 44 1,000 42 RF-SE-02-RI Rigaku, Inc 39 82 7 220 54 504 42 RF-SE-22-RI Rigaku. Inc 31 88 13 206 61 494 42 RF-SE-25-RI Rigaku, Inc 29 83 13 213 58 482 42 RF-SE-30-RI Rigaku, Inc 27 84 13 212 49 468 42 RF-SE-57-RI Rigaku. Inc 34 82 7 216 58 482 D-28 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 43 RF-SE-15-XX Reference Laboratory 1 3 UJ 120 6.2 72 820 23,000 390 43 RF-SE-24-XX Reference Laboratory 1.3 UJ 130 J+ 6.5 J+ 74 J+ 860 J+ 24,000 J+ 410 J+ 43 RF-SE-32-XX Reference Laboratory 1.3 UJ 120 5 1 64 770 20,000 330 43 RF-SE-43-XX Reference Laboratory 1.3 UJ 130 5 7 68 840 22,000 350 43 RF-SE-59-XX Reference Laboratory 1.3 UJ 140 5 9 73 890 23,000 380 43 RF-SIM5-RI Rigaku, Inc. 209 95 598 142 566 14,112 160 43 RF-SE-24-RI Rigaku,Inc 209 80 608 99 579 14,375 163 43 RF-SE-32-RI Rigaku, Inc 218 76 624 48 582 14,256 161 43 RF-SE-43-R! Rigaku,Inc 228 80 653 48 555 14,218 166 43 RF-SE-59-RI Rigaku, Inc. 229 84 617 74 552 14,169 166 44 RF-SE-05-XX Reference Laboratory 4.1 J+ 160 9 1 69 1,000 26,000 450 44 RF-SE-26-XX Reference Laboratory 2.2 J+ 140 84 64 990 23,000 440 44 RF-SE-39-XX Reference Laboratory 2 9 J+ 160 93 73 1,100 26,000 490 44 RF-SE-44-XX Reference Laboratory 2 7 J+ 140 8.2 64 970 24,000 420 44 RF-SE-56-XX Reference Laboratory' 3.5 J+ 180 9.6 75 1200 27,000 490 44 RF-SE-05-RI Rigaku,Inc 260 95 638 83 716 14,924 187 44 RF-SE-26-RI Rigaku,Inc 229 114 657 86 693 14,916 193 44 RF-SE-39-RI Rigaku, Inc. 243 86 617 50 693 14,579 174 44 RF-SE-44-RI Rigaku, Inc. 211 112 610 129 701 14,778 176 44 RF-SE-56-RI Rigaku, Inc. 273 84 658 94 697 14,768 183 45 RF-SE-04-XX Reference Laboratory 3 2 J+ 230 12 42 1,500 27,000 730 45 RF-SE-14-XX Reference Laboratory 4 4 J+ 260 12 47 1,700 30,000 800 45 RF-SE-19-XX Reference Laboratory 3.7 J+ 250 13 48 1,700 30,000 800 45 RF-SE-34-XX Reference Laboratory 2.9 J+ 210 10 39 1,400 24,000 660 45 RF-SE-52-XX Reference Laboratory 3 4 J+ 220 II 42 1,500 26.000 720 45 RF-SE-04-RI Rigaku, Inc. 252 119 611 65 947 15,229 327 45 RF-SE-I4-RI Rigaku,Inc 207 160 604 64 956 15,099 331 45 RF-SE-I9-RI Rigaku,Inc 212 154 591 91 946 15,270 326 45 RF-SE-34-RI Rigaku, Inc. 274 127 627 23 933 15,283 310 45 RF-SE-52-RI Rigaku, Inc. 220 148 600 109 952 15,259 316 D-29 ------- Appendix D: Analytical Data Summary, Kigaku ZSX Mini II and Reference Laboratory (Continued) Blend No Sample ID Source of Data MR Nl Se Ag V Zn 43 RF-SE-I5-XX Reference Lnbointory 2 6 160 1 4 36 45 1.300 43 RF-SII-24-XX Refcicncc Laboratory 2 3 170 J+ 1 3 U 3 S J+ 46 J+ 1.400 J- 43 RF-SE-32-XX Reference Laboratory 2.S 140 1 3 U 42 36 1,100 43 KI-Si:-43-XX Reference Laboratory 2 7 150 1 3 U 4 40 1,200 43 RF-SE-59-XX Reference Laboratoiy 0 09 U 160 1.3 U 45 42 1.300 43 RF-SE-I5-R1 Rigaku,Inc 22 90 12 202 64 637 43 RF-SE-24-RI Rigaku, Inc 21 96 11 202 68 665 43 RF-SE-32-RI Rigaku, Inc 27 85 6 209 58 649 43 RF-SE-43-RI Rigaku. Inc 14 S9 12 208 64 639 43 RF-SE-59-RI Rigaku.Inc 39 84 S 213 62 627 44 RF-SE-05-XX Reference Laboratoiy 26 150 3.1 74 J- 4S 1,800 44 RF-SE-26-XX Reference Laboratoiy 2 5 140 2 S 72 J- 42 1.700 44 RF-SE-39-XX Reference Laboiatoiy 2 2 150 2 6 8 2 J- 49 1,900 44 RF-SE-44-XX Refcicncc Laboiatory 2 3 140 2 4 7 2 J- 44 1.600 44 RF-SE-56-XX Refcicncc Laboratory 2 2 160 1 8 8 3 J- 51 1.900 44 RF-SE-05-RI Rigaku. Inc 32 80 7 223 61 833 44 RF-SE-26-RI Rigaku. Inc 15 76 12 211 64 837 44 RF-SE-39-RI Rigaku. Inc 25 76 7 220 57 802 44 RF-SE-44-RI Rigaku. Inc IS 77 11 207 62 796 44 RF-SE-56-RI Rigaku. Inc 35 73 7 220 67 809 45 RF-SE-04-XX Rcfciencc Laboiatoiy 4 2 130 2 8 12 J- 46 2,400 45 RF-SE-I4-XX Refcicncc Laboratory 4 7 140 3 13 J- 51 2.600 45 RF-SE-I9-XX Refcicncc Laboiatory 3 9 140 4 1 14 J- 52 2.700 45 RF-SE-34-XX Reference Laboiatory 4 5 120 1 9 10 J- 42 2,200 45 RF-SE-52-XX Reference Laboratory 4 1 130 2 1 1 J- 47 2,300 45 RF-SE-04-RI Rigaku, Inc 37 76 6 207 55 1,083 45 R F-SE-I4-RI Rigaku. Inc 3 75 12 204 52 1,066 45 RF-SE-I9-RI Rigaku. Inc -3 88 12 202 66 1,080 45 RF-SE-34-RI Rigaku. Inc 26 81 6 218 56 1.030 45 RF-SE-52-RI Rigaku. Inc 8 77 12 206 66 1,078 D-30 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 46 BN-SO-l 1-XX Reference Laboratory 4 J- 2,900 720 820 120 23,000 56 46 BN-SO-I4-XX Reference Laboratory 3.5 J- 2,800 690 800 120 22,000 51 46 BN-SO-23-XX Reference Laboratory 1 2 UJ 2,800 700 800 120 23,000 52 46 BN-SO-l 1-R1 Rigaku, Inc. 176 1,404 899 408 93 13,667 -30 46 BN-SO-I4-R1 Rigaku, Inc. 168 1,371 880 442 88 13,694 -22 46 BN-SO-23-RI Rigaku, Inc 152 1,306 837 376 86 13,626 -34 47 BN-SO-09-XX Reference Laboratory 750 J- 97 2,700 2,900 100 22,000 4,700 47 BN-SO-l 2-XX Reference Laboratory 750 J- 89 2,600 2,800 96 21,000 4,500 47 BN-SO-24-XX Reference Laboratory 810 J- 97 2,900 3,000 100 23,000 4,900 47 BN-SO-09-RI Rigaku, lnc 763 63 1,506 1,080 69 12,828 2,130 47 BN-SO-12-R1 Rigaku, Inc. 769 89 1,534 1,034 74 12,772 2,208 47 BN-SO-24-RI Rigaku, Inc. 699 89 1,516 1,089 70 12,869 2,186 48 SB-SO-09-XX Reference Laboratory 1.3 UJ 9 051 U 130 120 35,000 19 48 SB-SO-20-XX Reference Laboratory 1.3 UJ 11 0.51 U 170 150 44,000 24 48 SB-SO-3I-XX Reference Laboratory 1.3 UJ 8 J- 0.51 U 140 130 38,000 21 48 SB-SO-09-RI Rigaku, Inc. 169 0 563 137 78 19,548 -61 48 SB-SO-20-RI Rigaku, Inc. 231 23 686 130 27 18,103 -49 48 SB-SO-31 -Rl Rigaku, Inc. 202 7 601 147 87 19,821 -57 49 SB-SO-29-XX Reference Laboratory 1.2 U 9 © L/. C 140 130 41,000 19 49 SB-SO-36-XX Reference Laboratory 1.2 U 8 © i_Ai c 120 100 33,000 15 49 SB-SO-56-XX Reference Laboratory 1.2 U 10 05 U 150 140 42,000 20 49 SB-SO-29-RI Rigaku, Inc 223 0 606 159 75 19,982 -53 49 SB-SO-36-RI Rigaku, Inc. 215 10 589 142 81 20,196 -52 49 SB-SO-56-RI Rigaku, Inc 207 3 596 117 76 20,017 -59 50 SB-SO-04-XX Reference Laboratory 940 13 2,800 2,800 100 38,000 21 50 SB-SO-34-XX Reference Laboratory 980 12 2,500 2,500 91 34,000 18 50 SB-SO-49-XX Reference Laboratory 700 12 2,500 2,400 89 33,000 18 50 SB-SO-04-RI Rigaku, Inc. 323 18 1,717 1,224 70 18,689 -43 50 SB-SO-34-RI Rigaku, Inc 321 31 1,676 1,253 68 18,682 -38 50 SB-SO-49-RI Rigaku, Inc 302 8 1,688 1,288 68 18,764 -42 D-31 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Mr Ni Se Afi V Zn 46 13N-SO-I l-XX Rcfcicncc Laboratory 24 J- 2,900 140 140 J- 150 3,900 46 BN-SO-I4-XX Rcfctcnce Laboratoiy 26 2.S00 130 140 J- 150 3.S00 46 BN-SO-23-XX Rcfcicncc Laboratoiy 31 2,800 130 130 J- 150 3,800 46 BN-SO-I l-RI Rignku. Inc 40 1,353 44 225 113 2,044 46 BN-SO-14-RI Rignku, Inc 45 1.339 44 215 124 2,080 46 I3N-SO-23-RI Rigaku. Inc. 37 1,315 41 209 111 1.981 47 I3N-SO-09-XX Rcfcicncc Laboratoiy 0 39 1.500 290 100 J- 340 81 47 I3N-SO-12-XX Reference Laboratoiy 0 34 1,400 290 210 J- 310 74 47 BN-SO-24-XX Rcfcicncc Laboiatoiy 037 1,600 300 140 J- 350 81 47 I3N-SO-09-R1 Rigaku, Inc 17 639 87 214 199 59 47 I3N-SO-12-R] Rigaku, Inc 23 641 S3 215 185 63 47 13N-SO-24-RI Rigaku. Inc 19 625 84 224 1 S3 5S 48 SI3-SO-09-XX Reference Laboratoiy 30 2900 26 160 J- 120 3,600 48 SI3-SO-20-XX Reference Laboratory 10 3700 30 140 J- 160 4,500 48 SI3-SO-31 -XX Reference Laboiatory 32 3200 J- 28 J- 160 J- 140 3,900 