4>EPA
United States
Environmental Protection
Agency
Demonstration and Quality
Assurance Project Plan
XRF Technologies for Measuring
Trace Elements in Soil and Sediment
RESEARCH AND DEVELOPMENT
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EPA/600/R-05/009
May 2006
www.epa.gov
Demonstration and Quality
Assurance Project Plan
XRF Technologies for Measuring
Trace Elements in Soil and Sediment
Contract No. 68-C-00-181
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.
250 West Court Street, Suite 200VV
Cincinnati, OH 43202
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
182cmb06.RPT * 4/28/2006
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Concurrence Signatures
The primary purpose of the demonstration is to evaluate X-ray fluorescence (XKF) technologies for
measuring trace elements in soil and sediment based on their performance and cost as compared with
conventional, off-site laboratory analytical methods. The demonstration will take place under the
sponsorship of the U.S. Environmental Protection Agency Superfund Innovative Technology Evaluation
Program.
This document is intended to ensure that all aspects of the demonstration are documented and scientifically
sound and that operational procedures are conducted in accordance with quality assurance and quality
control specifications and health and safety regulations.
The signatures of the individuals specified below indicate their concurrence and agreement to operate in
compliance with the procedures specified in this document.
Stephen Billets
EPA
Project Manager
Date
John Patterson Date
Oxford Instruments Portable Division
Developer
George Brilis
EPA
Quality Assurance Manager
Date
David Mercuro
NITON LLC
Developer
Date
Michael Deliz
NASA
Remediation Project Manager
Date
Rune Gehrlein
Oxford Instruments Analytical
Developer
Date
Donald Sackett
Inriov-X Systems, Inc.
Developer
Date
Paul Smith
RONTEC USA, Inc.
Developer
Date
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Concurrence Signatures (Continued)
Jose Brum
Rigaku, Inc.
Developer
Date
Gregory Swanson
Tetra Tech
Project Manager
Date
Ronald Williams
Xcalibur XRF Services Inc.
Developer
Date
John Dirgo
Tetra Tech
Quality Assurance Manager
Date
Debbie Langley
Quality Assurance Officer
Shealy Environmental Services Inc.
Reference Laboratory
Date
Judy Wagner
Tetra Tech
Health and Safety Representative
Date
Daniel Wright Date
Laboratory Director/Project Manager
Shealy Environmental Services, Inc.
Reference Laboratory
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Notice
This document was prepared for the U.S. Environmental Protection Agency (EPA) Superfund Innovative
Technology Evaluation Program under Contract No. 68-C-00-181. The document has been subjected to the
EPA's peer and administrative reviews and has been approved for publication. Mention of corporation
names, trade names, or commercial products does not constitute endorsement or recommendation for use.
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the nation's
natural resources. Under the mandate of national environmental laws, the Agency strives to formulate and
implement actions leading to a compatible balance between human activities and the ability of natural
systems to support and nurture life. To meet this mandate, the EPA's Office of Research and Development
(ORD) provides data and scientific support that can be used to solve environmental problems, build the
scientific knowledge base needed to manage ecological resources wisely, understand how pollutants affect
public health, and prevent or reduce environmental risks.
The National Exposure Research Laboratory is the Agency's center for investigation of technical and
management approaches for identifying and quantifying risks to human health and the environment. Goals
of the laboratory's research program are to (1) develop and evaluate methods and technologies for
characterizing and monitoring air, soil, and water; (2) support regulatory and policy decisions; and
(3) provide the scientific support needed to ensure effective implementation of environmental regulations
and strategies.
The EPA's Superfund Innovative Technology Evaluation (SITE) Program evaluates technologies designed
for characterization and remediation of contaminated Superfund and Resource Conservation and Recovery
Act (RCRA) sites. The SITE Program was created to provide reliable cost and performance data to speed
acceptance and use of innovative remediation, characterization, and monitoring technologies by the
regulatory and user community.
Effective monitoring and measurement technologies are needed to assess the degree of contamination at a
site, provide data that can be used to determine the risk to public health or the environment, and monitor the
success or failure of a remediation process. One component of the EPA SITE Program, the Monitoring and
Measurement Technology (MMT) Program, demonstrates and evaluates innovative technologies to meet
these needs.
Candidate technologies can originate within the federal government or the private sector. Through the SITE
Program, developers are given an opportunity to conduct a rigorous demonstration of their technologies
under actual field conditions. By completing the demonstration and distributing the results, the Agency
establishes a baseline for acceptance and use of these technologies. The MMT Program is managed by the
ORD's Environmental Sciences Division in Las Vegas, Nevada.
Gary Foley, Ph.D.
Director
National Exposure Research Laboratory
Office of Research and Development
IV
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Abstract
A demonstration of technologies for measuring trace elements in soil and sediments is being conducted
under the U.S. Environmental Protection Agency Superfund Innovative Technology Evaluation Program.
The field demonstration will be occurring from January 24 to 28, 2005, at the Kennedy Athletic,
Recreational and Social Park at Kennedy Space Center on Merritt Island, Florida. The purpose of the
demonstration is to evaluate various field-portable instruments that employ X-ray fluorescence (XRF)
monitoring technologies. Instruments available from the technology developers listed below will be
demonstrated.
• Innov-X Systems, Inc.
• NITON LLC (2 instruments)
• Oxford Instruments Portable Division (formerly Metorex, Inc.)
• Oxford Instruments Analytical
• Rigaku, Inc.
• RONTEC USA Inc.
• Xcalibur XRF Services Inc. (Division of Elvatech Ltd.)
This demonstration plan describes the procedures that will be used to verify the performance and cost of the
XRF instruments provided by these technology developers. The plan incorporates the quality assurance and
quality control elements needed to generate data of sufficient quality to perform this verification. A separate
innovative technology verification report (ITVR) will be prepared for each instrument. The ITVRs will
present findings associated with each of the objectives of the demonstration.
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Contents
Chapter Page
Concurrence Signatures . i
Notice iii
Foreword iv
Abstract v
Acronyms, Abbreviations, and Symbols xii
Acknowledgements xvi
Executive Summary ES-1
1 Introduction 1
1.1 Description of SITE Program 2
1.2 Scope of Demonstration 4
1.3 General Description of XRF Technology 5
1.4 Analytical Suite of Target Elements 6
1.4.1 Antimony 6
1.4.2 Arsenic 7
1.4.3 Cadmium 7
1.4.4 Chromium 7
1.4.5 Copper 7
1.4.6 Iron 8
1.4.7 Lead 8
1.4.8 Mercury 8
1.4.9 Nickel 8
1.4.10 Selenium 9
1.4.11 Silver 9
1.4.12 Vanadium 9
1.4.13 Zinc 9
2 Demonstration Organization and Responsibilities 10
2.1 EPA Project Personnel 10
2.2 Tetra Tech Project Personnel 10
2.3 Developer Personnel 14
2.4 Demonstration Site Representatives 15
2.5 Laboratory Project Personnel 15
3 Developer Instrument Descriptions 16
3.1 Innov-X Systems XT400 Series XRF Analyzer 16
3.1.1 Technology Description 16
3.1.2 Operating Procedures 17
3.1.3 Advantages and Limitations 19
3.2 NITON XLi/XLt 700 Series 19
VI
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Contents (Continued)
Chapter Page
3.2.1 Technology Description 19
3.2.1.1 XLi 700 Series Technology Description 19
3.2.1.2 XLt 700 Series Technology Description 20
3.2.2 Operating Procedures 22
3.2.3 Advantages and Limitations 23
3.3 Oxford Instruments Analytical ED2000 24
3.3.1 Technology Description 24
3.3.2 Operating Procedures 24
3.3.3 Advantages and Limitations 26
3.4 Oxford Instruments Portable X MET 3000TX 26
3.4.1 Technology Description 27
3.4.2 Operating Procedures 28
3.4.3 Advantages and Limitations 29
3.5 Rigaku ZSXmini 29
3.5.1 Technology Description 29
3.5.2 Operating Procedure 31
3.5.3 Advantages and Limitations 31
3.6 RONTEC PicoTAX 32
3.6.1 Technology Description 32
3.6.2 Operating Procedure 33
3.6.3 Advantages and Limitations 34
3.7 Xcalibur XRF Services ElvaX 34
3.7.1 Technology Description 34
3.7.2 Operating Procedures 36
3.7.3 Advantages and Limitations 38
4 Demonstration and Sampling Site Descriptions 39
4.1 Description of Demonstration Site 39
4.2 Descriptions of Sampling Sites 41
4.2.1 Kennedy Athletic, Recreational & Social Park Site 41
4.2.2 Wickes Smelter Site 41
4.2.3 Burlington Northern-ASARCO East Helena Site 42
4.2.4 Alton Steel Mill Site 42
4.2.5 Navy Surface Warfare Center, Crane Division Site 43
4.2.6 Torch Lake Superfund Site 43
4.2.7 Leviathan Mine Site 44
4.2.8 Sulphur Bank Mercury Mine 45
4.2.9 Ramsay Flats-Silver Bow Creek Site 45
VII
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Contents (Continued)
Chapter Page
5 Demonstration Approach 47
5.1 Demonstration Objectives 47
5.2 Demonstration Design 48
5.3 Demonstration Samples 48
5.3.1 Environmental Samples 49
5.3.2 PE Samples 49
5.4 Pre-demonstration Sample Analysis 49
5.5 Data Analysis Procedures 49
5.5.1 Primary Demonstration Objectives 52
5.5.1.1 Primary Objective 1 —Method Detection Limits 52
5.5.1.2 Primary Objective 2 — Accuracy and Comparability 53
5.5.1.3 Primary Objective 3 — Precision 55
5.5.1.4 Primary Objective 4 — Impact of Chemical and Spectral Interferences 56
5.5.1.5 Primary Objective 5 — Effects of Soil Characteristics 57
5.5.1.6 Primary Objective 6 — Sample Throughput 57
5.5.1.7 Primary Objective 7 — Technology Costs 58
5.5.2 Secondary Demonstration Objectives 58
5.5.2.1 Secondary Objective 1 —Training Requirements 58
5.5.2.2 Secondary Objective 2 — Health and Safety 58
5.5.2.3 Secondary Objective 3 —Portability 58
5.5.2.4 Secondary Objective 4 — Durability 58
5.5.2.5 Secondary Objectives —Availability 59
5.6 Demonstration Schedule 59
6 Sample Collection, Preparation, and Handling Procedures 60
6.1 Sample Collection and Shipping 60
6.2 Sample Preparation and Homogenization 60
6.3 Sample Aliquots 61
6.4 Sample Handling 61
7 Reference Laboratory and Methods 63
7.1 Reference Laboratory Selection 63
7.2 Reference Method Selection 64
7.2.1 Available SW-846 Methods 64
7.2.2 Inductively Coupled Plasma-Atomic Emission Spectrometry, SW-846 6010A 64
7.2.3 Industively Coupled Plasma-Mass Spectrometry, SW-846 6020 64
7.2.4 Atomic Absorption-Graphite Furnace Spectrometry, SW-846 7000 Series 65
7.2.5 Atomic Absorption Flame Spectrometry, SW-846 7000 Series 65
7.2.6 Atomic Absorption Cold Vapor Spectrometry, SW-846 7471A 65
7.3 Method Selection 65
7.4 Sample Preparation and Analytical Methods for Reference Laboratory 66
7.4.1 Analysis of Metals by ICP-AES, Method 6010B 66
7.4.2 Cold Vapor Atomic Absorption Spectrometry, Method 7471A 66
7.4.3 Sample Management Procedures 66
8 Data Management 68
8.1 Data Reduction 68
8.2 Data Review 68
via
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Contents (Continued)
Page
8.2.1 Data Review by Developers 68
8.2.2 Data Review by Tetra Tech 68
8.3 Data Reporting 69
8.3.1 Developer Data Packages 69
8.3.2 Reference Laboratory Data Packages 69
8.3.3 Innovative Technology Verification Reports 69
8.4 Data Evaluation Report 70
8.5 Datastorage 70
9 Quality Assurance/Quality Control Procedures 71
9.1 Quality Assurance Objectives 71
9.2 Internal QC Checks 71
9.2.1 Reference Method QC Checks 71
9.2.1.1 Calibration and Method Blanks 73
9.2.1.2 Matrix Spike/Matrix Spike Duplicate 73
9.2.1.3 Laboratory Control Sample/Laboratory Control Sample Duplicate 74
9.2.1.4 Laboratory Matrix Duplicate 74
9.2.1.5 Performance Audit Sample 74
9.2.2 Developer Instrument QC Checks 74
9.3 Quality Indicators 74
9.3.1 Precision 75
9.3.2 Accuracy 75
9.3.3 Representativeness 75
9.3.4 Completeness 76
9.3.5 Comparability 76
9.3.6 Sensitivity 76
9.4 Audits, Corrective Actions, and QA Reports. 77
9.4.1 Technical Systems Audits 77
9.4.2 Performance Evaluation Audits 78
9.4.3 Corrective Action Procedures 79
9.4.4 QA Reports 79
10 Health and Safety Procedures 81
10.1 Personnel and Enforcement 82
10.1.1 Project Personnel 82
10.1.1.1 Project Manager and Field Manager 83
10.1.1.2 Site Safety Coordinator 83
10.1.1.3 Health and Safety Representative 83
10.1.1.4 Tetra Tech Employees 84
10.1.2 Technology Developers 84
10.1.3 Visitors 84
10.1.4 Health and Safety Procedure Enforcement 84
10.2 Site Background 84
10.2.1 Site Description 84
10.2.2 Site History 85
10.2.3 Activities Planned. 85
10.3 Site-Specific Hazard Evaluation 85
10.3.1 Chemical Hazards 85
IX
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Contents (Continued)
Chapter Page
10.3.1.1 Volatile Organic Compounds 86
10.3.1.2 Inorganic Substances 86
10.3.2 Site-Specific Environmental Hazards 88
10.4 Training Requirements 88
10.5 Personal Protection Requirements 89
10.5.1 Protective Equipment and Clothing 89
10.5.2 Reassessment of Protection Levels 90
10.5.3 Limitations of Protective Clothing 90
10.5.4 Respirator Selection, Use, and Maintenance 91
10.6 Medical Surveillance 91
10.6.1 Health Monitoring Requirements 92
10.6.2 Site-Specific Medical Monitoring 92
10.6.3 Medical Support and Follow-up Requirements 92
10.7 Environmental Monitoring and Sampling 93
10.8 Site Control 93
10.8.1 On-Site Communications 93
10.8.2 Site Control Zones 93
10.8.3 Site Access Control 94
10.8.4 Site Safety Inspections 94
10.8.5 Safe Work Practices 94
10.9 Decontamination 94
10.9.1 Personnel Decontamination 94
10.9.2 Equipment Decontamination 95
10.10 Emergency Response Planning 95
10.10.1 Pre-emergency Planning 95
10.10.2 Personnel Roles and Lines of Authority 96
10.10.3 Emergency Recognition and Prevention 96
10.10.4 Evacuation Routes and Procedures. 96
10.10.5 Emergency Contacts and Notifications 96
10.10.6 Hospital Route Directions 96
10.10.7 Emergency Medical Treatment Procedures 96
10.10.8 Protective Equipment Failure 97
10.10.9 Fire or Explosion 97
10.10.10 Weather-Related Emergencies 97
10.10.11 Spills or Leaks 97
10.10.12 Emergency Equipment and Facilities 97
10.10.13 Reporting 98
11 References 99
Appendix A Pre-demonstration Sampling and Analysis Plan
Appendix B Health and Safety Plan
Appendix C Field Forms
Appendix D XRF Demonstration Project Schedule
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Figures
2-1 Project Organization Chart 11
3-1 Innov-X XT400 Series Analyzer 18
3-2 Niton XLi/XLt Analyzer 23
3-3 Oxford Instruments Analytical ED2000 26
3-4 Oxford Instruments Portable X-MET 3000TX 29
3-5 Rigaku ZSXmini 29
3-6 RONTEC PicoTAX 32
3-7 Xcalibur XRF Services ElvaX 34
4-1 Kennedy Athletic Recreational and Social Park- Site Location 40
Tables
2-1 Demonstration Points of Contact 12
3-1 Innov-X XT400 Series Analyzer Technical Specifications 17
3-2A Niton XLi 700 Series Technical Specifications 21
3-2B Niton XLt 700 Series Technical Specifications 22
3-3 Oxford Instruments Analytical ED2000 Technical Specifications 26
3-4 Oxford Instruments Portable X-MET 3000TX Technical Specifications 28
3-5 Rigaku ZSXmini Technical Specifications 30
3-6 RONTEC PicoTAX Technical Specifications 33
3-7 Xcalibur XRF Services ElvaX Technical Specifications 35
4-1 Historical Analytical Data, KARS Park Site 41
4-2 Historical Analytical Data, Wickes Smelter Site-Roaster Slag Pile 42
4-3 Historical Analytical Data, BN-ASARCO East Helena Site 42
4-4 Historical Analytical Data, NSWC Crane Division-Old Burn Pit 43
4-5 Historical Analytical Data, Torch Lake Superfund Site 44
4-6 Historical Analytical Data, Leviathan Mine Site 45
4-7 Historical Analytical Data, Sulphur Bank Mercury Mine Site 45
4-8 Historical Analytical Data, Ramsay Flats-Silver Bow Creek Site 46
5-1 Target Concentration Ranges for Soil and Sediment 50
5-2 Soil and Sediment Sample Summary 51
5-3 Number of Soil and Sediment Environmental Sample Blends and Demonstration Samples 51
5-4 Number of Soil and Sediment Sample Blends and Demonstration Samples 52
5-5 Number of Pre-demonstration Samples 52
5-6 Number of Detection Limit Samples 53
5-7 Number of Samples by Concentration Range for Each Target Element 54
5-8 Number of Spectral Interference Samples 57
9-1 Data Quality Indicator Objectives 71
9-2 Reference Method Quality Control Checks 72
9-3 Technical System Audit of Activities 78
10-1 Task Hazard Analysis 87
XI
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Acronyms, Abbreviations, and Symbols
jig Micrograms
uA Micro-amps
mA Milli-amps
AC Alternating current
ADC Analog to digital converter
Ag Silver
Am Americium
ARDL Applied Research and Development Laboratory, Inc.
As Arsenic
ASARCO American Smelting and Refining Company
BN Burlington Northern
C Celsius
Cd Cadmium
CFR Code of Federal Regulations
CIH Certified industrial hygienist
cps Counts per second
CPU Central processing unit
Cr Chromium
Cu Copper
CVAA Cold vapor atomic absorption
DER Data evaluation report
EDXRF Energy dispersive XRF
EDD Electronic data deliverable
EPA U.S. Environmental Protection Agency
ESA Environmental site assessment
ETV Environmental Technology Verification (Program)
eV Electron volts
Fe Iron
FPT Fundamental Parameters Technique
F WHM Full width of peak at half maximum height
GB Gigabyte
Hg Mercury
HSP Health and safety plan
HSR Health and safety representative
Hz Hertz
xn
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Acronyms, Abbreviations, and Symbols (Continued)
ICP-AES
ICP-MS
IR
ITVR
KARS
keV
kg
KSC
kV
LCS
LCSD
LEAP
LiF
LMS
MB
MBq
MCA
mCi
MDL
mg/kg
MHz
mm
MMT
Mo
MS
MSD
MSDS
NASA
NERL
Ni
NIOSH
NRC
NSWC
OSHA
ORD
OSWER
P
PARCC
Pb
PC
Inductively coupled plasma — atomic emission spectromelry
Inductively coupled plasma — mass spectrometry
Infrared
Innovative Technology Verification Report
Kennedy Athletic, Recreational and Social (Park)
Kiloelectron volts
Kilograms
Kennedy Space Center
Kilovolts
Laboratory control sample
Laboratory control sample duplicate
Light Element Analysis Program
Lithium fluoride
Laboratory information management system
Megabyte
Mega Bequereb
Multi-Channel Analyzer
Millicurie s
Method detection limit
Milligrams per kilogram
Megahertz
Millimeters
Monitoring and Measurement Technology
Molybdenum
Matrix spike
Matrix spike duplicate
Material safety data sheet
National Aeronautics and Space Administration
National Exposure Research Laboratory
Nickel
National Institute for Occupational Safety and Health
Nuclear Regulatory Commission
Naval Surface Warfare Center
Occupational Safety and Health Administration
Office of Research and Development
Office of Solid Waste and Emergency Response
Phosphorus
Precision, accuracy, representativeness, completeness, and comparability
Lead
Personal computer
xni
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Acronyms, Abbreviations, and Symbols (Continued)
PDA
PCB
Pd
PE
Pel
PM2.5
PPE
ppb
ppm
Pu
QA
QAPP
QC
RCRA
Rh
RPD
RSD
%RSD
SAP
SBMM
SCBA
Se
Si
SITE
SOP
SRM
SSC
SVOC
SWP
TAP
Tetra Tech
Ti
TSA
TSP
TXRF
U
USFWS
Personal digital assistant
Polychlorinated biphenyls
Palladium
Performance evaluation
Pentaerythritol
Particulate matter less than 10 microns in aerodynamic diameter
Particulate matter less than 2.5 microns in aerodynamic diameter
Personal protective equipment
Parts per billion
Parts per million
Plutonium
Quality assurance
Quality assurance project plan
Quality control
Resource Conservation and Recovery Act
Rhodium
Relative percent difference
Relative standard deviation
Percent relative standard deviation
Sampling and analysis plan
Sulphur Bank Mercury Mine
Self-contained breathing apparatus
Selenium
Silicon
Superfund Innovative Technology Evaluation
Standard operating procedure
Standard reference material
Site safety coordinator
Semivolatile organic compound
Safe work practice
Thallium acid phthalate
Tetra Tech EM Inc.
Titanium
Technical systems audit
Total suspended particulates
Total reflection x-ray fluorescence spectroscopy
Uranium
U.S. Fish and Wildlife Service
V
V
Vanadium
Volts
xiv
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Acronyms, Abbreviations, and Symbols (Continued)
VOC Volatile organic compound
W Watts
WDXRF Wavelength-dispersive XRF
XRF X-ray fluorescence
Zri Zinc
xv
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Acknowledgements
Tetra Tech acknowledges the advice and support of the following individuals in preparing this document:
Stephen Billets and George Brilis of the U.S. Environmental Protection Agency's National Exposure
Research Laboratory; Donald Sackett of Innov-X Systems, Inc.; David Mercuro of NITON LLC; John
Patterson of Oxford Instruments Portable Division; Rune Gehrlein of Oxford Instruments Analytical; Jose
Brum of Rigaku, Inc.; Paul Smith of RONTEC USA Inc., Ronald Williams of Xcalibur XRF Services
Inc., and Jackie Quinn of the National Aeronautics and Space Administration (NASA), Kennedy Space
Center (K.SC). Tetra Tech also acknowledges the support of Michael Deliz of NASA KSC and Mark
Speranza of Terra Tech NUS, the consultant program manager for NASA.
xvi
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Executive Summary
Performance verification of innovative environmental technologies is an integral part of the regulatory
and research mission of the U.S. Environmental Protection Agency (EPA). The Superfund Innovative
Technology Evaluation (SITE) Program was established by the EPA Office of Solid Waste and
Emergency Response and the Office of Research and Development under the Superfund Amendments
and Reauthorization Act of 1986. The program is designed to meet three primary objectives: (1) identify
and remove obstacles to the 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) develop procedures and policies that encourage use of innovative
technologies at Superfund sites as well as other waste sites or commercial facilities. The intent of a SITE
demonstration is to obtain representative, high-quality data on performance and cost for innovative
technologies to ensure that potential users can assess a given technology's suitability for a specific
application.
This plan summarizes the activities that will be conducted during the SITE demonstration of analysis by
field-portable x-ray fluorescence (XRF) instruments of trace elements in soil and sediment. The
demonstration is being conducted under the Monitoring and Measurement Technology Program, which is
administered by the Environmental Sciences Division of EPA's National Exposure Research Laboratory
in Las Vegas, Nevada. The 13 target elements selected for analysis in this evaluation include antimony,
arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc.
This demonstration will be conducted from January 24 to 28, 2005, at the Kennedy Athletic, Recreational
arid Social Park at Kennedy Space Center in Merritt Island, Florida. The following XRF technology
developers will participate in the demonstration:
• Innov-X Systems, Inc.
• NITON LLC
• Oxford Instruments Analytical
• Oxford Instruments Portable Division
• Rigaku, Inc.
• RONTEC USA Inc.
• Xcalibur XRF Services Inc.
The performance and cost of the instruments provided by the technology developers will be compared
with conventional, off-site laboratory analytical methods. The performance and cost characteristics of
one instrument will not be compared with another instrument, however. A separate innovative
technology verification report (ITVR) will be prepared for each instrument.
Both primary and secondary objectives have been established for the demonstration. The primary
objectives are critical to the technology evaluation and require use of quantitative results to draw
conclusions on instrument performance. The secondary objectives pertain to information that is useful
but does not necessarily require use of quantitative results to draw conclusbns on technology
performance.
ES-1
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The following are the primary objectives of the demonstration for each of the participating XRF
instruments:
P1 Determine XRF method detection limits (MDL) for each target element.
P2 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.
P3 Evaluate the precision of XRF measurements for a variety of soil and sediment samples.
P4 Evaluate the effect of chemical and spectral interference on measurement of target elements.
P5 Evaluate the effect of soil characteristics on measurement of target elements.
P6 Measure sample throughput for the measurement of target elements.
P7 Estimate the costs associated with XRF field measurements.
The secondary objectives of the demonstration for each of the participating XRF instruments are as
follows:
SI Document the skills and training required to properly operate the instrument.
S2 Document health and safety concerns associated with operating the instrument.
S3 Document the portability of the instrument.
S4 Evaluate the instrument's durability based on its materials of construction and engineering
design.
S5 Document the availability of the instrument and of associated customer technical support.
Both environmental and performance evaluation (PE) samples will be analyzed during the demonstration
to address the demonstration objectives. The environmental samples were collected from multiple
sampling locations across the country before the demonstration to provide a diverse soil and sediment
matrix with varying sources and contaminant concentrations. The PE samples are certified, spiked, and
blank samples obtained from a commercial vendor. When the demonstration is complete, the results from
the XRF instruments and reference laboratory will be compared to evaluate the performance and
associated cost of each instrument. The ITVRs for the instruments will be submitted for peer review in
September 2005 and then published by EPA.
ES-2
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Chapter 1
Introduction
The U.S. Environmental Protection Agency (EPA), Office of Research and Development (ORD),
National Exposure Research Laboratory (NERL) has contracted with Tetra Tech EM Inc. (Tetra Tech) to
conduct a demonstration of field-portable x-ray fluorescence (XRF) instruments in trace element analysis
of soil and sediment. Thirteen target elements were selected for inclusion in the study: antimony, arsenic,
cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc. The
demonstration is being conducted as part of the EPA Superfund Innovative Technology Evaluation
(SITE) Monitoring and Measurement Technology (MMT) Program. The purpose of the demonstration is
to obtain reliable data on performance and cost for various field-portable XRF technologies to provide (1)
potential users with a better understanding of the technologies' performance and operating costs under
well-defined field conditions, and (2) the technology developers with documented results that will help
them promote acceptance and use of their instruments.
This demonstration plan describes the procedures that will be used to verify the performance of each XRF
instrument. The plan also includes a site health and safety plan and the quality assurance and quality
control (QA/QC) elements needed to generate data of sufficient quality to document each instrument's
performance. This plan has been prepared using the NERL's "A Guidance Manual for the Preparation of
Site Characterization and Monitoring Technology Demonstration Plans" (EPA 1996a) and in accordance
with the EPA National Risk Management Research Laboratory's "Quality Assurance Project Plan
Requirements for Applied Research Projects" (EPA 1998a).
This demonstration plan describes the procedures and methods that will be used to evaluate the specific
instruments provided by the technology developers. Specifically, this plan describes:
• The SITE Program, the scope of the demonstration, and the target elements of interest (Chapter
1).
• The organization and responsibilities of the participants in the demonstration (Chapter 2).
• The XRF instruments that will be demonstrated (Chapter 3).
• The demonstration site and eight sampling sites (Chapter 4).
• The demonstration approach, including the objectives, experimental design, data analysis
procedures, and demonstration schedule (Chapter 5).
• The sample collection, preparation, and handling procedures (Chapter 6).
• The reference laboratory and reference methods that will be used during the demonstration
(Chapter 7).
• The data management procedures (Chapter 8).
• The QA/QC procedures (Chapter 9).
• The health and safety procedures (Chapter 10).
• References (Chapter 11).
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1.1 Description of 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 the
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) develop procedures and policies that encourage use of innovative
technologies at Superfund sites as well as at other waste sites or commercial facilities.
The intent of a SITE demonstration is to obtain representative, high-quality data on performance and cost
on one or more innovative technologies so that potential users can assess a given technology's suitability
for a specific application. The SITE Program includes the following elements:
• 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
conventional technologies.
• Remediation Technology Program - Conducts demonstrations of 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 participating
technologies. The Technology Transfer Program also offers technical assistance, training, and
workshops to support the technologies.
The demonstration of XRF technologies for measuring trace elements in soil and sediment is being
conducted as part of the MMT Program, which provides developers of innovative hazardous waste
sampling, monitoring, and measurement technologies with an opportunity to demonstrate the performance
of their technologies under field conditions. These technologies may be used to sample, detect, monitor,
or measure hazardous and toxic substances in water, soil, soil gas, and sediment. The technologies
include chemical sensors for in situ (in place) measurements, groundwater samplers, soil and sediment
samplers, soil gas samplers, field-portable analytical equipment, and other systems that support field
sampling or data acquisition and analysis.
The MMT Program promotes acceptance of technologies that can be used to (1) accurately assess the
degree of contamination at a site, (2) provide data to evaluate potential effects on human health and the
environment, (3) apply data to assist in selecting the most appropriate cleanup action, and (4) monitor the
effectiveness of a remediation process. The program places a high priority on innovative technologies
that provide more cost-effective, faster, or safer methods for producing real-time or near-real-time data
than conventional, laboratory-based technologies. These innovative technologies are demonstrated under
field conditions, and the results are compiled, evaluated, published, and disseminated by the ORD. The
primary objectives of the MMT Program are as follows:
• Test and verify the performance of field sampling and analytical technologies that enhance
capabilities for sampling, monitoring, and site characterization.
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• Identity performance attributes of innovative technologies to address field sampling, monitoring,
and characterization problems in a more cost-effective and efficient manner.
• Prepare protocols, guidelines, methods, and other technical publications that enhance acceptance
of these technologies for routine use.
The MMT Program is administered by the Environmental Sciences Division of the NERL in Las Vegas,
Nevada. The NERL is EPA's center for investigating technical and management approaches for
identifying and quantifying risks to human health and the environment. Components of the NERL's
mission include (1) developing and evaluating methods and technologies for sampling, monitoring, and
characterizing water, air, soil, and sediment; (2) supporting regulatory and policy decisions; and (3)
providing the technical support needed to ensure effective implementation of environmental regulations
and strategies. By demonstrating XRF technologies for trace element analysis, the MMT Program is
supporting the development and evaluation of methods and technologies for XRF field measurement of
elements in a variety of soil and sediment types.
The MMT Program's technology verification process is designed to conduct demonstrations that will
generate high-quality data to ensure that potential users have reliable information on the performance and
cost of the technology. Four steps are inherent in the process: (1) needs identification and technology
selection, (2) demonstration planning and implementation, (3) report preparation, and (4) information
distribution. The first step of the technology verification process begins with identifying the technology
needs of the EPA and regulated community. The EPA regional offices, the U.S. Department of Energy,
the U.S. Department of Defense, industry, and state environmental regulatory agencies are asked to
identify technology needs for sampling, measuring, and monitoring environmental media. Next, a search
is conducted to identify suitable technologies that will address the need. The technology search and
identification process consists of examining industry and trade publications, attending related
conferences, and exploring leads from technology developers and industry experts. Selection of
technologies for field testing includes evaluation of the candidate technologies based on several criteria.
A suitable technology for field testing:
• is designed for use in the field or in a mobile laboratory
• is applicable to a variety of environmentally contaminated sites
• has the potential for solving problems that current methods cannot satisfactorily address
• has estimated costs that are lower than of conventional methods
• is likely to achieve better results than current methods in areas such as data quality and
turnaround time
• uses technologies that are easier or safer than current methods, and
• is commercially available.
Once candidate technologies are identified, their developers are asked to participate in demonstration
program planning. Participation in planning gives the developers an opportunity to describe the
technologies' performance and to learn about the MMT Program.
The second step of the technology verification process is to plan and implement a demonstration that will
generate high-quality data to assist potential users in selecting a technology. Demonstration planning
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includes a pre-demonstration sampling and analysis investigation that assesses existing conditions at the
proposed demonstration site or sites. The objectives of the pre-demonstration investigation are to (1)
confirm available information on applicable physical and chemical characteristics of contaminated media
at the sites to justify selection of site areas for the demonstration; (2) provide the technology developers
with an opportunity to evaluate the areas, analyze representative samples, and identify logistical
requirements; (3) assess the overall logistical requirements for conducting the demonstration; and (4)
provide the reference laboratory involved with an opportunity to identify any matrix-specific analytical
problems associated with the contaminated media and to propose solutions. Information generated
through the pre-demonstration investigation is used to develop the final demonstration design and
sampling and analysis procedures.
Demonstration planning also includes preparing a demonstration plan that describes the procedures to be
used to verify the performance and cost of each technology. The demonstration plan incorporates
information generated during the pre-demonstration investigation as well as input from technology
developers, demonstration site representatives, and technical peer reviewers. The demonstration plan also
incorporates the QA/QC elements needed to produce data of sufficient quality to document the
performance and cost of each technology.
During the demonstration, each technology is evaluated independently and, when possible and
appropriate, is compared with a reference technology. The performance and cost of one technology are
not compared with another technology evaluated in the demonstration, however. Rather, demonstration
data are used to evaluate the performance, cost, advantages, limitations, and field applicability of each
technology.
As part of the third step of the technology verification process, EPA publishes a verification statement
and a detailed evaluation of each technology in an innovative technology verification report (ITVR). The
ITVR is published only after comments from the technology developer and external peer reviewers are
satisfactorily addressed to ensure its quality. All demonstration data used to evaluate each technology are
summarized in a data evaluation report (DER) that constitutes a complete record of the demonstration.
The DER is not published as an EPA document, but an unpublished copy may be obtained from the EPA
project manager.
The fourth step of the verification process is to distribute information on the demonstration. To benefit
technology developers and potential technology users, the EPA distributes demonstration bulletins and
ITVRs through direct mailings, at conferences, and on the Internet. ITVRs and additional information on
the SITE Program are available on the EPA ORD web site (http://www.epa.gov/ord/SITE). A visitor's
day is usually held in conjunction with the demonstration to give potential users a first-hand look at the
technologies in operation.
1.2 Scope of Demonstration
Conventional analytical methods for measuring the concentrations of inorganic elements in soil and
sediment are time-consuming and costly. The use of a single, rapid, cost-effective field instrument for
elemental analysis would allow field personnel to quickly assess the extent of metals contamination at a
site. The instantaneous data provided by field-portable X-ray fluorescence (XRF) instruments could be
used to quickly assess risks to health associated with the site and allow development of a more focused
and cost-effective sampling strategy for conventional laboratory and analytical methods.
The first SITE MMT demonstration of XRF occurred in 1995, when six instruments were evaluated in the
analysis of 10 target elements. The results of this demonstration were ultimately published in individual
reports for each instrument (EPA 1996b, 1996c, 1998b, 1998c, 1998d, 1998e). In 2003, two XRF
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instruments were also included in a demonstration of field methods for the analysis of mercury in soil and
sediment. Individual ITVRs were prepared for each of these two instruments (EPA 2004a, 2004b).
Although XRF spectrometry is now considered a mature technology for elemental chemical analysis,
field-portable XRF instruments have evolved considerably over the past 10 years, and the models that
participated in the original demonstration are no longer manufactured. Advances in electronics and data
processing, coupled with new X-ray tube source technology, have produced substantial improvements in
the precision and speed of analysis. The demonstration of these new technologies with an expanded set of
target elements will provide valuable information on current state-of-the-art instrumentation to potential
users.
The field-portable XRF instruments will be assessed against laboratory analytical methods using both
performance evaluation (PE) standards and environmental samples so that users can attain a better
understanding of the performance of each instrument. To this end, soil and sediment samples will be
collected from various sites across the country that contain the target elements of concern and analyzed by
each XRF instrument during the demonstration. These sample materials will be homogenized and fully
characterized prior to packaging into sets of environmentally derived samples that contain target elements
at varying concentration ranges. PE samples containing known concentrations of trace elements will be
prepared by a commercial vendor and distributed during the field demonstration. The fie Id demonstration
will be conducted in January 2005 at Kennedy Athletic, Recreational and Social (KARS) Park on Merritt
Island, Florida, where the prepared environmental and PE samples will be analyzed. A visitor's day is
scheduled in conjunction with the demonstration to provide potential users with a first-hand look at the
XRF instruments in operation.