J- 48 SI3-SO-09-RI Rigaku, Inc 24 1,331 11 224 147 1,850 48 SI3-SO-20-RI Rigaku. Inc 346 94 4 233 121 59 48 SI3-SO-3I-RI Rigaku. Inc. 32 1.348 13 221 148 1,871 49 SI3-SO-29-XX Reference Laboratoiy 79 J 200 160 1 2 UJ 400 3,900 49 SI3-SO-36-XX Reference Laboratory 36 160 130 1 2 UJ 320 3,200 49 S13-SO-56-XX Rcfcicncc Laboratoiy 9 210 160 1 2 UJ 410 4.100 49 SI3-SO-29-RI Rigaku. Inc 39 104 46 216 246 1,952 49 S13-SO-36-RI Rigaku,Inc 36 106 44 207 248 1,958 49 SI3-SO-56-R1 Rigaku,Inc 37 103 47 206 272 1.935 50 SB-SO-04-XX Rcfcicncc Laboratory 40 3,300 390 1 3 UJ 58 86 50 SI3-SO-34-XX Rcfcicncc Laboratory 36 3,000 360 1 3 UJ 52 77 50 SB-SO-49-XX Reference Laboratoiy 36 2.800 330 1 2 UJ 52 72 50 SB-SO-04-R1 Rigaku, Inc 41 1.363 103 219 97 58 50 SB-SO-34-RI Rigaku, Inc 37 1,359 104 219 88 53 50 SB-SO-49-RI Rigaku, Inc 40 1,350 105 205 119 51 D-32 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 51 WS-SO-07-XX Reference Laboratory 3 8 53 1.9 640 4,400 25,000 1,700 51 WS-SO-I l-XX Reference Laboratory 1 2 U 46 1 4 570 3,900 19,000 1,500 51 VVS-SO-25-XX Reference Laboratory 1 2 U 59 3 1 730 4,900 24,000 1,900 5! WS-SO-07-RI Rigaku, Inc 299 54 575 357 3,374 15,153 1,017 51 WS-SO-1 l-RI Rigaku, Inc 251 57 564 391 3,324 15,055 1,011 51 WS-SO-25-RI Rigaku, Inc. 308 54 579 347 3,364 15,226 984 52 WS-SO-10-XX Reference Laboratory 1.3 U 83 1 8 67 76 19,000 1,900 52 WS-SO-20-XX Reference Laboratory I 3 U 100 1 9 81 90 23,000 2,300 52 WS-SO-23-XX Reference Laboratory 1 3 U 110 2.1 82 96 23,000 2,500 52 WS-SO-IO-R1 Rigaku, Inc. 339 80 571 89 86 15,292 1,369 52 WS-SO-20-RI Rigaku, Inc. 340 93 568 86 70 15,252 1,375 52 WS-SO-23-RI Rigaku, Inc. 317 118 562 134 77 15,199 1,426 53 AS-SO-03-XX Reference Laboratory 1 2 U 14 1,300 33 6,200 15,000 160 53 AS-SO-05-XX Reference Laboratory 1.2 U 9 900 23 4,500 11,000 110 53 AS-SO-08-XX Reference Laboratory 1.2 U 10 930 24 4,600 11,000 120 53 AS-SO-03-RI Rigaku, Inc. 160 38 1,091 62 3,421 10,202 41 53 AS-SO-05-RI Rigaku, Inc. 157 21 1,130 76 3,439 10,199 52 53 AS-SO-08-RI Rigaku, Inc. 154 8 1,085 47 3,447 10,116 30 54 LV-SO-03-XX Reference Laboratory 1 6 42 590 600 130 24,000 94 54 LV-SO-40-XX Reference Laboratory 2 7 42 580 590 130 24,000 92 54 LV-SO-49-XX Reference Laboratory 74 43 600 610 130 25,000 98 54 LV-SO-03-RI Rigaku, Inc 199 39 808 318 92 18,230 14 54 LV-SO-40-RI Rigaku, Inc. 191 36 810 308 96 18,375 -8 54 LV-SO-49-RI Rigaku, Inc. 194 32 824 313 94 18,292 3 55 LV-SO-04-XX Reference Laboratory 860 120 2,400 2,300 98 22,000 4.000 55 LV-SO-34-XX Reference Laboratory 870 J- 110 J- 2,300 J- 2,200 J- 87 20,000 J- 3,700 J- 55 LV-SO-37-XX Reference Laboratory 590 84 1,700 1,600 66 16,000 2,800 55 LV-SO-04-RI Rigaku, Inc 819 102 1,482 1,135 70 17.094 2,288 55 LV-SO-34-RI Rigaku, Inc. 720 83 1,472 1,094 78 16,931 2,192 55 LV-SO-37-R1 Rigaku, Inc. 778 94 1,473 1,137 75 17,016 2,264 D-33 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data "is Ni Se Ak V Zn 51 WS-SO-07-XX Reference Laboratory 0 26 260 1 2 U 400 J- 4S ISO 51 WS-SO-I l-XX Reference Laboratory 0.27 240 1 2 U 340 J- 43 160 51 WS-SO-25-XX Refcicnce Laboratory 0 25 300 1 2 U 450 J- 54 200 51 WS-SO-07-RI Rigaku, Inc 19 173 5 216 83 135 51 WS-SO-I l-RI Rigaku, Inc 28 170 6 20S 68 134 51 WS-SO-25-RI Rigaku. Inc 16 165 7 219 71 136 52 WS-SO-I 0-XX Rcfeience Laboratory 0 06 U 290 280 1.3 UJ 260 1,900 52 WS-SO-20-XX Rcfciencc Laboratoiy 0 06 U 350 340 1 3 UJ 320 2,300 52 WS-SO-23-XX Reference Laboratoiy 0 05 U 380 360 1 3 UJ 330 2,500 52 WS-SO-I 0-RI Rigaku. Inc 29 198 108 200 214 1,421 52 WS-SO-20-RI Rigaku. Inc 29 205 104 191 212 1.4 IS 52 WS-SO-23-RI Rigaku. Inc 27 207 108 195 212 1,452 53 AS-SO-03-XX Reference Laboratory 3.7 J- 520 200 480 J- 29 350 53 AS-SO-05-XX Reference Laboratoiy 2 5 J- 370 140 330 J- 23 250 53 AS-SO-08-XX Reference Laboratory 2 5 J- 380 140 280 J- 23 260 53 AS-SO-03-RI Rigaku. Inc 29 226 55 239 65 183 53 AS-SO-05-RI Rigaku. Inc 34 233 55 24 S 55 186 53 AS-SO-OS-RI Rigaku. Inc 33 221 55 237 54 182 54 LV-SO-03-XX Reference Laboiatory 48 J- 2.000 120 210 J- 120 3,700 54 LV-SO-40-XX Reference Laboratory 46 J- 1.900 120 210 J- 120 3,700 54 LV-SO-49-XX Reference Laboratory 52 J- 2,000 120 220 J- 120 3.800 54 LV-SO-03-RI Rigaku, Inc. 49 991 39 214 136 2,161 54 LV-SO-40-RI Rigaku, Inc 50 1,007 39 209 145 2.133 54 LV-SO-49-RI Rigaku, Inc. 52 989 41 212 149 2,120 55 LV-SO-04-XX Reference Laboratoiy 130 J- 2.000 230 1 2 UJ 260 53 55 LV-SO-34-XX Reference Laboratory 130 J- 1,900 J- 220 J- 1 2 UJ 230 J- 48 J- 55 LV-SO-37-XX Reference Laboiatory 130 J- 1,400 170 1 2 U 180 37 55 LV-SO-04-R1 Rigaku, Inc 89 995 71 201 212 51 55 LV-SO-34-R1 Rigaku, Inc 87 974 73 196 198 50 55 LV-SO-37-RI Rigaku,Inc 87 993 74 196 222 51 D-34 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 56 CN-SO-03-XX Reference Laboratory 22 87 63 17 72 15,000 130 56 CN-SO-06-XX Reference Laboratory 20 91 64 18 74 16,000 130 56 CN-SO-07-XX Reference Laboratory 20 90 63 19 72 17,000 130 56 CN-SO-03-RI Rigaku, lnc 193 104 638 62 68 12,600 52 56 CN-SO-06-R1 Rigaku, Inc. 194 72 677 30 62 12,004 43 56 CN-SO-07-RI Rigaku. Inc. 205 101 668 52 71 12,449 46 57 CN-SO-02-XX Reference Laboratory 230 19 820 290 140 22,000 490 57 CN-SO-05-XX Reference Laboratory 130 6 630 26 160 23,000 25 57 CN-SO-09-XX Reference Laboratory 120 6 580 21 140 19,000 23 57 CN-SO-02-RI Rigaku, lnc 190 44 858 42 112 12,591 -19 57 CN-SO-05-R1 Rigaku, lnc 169 46 825 13 112 12,750 -26 57 CN-SO-09-RI Rigaku, Inc. 186 10 828 64 98 12,514 -29 58 LV-SE-06-XX Reference Laboratory 30 23 160 540 30 18,000 1,600 58 LV-S1S-13-XX Reference Laboratory 31 24 160 540 30 18,000 1,600 58 LV-SE-41-XX Reference Laboratory 30 21 150 480 26 16,000 1,500 58 LV-SE-06-RI Rigaku,lnc 310 -8 652 299 22 14,762 996 58 LV-SIM3-RI Rigaku, Inc. 367 3 668 301 30 14,849 1,013 58 LV-SII-4I-RI Rigaku, lnc 430 1 662 309 23 14,832 1,008 59 LV-SI--05-XX Reference Laboratory 92 20 440 840 39 16,000 14 59 LV-S1I-20-XX Reference Laboratory 140 J+ 31 680 1,400 60 22,000 21 59 LV-SE-43-XX Reference Laboratory 160 J+ 24 550 1,100 47 19,000 17 59 LV-SE-05-R1 Rigaku, Inc. 225 30 857 558 43 15,135 -18 59 LV-SE-20-R1 Rigaku,lnc 205 36 836 475 32 15,081 -30 59 LV-SII-43-RI Rigaku,lnc 203 15 879 473 38 15,079 -22 60 LV-S1M5-XX Reference Laboratory 290 J+ 32 1,300 83 2,300 22,000 18 60 LV-SE-17-XX Reference Laboratory 280 J+ 31 1,300 79 2,200 21,000 17 J- 60 LV-Sli-51 -XX Reference Laboratory 210 J+ 26 1,100 72 2,000 19,000 15 60 LV-SE-15-RI Rigaku,Inc. 221 19 1,106 91 1,291 14,724 -32 60 LV-Sli-l 7-RI Rigaku,lnc 194 13 1,044 67 1,312 14,853 -43 60 LV-SE-51 -Rl Rigaku, Inc. 221 2 1,122 50 1,302 14,751 -34 D-35 ------- Appendix D: Analytical Data Summary, Rigaku Z.SX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Mr Nl Sc Afi V Zn 56 CN-SO-03-XX Reference Laboratory 34 J- 74 36 90 30 5S 56 CN-SO-06-XX Refeience Laboiatory 40 J- 76 38 94 32 59 56 CN-SO-07-XX Rcfcicncc Lnboralory 36 J- 75 37 91 33 58 56 CN-SO-03-RI Rigaku,Inc 43 69 18 226 69 55 56 CN-SO-06-R1 Rigaku, Inc 52 73 20 228 56 55 56 CN-SO-07-RI Rigaku.Inc 38 66 19 230 59 65 57 CN-SO-02-XX Rcfcicncc Laboratory 270 J- 530 190 6S 160 1.900 57 CN-SO-05-XX Refeience Laboratory 280 J- 360 190 78 160 2.200 57 CN-SO-09-XX Reference Laboratory 260 J- 330 170 74 140 2.100 57 CN-SO-02-RI Rigaku. Inc 140 1S3 55 216 117 1,159 57 CN-SO-05-RI Rigaku.Inc 134 186 51 205 117 1.191 57 CN-SO-09-RI Rigaku.Inc 136 187 51 211 119 1,135 58 LV-SI--06-XX Reference Laboratory 610 J- 360 160 1 10 480 52 58 LV-SI;-13-XX Reference Laboratory 640 J- 360 160 1 10 470 51 58 LV-SI--41-XX Reference Laboratory 610 J- 320 150 99 420 46 58 LV-SE-06-RI Rigaku.Inc 290 210 57 212 311 53 58 LV-SIM3-R1 Rigaku.Inc 288 211 55 21 1 309 54 58 LV-Sli-41 -Rl Rigaku.Inc 303 208 57 216 336 52 59 LV-SII-05-XX Reference Laboratory 2 6 J- 400 340 49 340 1.800 59 LV-SE-20-XX Reference Laboratory 2 S 660 500 75 J- 530 2.800 59 LV-SIJ-43-XX Reference Laboiatoiy 2 8 530 420 60 J- 430 2,300 59 LV-SL-05-R1 Rigaku,Inc. 31 271 120 216 308 1,216 59 LV-SE-20-R1 Rigaku, Inc. 33 263 123 221 270 1.196 59 LV-SL-43-R1 Rigaku. Inc. 33 269 127 222 276 1,211 60 LV-SIM5-XX Refeience Laboiatoiy 500 230 92 300 J- 180 62 60 LV-SIM7-XX Reference Laboiatoiy 490 220 89 200 J- 170 58 60 LV-Sli-51 -XX Reference Laboiatory 470 200 76 250 J- 160 54 60 LV-SI--15-RI Rigaku,Inc 241 115 27 250 147 71 60 LV-SK-I7-RI Rigaku.Inc 234 110 25 234 137 56 60 LV-Sli-51 -Rl Rigaku,Inc 252 106 31 246 134 54 D-36 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 61 TL-SE-05-XX Reference Laboratory + O o 34 0.34 J 40 4,900 24,000 1,200 61 TL-SE-09-XX Reference Laboratory + o o 33 0.24 J 39 4,800 23,000 1,200 61 TL-SE-13-XX Reference Laboratory 95 J+ 31 0 45 J 36 J+ 4,400 J+ 22,000 J+ © O 61 TL-SE-05-RI Rigaku, Inc 248 -27 542 84 2,111 15,461 454 61 TL-SE-09-RI Rigaku, Inc 260 9 540 57 2,112 15,340 461 61 TL-SE-13-RI Rigaku, Inc 275 17 545 35 2,152 15,446 474 62 TL-SE-06-XX Reference Laboratory 1.2 U 86 350 34 2000 22,000 1,700 62 TL-SE-17-XX Reference Laboratory 1.2 U 85 340 33 2100 21,000 1,700 62 TL-SE-28-XX Reference Laboratory 1.2 U 89 360 34 2100 22,000 1,700 62 TL-SE-06-RI Rigaku, Inc. 241 55 675 31 1,119 15,139 783 62 TL-SE-17-RI Rigaku, Inc 268 51 687 52 1,129 15,114 809 62 TL-SE-28-RI Rigaku, Inc 301 39 693 19 1,180 15,217 824 63 TL-SE-07-XX Reference Laboratory 30 II 48 66 2200 37,000 13 63 TL-SE-21-XX Reference Laboratory 33 13 51 73 2300 44,000 15 63 TL-SE-30-XX Reference Laboratory 31 11 47 64 2200 36,000 14 63 TL-SE-07-RI Rigaku, Inc. 184 -32 514 71 1,084 27,719 -85 63 TL-SE-21-RI Rigaku, Inc. 169 -43 490 88 1,076 28,311 -90 63 TL-SE-30-RI Rigaku, Inc 158 -36 467 65 1,051 27,607 -81 64 TL-SE-02-XX Reference Laboratory 77 15 160 64 3,100 32,000 12 64 TL-SE-08-XX Reference Laboratory 66 10 180 74 3,200 45,000 11 64 TL-SE-I6-XX Reference Laboratory 73 15 170 69 3,100 38,000 13 64 TL-SE-02-RI Rigaku, Inc. 181 -33 516 113 1,422 27,920 -93 64 TL-SE-08-RI Rigaku, Inc. 176 -15 510 89 1,466 28,667 -87 64 TL-SE-I6-RI Rigaku,Inc 174 -16 518 55 1,463 28,379 -97 D-37 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No Sample ID Source of Data MS Ni Sc Ag V Zn 61 TL-SH-05-XX Reference Laboratory 9S0 54 130 ISO J- 66 100 61 TL-SE-09-XX Reference Laboratory 820 53 130 170 J- 63 100 61 TL-SE-I3-XX Refcicnce Laboratory 990 49 120 160 J 59 J+ 96 61 TL-SE-05-RI Rigaku,Inc 325 39 34 195 117 58 61 TL-SE-09-RI Rigaku, Inc 30S 38 29 193 115 58 61 TL-SE-I3-RI Rigaku. Inc 304 38 32 197 113 64 62 TL-SE-06-XX Reference Labointory 2 2 44 45 56 78 83 62 TL-SE-17-XX Reference Laboratoiy 26 43 44 56 7S SI 62 TL-SE-28-XX Reference Laboratory 2 8 44 45 57 81 S3 62 TL-SE-06-R1 Rigaku, Inc 13 38 IS 198 110 63 62 TL-SE-I7-RI Rigaku, Inc. 14 39 15 193 116 57 62 TL-SE-28-R1 Rigaku, Inc. 20 34 17 196 111 57 63 TL-SE-07-XX Reference Laboratoiy 40 94 120 63 110 160 63 TL-SE-2I-XX Reference Laboratoiy 120 100 140 67 120 170 63 TI.-SI--30-XX Reference Laboratory 100 93 120 62 100 160 63 TL-SE-07-RI Rigaku.Inc 5 46 32 175 193 78 63 TL-SE-21-R1 Rigaku,Inc 16 48 33 169 192 78 63 TL-SE-30-RI Rigaku,Inc 4 48 28 158 178 74 64 TL-SE-02-XX Reference Laboratoiy 400 99 44 120 110 160 64 TL-SE-OS-XX Reference Laboiatoiy 350 100 39 130 120 170 64 TL-SE-I6-XX Reference Laboratory 420 100 44 120 110 160 64 TL-SE-02-RI Rigaku, Inc 44 48 8 165 174 81 64 TL-SE-08-RI Rigaku, Inc 42 47 10 162 I7S S3 64 TL-SE-I6-RI Rigaku. Inc 51 53 11 166 163 74 D-38 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 65 RF-SE-OI-XX Reference Laboratory 12 230 40 280 63 14,000 22 65 RF-SE-09-XX Reference Laboratory 10 260 45 310 71 16,000 26 65 RF-SE-I l-XX Reference Laboratory 11 240 43 300 72 15,000 25 65 RF-SE-I 7-XX Reference Laboratory 11 250 43 300 67 15,000 26 65 RF-SE-29-XX Reference Laboratory 13 280 49 330 75 17,000 26 65 RF-SE-37-XX Reference Laboratory 11 260 45 320 72 16,000 27 65 RF-SE-50-XX Reference Laboratory 8.9 230 40 280 65 14,000 23 65 RF-SE-01-RI Rigaku,Inc 190 192 661 176 56 12,047 -18 65 RF-SE-09-RI Rigaku, lnc 182 171 711 163 61 11,379 -14 65 RF-SE-I 1-R1 Rigaku, Inc 183 164 663 173 59 11,335 -16 65 RF-SE-17-RI Rigaku, Inc. 230 209 685 195 55 11,264 -21 65 RF-SE-29-R1 Rigaku, Inc. 229 203 665 276 54 11,433 -28 65 RF-SE-37-R1 Rigaku, Inc. 176 155 678 183 55 11,488 -27 65 RF-SE-50-RI Rigaku, Inc. 248 174 702 236 55 10,934 -30 66 RF-SE-08-XX Reference Laboratory 14 460 67 510 1,800 18,000 580 66 RF-SE-IO-XX Reference Laboratory 12 400 58 440 1,500 16,000 510 66 RF-SE-33-XX Reference Laboratory 13 440 64 490 1,700 18,000 570 66 RF-SE-08-RI Rigaku,Inc 241 269 662 308 1,327 12,503 295 66 RF-SE-10-RI Rigaku,Inc 225 273 647 258 1,318 12,340 299 66 RF-SE-33-RI Rigaku. Inc 242 257 658 272 1,258 12,280 284 67 RF-SE-16-XX Reference Laboratory 85 J- 72 J- 310 J- 820 J- 73 J- 16,000 J- 24 J- 67 RF-SE-4I-XX Reference Laboratory 100 82 360 950 85 18,000 25 67 RF-SE-48-XX Reference Laboratory 100 87 380 1,000 90 19,000 27 67 RF-SE-I 6-RI Rigaku,Inc 215 24 755 686 65 11,960 -21 67 RF-SE-4I-RI Rigaku, Inc. 178 49 787 475 66 12,153 -25 67 RF-SE-48-RI Rigaku, Inc. 238 40 801 616 63 11,987 -27 D-39 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Mr Nl Sc Afi V Zn 65 RF-SF-OI-XX Reference Laboratory 47 200 21 37 29 1.700 65 RF-SI--09-XX Refeienee Laboiatoiy 45 220 23 42 32 1.900 65 RF-SIM l-XX Refcicnce Laboratory 52 210 20 40 29 1,800 65 RF-SIM 7-XX Reference Laboratory 20 210 22 40 30 1,800 65 RF-SII-29-XX Reference Laboiatory 20 240 26 44 35 2,100 65 RF-SI--37-XX Reference Laboratory 22 220 23 44 32 1.900 65 RF-SF-50-XX Reference Laboratoiy 19 200 20 3S 29 1.700 65 RF-SF-01-R1 Rigaku. Inc 53 149 16 229 56 1.239 65 RF-SF-09-RI Rigaku. Inc 54 132 16 241 54 1.127 65 RF-SIM l-RI Rigaku, Inc. 54 131 13 231 53 1,113 65 RF-SIM 7-RI Rigaku, Inc 64 131 IS 214 50 1.112 65 RF-SI--29-RI Rigaku, Inc 71 131 18 215 50 1,117 65 RF-SF-37-RI Rigaku, Inc 54 139 15 228 54 1.123 65 R F-SF-50-RI Rigaku. Inc 59 125 17 223 41 1.041 66 RF-SF-08-XX Reference Laboiatoiy 29 250 42 0 39 U 120 120 66 RF-SF-10-XX Reference Laboiatoiy 27 220 39 0 34 U 100 110 66 RF-SF-33-XX Reference Laboratoiy 28 240 41 0 33 