1.3 General Description of XRF Technology
XRF spectroscopy is an analytical technique that exposes a sample (soil, alloy metal, filters, other solids,
an.d 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.
Tliree electron shells are generally involved in emission of x-rays during XRF analysis of samples; the K,
L, and M shells. Multiple-intensity peaks are generated from the emission of the K, L, or M shell
electrons in a typical emission pattern, also called an emission spectrum, for a given element. Most XRF
analyses focus on the x-ray emissions from the K and L shells because they are the most energetic lines.
K-lines are typically used for elements with atomic numbers from 11 to 46 (sodium to palladium), and L-
lines are used for elements above atomic number 47 (silver). M-shell emissions are measurable only for
metals with an atomic number greater than 57.
Characteristic radiation arises when the energy from the x-ray source is greater than the absorption edge
energy of inner shell electrons, ejecting one or more electrons. The electron vacancies are filled by
electrons cascading in from outer shell electrons. The energy states of the electrons in the outer shells are
higher than 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 emitted x-ray radiation is unique for each element.
An XRF analyzer consists of three major components: (1) a source that generates x-rays (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.
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Measurement times are variable (typically 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 precision and accuracy goals. Detection limits for elements are variable
among samples because of sample heterogeneity, other elements present in the sample and their
concentrations, and other interferences. The length of the measuring time will also affect the detection
limit. Generally, the longer the measuring time, the lower the detection limit; however, the usefulness of
the longer measuring period diminishes after a certain amount of time.
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)
3. Spectral interferences (peak overlaps)
4. Moisture content, which causes an effect on precision and accuracy above 10 percent.
Sample preparation and homogenization, instrument calibration, and laboratory confirmatory analysis are
all important aspects of an XRF sampling and analysis plan to determine and measure variability. EPA
SW-846 Method 6200 provides addit ional guidance on sampling and analytical methodology for XRF
analysis.
1.4 Analytical Suite of Target Elements
This section describes the inorganic elements of interest in samples of soil and sediment for the
technology demonstration along with the typical characteristics of each. Key criteria used in selecting the
elements included:
• Frequency with which the element is determined in environmental applications of XRF
instruments.
• Extent to which the element poses an environmental consequence, such as a potential adverse risk
to human or environmental receptors.
• The ability of the XRF technology to achieve meaningful detection limits with regard to typical
remediation goals and risk assessment considerations.
• Extent to which the element may interfere with the analysis of other target elements.
In consideration of these criteria, the critical target elements selected for this study are antimony, arsenic,
cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc. These 13
target elements are of significant concern for site cleanup projects and human health risk assessments
because most are highly toxic or interfere with the analysis of other elements. The demonstration will
focus on the analysis of these 13 elements in evaluating the various XRF instruments.
1.4.1 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 greater than 31 mg/kg
in soil may be hazardous to humans. Antimony may be found 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. Antimony is typically analyzed with success by inductively coupled plasma -
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atomic emission spectrometry (ICP -AES); however, antimony recovery in soil matrix spikes is typically
below QC limits (50 percent or less), caused by loss during the vigorous acid digestion. As such, results
using ICP-AES may be lower than results obtained by XRF.
1.4.2 Arsenic
Naturally occurring arsenic in surface soils typically ranges from 1 to 50 mg/kg; concentrations above 10
mg/kg are potentially phytotoxic. Concentrations of arsenic greater than 0.39 mg/kg may have
carcinogenic effects in humans, and concentrations greater than 22 mg/kg may result in adverse
noncarcinogenic effects. Typical detection limits for field-portable XRF instruments range from 10 to 20
mg/kg arsenic. Elevated concentrations of arsenic are associated with mine wastes and industrial
facilities. Historically, use of arsenic as a pesticide has resulted in elevated concentrations. Arsenic is
successfully analyzed by ICP-AES; however, spectral interferences between peaks for arsenic and lead
affect detection limits and accuracy for XRF analysis when the ratio of lead to arsenic is 10 to 1 or more.
RJsk-based screening bvels and soil screening levels for arsenic may be lower than the detection limits of
field-portable XRF instruments.
1.4.3 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 greater than 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 cadmium. 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.
1.4.4 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. The variable oxidation states of chromium affect
behavior and toxicity. Concentrations of hexavalent chromium greater than 30 mg/kg and concentrations
of trivalent chromium greater than 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 chromium. 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).
1.4.5 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 effects in humans. Typical detection limits for field-portable XRF instruments range from 10 to
50 mg/kg copper. 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
influence the detection limits and accuracy of the XRF analysis.
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1.4,6 Iron
Although iron is not considered as an element possessing a significant environmental consequence, it
interferes with the measurement of other elements and was therefore included in the study. Further, 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 primarily from parent rock material. The geochemistry of iron is complex, but generally
oxidizing and alkaline conditions promote precipitation, whereas acid and reducing conditions promote
formation of soluble iron compounds. 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 other element analyses in both techniques (ICP-AES
and XRF). Spectral interference from iron is mitigated in ICP-AES analysis by application of
interelement correction factors, as required by the analytical method. Differences in analytical results
between ICP -AES and XRF for other target elements are expected when there are high concentrations of
iron in the soil matrix.
1.4.7 Lead
Naturally occurring lead in surface soils typically ranges from 2 to 200 mg/kg; concentrations greater than
50 mg/kg are potentially phytotoxic. Concentrations greater than 400 mg/kg may result in adverse effects
in humans. Typical detection limits for field-portable XRF instruments range from 10 to 20 mg/kg lead.
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 affect detection limits and
accuracy when the ratio of lead to arsenic 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.
1.4.8 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 greater than 6.1 mg/kg may result in adverse effects in humans.
Typical detection limits for field-portable XRF instruments range from 10 to 20 mg/kg mercury. Mercury
ions may be converted to elemental mercury in reducing soil or sediment conditions and then converted to
methyl or ethyl mercury through biotic and abiotic processes. Elevated concentrations of mercury are
associated with the amalgamation of gold, mine waste, and at 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, but it is successfully measured by XRF. The EPA-
approved technique for laboratory analysis of mercury is by cold vapor atomic absorption (CVAA).
Differences between CVAA and XRF results are expected when mercury levels are high.
1.4.9 Nickel
Naturally occurring nickel in surface soils typically ranges from 5 to 500 mg/kg 30 mg/kg is potentially
phytotoxic. Concentrations greater than 1,600 mg/kg may result in adverse 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
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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.
1.4.10 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
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. The plant princes's plume (Stanley>apinnata) selectively uptakes selenium and, as it dies and
decays, causes the concentrations of selenium in surface soil to increase. Elevated concentrations have
also been identified in evaporite deposits in saline lakes. Selenium can be measured by both ICP-AES
and XRF; however, detection limits using XRF usually exceed the ecological risk-based soil screening
levels. Analytical results for selenium using ICP-AES and XRF are expected to be comparable.
1.4.11 Silver
Naturally occurring silver in surface soils typically ranges from 0.01 to 5 mg/kg; concentrations greater
than 2 mg/kg are potentially phytotoxic. Concentrations greater than 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 mobile and is a common contaminant in mine waste, as a byproduct of photographic
film development, and at metal processing sites. It is successfully analyzed by ICP-AES and XRF;
however, detection limits using XRF usually exceed the risk-based soil screening levels for silver.
1.4.12 Vanadium
Naturally occurring vanadium in surface soils typically ranges from 20 to 500 mg/kg; concentrations
greater than 2 mg/kg are potentially phytotoxic (although phytotoxicity bvels for naturally occurring
vanadium have not been documented). Concentrations greater than 550 mg/kg may result in adverse
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 may be
concentrated in organic shales, coal, and crude oil. It is successfully analyzed by both ICP-AES and XRF
with little interference.
1.4.13 Zinc
Naturally occurring zinc in surface soils typically ranges from 10 to 300 mg/kg concentrations greater
than 50 mg/kg are potentially phytotoxic. Zinc concentrations greater than 23,000 mg/kg may result in
adverse 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 and is highly
soluble, which is a common concern at many aquatic sites. Zinc is successfully analyzed by ICP-AES;
however, spectral interferences between peaks for copper and zinc may influence detection limits and the
accuracy of the XRF analysis.
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Chapter 2
Demonstration Organization and Responsibilities
This chapter identifies key project personnel and summarizes responsibilities during the demonstration.
Figure 2-1 presents an organizational chart that shows key personnel and the lines of communication.
Table 2-1 lists the primary point of contact for each organization involved in the demonstration and their
contact information. The participants will be asked to follow the health and safety procedures outlined in
Chapter 10 during the demonstration. However, each organization is directly and fully responsible for the
health and safety of its own employees.
2.1 EPA Project Personnel
The EPA project manager, Dr. Stephen Billets, has overall responsibility for the project. Dr. Billets will
review and concur with the project deliverables, including the demonstration plan, ITVRs, and the DER.
The EPA NERL QA officer, Mr. George Brilis, is responsible for reviewing and concurring with the
demonstration and quality assurance project plan.
2.2 Tetra Tech Project Personnel
The Tetra Tech project manager, Dr. Gregory Swanson, is responsible for day-to-day management of
Tetra Tech project personnel, maintaining direct communication with EPA and the developers, and
ensuring that all Tetra Tech personnel involved in the demonstration understand and comply with the
demonstration plan. Dr. Swanson is also responsible for distributing the draft and final demonstration
plans to all key project personnel and for reviewing measurement and analytical data obtained during the
demonstration. Ms. Linda Stemple, as special assistant to the project manager, will assist Dr. Swanson in
preparing project deliverables and in day-to-day project activities.
In consultation with EPA, Tetra Tech project personnel are responsible for the following elements of the
demonstration:
• Developing and implementing all elements of this demonstration plan.
• Scheduling and coordinating the activities of all demonstration participants.
• Coordinating environmental sample collection, homogenization, and characterization for
elements of concern.
• Comprehensive logistical support for the field demonstration at KARS Park, including
coordination with the site owner, set-up and demobilization of support equipment and facilities,
health and safety oversight, and waste disposal.
• Selection and procurement of the characterization and reference laboratories, data review and
validation, and data management.
• Preparation of all project plans and reports in the required EPA format as well as coordination of
document reviews and resolution of comments from developers and peer reviewers.
10
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Figure 2-1. Project Organization Chart
EPA NERL
QA Officer
George Brilis
Demonstration Site
Representative
Kennedy Space Center
Kennedy Athletic,
Recreational and Social
Park
Michael Deliz
Mark Speranza
Characterization
Laboratory Manager
ARDL
Dan Gillespie
Characterization
Laboratory
QA Manager
ARDL
Dick Curtain
EPA SITE MMT
Project Manager
Dr. Stephen Billets
Tetra Tech SITE MMT
Project Manager
Dr. Gregory Swanson
Special Assistant
Linda Stemple
Technical Leads
Julia Capri
Dr. Ed Surbrugg
Tetra Tech Project Staff
Mark Colsman
Steve Dyment
Candy Friday
Butch Fries
Stan Lynn
Chris Reynolds
Stephanie Wenning
Field XRF Instrument Developers
Innov-X Systems, Inc. - Donald Sackett
NITON LLC- Dave Mercuro
Oxford Instruments Portable- John Patterson
Oxford Instruments Analytical- Rune Gehrlein
Rigaku, Inc. - Jose Brum
RONTEC USA Inc. - Paul Smith
Xcalibur XRF Services Inc. - Ron Williams
Tetra Tech
Health & Safety Rep.
Judy Wagner
Tetra Tech
QA Manager
John Dirgo
PE Sample Vendor
Environmental Resource
Associates
John Laferty
Reference Laboratory
Manager
Shealy Environmental
Daniel Wright
Reference Laboratory
QA Manager
Shealy Environmental
Debbie Langley
11
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Table 2-1. Demonstration Points of Contact
Organization
Point of Contact
Contact Information
U.S. Environmental Protection
Agency
National Exposure Research
Laboratory
Dr. Stephen Billets
944 East Harmon Avenue
Las Vegas, NV 89119
Telephone: (702) 798-2232
Fax: (702)798-2107
Email: billets.stephen@epamail.epa.gov
National Aeronautics and Space
Administration
Kennedy Space Center
Mr. Michael Deliz
Mail Code TZ-C3
Building M7-355, Room 3035
Kennedy Space Center, FL 32899-0001
Email: michael.i.deliz@nasa.gov
Terra Tech NUS
(NASA/KSC support contractor)
Mr. Mark Speranza
661 Andersen Drive
Pittsburgh, PA 15220
(412)921-8916
Email: Speranzam@ttnus.com
Innov-X Systems, Inc.
Mr. Donald Sackett
10 Gill Street, Suite Q
Wobum,MA01801
Telephone: (781) 938-5005
Email: dsackett@Innov-Xsys.com
NITON LLC
Mr. David Mercuro
900 Middlesex Turnpike
Building #8
Billerica,MA01821
Telephone: (800) 875-1578, Ext. 333
Email: dmercuro@niton.com
Oxford Instruments Portable Div.
Mr. John Patterson
Princeton Crossroads Corporate Center
250 Philips Boulevard
Ewing,NJ08618
Telephone: (609) 406-9000 Ext. 122
Email: iohn.patterson@metorexusa.com
Oxford Instruments Analytical
Dr. Rune Gehrlein
Halifax Road, High Wycombe
HP1235E
Bucks County, UK
Telephone: 011-44-1494-442255
Email: rune.gehrlein@oxinst.co.uk
Rigaku, Inc.
Mr. Jose Brum
14 Ruth Circle
Haverhill,MA 01832
Telephone: (978) 374-7725
Email: ibrum@RigakuMSC.com
RONTEC USA Inc.
Mr. Paul Smith
90 Martin Street
Carlisle, MA 01741
Telephone: (978) 266-2900
Email: psmith@rontecusa.com
12
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Table 2-1. Demonstration Participants (Continued)
Organization
Point of Contact
Contact Information
Xcalibur XRF Services Inc.
Mr. Ronald
Williams
1340 Lincoln Avenue, Unit #6
Holbrook,NY11749
Telephone: (631)435-9749
Cellular: (516) 885-7398
Email: ronupa@aol.com
Tetra Tech EMI
(EPA NERL support contractor)
Dr. Greg Swanson
1230 Columbia Street, Suite 1000
San Diego, CA 92101
Telephone: (619)525-7188
Fax: (619)525-7186
Email: greg.swanson@rtemi.com
Environmental Resource Associates
John Laferty
6000 West 54"1 Ave.
Arvada, CO 80002
Telephone: (800) 372-0122
Email: ilafetrty@eraqc.com
Shealy Environmental Services, Inc.
Mr. Daniel Wright
106 Vantage Point Drive
Cayce, SC 29033
Telephone: (803) 791-9700
Email: dwright@shealylab.com
ARDL
Mr. Dan Gillespie
400 Aviation Drive
Mt. Vernon, IL 62864
Telephone: (618)244-3235
Email: dgillespie@ardlinc.com
Ms. Julie Capri and Dr. Ed Surbrugg will function as the technical leads in fulfilling many of Tetra Tech's
responsibilities for the demonstration. They are specifically responsible for developing and implementing
the demonstration plan. Their other specific responsibilities include:
• Coordinating meetings among the EPA, the developers, peer reviewers, and technical advisors.
• Interfacing with the representatives for the demonstration site and making logistical preparations
for the demonstration.
• Immediately communicating any deviation from the demonstration plan during field activities to
the project manager and discussing appropriate resolutions of the deviation.
• Providing required planning, scheduling, cost control, documentation, and data management for
field activities.
• Coordinating activities with the PE sample suppliers.
The Tetra Tech QA manager, Mr. John Dirgo, is responsible for providing senior-level oversight for
QA/QC matters. He is specifically responsible for reviewing and concurring with all project quality
assurance plans.
Tetra Tech's corporate health and safety representative, Ms. Judy Wagner, will review the procedures in
the site-specific health and safety to ensure compliance with the requirements of the Tetra Tech corporate
health and safety plan. Ms. Stephanie Wenning will serve as the site safety coordinator and will ensure
that all activities during the field demonstration comply with health and safety requirements.
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Ms. Candy Friday will serve as the project chemist for Tetra Tech. She will be responsible for selecting,
auditing, and providing oversight of subcontractor laboratories performing the material characterization
and reference analyses. Her specific responsibilities will include:
• Auditing the reference laboratory to evaluate whether the operations are properly carried out.
• Set up, implement, and evabate QC criteria for the demonstration.
• Evaluating all analytical data and their usability for meeting the project objectives.
• Preparing draft and final versions of the DER, consistent with the format and content of historical
documents.
Mr. Steve Dyment, and Mr. Chris Reynolds, as well as Ms. Friday, Dr. Surbrugg and Ms. Capri, will
function as observers for assigned technology developers/instruments during the field demonstration at
KARS Park. Their responsibilities as observers will include:
• Developing and maintaining the sample control process and distributing samples during the
demonstration.
• Observing the operation of the developer's XRF instrument and documenting the operation of
this instrument during the demonstration.
• Summarizing, evaluating, interpreting, and documenting field demonstration data for inclusion in
the ITVRs and DER.
• Evaluating and reporting on the performance and cost of each instrument.
Mr. Stan Lynn will serve as the site superintendent during the field demonstration at KARS Park. He will
be responsible for the following:
• Coordinating shipping of supplies and equipment to the field demonstration site.
• Photographing field demonstration activities for purposes of providing complete documentation
of site activities.
• Managing demobilization activities, including proper waste disposal.
Mr. Mark Colsman and Mr. Butch Fries will serve as the primary author and technical editor for the draft
and final versions of the ITVRs (one for each instrument).
23 Developer Personnel
Developers of the participating XRF instruments will be responsible for providing, mobilizing and
demobilizing, and operating the instruments they select for demonstration. The developers will also be
responsible for the following:
• Providing Tetra Tech with information on the instruments.
• Reviewing and providing input on the demonstration plan.
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• Informing Tetra Tech of any technology-specific requirements for the demonstration, such as the
type of power supply and work space needed.
• Provid ing all personnel and supplies needed for the technology demonstration.
• Analyzing all field samples as specified in the demonstration plan and providing analytical results
as required in a timely fashion.
• Provid ing the XRF instrument demonstration results to Tetra Tech at the end of the
demonstration.
• Reviewing and providing input on the instrument-specific ITVRs.
2,4 Demonstration Site Representatives
The representative for the demonstration site, KARS Park at Kennedy Space Center, is Mr. Michael
Deliz, the National Aeronautics and Space Administration (NASA) remediation project manager. All
work at the demonstration site will be coordinated and conducted with the permission of Mr. Deliz. All
site-related activities will be coordinated through Mr. Mark Speranza of Telra Tech NUS, the consultant
program manager for NASA. The demonstration plan will be submitted to the representatives of the
demonstration site for review and comment.
2,5 Laboratory Project Personnel
Two subcontractor laboratories are required for the demonstration project: (1) a characterization
laboratory responsible for processing and characterizing sample material; and (2) a reference laboratory
that will independently verify element concentrations in each sample batch in conjunction with analys is
by the developers. Applied Research and Development Laboratory, Inc. (ARDL), in Mount Vernon,
Illinois, will function as the characterization laboratory. The ARDL project manager, Mr. Dan Gillespie,
is responsible for overall planning, scheduling, budgeting, and reporting laboratory activities. All ARDL
work will be under the direct supervision of Mr. Gillespie, who will be the primary contact for the Tetra
Tech project manager. Mr. Gillespie is also responsible for reviewing and concurring with the
demonstration plan and will immediately discuss with the Tetra Tech project manager appropriate
resolutions of any deviation from the activities specified in the plan. ARDL's QA manager, Mr. Dick
Curtain, will assist Mr. Gillespie in ensuring adherence to all QA/QC elements specified in the
demonstration plan that pertain to the analyses at the laboratory.
Shealy Environmental Services, Inc. (Shealy), in Cayce, South Carolina, will function as the reference
laboratory. The Shealy project manager, Mr. Daniel Wright, is responsible for overall planning,
scheduling, budgeting, and reporting of laboratory activities. All Shealy work will be under the direct
supervision of Mr. Wright, who will be the primary contact for the Tetra Tech project manager. Mr.
Wright is also responsible for reviewing and concurring with the demonstration plan and will immediately
discuss with the Terra Tech project manager appropriate resolutions of any deviation from the activities
specified in the plan. Shealy's QA manager, Ms. Debbie Langley, will assist Mr. Wright in ensuring
adherence to all QA/QC elements specified in the demonstration plan that pertain to the reference
analyses at the laboratory. Data obtained from the reference laboratory will be used to establish a
reference value for all samples.
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Chapter 3
Developer Instrument Descriptions
This chapter describes each XRF instrument that is participating in the demonstration, including the
technology, operating procedures, and advantages/limitations. This information was provided by the
developers; Terra Tech incorporated only editorial changes to ensure consistency and meet the needs of
this document. Many of the claims represented by the developers will be tested during the demonstration.
3.1 Innov-X Systems XT400 Series XRF Analyzer
The Innov-X Systems XT400 Series XRF Analyzer is a hand-held XRF analyzer featuring a miniature,
rugged x-ray tube source. The x-ray tube provides a high level of performance while eliminating the
regulatory requirements associated with isotope source systems. The XT400 Series XRF Analyzer is
engineered for fast, on-the-spot elemental analysis using a standard program for a wide variety of
elements and sample types. A Light Element Analysis Program (LEAP) is available for improved
analysis of light elements.
3.1.1 Technology Description
The Innov-X Systems XT400 Series XRF Analyzer features a miniature, rugged x-ray tube that provides
high-level analytical performance for challenging alloy, environmental, and other analytical samples. The
x-ray tube source and LEAP technology can analyze elements that would require three isotope sources in
traditional XRF analyzers. Features include:
• Multiple x-ray beam filters
• Adjustable tube voltages and currents
• Several calibration methods:
o Fundamental parameters
o Compton normalization
o Empirical - factory and user-generated linear, quadratic and exponential calibrations
o Scatter normalization (trace metals, low-density matrices)
o Spectral matching (rapid material sorting, product authentication)
The instrument weighs 4.5 pounds and has a Silicon-PiN diode detector with a typical resolution of 250
electron volts (eV) or better. The XT400 Series XRF Analyzer can be powered in the field with a
lithium-ion battery (run time is 4 to 8 hours, depending on usage), or can use AC power, if available.
Rather than relying on an embedded processor and proprietary software that may quickly become
obsolete, Innov-X has designed the analyzer around a Hewlett-Packard (HP) iPAQ Pocket PC. The iPAQ
can store a minimum of 10,000 tests with spectra in its 64 MB memory. The iPAQs have color, high
resolution displays with variable backlighting and can be fitted with Bluetooth wireless printing and data
downloading, an integrated bar-code reader, and wireless data and file transfer.
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The Innov-X XT400 Series XRF Analyzer can analyze elements from potassium to uranium in suites of
25 elements simultaneously. Typical applications are:
• Alloy analysis - Chemistry and grade identification of most alloys, metal powders, sintered
alloys, and metallic coatings.
• Environmental samples - Analysis of metals in soils, slurries, liquids, filters, and dust wipes.
• Process analytical - Elemental analysis of powders, ores, and mining samples; coatings
thickness, other samples, including oils, water, plastics, ceramics, and glass.
The technical specifications for the XT400 Series XRF are presented in Table 3-1.
Table 3-1.
Innov-X XT400 Series Analyzer Technical Specifications
Weight:
Excitation Source:
LEAP:
Detector:
Temperature Range:
Operation:
Power:
Battery Life:
Number of Elements:
Display:
Data Display:
Memory, Data storage:
Processor:
Operating System:
Software Modes:
2kg.
X-ray tube, Ag anode, 10-35 kV, 10-50 uA.
Delivers industry- leading detection limits on critical elements Cr, V,
Ti, P, S, Cl, Ca, K.
Si-PiN diode detector, <250 eV FWHM at 5.95 keV Mn K-alpha
line.
-10°Cto+50°C.
Trigger or Start/Stop Icon for in situ analysis. Optional control from
external PC.
Li- ion batteries, rechargeable (charger included). Powers analyzer
and iPAQ simultaneously. AC adapter optional.
8 hours (typical duty cycle), 3 hours continuous (tube on) operation.
Standard package includes 20 elements. Customer may specify 5
additional, or use multiple suites of 25 elements each.
Color, high-resolution, touch screen. Variable brightness provides
easy viewing in all ambient lighting conditions.
Concentrations in ppm, spectra or peak intensities (count rate) or
user-specified units, depending on software mode selected.
Minimum 20,000 test results with spectra, upgradeable to 100,000
rest results with upgrade to 1 GB flash card. 128 MB standard
memory.
Intel 400 MHz StrongArm processor.
Microsoft Windows CE (portable system) or Windows (PC-based).
Soil, wipe/filter, lead paint, empirical, many others.
3.1.2 Operating Procedures
Field-portable XRF is generally used in three ways to test for metals in soil (described below). Most
field-portable XRF operations use a combination of in situ and prepared sample testing.
1. In situ soil testing. The XRF is placed directly onto the ground for soil testing (Figure 3-1).
Operators remove any plant growth and foreign objects so that the analyzer probe is flush to the
soil.
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2. Bagged soil sample testing. A soil sample is collected in a thin plastic bag and tested directly
through the bag. Except for a few elements, namely chromium, vanadium, and barium, testing
through the thin plastic used for a plastic bag has little effect on the test result. Results for
chromium, vanadium, and barium will be lower by 20 to 30 percent.
3. Prepared soil sample testing. Prepared sample testing assures the operator of the maximum
possible accuracy. Prepared sample tests require a sample to be collected, dried if necessary,
sieved, and ground into a powder. The prepared sample is then placed into a baggie or XRF cup
for analysis.
Figure 3-1. Innov-X XT400 Series Analyzer
QA/QC is important for the proper use of the analyzer and for verifying the data quality of the results.
All XRF operators should implement QA/QC procedures, regardless of the data quality objectives.
Innov-X Systems recommends that XRF operators verify the quality of the XRF results when using the
data to guide reporting or remediation decisions. The procedures listed below have been taken from FPA
Method 6200 and updated by Innov-X to be specific to the XT400 Series XRF Analyzer. QA/QC
procedures consist primarily of testing known standards to verify calibration, testing blank standards to
establish the limits of detection, and checking for sample cross-contamination or instrument
contamination. The specific components of Innov-X QA/QC recommendations are:
1. An energy calibration check sample at least twice daily.
2. An instrument blank for every 20 environmental samples.
3. A method blank for every 20 prepared samples.
4. A calibration verification check sample for every 20 samples.
5. A precision sample at least one per day.
6. A confirmatory sample for every 10 environmental samples.
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5.7.3 Advantages and Limitations
The primary advantages of the Innov-X XT400 Series XRF Analyzer are the miniature, rugged x-ray tube
source (no radioactive isotopes); the friendly, flexible software; the broad range of elemental analysis;
and the versatility. (It can analyze alloys, powders, soils, ores, liquids, coatings, paints, and filter media.)
The test conditions can be selected based on specific project precision or action levels, which can
dramatically reduce testing times while ensuring that analytical requirements are met.
Conversely, as with most XRF analyses, the detection limits for certain elements may be above specific
risk-based remediation goals or actions levels. Other limitations include battery life, ease of reading the
iPAQ screen display, and length of testing to achieve the best data quality.
3.2 NITON XLi/XLt 700 Series
The NITON XLi and XLt 700 Series XRF instruments combine the performance of a laboratory-grade
unit with unmatched portability and ease of use. Offering the customer the choice from a full suite of
excitation options, including a miniaturized x-ray tube with PERFECT (Programmable Excitation by
Regulation of Filters, Energy, Current, and Time) technology and various isotope configurations, NITON
has the appropriate analyzer for rapid chemical characterization of soils, sediment, and other thick
homogeneous samples.
3.2.1 Technology Description
The NITON XLi and XLt 700 Series XRF instruments feature a choice of either a full suite of traditional
isotope sources or a miniaturized x-ray tube for rapid chemical characterization of soils, sediment, and
other thick homogeneous samples. The preset factory calibration allows simultaneous analysis of up to
25 elements, including all eight Resource Conservation and Recovery Act (RCRA) metals, in bulk
materials with no requirement for site-specific calibrations or standards. Whether testing is performed in
situ (directly onto the ground) or ex situ (bagged or prepared samples), sophisticated software
automatically compensates for matrix variations from sample to sample, allowing the operator to simply
"point and shoot" any bulk sample without unnecessary data entry or additional calibrations. User-
generated empirical calibration capability is also available. With typical testing times of less than 60
seconds, the XLi and XLt analyzers are well suited for:
• Site characterization
• On-site clearance screening
• Soil stabilization control
• Remediation quality control
3.2.1.1 XLi 700 Series Technology Description
NITON's XLi 700 Series analyzers are easy to operate, light weight, ergonomic, and are an advanced
isotope-based environmental XRF instrument. NITON offers various isotope options to best optimize
performance for the environmental application. NITON offers the XLi 702 with a 40 mCi 109Cd source
for those customers with project requirements that call for the highest performance available in field-
portable, isotope-based XRF. This isotope provides the user with the best sensitivity for many of the
crucial elements measured in bulk material, including lead, mercury, and arsenic. Available with an
optional 14 mCi 241Am source and 20 mCi 55Fe source, this configuration is the ideal high-performance
environmental analyzer for testing light and heavy metals.
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NITON's patented XLi 712 with Infiniton is the first isotope-sourced portable XRF environmental
analyzer that never slows down or requires source replacements. The XLi 712 with Infiniton source
employs a 30mCi 241Am source and a proprietary combination of detector settings and software that
enables the NITON analyzer to rapidly measure up to 25 elements in a sample. Offering all-purpose
performance for many key elements in most environmental applications, the NITON XLi 712 with
Infiniton can be a viable low-maintenance alternative when the ultra-high-performance of the 40mCi
109Cd source and x-ray tube or the reduced regulatory requirements of the miniature x-ray tube are not
required.
The XLi analyzer provides the following features:
• Patented, high-speed electronic s for superior performance.
• Integrated touch-screen display with easy-to-use, intuitive user menus; no Windows CE
experience is required
• A full suite of excitation options, including the patented Infiniton configuration that never
requires replacement and never slows down.
• Truly portable, one-piece package.
• Environmental sealed housing for use in virtually any climate.
• Quick-swap lithium ion batteries to allow continued use with minimal downtime, or can use AC
power if available.
• Integrated bar code reader and virtual keypad for fast, easy data entry.
• Remote operation and custom report generation capability from a Windows-based PC
• Lightweight and shielded bench-top test stand to facilitate fixed-site or trailer use.
• Optional Bluetooth wireless communication to a laptop or PDA
• New features and software upgrades via the Internet
The technical specifications for the XLi 700 Series XRF are presented in Table 3-2A.
3.2.1.2 XLt 700 Series Technology Description
The XLt 700 Series analyzer offers the user the speed and efficiency of x-ray tube excitation, while
greatly reducing the regulatory demands encountered with isotope-based units. The XLt can be easily
shipped from state to state and between most countries with minimal documentation and expense. The
XLt 700 features a miniaturized x-ray tube with PERFECT technology. This technology allows for
enhanced detection of light elements, including ultra-low detection limits for vanadium and chromium,
and eliminates the need for multiple sources.
The XLt analyzer provides the following features:
• Patented, high-speed electronic s for superior performance.
• Integrated touch-screen display with easy-to-use, intuitive user menus; no Windows CE
experience required.
• A miniaturized x-ray tube for high performance and reduced regulatory requirements.
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Optional PERFECT technology for analysis of light elements or optimizing detection limits for a
suite of elements specific to the application.
Truly portable, one-piece packages.
Environmental sealed housing for use in virtually any climate.
Quick-swap lithium ion batteries to allow continued use with minimal downtime.
Integrated bar code reader and virtual keypad for fast, easy data entry.
Remote operation and custom report generation capability from a Windows-based PC
Lightweight and shielded bench-top test stand to facilitate fixed-site or trailer use.
Optional Bluetooth wireless communication to a laptop or PDA
New features and software upgrades via the Internet
Table 3-2A.
NITON XLi 700 Series Technical Specifications
Weight:
Dimensions:
Excitation source:
X-ray Detector:
Systems Electronics:
Batteries:
Display:
Analysis range:
Testing modes:
Data storage:
Standard accessories:
1.7 pounds (0.8 kg)
1 1.5 x 3.5 x 3.0 inches (292 x 89 x 76 mm)
• Primary: 241 Am maximum 30mCi (1,1 10 MBq) — Infiniton, or
109Cd maximum 40mCi (1,480 MBq)
• Secondary: 241 Am maximum 14mCi (520 MBq) or 55Fe
maximum 20mCi (740 MBq)
High-performance Si-PiN detector, Peltier cooled
Hitachi SH-4 CPU ASICS high-speed DSP 4096 channel MCA
(2) Rechargeable Lithium- ion battery packs with quick-swap
capability; 6-12 hours (maximum depends on platform and duty
cycle), 2-hour recharge cycle.
Vi Backlit VGA touch screen LCD
• Up to 25 standard elements in the range Ti(22) to Pu(94).
• Some nonstandard in-range elements available at additional
cost.
• Bulk sample Mode
• Thin sample Mode, including dust wipe mode and 37 mm filter
mode
Internal: 3,000 readings with x-ray spectra (maximum)
• Soil Sampling Kit/Thin Sample Kit (varies by model and
configuration)
• Lockable, shielded waterproof carrying case
• Shielded belt holster
• Spare lithium- ion battery pack with holster
• 1 1 0/220 V AC battery charger/adapter
• PC interface cable
• NOT (NITON Data Transfer) PC software
• Safety lanyard
• Check/verification standards
• Integrated bar code scan engine/Virtual keypad for rapid and
reliable entry of sample information
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The technical specifications for the XLt 700 Series XKF are presented in Table 3-2B.
Table 3-2B.
NITON XLt 700 Series Technical Specifications
Weight:
Dimensions:
Excitation source:
X-ray Detector:
Systems Electronics:
Batteries:
Display:
Analysis range:
Testing modes:
Standard accessories:
3.0 pounds (1.4 kg)
9.75 x 10.5 x 3.75 inches (248 x 273 x 95 mm)
Miniature x-ray tube and power supply (40 kV/SOuA maximum) with optional
PERFECT technology
High-performance Si-PiN detector, Peltier cooled
Hitachi SH-4 CPU ASICS high-speed DSP 4096 channel MCA
(2) Rechargeable Lithium- ion battery packs with Quick-swap capability, 6-12
hours (maximum depends on platform and duty cycle), 2-hour recharge cycle.
!/4 Backlit VGA touch screen LCD
• Up to 25 standard elements in the range Ti(22) to Pu(94).
• Some Nonstandard in -range elements available at additional cost.
• Bulk sample mode
• Thin sample mode, including dust wipe mode and 37 mm filter mode
• Soil Sampling Kit/Thin Sample Kit (varies by model and configuration)
• Lockable, shielded waterproof carrying case
• Shielded belt holster
• Spare lithium- ion battery pack with holster
• 1 1 0/220 V AC battery charger/adapter
• PC interface cable
• NDT (NITON Data Transfer) PC software
• Safety Lanyard
• Check/verification standards
• Integrated bar code scan engine/virtual keypad for rapid and reliable entry
of sample information
3.2.2 Operating Procedures
XRF analysis with the NITON XLi/XLt is typically used in an in situ (Figure 3-2) or an ex situ mode. In
situ testing with the XLvXLt analyzer involves placing the window directly on the ground or on plastic
bagged samples and allows collection of a large number of data points in a short time. In situ sampling is
the fastest and most effective way of delineating contamination patterns and achieving a more economical
site remediation. NITON's XLi/XLt analyzers fully comply with EPA Method 6200, "Field Portable
XRF Spectrometry for the Determination of Elemental Concentrations in Soil and Sediment."
Ex situ testing involves properly preparing samples, placing the samples in x-ray cups, and analyzing
them in a controlled area generally free from dust and weather extremes. Samples analyzed with the
XLi/XLt analyzers in an ex situ mode provide rapid laboratory-grade data quality without the wait or the
costs associated with an off-site laboratory. The XLi/XLt analyzer is equipped with a soil sampling kit,
complete with soil grinding apparatus, sieve set, and x-ray sample cups. Since XRF analysis is
nondestructive, samples analyzed may be sent to an accredited laboratory to confirm the result. Most
field-portable XRF operations use a combination of in situ and ex situ (bagged and prepared) sample
testing.
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Figure 3-2. NITON XLi/XLt Analyzer
The NITON XLi/XLt analyzer can also be used to analyze thin samples, including dust wipes for lead
inspection, risk assessment and Occupational Safety and Health Administration (OSHA) compliance, and
various other filter media. Results are reported in micrograms (ug) of loading per sample. Using the
area, volumetric flow-rate, or air sampling time (or a combination), the results can be easily converted to
the appropriate concentration units. With the XLi/XLt factory calibrations and analysis software, on-site
testing of the following thin film sample types is made simple and rapid:
• Lead in dust wipes as specified by the EPA Environmental Technology Verification (ETV)
Program and OSHA-regulated industrial hygiene applications.