U 120 130 66 RF-SF-OS-RI Rigaku. Inc 65 147 20 216 98 83 66 RF-SIM O-RI Rigaku. Inc 60 141 20 221 90 84 66 RF-SF-33-RI Rigaku, Inc 64 129 19 222 92 86 67 RF-SIM 6-XX Reference Laboratoiy 260 1,700 J - 1 2 U 130 J- 32 J- 760 J- 67 RF-S l;-41-XX Reference Laboratory 230 1,900 1 2 U 140 39 830 67 RF-SF-48-XX Reference Laboiatory 250 2.000 2 2 150 40 S80 67 RF-SIM 6-RI Rigaku,Inc 183 941 13 214 56 441 67 RF-SI--4I-RI Rigaku, Inc 170 956 7 228 48 455 67 RF-Sli-48-RI Rigaku, Inc 185 922 14 218 54 442 D-40 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Sb As Cd Cr Cu Fe Pb 68 RI:-SE-18-XX Reference Laboratory 320 810 770 950 78 16,000 860 68 RF-SE-35-XX Reference Laboratory 300 740 700 860 70 15,000 780 68 RF-SE-54-XX Reference Laboratory 320 880 840 1,000 86 18,000 920 68 RF-SE-18-RI Rigaku, Inc. 246 619 957 631 57 11,434 457 68 RF-SE-35-R1 Rigaku, Inc. 283 432 946 383 57 11,390 448 68 RF-SE-54-RI Rigaku, Inc. 235 609 945 633 57 11,492 460 69 RF-SE-20-XX Reference Laboratory 550 1300 540 94 93 20,000 28 69 RF-SE-46-XX Reference Laboratory 270 590 240 44 40 8,900 13 69 RF-SE-51-XX Reference Laboratory 480 1100 450 77 77 17,000 23 69 RF-SE-20-RI Rigaku, Inc 238 811 803 91 54 12,122 -16 69 RF-SE-46-RI Rigaku, Inc. 238 804 814 48 57 12,343 -15 69 RF-SE-51-RI Rigaku. Inc. 233 817 807 33 62 12,212 -8 70 RF-SE-2I-XX Reference Laboratory 1 3 U 62 1,700 76 1,000 16,000 2,100 70 RF-SE-40-XX Reference Laboratory 1.3 U 70 1,900 85 1,100 18,000 2,400 70 RF-SE-47-XX Reference Laboratory 1 3 U 72 1,900 90 1,200 19,000 2,400 70 RF-SE-2I-R1 Rigaku, Inc. 201 158 1,368 41 734 11,906 1,311 70 RF-SE-40-RI Rigaku, Inc. 442 58 1,407 89 759 11,948 1,356 70 RF-SE-47-RI Rigaku, Inc. 196 154 1,326 71 713 12,192 1,268 D-41 ------- Appendix D: Analytical Data Summary, Rigaku ZSX Mini II and Reference Laboratory (Continued) Blend No. Sample ID Source of Data Hr Ni Se Ar V Zn 68 RF-SE-18-XX Rcfcicnce Laboratory 600 390 140 140 390 120 68 RF-SE-35-XX Reference Laboratory 650 350 140 150 340 110 6S RF-SII-54-XX Refciencc Laboratory 670 420 160 ISO 410 120 68 RF-SE-I8-RI Rigaku.Inc 327 205 49 215 232 96 68 RF-SE-35-RI Rigaku.Ine 384 202 54 231 246 89 68 RF-SE-54-RI Rigaku. hie 334 201 48 216 237 77 69 RF-SE-20-XX Refcicncc Laboratory 0.48 1.400 3S0 59 36 1.400 69 RI-SH-46-XX Rercrcnee Laboratory 0 45 650 170 26 16 650 69 RF-SE-5I-XX Rererence Laboratory 0 48 1.200 320 48 30 1.200 69 RF-SE-20-RI Rigaku.Inc 53 636 92 207 52 655 69 RI--SE-46-RI Rigaku. Inc. 53 634 93 211 48 698 69 RI:-SE-51 -R1 Rigaku. Inc. 48 63S 92 205 51 671 70 RF-SE-21-XX Reference Laboratory 320 220 440 120 130 100 70 RF-SE-40-XX Reference Laboratory 280 250 480 100 150 120 70 R F-SE-47-XX Reference Laboratory 320 250 510 120 150 120 70 RF-SE-21 -R1 Rigaku,Inc 29 113 124 216 98 72 70 RF-SE-40-RI Rigaku.Inc 210 127 150 232 105 83 70 RF-SE-47-R1 Rigaku.Inc 38 10S 125 211 116 75 Notes: All concentrations reported in milligrams per kilogram (mg/kg), or parts per million (ppm). Sample results for which "0" or no value was reported were considered nondetections as reported by Xcalibur. Reference laboratory data qualifiers were as follows: J Estimated concentration J+ Concentration is considered estimated and biased high. J- Concentration is considered estimated and biased low. U Analyte is not detected; the associated concentration value is the sample reporting limit. D-42 ------- APPENDIX E STATISTICAL DATA SUMMARIES ------- E-l ------- Figure E-3: Linear Correlation Plot for Cadmium Reference Laboratory (ppm) Figure E-4: Linear Correlation Plot for Chromium Reference Laboratory (ppm) E-2 ------- Figure E-5: Linear Correlation Plot for Copper Reference Laboratory (ppm) Figure E-6: Linear Correlation Plot for Iron Reference Laboratory (ppm) E-3 ------- Figure E-7: Linear Correlation Plot for Lead Reference Laboratory (ppm) Figure E-8: Linear Correlation Plot for Mercury Reference Laboratory (ppm) E-4 ------- Figure E-9: Linear Correlation Plot for Nickel Reference Laboratory (ppm) Figure E-10: Linear Correlation Plot for Selenium Reference Laboratory (ppm) E-5 ------- Figure E-ll: Linear Correlation Plot for Silver Reference Laboratory (ppm) Figure E-12: Linear Correlation Plot for Vanadium Reference laboratory (ppm) E-6 ------- Figure E-13: Linear Correlation Plot for Zinc Reference Laboratory (ppm) E-7 ------- Box Plot for Relative Percent Difference (RPD) Rigaku ZSX Mini II Median; Box: 25%-75%; Whisker: Non-Outlier Range Sb-RL As Cr Fe Hg Se V Sb-CV Cd Cu Pb Ni Ag Zn 0 Median ~ 25%-75% 1 Non-Outlier Range o Outliers * Extremes Notes: The "box" in each box plot presents the range of RPD values that lie between the 25lh and 75lh percentiles (that is, the "quartiles") of the full RPD population for each element. In essence, the box displays the "interquartile range" of RPD values. The square data point within each box represents the median RPD for the population. The "whiskers" emanating from the top and bottom of each box represent the largest and smallest data points, respectively, that are within 1.5 times the interquartile range. Values outside the whiskers are identified as outliers and extremes. Some of the more significant extremes and outliers are labeled with the associated Blend numbers and sample site abbreviations (see the footnotes of Table E-5 for definitions). Also refer to Appendix D for the sampling site and analytical data associated with each Blend number. Figure E-14. Box and Whiskers Plot for Mean RPD Values Showing Outliers and Extremes for Target Elements, Rigaku ZSX Mini II Data Set. E-8 ------- Tabic E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rigaku ZSX Mini II Cone Antimony Matrix Range Statistic Kef Lab ERA Spike Arsenic Cadmium Chromium Copper Iron Lead Mercury Soil Level 1 Number 8 1 8 7 23 16 5 4 7 Minimum 28.3% 84.9% 1.0% 85 3% 2.0% 7.6% 6.1% 43.1% 3 6% Maximum 181.5% 84.9% 98.1% 165 0% 88.7% 97.9% 116.7% 104.1% 139.3% Mean 142.1% 84.9% 32.7% 126.8% 27.5% 38 9% 75.9% 78.9% 38.5% Median 161 2% 84.9% 14.0% 116.1% 21.0% 32.2% 93.3% 84 1% 24.3% Level 2 Number 5 1 4 7 4 8 13 4 6 Minimum 12.7% 84.8% 58.5% 5.5% 55.7% 27.0% 12.8% 42.4% 65 4% Maximum 150.7% 84.8% 79 1% 36 4% 65.5% 65.0% 53.7% 90.7% 134.7% Mean 70.4% 84 8% 71.6% 23.2% 60.5% 47.1% 40.0% 67.7% 103.0% Median 32.1% 84.8% 74 4% 21.4% 60.4% 49 3% 48.6% 68.9% 106.6% Level 3 Number 4 3 4 2 2 2 13 8 2 Minimum 0 1% 96.1% 70.2% 42.2% 68.7% 27 0% 49.8% 43 6% 104.3% Maximum 93 9% 162.0% 87.8% 57.1% 92.4% 39.0% 15.6% 104.9% 120.0% Mean 37 9% 122.1% 80.7% 49.7% 80.5% 33.0% 60.9% 65.2% 1 12.1% Median 28.8% 108.3% 82.4% 49.7% 80.5% 33.0% 60.3% 65 1% 112.1% Level 4 Number Minimum Maximum Mean Median -- — — -- -- — 7 49.6% 109.1% 76.3% 70.8% 5 49.2% 73 9% 64.4% 64 5% -- All Soil Number 17 5 16 16 29 26 38 21 15 Minimum 0.1% 84.8% 1.0% 5.5% 2 0% 7.6% 6.1 % 42.4% 3.6% Maximum 181.5% 162.0% 98.1% 165.0% 92 4% 97.9% 116.7% 104.9% 139.3% Mean 96.5% 107.2% 54.4% 71.9% 35.7% 41.0% 58.6% 68.1% 74.1% Median 1 16.8% 96.1% 71.3% 49.7% 29 3% 40.0% 58.5% 66.7% 78.3% ------- Tabic E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rigaku ZSX Mini II (Continued) Cone Matrix Range Statistic Nickel Selenium Silver Vanadium Zinc Soil Level 1 Number 23 4 3 12 19 Minimum 1.0% 57.9% 63.9% 13.7% 0.3% Maximum 101.3% 101.5% 96.7% 91.1% 138.0% Mean 45.1% 78.6% 84.2% 48.6% 35.6% Median 50.0% 77.6% 91.9% 57.8% 27.2% Level 2 Number 5 5 3 4 6 Minimum 44.4% 97.5% 40.4% 1.0% 43.8% Maximum 74.7% 110.8% 85.3% 26.5% 81.4% Mean 60.3% 103.5% 56.9% 17.7% 61.4% Median 60.6% 102.3% 45.1% 21.7% 58.7% Level 3 Number 6 4 7 4 9 Minimum 56.6% 95.8% 0.9% 6.0% 54.3% Maximum 111.8% 110.4% 59.6% 55.4% 104.2% Mean 77.2% 104.5% 33.7% 33.7% 72.0% Median 74.1% 105.9% 37.0% 36.8% 65.2% Level 4 Number Minimum Maximum Mean Median -- — — -- -- All Soil Number 34 13 13 20 34 Minimum 1.0% 57.9% 0.9% 1.0% 0.3% Maximum 111.8% 110.8% 96.7% 91.1% 138.0% Mean 53.0% 96.2% 50.7% 39.4% 49.8% Median 57.7% 101.5% 40.4% 31.4% 50.4% E-10 ------- Tabic E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rigaku ZSX Mini II (Continued) Cone Antimony Matrix Range Statistic Ref Lab ERA Spike Arsenic Cadmium Chromium Copper Iron Lead Mercurv Sediment Level 1 Number 4 4 8 3 7 8 3 6 2 Minimum 138 0% 25 1% 10.2% 100.7% 0.4% 19.9% 105.0% 14.5% 58.1% Maximum 179 7% 134 7% 82.3% 164.9%) 119.8% 55.0% 148.5% 91.3% 77.0% Mean 166.6% 90.8% 47.5% 129 7% 32.5% 29.6% 125.3% 62.7% 67.5% Median 174.4% 101.7% 47.3% 123 3% 9.3% 26.7% 122 4% 82.0% 67.5% Level 2 Number 4 4 3 4 3 4 19 4 4 Minimum 47.1% 35.3% 32 0% 42.5% 40.7% 38 4% 15.7% 60.9% 31.8% Maximum 90.6% 108 9% 158.7% 76.2% 52.9% 40 2% 44.7% 86.4% 158.1% Mean 74 4% 77.7% 79.5% 62.2% 48.8% 39.5% 32.5% 72.0% 91.0% Median 79 9% 83 3% 47.7% 65.0% 52.7% 39.7% 33.4% 70.3% 87.1% Level 3 Number 3 3 2 3 3 10 4 3 3 Minimum 20.3% 111 7% 20.6% 12.3% 43.7% 24.7% 30.0% 43.6% 59.0% Maximum 58.7% 134 0% 37.7% 29.2% 75 7% 84.2% 57.1% 71 4% 99.4% Mean 33.2% 120.6% 29.1% 20.8% 57 2% 62.9% 43.1% 56.6% 76.6% Median 20.6% 116.2% 29.1% 20.9% 52.2% 71.4% 42.7% 54.7% 71.4% Level 4 Number Minimum Maximum Mean Median -- -- -- -- -- -- 6 55.6% 92.1% 71.5% 70.5% -- -- All Sediment Number 11 11 13 10 13 22 32 13 9 Minimum 20.3% 25.1% 10.2% 12.3% 0.4% 19.9% 15.7% 14.5% 31.8% Maximum 179.7% 134.7% 158.7% 164.9% 119.8% 84.2% 148.5% 91 3% 158.1% Mean 96.7% 94.2% 52.1% 70 0% 42.0% 46.6% 49.9% 64 1% 81.0% Median 84.3% 108.9% 45.5% 65 0% 43.7% 40.0% 38.0% 71.4% 71.4% E-l 1 ------- Tabic E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rigaku ZSX Mini II (Continued) Cone Matrix Range Statistic Nickel Selenium Silver Vanadium Zinc Sediment Level 1 Number 18 5 5 6 18 Minimum 31.3% 30.1% 89.3% 27.7% 4.1% Maximum 104.7% 127.1% 138.9% 59.0% 80.9% Mean 64.2% 83.8% 116.2% 41.1% 41.4% Median 62.0% 89.6% 112.6% 39.2% 39.6% Level 2 Number 6 4 4 8 5 Minimum 45.9% 94.0% 13.7% 3.1% 46.5% Maximum 69.5% 121.3% 66.8% 52.1% 68.1% Mean 57.3% 108.0% 38.3% 24.7% 58.2% Median 57.1% 108.4% 36.3% 20.9% 59.4% Level 3 Number 4 3 3 3 4 Minimum 52.0% 103.6% 2.6% 35.5% 48.4% Maximum 79.8% 112.9% 64.0% 45.8% 78.3% Mean 66.0% 108.5% 33.5% 40.9% 65.8% Median 66.0% 109.1% 34.0% 41.4% 68.3% Level 4 Number Minimum Maximum Mean Median -- -- — — -- All Sediment Number 28 12 12 17 27 Minimum 31.3% 30.1% 2.6% 3.1% 4.1% Maximum 104.7% 127.1% 138.9% 59.0% 80.9% Mean 63.0% 98.1% 69.6% 33.4% 48.1% Median 63.1% 103.2% 65.4% 35.5% 48.6% E-l 2 ------- Tabic E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rigaku ZSX Mini II (Continued) Cone Antimony Matrix Range Statistic Kef Lab ERA Spike Arsenic Cadmium Chromium Copper Iron Lead Mercury All ZSX Mini II Number 28 16 29 26 42 48 70 34 24 Samples Minimum 0.1% 25.1% 1 0% 5.5% 0.4% 7.6% 6.1 % 14.5% 3.6% Maximum 181.5% 162.0% 158 7% 165.0% 119.8% 97.9% 148.5% 104.9% 158.1% Mean 96.6% 98.2% 53.4% 71.1% 37.7% 43.5% 54.6% 66.6% 76 7% Median 92.2% 102.2% 49.2% 60 9% 37.2% 40.0% 52.4% 66.8% 74 2% All All Instruments Number 206 1 10 320 209 338 363 558 392 192 Samples Minimum 0.1% 0.1% 0 2% 0.1% 0 1% 0.2% 0.0% 0.1% 0.0% Maximum 181.5% 162.0% 182.8% 168.1% 151.7% 1 11 1% 190.1% 135 2% 158.1% Mean 80.6% 62 7% 36.6% 29.6% 30.8% 24 6% 35.4% 30.9% 62.5% Median 84.3% 70 6% 26.2% 16.7% 26.0% 16.2% 26.0% 21 5% 58.6% Table E-l. Evaluation of Accuracy - Relative Percent Differences Versus Reference Laboratory Data Calculated for the Rigaku ZSX Mini II (Continued) Cone Matrix Range Statistic Nickel Selenium Silver Vanadium Zinc All ZSX Mini II Number 62 25 25 37 61 Samples Minimum 1.0% 30 1% 0 9% 1.0% 0 3% Maximum 111.8% 127.1% 138.9% 91 1% 138.0% Mean 57.5% 97 1% 59.8% 36.7% 49.0% Median 60.4% 101.5% 45.1% 35.2% 48.6% All All Instruments Number 403 195 177 218 471 Samples Minimum 0 3% 0.0% 0.0% 0 1% 0.0% Maximum 146.5% 127 1% 129.7% 129 5% 138 0% Mean 31 0% 32.0% 36.0% 42.2% 26.3% Median 25.4% 16.7% 28.7%. 38 3% 19 4% Notes: All RPDs presented in this table arc absolute values No samples reported by the reference laboratory 111 this concentration range Number Number of demonstration samples evaluated. Cone Concentration. Ref Lab Reference laboratory (Shcaly Environmental Services. Inc ) ERA Environmental Resource Associates, Inc RPD Relative percent difference E-l 3 ------- Tabic E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Minii Cone Matrix Range Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Soil Level 1 Number 8 8 7 23 16 5 4 7 23 Minimum 3.4% 3.4% 0.9% 6.2% 1.6% 0.5% 3.6% 1.4% 1.4% Maximum 41.4% 20.1% 4.1% 29.5% 50.5% 2.5% 26.3% 136.8% 164.2% Mean 12.9% 13.2% 2.2% 15.7% 7.7% 1.2% 11.2% 26.2% 11.6% Median 6.2% 13.0% 1.8% 14.8% 4.5% 1.0% 7.5% 9.6% 4.7% Level 2 Number 5 4 7 4 8 13 4 6 5 Minimum 6.3% 1.6% 0.4% 1.6% 0.8% 0.2% 1.7% 2.2% 1.1% Maximum 7.3% 11.4% 3.6% 8.1% 4.3% 2.5% 2.6% 49.8% 2.7% Mean 6.9% 4.9% 2.0% 4.6% 2.1% 0.6% '2.1% 12.8% 2.1% Median 6.9% 3.2% 2.2% 4.3% 1.9% 0.5% 2.1% 5.2% 2.3% Level 3 Number 4 4 2 2 2 13 8 2 6 Minimum 3.7% 0.7% 0.9% 2.6% 0.4% 0.2% 0.4% 2.3% 0.5% Maximum 6.5% 3.7% 1.2% 2.7% 0.8% 43.2% 2.2% 2.6% 77.8% Mean 5.0% 1.9% 1.1% 2.7% 0.6% 4.3% 1.6% 2.4% 13.9% Median 4.9% 1.7% 1.1% 2.7% 0.6% 0.6% 1.8% 2.4% 1.3% Level 4 Number Minimum Maximum Mean Median -- — — — -- 7 0.4% 1.3% 0.8% 0.7% 5 0.5% 1.4% 0.9% 0.8% -- — All Soil Number 17 16 16 29 26 38 21 15 34 Minimum 3.4% 0.7% 0.4% 1.6% 0.4% 0.2% 0.4% 1.4% 0.5% Maximum 41.4% 20.1% 4.1% 29.5% 50.5% 43.2% 26.3% 136.8% 164.2% Mean 9.3% 8.3% 2.0% 13.2% 5.5% 2.0% 3.3% 17.7% 10.6% Median 6.3% 6.1% 1.8% 13.0% 3.4% 0.6% 1.8% 5.3% 3.9% E-14 ------- Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Minii Cone Matrix Range Statistic Nickel Selenium Silver Vanadium Zinc Soil Level 1 Number 23 4 3 12 19 Minimum 1.4% 3.9% 2.4% 9.7% 0.9% Maximum 164 2% 49 2% 3.4% 22.4% 192.9% Mean 1 1.6% 17.2% 2 8% 13.6% 14.3% Median 4.7% 7.9% 2.5% 12.3% 4.2% Level 2 Number 5 5 3 4 6 Minimum 1.1 % 0.1 % 0.9% 1 1% 0.8% Maximum 2.7% 4.6% 3.5% 11 1% 2.4% Mean 2.1% 2.8% 2.1% 5.8% 1.5% Median 2.3% 3.2% 2.0% 5.5% 1.4% Level 3 Number 6 4 7 4 9 Minimum 0.5% 1.2% 1 2% 0.4% 0.6% Maximum 77.8% 2.3% 2.8% 5.8% 82 5% Mean 13.9% 1.8% 2 3% 4 1% 10.2% Median 1 3% 1.9% 2.4% 5.2% 1 0% Level 4 Number