• Total suspended particulates (TSP), particulate matter with an aerodynamic diameter less than 10
microns (PMio), and particulate matter with an aerodynamic diameter less than 2.5 microns
(PM2.5) for particulate monitoring of airborne metals.
• Ion-exchange filter media for suspended and dissolved metals in liquids.
• 25-millimeter- and 37-millimeter-diameter cellulose-ester filter used for OSHA compliance and
industrial hygiene.
The NITON XLi/XLt analyzer is ideal for clearance testing of metals for negative exposure and
residential risk assessment. NITON's portable XRF analyzer has been proven in EPA ETV studies for
lead in dust wipe testing and is the only XRF analyzer listed in National Institute of Occupational Safety
and Health (NIOSH) Method 7702 for monitoring airborne lead.
3.2.3 Advantages and Limitations
NITON revolutionized the environmental marketplace when it introduced the first hand-held multi-
element analyzer in 1995, the XL-700. Nearly 10 years of experience and thousands of satisfied
customers led to the XLi and XLt 700 Series analyzers. NITON offers the customer a choice of
traditional isotope configurations or the miniaturized x-ray tube along with powerful software; remote
operation; automatic analytical calculations; real-time data collection to maximize worker safety and
productivity; and versatility (for its ability to analyze in situ, ex situ, slurries, thin samples, and alloy).
As with most XRF analysis, the detection limits for certain elements may be above specific risk-based
remediation goals or action levels. Battery life and length of testing to achieve the best data quality are
also limitations.
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33 Oxford Instruments Analytical ED2000
The flexibility of the Oxford Instruments Analytical (Oxford) ED2000 makes it ideal for elemental
analysis of potentially contaminated lands and mineral waste. Its speed of analysis provides fast
turnaround of sample data. A determination of key toxic elements such as arsenic, cadmium, chromium,
copper, mercury, nickel, lead, thallium, vanadium, and zinc takes just a few minutes with minimal sample
preparation. This general-purpose instrument combines precision and accuracy of measurement with low
limits of detection for important toxic elements. A wide range calibration with certified reference
materials from internationally recognized sources allows the determination of toxic elements in
potentially contaminated soil, sediments, dried sludge, fly ash, or general trace element analysis in the
element range vanadium-uranium. The measurement of major elements (sodium-iron) is now possible
when the samples are prepared as pressed pellets. Oxford Instruments provides an instrument calibration
service as an option to customers.
3.3.1 Technology Description
The Oxford ED2000 bench-top analyzer is an energy dispersive XRF that can accommodate a variety of
sample sizes and matrices. The flexibility of the Oxford ED 2000 makes it ideal for elemental analysis of
potentially contaminated lands and mineral waste. Its speed of analysis provides fast turnaround of
sample data. A determination of key toxic elements such as arsenic, cadmium, chromium, copper,
mercury, nickel, lead, thallium, vanadium, and zinc takes just a few minutes with minimal sample
preparation. This general-purpose instrument combines precision and accuracy of measurement with low
limits of detection for important toxic elements. A wide range calibration with certified reference
materials from internationally recognized sources allows the determination of toxic elements in
potentially contaminated soil, sediments, dried sludge, fly ash, or general trace element analysis in the
element range vanadium-uranium. The measurement of major elements (sodium to iron) is now possible
when the samples are prepared as pressed pellets. Oxford Instruments provides an instrument calibration
service as an option to customers.
The Oxford ED 2000 is fitted with the new generation SMART digital pulse processor, which handles
even higher count rates (up to 90,000 counts per second {CPS} output rate). A dramatic enhancement in
count rate capability without degradation in special resolution provides faster analysis, improved
precision and lower detection levels. The latest version of Oxford Instruments' XpertEase 32 software
permits the energy dispersive channel detector to work at its full specification at all times. The analysis
condition is optimized on each individual sample to achieve best sensitivity. The regression data are
improved by using new fixed conditions and new regions of interests for background. Limits of detection
are reduced by a factor of three for mercury. With the ED2000's closely coupled excitation-sample
geometry, a low-power air-cooled x-ray tube is successfully employed for excitation. In combination,
these improvements lead to a minimum number of excitation conditions to cover the wide elemental
range of analysis for contaminated land and material waste. The ED2000 technical specifications are
provided in Table 3-3.
3.3.2 Operating Procedures
A 16-position sample tray allows automatic calibration and sample measurements, thus releasing the
operator for other tasks. Oxford Instrument's Microsoft Windows-based XpertEase 32 software can
perform analytical tasks and calculations such as accessing threshold limits for elements or combinations
of elements. This capability allows "go"/"no-go" decisions to be made quickly and objectively.
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Table 3-3.
Oxford Instruments Analytical ED2000 Technical Specifications
Element Range:
Number of Elements:
Concentration Range:
Sample Form:
Sample sizes:
Sample chamber:
X-ray Excitation:
Filters:
X-ray Detection:
Computer:
Interface:
Software:
Operating Environment:
Humidity:
Power Requirements:
Sodium to uranium.
Up to 75 elements for qualitative analysis and full quantitative
analysis.
ppm to 100%.
Solids, liquids, powders, granules, filter papers, films.
From 0.2 mm to 250 mm diameter.
Air path, helium/vacuum options.
250 mm diameter x 90 mm deep.
Standard automated 16-position sample carousel. Options
include 8-position sample carousel and sample spinner.
X-ray tube programmable 4-50kV, 1-1,000 uA (maximum 50
watts).
Stability <0.2%/8 hrs. Ag x-ray tube target.
Fully programmable ; 8 filter positions.
Patented Pentafet detector and digital pulse processor.
Guaranteed resolution of <150eV with 1 7,000 cps input rate.
Output count rate >90,000 cps. Liquid Nitrogen Dewar, 10-
liter capacity.
IBM compatible computer, 2.8 GHz Pentium IV processor, 80
GB hard disk, 128 MB RAM, including 15- inch SVGA color
monitor, 105-key keyboard, two-button mouse and associated
ink jet printer.
External RS232 port.
Oxford Instruments owns XpertEase Windows software
package. Allows qualitative, semi-quantitative, and full
quantitative analysis.
Special features include pre-programmed analytical parameters;
full spectrometer control, data library, x-ray mathematical
models.
Temperature: 5 to 30 °C.
20 to 80% relative (non-condensing).
220-250V AC, 50/60 Hz 10 amps.
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Figure 3-3. Oxford Instruments Analytical ED2000
3.3.3 Advantages and Limitations
Each unit comes equipped with a modem so that the instrument can be controlled remotely for ease of
operation. This feature also allows qualified technicians to evaluate system functionality and provide
troubleshooting guidance for inexperienced users from a remote location providing fast inexpensive unit
service.
The Oxford ED2000 provides a choice of the following analysis:
Qualitative:
Semi-quantitative:
Quantitative:
Rapid, elemental identification.
Fundamental parameter analysis:
- Standardless: where no standards are available
- Similar standard: where one of a few standards is available.
Calibrations: for highest accuracy and traceability using a range of standards.
The ED2000's powerful performance includes high-resolution EDXRF technology and the unique
patented Pentafetdetector; the instrument's highest x-ray intensity gives excellent precision and
consistent results with lowest limits of detection.
Many hundreds of these instruments have been delivered worldwide, with about 80 percent exported.
This commitment to overseas markets is demonstrated by wholly owned subsidiaries in the USA,
Germany, France, and Japan, and by an extensive network of agents providing worldwide service and
support.
3.4 Oxford Instruments Portable X-MET 3000TX
The Oxford Instruments Portable X-MET 3000TX is a hand-held XRF analyzer, featuring advanced x-ray
tube technology. The x-ray tube provides a high level of performance while eliminating the regulatory
requirements associated with isotope systems. The X-MET 3000TX is engineered for fast, on-the-spot
elemental analysis for a wide variety of elements and sample types.
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3.4.1 Technology Description
Oxford Instruments Portable XRF instruments feature a miniature, advanced x-ray tube source that
provides high-level analytical performance for challenging alloy, environmental, and other analytical
samples. The X-MET 3000TX can analyze elements that would require three isotope sources in
traditional XRF analyzers. Features include:
• Multiple x-ray beam filters.
• Adjustable tube voltages and currents.
• Several calibration methods:
o Fundamental parameters.
o Empirical - factory- and user-generated linear, quadratic, and exponential
calibrations.
o Spectra comparison identification
The instrument weighs 4 pounds and has a high-resolution Peltier cooled silicon-PiN diode detector
(resolution is less than 275 eV). The X-MET 3000TX can be powered in the field with two lithium-ion
batteries (with a lifespan of 4 hours each), or can use AC power if available. Oxford Instruments has
designed the analyzer around an HP iPAQ Pocket PC. The iPAQ can store a minimum of 10,000 tests
with spectra with its 64 MB memory. The iPAQs feature color, high-resolution displays with variable
backlighting. The data can be transferred from the iPAQ to a personal computer (PC) by inserting the
flash card into the PC, where it will appear as an additional removable disk drive or by using Microsoft
ActiveSync software over a USB cable. The iPAQ can be fitted with Bluetooth wireless printing and data
downloading for wireless data and file transfer.
The Oxford Instruments Portable X-MET 3000TXcan analyze all elements from titanium to uranium
simultaneously. Elements from potassium to scandium can be analyzed with higher detection limits.
Typical applications are:
• Alloy analysis - Chemistry and grade identification of most alloys, metal powders, sintered
alloys, and metallic coatings.
• Environmental samples - Analysis of metals in soils, slurries, liquids, filters, and dust wipes.
• Process analytical - Elemental analysis of powders, ores, and mining samples; equipment
surfaces, coatings, and other samples, including vegetation, oils, water, plastics, ceramics, and
glass.
The technical specifications for the X-MET 3000TX XRF instrument are presented in Table 3-4.
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Table 34.
Oxford Instruments Portable X-MET 3000TX Technical Specifications
Weight:
Configuration:
Analysis Range:
Excitation Source:
Detector:
Display:
Memory:
Batteries:
Battery Charger/AC Adaptor:
X-Ray Tube:
Operation Temperature:
Safety Features:
Software Interface:
Data Transfer:
Bench-top Operation:
Warranty:
1.8kg
Hand-held portable tube excited XRF.
Ti to U.
Miniature x-ray tube.
Si-PiN Diode.
Color TFT 320 x 240 pixels.
65,536 colors.
64MB.
Stores a minimum of 15,000 spectra.
Unlimited results.
(2) Li ion batteries.
110/220 VAC, 45-65 Hz.
40 kV, 40 uamps - programmable.
-10 °C to +50 °C.
IR sample sensor.
Failsafe status lights.
Safety shield for small parts.
Windows CE.
USB or wireless Bluetooth via Microsoft
ActiveSync.
Bench top instrument stand.
PDA cradle and remote extension cable standard.
Instrument - 2 years.
X-ray tube - 5 years.
3.4.2 Operating Procedures
Field-portable XRF is generally used in three ways to test for metals in soil (described below). Most
field-portable XRF operations use a combination of in situ and prepared sample testing.
1. In situ soil testing. The XRF instrument is placed directly onto the ground for soil testing
(Figure 3-4). Operators remove any plant growth and foreign objects so that the analyzer probe is
flush to the soil.
2. Bagged soil sample testing. A soil sample is collected in a thin plastic bag and tested directly
through the bag. Except for a few elements, namely chromium, vanadium, and barium, testing
through the thin plastic used for a plastic bag has little effect on the test result. Results for
chromium, vanadium, and barium will be lower by 20 to 30 percent.
3. Prepared soil sample testing. Prepared sample testing assures the operator of the maximum
possible accuracy. Prepared sample tests require a sample to be collected, dried if necessary,
sieved, and ground into a powder. The prepared sample is then placed into a baggie or XRF cup
for analysis.
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Figure 3-4. Oxford Instruments Portable X-Met 3000TX
3.4.3 Advantages and Limitations
The primary advantages of the Oxford Instruments Portable X-MET 3000TX analyzer is the miniature,
advanced x-ray tube source with a 5-year warranty (no radioactive isotopes); the friendly, flexible
software; the broad range of elemental analysis; the automatic analytical calculation; real-time data
collection; and versatility (it can analyze alloys, powders, soils, ores, liquids, coatings, paints, and filter
media). The test conditions can be selected based on specific project precision or action levels, which can
dramatically reduce testing times while ensuring that analytical requirements are met.
As with most XRF analyses, the detection limits for certain elements may be above specific risk-based
remediation goals or actions levels. Battery life, ease of reading the iPAQ screen display, and length of
testing to achieve the best data quality are also limitations.
3.5 Rigaku ZSXmini
The Rigaku ZSXmini is a wavelength-dispersive XRF (WDXRF) spectrometer, which differentiates it
from the other, EDXRF spectrometers to be used in this demonstration. Although energy-dispersive
instruments differentiate x-ray energies emitted from the sample (and thus target analytes) based on
voltages measured by the detector, WDXRF spectrometers disperse the x-rays from the sample into
different wavelength ranges using crystals. WDXRF instruments thus can achieve higher resolving power
and better sensitivity than EDXRF instruments in some applications. For example, WDXRF
spectrometers can better resolve significant
concentrations of arsenic and lead in many sample
matrixes.
3.5.1 Technology Description
WDXRF spectrometers have historically been large,
laboratory-bound instruments with significant
requirements for power and cooling. The ZSXmini is
one of a new generation of smaller, transportable units
that can operate without cooling water on standard
110-volt circuits. Other features of the ZSXmini are:
• Analysis of very light to heavy elements, from
fluorine to uranium.
Figure 3-5. Rigaku ZSXmini
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• A 50-watt, 40 kV, 1.25 milli-amp (mA) air-cooled end-window x-ray tube (with palladium
or rhodium as an anode material).
• Vacuum or helium environments for enhanced performance in analyzing light elements
(optional).
• A sample compartment that can be used as a single sample holder or as an optional 12-position
sample changer, or that can be adapted to accept irregular objects.
• An available sample spinner.
• Multifunction Windows software (that includes FPT method).
Analyzing crystals for x-ray dispersion include lithium fluoride (LiF), pentaerythritol (PeT), and thallium
acid phthalate (TAP) operating on a revolving changer. Other optional crystals include RX35 and
germanium. The unit can employ an economical gas proportional counter as a detector rather than a
diode detector with an MCA that is used in EDXRF instruments because wavelength resolution is
achieved with the crystals.
The technical specifications for the ZSXmini XRF are presented in Table 3-5.
Table 3-5.
Rigaku ZSXmini Technical Specifications
Weight:
Size:
Element Range:
Excitation Tube:
X-ray Optics:
Detector:
Sample:
Signal Processing:
Software:
Variants:
Power:
Temperature:
Humidity:
120 kg.
570 mm wide, 500 mm deep, 250 mm high
From fluorine to uranium.
50- W, 40- kV, 1.25-milli-amp, air-cooled end-window x-ray tube.
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.
Uses a 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.
25 mm plastic sample cups with polypropylene windows.
Digital signal processing unit
Windows XP based, multi-function software package for instrument
control, spectra accumulation, calibration, and quantification.
ZSXmini with single sample changer.
ZSXmini 12 position sample changer.
ZSXmini can be adapted to accommodate oversize or irregular
objects.
AC single phase 1 10 V, 10 A, 50/60 Hz
15-28 °C
Less than 75% relative humidity (non-condensing).
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3.5.2 Operating Procedure
Rigaku recently performed an application study to assess the ability of the ZSXmini to resolve arsenic and
lead in soils. This study analyzed prepared (ground and homogenized) soil samples in plastic sample
cups with polypropylene windows. Using the ZSXmini, these samples were run in air using a palladium
(F'd) anode and a LiF crystal with the sample spinner running. The following additional measurement
parameters were applied:
Element
X-ray line
Peak scan, sec
Background scan, sec
Pulse Height Analyzer
As
K6-1
60
30
150-280
Pb
LB-1
30
2x10
140-280
Pd Source (Compton)
Compton
10
~
100-300
After initial screening analysis showed it was possible to separate the arsenic and lead peaks, an empirical
calibration method was assessed to be more robust than an FPT method. The initial study also refined
other aspects of the instrument method, including background subtraction and normalization to the
Compton scattering peak from the palladium source. The total measurement time for the samples was
less than 150 seconds.
A set of six different reference samples was used for calibration. Two of the mid-range reference
standards were also used to measure MDLs in accordance with the requirements at Title 40 Code of
Federal Regulations (CFR) Parts 136 and SW-846. MDLs were calculated of 34 ppm for arsenic and 50
ppm for lead. Other quality control protocols during the sample runs included analysis of silicon dioxide
blanks and another standard reference material as a calibration verification check, each analyzed at the
beginning, middle, and end of the sample runs. Replicate analyses were also performed for multiple
samples to assess precision.
The study found that the concentrations measured in many samples far exceeded the available calibration
standards that were used and recommended that other standards be found to extend the calibration range.
For this reason, method accuracy or comparisons to other analytical methods were not assessed in detail.
However, other method checks indicated acceptable method performance. Correlation coefficients of
0.999 were obtained in the calibration. Silicon dioxide blank results were all below the MDL, and
calibration verification results were within plus or minus 20 percent difference from the known standard
concentration. In addition, the percent relative standard deviations (%RSD) for all replicate sample sets
except one were less than 5 percent, and for the remaining sample set, it was 13 percent.
Rigaku has also completed application studies for other solid media, such as industrial waste and cements.
Although sample preparation methods varied, these other applications generally used similar calibration
and QC protocols, including empirical methods and Compton normalization. These application studies
are available at http://www.rigakumsc.com/xrf/.
3,5.3 Advantages and Limitations
The primary advantage of the ZSXmini XRF is that its wavelength-dispersive features can produce higher
resolution of sample peaks, improving data quality for some metals (such as arsenic and lead) in complex
sample matrixes. It is also easier to use and transport than other WDXRF units, with lower power
requirements and no need for water or other coolants. Its powerful software package allows a number of
calibration modes (FPT, empirical, and Compton), and can accommodate a broad range of sample types.
In addition, because it is wavelength-dispersive, the ZSXmini can employ a sealed gas proportional
counter as a detector that is more rugged and economical than the detection systems used for EDXRF
units.
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Despite improved resolution, the detection limits for many elements are in the same range as for EDXRF
spectrometers (low parts per million [ppm]), as demonstrated by the soil application study above. The
detection limits are the result of the loss of x-ray intensity across the crystals used for wavelength
selection. In addition, the unit cannot operate on battery power and although it has improved
transportability relative to other WDXRF units, it is still somewhat bulky at 265 pounds. The ZSXmini
requires use of a flow proportional counter as a detector rather than a sealed proportional counter for the
analysis of light elements, so that gases (argon/methane) must be managed.
3.6 RONTEC PicoTAX
The RONTEC PicoTAX or Pg-Trace x-ray analyzer is a portable bench-top device that provides
quantitative and semi-quantitative multi-element microanalysis of soils and sediments using total
reflection x-ray fluorescence spectroscopy (TXRF).
3.6.7 Technology Description
The PicoTAX is a portable bench-top device realized by
applying a state-of-the-art compact, fine-focus x-ray
tube, multilayer x-ray optics, and Flash Peltier-cooled
detector. The spectrometer includes a 40-watt metal
ceramic molybdenum-tube excitation source, with a
focal length of 1.2 millimeters and a focal width of 100
um. This tube works with a grounded cathode and air
cooling. The compact design of this system provides for
a short distance of 15 millimeters between the target and
the tube window. The grounded cathode provides for a
small and inexpensive high-voltage generator technique.
The main element of the beam adapting unit is a one-
stage Ni/C multilayer monochromator with a reflectivity
for the Mo-K line higher than 80 percent. The module is
adaptable to the energy of interest — beginning from the
total reflection mode up to the Bragg reflection of the
multilayer. This system provides for a better
background reduction compared with a cutoff reflector. A thermoelectrically cooled silicon drift (Si
Drift) x-ray detector was selected for use in this portable system. The main advantage with this detector
is the exceptional resolution of less than 160 eV and the maximum count rate of several 10,000 cps. A
tradeoff of this resolution is the low efficiency for high-energy photons and a relatively long warm-up
time. The detector is capable of analyzing for a broad range of elements, from aluminum to yttrium and
from palladium to uranium. The instrument typically provides for detection levels for these elements
down to 10 ppm for soils and sediments. Interesting for portable use is that the complete system in the
configuration needs only 180 watts of power. The system dimensions are 600 by 300 by 450 millimeters,
and the total weight is 37 kilograms. The instrument is equipped with two handles for easy
transportation.
The PicoTAX uses an internal standard for instrument calibration, so that a standard procedure for initial
calibration is not required. A solution of internal standard that contains a project-specific element
(gallium was selected for this effort) is added to each sample analyzed to establish response factors
(determined by the software). Element quantitation is determined by comparing the response of the
unknown element with the response of the internal standard with the known concentration. AnICP-AES
solution such as a gallium standard, concentration 1000 ug/L (10 ul per sample) is an example of an
internal standard solution that may be used for sample analysis.
Figure 3-6. RONTEC PicoTAX
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The PicoTAX control software provides for control of all hardware functions, measurements,
visualization, storage of spectral energy and channel calibration, FWMH calibration, element
identification by the operator, background calculation, peak deconvolution, peak net area calculation, and
gain control for peak shift correction.
The PicoTAX Quantum software calibrates the instrument, handbs measurement data and methods, and
provides quantitative TXRF analysis for a wide variety of sample matrices that includes soils and
sediments, statistical functions, reporting functions, and data and spectra export.
Title technical specifications for the PicoTAX x-ray analyzer are presented in Table 3-6.
Table 3-6.
RONTEC PicoTAX Technical Specifications
Weight:
Dimensions:
Element Range:
Excitation tube:
X-ray Optics:
Detector:
Carrier:
Signal Processing:
Software:
Variants:
Power:
28kg.
420 x 590 x 300 mm.
From magnesium to uranium; elements from niobium to rhodium are
not detectable.
SOW metal ceramic x-ray tube, Mo-target, air cooled, 1.2 x
0.1 focus.
Ni/C multilayer, 17.5 keV, 80% reflectivity.
XFlashDetector, 10 mm', 160 eV FWHM.
30 mm quartz disk.
Digital signal processing unit, data interchange, and control
interface.
via RS232
Modular software package for instrument control, spectra
accumulation, calibration, and quantification.
PicoTAX Basic with single sample changer.
PicoTAX Automatic with automatic changer for 25 sample
discs.
180W.
3.6.2 Operating Procedure
Before the system is operated, a gain correction for energy calibration is performed by an automatic
software procedure. Blanks or calibration samples are not required for system operation. Samples are
prepared on quartz discs and then applied to the sample chamber for analysis.
In preparation for analysis, approximately 150 mg of sample is crushed in a mortar and pestle into a finely
ground material with a particle size less than 75 u to achieve the effect of total reflection and minimize
matrix effects. The pulverized sample and internal standard solution is suspended in a solution of Triton
X®-100. A drop of this suspension is added to the center of the quartz disc and then the disc is placed on
a hot plate to evaporate the sample into a surface residue for analysis. Prepared sample discs are placed
into a sample holder that is provided with the instrument. This holder is capable of holding 25 discs at a
time for analysis. Of the 25 slots in the holder for the autosampler, 22 sample discs will be of prepared
samples. Additional slots are used for a blank check standard, a quality control check sample, and a gain
correction sample.
Analysis typically requires from 100 to 2,000 seconds per run. The format of data output can be a printed
report with spectrum and results, a printed report of quantitative results, an export of ASCII files for
spectrum data and results, or a copy of spectra and results sent to the clipboard.
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3.6.3 Advantages and Limitations
Advantages of the PicoTAX method include the ability to analyze different sample matrices and
applications. The systems provides for a broad range of elements in a multi-element analysis. Detection
limits for this instrument range from parts per billion (ppb) to low ppm. Analysis requires small sample
amounts in the microgram range. Quantification is easy with the use of an internal standard. The
instrument performance is not affected by matrix or memory effects. The system is inexpensive to
operate and requires minimum power utilization. Limitations of the PicoTAX method include the need to
place the unit on a truck bed, mobile laboratory, or a van for use in a field setting. If the length of
analysis time requires 5 to 10 minutes per sample in order to meet accuracy and precision objectives then
the sample throughput will be reduced. Apart from a 110-volt power supply, no additional media (liquid
nitrogen, cooling water, or detector gases) are needed for operation of the PicoTAX.
3.7 Xcalibur XRF Services ElvaX
Xcalibur XRF Services provides sales, service, and support for a range of EDXRF equipment used in the
plating and elemental analysis industries. The Xcalibur XRF Services product line includes a state-of-
the-art portable XRF analyzer, the ElvaX manufactured by Elvatech, Inc., of Ukraine. This system
provides fast quantitative analysis, attaining data quality comparable to stationary laboratory
spectrometers at a lower cost than comparable systems. Xcalibur XRF Services ElvaX is capable of
detecting elements from magnesium to uranium. ElvaX applications include jewelry, metallurgy,
customs, forensics, medical diagnostics, food testing, environmental testing, and scientific research. The
ElvaX can be used for quantitative and qualitative analysis of metal alloys, liquid food, biological
samples, and powder assays, as well as samples deposited on surfaces or filters. The manufacturer reports
accuracy better than plus or minus 0.3 percent for metal alloys and detection limits in the range of 1 ppm
or lower for most elements in "light" matrices.
3.7.1 Technology Description
Technical specifications for the ElvaX are presented in Table 3-7. A PC for control via the USB port is
provided by Xcalibur XRF Services.
Figure 3-7. Xcalibur XRF Services ElvaX
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Table 3-7.
Xcalibur XRF Services ElvaX Technical Specifications
Weight:
Size:
Element Range:
Excitation Tube:
Detector:
Signal Processing:
Software:
Power:
18 kg.
430x340x210 mm.
From magnesium to plutonium.
5W x-ray tube; 4 to 50 kV (1-100 (JA) adjustable power supply; W anode
(Ti, Rh also available); air cooled; 0.14 mm Be window; stability 0.1%
over 8 hours.
PF-550 from Moxtek, Inc., 7 mrrf Si-PiN, 8 mm Be window, Peltier
cooled, 180 eV resolution (FWHM) at 5.9 keV.
Multi-channel analyzer; fast-shaping amplifier; pile -up rejection;
automatic adaptation to count rate; ADC resolution 4,096 channels, 1032
counts/channel (with successive approximation and "sliding scaling");
real and "live" time.
ElvaX menu-driven software (Windows 9x/2000/NT/XP) with USB
support for:
• Instrument control - tube parameters, spectrometric processor,
detector temperature, radiation safety, data acquisition, sample and
filter selection.
• Display - spectra, marker scaling, peak attributes, analysis
parameters.
• Data processing - calibrations, automatic peak search and ID,
deconvolution of overlapped peaks, background subtraction,
analytical intensities.
• Quantitative analysis - standardless FP, FP regression with post
processing, full-square regression with standards.
110-240V, 50 Hz, SOW.
X-ray Tube
• Titanium target, 140-micron beryllium window, air cooled (tungsten and rhodium target also
available).
Output of 4 to 50 kV in 0.5 kV increments, current 0 to 100 |iA in 0.2-jiA increments.
Auto primary filter
Change Beam size 3 mm (optional 10 mm).
Maximum power: 5 watts.
Stability of 0.1 percent over 8 hours.
Detector
• PF-550 solid state silicon-PiN diode, Peltier cooled (manufactured by MOXTEK, Inc.).
• Area: 5 square millimeters.
• Resolution: 180 eV for Fe55 5.9 keV.
• Beryllium window: 8 microns.
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Data Acquisition
• MCA (pulse processor) features time variant shaping, baseline restorer, pile-up rejecter, rise time
discriminator, and automated adaptation to count rate.
• ADC features 4,096 channels, successive approximation, sliding scale, 2 microsecond conversion
time.
• Data memory: 1032 pulses (counts) per channel capacity.
• Real and live timers.
Software
• Microsoft Windows 95/98/Me or 2000/NT/XP platform with USB support.
• Controls include x-ray tube parameters, spectrometric processor, data acquisition system
parameters, sample and filter selection (optional), detector temperature, and radiation safety.
• Displays x-ray spectrum, markers, scaling, peak attributes, and analysis parameters.
• Processing capabilities include calibrations, automatic peak search, overlapped peak
deconvolution, background removal, automatic element identification, and net peak intensities
above background.
• Various quantitative analysis methods, including standard-free FPT, full square regression using
calibration standards, and FPT with regression post-processing.
Additional Available Options
• Single and multiple primary fibers.
• Multiple sample table.
• Additional beam sizes.
• Larger sample chamber.
• Video Camera.
• He purge.
• Mobile support package.
3.7.2 Operating Procedures
Soil sample preparation:
To insure accuracy it is recommended that measured soil samples are first prepared by drying and ground
into a fine powder. A sample cup using a thin film support is prepared, preferably a support with low
level trace element impurities. The easiest method of analyzing a loose powder is to simply fill a sample
cup approximately 3/4 full and analyze it without any additional preparation. Tapping the cup on a clean
surface will pack it to a more consistent density. This method works best on homogenous soil samples as
grain size variation can cause the readings to vary because finer grains can be forced to the surface during
tapping. Alternately, samples can be pressed into pellets prior to measurement.
Elvatech has not established generalized standard operating procedures (SOPs) for preparation of soil
samples, instead relying on published methods and references. Elvatech and Xcalibur work with users of
36
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the ElvaX to identify or develop appropriate sample preparation techniques for an application. Once a
sample is prepared, it is analyzed quickly by placing the solid, powder, pellet or pressed, liquid, or
ga.seous sample in the sample chamber (no multiposition autosampler is available). Spectral acquisition
can be controlled manually or by pre-specifying live time, real time, maximal count time, or integral
value (within a count range) using the instrument software. Excitation conditions that can also be
controlled using the instrument software include tube current, anode voltages (for unusual or light
spectra), and count rate stabilization range. The ElvaX's pulse processor features time variant shaping,
baseline restoration, pile -up rejection, rise time discrimination, and automated adaptation to count rate.
The 4,096 channel ADC features successive approximation, sliding scale, and a 2-microsecond
conversion time.
Once collected, spectra can be processed using any of the following algorithms:
• Fundamental parameters with automatic peak identification.
• Fundamental parameters for a list of select elements.
• Regression algorithm set up by the user for samples of specific composition.
The FPT model is used to provide general results independent of sample preparation and assumes that
samples are infinitely thick, homogeneous, and have well-defined, flat surfaces. This model is mainly
used for assessing alloy content. The ElvaX regression algorithm (an empirical calibration protocol) is
recommended for more specialized determinations and quantifies based on a quadratic regression model
established using the spectra of specific reference samples along with their certified concentrations and
errors.
The ElvaX can collect linked spectra for a sample under multiple excitation conditions. These spectra are
acquired at constant tube currents but at different voltages. The spectrometer automatically adjusts
attenuator foil and helium flow (if required for specific matrixes) for optimal acquisition of different parts
of the x-ray spectrum. The instrument software provides a variety for data and spectral display,
evaluation, and comparison. '
The instrument software for the regression (empirical) algorithm allows evaluation of accuracy by
summarizing the following errors associated with the sample analysis:
• Standard deviation — Deviation of concentrations, determined for the reference samples using
the regression model, from their certified values.
• Minimal model error — Minimal possible error of the model determined from the certifie d
concentration error values of reference samples, estimated as an average of all certified
concentration errors.
• General analyte error — Summarized error for a given analyte, taking into account the standard
deviation and the minimal model error.
• Maximal error — The maximum of general analyte errors for all elements in the sample.
• Average method error — Average error of all certified analytes included in the model.
In general, the overall accuracy of results depends on the set of measured concentrations compared with
the reference samples. If the results differ significantly from the set of reference points, the accuracy of
measurements will be extremely low. The ElvaX software automatically tests these conditions of
consistency between the samples references and shows a warning message when necessary.
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3.7.3 Advantages and Limitations
The ElvaX portable spectrometer available from Xcaliber XRF is compact and economical when
compared with other bench-top, laboratory-grade XRF spectrometers, while providing comparable data
quality. The instrument provides fast, high-precision determinations of element concentration in a variety
of media, including alloys, liquids, food, biological samples, solids and powders, surfaces, and filters.
The instrument allows for fully automated adjustment and operation and is controlled by a powerful
software package that allows a broad range of data evaluation and presentation options.
As is true for the other bench-top units included in this demonstration (such as the XR1000), the
portability of the ElvaX is limited relative to hand-held XRF units given its size and lack of battery
power. The instrument was designed for the versatility and broad applications of a laboratory bench-top
instrument rather than focused specifically for environmental applications. Thus, the manufacturer has
established only limited procedures and performance data for environmental applications. In addition, the
instrument can be provided, as an option, with an autosample changer/carousel.
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Chapter 4
Demonstration and Sampling Site Descriptions
The field demonstration will take place at KARS Park, which is part of the Kennedy Space Center on
Merritt Island, Florida (the "demonstration site"). However, environmental samples will be collected
from several other sites around the country ("sampling sites") for use during the field demonstration.
This chapter describes the demonstration site and the sampling sites, as well as the rationale for selection
of each. The types of contaminated matrices and the target elements at each site are also discussed.
4.1 Description of Demonstration Site
There were several criteria that were used to assess potential demonstration sites, including:
• The ability to provide the best variety of target elements under chaflenging conditions,
• Convenience and accessibility to demonstration participants,
• Availability of contaminants of concern in the soil or sediments,
• The opportunity to provide cost-effective support from local Tetra Tech offices with utilization of
local staff,
• Ease of access to the site with a reasonably sized airport that can accommodate travel schedules
for participants,
• Program support and cooperation of the site owner,
• Sufficient space and power to support developer testing,
• Adequate conference room space to support visitor's day activities, and
• A temperate climate for performance of the demonstration in January.
After an extensive search for candidates, the site selected for the demonstration was KARS Park. The
location of KARS Park in relation to other facilities of the Kennedy Space Center is shown on Figure 4-1.
KARS Park was selected as the demonstration site for the following reasons:
• Access and Site Owner Support — Representatives from NASA will support the demonstration
by providing access to the site and will assist in logistical support during the demonstration as
well as on visitor's day.
• Facilities Requirements and Feasibility — The demonstration will take place in a conference
building located south of the gunnery range. This pavilion is a sufficient size and is roofed to
protect all participants in the event of rain. The site has sufficient power and adequate space for
all developers to comfortably participate in the demonstration. The site is located about 45
minutes away from Orlando International Airport, which is easily accessible by direct flight from
many airports in the country. Cape Canaveral Hospital, located nearby in Cocoa Beach, Florida,
is within 15 minutes driving distance of the site. Because the site is located in a popular tourist
area, many hotels are located within 10 minutes of the site along the coast at Cocoa Beach.
Weather in this area of central Florida in January is relatively dry and sunny, with pleasant
daytime temperatures into the 70s (F) and cool nights.
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KARS Park Location Map
Menrtt tefanrf
MM/ W
RefugQ
KSC Visitor Compku
KENNEDY ATHLETIC,
RECREATIONAL AND SOCIAL PARK
MERRITT ISLAND, FLORIDA
FIGURE 4-1
SITE LOCATION
Tetra Tech EM Inc.
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• Site Diversity — The different levels and types of elements in the soil and sediment in the areas
of the KARS Park gunnery range will provide unique and challenging samples for the instrument
evaluated in the demonstration.
At KARS Park, soil and sediment contamination have resulted from historical facility operations and
impacts from the former gun range. Native and contaminated soil and sediment from gun range
operations at the site contain some of the target elements for the demonstration. Specifically, antimony,
arsenic, chromium, copper, lead, and zinc have been identified in sandy soil and sediment matrices at the
site.
4.2 Descriptions of Sampling Sites
Ssimpling sites should represent variable soil texture (sand, silt, and clay) and iron content, two factors
that significantly impact instrument performance. Appropriate sites for collecting source material for the
evaluation include ammunition depots, battery processing, mining, and machine shop and smelter sites.
Eight sampling sites were selected for the demonstration, one of which is the KARS Park site.
This section provides an overview of the eight sampling sites and describes the types of metal-
contaminated soils or sediments that can be found at each site. This information is based on historical
data that were provided by the site owners or EPA regional project managers for each site. More detailed
information regarding these sites, including references for site-specific information, is provided in the
pre-demonstration sampling and analysis plan (Appendix A). The pro-demonstration sampling and
analysis plan also documents the requirements for environmental sample collection and processing at
these sites.
4.2.1 Kennedy Athletic, Recreational & Social Park Site
As discussed in Section 4.1, soil and sediment at the KARS Park site are contaminated from former gun
range operations and contain some of the target elements for the demonstration. The specific elements of
concern for the KARS Park site include antimony, arsenic, chromium, copper, lead, and zinc.
Several soil and sediment samples were collected from various locations at the KARS Park site for the
XRF demonstration. Table 4-1 presents historical analytical data (maximum concentrations) for soil and
sediment at KARS Park.
Table 4-1. Historical Analytical Data, KARS Park Site
Metal
Antimony
Arsenic
Chromium
Copper
Lead
Zinc
Maximum Concentration (me/kg)
8,500
1,600
40.2
290,000
99,000
16,200
4.2.2 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 have been detected in previous soil samples collected 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
41
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wastes are found in discrete piles and are mixed with soil. Several soil samples were collected from the
pile of roaster slag at the site. Table 4-2 presents historical analytical data (maximum concentrations) for
the roaster slag pile.