Minimum Maximum Mean Median -- — -- -- -- All Soil Number 34 13 13 20 34 Minimum 0.5% 0.1% 0.9% 0 4% 0.6% Maximum 164.2% 49.2% 3.5% 22 4% 192.9% Mean 10.6% 6.9% 2.3% 10 2% 10.9% Median 3.9% 3.2% 2.4% 11 1% 2.1% E-15 ------- Tabic E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Mini (Continued) Cone Matrix Range Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Sediment Level 1 Number 4 8 3 7 8 3 6 2 Minimum 3.9% 8.8% 0.8% 6.1% 0.6% 0.4% 1.6% 3.8% Maximum 16.3% 46.2% 1.2% 22.0% 7.1% 1.4% 6.2% 11.4% Mean 10.5% 19.4% 1.1% 17.1% 3.8% 0.7% 3.8% 7.6% Median 11.0% 15.8% 1.2% 17.8% 3.4% 0.4% 4.0% 7.6% Level 2 Number 4 3 4 3 4 19 4 4 Minimum 2.0% 3.2% 0.7% 1.8% 1.3% 0.2% 1.4% 3.6% Maximum 14.4% 15.8% 3.0% 20.5% 3.1% 2.9% 2.6% 110.0% Mean 6.8% 10.0% 1.9% 10.5% 2.2% 0.9% 2.2% 32.1% Median 5.5% 11.2% 1.9% 9.1% 2.1% 0.7% 2.3% 7.3% Level 3 Number 3 2 3 3 10 4 3 3 Minimum 1.2% 0.8% 0.7% 9.7% 0.8% 0.5% 0.9% 2.7% Maximum 10.0% 19.0% 3.7% 26.2% 2.9% 1.4% 3.3% 9.0% Mean 6.1% 9.9% 2.5% 18.0% 1.7% 1.0% 2.3% 5.1% Median 7.2% 9.9% 3.0% 18.2% 1.7% 1.1% 2.6% 3.6% Level 4 Number Minimum Maximum Mean Median -- -- -- -- -- 6 0.3% 17.8% 3.5% 0.7% -- -- All Sediment Number 11 13 10 13 22 32 13 9 Minimum 1.2% 0.8% 0.7% 1.8% 0.6% 0.2% 0.9% 2.7% Maximum 16.3% 46.2% 3.7% 26.2% 7.1% 17.8% 6.2% 110.0% Mean 8.0% 15.8% 1.8% 15.8% 2.6% 1 4% 3.0% 17.6% Median 7.2% 14.4% 1.3% 17.8% 2.1% 0.7% 2.6% 4.5% E-16 ------- Tabic E-2. Evaluation of Precision - Relative Standard Deviations Calculated lor the Kigaku ZSX Mini (Continued) Cone Matrix Range Statistic Nickel Selenium Silver Vanadium Zinc Sediment Level 1 Number 18 5 4 6 18 Minimum 1.8% 2.5% 1.2% 1 7% 1 8% Maximum 25 5% 12 6% 5.2% 7.4% 18.4% Mean 5.7% 9.4% 2.3% 4.3% 6.1% Median 4.0% 10.8% 1 4% 4 4% 4.8% Level 2 Number 6 4 4 8 18 Minimum 0.7% 2.0% 0 9% 3.1% 1.8% Maximum 8.4% 7.6% 3 3% 19.2% 3.6% Mean 4 5% 6.0% 1.7% 6.8% 2.7% Median 5 2% 7 2% 1.3% 4.7% 2.8% Level 3 Number 4 3 3 3 4 Minimum 0.3% 0.9% 3.6% 2.8% 0.8% Maximum 1.8% 11.2% 5.0% 7 1% 5 2% Mean 1.3% 5 0% 4 2% 4 9% 2.6% Median 1.6% 3.1% 4.1% 4 7% 2.2% Level 4 Number Minimum Maximum Mean Median -- -- -- -- — All Sediment Number 28 12 11 17 27 Minimum 0.3% 0.9% 0.9% 1 7% 0.8% Maximum 25.5% 12.6% 5.2% 19 2% 1 8.4% Mean 4.8% 7.2% 2.6% 5 6% 5.0% Median 3.7% 7.6% 1.5% 4.7% 3.6% E-17 ------- Tabic E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Mini (Continued) Cone Matrix Range Statistic Antimonv Arsenic Cadmium Chromium Copper Iron Lead Mercury All Samples ZSX Mini II Number 28 29 26 42 48 70 34 24 Minimum 1.2% 0.7% 0.4% 1.6% 0.4% 0.2% 0.4% 1.4% Maximum 41.4% 46.2% 4.1% 29.5% 50.5% 43.2% 26.3% 136.8% Mean 8.8% 11.6% 1.9% 14.0% 4.1% 1.7% 3.2% 17.7% Median 6.4% 10.1% 1.6% 14.7% 2.3% 0.6% 2.0% 4.9% All Samples All Instruments Number 206 320 209 338 363 558 392 192 Minimum 0.5% 0.2% 0.4% 0.6% 0.1% 0.1% 0.2% 1.0% Maximum 97.7% 71.7% 92.8% 116.3% 58.3% 101.8% 115.6% 137.1% Mean 8.9% 11.2% 8.2% 15.9% 7.5% 5.2% 9.3% 14.3% Median 6.1% 8.2% 3.6% 12.1% 5.1% 2.2% 4.9% 6.8% Table E-2. Evaluation of Precision - Relative Standard Deviations Calculated for the Rigaku ZSX Mini (Continued) Cone Matrix Range Statistic Nickel Selenium Silver Vanadium Zinc All Samples ZSX Mini II Number 62 25 24 37 61 Minimum 0.3% 0.1% 0.9% 0.4% 0.6% Maximum 164.2% 49.2% 5.2% 22.4% 192.9% Mean 8.0% 7.0% 2.5% 8.1% 8.3% Median 3.7% 3.9% 2.4% 5.9% 2.5% All Samples All Instruments Number 403 195 177 218 471 Minimum 0.3% 0.1% 0.6% 0.4% 0.1% Maximum 164.2% 98.8% 125.3% 86.1% 192.9% Mean 10.8% 7.2% 10.3% 12.5% 8.0% Median 7.0% 4.5% 5.2% 8.5% 5.3% Notes: No samples reported by the reference laboratory in this concentration range. Number Number of demonstration samples evaluated. RSD Relative standard deviation E-18 ------- Tabic E-3. Evaluation of Precision - Relative Standard Deviations Calculated for the Reference Laboratory Matrix Statistic Antimony Arsenic Cadmium Chromium Copper Iron Lead Mercury Nickel Selenium Silver All Soil Number 17 23 15 34 26 38 33 16 35 13 13 Minimum 3.6% 1.4% 0.9% 1.4% 0 0% 1.6% 0.0% 0 0% 0.0% 0.0% 2.3% Maximum 38 0% 45.8% 21.4% 137.0% 21.0% 46 2% 150.0% 50.7% 44.9% 22.7% 37.1% Mean 14 3% 11.7% 1 1.1% 14.3% 10.1% 10 2% 17.6% 13.8% 1 1 4% 8.9% 12.4% Median 9.8% 12.4% 9 0% 10 6% 9.1 % 8.7% 13 2% 6.6% 10 0% 7.1% 7.5% All Sediment Number 7 24 10 26 21 31 22 10 27 12 10 Minimum 2 9%, 2 4% 2.9% 4.6% 1.8% 2 7% 0.0% 2.8% 0.6% 1.3% 1 0% Maximum 33.6% 36.7% 37.5% 35.5% 38 8% 37.5% 41.1% 48 0% 35.8% 37.3% 21.3% Mean 14 4% 10.7% 11.4% 9.8% 9 7% 9.9% 1 1.6% 14.3% 9.4% 10.0% 9.4% Median 9.1 % 9.2% 8.2% 7 5% 8 9% 8.1% 7.4% 6 9% 7.3% 7.6% 6.6% All Number 24 47 25 60 47 69 55 26 62 25 23 Minimum 2.9% 1.4% 0.9% 1.4% 0.0% 1.6% 0.0% 0.0% 0 0% 0.0% 1.0% Maximum 38.0% 45.8% 37.5% 137 0% 38 8% 46.2% 150.0% 50.7% 44.9% 37.3% 37.1% Mean 14 3% 11.2% 1 1.2% 12.4% 9.9% 10 1% 15.2% 14 0% 10.6% 9.4% 11 1% Median 9.5% 9.5% 9 0% 8.4% 8.9% 8.5% 8 6% 6.6% 8.2% 7.4% 7.1% IE-19 ------- Tabic E-3. Evaluation of Precision - Relative Standard Deviations Calculated for the Reference Laboratory (Continued) Matrix Statistic Vanadium Zinc All Soil Number 21 35 Minimum 0.0% 1.0% Maximum 18.1% 46.5% Mean 8.4% 10.4% Median 6.6% 9.1% All Sediment Number 17 27 Minimum 2.2% 1.4% Maximum 21.9% 35.8% Mean 8.4% 8.9% Median 8.1% 6.9% All Number 38 62 Minimum 0.0% 1.0% Maximum 21.9% 46.5% Mean 8.4% 9.8% Median 7.2% 7.4% Notes: Number Number of demonstration samples evaluated. RSD Relative standard deviation E-20 ------- Table E-4. Evaluation of the Effects of liitcrfcrent Elements on RPDs (Accuracy) of Other Target Elements1 Parameter Statistic Lead Effects on Arsenic Copper Effects on Nickel Nickel Effects on Copper Intcrfcrcnt/Elcinent Ratio <5 5- 10 >10 <5 5 - 10 >10 <5 5 - 10 >10 Number of Samples 15 7 7 43 5 14 39 1 8 RPD of Target Element2 Minimum -3.3% 40.7% -57.9% -56.5% 44.6% 1.0% 7.6% 31 1% 11.9% Maximum 158.7% 87.8% 82.1% 111.8% 66.4% 78.8% 97.9% 31.1% 70.2% Mean 54.2% 71.1% 15.1% 57.7% 56 4% 47.8% 46.3% 31.1% 31.4% Median 45 5% 76.5% 11.7% 62.7% 55 3% 53 3% 46.1% 31.1% 30.1% RPD of Target Element Minimum 3.3% 40 7% 1 0% 7.9% 44.6% 1 0% 7.6% 31.1% 11.9% (Absolute Value)2 Maximum 158.7% 87 8% 82.1% 111.8% 66.4% 78.8% 97.9% 31 1% 70.2% Mean 54.7% 71 1% 32.9% 60.8% 56.4% 47.8% 46.3% 31 1% 31.4% Median 45.5% 76.5% 16.3% 62.7% 55.3% 53.3% 46.1% 31.1% 30.1% Interferent Minimum 47 317 805 1 494 385 33 203 635 Concentration Range Maximum 455 21053 9647 735 1301 3436 355 203 1357 Mean 206 7435 2654 98 754 1398 94 203 976 Median 173 3716 1390 62 700 1017 80 203 963 Target Element Minimum 49 77 48 18 58 38 30 57 57 Concentration Range Maximum 1361 2016 844 1357 139 226 3436 57 94 Mean 264 762 192 273 92 81 724 57 73 Median 92 487 93 99 88 60 565 57 70 E-21 ------- Tabic E-4. Evaluation of the Effects of Intcrfcrcnt Elements on RPDs (Accuracy) of Other Target Elements' (Continued) 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 48 3 10 RPD of Target Element Minimum 7.6% 40.9% 12.0% -138.0% 11.2% -4.1% Maximum 84.2% 47.4% 97.9% 104.2% 80.9% 72.3% Mean 44.1% 44.1% 41.7% 42.3% 43.5% 44.4% Median 40.2% 44.1% 31.0% 50.2% 38.4% 46.2% RPD of Target Element Minimum 7.6% 40.9% 12.0% 0.3% 11.2% 4.1% (Absolute Value) Maximum 84.2% 47.4% 97.9% 138.0% 80.9% 72.3% Mean 44.1% 44.1% 41.7% 50.2% 43.5% 45.2% Median 40.2% 44.1% 31.0% 53.0% 38.4% 46.2% Interferent Minimum 51 401 446 16 565 708 Concentration Range Maximum 3102 3980 2670 1316 735 3436 Mean 509 2190 1487 218 659 1682 Median 92 2190 1430 73 676 1301 Target Element Minimum 30 99 56 37 77 59 Concentration Range Maximum 3436 965 107 3980 92 184 Mean 771 532 76 827 86 90 Median 567 532 77 410 88 78 Notes: 1. Concentrations arc 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 E-22 ------- Tabic E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements Antimony Arsenic Cadmium Matrix Reference Laboratory Certified Value Reference Laboratory Reference Laboratory Matrix Site Description Statistic RPI) KPDABS Val RPI) KPI) A US Val KPI) KPI) A US Val KPI) KPI) ABS Val Soil AS Fine to medium sand (steel processing) Number Minimum Maximum Mean Median -- - — - - - 3 -162.5% -5.5% -94 7% -116 1% 3 5.5% 162.5% 94.7% 116.1% Soil BN Sandy loam, low Number 4 4 1 1 6 6 5 5 organic (ore residuals) Minimum -160 3% 3.5% 108.3% 108.3% 16.3% 16.3% -87.4% 19.6% Maximum 3 5% 160 3% 108.3% 108 3% 79.1% 79 1% 57.1% 87.4% Mean -112.2% 114.0% 108.3% 108.3% 56.2% 56 2% -11.8% 42.4% Median -146.1% 146.1% 108.3% 108.3% 64.4% 64.4% -21 4% 26.8% Soil CN Sandy loam (burn pit Number 2 2 2 2 1 1 2 2 residue) Minimum -162.1% 12.7% -84.9% 84.8%. -3.3% 3.3% -165 0% 21.2% Maximum -12.7% 162.1% 84 8% 84.9% -3.3% 3.3% -21 2% 165.0% Mean -87.4% 87.4% 0.0% 84.9% -3.3% 3.3% -93.1% 93 1% Median -87.4% 87.4% 0 0% 84.9% -3.3% 3.3% -93.1% 93.1% Soil & KP Soil: Fine to medium Number 2 2 -- — — -- __ Sediment quartz sand. Sed.: Sandy loam, high organic. (Gun and skeet ranges) Minimum Maximum Mean Median -169.5% -137.3% -153.4% -153.4% 137 3% 169 5% 153.4% 153.4% - - — - - - Sediment LV Clay/clay loam, salt Number 4 4 4 4 3 3 5 5 crust (iron and other precipitate) Minimum Maximum -169 6% 20 3% 0.1% 169.6% -84.4% 116.2% 81.3% 116 2% 11.7% 158.7% 11.7% 158 7% -123.3% 36.4% 12.3% 123.3% Mean -49.1% 59.3% 52.3% 94.5% 84.2% 84.2% -29.8% 49.3% Median -23.5% 33.7% 88 7% 90 2% 82.3% 82.3% -31.9% 36.4% Sediment RF Silty fine sand (tailings) Number 5 5 5 5 10 10 5 5 Minimum -179.7% 20.6% -134 7% 35.3% -57.9% 10.2% -164 9% 20.9% Maximum 58.7% 179.7% 134 0% 134.7% 49.2% 51.9% 29 2% 164.9% Mean -71.0% 102.7% 5 5% 106.9% 26.3% 37.9% -59.6% 71.3% Median -75.6% 75.6% 35.3% 118.9% 36.6% 40.2% -65.4% 65 4% E-23 ------- Tabic E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) Antimony Arsenic Cadmium Matrix Reference Laboratory Certified Value Reference Laboratory Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Val Soil SB Coarse sand and gravel (ore and Number Minimum 5 -181.5% 5 14.8% 1 162.0% 1 162.0% 2 86 1% 2 86.1% 1 42.2% 1 42.2% waste rock) Maximum 93.9% 181.5% 162.0% 162.0% 98 1% 98.1% 42.2% 42.2% Mean -10 2% 75.3% 162.0% 162.0% 92 1% 92.1% 42.2% 42.2% Median 14.8% 54.1% 162.0% 162 0% 92.1% 92.1% 42.2% 42.2% Sediment TL Silt and clay (slag- enriched) Number Minimum 3 -138.0% 3 84.3% 3 25.1% 3 25.1% 1 56 8% 1 56.8% 2 -100.7% 2 64.7% Maximum -84.3% 138.0% 108.9% 108 9% 56.8% 56.8% -64.7% 100.7% Mean -104.3% 104.3% 73.1% 73 1% 56.8% 56.8% -82.7% 82 7% Median -90 6% 90.6% 85.4% 85.4% 56.8% 56 8% -82.7% 82.7% Soil WS Coarse sand and gravel (roaster slag) Number Minimum 3 -180.9% 3 28.3% - - 6 -4.5% 6 1.0% 3 -158.6% 3 85.3% Maximum -28.3% 180.9% - - 87 8% 87.8% -85.3% 158.6% Mean -108.7% 108.7% - - 54 3% 55.8% -118.9% 118.9% Median -116.8% 116.8% - — 79 3% 79.3% -112.8% 112.8% All Number 28 28 16 16 29 29 26 26 Minimum -181.5% 0 1% -134 7% 25.1% -57.9% 1.0% -165.0% 5.5% Maximum 93 9% 181.5% 162.0% 162.0% 158.7% 158.7% 57 1% 165.0% Mean -77 6% 96.6% 45 4% 98.2% 48.8% 53.4% -56.0% 71.1% Median -87.4% 92 2% 85.1% 102.2% 47.7% 49.2% -53.6% 60.9% E-24 ------- Tabic E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Clements (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 Val Soil AS Fine to medium sand (steel processing) Number Minimum 2 38 3% 2 38.3% 3 39.0% 3 39 0% 3 19 2% 3 19 2% Maximum 48 5% 48.5% 97 9% 97.9% 109 1% 109.1% Mean 43.4% 43.4% 70.4% 70 4% 74 1% 74 1% Median 43 4% 43.4% 74.3% 74 3% 94.0% 94 0% Soil BN Sandy loam, low organic (ore residuals) Number Minimum 4 -14 2% 4 14.2% 6 29 7% 6 29.7% 7 48.6% 7 48.6% Maximum 92.4% 92.4% 53 6% 53.6% 58.9% 58.9% Mean 45 2% 52 3% 40 7% 40.7% 52.5% 52.5% Median 51.4% 51 4% 40 0% 40 0% 52 7% 52 7% Soil CN Sandy loam (bum pit residue) Number Minimum 1 16.5% 1 16 5% 3 7.6% 3 7 6% 3 25 7% 3 25 7% Maximum 16.5% 16 5% 65.0% 65.0% 76.3% 76.3% Mean 16.5% 16.5% 34.5% 34.5% 51.1% 51.1% Median 16.5% 16.5% 31.0% 31.0% 51.3% 51 3% Soil & Sediment KP Soil. Fine to medium quartz sand Scd.: Sandy loam, high organic. Number Minimum Maximum 3 27 1% 43.0% 3 27 1% 43 0% 2 12.5% 27.0% 2 12 5% 27 0% 6 -148.5% -70.3% 6 70 3% 148 5% (Gun and skeet ranges) Mean 35 7% 35.7% 19.8% 19 8% -107.4% 107 4% Median 37.0% 37 0% 19.8% 19 8% -105.0% 105 0% Sediment LV Clay/clay loam, salt crust (iron and other precipitate) Number Minimum 7 -119 8% 7 0.4% 4 1 1.9% 4 11 9% 12 -105.0% 12 12 8% Maximum 75 7% 119 8% 55 0% 55 0% 92.1% 105 0% Mean 8 7% 62.6% 37 2% 37 2% 31 3% 48.8% Median 52 7% 62.9% 40 9% 40 9% 33 7% 39.4% Sediment RF Silly fine sand (tailings) Number 6 6 13 13 13 13 Minimum -9 3% 0 9% 19.9% 19.9% 22 3% 22 3% Maximum 52 9% 52.9% 48 9% 48.9% 57.1% 57 1% Mean 29 9% 33 3% 31 8% 31 8% 37.0% 37 0% Median 42.2% 42 2% 31 1% 31 1% 35 2% 35.2% E-25 ------- Tabic 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 Val Soil SB Coarse sand and gravel Number 10 10 4 4 12 12 (ore and waste rock) Minimum -46.3% 2.0% 30.6% 30.6% -6.1% 6 1% Maximum 68.7% 68.7% 70 2% 70.2% 75 6% 75.6% Mean -1 1% 17 5% 48.6% 48.6% 55.9% 56.9% Median -3.8% 7.8% 46.9% 46 9% 59.7% 59.7% Sediment TL Silt and clay (slag- Number 2 2 7 7 7 7 enriched) Minimum -5 0% 5.0% 57 6% 57 6% 20.7% 20 7% Maximum 23 3% 23.3% 84.2% 84.2% 76.5% 76.5% Mean 9.1% 14.1% 72.3% 72.3% 42.7% 42 7% Median 9.1% 14 1% 72.5% 72.5% 35.4% 35.4% Soil WS Coarse sand and gravel Number 7 7 6 6 7 7 (roaster slag) Minimum -88.7% 16.8% 12.0% 12.0% 34.8% 34.8% Maximum 55.7% 88.7% 50.8% 50.8% 69.5% 69.5% Mean -19.0% 45 7% 38.1% 38.1% 55.1% 55.1% Median -22.0% 29.3% 44.1% 44.1% 60 3% 60.3% All Number 42 42 48 48 70 70 Minimum -119 8% 0.4% 7 6% 7.6% -148.5% 6 1% Maximum 92 4% 119.8% 97.9% 97.9% 109.1% 148.5% Mean 12.0% 37.7% 43.5% 43.5% 33.0% 54.6% Median 16.7% 37.2% 40.0% 40.0% 46.6% 52.4% E-26 ------- Tabic E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) Matrix Lead Reference Laboratory Mercury Reference Laboratory Nickel Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Val Soil AS Fine to medium sand (steel proeessing) Number Minimum Maximum Mean Median 3 90.7% 104 9% 99.9% 104 1% 3 90 7% 104.9% 99.9% 104 1% -- - 3 60.6% 101.3% 77 7% 71 3% 3 60.6% 101.3% 77.7% 71 3% Soil BN Sandy loam, low organic (ore