Table 4-2. Historical Analytical Data, Wickes Smelter Site-Roaster Slag Pile
Metal
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Nickel
Silver
Zinc
Maximum Concentration (mg/kg)
79.02
3,182
69.7
13.55
947.6
24,780
33,500
7.29
83.09
5,299
4,2.3 Burlington Northern-ASARCO East Helena Site
The Burlington Northern (BN)-ASARCO East Helena 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 has not
been remediated and contains some of the target elements in soil.
At the request of EPA, CH2M Hill collected surface soil samples 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. CH2M Hill collected 24 surface soil samples (16 in November 1997 and 8 in April 1998).
The soils were found to contain up to 2,018 ppm arsenic, 876 ppm cadmium, and 43,907 ppm lead.
Several soil samples were collected near these sample points with the highest concentrations for the
demonstration. Table 4-3 presents the CH2M Hill data for arsenic, cadmium, and lead (maximum
concentrations) from the 1997 and 1998 sampling events.
Table 4-3. Historical Analytical Data, BN-ASARCO East Helena Site
Metal
Arsenic
Cadmium
Lead
Maximum Concentration (mg/kg)
2,018
876
43,906
4.2.4 Alton Steel Mill Site
The Alton Steel Mill (Alton) site (formerly the Laclede Steel site) is located at 5 Cut Street in Alton,
Illinois. (The 400-acre site is located in Alton's industrial corridor.) The Alton site was operated by
Laclede Steel Company from 1911 until it closed as a bankrupt facility in July 2001. The site was
purchased by Alton Steel, Inc., from the bankruptcy estate of Laclede Steel in May 2003. As a result of
more than 90 years of steel production, the Alton site is heir to numerous environmental concerns,
including contamination by polychlorinated biphenyls (PCBs) and heavy metals. Laclede Steel was cited
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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.
Tetra Tech conducted a Phase I environmental site assessment (ESA) in May 2002, which identified
volatile organic compounds (VOCs), semivolatile organic compounds (SVOCs), total priority pollutant
metals, and PCBs as potential contaminants of concern at the site.
Based on the data gathered during the Phase I ESA in 2002 and on discussions with Alton personnel,
several soil samples were collected from two areas at the Alton site, including the Rod Patenting Building
and Tube Mill Building, for the demonstration. This site was selected to be included in the demonstration
because it has not been remediated and the areas around the two buildings contain elevated concentrations
of cadmium, chromium, lead, nickel, zinc, and iron in soil. Specific analytical data for metals in soil were
not available.
4.2.5 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 in 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 from 1942 to 1971 for daily refuse
burning. Residue from the pit was buried 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 previous soil samples collected from this area. The maximum concentrations of the target
elements detected in surface soil during previous investigations are summarized in Table 4-4.
Table 4-4. Historical Analytical Data, NSWC Crane Division-Old Burn Pit
Metal
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Silver
Zinc
Maximum Concentration (me/kg)
301
26.8
31.1
112
1,520
105,000
16,900
0.43
62.6
7.5
5,110
4.2.6 Torch Lake Superfund Site
The Torch Lake Superfund site was selected because native and contaminated sediment from copper
mining, milling, and smelting contain the elements targeted for the demonstration. The specific metals of
concern for the Torch Lake Superfund site include 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
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Priorities List in June 1986. Approximately 200 million tons of mining wastes were dumped into Torch
Lake and reportedly filled approximately 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 4-5 presents analytical data (maximum concentrations) for the
target elements detected at elevated concentrations in sediment samples collected from Torch Lake during
the baseline study. Sediment samples were collected at various locations from Torch Lake for the
demonstration.
Table 4-5. Historical Analytical Data, Torch Lake Superfund Site
Metal
Arsenic
Chromium
Copper
Lead
Mercury
Selenium
Silver
Zinc
Maximum Concentration'(mg/kg)
40
90
5,850
325
1.2
0.7
6.2
630
4,2.7 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 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 (California Regional Water Quality Control Board, Lahontan
Region 1995).
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 4-6 presents historical analytical
data (maximum concentrations) for the target elements detected at elevated concentrations in sediment
samples collected along the three creeks. Sediment samples were collected at various locations
downstream along the three creeks for the demonstration.
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Table 4-6. Historical Analytical Data, Leviathan Mine Site
Metal
Arsenic
Cadmium
Chromium
Copper
Nickel
Maximum Concentration (nig/kg)
2,510 '
25.7
279
837
2,670
4.2.8 Sulphur Bank Mercury Mine
Sulphur Bank Mercury Mine (SBMM) is a 160-acre inactive mercury mine located on the eastern shore of
the Oaks Arm of Clear Lake in Lake County, California, 100 miles north of San Francisco. Between
1864 and 1957, SBMM was the site of underground and open-pit mining operations located at the
hydrothermal vents and hot springs. Mining disturbed about 160 acres of land at SBMM and generated
large quantities of waste rock (rock that did not contain economic concentrations of mercury and was
removed to gain access to ore), tailings (the waste material from processes that removed the mercury from
ore), and ore (rock that contained economic concentrations of mercury that was mined and stockpiled for
mercury extraction). The waste rock, tailings, and ore are distributed in piles throughout the property.
Table 4-7 presents historical analytical data (maximum concentrations) for the target elements detected at
elevated concentrations in surface samples collected at SBMM. Soil samples were collected at various
locations for the demonstration project.
Table 4-7. Historical Analytical Data, Sulphur Bank Mercury Mine Site
Metal
Antimony
Arsenic
Lead
Mercury
Maximum Concentration (mg/kg)
3,724
532
900
4,296
4.2.9 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 previously collected 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 mining, milling, and smelting wastes were dumped directly into Silver
Bow Creek and were subsequently transported downstream. EPA listed Silver Bow Creek and a
contiguous portion of the upper Clark Fork River as a Superfund site in 1983.
A large volume of tailings was deposited in a low-gradient reach of Silver Bow Creek in the Ramsay Flats
area. Tailings at Ramsay Flats extend several hundred feet north of the Silver Bow channel. About 18
inches of silty tailings overlie texturally stratified natural sediments consisting of low-permeability silt,
silty-clay, organic layers, and stringers of fine sand.
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Two surface soil samples were collected from the Ramsay Flats tailings area and analyzed for a suite of
metals using a field-portable XRF. The maximum concentrations of the target elements detected in the
samples are summarized in Table 4-8.
Table 4-8. Historical Analytical Data, Ramsay Flats-Silver Bow Creek Site
Metal
Arsenic
Cadmium
Copper
Iron
Lead
Zinc
Maximum Concentration (mg/kg)
176
141
1,110
20,891
394
1,459
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Chapter 5
Demonstration Approach
This chapter presents the demonstration approach in terms of the requirements of the MMT Program. This
chapter describes the demonstration objectives, experimental design, data analysis procedures, and
schedule.
5.1 Demonstration Objectives
The overall purpose of the XRF technology demonstration will be to evaluate the performance of various
field XRF instruments in detecting and quantifying concentrations of metallic analytes in soils and
sediments from a variety of sites around the U.S. The demonstration will evaluate technical performance in
teirms of analytical accuracy and precision, as well as factors such as costs and operating requirements.
Instrument technical performance and cost will be evaluated in accordance with established SITE MMT
program requirements.
The demonstration has both primary and secondary objectives. Primary objectives are critical to the
technology 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 objectives for the demonstration of the individual field measurement instruments are as
follows:
P1 Determine the MDL for each target element
P2 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
P3 Evaluate the precision of XRF measurements for a variety of contaminated soil and sediment
samples
P4 Evaluate the effect of chemical and spectral interference on measurement of target elements
P5 Evaluate the effect of soil characteristics on measurement of target elements
P6 Measure sample throughput required for the measurement of target elements
P7 Estimate the costs associated with XRF field measurements
The secondary objectives for the demonstration of the individual field measurement instruments are as
follows:
SI Document the skills and training required to properly operate the instrument
S2 Document health and safety concerns associated with operating the instrument
S3 Document the portability of the instrument
S4 Evaluate the instrument's durability based on its materials of construction and engineering design
S5 Document the availability of the instrument and of associated customer technical support
The objectives for the demonstration were developed based on input from MMT Program stakeholders,
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The objectives for the demonstration were developed based on input from MMT Program stakeholders,
general expectations for the users of field measurement instruments, the characteristics of the demonstration
areas, the time available to complete the demonstration, and the capabilities of the instruments that the
developers participating in the demonstration intend to highlight.
5.2 Demonstration Design
The design of the demonstration focuses on the analysis of 13 elements that will provide the basis for
evaluating the primary objectives. These elements are antimony, arsenic, cadmium, chromium, copper,
iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc.
To address the demonstration objectives, both environmental and performance evaluation (PE) samples will
be analyzed during the field demonstration. The environmental samples were collected prior to the field
demonstration from multiple sampling locations across the country, as described in Chapter 4, to provide
diverse soil and sediment matrices along with varying sources and contaminant concentrations. When
necessary, artificially fortified environmental matrices (soil and sediment) were created to supplement these
samples for the field demonstration. These fortified samples provide a wider range of concentrations and
combination of elements to be present for developers to evaluate. The PE samples are certified, spiked, and
blank samples obtained from a commercial vendor.
Upon completion of the field demonstration, the results obtained using the XRF instruments will be
compared to reference laboratory results to evaluate the performance of each instrument in terms of
accuracy and comparability. Precision in various concentration ranges and the MDL will be evaluated
based on the XRF instrument results for replicate blind samples. Each of these quantitative evaluations of
instrument performance will be performed for each target element. The effect of chemical/spectral
interferences and of soil characteristics will be evaluated where such effects may explain the deviations of
XRF results in comparison to laboratory reference methods for specific target elements.
During the field demonstration, detailed notes will be taken regarding the operation of the instrument and
appurtenances. Observations regarding the durability of the instrument and its portability will also be
noted. Further, the developer representatives will be interviewed to collect detailed information regarding
the cost of the instrument and availability of operating manuals and customer support. This information
will be used to address the secondary objectives of the demonstration.
5.3. Demonstration Samples
The goal of the demonstration is to conduct a detailed evaluation of the overall performance of each
instrument in a field environment. The primary demonstration objectives for the performance evaluation
will be achieved by analyzing a set of specially processed and characterized samples of soil and sediment.
These demonstration samples were blended from contaminated and native soil and sediments collected at
the sampling sites or are PE (spiked) samples. Seventy separate blends of soil and sediment or PE samples
were used to prepare the set of 326 samples being provided to each developer, with each blend or PE
sample included in replicate either three, five, or seven times. The blend ratios or spike concentrations were
selected to create samples that cover the concentration range of each target element that may be reasonably
found in the environment. Three target concentration ranges were prepared for analyte measurement in soil
and sediment, including: (1) near the detection limit, (2) intermediate concentrations, and (3) high
concentrations. A fourth concentration range was added for very high concentrations for lead, iron, and
zinc in soil and for iron in sediment. Table 5-1 lists the target concentration ranges for each of these levels
(1 through 4) for target element. Section 5.3.1 discusses the environmental samples, and Section 5.3.2
discusses the PE samples.
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5.3.1 Environmental Samples
A total of 25 separate environmental samples were collected from the nine sampling sites described in
Chapter 4. Table 5-2 lists the number and type of samples that were collected from each site for the
demonstration. The environmental samples were dried, crushed, sieved, and homogenized before the initial
elemental analysis. The analytical results were then used to develop different sample blends with
concentrations of metals that fall within the ranges listed in Table 5-1. Either five or seven replicate
samples will be included in the sample set for each developer for each blend of soil or sediment established
for analysis during the demonstration. The 14 soil samples were used to create 26 separate sample blends
and a total of 144 demonstration samples. The 11 sediment samples were used to create 19 separate sample
blends and a total of 103 demonstration samples. Table 5-3 lists the sampling site and the number of
sample blends generated from material collected there and the resulting number of demonstration samples
prepared to be included in each set provided to developers.
5.3.2 PE Samples
PE samples were created by spiking soil and sediment collected from the sampling sites with known
concentrations of target elements. The spiked concentrations were selected to ensure that a minimum of
three samples were available for all target concentration ranges for each target element. Three or seven
replicate samples from each spiked sample of soil or sediment will be included in the demonstration sample
set provided to each developer. Six soil samples were used to create 12 separate spiked samples, generating
a total of 36 demonstration samples. Four sediment samples were also used to create 13 separate spiked
samples, for a total of 43 demonstration samples. Table 5-4 lists the sample site, the number of individual
spiked samples that were prepared, and the resulting number of demonstration samples.
5.4 Pre-demonstration Sample Analysis
A preliminary set of prepared samples was provided to the XRF technology developers before the
demonstration for analysis using their XRF instrument. The pre-demonstration sample set consisted of 20
characterized samples; 17 were environmental samples and 3 were PE samples, and all spanned the
established concentration ranges for the target elements. At least one sample from each sampling site was
included in the pre-demonstration sample set Table 5-5 presents the number of pre-demonstration samples
for each sampling site.
The pre-demonstration sample set was submitted to the developers without any information regarding the
concentrations of the target elements in the samples. Once all the XRF instrument results for these pre-
demonstration samples had been reported and compiled, reference laboratory results for these samples were
provided to each developer to allow for a self-evaluation of their instrument's performance.
It was intended that the developers would use the pre-demonstration samples to establish the best operating
procedures for the instrument on the types of samples to be processed during the demonstration. Further,
the developers were allowed to use these pre-demonstration sample results to calibrate their instruments
during the demonstration.
5.3 Data Analysis Procedures
The demonstration samples, which contain variable concentrations of the target elements, will be analyzed
by each technology developer. Analytical results for the target elements will be used to evaluate the
primary demonstration objectives. Ancillary data collected during the technology observer's oversight of
the demonstration sample analysis process and information provided by developers will be used to evaluate
the secondary demonstration objectives.
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Table 5-1.
Target Concentration Ranges for Soil and Sediment
Analyte
Level 1
Target Range
(mg/kg)
Level 2
Target Range
(mg/kg)
Level 3
Target Range
(mg/kg)
Level 4
Target Range
(mg/kg)
SOIL
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
40 - 400
20 - 400
50 - 500
50 - 500
50 - 500
60 - 6,000
20 - 1,000
20 - 200
50 - 250
20 - 100
45-90
50 - 100
30 - 1,000
400 - 2,000
400 - 2,000
500 - 2,500
500 - 2,500
500 - 2,500
5,000 - 25,000
1,000 - 2,000
200-1,000
250 - 1,000
100-200
90-180
100-200
1,000 - 3,500
>2,000
>2,000
>2,500
>2,500
>5,000
25,000 - 40,000
2,000 - 10,000
>1,000
>1,000
>200
>180
>200
3,500 - 8,000
>40,000
>10,000
>8,000
SEDIMENT
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
40 - 250
20 - 250
50 - 250
50 - 250
50 - 500
60 - 5,000
20 - 500
20 - 200
50 - 200
20- 100
45-90
50 - 100
30 - 500
250 - 750
250 - 750
250 - 750
250 - 750
500- 1,500
5,000 - 25,000
500 - 1,500
200 - 500
200-500
100-200
90-180
100-200
500 - 1,500
>750
>750
>750
>750
>1,500
25,000 - 40,000
>1,500
>500
>500
>200
>180
>200
> 1,500
>40,000
50
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Table 5-2.
Soil and Sediment Sample Summary
Site
Kennedy Athletic,
Recreational & Social Park
Site
Wickes Smelter Site
Burlington Northem-
ASARCO East Helena Site
Alton Steel Mill Site
Navy Surface Warfare Center,
Crane Division Site
Torch Lake Superfund Site
Leviathan Mine Site
Sulphur Bank Mine Site
Silver Bow Creek Superfund
Site
Sample
KP-01
KP-02
KP-03
KP-04
WS-01
WS-02
BN-01
BN-02
AS-01
AS-02
CN-01
CN-02
TL-01
TL-02
TL-03
LV-01
LV-02
LV-03
LV-04
LV-05
SB-01
SB-02
SB-03
RF-01
RF-02
Matrix
Contaminated Soil
Contaminated Sediment
Clean Sediment
Clean Soil
Clean Soil
Contaminated Soil
Clean Soil
Contaminated Soil
Clean Soil
Contaminated Soil
Contaminated Soil
Clean Soil
Contaminated Sediment
Contaminated Sediment
Contaminated Sediment
Contaminated Sediment
Contaminated Sediment
Contaminated Sediment
Clean Sediment
Clean Soil
Contaminated Soil
Contaminated Soil
Clean Soil
Contaminated Sediment
Clean Sediment
Table 5-3.
Number of Soil and Sediment Environmental Sample Blends and
Demonstration Samples
Site
Kennedy Athletic, Recreational &
Social Park Site
Wickes Smelter Site
Burlington Northern- ASARCO East
Helena Site
Alton Steel Mill Site
Navy Surface Warfare Center, Crane
Division Site
Torch Lake Superfund Site
Leviathan Mine Site
Sulphur Bank Mercury Mine Site
Silver Bow Creek Superfund Site
Number of
Sample Blends
6
5
5
2
1
3
7
9
7
Number of
Demonstration Samples
32
31
29
10
5
19
37
47
41
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Table 5-4.
Number of Soil and Sediment Sample Blends and
Demonstration Samples
Site
Wickes Smelter Site
Burlington Northern-ASARCO East
Helena Site
Alton Steel Mill Site
Navy Surface Warfare Center, Crane
Division Site
Torch Lake Superfund Site
Leviathan Mine Site
Sulphur Bank Mine Site
Silver Bow Creek Superfund Site
Number of
Sample Spikes
2
2
1
2
4
5
3
6
Number of Demonstration
Samples
6
6
3
6
12
15
9
22
Table 5-5.
Number of Pre-Demonstration Samples
Site
Kennedy Athletic, Recreational &
Social Park Site
Wickes Smelter Site
Burlington Northern-ASARCO
East Helena Site
Alton Steel Mill Site
Navy Surface Warfare Center Crane
Division Site
Torch Lake Superfund Site
Leviathan Mine Site
Sulphur Bank Mine Site
Silver Bow Creek Superfund Site
Number of
Pre -demonstration Samples
2
2
2
1
3
2
3
3
2
5.5.7 Primary Demonstration Objectives
Data analysis procedures relating to each primary objective are described below.
5.5.1.1 Primary Objective 1 — Method Detection Limits
The method detection limit (MDL) for each target element will be evaluated by analyzing a minimum of
seven replicate samples that contain the target element at concentrations within plus or minus 50 percent of
the typical detection limit for hand-held, field-portable XRF instruments. Typical detection limits for field-
portable desktop XRF instruments are approximately two to six times lower than for hand-held XRF
instruments. Therefore, the sample concentrations to evaluate the MDL were set at a level so that all
developers may participate. The concentrations of the target elements are less than five times the typical
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detection limit for desktop XRF instruments. The seven replicate samples will be from the same batch of
homogenized soil.
The MDL will be calculated using the procedures found in Title 40 CFR Part 136, Appendix B, Revision
1.11. The following equation will be used:
= t(n.U-8=0.99)(S)
where
MDL = method detection limit
t = Student's t value for a 99 percent confidence level and a standard deviation
estimate with n-1 degrees of freedom
n = number of analysis
S = standard deviation
The MDL will be calculated for each target element and instrument using the data supplied by each
developer. Table 5-6 lists the number of different sample blends or sample spikes that may be used to
evaluate the detection limit for each target element.
Table 5-6.
Number of Detection Limit Samples
Target Element
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Soil Detection
Limit Samples
3
2
2
4
1
0
3
1
2
1
2
1
1
Sediment
Detection Limit
Samples
1
2
1
3
2
0
4
1
3
1
1
3
3
It should be noted that there are no detection limit samples available for iron because all the samples
collected contained substantial concentrations of iron and because detection limits are not an issue for this
element.
5.5.1.2 Primary Objective 2 —Accuracy and Comparability
Accuracy and comparability of the field XRF measurement method with standard laboratory methods will
be evaluated using the data generated by analyzing the demonstration samples. Each developer will analyze
a minimum of three replicates of each demonstration sample. Demonstration samples that yield one or
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more non-detect values for an individual target element will be excluded from the evaluation of the target
element.
Accuracy is defined for this demonstration as the correspondence between the XRF data and the reference
concentration as determined by the PE sample certification or reference laboratory results. Accuracy will
be evaluated by comparing the XRF data for the target elements with the laboratory data over a range of
concentrations. Table 5-7 lists the number of samples that will be available for the evaluation of accuracy
by concentration range (Level 1, 2, 3, and 4 indicate low, intermediate, high, and very high concentrations
as described in Section 5.3). As shown, the demonstration samples have been prepared to cover the
complete concentration range for each target element.
Table 5-7.
Number of Samples by Concentration Range for Each Target Element
Analyte
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Analyte
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Soil Samples
Level 1
12
17
10
17
15
22
18
9
16
4
4
9
19
Level 2
4
3
5
3
8
12
4
5
5
5
4
4
7
Level 3 & 4
3
3
3
3
3
7
14
3
6
4
5
4
8
Sediment Samples
Level 1
4
16
5
10
10
3
15
5
17
5
5
5
17
Level 2
4
4
3
3
6
19
4
3
4
4
4
7
5
Level 3 & 4
3
3
3
3
8
8
4
3
4
3
3
3
4
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To assess accuracy, the mean detected concentration from the XRF analysis will be compared with the
mean reference laboratory result for the sample. The following equation will be used to evaluate accuracy:
R = C/CR x 100
where C is the average value calculated from the XRF instrument replicate measurements and CR is the
reference concentration. If the reference laboratory's average measured value is within 10 percent of the
certified PE sample value, then the reference laboratory value will be used to establish the accuracy of the
instrument. If the reference laboratory value is greater than 10 percent different, then the certified PE
sample value will be used.
XRF instrument results will also be compared with the data from the corresponding reference laboratory by
calculating a relative percent difference (RPD) for each paired measurement. The equation for RPD is as
follows:
RPD = average (MR,
where MR is the reference laboratory measurement and MD is the XRF instrument measurement. RPD
values less than 25 percent will indicate good agreement between the two measurements. Negative RPD
values can be obtained (which would indicate that the XRF instrument measurements were less than the
reference laboratory measurements) because the absolute value will not be taken. As such, the median RPD
value will be calculated, rather than the average RPD, where the negative and positive values would be
neutralized. This median value will provide a summary calculation of comparability between each
instrument's results and the reference value.
Comparability evaluations for primary objective 2 may be further supported through other statistical means
such as the preparation of linear correlation plots. These correlation plots will depict the linear relationships
between the XRF and laboratory datasets for each analyte using a linear regression calculation with an
associated correlation coefficient (r2). These plots may identify general biases between the XRF and the
laboratory data sets.
5.5.1.3 Primary Objective 3 — Precision
Precision is defined as the reproducibility of the XRF data. The precision of the XRF analysis will be
evaluated by comparing replicate measurements (internal blind samples) for each target element in each
sample. All samples (including environmental and PE samples) will be analyzed in at least quadruplicate
by each participating developer. Replication is important in this process since precision will be evaluated at
both low and high concentrations and across different matrices. The precision of the data will be evaluated
by calculating the mean relative standard difference (RSD). Low RSD values indicate higher precision.
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The equation to calculate the RSD for replicate measurements is:
RSD =
SD
xlOO
. C
where
RSD = Relative standard difference
SD = Standard deviation
C = Mean concentration
The standard deviation will be calculated using the equation:
i
r i
where
SD = Standard deviation
n = Number of samples
Ck = Concentration of sample K
C = Mean concentration
For a given set of replicate samples, the RSD of a given XRF instrument's results will be compared with
the RSD of the reference laboratory's results to compare the precision of the two approaches.
Table 5-7 (presented in Section 5.1.1,2) lists the number of samples that will be available for the
evaluation of precision by concentration range (Level 1, 2, 3, and 4 indicate low, intermediate, high, and
very high concentrations as described in Section 5.3). As shown, the demonstration samples have been
prepared to cover the complete concentration range for each target element.
5.5.1.4 Primary Objective 4—Impact of Chemical and Spectral Interferences
Chemical and spectral interferences can affect the accuracy and precision of analytical results obtained
using XRF. The most common interference is lead with arsenic, where the lead La peak overlaps the
arsenic Ka peak. Spectral interferences can also occur when high concentrations of one element cause
spectral overlap on the peak for an element that is adjacent on the periodic table. For example, copper
and zinc are adjacent on the periodic table; the Ka peaks are at 8.041 keV for copper and 8.631 keV for
zinc. Depending on the resolution of the XRF instrument, high concentrations of copper or zinc may
interfere with lower concentrations of the other.
The effects of chemical and spectral interference of lead with arsenic will be evaluated by identifying
samples with concentrations of lead that are greater than 10 times the concentration of arsenic. The
potential for chemical and spectral interference between adjacent elements on the periodic table will be
evaluated by the accuracy and precision of the XRF data for the following element pairs:
vanadium/chromium, nickel/copper, and copper/zinc. The concentration of one of the elements must be
greater than 10 times the concentration of the other element to be included in the evaluation.
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The data will be evaluated by statistically comparing the data with the potential for chemical or spectral
interference with the remaining data. Only results for samples with detectable concentrations of both
potentially interfering elements will be included in the statistical test. The first step is to calculate the
RPD between the mean XRF concentrations and the mean reference value, as described above. The
Wilcoxon rank sum test will then be used to assess whether the RPD for measurements with potential
interference are different than the RPD for measurements with little potential for interference. The null
hjrpothesis will be that the mean is the same for the populations from which the two data sets have been
drawn. The Wilcoxon rank sum test does not require normal or lognormal distribution for the
populations, as does the Student t-test. Table 5-8 lists the number of samples that will be available to
evaluate chemical and spectral interferences.
Table 5-8.
Number of Spectral Interference Samples
Pb/As
Cu/Ni
Ni/Cu
Zn/Cu
Cu/Zn
Concentrations
Pb>1000, As 50 to 100 mg/kg
Cu>1500, Ni 100 to 150 mg/kg
Ni>1500, Cu 100 to 150 mg/kg
Zn>1500,Cu 100 to 150 mg/kg
Cu>1500, Zn 100 to 150 mg/kg
Number of Samples
12
13
10
11
11
5.5.1.5 Primary Objective 5 — Effects of Soil Characteristics
Soil and sediment sample s were collected from nine locations across the U.S. that represent a variety of
soil types and lithologies. More than one soil type was collected at KARS Park, the Sulphur Bank
Mercury Mine, and the Leviathan Mine. All soil samples will be subjected to a procedure of drying,
grinding, and homogenization to remove any potential effects of moisture content and grain size. Each
XRF instrument's analytical accuracy and precision will be compared to assess the impact of soil
characteristics on performance. Accuracy will be calculated for each soil type by the procedure described
in Section 5.5.1.2. An outlier analysis will then be completed on the data using Rosner's test for
detecting outliers (Gilbert 1987). A qualitative evaluation will then be completed on any outliers
identified to ascertain whether they may be correlated to a specific matrix effect. Rosner's test for
outliers will also be applied to the RSD values calculated as part of primary objective 2 to evaluate
precisioa Again, a qualitative evaluation will then be completed on any outliers identified to ascertain
whether they may be correlated to a specific matrix effect.
5,5.1.6 Primary Objective 6 — Sample Throughput
Siimple throughput is a calculation of the total number of samples that can be evaluated in a specified
time. The primary factors that affect sample throughput include 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 a demonstration sample for analysis will be recorded 10 times per each
day that demonstration samples are analyzed. The time will start when the sample bottle is grasped for
sample preparation. The time will end when the prepared sample is placed in an auto sampler or in the
instrument for analysis. The time required to analyze the sample will also be recorded 10 times per day
that demonstration samples are analyzed. The time will start when the prepared sample is grasped for
loading into the instrument for analysis. The time will end when the next prepared sample is grasped for
loading into the instrument. The start time for instruments with autosamplers will be when the first
sample is grasped for loading into the auto sampler, and the end time will be when the analysis of the last
sample is finished. A mean sample preparation time and a mean analytical tune will then be calculated.
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Data acquisition is another aspect of sample throughput. Data processing and tabulation are essential for
interpretation after the analysis is complete. As such, data acquisition and tabulation time will be
monitored and the length of time recorded
5,5,1.7 Primary Objective 7— Technology Costs
The costs for analysis are an important evaluation factor and include the instrument, analytical supplies,
and labor. Based on input from each technology developer, the instrument cost will be established for
purchase of the equipment and for daily, weekly, and monthly rental The costs associated with leasing
agreements will be specified in the report, if available. Analytical supplies may include sample cups,
spoons, x-ray film, Mylar, reagents, and personal protective equipment. The rate that supplies are
consumed will be monitored and recorded during analysis of demonstration samples. The cost of
analytical supplies will be estimated per sample. The labor costs include 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 will be recorded
during the demonstration. The time required to prepare and analyze the samples will be reported as hours
per sample. The time required for setting up and dismantling the equipment will be reported as hours per
analytical event.
5.5.2 Secondary Demonstration Objectives
Data analysis procedures relating to each secondary objective are described below.
5.5.2.1 Secondary Objective 1 — Training Requirements
Each XRF instrument requires that the operator be trained to safely set up and operate the instrument.
The amount of training required depends on the complexity of the instrument and the associated software.
Most developers have established standard training programs. The time required to complete the
developer's training program will be estimated. The major subjects of the training will also be identified.
5.5.2.2 Secondary Objective 2 —Health and Safety
The health and safety requirements for operation of the instrument will be identified. Included in the
evaluation will be potential risks for exposure to radiation and to reagents. Not incbded in the evaluation
are potential risks from exposure to site-specific hazardous materials or physical safety hazards.
5.5.2.3 Secondary Objective 3 —Portability
The portability of the instrument depends on the instrument size, weight, number of components, power
requirements, and reagent required. The size of the instrument, including physical dimensions and
weight, will be recorded. The number of components, power requirements, support structures, and
reagent requirements will also be reported.
5.5.2.4 Secondary Objective 4 —Durability
The durability of the instrument will be evaluated only by gathering information on the instrument's
warranty and expected lifespan of the radioactive source or x-ray tube. The ability to upgrade software or
hardware also will be evaluated Weather resistance will be 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.
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5.5.2.5 Secondary Objective 5 —Availability
The availability of the instrument from the developer, distributors, and rental agencies will be
documented.
5.6 Demonstration Schedule
The schedule for the XRF demonstration, including plan preparation and draft reviews, developer
conference calls, the field demonstration, and demonstration reporting, is provided in Appendix D.
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Chapter 6
Sample Collection, Preparation, and Handling Procedures
This chapter describes the requirements for sampling, preparing, and handling soil and sediment samples
for this XRF demonstration. Terra Tech prepared a pre-demonstration sampling and analysis plan (SAP)
that describes the procedures for collecting the environmental samples from the sampling sites and for
preparing and characterizing those bulk soil and sediment samples (presented in Appendix A).
6.1 Sample Collection and Shipping
Large quantities of soil and sediment were needed for processing into well-characterized samples for this
demonstration. As a result, 15 soil samples and 10 sediment sampbs were collected across nine sites.
(See Section 4.2 for descriptions of the soil and sediment sampling sites.) Approximately 1,500
kilograms of unprocessed soil and sediment were collected, which yielded more than 1,000 kilograms of
soil and sediment materials after they had been dried. The soil samples were collected using clean
shovels and trowels to excavate the selected material and placed into clean, plastic 5-gallon buckets.
Plastic lids were then placed on each bucket, the lids were secured with tape, and each bucket was labeled
with a unique sample number. Sediment samples were collected in a similar method at all sites except at
Torch Lake, where sediments were collected using a Vibracore or Ponar sediment sampler operated from
a boat. Each 5-gallon bucket was overpacked in a plastic cooler and shipped under chain of custody via
overnight delivery to the characterization laboratory (ARDL).
6.2 Sample Preparation and Homogenization
Bulk samples were packaged in multiple buckets because of the large quantity of material needed. Soil
and sediment samples were removed from the shipping buckets and set on large trays at ARDL to
promote uniform air drying. Some sediment samples required more than 2 weeks to dry because of the
wet matrix. The mass weight of soil and sediment in each 5-gallon bucket varied, but averaged about 50
pounds per bucket.
The air-dried soils and sediment samples were sieved through a custom-made screen to remove coarse
material larger than about 1 inch. Next, the material in each 5-gallon bucket was mechanically crushed
using a hardened stainless-steel hammer mill until the particle size was sub-60-mesh sieve (less than 0.25
millimeters). The duration of crushing to achieve the desired particle size varied based on soil type and
volume of coarse fragments. The particle size of the processed soil and sediment was verified using
standard sieve technology, and the particles that were still larger than 60-mesh were returned to the
crushing process.
The mass of soil and sediment needed for this demonstration required that multiple 5-gallon buckets of
soil and sediment be collected from each location, where possible. The multiple buckets of material were
mixed and homogenized to create a uniform soil batch with similar concentrations of elements. After the
material had been crushed and sieved, the soil and sediment from the multiple 5-gallon buckets were
mixed and homogenized using a Model T 50A Turbula shaker-mixer. This shaker was capable of
handling up to 50 gallons of sample material Smaller batches of soil and sediment were mixed and
homogenized using a Model T 10B Turbula shaker-mixer capable of handling up to 10 gallons. Aliquots
from each homogenized soil and sediment batch were sampled and analyzed in triplicate using ICP-AES
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arid CVAA for the target elements. If the percent difference between the highest and lowest result was
greater than 10 percent RSD, the entire batch of soil and sediment was returned to the shaker-mixer for
additional homogenization.
6.3 Sample Aliquots
Each prepared demonstration sample required approximately 3 kilograms of dried and homogenized soil
or sediment to yield a 100-gram aliquot for each participating XRF developer, two 100-gram aliquots for
archiving and replacement at the demonstration for breakage or spills, and one 100-gram aliquot for
analysis at the reference laboratory. Any material remaining (approximately 700 grams) was archived
and stored in bulk.
Soil and sediment materials required blending to achieve the desired element concentrations for specific
samples. Therefore, contaminated soil and sediment were blended with uncontaminated soil and
sediment similar in texture and mineral composition. Each blended soil and sediment batch contained
approximately 3 kilograms and was subdivided into the thirteen 100-gram aliquots; the remaining blended
soil was stored and archived.
Each demonstration sample was transferred to an 8-ounce wide-mouth sample jar, which can store
approximately 100 grams of soil or sediment sample. Thirteen sets of samples were prepared for
distribution to the developers (1 set to each), to the reference laboratory (1 set), and for archive.
Purchased PE samples (standard reference materials and synthetic spiked materials) were transferred from
the original packaging to the 4-ounce wide-mouth jars used in the demonstration so that the
environmental and PE samples will be visually indistinguishable.
6.4 Sample Handling
The samples will be randomized in two fashions. First, the order the filled jars will be distributed will be
randomized, such that the same developer will not always receive the first jar filled for a sample batch.
Second, the distribution of samples for analysis will be randomized so that each developer analyzes the
same set of samples but in a different order. PE materials will be integrated with the environmental
samples collected in a randomized manner so that the PE samples are indistinguishable from other
samples.
Each soil and sediment sample analyzed by the developers and reference laboratory will be assigned a
unique identification number, as follows:
• AS-SO-01-05-MX
Where:
AS = Site code (Alton Steel site)
SO = Soil sample or SD = sediment sample
01 = Numerical sequence of the prepared batches
05 = Numerical sequence of the aliquot (1 through 13)
MX = Developer code
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The two-alphabetic character site codes are:
• AS = Alton Steel
• BN = BN/ASARCO site
• CN = Crane Naval shipyard
• KP = KARS Park
• LV = Leviathan Mine
• RV = Ramsay Flats
• SB = Sulfur Bank
• TL = Torch Lake
• WS = Wickes Smelter Site
Developer codes will include two-alphabetic characters, as follows:
• DC = Innov-X Systems, Inc.
• MX = Oxford Instrument Portable Div. (formerly Metorex)
• NC = NITON LLC
• OI = Oxford Instrument Analytical
• RI = Rigaku, Inc.
• RU = RONTEC USA Inc.
• XC = Xcalibur SRF Services
• XX = Reference Laboratory
All jars are pre-labeled with a unique identifier to provide the developers with a blind sample for analysis.
The prepared samples will be shipped to the demonstration site and presented to each developer at the
beginning of the demonstration. All samples that are not in the possession of the developer during the
demonstration will be securely stored in the Tetra Tech trailer. The trailer will be locked after hours. The
samples will be stored at room temperature during the demonstration, in accordance with the QA/QC
requirements established for this project.
Tetra Tech will be responsible for distributing samples during the demonstration. Each developer will go
to a sample distribution point to retrieve the samples when their team is ready to begin the analysis. The
samples will be distributed in batches of 80 (approximately 1 day's throughput) and will be released at
each developer's request. More than one batch of samples can be relinquished at a time, if the develop
desires. Chain-of-custody forms will document sample transfer.
The two archived sets of samples will be maintained at the demonstration site in case a sample is dropped,
the integrity is comprised, or a sample jar is broken during transit to the site. After the demonstration, all
unused demonstration samples will be returned to Tetra Tech for archival until after the reports are final.
Debris from the demonstration will be discarded in specially marked trash containers located around the
demonstration area. Sample by-products, including unused sample, aqueous solutions, and miscellaneous
used supplies (such as glassware, pipette tips, booties, and gloves), will be returned to Tetra Tech for
confirmation and quantification of by-products generated by each of the participating instruments. Tetra
Tech will be responsible for disposal of all demonstration materials in accordance with all regulatory
requirements.
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Chapter 7
Reference Laboratory and Methods
Tliis chapter describes the process for selecting the reference laboratory and the reference methods as well
as the procedures for sample preparation and analysis at the reference laboratory.
7.1 Reference Laboratory Selection
The reference laboratory was procured as a competitive bid process using the Federal Acquisition
Regulation. The procurement process involved three stages of selection: (1) a technical proposal, (2)
analysis-of performance audit samples, and (3) an on-site laboratory audit. 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 for sample receipt, laboratory
information management, sample preparation and analysis of metals, current instrument lists, results of
recent performance evaluation sample analysis and audits, method detection limit studies for the target
analytes, professional references, laboratory personnel experience, and unit prices.
Nine of the 12 laboratories invited submitted formal written proposals. The proposals were scored based
on technical merit and cost, and a short list of five laboratories was selected. The scoring was weighed
heavier for technical merit than for price. The five laboratories that received the highest score were
advanced to the Stage 2 evaluation.
In Stage 2, each of the laboratories was provided with a set of six performance evaluation (PE) samples.
The samples consisted of both certified reference materials at custom spiking concentrations as well as
actual demonstration material. Precision and accuracy were assessed based on the results received from
each laboratory. In addition, the overall data package and electronic deliverable were reviewed. Scoring
at this stage was based on precision (reproducibility of results), accuracy (comparison to certified values),
and completeness of the data package and electronic data deliverable. The two laboratories that received
the highest score were advanced to the Stage 3 evaluation.
In Stage 3, the two candidate laboratories were subjected to a thorough on-site audit conducted by the
project chemist. The audit consisted of a direct comparison of elements submitted in the technical
proposal to actual laboratory procedures and conditions. The audit also included tracking the PE samples
through the laboratory processes from sample receipt to results reporting. Each audit was scored on
identical checklists. The reference laboratory was selected based on the highest score. The weights of the
final scoring selection were as follows:
Element
Audits (on site)
PE samples, including data package
and electronic data deliverable
Price
Relative Importance
40%
50%
10%
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Based on the above-described evaluation process, Shealy Environmental Services, Inc. of Cayce, South
Carolina received the highest score and was therefore selected as the reference laboratory.
7.2 Reference Method Selection
The reference methods were selected to quantitate the 13 target elements based on the following criteria:
• It is not a field-screening method.
• It is widely used and an EPA-approved method.
• It measures all 13 of the target elements.
• It meets project-specific requirements for reporting limits.
The goal was to obtain reliable analytical results with regard to the nature of the matrices (soil and
sediments contaminated with metals). Therefore, suitable preparation and analytical methods were
identified within the EPA-approved compendium of methods, "Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods" (SW-846) (EPA 1996d).
7.2.1 Available SW-846 Methods
A brief summary of laboratory-based analytical methods typically used to measure the target elements in
soil and sediment is provided below.
7.2.2 Inductively Coupled Plasma - Atomic Emission Spectrometry, SW-846 6010B
ICP-AES measures trace elements in the low parts per million (ppm) and parts per billion (ppb)
concentration ranges in various environmental media. This method can be applied to groundwater,
toxicity extracts, industrial and organic wastes, soils, sludges, and sediments. All matrices, excluding
filtered groundwater, require acid digestion before analysis to solubilize metals into an aqueous matrix for
analysis. ICP-AES uses an optical system to measure emission spectra that are uniquely characteristic to
elements. Samples are nebulized, and the resulting aerosol is transported to the plasma torch. Element-
specific emission spectra are produced by radio-frequency inductively coupled plasma. The spectra are
dispersed by a grating spectrometer, and the intensities of the emission lines are monitored by
photosensitive devices. The instrument is calibrated against standards and corrected for spectral
background interferences before samples are analyzed
7.2.3 Inductively Coupled Plasma - Mass Spectrometry, SW-846 6020
Inductively coupled plasma-mass Spectrometry (ICP -MS) is a technique that can be applied to achieve
detection limits in the ppb range of a large number of elements in various environmental media after
sample preparation. An acid digestion is required for analysis for groundwater, aqueous samples,
industrial wastes, soils, sludges, sediments, and other solid waste that require acid-leachable elements.
Internal standards are used for quantitation of the target elements. Samples are nebulized, and the
resulting aerosol is transported by argon gas to the plasma torch. The ions produced are entrained in the
plasma and introduced, by means of a water-cooled interface, into a quadrapole mass spectrometer. The
ions produced in the plasma are sorbed according to their mass-to-charge ratios and are quantified with a
channel electron multiplier. Interferences must be assessed and valid correction factors applied, or the
data must be flagged to indicate the problems. Interference correction my include compensation for
background ions contributed by the plasma gas, reagents, and constituents of the sample matrix.
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7.2.4 Atomic Absorption-Graphite Furnace Spectrometry, SW-846 7000 Series
Metals in solution may be readily measured by atomic absorption spectroscopy. Sample matrices require
acid digestion for analysis. Detection limits, sensitivity, and optimum ranges of the metals will vary with
the matrices and the model of atomic absorption spectrophotometers. In graphite furnace atomic
absorption, a representative aliquot of sample is placed in the graphite tube in the furnace, evaporated to
diyness, charred, and atomized. As a greater percentage of available atoms in the analyte is vaporized
and dissociated for absorption in the tube, the use of smaller sample volumes and detection of lower
concentrations of elements are possible as compared with flame atomic absorption because the graphite
furnace atomizes the sample. Radiation from an excited element is passed through the vapor that contains
ground-state atoms of the element. The intensity of the radiation transmitted decreases in proportion to
the amount of the ground-state element in the vapor. The metal atoms to be measured are inserted in the
beam of radiation by increasing the temperature of the furnace, volatilizing the injected specimen. A
monochromator isolates the characteristic radiation from the hollow cathode lamp, and a photosensitive
device measures the attenuated transmitted radiation. However, issues in this technique include spectral,
chemical, ionization, and physical interferences. The sensitivity is in the parts per billion range for many
elements.
7.2.5 Atomic Absorption Flame Spectrometry, SW-846 7000 Series
Metals in solution may be readily measured by atomic absorption spectroscopy. Sample matrices require
acid digestion for analysis. Detection limits, sensitivity, and optimum ranges of the metals will vary with
the matrices and the model of atomic absorption spectrophotometers. In flame (direct-aspiration) atomic
absorption, a representative aliquot of sample is aspirated and atomized by a flame. A light beam from a
hollow cathode lamp is directed through the flame into a monochromator and then onto a detector that
measures the amount of absorbed light. Absorption depends on the presence of free, unexcited ground-
state atoms in the flame. Because the wavelength of the light beam is characteristic of only the metal
being measured, the light energy absorbed by the flame is a measure of the concentration of the metal in
the sample. This principle is the basis of atomic absorption spectroscopy. However, issues in this
technique include spectral, chemical, ionization, and physical interferences. The sensitivity is in the parts
per million range for many elements.
7.2.6 Atomic Absorption Cold Vapor Spectrometry, SW-846 7471A
This method is approved for measuring total mercury (organic and inorganic) in soils, sediments, and
other solid matrices. All samples are subjected to an acid digestion process to dissolve the mercuric
compounds into an aqueous solution. This method uses cold-vapor atomic absorption as the analytical
technique and is based on the absorption of radiation at the 253.7-nanometer wavelength by mercury
vapor. The mercury is reduced to the elemental state and aerated from solution in a closed system. The
mercury vapor passes through a cell positioned in the light path of an atomic absorption
spectrophotometer. Absorbance (as peak height) is measured as a function of mercury concentration.
The typical detection limit for mercury by this method is about 0.1 ppm.
7.3 Method Selection
It was found that 12 of the 13 target elements are easily analyzed by inductively ICP-AES, while mercury
is best analyzed by CVAA.
Metals by ICP-AES. Method 6010B (metals by ICP-AES) was selected to the analytical method for 12
target elements because its demonstrated suitable accuracy and precision meet the requirements of this
project 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 it meets the project objectives. ICP- MS
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was considered as a possible analytical technique; however, is it less widely available, and fewer data are
available to support the claims of accuracy and precision. In addition, ICP-MS is a trace element analysis
and often requires serial dilutions to mitigate the effect of high concentrations of interfering ions or other
matrix interferences. These dilutions can introduce the possibility of error and contaminants that might
otherwise bias the results. Cost per analysis is also significantly higher for ICP-MS than ICP-AES. Since
the matrices (soil and sediment) are designed to contain high concentrations of metals and interfering
ions, ICP-AES was selected over ICP-MS as the analytical method best suited to meet the project
objectives.
Soil/Sediment Sample Preparation by Acid Digestion. The metals must be dissolved from the matrix into
an aqueous solution by acid digestion to analyze a soil or sediment sample by ICP-AES. Method 3050B
was selected as the preparation method and involves digestion of the matrix using a combination of nitric
and hydrochloric acids, with the addition of hydrogen peroxide to assist in degrading organic matter in the
samples. Method 3050B was selected as the reference preparation method because extensive data are
available that suggest it will meet the project objectives. It is recognized that Method 3050B digestion
accomplishes not a "total" digestion but a solubilization of "environmentally available" metals. The
"total" digestion approach solubilizes more interfering elements and may contribute other matrix effects
that are not consistent with the project objectives. Method 3052 (microwave-assisted digestion) was
considered, but was not selected because it is not as readily available in laboratories.
Soil/Sediment Sample Preparation for Mercury Analysis by CVAA. CVAA and its associated digestion
procedure, Method 7471 A, is the most effective method to analyze a sample of soil or sediment for
mercury. As with the other methods, this technique is widely available, and extensive data are available
that support the ability of this method to meet the objectives.
7.4 Sample Preparation and Analytical Methods for Reference Laboratory
This section briefly describes the procedures for instrument setup and calibration for the selected
methods. In addition, sample management procedures are also discussed.
7.4.1 Analysis of Metals by ICP-AES Method 6010B
Background correction is required and is monitored during each analysis. Before the instrument is
calibrated and the sample analyzed, the plasma conditions of the ICP must be optimized, interelement
interference studies and method detection limit studies must be completed, and the upper limits of the
dynamic linear range of the instrument must be verified for each element. A calibration curve is prepared
for the ICP by analyzing (at a minimum) a blank and one calibration standard. Calibration must be
verified after every 10 analyses, and the instrument must be recalibrated at the start of each day of
operation. QA/QC requirements for this method are described in Chapter 9.
7.4.2 Cold Vapor Atomic Absorption Spectrometry, Method 7471A
A calibration curve is prepared for the CVAA by analyzing (at a minimum) a blank and three calibration
standards at concentrations ranging from the expected detection limit to the upper linear limit.
Calibration must be verified after every 10 analyses, and the instrument must be recalibrated at the start of
each day of operation. QA/QC requirements for this method are described in Chapter 9.
7.4.3 Sample Management Procedures
Critical aspects of laboratory analysis of samples include receiving, handling, and disposing of the
sample, as well as its integrity throughout the process. Field samples will be provided in the appropriate
sample container and will be labeled with the information described h Chapter 6. The laboratory must
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prepare a sample receipt condition checklist as samples are received and report any abnormalities to Terra
Tech personnel immediately. Samples are then logged into the laboratory information management
system (LIMS) and assigned a unique laboratory identification number. From that point until results are
reported, the laboratory identification number is the tracking number within the LIMS. The laboratory
identification number must be transferred exactly to all intermediate glassware, reaction vessefc, and
digest vials. In addition, the laboratory identification number must be transferred exactly to all laboratory
notebooks and instrument run logs. All data will initially be reported using the laboratory identification
number. Before they are reported, all data will be cross-referenced back to the client identification
number. All reports will contain both the client and laboratory identification numbers. When Terra Tech
has reviewed all reports, written notification will be required before the laboratory may dispose of any
sample or sample digest. All samples and digest must be disposed of according to all applicable federal
disposal requirements. Documentation to that effect will be required.
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Chapter 8
Data Management
Standardized procedures will be used for data management to ensure that the demonstration data are
scientifically valid, defensible, and comparable. This chapter discusses (1) data reduction, (2) data
review, (3) data reporting, and (4) data storage procedures for the XRF demonstration.
8.1 Data Reduction
The operating manual for each XRF measurement instrument contains instructions and equations for
generating results. Each XRF developer will be responsible for acquiring and reducing its own data and
for providing final results to Tetra Tech in an appropriate format. The reference laboratory will generate
data on the concentration of total metals for all 13 elements using the EPA methods described in Section
7.2. The reference laboratory will generate analytical data in compliance with EPA method requirements
in the required format, and Tetra Tech will review results using a standard data validation process.
Statistical comparisons between data from the developer and the reference laboratory will be the same for
each developer; however, the data may be formatted differently depending on how the developer's data
are reported.
8.2 Data Review
The XRF developer's results will be compared independently with laboratory analytical data. Tetra Tech
will also review all field and laboratory data. A specific XRF developer's results will not be compared
against data of another XRF developer. The processes to be used to review the analytical data from the
developer and laboratory are described below.
8.2.1 Data Review by Developers
Developers will review all results generated from their instruments, including internal QC results (such as
calibration samples and method blanks). Each developer will report results to Tetra Tech using the
unique identification number for each sample described in Section 6.4. Tetra Tech will provide the pre-
demonstration sample results to each developer after they have been submitted, which creates a second
level of calibration for the XRF instruments during the field demonstration.
8.2.2 Data Review by Tetra Tech
The Tetra Tech project manager and the members of the Tetra Tech technology observation team will
review the laboratory and developers' results based on the demonstration objectives. The project QA
manager will be responsible for data validation for 100 percent of the reference laboratory results. Tetra
Tech will consider all data acceptable if QC criteria are met and this validation reveals no oversights or
problems. The project manager for the reference laboratory will be consulted if oversights or problems
are identified. Tetra Tech's assessment of the data and QC results will be summarized for discussion with
the EPA project manager and will be incorporated into the DER. Tetra Tech will identify outlier data
through graphical and statistical methods during review and will report these data to the EPA project
manager. Outliers are defined as data outside specified acceptance limits established around the central
tendency estimator (the arithmetic mean) of the data set for an area or for all areas taken together. The
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specified acceptance limits for data known or assumed to be normally distributed will be the 95 percent
confidence limits defined by the Student's two-tailed t-distribution. Consistent procedures will be used to
identify outliers for both laboratory and developer data. No data will be rejected simply because they are
statistical outliers. However, Terra Tech will conduct a thorough check to identify the reasons for the
outliers and will explain to the EPA project manager why some data may appear to be outliers.
8.3 Data Reporting
Each developer and the reference laboratory will prepare and submit data packages that report the results.
The reference laboratory will also prepare and submit electronic data deliverables (EDD). Terra Tech will
use these data to prepare the ITVR for each instrument and the DER for the entire demonstration.
Described below are the data reporting requirements for (1) developer data packages, (2) reference
laboratory data packages, (3) ITVRs, and (4) the DER.
8.3.1 Developer Data Packages
During the field demonstration, the developers will compile the results on standard forms provided by
Terra Tech. The forms will contain sample identification numbers and spaces for a developer to enter the
appropriate results. (Each form will be unique to each developer.) Electronic reporting of results will not
be required; however, the form will be provided to the developers in a standard spreadsheet software
format (such as Excel). To assure the integrity of the developers' data, each developer will be expected to
submit their complete results for the demonstration samples before they leave the demonstration site.
8.3.2 Reference Laboratory Data Packages
The reference laboratory will provide the data package to Terra Tech in standard analytical data forms and
in electronic format.
8.3.3 Innovative Technology Verification Reports
In accordance with the demonstration plan, Terra Tech will evaluate the data on performance, throughput,
and cost for each XRF instrument for inclusion into the ITVR. Each ITVR will be a focused report of
about 100 pages and will primarily include the following:
« An introduction
• A description of the XRF instrument
• Sample site materials and the demonstration design
• A description of the reference method and its performance
• A description of the XRF instrument's performance
• An economic analysis
• A summary of demonstration results.
Terra Tech will prepare individual ITVRs in accordance with the format specified in the "Handbook for
Preparing Office of Research and Development Reports" in its March 16,1998, update (EPA 1998f); and
project-specific guidance from the EPA program manager. The reports will be written in a manner that a
reader with a basic background in science can understand. The ITVRs will undergo a rigorous review
process that will include reviews by the EPA program manager, the developers, and external peer
reviewers.
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8.4 Data Evaluation Report
Tetra Tech will prepare a data evaluation report (DER) that contains tabular summaries of XRF analytical
and QA/QC data from the demonstration, as well as the results of the performance audits. The DER will
primarily discuss the following:
• Pre-demonstration activities
• Demonstration activities
• Post-demonstration activities
• Deviations from the demonstration plan
• All demonstration sample data
• QA/QC data
• Audit results.
8.5 Data Storage
The reference laboratory analysts responsible for measurements will enter raw data into logbooks or on
datasheets. In accordance with standard document control procedures, the laboratory will maintain on file
the original logbooks or datasheets, which will be signed and dated by the laboratory analysts responsible
for them. Similar procedures will be used for all data entered directly into the LIMS. The laboratory will
maintain separate instrument logs to allow reconstruction of the run sequences for individual instruments.
The reference laboratory will maintain all raw data, including raw instrument output on tape or diskette,
on file for 5 years after the data packages have been submitted to Tetra Tech. Data documents will be
kept in secure archive file cabinets accessible only to designated laboratory personnel. The data will be
disposed of after EPA issues instructions to do so or after 5 years, whichever is sooner. A central project
file for the demonstration will be established in Tetra Tech's Cincinnati office. This file will be a
repository for all relevant field and laboratory project documentation. Tetra Tech will offer the central
project file to EPA at the end of the demonstration project, if so requested.
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Chapter 9
Quality Assurance/Quality Control Procedures
Tliis chapter presents field and laboratory QA/QC requirements for generating scientifically valid and
legally defensible data that meet the demonstration objectives.
9.1 Quality Assurance Objectives
The overall QA objective for the demonstration is to produce well-documented data of known quality.
Data quality will be measured in terms of the data's precision, accuracy, representativeness,
completeness, and comparability (PARCC). Table 9-1 contains the objectives for the data quality
indicators. If analytical data from the reference laboratory fail to meet the QA objectives described in this
section (except for comparability, which does not apply), the source of the errors will be investigated and
corrective actions will be taken, as appropriate. (Corrective actions associated with the reference method
are outlined in Table 9-1 and are further discussed in Section 9.4.) If analytical data from the field XRF
instruments fail to meet the QA objectives, the ITVR will describe the failure, as well as the usefulness
and limitations of the data generated.
Table 9-1.
Data Quality Indicator Objectives
Data Quality
Indicator
Precision
Accuracy
Representativeness
Comparability to
reference method
Completeness
Calculation
RSD of replicate samples
Percent recovery of certified or spiked PE
values
Valid samples from each soil and
sediment type
RPD
Percent of total samples analyzed and
valid results provided
Objective
Average <20 percent
75 to 125 percent
At least one valid sample result
generated from each soil and
sediment location
< ± 25 percent
98 percent
9.2 Internal QC Checks
The following sections describe performance specifications for QC checks for the reference method and
for each XRF instrument.
9.2.1 Reference Method QC Checks
Table 9-2 summarizes the QC checks that the reference laboratory will use for analysis of total metals by
Method 6010B and of total mercury by Method 7471A, as specified by the method requirements.
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Table 9-2. Reference Method Quality Control Checks
Parameter
Method
QC Check
Freque ncy
Criterion
Corrective Action
Reference Method
Target Metals
(12 ICP metals
andHg)
Percent moisture
3050B/6010B
and 7471 A
Method and
instrument blanks
MS/MSD
LCS/LCSD
Performance
audit samples
Laboratory
duplicates
One per
analytical batch
of 20 or less
One per
analytical batch
of 20 or less
One per
analytical batch
of 20 or less
One per
analytical batch
of 20 or less
One per
analytical batch
of 20 or less
Less than the
reporting limit
75 to 125 percent
recovery
RPD = 25
80 to 120 percent
recovery
RPD = 20
Within acceptance
limits
RPD = 20
1. Check calculations
2. Assess and eliminate source of
contamination
3. Reanalyze blank
4. Inform Tetra Tech project manager
5. Flag affected results
1. Check calculations
2. Check LCS/LCSD and digest
duplicate results to determine whether
they meet criterion
3. Inform Tetra Tech project manager
4. Flag affected results
1. Check calculations
2. Check instrument operating conditions
and adjust as necessary
3. Check MS/MSD and digest duplicate
results to determine whether they meet
criterion
4. Inform Tetra Tech project manager
5. Redigest and reanalyze the entire batch
of samples
6. Flag affected results
1. Evaluated by Tetra Tech QA chemist
2. Inform laboratory and recommend
changes
3. Flag affected results
1. Check calculations
2. Reanalyze sample batch
3. Inform Tetra Tech project manager
4. Flag affected results
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9.2.1.1 Calibration and Method Blanks
Two types of blanks are required for the analysis of samples prepared by any method. The calibration
blank is used in establishing the analytical curve, and the method blank is evaluated to identify possible
contamination that results from the varying amounts of the acids used in the sample processing.
Calibration Blank. The calibration blank is prepared by acidifying reagent water to the same
concentrations of the acids found in the standards and samples. A sufficient quantity should be prepared
to flush the system between standards and samples. The calibration blank will also be evaluated for all
initial and continuing calibration blank determinations.
Method Blank. A method blank is an analyte-free matrix to which all reagents are added in the same
volumes or proportions as all other samples. The method blank sample should be processed through the
complete sample preparation and analytical procedure. The method blank is used to document
contamination resulting from the analytical preparation and measurement process. The method blank
must contain all of the reagents in the same volumes as was used in processing the samples. The method
blank must be processed through the complete procedure and contain the same acid concentration in the
final solution as the sample solution used for analysis. Silica is often employed as an analyte-free matrix
for the preparation of method blanks for soil sample analysis.
For a method blank to be acceptable for use with the accompanying samples, the concentration in the
blank of any analyte of concern should not be higher than the highest of either:
• The method detection limit, or
• Five percent of the measured concentration in the sample.
9.2.1.2 Matrix Spike/Matrix Spike Duplicate
A matrix spike (MS) is an aliquot of sample spiked with a known concentration of target analytes. The
spiked sample is subjected to the same entire analytical procedures as the environmental samples to be
analyzed. This matrix spike analysis indicates the appropriateness of the method for the matrix by
measuring the recovery of the spike.
Matrix spike duplicates (MSD) are intralaboratory split samples spiked with identical concentrations of
target analytes. The spiking occurs before the sample is prepared and analyzed. They are used to
document the precision and bias of a method in a sample matrix and are analyzed at a frequency of one
per matrix batch. The spiked sample or spiked duplicate recovery is to be within 25 percent of the actual
value (the amount spiked into the sample) or within the documented historical acceptance limits for each
matrix.
Matrix spike duplicate samples will be analyzed at a frequency of one per matrix batch. A matrix
duplicate sample is processed through the entire sample preparation and analytical procedure in duplicate.
The relative percent difference between spiked matrix duplicate determinations is to be calculated
according to the equation provided in Section 9.3.1 A control limit of 20 percent RPD or within the
documented historical acceptance limits for each matrix will be used for sample values greater than 10
times the instrument detection limit.
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9.2.1.3 Laboratory Control Sample/Laboratory Control Sample Duplicate
Laboratory control samples (LCS) are aliquots of reagent water spiked with a group of target compounds
that are representative of the method analytes and processed through every aspect of the procedure,
including preparation and analysis. These samples are analyzed to monitor the accuracy of the analytical
procedure, independent of matrix effects. An LCS can be measured in duplicate to provide additional
data on precision.
The LCS or LCS duplicate (LCSD) recovery is to be within 25 percent of the actual value or within the
documented historical acceptance limits. The RPD between the duplicate results should be plus or minus
20 percent or within the documented historical acceptance limits.
9.2.1.4 Laboratory Matrix Duplicate
Laboratory matrix duplicates are second aliquots of samples that are processed through every aspect of
the procedure, including preparation and analysis. Matrix duplicate samples are analyzed to evaluate the
precision of the analytical procedure. The concept of matrix duplicates is similar to the matrix spike
duplicates, except that target analytes are not spiked into the sample. The RPD between the two
determinations is calculated and compared with defined laboratory acceptance criteria.
9.2.1.5 Performance Evaluation Sample
A PE sample is a well-characterized material produced in quantity to improve measurement science. The
"true value" for each analyte is certified by the vendor for specific chemical or physical properties. A PE
sample will be prepared and submitted for analysis for this project. Results from the PE audit sample will
be used for the following three main purposes:
1. To verify the accuracy of the analytical method.
2. To verify calibration of the measurement system.
3. To assure the long-term adequacy and integrity of measurement quality assurance programs.
The results for the PE samples will be assessed against the acceptance limits established by the vendor or
other organization responsible for providing the PE sample.
9.2.2 Developer Instrument QC Checks
Quality control checks for the XRF instruments during the demonstration will be completed at the
discretion of each developer. It is highly recommended that quality control checks such as blanks,
duplicates, calibration standards, and interference check samples be systematically analyzed throughout
the demonstration.
9.3 Quality Indicators
All analytical results will be evaluated in accordance with the PARCCS parameters to document the
quality of the data and to ensure that the data are of sufficient quality to meet the project objectives. Of
these PARCCS parameters, precision and accuracy will be evaluated quantitatively through the QC
samples and checks discussed in Section 9-2.
The following sections describe each of the PARCCS parameters and how they will be assessed for this
project.
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9.3.1 Precision
Precision is the degree of mutual agreement between individual measurements of the same property under
similar conditions and is evaluated by analyzing duplicate samples and then calculating the variance
between the analytical results, typically as an RPD (see Chapter 5 for RPD calculation). Laboratory
analytical precision is evaluated by analyzing laboratory duplicates or MS and MSD samples. MS/MSD
samples will be generated for all analytes for this project. The analytical results for each MS/MSD pair
will be used to calculate an RPD for evaluating precision.
9.3.2 Accuracy
A series of spiked sample s will be analyzed to evaluate laboratory accuracy. This series of samples to be
analyzed includes the MS and MSD samples, LCS or blank spikes, surrogate standards, and method
blanks. MS and MSD samples will be prepared and analyzed at a frequency of 5 percent for soil and
sediment samples. LCS or blank spikes are also analyzed at a frequency of 5 percent. Surrogate
sttindards, where available, are added to every sample analyzed for organic constituents. The results of
the spiked samples are used to calculate the percent recovery for evaluating accuracy.
S — C
Percent Recovery = x 100
where
S = Measured concentration in spike sample
C = Sample concentration
T = True or actual concentration of the spike
Results that fall outside the accuracy goals will be further evaluated on the basis of the results for other
QC samples.
When a standard reference material is used, the following equation is often used to calculate %R:
%R = 100 x
where
%R = Percent recovery
Cm = Measured concentration of standard reference material
Csrm = Actual concentration of standard reference material
9.3.3 Representativeness
Representativeness expresses the degree to which sample data accurately and precisely represent the
characteristics of a population, variations in a parameter at a sampling point, or an environmental
condition that they are intended to represent. Representative data for this project will be obtained through
careful selection of samples, sample replicates, and analytical parameters for evaluation by the technology
developers.
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Representativeness will be satisfied by (1) ensuring that the project demonstration plan is followed,
(2) ensuring that samples are collected in accordance with appropriate SOPs, (3) ensuring that project-
specified analytical procedures are followed, and (4) ensuring that required holding times are not
exceeded in the laboratory. There is no mathematical equation for representativeness.
9.3.4 Completeness
Completeness is a measure of the percentage of project-specific data that are valid. Valid data are
obtained when samples are collected and analyzed in accordance with QC procedures outlined in this plan
and when none of the QC criteria that affect data usability are exceeded. The percent completeness value
will be calculated when all data validation is completed by dividing the number of useable sample results
by the total number of sample results planned for this demonstration.
Completeness for most measurements is defined as the percentage of results judged to be valid and is
calculated as follows:
*[-!
L«J
%c = 100%
where
%C = Percent completeness
V = Actual number of measurements judged valid (the validity of a
measurement result is determined by judging its suitability for its
intended use)
n = Total number of measurements planned to achieve a specified level of
confidence in decision-making
9.3.5 Comparability
Comparability expresses the confidence with which one portion or set of data can be compared with
another. Generally, comparability will be attained by achieving the QA objectives presented in this
demonstration plan for sensitivity, accuracy, precision, completeness, and representativeness.
Comparability of data will also be attained by following field and laboratory procedures consistently for
individual sites. EPA-approved standard field procedures, presented in this demonstration plan, will be
used to the maximum extent possible. EPA-approved laboratory methods will be used to increase the
comparability of laboratory analytical data. There is no mathematical equation for comparability.
Statistical analys is including, but not limited to, linear regression may be used to assess comparability
between field XRF data and reference laboratory results.
9.3.6 Sensitivity
The MDL is the minimum concentration of an analyte that can be reliably distinguished from background
noise for a specific analytical method. The quantitation limit represents the lowest concentration of an
analyte that can be accurately and reproducibly quantified in a sample matrix.
The achievement of MDLs depends on instrument sensitivity and matrix effects. Therefore, it is
important to monitor the instrument sensitivity to ensure data quality and to ensure that the analysis meets
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the QA objectives established for sensitivity in the project demonstration plan. Method sensitivity is
typically evaluated in terms of the MDL and, for many measurements, is calculated as follows:
= t(n-l,l-a = 0.99) S
where
MDL = Method detection limit
t(n- 1, i-a=o.99> = Student's t-value for a one-sided 99 percent confidence level and a
standard deviation estimate with n- 1 degrees of freedom
n = Number of measurements
a = Statistical significance level
s = Standard deviation of the replicate analyses
9.4 Audits, Corrective Actions, and QA Reports
Demonstration measurement systems and associated data will be assessed both on a day-to-day basis by
Terra Tech project personnel (routine assessments) and on a periodic basis by independent personnel
(audits). Corrective actions will be formulated and implemented in response to any data quality issues
that arise during routine assessments or audits. Routine assessments and corrective actions are presented
in Table 9-2. Although routine assessment is generally the most effective means to identify data quality
issues, personnel directly involved in a project may not always recognize a data quality issue. Therefore,
audits will be conducted to provide an independent view of measurement systems and data during the
demonstration as well as additional assurance that data quality issues are identified and appropriate
corrective actions are taken.
QA audits are independent assessments of measurement systems and associated data and are more
rigorous than routine assessments. QA audits may be internal or external and most commonly incorporate
technical system reviews and analysis of blind or double -blind performance audit samples. System
audits, performance audits, and associated corrective action procedures are described below.
9. 4. 1 Technical Systems A udits
Technical system audits (TSA) include thorough evaluations of field and laboratory sampling and
measurement systems. Terra Tech will conduct an internal system audit of sampling and measurement
systems during the demonstration. In addition, Terra Tech will conduct a TSA of the reference laboratory
during critical measurements.
The activities that will be audited during demonstration and laboratory measurement system audits are
summarized in Table 9-3.
EPA may also conduct external system audits of demonstration and laboratory measurements at the
discretion of the EPA project manager and QA officer. If the EPA elects to perform a field TSA, Tetra
Tech will coordinate an internal audit with EPA's external audit and will schedule the audits on
consecutive days. The internal system audit will then be identified as a pre-audit and will be used to
identify issues for resolution during EPA's system audit. If the EPA elects not to audit the demonstration
or laboratory system, Tetra Tech will include the EPA project manager and QA officer in the debriefing
for each internal system audit and will submit all audit documentation to EPA for review.
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Table 9-3. Technical System Audit of Activities
Demonstration Activities
Sample verification
Sample measurement
Data reporting
QA/QC procedures
Project management and QA
activities that may affect
data quality
Laboratory Measurement Activity
Sample receipt and storage
Internal chain-of-custody procedures
Sample preparation
Standard preparation and storage
Use of second source standards
Calibration
QA/QC procedures
Data reduction, validation, and
reporting
Project management and QA activities
that may affect data quality
Internal TSAs will be conducted in accordance with (1) Tetra Tech's internal guidance for SITE projects,
and (2) applicable EPA technical directives and guidance. Based on Tetra Tech's internal guidance, the
audit process to be implemented by the assigned auditor for a field or laboratory audit is summarized
below.
• A checklist is developed based on the EPA-approved demonstration plan and any
standard operating procedures or reference methods.
• Actual field or laboratory activities are observed and compared with the activities
described in the EPA-approved demonstration plan using the checklist.
• Nonconformances and corrective actions are discussed on site; any immediate corrective
action is observed and documented, when possible.
• A draft technical system audit report is prepared to document any observed
nonconformance as well as any immediate corrective action that was implemented.
• Tetra Tech personnel review the draft technical system audit report for technical,
editorial, and overall quality.
• The draft technical system audit report is distributed to the field team or laboratory, the
EPA project manager and QA officer, the Tetra Tech project manager, and the SITE QA
manager.
• Any response by the field team or laboratory to the draft TSA report is reviewed to assess
its impact on the issue or proposed corrective action.
A final technical system audit report is prepared, subjected to Tetra Tech's internal review process, and
distributed to the laboratory, the EPA project manager and QA officer, and the Tetra Tech project
manager and quality control coordinator.
9.4.2 Performance Evaluation Audits
The developers and reference laboratory analyzed single-blind performance evaluation samples as part of
the pre-demonstration investigation and laboratory selection process. The findings of this performance
audit were discussed with the EPA project manager and all other participants in the demonstration.
As directed by the EPA project manager, a performance audit of field measurement instruments and
reference laboratory measurements will be conducted for analysis of metals in soil and sediment during
the demonstration. Tetra Tech will obtain performance audit samples from EPA and will ask the
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developers and the reference laboratory to analyze them as blind samples. Results of the analysis of
performance audit samples will be reviewed by Tetra Tech and will be reported to the EPA project
manager, the developers, and the reference laboratory's project manager. Findings from the performance
audit, any nonconformances, and their resolutions will be documented in the DER for the demonstration.
9.4.3 Corrective Action Procedures
Corrective action procedures will depend on the type and severity of the finding. The auditor will classify
assessment findings as either deficiencies or observations. Deficiencies are findings that may have a
sijgnificant impact on data quality and that will require corrective action. Observations are findings that
do not directly affect data quality but are suggestions for consideration and review. The following
procedures will be followed if a deficiency is detected during a system or performance audit:
• The Tetra Tech project manager will immediately discuss the problem and any corrective
action to be taken with the field or laboratory personnel responsible and all other
appropriate personnel.
• The Tetra Tech project manager, the developer or the laboratory project and QA
managers (as appropriate), and the EPA project manager will develop a plausible course
of corrective action.
• The Tetra Tech project manager and the developer or the laboratory project manager (as
appropriate) will implement the corrective action and assess its effectiveness.
• The audit report and associated response will serve as the documentation of the problem
and corrective action.
The Tetra Tech project manager and the developer or laboratory project manager (as appropriate) will be
responsible for ensuring that corrective actions identified through the audit process are fully implemented.
9.4.4 QA Reports
The outcome of each audit will be fully documented. The QC coordinator will archive all audit
documentation collected on the project. The QC coordinator will report the findings of each audit to the
Tetra Tech or laboratory project manager, as appropriate, who will then address the findings and provide
a response. QA reports require a written response by the person responsible for the activity inspected and
acknowledgment of the audit by the Tetra Tech project manager.
Authority to report all technical system audits is designated to the QC coordinator or designee. These
reports should:
• Identify and document problems that affect quality and the achievement of objectives required by
the quality assurance project plan and any associated standard operating procedures.
• Identify and cite noteworthy practices that may be shared with others to improve the quality of
their operations and products.
• Propose recommendations (if requested) for resolving problems that affect quality.
• Independently confirm implementation and effectiveness of solutions.
• Provide documented assurance (if requested) to line management that, when problems are
identified, further work is monitored carefully until the problems are suitably resolved.
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Responses to adverse findings are addressed immediately during a debriefing after the assessment is
completed, and preferably at the site of the assessment. Responses to each adverse finding will be
documented in the QA report. The QA report will be distributed to all parties for review, and clarification
of any corrective action to be implemented will be requested. The response will indicate the corrective
action taken or planned to address the adverse finding.
Any corrective action that cannot be immediately implemented will be verified after it has been
completed by the QA manager or designee. Once all corrective actions associated with a QA report have
been taken, the QA manager or designee will initial the corrective action in the QA report, thus
documenting that the corrective action has been verified Any impact of an adverse finding on the quality
of project data is addressed in the project report. The QA report, with responses to adverse findings
recorded, is sent to the Terra Tech project and QA managers, as appropriate.