residuals) Number Minimum 5 63 6% 5 63.6% 1 -39.9% 1 39 9% 6 31.7% 6 31 7% Maximum 74 7% 74.7% -39.9% 39.9% 81.0% 81.0% Mean 70 5% 70 5% -39 9% 39.9% 58.9% 58.9% Median 73 5% 73 5% -39 9% 39.9% 62 0% 62.0% Soil CN Sandy loam (burn pit residue) Number Minimum 2 86.3% 2 86.3% 2 -18 8% 2 18.8% 3 7 9% 3 7 9% Maximum 93.6% 93.6% 65 4% 65.4% 74 7% 74 7% Mean 90.0% 90 0% 23.3% 42.1% 51 4% 51 4% Median 90.0% 90 0% 23 3% 42.1% 71.5% 71.5% Soil & Sediment KP Soil: Fine to medium quartz sand. Sed.. Sandy loam, high organic. (Gun and skeet ranges) Number Minimum Maximum Mean Median 6 -14.5% 64.5% 34.4% 42.8% 6 14 5% 64 5% 39 3% 42 8% — - 3 -10.0% 11 9% 4 6% 11 8% 3 10 0% 11 9% 11 2% 11 8% Sediment LV Clay/clay loam, salt crust (iron and other precipitate) Number Minimum 2 43.6% 2 43.6% 4 -3.6% 4 3 6% 11 48 8% 11 48 8% Maximum 43.6% 43 6% 71.4% 71 4% 104.7% 104.7% Mean 43.6% 43.6% 43.4% 45 1% 70.4% 70 4% Median 43.6% 43.6% 52.8% 52 8% 65.5% 65 5% Sediment RF Silty fine sand (tailings) Number 8 8 5 5 13 13 Minimum 54 7% 54 7% -77.0% 31.8% 45.9% 45.9% Maximum 91 3% 91 3% 107.2% 107 2% 69.5% 69 5% Mean 75 3% 75 3% 12.6% 66 6% 57.8% 57 8% Median 78.5% 78.5% 31.8% 59 0% 55.9% 55 9% E-27 ------- Tabic E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) Lead Mercury Nickel Matrix Reference Laboratory Reference Laboratory Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Val Soil SB Coarse sand and gravel Number — — 10 10 10 10 (ore and waste rock) Minimum -- -- -139.3% 5.3% -56.5% 50.0% Maximum - -- 134.7% 139.3% 111 8% 111 8% Mean -- -- 65.7% 94 6% 58.4% 69.7% Median -- — 97.8% 112.1% 65.3% 65.3% Sediment TL Silt and clay (slag- Number 2 2 2 2 6 6 enriched) Minimum 71.4% 71.4% 99.4% 99.4% 31.3% 31 3% Maximum 86.4% 86.4% 158 1% 158.1% 78.8% 78.8% Mean 78 9% 78 9% 128.8% 128.8% 60.0% 60 0% Median 78.9% 78.9% 128.8% 128.8% 66.8% 66.8% Soil WS Coarse sand and gravel Number 6 6 -- 7 7 (roaster slag) Minimum 46.5% 46.5% - - 1.0% 1.0% Maximum 70.7% 70.7% - - 50 4% 50.4% Mean 58.1% 58.1% - -- 29 8% 29.8% Median 57.6% 57.6% — — 37.6% 37.6% All Number 34 34 24 24 62 62 Minimum -14.5% 14.5% -139.3% 3.6% -56.5% 1 0% Maximum 104.9% 104.9% 158.1% 158 1% 111.8% 111.8% Mean 65.7% 66.6% 48 2% 76.7% 55.4% 57.5% Median 66.8% 66.8% 66.2% 74.2% 60 4% 60.4% E-28 ------- Tabic E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) Selenium Silver Vanadium Zinc Matrix Reference Laboratory Reference Laboratory Reference L iboratorv Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Val Soil AS Kmc to medium sand (steel processing) Number Minimum 1 97.5% 1 97 5% 1 40.4% 1 40.4% 1 13 7% 1 13.7% 3 43 7% 3 43.7% Maximum 97.5% 97 5% 40.4% 40.4% 13.7% 13 7% 89 3% 89.3% Mean 97 5% 97 5% 40.4% 40 4% 13.7% 13 7% 71.5% 71 5% Median 97 5% 97 5% 40 4% 40 4% 13.7% 13 7% 81 4% 81.4% Soil 13 N Sandy loam, low Number 4 4 4 4 4 4 7 7 organic (ore residuals) Minimum 57.9% 57.9% -91 9% 36 8% -27 6% 19.6% 21 2% 21 2% Maximum 1 10 4% 110 4% -36.8% 91 9% 55 4% 55 4% 74 4% 74 4% Mean 90.2% 90 2% -53.6% 53 6% 8.4% 32 1% 51 1% 51.1% Median 96.2% 96 2% -42.8% 42.8% 3.0% 26 6% 54.6% 54.6% Soil CN Sandy loam (burn pit residue) Number Minimum 2 65 0% 2 65.0% 2 -96 7% 2 85 3% 1 26 5% 1 26.5% 3 0.3% 3 0 3% Maximum 1 10.8% 110 8% -85.3% 96 7% 26 5% 26.5% 61 3% 61.3% Mean 87 9% 87.9% -91.0% 91 0% 26.5% 26 5% 39 2% 39.2% Median 87 9% 87.9% -91.0% 91 0% 26.5% 26 5% 56.1% 56.1% Soil & Sediment KP Soil: Fine to medium quartz sand. Sed.: Sandy loam, high organic. (Gun and skcct ranges) Number Minimum Maximum Mean Median -- -- - - — - 2 -23 3% 11.2% -6.0% -6 0% 2 1 1 2% 23 3% 17.2% 17.2% Sediment LV Clay/clay loam, salt crust (iron and other precipitate) Number Minimum Maximum 5 94 0% 109 1% 5 94 0% 109.1% 4 -112 6% 2 6% 4 0 9% 1 12.6% 9 -40.3% 41 4% 9 3.1% 41 4% 9 -9 9% 62.3% 9 4 1% 62 3% Mean 100.4% 100.4% -44 0% 45 7% 1 0% 22.5% 24.2% 28.8% Median 100 3% 100.3% -33.0% 34 7% 3.1% 19.8% 17 4% 17.4% Sediment RF Silty fine sand (tailings) Number Minimum 5 30 1% 5 30.1% 5 -138.9% 5 34.0% 3 19.2% 3 19 2% 13 28 4% 13 28 4% Maximum 1 12 9% 112.9% -34 0% 138.9% 45 8% 45 8% 78.3% 78 3% Mean 82.7% 82.7% -82 2% 82.2% 31 6% 31 6% 52 5% 52.5% Median 97.6% 97 6% -64.0% 64 0% 29 7% 29.7% 48.4% 48.4% E-29 ------- Table E-5. Evaluation of the Effects of Soil Type on RPDs (Accuracy) of Target Elements (Continued) Selenium Silver Vanadium Zinc Matrix Reference Laboratory Reference Laboratory Reference Laboratory Reference Laboratory Matrix Site Description Statistic RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Val RPD RPD ABS Val Soil SB Coarse sand and Number 3 3 1 1 9 9 10 10 gravel (ore and Minimum 101 5% 101.5% -38.3% 38.3% -91.1% 1.0% -138 0% 10.8% waste rock) Maximum 110 3% 110.3% -38.3% 38.3% 38.3% 91.1% 104.2% 138 0% Mean 106.1% 106.1% -38.3% 38.3% -48.3% 57.0% 20.6% 50.3% Median 106 6% 106.6% -38.3% 38.3% -60.9% 60.9% 30.9% 36.2% Sediment TL Silt and clay Number 4 4 4 4 7 7 7 7 (slag-enriched) Minimum 89.6% 89.6% -110.6% 13.7% -59.0% 22 0% 33 0% 33.0% Maximum 127.1% 127.1% -13.7% 110.6% -22.0% 59.0% 80 9% 80.9% Mean 114 3% 114 3% -60.5% 60.5% -42.0% 42 0% 60 2% 60.2% Median 120 3% 120 3% -58.8% 58.8% -41.0% 41.0% 63.9% 63.9% Soil WS Coarse sand and Number 1 1 4 4 3 3 7 7 gravel (roaster Minimum 101.5% 101 5% -63.9% 22.8% -27.6% 20.7% 28 6% 28 6% slag) Maximum 101.5% 101 5% 59.6% 63.9% 35.2% 35.2% 76 1% 76 1% Mean 101.5% 101.5% 13 9% 45.8% -4.4% 27.8% 57 1% 57.1% Median 101.5% 101.5% 29 9% 48 3% -20.7% 27.6% 60.1 % 60.1% All Number 25 25 25 25 37 37 61 61 Minimum 30.1% 30.1% -138 9% 0.9% -91.1% 1.0% -138 0% 0 3% Maximum 127.1% 127.1% 59 6% 138.9% 55.4% 91.1% 104.2% 138.0% Mean 97.1% 97.1% -46 7% 59.8% -15.2% 36.7% 42 7% 49.0% Median 101.5% 101.5% -44 3% 45.1% -20.7% 35 2% 48 4% 48.6% Notes Difference is ihe mean of all RPDs minus the mean site RPD (absolute values). Ramsey Flats - Silver Bow Creek Sulfur Bank Mercury Mine Torch Lake Superfund Site Wiekes Smelter Site Other Notes: No samples reported by the reference laboratory in this concentration range Number Number of demonstration samples evaluated RPD Relative Percent Difference (raw value). RPD ABS Val Relative Percent Difference (absolute value). AS Alton Steel Mill RF BN Burlington Northern Railroad/ASARCO East SB CN Naval Surface Warfare Center, Crane Division TL KP KARS Park - Kennedy Space Center WS LV Leviathan Mine/Aspen Creek E-30 ------- &EPA United States Environmental Protection Agency Office of Research and Development (8101R) Washington, DC 20460 Official Business Penalty for Private Use $300 E PA/540/R-06/001 April 2006 www.epa gov Please make all necessary changes on the below label, detach or copy, and return to the address in the upper left-hand corner If you do not wish to receive these reoorts CHECK HERE ~, detach, or copy this cover, and return ;o the address in the upper left-hand corner PRESORTED STANDARD POSTAGE & FEES PAID EPA PERMIT No. G-35 Recycled/Recyclable Primed with vegetable-based ink on paper thai contains a minimum of 50% post-consumer fiber content processed chlorine free ------- |