Effective management of data collection efforts during the demonstration will require timely assessment
and review. Effective interaction and feedback among project team members will, therefore, be essential.
When appropriate, the Tetra Tech project manager will discuss QA issues with the EPA project manager
as they arise. The Tetra Tech project manager will also summarize QA issues and their resolutions in
monthly status reports to the EPA project manager. QA issues may pertain to the following matters:
• Deviations from the demonstration plan
• Corrective action activities
• Outstanding issues and proposed resolutions
• Audit results
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Chapter 10
Health and Safety Procedures
The field evaluation of XRF technologies will be conducted at the KARS Park site at Cape Canaveral,
Florida. Samples that will be evaluated during the demonstration include material collected from the
KARS Park site as well as eight other sites around the U.S. Pre-demonstration sampling and site and
material characterization were completed in the summer of 2004 at the KARS Park site as well as the
ei|*ht other sampling sites (see Chapter 4). Sample collection and handling and health and safety
protocols specifically designed to address chemical and physical hazards associated with the materials, as
well as the individual sampling sites, were addressed in the site-specific health and safety plans (HSP) for
pre-demonstration sampling at each site.
The sampled materials were further prepared (homogenized, divided into aliquots, and placed into jars) by
the characterization laboratory. These contained materials will be evaluated during the XRF technology
demonstration at KARS Park. Additional field sampling is not anticipated during the demonstration. In
addition, because the sample material is contained in wide mouth jars, the potential for contact with
contaminated material is low. For these reasons, the health and safety program for the field
demonstration will address (1) potential physical hazards associated with general on-site activities at the
KARS Park site, and (2) potential chemical hazards associated with handling the prepared sample
materials.
Field activities will include oversight of the operation of innovative XRF field measurement instruments
by technology vendors and oversight and support by Tetra Tech and EPA personnel. This section
addresses items specified under OSHA Title 29 CFR Part 1910.120 (b), "Final Rule," and will be
available to all personnel who may be exposed to hazardous conditions on site, including Tetra Tech and
developer personnel participating in the demonstration, and all site visitors, such as representatives of the
regulatory agencies. All personnel on site, including Tetra Tech and site visitors, must be informed of
emergency response procedures and any potential fire, explosion, health, or safety hazards associated with
on-site activities. This section summarizes potential hazards and defines protective measures planned for
the demonstration. Developers, EPA personnel, and site visitors may choose to follow the Tetra Tech
health and safety procedures described in this section. However, each employer is directly and fully
responsible for the health and safety of its own employees; Tetra Tech assumes no responsibility for non-
Tetra Tech personnel. The health and safety procedures described in this section have been reviewed and
approved by the Tetra Tech health and safety representative (HSR) and the Tetra Tech project manager.
Some of the XRF instruments that will be evaluated at KARS Park use small radioactive sources. The
potential for exposure to ionizing radiation from these sources is minimal, however. Proper maintenance,
handling, shipping, storage, and operation of these sources are required by the licenses issued through the
U.S. Nuclear Regulatory Commission (NRC). Personnel from the technology developers must hold all
required licenses and comply with all training and certification requirements for the technology.
However, each technology developer is responsible for preparing and complying with plans to address
special requirements for its on-site personnel to operate and handle the equipment. The vendor also will
be responsible for limiting any access to, or any activities conducted near, the equipment, whether by
EPA, Tetra Tech, or visitors that would not comply with licensing requirements or would otherwise result
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in potential exposure to ionizing radiation. For these reasons, this plan does not address potential hazards
associated with use of the equipment.
Protocols established in this section are based on site conditions, health and safety hazards known or
anticipated to be present on site, and available site data. The health and safety procedures described in
this section are intended solely for use during the proposed activities described in this demonstration plan.
An HSP that summarizes health and safety procedures and presents emergency information is presented
in Appendix B. A copy of this plan will be available at the demonstration site. Specifications are subject
to review and revision based on actual conditions encountered in the field during the demonstration. The
Terra Tech project manager and the Terra Tech HSR must approve significant revisions to the health and
safety procedures. Terra Tech employees must also follow safety requirements taught during safety
training and described in the Terra Tech, Inc., "Health and Safety Manual."
This chapter is organized in the following 10 sections:
• Personnel and Enforcement (Section 10.1)
• Site Background (Section 10.2)
• Site-Specific Hazard Evaluation (Section 10.3)
• Training Requirements (Section 10.4)
• Personal Protection Requirements (Section 10.5)
• Medical Surveillance (Section 10.6)
• Environmental Monitoring and Sampling (Section 10.7)
• Site Control (Section 10.8)
• Decontamination (Section 10.9)
• Emergency Response Planning (Section 10.10)
10.1 Personnel and Enforcement
This section describes the responsibilities of project personnel; summarizes requirements for developers
and visitors who wish to enter the KARS Park site; and discusses enforcement of health and safety
procedures.
10.1.1 Project Personnel
The following personnel and organizations are associated with activities planned at the demonstration
sites. The organizational structure will be reviewed and updated as necessary during the project.
Name Responsibility Telephone No.
Client Representative:
Stephen Billets EPA Project Manager (702) 798-2232
Site Representative:
Michael Deliz NASA KSC KARS Park Site Manager (321) 867-6971
Mark Speranza Terra Tech NUS for NASA (412) 921 - 8916
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Name Responsibility Telephone No.
Tetra Tech Personnel:
Gregory Swanson Project Manager (619)525-7188
SlanLynn Site Superintendent (513)564-8349
Ed Surbrugg Technical Lead (406) 442-5588
Julia Capri Technical Lead (513)564-8342
Stephanie Wenning Site Safety Coordinator (SSC) (513) 564- 8346
Judith Wagner Health and Safety Representative (847) 818-7192
Technology Developers:
Don Sackett Innov-X Systems, Inc. (781) 938-5005
John Patterson Oxford Instruments Portable Div. (609) 406-9000
Dave Mercuro NITON LLC (800) 875-1578, Ext. 333
Rune Gehrlein Oxford Instruments Analytical (847) 439-4404
Jose Bram Rigaku, Inc. (978) 374-7725
Paul Smith RONTEC USA Inc. (978) 266-2900
Ron Williams Xcalibur XRF Services Inc. (631) 435-9749
W.I. 1.1 Project Manager and Field Manager
The Tetra Tech project manager has ultimate responsibility for ensuring that the requirements set forth in
this section are implemented. Some of this responsibility may be fulfilled by delegating duties to site-
dedicated personnel who report directly to the project manager. The project manager will regularly
confer with site personnel on health and safety compliance.
The Tetra Tech field manager will oversee and direct demonstration activities and will have day-to-day
responsibility for ensuring that the health and safety procedures are implemented. The field manager will
report any health and safety-related issues directly to the project manager.
10.1.1.2 Site Safety Coordinator
The Tetra Tech site safety coordinator (SSC) will be responsible for field implementation of tasks and
procedures discussed in this section, including air monitoring, establishing a decontamination protocol,
and ensuring that all personnel working on site sign the Daily Tailgate Safety Meeting Form (included h
Appendix C). The SSC will have advanced experience in field work and will be familiar with health and
safety requirements specific to the project. The SSC will also maintain the Daily Site Log included in
Appendix C.
10.1.1.3 Health and Safety Representative
The Tetra Tech HSR is responsible for administering the company health and safety program. The HSR
will act in an advisory capacity to the Tetra Tech project manager and personnel on project-specific health
and safety issues. The project manager will establish a liaison among representatives of EPA;
representatives of the KARS Park site; and the HSR for matters relating to health and safety.
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10.1.1.4 Tetra Tech Employees
Tetra Tech employees are expected to fully participate in implementing the site-specific health and safety
procedures by obtaining necessary training, attending site safety meetings, always wearing designated
personal protective equipment (PPE), complying with site safety and health rules, and advising the Tetra
Tech SSC of health and safety concerns at the sites.
10.1.2 Technology Developers
The technology developers' personnel involved in field operations will be provided with a copy of this
section. Field subcontractors are not anticipated for this project. The developers must comply with all
applicable requirements for training, fit testing, and medical surveillance specified at 29 CFR 1910.120,
as applicable. The developers are responsible for providing PPE required for their personnel (see Section
10.5.1, Protective Equipment and Clothing) and are directly responsible for the health and safety of their
employees. As previously discussed, personnel for the technology developers must hold all required
licenses and comply with all training and certification requirements for the technology.
10.1.3 Visitors
All site visitors will be briefed on the site-specific health and safety procedures. Site visitors will be
escorted by Tetra Tech personnel during visitor's day.
10.1.4 Health and Safety Procedure Enforcement
The health and safety procedures described in this section apply to all demonstration activities and all
Tetra Tech personnel working on the KARS Park site. Violators of the procedures will be verbally
notified on the first violation, and the Tetra Tech SCC will note the violation in a field logbook. On a
second violation, the violator will be notified in writing, and the Tetra Tech project manager and the
violator's supervisor or their company's lead contact will be notified. A third violation will result in a
written notification and the violator's eviction from the site. The written notification will be sent to the
Tetra Tech HSR. Personnel will be encouraged to report to the Tetra Tech SSC any conditions or
practices that they consider detrimental to their health or safety or that they believe violate applicable
health and safety standards. These reports may be made orally or in writing. Personnel who believe that
an imminent danger threatens human health or the environment must bring the matter to the immediate
attention of the SSC for resolution.
A copy of the HSP will be available on site for all site personnel. The SSC will discuss minor changes to
the health and safety procedures discussed in this plan at the beginning of each work day at the daily
tailgate safety meeting, and these changes will be noted in the field logbook. Significant revisions to the
procedure must be discussed with the Tetra Tech HSR and project manager.
10.2 Site Background
The following sections describe the demonstration site and the activities planned for the demonstration.
10.2.1 Site Description
KARS Park is a NASA employee recreational park on the Kennedy Space Center property, located just
outside the Cape Canaveral base in Merritt Island, Florida. Contaminants in the park (primarily
antimony, as well as lead, arsenic, chromium, and copper) resulted from historical facility operations and
impacts from the former gun range. The land north of KARS Park is owned by NASA and is managed by
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USFWS as part of the Merritt Island National Wildlife Refuge. Chapter 4 describes the KARS Park site
in more detail. Figure 4-1 shows the site location.
10,2.2 Site History
KARS Park was purchased in 1962 and has been used by employees of NASA, other civil servants, and
guests as a recreational park since 1963. Contaminants in the park resulted from historical facility
operations and impacts from a former recreational firing range.
10.2.3 Activities Planned
The demonstration approach and procedures for on-site sample evaluation to be followed at KARS Park
are fully described in Chapters 5 and 6. As previously discussed, collection of additional field samples
from the KARS Park site is not anticipated during the demonstration. The demonstration activities
planned include the following tasks:
• Handling and analyzing prepared jars of soil and sediment sample aliquots from the nine
sampling sites by each technology developer using their XRF instrument.
• Oversight of XRF field measurements at the KARS Park site by EPA (SITE MMT Program) and
Tetra Tech personnel. One Terra Tech representative will be assigned to every two technology
developer teams to provide general sample management and logistical support during the
demonstration and to ensure that the project demonstration plan and quality assurance project
plan (QAPP) are followed consistently among all developers.
10.3 Site-Specific Hazard Evaluation
This section provides information on potential hazards related to the demonstration and the nature of
impacts from hazardous materials. Demonstration activities and physical features of the demonstration
site may expose field personnel to a variety of hazards. However, the potential for exposure is anticipated
to be limited, as the demonstration will be conducted in a protected setting (a picnic shelter) using pre-
characterized, prepared vials of sample materials. Field sampling was completed as part of the pre-
demonstration and is not anticipated to be required for the demonstration; therefore, potential chemical
hazards associated with handling the prepared sample materials are anticipated to be minimal, as direct
contact with contaminated materials will not occur. Physical hazards are limited to any that are
associated with conducting limited, nonintrusive outdoor activities in the environmental setting of KARS
Park. Potential chemical, physical, and site-specific environmental hazards related to the demonstration
are discussed below.
10.3.1 Chemical Hazards
Chemical hazards that may be encountered at the KARS Park site primarily involve inorganic substances
(antimony, lead, chromium, and arsenic). Trichloroethene has also been detected in subsurface soils in
some portions of the site; however, the demonstration will not be conducted in these areas. Historical
data for on-site concentrations of inorganic substances are presented in Table 4-1 of Chapter 4.
These chemicals pose various physical, chemical, and toxicological hazards. Potential routes of exposure
to these chemicals include dermal (skin) contact, inhalation, and ingestion. The chemicals may also
contaminate equipment, vehicles, instruments, and personnel. The overall threat to health associated with
exposure to these chemicals is uncertain because (1) actual concentrations that personnel could be
exposed to cannot be predicted, (2) the actual duration of exposure is unknown, and (3) the effects of low-
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level exposure to a mixture of chemicals cannot be predicted. However, Tetra Tech believes that the
potential for high-level exposure is limited, as the areas that have been identified as contaminated will not
be used or accessed by personnel involved in the demonstration. Activities will be limited to the shelter
and the immediate surrounding area. Exposure to potential chemical hazards will be limited to personnel
who handle the prepared samples that will be evaluated by XRF; however, these materials will be
contained in jars; therefore, the potential for direct contact with these materials is low. Each technology
developer will be responsible for ensuring that its field personnel are trained and familiar with appropriate
techniques for handling these materials. EPA and Tetra Tech personnel and visitors are not anticipated to
contact inorganic contaminants. Tetra Tech personnel may assist the technology developers in sample
handling and will follow appropriate measures to mitigate potential exposures. Table 10-1 provides a task
hazard analysis of the demonstration activities planned that are listed in Section 10.2.3.
All samples that will be analyzed during the demonstration will be prepared off site and contained in glass
jars before the field demonstration. It is not anticipated that Tetra Tech or the developers will bring
materials typically associated with decontamination or sample preparation to the site because intrusive
sampling activities and decontamination will be not required. These materials include laboratory
reagents, decontamination solutions, and sample preservatives. For this reason, Material Safety Data
Sheets (MSDS) are not required for this demonstration. The developers will be responsible for making
MSDSs available on site if any of these materials are required to support the specific technologies.
10.3.1.1 Volatile Organic Compounds
Generally, volatile organic compounds (VOCs) are central nervous system depressants. Exposure to
some VOCs may occur through skin absorption. General symptoms of exposure to VOCs, both acute and
chronic, may include euphoria, headache, weakness, dizziness, nausea, narcosis, and possibly coma.
Certain VOCs are also skin and eye irritants. However, field activities at the KARS Park demonstration
site will be limited to uncontaminated areas. For this reason, exposure to VOCs is not anticipated during
the demonstration.
10.3.1.2 Inorganic Substances
Inorganic substances do not contain carbon in their molecular structure. Heavy metals such as lead are
inorganic substances. The symptoms of acute exposure to metals include, but are not restricted to,
abdominal pain, hypertension, anemia, insomnia, and restrictive pulmonary function. Chronic exposure
to some metals may lead to development of cancer. However, field activities at the KARS Park
demonstration site will be limited to uncontaminated areas; sample materials that will be evaluated will be
contained in wide mouth jars. For this reason, potential exposure to inorganic substances is limited.
Injuries that could result from physical hazards can be avoided by using safe work practices (SWPs) and
employing caution when working with machinery. Specific SWPs that apply to the demonstration are
listed in Section 10.8.5 and will be available on site during the demonstration. The Tetra Tech SSC will
conduct and document regular safety inspections and will make sure that all workers and visitors are
informed of any potential physical hazards related to the sites to ensure safe working conditions.
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Table 10-1. Task Hazard Analysis
Task
Oversight of Sample
Analysis by XRF
Instruments (analyses to
be conducted by
Technology Developer
Personnel)
Potential Hazard
Physical Injury
Dermal Exposure (contact
with contaminated soils)
Heat Stress
Electrical Shock
Sun Exposure
Working Near Vehicles
Contact with Wildlife
(Venomous Snakes;
Alligators)
Biting and Stinging Insects
Severe Weather Hazards
(Lightning, Tornadoes)
Exposure to Radioactive
Source Material
Control Measure
Exercise caution; secure and mark locations of
electrical cords; conduct all activities during daylight
hours.
Avoid contaminated areas; conduct activities only in
designated demonstration area.
Maintain proper hydration; provide appropriate rest
periods relative to temperature and humidity.
Ensure electrical cords and connections are properly
sized for required loads; secure and seal connections;
use ground fault interrupter circuits; avoid handling
electrical equipment if wet; inspect cords and
connections for wear, abrasions, or exposed wires.
Avoid prolonged exp osure to direct sun; wear
appropriate clothing; use sunscreen.
Exercise caution when vehicles are entering or leaving
the site.
Avoid all contact; notify SSC of presence and location
if sighted; notify site personnel if problem persists;
inspect work areas and perimeter each day; avoid
leaving open, unattended boxes and cases in work area.
Wear long-sleeved clothing and use appropriate
repellents; ensure that trash related to food and
beverages is properly disposed of; inspect
demonstration area for concentrations of biting or
stinging insects before the field demonstration begins.
Cease field operations if lightning, thunder, or other
indications of severe weather are noted; proceed to
appropriate shelter.
Comply with technology developer's HSP at all times,
if applicable, for instruments employing regulated
sources.
Initial Level of Protection
Level D, as described in
Section 10.5.1. including:
- Coveralls or work clothes
- Steel toe/shank boots
- Hard hat
- Disposable gloves (latex or
nitrile)
- Safety glasses or goggles
Upgraded (Contingency
Level of Protection)
Level D, as described in
Section 10.5.1. including:
- Coveralls or work
clothes
- Chemical-resistant
clothing (such as Tyvek
or Saranex coveralls)
- Outer gloves (neoprene,
nitrile, or other), if
applicable
- Disposable inner gloves
(latex or vinyl)
- Boots with steel-toe
protection and steel
shanks
- Disposable boot covers
or chemical-resistant
outer boots
- Safety glasses or
goggles
- Hard hat (face shield
optional)
- Hearing protection (for
areas with a noise level
exceeding 85 decibels on
the A-weighted scale)
Note: The upgraded (contingency level of protection) will be used if a sample container breaks and its contents need to be cleaned up.
Decontamination procedures need to be implemented in this instance.
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10.3.2 Site-Specific Environmental Hazards
The KARS Park site is located in an environmental setting that may present additional hazards through
potential contact with alligators, venomous snakes, and biting or stinging insects. Based on observations
during the pre-demonstration sampling in July 2004, however, the potential for these hazards to present
serious risks appears low, as field activities will be limited to the shelter and immediate surrounding area.
Exposure to biting insects is anticipated to be limited because of the time of year (winter) scheduled for
the demonstration. However, on-site personnel should be aware of these potential hazards and will
address them as necessary.
10.4 Training Requirements
All Tetra Tech personnel who may be exposed to hazardous conditions on site will be required to meet
the training requirements outlined in 29 CFR 1910.120, "Hazardous Waste Operations and Emergency
Response." All personnel and visitors entering the sites will be required to sign the Daily Tailgate Safety
Meeting Form included in Appendix C.
The Tetra Tech SSC will present a briefing for all personnel who will participate in on-site activities
before activities begin at the KARS Park site. The following topics will be addressed during the prework
briefing:
• Names of the SSC and a designated alternate
• Site history
• Tasks
• Hazardous chemicals that may be encountered on site
• Physical hazards that may be encountered on site
• PPE to be used for work
• Training requirements
• Use and maintenance of environmental surveillance equipment (not anticipated)
• Action levels and situations requiring upgrade or downgrade of level of protection
• Site control measures, including site communications, control zones, and SWPs
• Decontamination procedures
• Emergency communication signals and codes
• Environmental accident emergency procedures (in case contamination spreads outside the
exclusion zone)
• Personnel exposure and accident emergency procedures (in case of falls, exposure to hazardous
substances, and other hazardous situations)
Fire and explosion emergency procedures
Emergency telephone numbers
Emergency routes
Any other health and safety-related issues that may arise before on-site activities begin will also be
discussed during the prework briefing. Issues that arise during on-site activities will be addressed during
tailgate safety meetings to be held daily before the work day or shift begins. These issues will be
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documented in the Daily Tailgate Safety Meeting Form. Any changes in procedures or site-specific
health and safety-related matters will be addressed during these meetings.
1(1.5 Personal Protection Requirements
The levels of personal protection to be used for work at the KARS Park site have been selected based on
known or anticipated physical hazards; types and concentrations of contaminants that may be encountered
on site; and contaminant properties, toxicity, exposure routes, and matrices. The following sections
describe protective equipment and clothing; reassessment of protection levels; limitations of protective
clothing; and respirator selection, use, and maintenance.
10.5.1 Protective Equipment and Clothing
Personnel will wear protective equipment when (1) the demonstration involves known or suspected
atmospheric contamination; (2) the demonstration may generate vapors, gases, or particulates; or (3)
direct contact with hazardous materials may occur. The anticipated levels of protection selected for use
by field personnel during the demonstration are listed in Table 10-1, Task Hazard Analysis. Based on the
anticipated hazard level, personnel will initially conduct field tasks in Level D protection. In addition,
on-site personnel should have insect repellent available based on the potential for contact with biting
insects.
All field personnel will withdraw from the site, immediately notify the Terra Tech SSC, and wait for
further instructions if site conditions or the results of air monitoring during on-site activities warrants a
higher level of protection.
Equipment and clothing required for Level D, Level C, and Level B protection are described below.
Level D:
Coveralls or work clothes
Boots with steel-toe protection and steel shanks
A hard hat (face shield optional)
Disposable gloves (latex or nitrile)
Safety glasses or goggles
Hearing protection (for areas with a noise level that exceeds 85 decibels on the A-weighted scale)
Chemical-resistant clothing (such as Tyvek or Saranex coveralls)
Outer gloves (neoprene, nitrile, or other), if applicable
Disposable inner gloves (latex or vinyl), if applicable
Disposable boot covers or chemical-resistant outer boots, if applicable
Level C:
Coveralls or work clothes
Chemical-resistant clothing (such as Tyvek or Saranex coveralls)
Outer gloves (neoprene, nitrile, or other), if applicable
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Disposable inner gloves (latex or vinyl)
Boots with steel-toe protection and steel shanks
Disposable boot covers or chemical-resistant outer boots
A full- or half-face, air-purifying respirator with NIOSH-approved cartridges to protect against
vapors, dust, fumes, and mists. (Cartridges used for gas and vapors must be replaced in
accordance with the change-out schedule described in the respiratory hazard assessment form
included in Appendix C.)
Safety glasses or goggles (with half-face respirator only)
A hard hat (face shield optional)
Hearing protection (for areas with a noise level that exceeds 85 decibels on the A-weighted scale)
Level B:
Chemical-resistant clothing (such as Tyvek or Saranex coveralls)
Outer gloves (neoprene, nitrile, or other)
Disposable inner gloves (latex or vinyl)
Boots with steel-toe protection and steel shanks
Disposable boot covers or chemical-resistant outer boots
A NIOSH-approved, pressure-demand airline respirator with a 5-minute escape cylinder or self-
contained breathing apparatus (SCBA)
A hard hat (face shield optional)
Hearing protection (for areas with a noise level that exceeds 85 decibels on the A-weighted scale)
10.5.2 Reassessment of Protection Levels
PPE levels will be upgraded or downgraded based on a change in site conditions or findings of the
investigation. Hazards will be reassessed when site conditions change significantly. Some indicators of
the need for reassessment are as follows:
• A change in tasks during a work phase
• A change of season or weather
• Temperature extremes or individual medical considerations that could limit the effectiveness of
PPE
• Discovery of contaminants other than those previously identified
• A change in the scope of work that affects the degree of contact with contaminated media
10.5.3 Limitations of Protective Clothing
PPE clothing ensembles designated for use during the demonstration have been selected to protect against
contaminants at known or anticipated on-site concentrations and physical states. However, no protective
garment, glove, or boot is entirely chemical-resistant, and no protective clothing protects against all types
of chemicals. Permeation of a given chemical through PPE depends on the contaminant concentration,
environmental conditions, physical condition of the protective garment, and resistance of the garment to
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the specific contaminant. Chemical permeation may continue even after the source of contamination has
been removed from the garment. All on-site personnel will use the procedures presented below to obtain
optimum performance from PPE.
• When chemical-protective coveralls become contaminated, don a new, clean garment after each
rest break or at the beginning.of each shift
• Inspect all clothing, gloves, and boots both before and during use for the following:
o Imperfect seams
o Nonuniform coatings
o Tears
o Poorly functioning closures
• Inspect reusable garments, boots, and gloves both before and during use for visible signs of
'chemicalpermeation, such as the following:
o Swelling
o Discoloration
o Stiffness
o Brittleness
o Cracks
o Any sign of puncture
o Any sign of abrasion
Reusable gloves, boots, or coveralls that exhibit any of the characteristics listed above must be discarded.
Reusable PPE will be decontaminated in accordance with the procedures described in Section 10.9 and
will be neatly stored in the support zone away from work zones.
10.5.4 Respirator Selection, Use, and Maintenance
Use of respirators is not anticipated for this demonstration. Inorganic contaminants are the primary
contaminants of concern (COCs) associated with the KARS Park site. In addition, materials that will be
handled during the demonstration will be laboratory-prepared soil and sediment samples contained in
wide mouth jars. Field activities will not be conducted in contaminated areas and will not include
intrusive sampling or excavation of contaminated materials. For these reasons, a significant potential for
generation of, or exposure to, airborne dusts that could contain particulate inorganic contaminants is not
anticipated. Tetra Tech maintains a respiratory protection program for its employees, and respiratory
protection can be provided for field personnel should on-site conditions differ from those anticipated.
10i.6 Medical Surveillance
The following sections describe Tetra Tech's medical surveillance program, including requirements for
health monitoring, site-specific medical monitoring, and medical support and follow-up. Procedures
documented in these sections will be followed for all activities at the KARS Park site. Additional
requirements are defined in the Tetra Tech, Inc., "Health and Safety Manual."
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10.6.1 Health Monitoring Requirements
All Tetra Tech personnel involved in on-site activities at the KARS Park site must participate in a health
monitoring program, as required by 29 CFR 1910.120(f). Tetra Tech has established a health monitoring
program with WorkCare, Inc., of Orange, California. Under this program, Tetra Tech personnel receive
baseline and annual or biennial physical examinations that consist of the following:
• Complete medical and work history
• Physical examination
• Vision screening
• Audiometric screening
• Pulmonary function test
• Resting electrocardiogram
• Chest x-ray (required once every 3 years)
• Blood chemistry, including hematology and serum
• Urinalysis
Tetra Tech receives a copy of the examining physician's written opinion for each employee after post-
examination laboratory tests have been completed; the Tetra Tech employee also receives a copy of the
written opinion. This opinion includes the following information (in accordance with 29 CFR
1910.120[f][7]):
• The results of the medic al examination and tests.
• The physician's opinion as to whether the employee has any medical conditions that would place
the employee at an increased risk of health impairment from work involving hazardous waste
operations or during an emergency response.
• The physician's recommended limitations, if any, on the employee's assigned work; special
emphasis is placed on fitness for duty, including the ability to wear any required PPE and
respirators under conditions expected on site (for example, temperature extremes).
• A statement that the employee has been informed by the physician of the results of the medical
examination and of any medical conditions that require further examination or treatment.
10.6.2 Site-Specific Medical Monitoring
No specific medical tests will be required before staff enter the exclusion or decontamination zone for
activities at the KARS Park site (see Section 10.8.2, Site Control Zones).
10.6.3 Medical Support and Follow-up Requirements
All Tetra Tech employees are entitled to and encouraged to seek medical attention and physical testing as
a follow-up to an injury that requires care beyond basic first aid or to possible exposure above established
exposure limits. These injuries and exposures must be reported to the Terra Tech HSR. Depending on
the type of injury or exposure, follow-up testing, if required, must be administered within 24 to 48 hours
of the incident. Tetra Tech's medical consultant is responsible for advising the type of test required to
accurately monitor for exposure effects. The Accident and Illness Investigation Report (included in
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Appendix C) must be completed by the Tetra Tech SSC in the event of an accident, illness, or injury. A
copy of this form must be forwarded to the HSR for use in assessing the recordability of the incident and
for inclusion in Tetra Tech's medical surveillance records.
10.7 Environmental Monitoring and Sampling
Historical site characterization and sampling completed during the pre-demonstration phase characterized
the potential chemical hazards associated with the materials at the KARS Park site. The potential for on-
site personnel to be exposed to inorganic compounds and VOCs at the site during the demonstration is
low. These data were used to assess personnel exposure levels as well as site conditions and to establish
appropriate levels of PPE. Air monitoring will not be required for this demonstration. No heavy
equipment that will generate high noise levels will be used; therefore, noise monitoring will not be
required.
Additional monitoring that will be required for the demonstration will be limited to thermal stress. Heat
stress and cold stress are common and serious threats at hazardous waste sites. The field demonstration is
anticipated to occur in South Florida in January. Risk of heat stress will be reduced because of the
moderate ambient temperatures typically encountered in the demonstration area in January and also based
on the limited PPE that will be required. Weather conditions conducive to cold stress are unlikely to
occur in southern Florida.
10.8 Site Control
Site control is an essential component of implementing health and safety procedures. The following
sections discuss measures and procedures for site control, including on-site communications, site control
zones, site access control, site safety inspections, and SWPs.
10.8.1 On-Site Communications
Successful communication between field teams and personnel in the support zone is essential. Cellular
telephones will be available during the demonstration to facilitate communications.
The hand signals listed below will be used by on-site personnel in emergencies or when verbal
communication is difficult.
Signal Definition
Hands clutching throat Out of air or cannot breathe
Hands on top of head Need assistance
Thumbs up Okay, I am all right, or I understand
Thumbs down No or negative
Arms waving upright Send backup support
Gripping partner's wrist Exit area immediately
10.8.2 Site Control Zones
On-site work areas may be divided into an exclusion zone, a decontamination zone, and a support zone to
control the spread of contamination and employee exposures to chemical and physical hazards. Access to
the exclusion and decontamination zones will be restricted to authorized personnel Any visitors to these
areas must present proper identification and be authorized to be on site. The Tetra Tech SSC will identify
areas that visitors or personnel are authorized to enter and will enforce site control measures. The
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following sections describe the exclusion zone, the decontamination zone, and the support zone, as well
as procedures to be followed in each.
10.8.3 Site Access Control
A security guard stationed at the entrance to KARS Park screens all potential visitors to limit park access
to NASA employees and invited guests. The instruments will be set up in a conference building in the
park near the shooting range that will be locked after hours. The former shooting range is fenced to limit
area access and contains the areas with the most significant amounts of contamination at the site. Site
representatives will be present during the demonstration to control visitor access. Tetra Tech
representatives will be present at all times during the demonstration and will be responsible for
management of technology developer personnel while on site. Each technology developer must be
responsible for securing its equipment against tampering or theft because restricted access to the site can
not be guaranteed. All equipment must be secured at the end of activities each day.
10.8.4 Site Safety Inspections
The Tetra Tech SSC will conduct periodic site safety inspections to ensure safe work areas and
compliance with the health and safety procedures described in this section. Results of the site safety
inspections will be recorded in the field logbook or on a Field Audit Checklist, included in Appendix C.
If venomous snakes or alligators are observed in or near the perimeter of the demonstration area, the SSC
will notify on-site personnel, ensure that personnel avoid the area, and notify the site representative if the
problem persists.
10.8.5 Safe Work Practices
The following SWPs apply to the demonstration. These SWPs will be available on site.
• S WP 6-1, General Safe Work Practices
• SWP 6-14, Spill and Discharge Control Practices
• SWP 6-15, Heat Stress
10.9 Decontamination
Decontamination is the process of removing or neutralizing contaminants on personnel or equipment.
When properly conducted, decontamination procedures protect workers from contaminants that may have
accumulated on PPE, tools, and other equipment. Although site activities will not likely require
decontamination personnel or equipment, procedures are included in the event that site conditions or
activities change. Proper decontamination also prevents transport of potentially harmful materials to
uncontaminated areas. Personnel and equipment decontamination procedures are described in the
following sections.
10.9.1 Personnel Decontamination
The need for personnel decontamination at the demonstration site will be limited by using disposable PPE
whenever possible. Any personnel decontamination procedures will follow guidance in the Occupational
Safety and Health Guidance Manual for Hazardous Waste Site Activities (NIOSH and others 1985).
Liquid and solid wastes generated during decontamination will be collected and drummed. Additional
decontamination procedures listed below will be implemented if personnel decontamination is required;
however, their use is currently not anticipated:
94
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• Wash neoprene boots or disposable booties with a Liquinox or Alconox solution, and rinse them
with water. Remove and retain neoprene boots for reuse, if possible. Place disposable booties in
plastic bags for disposal.
• Wash outer gloves in a Liquinox or Alconox solution, and rinse them in water. Remove outer
gloves, and place them in a plastic bag for disposal.
• Remove chemical-resistant clothing, and place it in a plastic bag for disposal.
• Remove the air-purifying respirator, if used, and place the spent filter in a plastic bag for disposal.
Change the filter in accordance with the Respiratory Hazard Assessment Form included in
Appendix C. Clean and disinfect the respirator and place it in a plastic bag for storage.
• Remove inner gloves, and place them in a plastic bag for disposal.
• Thoroughly wash the hands and face with water and soap.
Used, disposable PPE will be collected in scalable containers and will be disposed of in accordance with
local environmental regulations. Personnel decontamination procedures may be modified on site, if
necessary.
10.9.2 Equipment Decontamination
Field sampling and, thus, decontamination of sampling and field monitoring equipment is not anticipated
to be required. If required, the general procedures will be as follows:
• Scrub the equipment with a brush in a bucket that contains Liquinox or Alconox solution and
distilled water.
• Triple-rinse the equipment with distilled water, and allow it to air dry.
• Reassemble the equipment, and place it on plastic or aluminum foil in a clean area. If aluminum
foil is used, wrap the equipment with the dull side of the aluminum foil toward the equipment.
10.10 Emergency Response Planning
This section describes emergency response planning procedures to be implemented for the demonstration.
This section is consistent with local, state, and federal disaster and emergency management plans. The
following sections discuss pre-emergency planning, personnel roles and lines of authority, emergency
recognition and prevention, evacuation routes and procedures, emergency contacts and notifications,
hospital route directions, emergency medical treatment procedures, protective equipment failure, fire or
explosion, weather-related emergencies, spills or leaks, emergency equipment and facilities, and
reporting.
10.10.1 Pre-emergency Planning
All on-site employees will be trained in and reminded of the provisions of Section 10.10, site
communication systems, and site evacuation routes during the pre-work briefing and daily tailgate safety
meetings. The emergency response provisions will be reviewed regularly by the Tetra Tech SSC and will
be revised, if necessary, to ensure that they are adequate and consistent with prevailing site conditions.
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10.10.2 Personnel Roles and Lines of Authority
The Tetra Tech SSC has primary responsibility for responding to and correcting emergencies and for
taking appropriate measures to ensure the safety of on-site personnel and the public. Possible actions may
include evacuation of personnel from the site. The SSC is also responsible for ensuring that corrective
measures have been implemented, appropriate authorities have been notified, and follow-up reports have
been completed. Personnel are required to report all injuries, illnesses, spills, fires, and property damage
to the SSC. The SSC must be notified of any on-site emergencies and is responsible for ensuring that the
emergency procedures described in this section are followed.
10.10.3 Emergency Recognition and Prevention
Table 10-1 provides information on the hazards associated with the various tasks planned for the
demonstration site. On-site personnel will be made familiar with this information and with the techniques
of hazard recognition through pre-work training and site briefings.
10.10.4 Evacuation Routes and Procedures
In the event of an emergency that necessitates evacuation of a work area or the site, the Tetra Tech SSC
will contact all nearby personnel using the on-site communications discussed in Section 10.8.1 to advise
personnel of the emergency. The personnel will proceed along roads at the site to a safe area upwind
from the source of the hazard. The personnel will remain in that area until the SSC or an authorized
individual provides further instructions.
10.10.5 Emergency Contacts and Notifications
The Health and Safety Plan in Appendix B provides the names and telephone numbers of emergency
contact personnel for the KARS Park site. The information in these appendixes must be posted on site or
must be readily available at all times. In the event of a medical emergency, personnel will notify the
appropriate emergency organization and will take direction from the Tetra Tech SSC. In the event of a
fire, explosion, or spill at a site, the SSC will notify the appropriate local, state, and federal agencies and
will follow the procedures discussed in Sections 10.10.9 or 10.10.11.
10.10.6 Hospital Route Directions
Before the demonstration begins at the site, Tetra Tech personnel will conduct a pre-emergency run to
familiarize themselves with the route to the local hospital. A map that shows the route to the hospital is
provided in Appendix B. This map must be posted on site.
10.10.7 Emergency Medical Treatment Procedures
A person who becomes ill or injured during work may require decontamination. If the illness or injury is
minor, any decontamination necessary will be completed and first aid will be administered before the
patient is transported. If the patient's condition is serious, partial decontamination will be completed at a
minimum (such as complete disrobing of the person and redressing the person in clean coveralls or
wrapping the person in a blanket). First aid will be administered until an ambulance or paramedics arrive.
All injuries and illnesses must be immediately reported to the Tetra Tech project manager and HSR.
Any person transported to a clinic or hospital for treatment for chemical exposure will be accompanied by
information on the chemical that he or she has been exposed to at the site, if possible.
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10.10.8 Protective Equipment Failure
If any worker in the exclusion zone experiences a failure of protective equipment (either engineering
controls or PPE) that affects his or her personal protection, the worker and all coworkers will immediately
leave the exclusion zone. Re-entry to the exclusion zone will not be permitted until (1) the protective
equipment has been repaired or replaced, (2) the cause of the equipment failure has been identified, and
(3) the equipment failure is no longer considered a threat.
10.10.9 Fire or Explosion
The local fire department will be immediately summoned in the event of a fire or explosion on site. The
Tetra Tech SSC or a site representative will advise the fire department of the location and nature of any
hazardous materials involved. On-site personnel will implement the provisions of Section 10.10.
10.10.10 Weather-Related Emergencies
Site work will not be conducted during severe weather, including high-speed winds or lightning. In the
event of severe weather, field personnel will stop work, secure and lower all equipment, and leave the
site. Thermal stress caused by excessive heat may occur as a result of extreme temperatures, workload, or
the PPE used. Heat stress treatment will be administered as described in SWPs, which will be available
on site. Cold stress is not anticipated during the demonstration.
10.10.11 Spills or Leaks
In the event of a severe spill or a leak, site personnel will follow the procedures listed below.
• Evacuate the affected area, and relocate personnel to an upwind location.
• Inform the Tetra Tech SSC, a Tetra Tech office, and a site representative immediately.
• Locate the source of the spill or leak, and stop the flow if it is safe to do so.
• Begin containment and recovery of spilled or leaked materials.
• Notify appropriate local, state, and federal agencies.
• Additional information on spill and leak control is presented in the SWPs, which will be available
on site.
10.10.12 Emergency Equipment and Facilities
The following emergency equipment and facilities will be available on site:
• First-aid kit
• Eye wash (portable)
• Fire extinguisher
• Site telephone
• Cellular telephone
• Drums
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10.10.13 Reporting
All emergencies require follow-up and reporting. Appendix C contains the Tetra Tech Accident and
Illness Investigation Report. This report must be completed and submitted to the Tetra Tech project
manager within 24 hours of an emergency. The project manager will review the report and then forward
it to the Tetra Tech HSR for review. The report must include proposed actions to prevent similar
incidents from occurring.
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Chapter 11
References
California Regional Water Quality Control Board, Lahontan Region. 1995. Leviathan Mine 5-Year
' Work Plan. July.
Gilbert, R. O., 1987. Statistical Methods for Environmental Pollution Monitoring. VanNostrand
Reinhold, New York.
National Institute for Occupational Safety and Health. 1985. Occupational Safety and Health Guidance
Manual for Hazardous Waste Site Activities.
Tetra Tech EM Inc. (Tetra Tech). 2004. Pre-demonstration Sampling and Analyst Plan. Prepared for:
U.S. Environmental Protection Agency, Superfund Innovative Technology Evaluation Program.
July 21.
U.S. Environmental Protection Agency (EPA). 1995. "Handbook for Preparing Office of Research and
Development Reports." ORD. Washington, DC, EPA/600/K-95-002. August.
EPA. 1996a. "A Guidance Manual for the Preparation of Site Characterization and Monitoring
Technology Demonstration Plans." NERL. October.
EPA, 1996b. "TN Spectrace TN 9000 and TN Pb Field Portable X-ray Fluorescence Analyzers."
EPA/600/R-97/145. March.
EPA, 1996c. "Field Portable X-ray Fluorescence Analyzer HNU Systems SEFA-P." EPA/600/R-97/144.
March.
EPA. 1996d. "Test Methods for Evaluating Solid Waste, Physical/Chemical Methods (SW-846)."
December.
EPA. 1998a. "Quality Assurance Project Plan Requirements for Applied Research Projects."
Unpublished. NRMRL.
EPA, 1998b. "Environmental Technology Verification Report; Field Portable X-ray Fluorescence
Analyzer, Metorex X-Met 920-MP", EPA/600/R-97/151. March.
EPA, 1998c. "Environmental Technology Verification Report; Field Portable X-ray Fluorescence
Analyzer, Niton XL Spectrum Analyzer." EPA/600/R-97/150. March.
EPA, 1998d. "Scitect MAP Spectrum Analyzer Field Portable X-Ray Fluorescence Anafyzers."
EPA/600/R-97/147. March.
EPA, 1998e. "Metorex X-MET 920-P and 940 Field Portable X-ray Fluorescence Analyzers."
EPA/600/R-97/146. March.
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EPA. 1998f. "Handbook for Preparing Office of Research and Development Reports." March 16.
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.
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Appendix A
Pre-demonstration Sampling and Analysis Plan
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Pre-demonstration
Sampling and Analysis Plan
Demonstration of
XRF Technologies for
Measuring Trace Elements in
Soil and Sediment
Prepared by:
Tetra Tech EM Inc.
Cincinnati, Ohio
Contract No. 68-C-00-181
Dr. Stephen Billets
Environmental Sciences Division
National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Las Vegas, Nevada 89119
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Concurrence Signatures
The primary purpose of the demonstration is to evaluate XRF technologies for measuring trace elements in
soil and sediment based on their performance and cost as compared with conventional, off-site laboratory
analytical methods. The demonstration will take place under the sponsorship of the U.S. Environmental
Protection Agency Superfund Innovative Technology Evaluation Program.
This document is intended to ensure that all aspects of pre-demonstration sample material collection and
characterization are documented and scientifically sound and that operational procedures are conducted in
accordance with quality assurance and quality control specifications.
The signatures of the individuals listed below indicate their concurrence with and agreement to operate in
compliance with the procedures specified in this document.
Stephen Billets Date
EPA Project Manager
Julia Capri Date
Terra Tech Project Manager
Candy Friday Date
Terra Tech Quality Assurance Manager
Dan Gillespie Date
ADRL Technical Services Manager
Richard Curtain Date
ARDL Laboratory QA Manager
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CONTENTS
SECTION PAGE
Acronyms List v
1.0 Introduction 1
1.1 Project Background and Objectives 2
1.2 Project Organization 6
1.2.1 EPA Project Personnel 6
1.2.2 Tetra Tech Project Personnel 6
1.2.3 Demonstration Site Representatives 9
1.2.4 Laboratory Project Personnel 9
2.0 Field Screening and Sampling Procedures 10
2.1 XRF Field Screening Procedures 10
2.2 Soil and Sediment Sampling Procedures 11
2.3 Sample Processing Procedures 13
2.4 Sample Integrity Requirements 15
2.4.1 Sample Labeling 15
2.4.2 Sample Containers, Preservation, and Holding Times 16
2.4.3 Sample Custody and Shipping Procedures 17
2.5 Equipment Decontamination 18
2.6 Investigation-Derived Waste Management 18
3.0 Testing and Measurement Protocols 18
4.0 Quality Assurance/Quality Control Procedures 21
4.1 Field QA/QC Procedures 22
4.1.1 Calibration 22
4.1.2 Blank Sample Check. 22
4.1.3 Target Analyte Response Check 22
4.1.4 Duplicate Measurements 23
4.2 Laboratory QA/QC Procedures 23
4.2.1 Instrument Calibration Check 23
4.2.2 Method Blanks 24
4.2.3 Interference Check Sample 24
4.2.4 Laboratory Control Sample 25
4.2.5 Matrix Spikes and Matrix Spike Duplicates 25
5.0 Data Reduction, Validation, and Reporting 25
5.1 Data Reduction 26
5.2 Data Validation 27
5.3 Reporting Requirements 27
5.4 Data Management 28
6.0 References 31
in
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CONTENTS (Continued)
Tables
1 Demonstration of XRF Technologies for Measuring Trace Elements in Soil
and Sediment, Preliminary List of Demonstration and Sampling Sites 4
2 Pre-operational XRF Checks 11
3 Analytical Methods for Total Elements 19
4 Detection Limits Required for Field Screening XRF 20
5 Target Analytes and Required Method Detection Limits 21
Figures
1 Project Organization Chart 8
2 Scribe System Overview 29
Addendum
Site-Specific Field Sampling Plans
IV
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ACRONYMS LIST
Ag Silver
ARDL Applied Research and Development Laboratory, Inc.
As Arsenic
ASARCO American Smelting and Refining Company
Cd Cadmium
CIH Certified industrial hygienist
Cr Chromium
Cu Copper
CVAA Cold vapor atomic absorption
DER Data evaluation report
EPA U.S. Environmental Protection Agency
ERT Environmental Response Team
ES&H Environmental Safety and Health
Fe Iron
GPS Global positioning system
Hg Mercury
ICP-AES Inductively coupled plasma - atomic emission spectrometer
ICS Interference check sample
IDW Investigation-derived waste
ITVR Innovative Technology Verification Report
KARS Kennedy Athletic, Recreational and Social (Park)
kg Kilogram
LCS Laboratory control sample
LIMS Laboratory information management system
MDL Method detection limit
mg/kg Milligram per kilogram
MMT Monitoring and measurement technology
MS Matrix spike
MSD Matrix spike duplicate
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ACRONYMS LIST (Continued)
NERL National Exposure Research Laboratory
Ni Nickel
ORD Office of Research and Development
OSWER Office of Solid Waste and Emergency Response
Pb Lead
PDA Personal digital assistant
pdf Portable document format
PPE Personal protective equipment
QA Quality assurance
QC Quality control
RPD Relative percent difference
SAP Sampling and analysis plan
Se Selenium
SITE Superfund Innovative Technology Evaluation
SOP Standard operating procedure
TBD To be determined
Tetra Tech Tetra Tech EM Inc.
V
XRF
Zn
Vanadium
X-ray fluorescence
Zinc
VI
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1.0 INTRODUCTION
The U.S. Environmental Protection Agency (EPA) Office of Research and Development (ORD) National
Exposure Research Laboratory (NERL) has contracted with Tetra Tech EM Inc. (Tetra Tech) to conduct
a demonstration of innovative field measurement instruments for 13 target analyte elements (antimony,
arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel, selenium, silver, vanadium, and zinc) in
soil and sediment using field-portable x-ray fluorescence (XRF) instruments. The demonstration is being
conducted as part of the EPA Superfund Innovative Technology Evaluation (SITE) Monitoring and
Measurement Technology (MMT) Project.
This pre-demonstration sampling and analysis plan (SAP) describes the procedures that will be used to
collect bulk material and to prepare and characterize soil and sediment batch samples that contain the
target analytes for use as reference material in the demonstration of field-portable XRF analysis. The goal
of the demonstration is to verify the performance and associated cost of each XRF instrument. This SAP
incorporates the quality assurance and quality control (QA/QC) elements that are needed to generate data
of sufficient quality to document the preparation and characterization of each batch of reference material
for use in the demonstration. This SAP has been prepared using the NERL document, "A Guidance
Manual for the Preparation of Site Characterization and Monitoring Technology Demonstration Plans"
(EPA 1996a).
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 (OSWER) 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
the 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 the 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) develop procedures and policies that encourage use of innovative
technologies at Superfund sites as well as at other waste sites or commercial facilities.
The intent of a SITE demonstration is to obtain representative, high-quality data on performance and cost
on one or more innovative technologies so that potential users can assess a technology's suitability for a
specific application.
1
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The MMT project provides developers of innovative hazardous waste sampling, monitoring, and
measurement technologies with an opportunity to demonstrate performance of their devices under actual
field conditions. These devices may be used to sample, detect, monitor, or measure hazardous and toxic
substances in water, soil, soil gas, and sediment. The technologies include chemical sensors for in situ (in
place) measurements, groundwater samplers, soil and sediment samplers, soil gas samplers, field-portable
analytical equipment, and other systems that support field sampling or data acquisition and analysis.
The Environmental Sciences Division of NERL, in Las Vegas, Nevada, administers the MMT project
NERL is EPA's center for investigation of technical and management approaches to identify and quantify
risks to human health and the environment. The components of NERL's mission include (1) developing
and evaluating methods and technologies for sampling, monitoring, and characterizing water, air, soil, and
sediment; (2) supporting regulatory and policy decisions; and (3) providing the technical support needed to
ensure effective implementation of environmental regulations and strategies. By demonstrating selected
innovative field XRF instruments for measuring elements in soil and sediment, the MMT project is
supporting development and evaluation of methods and technologies for field measurement of the
concentrations of elements in a variety of soil and sediment matrices.
1.1 Project Background and Objectives
The objective of the pre-demonstration is to collect soil and sediment for characterizing and processing into
batches of media (soil and sediment) that contain the target analytes from selected sampling sites. The
sample material collected will be homogenized into batches and characterized for the content of each
target element. Batches will be blended to produce a minimum of 200 unique sample sets that contain
varying concentrations of elements to analyze the performance of the technology.
The following sites were selected as candidates for collection of soil or sediment samples (or both) for the
demonstration:
• Kennedy Athletic, Recreational and Social Park, Kennedy Space Center, Merritt
Island, Florida - Soil and swamp sediment sampling areas at the park are contaminated by
elements from a former gun range. Antimony, arsenic, chromium, copper, lead, and zinc have
been identified in sandy soil and sediment matrices.
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• Burlington Northern Railroad-ASARCO East Helena Smelter Site, East Helena,
Montana - This area of a railroad yard was a staging area for smelter ores; contaminated
soils resulted from intentional dumping and unintentional spillage of highly concentrated ores.
Elements of concern at this site include lead, copper, zinc, arsenic, cadmium, and possibly
others.
• Crane Naval Surface Warfare Center, Crane, Indiana - Portions of the base were used
for open disposal and burning of general refuse and waste associated with aircraft
maintenance. Antimony, arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel,
silver, and zinc have been identified in soil and sediment media in the area.
• Wickes Smelter Site, Jefferson City, Montana - The site is an abandoned smelter
complex with contaminated soils and mineral-processing wastes, including remnant ore piles,
decomposed roaster brick, slag piles and fines, amalgamation sediments with some mercury,
and other contaminated materials. Arsenic, cadmium, copper, lead, mercury, and zinc have
been identified in soil at the site.
• Leviathan Mine Site, Leviathan and Aspen Creek, Alpine County, California - This
abandoned open-pit sulfur mining operation has contaminated a 9-mile stretch of Leviathan
and Aspen Creeks with heavy metals. Antimony, arsenic, cadmium, chromium, copper, iron,
lead, mercury, nickel, selenium, silver, vanadium, and zinc have been identified in soil and
sediments in and around this area.
• Great Lakes Area of Concern, Torch Lake Site, Houghton County, Michigan - This
area of concern contains widely scattered deposits from 100 years of copper mining, milling,
smelting, and recovery. Wastes are found in an upland area and in the lake and occur in four
forms: poor rock piles, slag and slag-enriched sediments, stamp sands, and abandoned settling
ponds for mine slurry. Arsenic, chromium, copper, lead, mercury, and silver have been
identified in sediment on this site.
• Alton Steel, Alton, Illinois - Soil at this steel manufacturing facility is contaminated
primarily from metal arc furnace dust. The site also includes a metal scrap yard and a slag
recovery facility. Cadmium, chromium, iron, lead, nickel, and zinc have been identified in soil
and sediment in this area.
• Rocky Mountain Arsenal - The arsenal includes 17,000 acres of land where chemical
weapons, such as mustard gas, white phosphorus, and napalm, as well as agricultural
pesticides, were manufactured. No chemicals or chemical weapons are now produced or
stored at the facility. This site is believed to contain soil with naturally occurring selenium and
antimony.
Both contaminated "hot spots" and unspoiled or "clean" soil and sediment will be collected for blending
into sample batches to produce sufficient material to provide a minimum of 200 samples at varying
concentrations of target analytes. Contaminated areas will be identified from site owners or by review of
historical data. Unspoiled blend material will be collected from the least-contaminated areas at the site. A
complete list of all potential sites and contact information for the demonstration is included in Table 1.
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Table 1.
Demonstration of XRF Technologies for Measuring Trace Elements in Soil and Sediment
Preliminary List of Demonstration and Sampling Sites
Demonstration & Sampling
Sites
Kennedy Athletic, Recreational
and Social Park,
Kennedy Space Center, Merritt
Island, Florida
Michael Deliz (321) 867-6971
Burlington Northern
Railroad/ASARCO East Helena,
Smelter Site -East Helena,
Montana
Scott Brown (406) 457-5035
Crane Naval Surface Warfare
Center - Crane, Indiana
Peter Ramanauskus (312) 886-
7890
Wickes Smelter Site
Jefferson City, Montana
Vic Andersen (406) 841-5025
Relative
Ranking
Host Site
1
2
3
Sources of Contamination
Demonstration Site
Park just outside the Kennedy Space
Center with contaminants in soil and
swamp sediment from former gun
range operations.
Sampling Sites
Railroad yard staging area for
smelter ores. Contaminated soils
resulted from intentional dumping
and unintentional spillage of highly
concentrated ores containing lead,
copper, and zinc. Other elements
include arsenic, cadmium, and
others.
Areas of the base were used for
open disposal and burning of general
refuse and waste associated with
aircraft maintenance.
Abandoned smelter complex with
contaminated soils and mineral-
processing wastes, including remnant
one piles, decomposed roaster brick,
slag piles and fines, amalgamation
sediments with some mercury, and
other contaminated materials.
Matrix
(soil/sediment
)
Soil and
Sediment
Soil
Soil
Soil
Potential Elements & Maximum
Concentrations (mg/kg) of Concern
for XRF Demonstration
Sb, As, Cr, Cu, Pb, and Zn
As, Cd, Cu, Pb, and Zn
Sb, As, Cd, Cr, Cu, Fe, Pb, Hg, Ni, Ag,
andZn
As, Cd, Cu, Pb, Hg, and Zn
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Table 1. (Continued)
Demonstration of XRF Technologies for Measuring Trace Elements in Soil and Sediment
Preliminary List of Demonstration and Sampling Sites
Demonstration & Sampling
Sites
Relative
Ranking
Sources of Contamination
Matrix
(soil/sediment
)
Potential Elements & Maximum
Concentrations (mg/kg) of Concern
for XRF Demonstration
Sampling Sites (Continued)
Leviathan Mine Site/Leviathan
Creek
Alpine County, California
Kevin Mayer (415) 972-3176
Great Lakes Area of Concern,
Torch Lake Site
Houghton County, Michigan
Brenda Jones (312) 886-7188
Alton Steel
Alton, Illinois
Jeannine Kelly
(618) 463-4490 (ext. 2533)
Rocky Mountain Arsenal,
Commerce City, Colorado
Contact TBD
4
5
6
7
Leviathan is an abandoned open-pit
sulfur mining operation that
contaminated a 9-mile stretch of
Leviathan Creek with heavy metals.
Widely scattered deposits from 100
years of copper mining, milling,
smelting, and recovery. Wastes
occur both on the uplands and in the
lake and are found in four forms:
poor rock piles, slag and slag-
enriched sediments, stamp sands, and
abandoned settling ponds for mine
slurry.
Steel manufacturing facility where
soils are contaminated by metals
from metal arc furnace dust. The
site also has a metal scrap yard and a
slag recovery facility.
Former U.S. Army arsenal that is
undergoing remediation. Selenium
and antimony are found to naturally
occur in soil at this site.
Soil and
Sediment
Soil and
Sediment
Soil
Soil
Sb, As, Cd, Cr, Cu, Fe, Pb, Hg, Ni, Se,
Ag, V, and Zn
As, Cr, Cu, Pb, and Hg
Cd, Cr, Fe, Pb, Ni, and Zn
Sb and Se
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Tetra Tech will prepare a field sampling plan for each site where sample material is collected for the
demonstration. In preparing this site-specific plan, information on the site owner and historical data will
be used to identify target areas for directing screening operations. This plan will include background
information on the site, a map that details target collection areas for sample material, and instructions
for sampling and collecting source material. Site-specific requirements will also be identified for field
screening using field-portable XRF unit with global positioning systems (GPS) to guide and document
sample location. Finally, the site-specific field sampling plans will specify the requirements for
confirmation analysis by a fixed laboratory.
The field sampling plan will be submitted to site representatives and sampling teams for review and
concurrence before activities begin at each site and will be incorporated into this pre-demonstration
SAP in the form of an attachment.
1.2 Project Organization
A cooperative effort that involves several government agencies and private parties is required for the
success of these pre-demonstration activities. This section identifies key project personnel and
summarizes their responsibilities during this demonstration. Figure 1 is an organizational chart that
shows key project personnel and the lines of communication among them.
1.2.1 EPA Project Personnel
The EPA project manager, Dr. Stephen Billets, has overall responsibility for the project. Dr. Billets will
review and concur with the project deliverables, including the SAP, demonstration plan, fact sheets,
Innovative Technology Verification Reports (ITVRs), and the Data Evaluation Report (DER).
The EPA NERL QA officer, George Brilis, will ensure that the project conforms to the quality
standards established by the EPA and is responsible for reviewing and concurring with the quality
assurance and demonstration plan.
1.2.2 Tetra Tech Project Personnel
The Tetra Tech project manager, Julia Capri, is responsible for day-to-day management of Tetra Tech
project personnel, maintaining direct communication with EPA and the developers, and ensuring that all
Tetra Tech personnel involved in the pre-demonstration sampling and analysis understand and comply
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with the pre-demonstration SAP. Ms. Capri is also responsible for distributing the draft and final pre-
demonstration plans to all key project personnel and for reviewing measurement and analytical data
obtained during the pre-demonstration. Tetra Tech project personnel will assist Ms. Capri in preparing
project deliverables and in day-to-day project activities.
In consultation with the EPA, Tetra Tech project personnel are responsible for the following elements
of the demonstration:
• Developing and implementing all elements of this demonstration plan.
• Scheduling and coordinating the activities of all participants in the demonstration.
• Coordinating collection of samples, homogenizing samples, and performing characterization
analysis for elements of concern.
• Coordinating meetings among the EPA, the developers, and the demonstration panel.
• Providing required planning, scheduling, cost control, documentation, and data management for
field activities.
• Managing mobilization.
• Immediately communicating any deviation from the demonstration plan during field activities to
the EPA program manager and discussing appropriate resolutions of the deviation.
• Interfacing with the demonstration site representatives and making logistical preparations for
the demonstration.
The deputy project manager, Dr. Ed Surbrugg, is responsible for providing technical support and review
for demonstration planning activities, including planning and implementing the pre-demonstration SAP.
Dr. Surbrugg will also contribute as technical reviewer for the technology observation team.
Pre-demonstration sampling team leaders, Christopher Reynolds and Robert Porges, are responsible for
field sample collection and for reporting site conditions to the project manager. Sample team leaders
will monitor sample collection, as well as preparation and delivery to the characterization laboratory to
ensure that procedures set forth in the SAP are followed. Sample team leaders will also ensure that
chain-of-custody procedures and applicable U.S. Department of Transportation shipping regulations are
followed for sample shipment from the sample collection sites to the pre-demonstration site and
characterization laboratory, as well as from the pre-demonstration site to the reference laboratory.
The project QA manager, Candy Friday, is responsible for overall project QA. She will work with the
entire project team to set up, implement, and evaluate QA criteria for the pre-demonstration. In
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FIGURE 1.
PROJECT ORGANIZATION CHART
EPA NERL
QA Officer
George Brills
Demonstration Site
Representative
Kennedy Space Center
Michael Deliz
Mark Speranza
EPA SITE MMT
Project Manager
Dr. Stephen Billets
Field XRF Vendors
Innov-X Systems Inc — Rose Koch
NITON Corp. - Dave Mercuro
Oxford Instruments Portable - John Patterson
Oxford Instruments Analytical - Rune Gehrlein
Rigaku, Inc. - John Martin
RONTEC USA Inc. - Paul Smith
- Yralihnr YRF ^prvip^Q Inr Rnn Will lame
XRF Corporation - Tom Hazlett
Sampling Site Representatives
Burlington Northern/ASARCO East
Helena Smelter Site - Scott Brown
Atlas Mint; and Mill Site - Linda
Lanham
Wickes Smelter Site - Vic Andersen
Leviathan Mine Site - Kevin Mayer
Torch Lake Site - Brenda Jones
Crane Naval Warfare Center -
Peter Ramanauskus
Alton Steel - Jeannine Kelly
I
Characterization
Laboratory Manager
ARDL
Dan Gillespie
Laboratory
QA Manager
Dick Curtain
Tetra Tech SITE MMT
Project Manager
Julia Capri
Deputy Project
Manager
Dr. Ed Surbrugg
Tetra Tech Project Staff
Mark Colsman
Butch Fries
Stanley Lynn
Ron Ohta
Alan Pate
Robert Porges
Chris Reynolds
Stephanie Wenninq
Tetra Tech
Health & Safety Mgr.
James Romine, CIH
Tetra Tech Project
QA Manager
Candy Friday
PE Sample Laboratory
Environmental Resource
Associates
John Laferty
Reference
Laboratory Manager
TBD
Laboratory
QA Manager
TBD
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addition, Ms. Friday will be responsible for selecting, auditing, and providing oversight of contractor
laboratories assigned the material characterization and reference analyses. She will be responsible for
evaluating all analytical data and their usability for meeting the project objectives.
Tetra Tech's environmental safety and health representative, James Romine, CIH, will review the site-
specific health and safety procedures and ensure compliance with the requirements of the Tetra Tech
corporate health and safety plan.
1.2.3 Demonstration Site Representatives
The representative for the demonstration site, the Kennedy Athletic, Recreational and Social Park
(KARS) at Kennedy Space Center, is Michael Deliz, NASA remediation project manager. All work at
the demonstration site will be coordinated and conducted with the permission of Mr. Deliz. All site-related
activities will be coordinated through Mr. Mark Speranza, Tetra Tech NUS and consultant program
manager for NASA. The pre-demonstration SAP will be submitted to the demonstration site
representative for review and comment before sample material is collected.
A site owner representative has been designated for each sampling site and is identified in Table 1.
Similarly, all site-specific sample collection will be coordinated and conducted with the permission of the
designated representative, and site sampling plans will be submitted as requested for review before sample
material is collected at the site.
1.2.4 Laboratory Project Personnel
Two subcontractor laboratories are required for the demonstration project: (1) a characterization
laboratory responsible for processing and characterizing sample material; and (2) a reference laboratory
that will independently verify element concentration in each sample batch in conjunction with analyses by
the developer. For this project, Applied Research and Development Laboratory, Inc. (ARDL), in Mount
Vernon, Illinois, will function as the characterization laboratory. The ARDL project manager, Dan
Gillespie, is responsible for overall planning, scheduling, budgeting, and reporting of laboratory activities.
All ARDL work will be under the direct supervision of Mr. Gillespie, who will be the primary contact for
the Tetra Tech project manager. Mr. Gillespie is also responsible for reviewing and concurring with the
pre-demonstration plan and will immediately discuss appropriate resolutions of any deviation from the
activities specified in the plan with the Tetra Tech project manager. ARDL's QA manager, Dick Curtain,
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will assist Mr. Gillespie in ensuring adherence to all QA/QC elements specified in the pre-demonstration
plan that pertain to the analyses performed at the laboratory.
The reference laboratory has not been selected for this project However, the reference laboratory will
analyze reference material along with the XRF vendors for comparison. The responsibilities of the
laboratory and QA manager for the reference laboratory are similar to the characterization laboratory.
2.0 FIELD SCREENING AND SAMPLING PROCEDURES
This section describes basic procedures for (1) field screening using XRF to identify soils and sediments
that contain the target elements for sampling at each sampling site; (2) sample processing for ensuring
samples are properly ground, homogenized, and blended; (3) sample handling; (4) equipment
decontamination; and (5) managing investigation-derived waste (IDW). Although each of these basic
procedures will be the same at each sampling site, site-specific sampling information will be provided later
and will be incorporated as an addendum to this SAP.
2,1 XRF Field Screening Procedures
Historical analytical data will be used to the extent possible at each of the sampling sites to identify
locations where element-containing soil or sediment and background soil or sediment will be collected. A
hand-held XRF instrument, capable of detecting all 13 target elements, will be used for field analysis of soil
and sediment at each location. Table 2 lists the general XRF pre-operational checks and their frequency.
These checks and their frequencies are based on manufacturer-recommended operating procedures.
Additionally, the instrument will be operated in compliance with the model-specific standard operating
procedure (SOP). Each sample of soil and sediment will be analyzed for all 13 target elements, and the
concentrations will be electronically recorded for use in preparing sample material batches. Run time for
the instrument analyses will be of sufficient length (typically 60 to 600 seconds) to yield data of usable
quality (assessed as a relative standard deviation of the count statistic of 5 percent). Run-time
requirements are specified on a site-specific basis and are provided in the field sampling plans.
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Table 2.
Pre-Operational XRF Checks
Equipment Check
Blank Sample Check
Target Element Response Check
Instrument Calibration
Duplicate Measurements
Frequency
Once at the beginning of each working day, after every
20 sample analyses, and at the end of the working day
Check run at beginning of the working day
Calibration run after each battery change (about 4 hours)
One per 10 field analyses
Once areas of element-containing material and background soil and sediments are identified, samples will
be collected by the procedures outlined in Section 2.2.
2.2 Soil and Sediment Sampling Procedures
The following procedures will be used to collect samples of soil and sediment from each sampling site.
Historical data will be used to identify the general sample locations. These general sample locations will
be refined and delineated by analyzing representative samples from the prospective locations. Site-
specific grid configuration and sampling requirements are specified in the site-specific sampling plan
provided as addenda to this SAP.
Surface materials will be collected from a 3-foot by 3-foot plot. A layer approximately 1 inch deep across
the entire sample plot will be collected to obtain the required 50 to 70 pounds of bulk material Subsurface
materials will be collected using a backhoe, or a Geoprobe will be employed to collect cores of bulk
material.
A screening-level XRF analysis will be performed for each lot of sample s collected to qualitatively identify
the target elements present and their concentrations. A five-part composite sample will be screened that
consists of 20-gram aliquots collected from each corner and the center of the prospective sample plot or
from subdivided core depth intervals. This screening sample will be placed in a ziplock bag, homogenized
by hand, and analyzed with a field-portable XRF instrument capable of detecting all 13 target elements.
Duplicate XRF analysis will be conducted on 1 per 10 field measurements to assess the precision of the
XRF instrument and the homogeneity of the matrix. If the target elements and general concentration
ranges are not detected in this sample in the ziplock bag, the sample plot will be moved to another location.
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If the target elements and concentrations detected are acceptable, approximately 1 inch of soil will be
removed from the entire 3-foot by 3-foot sample plot and placed in a clean, decontaminated 5-gallon
plastic bucket using a shovel or trowel.
The sample collected will be homogenized in the field by pouring the material back and forth between the
original bucket and a second clean, decontaminated 5-gallon plastic bucket. After the sample has been
transferred between buckets multiple times (four to six repetitions), a second five-part composite sample
consisting of 20-gram aliquots will be collected from the bucket and placed in a ziplock bag. The second
sample will be homogenized by hand and again analyzed with the XRF. No sample preparation (sieving or
grinding) will be performed on either the first or second field XRF samples. If the target elements and
general concentration ranges are not found in this bucket sample, the material will be returned to the
sample plot and another potential sample location will be identified. If the target elements and
concentrations are acceptable, the bucket will be labeled with a unique sample number, custody seals will
be: affixed to the sealed container, and the sample plot location will be surveyed using a hand-held GPS
instrument. All bulk samples will be shipped to the analytical laboratory in the 5-gallon plastic buckets
(overpacked in a sample cooler) via Federal Express or similar overnight service. Confirmational samples
will be shipped in 8-ounce plastic containers.
Sediment samples will be collected using an approach that is similar but modified slightly because of the
water content in the sample. Surface sediments will be collected over a 3-foot by 3-foot area to a depth
of about 6 inches using a Ponar or other appropriate grab sediment sampler. Shallow water sediments
may also be collected using a stainless steel shovel or trowel. Deeper sediments will be collected using
gravity core or vibracore sampling devices. Before the sediment samples are analyzed with the XRF, the
water in the sample will be allowed to freely drain to reduce the moisture content to the lowest amount
possible. The sample will be placed on a paper filter on top of clean paper towels to absorb excess water.
Excess water will be decanted from the bucket samples before they are sealed and shipped to the
laboratory. Sediment samples collected using a coring device with disposable sleeves, such as a cellulose
acetate butyrate tube, may be kept sealed inside the sleeve and shipped undisturbed to the characterization
laboratory. Target elements will be screened at the laboratory, and sediment will be subdivided into
SEimple batches before the sample is homogenized.
The sampling depth, implements used, and methods selected will vary based on the site-specific factors at
each sample plot. A clean, decontaminated shovel, plastic or stainless steel trowel, or soil auger will be
used to collect surface soil and deposit it into the 5-gallon plastic sample containers. A shovel or backhoe
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will be used to expose the desired sampling zone for locations where the desired sampling zone is just
below the surface, and a clean shovel or trowel or a Geoprobe or core sampler will be used to collect the
desired material Each sampling location will be recorded in the sampler's field logbook, and a sketch of
the area with measured landmarks will be included so the sampler may return to the location if additional
material is required. The logbook will contain the site name, site area, sampled medium (soil or sediment),
date and time of collection, depth, interval, expected contamination concentrations, rationale for selection, a
unique identification number for the bulk sample, and the sampler's initials. The 5-gallon container will be
labeled as required in Section 2.4 and will be shipped to the characterization laboratory for processing as
described in Section 2.3.
2.3 Sample Processing Procedures
This section describes the grinding, homogenizing, and blending procedures to be used by the
characterization laboratory to ensure that sample s provided to each developer and the reference laboratory
during this demonstration are identical and within established quality control limits. A homogeneous
sample batch is critical to ensure minimum variability in the results from the impact of the sample matrix.
Approximately 1,000 kilograms (kg) of bulk soil and sediment from the sampling sites will be delivered to
the characterization laboratory (ARDL) for preparation. The soil and sediment material will be dried, pre-
sieved, crushed, finely sieved, and homogenized to create an estimated 200 sample batches of
approximately 5 kg each. The batches will ideally include concentrations for many of the elements at (1)
levels near the instrument detection limits; (2) 10 to 100 times the detection limits; (3) 50 to 500 times the
detection limits; and (4) 100 to 1,000 times the detection limits. Soil and sediments will likely require
blending of high and low element concentrations to achieve the desired concentrations of the target
elements; therefore, unspoiled or clean bulk soil will be needed. All 13 target elements will not be present
in each individual sample but will be found across approximately 320 sample batches. A minimum of four
samples and up to 10 unique samples will be prepared for each element from at least two sites for soil
samples and one site for sediment samples.
Each batch of soil and sediment will be subdivided into 20 aliquots, each containing approximately 200
grams. All remaining soil from the batches will be stored and archived. ARDL will prepare 4,000
individual soil samples (each weighing 200 grams) to achieve the demonstration goal The 4,000 samples
are based on 20 soil samples from each of the 200 (5 kg) soil batches.
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The detailed procedures for processing, blending, and homogenization are provided in the following
numbered paragraphs.
1. Drying. Original bulk soils and sediments will be air-dried on trays, with exposure to warmed air
as required to achieve uniform drying.
2. Pre-crush sieving. Air-dried bulk soils and sediments will be sieved through a custom made
device to remove matter from the batch that is larger than approximately 1 inch in diameter.
3. Crushing. Bulk soils will be reduced in particle size using a hardened stainless steel hammer mill
(Type 1200) until all material is less than 60-mesh sieve (0.2 millimeters). Actual duration of
crushing to achieve the desired particle size will vary based on soil type.
4. Sieving. Particle size of bulk soils will be verified using standard sieve technology. Material larger
than 60-mesh will be returned to the crushing process.
5. Homogenizing. Bulk soils will be homogenized using a Model T 10B Turbula Shaker-mixer or a
Model T 50A Turbula Shaker-mixer. Sodium fluorescein will be added as necessary before
homogenization. Post-homogenization samples will be inspected with an ultra-violet light to
qualitatively verify that homogenization is complete.
6. Preliminary analysis. Aliquots from each bulk sample of soil will be sampled and analyzed in
triplicate using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and cold
vapor atomic absorption (CVAA) spectroscopy by EPA methods SW-846 6010B and 7471A for
the target elements (EPA 1996b). If the relative standard deviation between the triplicate results
is greater than 10 percent, the batch will be returned to Step 5 for further homogenization.
7. Blending. Once bulk soils have been adequately analyzed, calculated proportions of various bulk
soils (similar soils with varying element concentrations) will be blended to achieve the desired
approximate element concentrations to produce sample batches. Some element concentrations
are expected be in the parts per billion range in bulk samples. Sample batches will be blended into
4 to 10 contaminant levels that include at a minimum: (1) near the detection limit (2) 10 times the
detection limit, (3) 100 times the detection limit, and (4) 500 times the detection limit. The blended
soil batches with prescribed element concentrations will be thoroughly homogenized again using
the Model T 10B Turbula Shaker-mixer or a Model T50A Turbula Shaker-mixer (presented in
Step 5). The "recipe" for each soil batch will be recorded by indicating the quantities of material
from bulk samples used to generate the batch.
8. Final analysis. After the soil batches have been blended and re-homogenized, triplicate samples
will be collected and analyzed. If the percent difference standard deviation of all three results
exceeds 10 percent, the batch will be returned to Step 7 for further homogenization.
9. Packaging. Two hundred-gram aliquot reference samples from each batch will be packaged into
new 8-ounce screw-cap glass bottles labeled appropriately with tamper-resistant custody seals
affixed over the side of the lid, as required in Section 2.4.
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Packaged soil and sediment will be delivered to the developers for pre-demonstration XRF analysis and to
the KARS Park demonstration site for analysis during the actual demonstration. Confirmation samples
will also be sent to the reference laboratory for analysis by ICP-AES and CVAA.
In addition, selected soil and sediment sample material will be prepared from each site for XRF instrument
calibration standards. Two standard samples consisting of a low standard (element concentrations near
the XRF instrument detection limit) and a high standard (element concentrations with 10 to 500 times the
detection limit) will be prepared and distributed to each developer with the pre-demonstration sample sets.
2.4 Sample Integrity Requirements
This section describes the sample integrity requirements, including labeling, containerization, preservation,
holding times, and custody and shipping procedures.
2.4.1 Sample Labeling
Bulk soil and sediment samples will be collected at the sampling sites using new, clean, decontaminated 5-
gallon scalable plastic buckets or disposable core sleeves. The sample containers must be labeled with the
following information: site name, site area, medium (soil or sediment), date and time of collection, depth,
interval, element concentrations as measured in the field by the XRF, rationale for selection, the sampler's
initials, and a unique identification number. The information should exactly match the sampler's logbook.
Identification numbers for the bulk materials will be a two-character code that is unique to the sampling
site, a "U" to signify that the sample is unprepared, followed by the numerical sequence starting with "01."
For example, "RM-U-01" will be the sample identification number for the first bulk sample (unprepared)
collected at the Rocky Mountain Arsenal site. The following two-character codes will be used for each
sampling site:
• AS = Alton Steel, Illinois
• BN = Burlington Northern Railroad-ASARCO, Montana
• CN = Crane Naval Surface Warfare Center, Indiana
• KR= Kennedy Athletic, Recreational, and Social Park
• LC = Leviathan Mine Site/Leviathan and Aspen Creek, California
• RM = Rocky Mountain Arsenal, Colorado
• TL = Torch Lake Site, Houghton County, Michigan
• WS = Wickes Smelter Site, Montana
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The laboratory will use the available information from the sampler's logbook and chain-of-custody form to
identify the bulk lot material that contains higher levels of elements versus those that were collected from
background soil and sediment areas (clean or unspoiled material).
ARDL prepares the blended batches from the homogenized material, ARDL will record the
quantities of each bulk sample used to prepare the blended samples. This documentation will allow the
batches to be traced to their original "recipe" from the bulk samples. Twenty aliquots of 200 grams each
from each bulk sample batch will be containerized for use in the demonstration. Each of the 20 aliquots of
soil and sediment sample material sent to the developers and reference laboratory will be assigned a
umque identification number, as follows:
• RM-P-01-05-MX
Where:
RM = Site code (Rocky Mountain Arsenal, for this example)
P = Prepared sample
01 = Numerical sequence of the prepared batches
05 = Numerical sequence of the aliquot (1 through 20)
MX = Vendor code
Vendor codes will include two alphabetic characters, as follows:
• DC = Innov-X Systems, Inc.
• MX = Oxford Instrument Portable (formerly Metorex)
• NT = Niton Corporation
• OI = Oxford Instrument Analytical
• RU = Rigaku, Inc.
• RN = RONTEC USA Inc.
• XC = Xcalibur SRF Services
Each aliquot of sample material will be contained in 8-ounce glass jars and labeled with the demonstration
name, aliquot number (from the example above), and the date the aliquot was prepared. Aliquots from
each batch will be submitted to the developers and to the reference laboratory for analysis. Developers
and the reference laboratory will report results using the unique identification number assigned
2.4.2 Sample Containers, Preservation, and Holding Times
Bulk soil and sediment samples will be collected in the field and placed into new 5-gallon plastic buckets
with lids that seal. Each bucket of bulk sample will be labeled as required in Section 2.4.1. The 5-gallon
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buckets will be over-packed into containers and sealed for shipment according to the custody and shipping
procedures discussed in Section 2.4.3.
No chemical (for example, pH adjustment) or physical (cooling) preservation is required for these samples.
As such, samples will not be chemically preserved or cooled at any time from sample collection through
aliquot analysis. The standard holding time for total element analysis in soil and sediment samples for this
project is 6 months.
2.4.3 Sample Custody and Shipping Procedures
Tetra Tech's sample custody will begin when samples are placed in the 5-gallon container by the samplers
and will remain in Tetra Tech's custody until shipment to ARDL. Bulk samples require no chemical or
physical preservation and will be over-packed in sealed containers and shipped to ARDL by overnight
courier. Chain-of-custody forms will be completed and initialed by Tetra Tech personnel and will
accompany each bulk sample shipped to ARDL. The following information will be provided on each
chain-of-custody form:
• Project Name: XRF Demonstration
• Project Manager: Julia Capri
• Tetra Tech project manager's telephone number: (513) 564-8342
• Sampler names, initials, and signatures
• ARDL address and contact phone number
• Field sample identification number: unique sample identification number assigned by the
sampling team
• Matrix: sample matrix (SS for soil and SD for sediment)
• Date sample was collected
• Time sample container was filled
• Sampling team leader's initials
• Requested analyses: Method 601 OB for total metals and Method 7471A for mercury
When all appropriate line items are completed, Tetra Tech's sampling team leader will confirm that all
descriptive information on the form is complete and will sign and date the form. Each individual who
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subsequently assumes responsibility for the samples will sign the chain-of-custody form. The courier
service (when used) will not sign the chain-of-custody form; instead, the airbill invoice will serve as part of
the chain-of-custody documentation. Use of the chain-of-custody form will end when ARDL receives the
szimples and enters the ARDL sample identification numbers on the form. The Terra Tech field
superintendent will retain a copy of the chain-of-custody form for the project files. Original chain-of-
custody documentation will be included in each container shipped to ARDL.
2.5 Equipment Decontamination
This section describes equipment decontamination procedures for soil and sediment sampling equipment.
Soil sampling equipment may include shovels, plastic or stainless steel trowels, or soil augers. Sediment
sampling equipment may include corers or Ponar grab samplers. Before every sample is collected, all
sampling equipment (that is not disposable) will be washed with a nonphosphate detergent followed by two
rinses with deionized water. All decontamination wash and rinse waters will be collected hi suitable
containers for proper and immediate disposal at the end of the sampling event.
2.,6 Investigation-Derived Waste Management
The sampling team will take steps to minimize the volume of investigation-derived waste (IDW). All
IDW, including unused sample material and decontamination water that has come into contact with
contaminated material, will be managed and disposed of in accordance with standard IDW management
practices. No hazardous waste is expected to be generated during sampling procedures for this
demonstration project. Solid wastes generated during the demonstration include personal protective
equipment (PPE) and unused or extra soil or sediment samples. These nonhazardous solid wastes will be
properly disposed of in a nearby waste receptacle, as directed by the site representative. Decontamination
water is the only liquid waste expected and will be properly disposed of on the surface near the sampling
area and allowed to infiltrate or in a municipal water treatment drain.
3.0 TESTING AND MEASUREMENT PROTOCOLS
This section describes the methods to be used for analyzing soil and sediment material during collection
and processing in preparing demonstration samples. Four sets of analyses will be conducted on the sample
material for the demonstration: (1) field screening at the sampling site to delineate areas for material
collection; (2) characterization of bulk samples for customized blending; and (3) characterization of
blended batches by the characterization laboratory to verify the homogeneity and concentration of
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elements. Field screening analysis will be performed using a portable XRF instrument. The analytical
methods for the bulk sample and blended batch characterization analyses use standard ICP-AES and
CVAA. These methods are listed in Table 3 and are summarized in the following paragraphs. QA/QC
procedures are described in Section 4.0. Field screening procedures for determination of total elements on
bulk samples at the sampling site are described in Section 2.0.
Field screening at the site for total element analysis will use SW-846 Method 6200 (revised to incorporate
instrument-specific requirements). Screening analysis will comply with the manufacturer's instructions
provided in the operating manual that accompanies the unit. Detection limits required for the XRF unit
used in the analysis of sandy and soil sample matrices for total metals are summarized in Table 4. In
performing the field screening analysis, an instrument setting of 5 to 10 percent RSD will provide adequate
resolution for measurement accuracy and precision. Site-specific requirements for measurement
resolution are specified in the appropriate field sampling plans.
Bulk and batch samples for total element analysis will be prepared using acid digestion by SW-846 Method
3050B and analyzed using ICP-AES by SW-846 Method 6010B. Method 3050B is not a "total" digestion
technique; however, it is a strong acid digestion that will dissolve almost all elements that could become
environmentally available. This method is suitable for digestion of soils and sediments for analysis by ICP-
AES. A representative 1-gram sample is digested at a constant temperature of 95° Celsius with repeated
additions of nitric acid and hydrogen peroxide. For ICP-AES analysis, hydrochloric acid is also added to
the initial digestate to enhance the solubility of some inorganic salts. After digestion, samples are cooled,
filtered, and made up to final volume for ICP-AES analysis.
Table 3.
Analytical Methods for Total Elements
Analysis
Field screening for total elements
in soil and sediment samples
Total elements in soil and
sediment samples
Total mercury in soil and
sediment
Method l
SW-846 Method 6200
(modified)
SW-846 Method
3050B/6010B by ICP-AES
SW-846 Method 7471A by
CVAA
CVAA = cold vapor atomic absorption
ICP-AES = inductively coupled plasma-atomic emission spectrometer
1 EPA1996b. "Test Methods for Evaluating Solid Waste." Volumes 1A through 1C. SW-846. Third Edition.
Update III. OSWER. Washington, D.C. December
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Table 4.
Detection Limits Required for Field Screening XRF
XRF Field Screening Detection Limits1
Units = parts per million (ppm)
Element
Chromium
Iron
Nickel
Copper
Zinc
Arsenic
Selenium
Gold
Cadmium
Antimony
Mercury
Lead
Vanadium
Sandy Matrix
25
100
45
43
20
9
8
40
40
95
11
13
45
Soil Matrix
45
NA
70
50
30
13
9
45
50
115
14
16
70
1 = Estimated limits of detection, based on a 99.7 percent confidence level for a 120-second test.
NA = Not Applicable.
ICP-AES analysis of soil and sediment digests from bulk and batch samples will be conducted by SW-846
Method 6010B. ICP-AES determines trace elements, including elements in solution. This method is
applicable to digestates of soil and sediments prepared by Method 3050B and for the analysis of 12 of the
13 target elements (antimony, arsenic, cadmium, chromium, copper, iron, lead, nickel, selenium, silver,
viinadium, and zinc); mercury is excluded because of its volatile nature. In addition, Method 601 OB has
been demonstrated to meet the required method detection limit (MDL), as listed in Table 5.
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Table 5.
Target Analytes and Required Method Detection Limits
Target Analyte
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Vanadium
Zinc
Required MDL
(mg/kg)
2.0
2.5
0.5
0.5
1.0
5.0
2.5
0.08
1.5
5.0
0.5
0.5
0.5
MDL = Method detection limit
mg/kg = Milligram per kilogram
Bulk and batch samples for analysis of mercury will be prepared using the acid digestion procedure in SW-
846 Method 7471A and analyzed using CVAA, also by SW-846 Method 7471 A. This method is suitable
for digestion of soils and sediments for analysis of mercury by CVAA. A representative 0.2-gram sample
is digested at a constant temperature of 95° Celsius with aqua regia and additions of potassium
permanganate to reduce the organic matter in the sample. After the sample has been digested, the sample
vessel is purged with nitrogen into the CVAA instrument. The addition of stannous chloride results in the
evolution of any mercury vapors from the sample, which are then swept into the instrument by the
nitrogen. The instrument is calibrated and set for reading absorbance of radiation at a wavelength of 253
nanometers. Method 7471A has been proven to meet the method detection limit (MDL) required for
mercury, as listed in Table 5.
4.0 QUALITY ASSURANCE/QUALITY CONTROL PROCEDURES
This section describes the QA/QC procedures that will be followed in both field and laboratory analyses of
samples for this demonstration project. QA/QC ensures that high-quality, scientifically valid, and legally
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defensible data are generated that meet the demonstration objectives. The overall QA objective for the
demonstration is to produce well-documented data of known quality. Data quality will be measured in
terms of reporting limits, precision and accuracy, completeness, representativeness, and comparability.
These parameters will be discussed in detail in the demonstration plan. Field and laboratory QA/QC
procedures for the demonstration are summarized in the following sections.
4.1 Field QA/QC Procedures
This section describes field QC measures necessary to ensure that quality data are generated from the
field operations, including calibration of the XRF instrument used to identify "hot spots" during sampling.
This section discusses each type of QC, its importance, and acceptance criteria.
4.1.1 Calibration
The portable XRF unit is calibrated with a specially designed stainless steel plate as source material that
clips on top of the instrument directly in front of the analyzer window. The display menu shows on a
calibration screen when the instrument is turned on. With the steel plate locked into its position, the
"calibrate" button is activated; then the unit will turn off in about 200 seconds and notify the user whether
the calibration results met acceptance criteria. The instrument must be calibrated each time the battery is
changed (about 4 hours).
4 1.2 Blank Sample Check
The blank samples check consists of a Teflon block analyzed by the instrument at the beginning of each
working day, after every 20 samples, and at the end of the working day. No elements above the MDL
should be detected in the blank check. If concentrations are detected above the MDL, then the probe
window or the surface of the Teflon block should be cleaned. If the blank sample check fails the required
criterion a second time, then the manufacturer's SOP will be consulted, or the manufacturer will be
contacted for assistance. No samples will be analyzed until the issue is resolved.
4..1.3 Target Analyte Response Check
The target analyte or calibration verification check source consists of a certified sample that contains
target analytes. This check is used to measure the accuracy of the instrument and to assess the stability
and consistency of the analysis for the target analytes. The check will be analyzed at the beginning of
each working day, after every 20-samples, and at the end of the working day. The measured value of
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each target analyte should be within 20 percent of the true value for the target analyte response check. If
a measured value is outside this range, then the check sample will be reanalyzed. If the value is outside
the acceptance range, the instrument calibration should be verified using the target element response
check If the criterion is not met, then the manufacturer's SOP will be consulted, or the manufacturer will
be contacted for resolution.
4.1.4 Duplicate Measurements
At least 1 sample per 10 (10 percent frequency) will be analyzed in duplicate. The relative percent
difference (RPD) between duplicate measurements should not be greater than 20 percent. If so, then a
third analysis should be conducted If the RPD is within 20 percent of either of the first two, then the
analysis can continue; however, if not, instrument calibration and blanks should be checked
4.2 Laboratory QA/QC Procedures
All laboratories that perform analytical work under this project must adhere to a QA program that is used
to monitor and control all laboratory QC activities. Each laboratory must have in place a written QA
manual that describes the QA program in detail. The laboratory QA manager is responsible for ensuring
that all QC checks internal to the laboratory are conducted in accordance with EPA methods and
protocols, the laboratory's QA manual, and the requirements of this SAP.
Laboratory analysis for the demonstration bulk and batch samples requires preparation and analysis of QC
samples and will include the following types: (1) instrument calibration checks, (2) method blanks, (3)
interference check samples, (4) laboratory control samples (LCS), and (5) matrix spike (MS) and matrix
spike duplicate (MSD) samples. The following subsections discuss the laboratory QC checks that will be
required for this project.
4.2.1 Instrument Calibration Check
The ICP will be calibrated using at least a blank and one calibration standard that includes the 13 target
analytes. The CVAA will be calibrated using at least a blank and three varying concentrations of
mercury; the correlation coefficient must be greater than or equal to 0.995. If not, then the instrument
must be recalibrated. An instrument calibration check must be analyzed immediately after the instrument
is calibrated, after every 10-samples, and at the end of the working day to verify the calibrations of both
the ICP and CVAA. The percent difference is calculated between the reported value for each target
analyte, and its "true value" must be less than or equal to 10 percent. If not, then the instrument
23
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calibration check may be analyzed once more to meet the criterion. If the criterion is not met the second
time, then the instrument must be recalibrated and all samples analyzed since the last successful calibration
check must be reanalyzed.
4.2.2 Method Blanks
Method blanks, which are also known as preparation blanks, are analyzed to assess the level of
background interference or contamination in the analytical system. Contamination or interference may
result in erroneously elevated concentration levels or false-positive data. Method blanks will be required
for all laboratory analyses and will be prepared and analyzed at a frequency of one method blank per
every 20 samples processed by the analytical system. One method blank will be analyzed with every
batch of samples that is processed for batches that are composed of fewer than 20 samples
A method blank consists of reagents that are specific to the analytical method and are carried through
every aspect of the analytical procedure, including sample preparation, cleanup, and analysis. The results
of the method blank analysis will be evaluated in conjunction with other QC information to assess the
acceptability of the data generated for that batch of samples.
If the method blank value for any target analyte exceeds the MDL (listed in Table 4), the source of
contamination must be investigated, and appropriate corrective action must be taken and documented.
This investigation includes an evaluation of the data to determine the extent of the contamination and its
effect on sampling results. If the associated sample results are greater than 10 times the blank value, then
the effect is considered negligible. If the associated sample results are less than 10 times the blank value,
then the source must be corrected and the sample must be redigested and reanalyzed.
4.2.3 Interference Check Sample
Trie interference check sample (ICS) is used to verify the absence of spectral interference from the ICP-
AES settings that may enhance or suppress the signal used for quantitation of a target analyte. ICS is not
applicable to CVAA analyses. The ICS contains target analytes at mid-range concentrations and
interfering analytes (aluminum, iron, calcium, and magnesium) at concentrations about 1,000 times more
than the target analytes. The effects of the potentially interfering ions should be negligible. Results for the
target analytes from the ICS should be within 20 percent of the true value for the target analyte in the
ICS. If the criterion is not met, instrument setting should be evaluated to rectify the interference. After
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instrument settings have been adjusted to resolve the interference, the instrument will be recalibrated and
all samples associated with the ICS will be reanalyzed.
4.2.4 Laboratory Control Sample
Performance evaluation or control samples are thoroughly characterized, laboratory-generated samples
that are used to monitor the laboratory's day-to-day performance of analytical methods. Results for the
target analytes from the LCS should be within 20 percent of the true value for the target analyte in the
LCS. If the LCS recoveries are not within the criterion, appropriate action will be taken. Appropriate
corrective actions will include (1) stopping the analysis, (2) examining instrument performance or sample
preparation and analysis information, and (3) determining whether samples should be re-prepared or
reanalyzed.
4.2.5 Matrix Spikes and Matrix Spike Duplicates
MSs and MSDs are aliquots of an environmental sample to which known concentrations of target analytes
and compounds have been added. MS and MSD samples will be prepared and analyzed at a frequency of
one set for every 20 samples that are prepared in one batch. The percent recoveries of the target
analytes and compounds are calculated and used to evaluate the effects of the matrix on the precision and
accuracy of the method. Percent recoveries for target analytes from the MS and MSD should be within
25 percent of the amount spiked for each target analyte. If the MS or MSD recoveries are not within the
criterion and the indigenous concentration is less than or equal to four times the amount spiked into the
sample, then the discrepancy is probably matrix interference and will be qualified. When the indigenous
concentration of the target analyte exceeds four times the amount of spike added, the percent recovery is
meaningless for determining matrix interference, and no qualification is required.
The RPD between the MS and MSD results is used to evaluate method precision. Results are expressed
as RPD and percent recovery and are compared with control limits that have been established for each
analyte. If results fall outside control limits and the concentrations are at least five times the MDL, then
the results will be qualified. Section 5.2 discusses qualification of data as a result of matrix interferences
and other issues that affect data quality.
5.0 DATA REDUCTION, VALIDATION, AND REPORTING
This section discusses data reduction, validation, and reporting procedures. Data reduction, validation, and
reporting are essential functions for preparing data that can be used effectively to support project
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objectives. These functions must be carried out accurately and in accordance with EPA-approved
procedures and techniques. Data reduction includes all computations and data manipulations that produce
the final results that are used during the demonstration. Data validity is assessed by comparing the data
with a predetermined set of QC limits. Data validation also includes review of all procedures that field or
laboratory personnel conduct to ensure that results are correct, acceptable, and in accordance with the
QA objectives that are stated in this plan. Data reporting include the hard copy and electronic formats for
reporting data.
5.1 Data Reduction
This section describes the standard document control procedures for reduction of both field and laboratory
data. Field personnel will record, in a field logbook, all raw data from chemical and physical field
measurements. The field superintendent has the primary responsibility for (1) verifying that field
measurements were made correctly, (2) confirming that sample collection and handling procedures
specified in the SAP were followed, and (3) ensuring that all field data reduction and review procedures
were followed. The project manager is also responsible for assessing preliminary data quality and for
advising the data user of any potential QA/QC problems with field data. Data reduction methods will be
fully documented if field data are used in a project report.
Reduction of field data will be verified by reviewing field logbooks against reported field data. Checks will
be performed before results are presented. If unchecked results are presented or used, transmittals or
subsequent calculations will be marked "PRELIMINARY" or "DRAFT" until the results have been
checked and determined to be correct.
The subcontracted laboratories will complete data reduction for chemical and physical laboratory
measurements and will complete an in-house review of all laboratory analytical results. Laboratory raw
data will be electronically transferred to the laboratory information management system (LIMS), where
the appropriate dilution factors, dry-weight factors, and reporting units will be applied. Ideally, no data
should be hand-entered into the LIMS. If data are hand-entered, a secondary review of 100 percent of
the data will be conducted to verify that calculations and entries are accurate. Both the electronic data
files (Excel format) and hard-copy results forms are generated from the LIMS. All other supporting
documentation specified in Section 5.3 will be generated with as little hand entry as possible.
The laboratory QA manager will be responsible for ensuring that all laboratory data reduction and review
procedures follow the requirements stated in this QAPP. The laboratory QA manager will also be
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responsible for assessing data quality and for advising the Terra Tech QA manager of possible QA/QC
problems with laboratory data.
5.2 Data Validation
All data that are used to support the demonstration will undergo data validation. This section outlines the
basic data validation procedures that will be followed for all field and laboratory measurements, including
applicable EPA data validation guidance.
The project QA manager has primary responsibility for coordinating Terra Tech's data validation. Terra
Tech will validate 100 percent of all subcontracted laboratory data for demonstration samples. Data
validation will be completed by one or more experienced data reviewers.
The validity of a data set is determined by comparing the data with a predetermined set of QC limits.
Terra Tech data reviewers will systematically review the data for compliance with the established QC
limits that are presented in Section 4.0 of this plan. The data review will identify any out-of-control data
points or omissions. Terra Tech will follow the most current EPA data validation guidelines (EPA 2002)
for all applicable test methods. A QC summary will be prepared to document the process and findings of
data validation.
5.3 Reporting Requirements
This section describes the laboratory reporting requirements for analytical results generated during the
demonstration. Terra Tech will require contractor laboratories (both characterization and reference) to
prepare and submit data packages that include all applicable documentation for independent validation of
data. The following documentation will be required for full data validation:
• Case narratives, which will describe all QC nonconformances that are encountered during the
analysis of samples, in addition to any corrective actions that are taken, including, but not
limited to (1) a statement of samples received, (2) descriptions of any deviations from the
analytical methodologies specified, (3) explanation of any data qualifiers assigned to data, and
(4) any other significant problems that were encountered during analysis.
• Tables that cross-reference field and laboratory sample numbers.
• Chain-of-custody forms, which pertain to each sample delivery group or sample batch that is
analyzed
• Laboratory reports, which must show traceability to the sample analyzed and must contain the
following specified information:
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- Project identification
- Field sample number
- Laboratory sample number
- Sample matrix description
- Dates and times of sample collection, receipt at the laboratory, preparation, and analysis
- Description of analytical method and reference citation
- Results of individual parameters, with concentration units, including second column results,
second detector results, and other confirmatory results, where appropriate
- Quantitation limits achieved
- Dilution or concentration factors
• Data summary forms and QC summary forms showing analytical results, if applicable.
- Samples
- Instrument calibration checks
- Method blanks
- ICP-AESICS
- LCS
- MS/MSD
- Other QC samples
• Laboratory bench data.
- Raw data
- Instrument printouts
- Laboratory bench sheets for preparation of samples
• MDL study results.
• Electronic data, all samples results and QC summaries provided in Microsoft Excel format
5.,4 Data Management
All data generated during the pre-demonstration sampling will be managed using the U.S. EPA
Environmental Response Team (ERT) Scribe software. Scribe captures sampling, observation, and
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monitoring field data. Scribe can also import electronic data, including anafytical laboratory results and
sampling location data such as GPS, and can also be configured to import sampling data collected on hand-
held computers.
Scribe
Environmental Data Management
System Overview
Desktop
Applications
Figure 2. Overview of Scribe System
Field Data
All data collected in the field will be electronically recorded using personal digital assistants (PDAs).
These data will include all field screening measurements from the hand-held XRF instrument, as well as
the logbook information described in Section 2.1, XRF Field Screening Procedures. GPS location data will
be surveyed using a hand-held GPS unit. This information will also be recorded electronically. Once all
field data have been collected, it will be downloaded from the PDA units into an Excel file format. This
file will then be imported into the Scribe database.
Pre-demonstration Samples
Once the bulk samples have been processed by the characterization laboratory (ARDL), the 4,000
prepared samples will each be assigned a unique sample number, as detailed in Section 2.4.1, Sample
Labeling. ARDL will provide the characterization analytical data package required in Section 5.3,
Reporting Requirements. Each developer and the reference laboratory will receive 200 samples. ARDL
will provide chain-of-custody information for each set of samples shipped from the laboratory.
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Analytical data will be generated for each of these 4,000 prepared samples. The reference laboratory will
provide the documentation required in Section 5.3. These data will then be imported into the Scribe
database. Developers will need to provide, at a minimum, the following information: developer code,
technology (instrument used), sample number, analyte, date received, date analyzed, custody seal number,
matrix, result, units, qualifier, QA/QC comment, and comments. Excel is the preferred format for these
results. All data from the reference laboratory and the developers must be reported using the unique
sample identification number originally assigned at ARDL.
Once all data have been received and imported into the Scribe database, the data can be queried and
sorted as needed. Data will be exported to spreadsheet or text files (or both) for final formatting.
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6.0 REFERENCES
U.S. Environmental Protection Agency (EPA). 1996a. "A Guidance Manual for the Preparation of Site
Characterization and Monitoring Technology Demonstration Plans." National Environmental
Research Laboratory. October.
EPA. 1996b. "Test Methods for Evaluating Solid Waste: Physical/Chemical Methods." SW-846. Third
Edition. Update III. Office of Solid Waste and Emergency Response (OSWER). December.
EPA. 2002. "Contract Laboratory Program National Functional Guidelines for Inorganic Data Review."
EPA 540-R-01-008. Office of Solid Waste and Emergency Response (OSWER). Washington,
DC. July
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Site-specific Field Sampling Plans
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Alton Steel Mill
Site-specific Field Sampling Plan
1.0 Site-specific Objectives
The Alton Steel Mill (Alton) site was selected as a source of sample material for the X-ray fluorescence
(XRF) technologies demonstration. The site contains native and contaminated soil as a result of steel
manufacturing operations that contains some of the key elements targeted for the demonstration. The
specific metals of interest for the Alton site include arsenic, cadmium, chromium, lead, selenium, and
silver. This site-specific addendum to the pre-demonstration sampling and analysis plan (SAP) describes
the site location, proposed sample locations, and methodology for collecting soil samples.
2.0 Site and Sample Locations
The Alton site (formerly the Laclede Steel site) is located at 5 Cut Street, Alton, Illinois (400-acre site
located in Alton's Industrial Corridor). The Alton site was operated by Laclede Steel Company (Laclede
Steel) from 1911 until its closure as a bankrupt facility in July 2001. The site remained vacant for nearly
two years and was purchased by Alton Steel, Inc. from the bankruptcy estate of Laclede Steel in May
2003. Steelmaking operations have resumed in the centermost area of the property, comprising
approximately 100 acres. The remaining acreage comprising the western and eastern portions of the site
are being developed for commercial and industrial tenants. Alton entered into a Settlement Agreement
with Laclede Steel, the United States of America, and the State of Illinois which includes a Compliance
Plan designed to bring the facility back into compliance with the existing RCRA permit. Under the terms
of such settlement agreement, Alton Steel is also allowed to address any contamination at the site
identified in the Phase II Environmental Site Assessment (ESA) (which is anticipated to be conducted in
October or November 2004), and not already identified as a Solid Waste Management Unit as listed in the
settlement agreement, under Illinois EPA's Site Remediation Program.
As a result of more than 90 years of steel production, the site is heir to numerous environmental concerns,
including PCS and heavy metals contamination. Laclede Steel, during its operating years, was cited for
improper management and/or disposal of PCB wastes and electric arc furnace dust wastes containing
heavy metals, such as lead and cadmium. Some of those wastes are contained in exposed waste piles and
lagoons at the site, and in seepage and wastewater that is managed by the wastewater treatment plant at
the site. Alton Steel retained Tetra Tech to perform a Phase I ESA to assess the site's environmental
conditions. The Phase I ESA, dated May 17,2002 (amended October 25, 2002), identified VOCs,
SVOCs, total priority pollutant metals, and PCBs as potential contaminants of concern at the site. In the
Phase II ESA work plan, Tetra Tech also proposed analyzing certain sample points for the entire list of
inorganic metals listed in the Tier I Soil Remediation Objectives for Industrial/Commercial Properties.
Several potentially metals-contaminated soils locations at the site will be investigated for the XRF
demonstration. Based on data gathered during the Phase I ESA in 2002, the specific areas identified for
potential collection of soil samples include the Rod Patenting building and Tube Mill building. A sample
AS-1
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of background soil will be collected from an area topographically upgradient of and not near the
production areas on the Alton Steel property.
3.0 Site-Specific Soil Sampling Procedures
This section discusses specific sampling procedures to be used at the Alton site. The procedures listed in
Section 2.0 of the pre-demonstration SAP for completing the field analysis, collecting soil samples,
sample processing, and for maintaining sample integrity will be followed.
Title in situ and composite soil samples for XRF analysis will be collected using the procedures described
in the pre-demonstration SAP. The elements of interest at the Alton site for sample collection are arsenic,
cadmium, chromium, lead, and silver. Selenium-contaminated materials will also be targeted but may not
be found.
Soil Samples
Available historical data on the Alton site were used to identify general areas where metals-containing
and background soil will be collected. Sampling areas will be delineated and refined by establishing 10-
foot by 10-foot grids near known hot spots. Each grid will be subdivided into 1-foot by 1-foot grid cells.
Soil samples will be collected from five of the grid cells and homogenized for XRF field screening. The
sample design and homogenization procedures to be followed in the field are described in more detail in
the pre-demonstration SAP.
It may be necessary at some locations to remove vegetation before the XRF screening measurement can
begin. The XRF field screening will be carried out in accordance with the procedures detailed in the
SAP. After soil has been screened in the field to confirm that elements of interest are present, soil
samples will be collected using a decontaminated shovel or similar sampling device. The sample material
will be sieved using a coarse mesh size to remove any large fragments of metal or other debris from the
soil. After the soil has been sieved, the remaining portion of soil will be placed in a 5-gallon bucket,
which will be packaged at the site and shipped to the characterization laboratory for sample processing
and analysis.
AS-2
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BN-ASARCO East Helena Site
Railroad Right-of-Way Surface Soils
Site-specific Field Sampling Plan
1.0 Site-specific Objectives
The ASARCO East Helena Smelter site was an active smelter for over 100 years and recently
closed in 2002. Most of the ore processed at the smelter was delivered on railroad cars. An area
west of the plant site (BN Property) was used for temporary staging or ore cars and consists of
numerous side tracks to the primary railroad line into the smelter. At the request of EPA, CH2M
Hill collected surface soil samples in this area in November 1997 and April 1998 and analyzed
them for arsenic, cadmium, and lead; they reported elevated concentrations for all three metals.
This site was selected for inclusion in the demonstration of X-ray fluorescence (XRF)
technologies for measuring elements in soil and sediments because it has not been remediated and
contains elevated elements of interest. This site-specific addendum to the Pre-demonstration
Sampling and Analysis Plan defines the site location, proposed sample locations, and soil sample
collection methodology.
2.0 Site and Sample Locations
The BN-ASARCO Site is located in the southwest part of East Helena, Montana. The elevated
elements in the railroad right-of-way surface soils have resulted from uncontrolled releases of
metals associated with the historic staging of railroad ore cars in the area. In addition, during
several labor strikes during the smelter's history, some ore cars were purposely dumped by the
railroad operators in order for the ore cars to be used at other locations.
CH2M Hill collected 24 surface soil samples (16 in November 1997 and 8 in April 1998) and
analyzed them for arsenic, cadmium, and lead. The soils were found to contain up to 2,0188 parts
per million (ppm) arsenic, 876 ppm cadmium, and 43,907 ppm lead. The materials targeted for
this XRF demonstration are surface soils near sample points 1 and 1A with particular interest in
collecting soils with elevated cadmium levels (greater than 400 ppm). Previous soil samples were
only analyzed for arsenic, cadmium, and lead but likely contained elevated levels of other
elements (e.g., copper, nickel, zinc). Table BN-1 presents the CH2M Hill data for arsenic,
cadmium, and lead from the 1997 and 1998 sampling events. The targeted surface soils are easily
accessible and are on the surface with no vegetative cover. A sample of relatively clean soil will
be collected from the BN railroad right-of-way approximately 2 miles east of the smelter.
BN-1
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TABLE BN-1.
HISTORIC AL ANALYTICAL DATA, BN-ASARCO EAST HELENA SITE
Metal
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Maximum Concentration (mg/kg)
Not Analyzed
2018
876
Not Analyzed
Not Analyzed
Not Analyzed
43,906
Not Analyzed
Not Analyzed
Not Analyzed
Not Analyzed
Not Analyzed
mg/kg = milligrams per kilogram
3.0 Site-specific Soil Sampling Procedures
The high concentrations for three elements of interest for this XRF demonstration were found in
surface soil samples collected from the BN-ASARCO East Helena site. A 3-foot by 3-foot
sampling grid will be centered near previous CH2M Hill sample point 1A. The procedures listed
in Section 2.0 of the Pre-Demonstration Sampling Plan for completing the field analysis, soil
sample collection, sample processing, and for maintaining sample integrity will be followed. The
soil samples will be collected using a decontaminated shovel to fill the five-gallon buckets. The
background soil samples will be collected from the BN railroad right-of-way approximately 2
miles east of the East Helena Smelter. The background soil sample will be collected by removing
the vegetative and woody debris and then using a clean shovel to fill the required number of five-
gallon buckets.
BN-2
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Old Burn Pit
Navy Surface Warfare Center, Crane Division
Site-specific Field Sampling Plan
The Old Bum Pit at the Naval Surface Warfare Center (NSWC), Crane Division was selected for
inclusion in the demonstration of X-ray fluorescence (XRF) technologies for measuring the target
analytes because elevated concentrations of metals have been detected in surficial soil and
sediment samples. This site specific addendum to the Pre-demonstration Sampling and Analysis
Plan defines the site location, proposed sample location, and soil sample collection methodology.
1.0 Site and Sample Locations
The NSWC, Crane Division site is located near the city of Crane in south-central Indian
approximately 75 miles south of Indianapolis and 71 miles northeast of Louisville, Kentucky.
There are 31 solid waste management units (SWMU) at NSWC. The Old Burn Pit (SWMU 5) is
located in the northwest portion of NSWC near the intersection of Highway 5 and Highway 331.
The Old Burn Pit was used from 1942 to 1971 for burning of daily refuse. Residue from the pit
was buried with non-burnable metallic items in a gully north of the pit. The burn pit was covered
with gravel and currently serves as parking area for delivery trailers. The gully north of the
former burn pit has been revegetated. Miscellaneous metal debris consisting of partially buried
and decomposing drums and other metal objects litter the area. Target analytes detected in
surficial soil are summarized in Table CN-1.
TABLE CN-1.
HISTORICAL ANALYTICAL DATA
OLD BURN PIT
Metal
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Concentration
(mg/kg)
301
26.8
31.1
112
1,520 .
105,000
16,900
0.43
62.6
Not Detected
7.5
5,110
mg/kg milligrams per kilogram
CN-1
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2.0 Site-specific Soil Sampling Procedures
The highest concentrations of target analytes detected in surficial soil and sediment samples were
collected at soil boring 05SB06. One exception is mercury, which was detected at soil boring
05SB01. The mercury detection at 05SB01 appears to be anomalous as the other target analytes
were of relatively low concentration.
The area near soil boring 05SB06 will be targeted for sampling. A sampling grid centered on
05SB06 will be laid out across the area. The grid will consist of 3 ft x 3 ft grid squares and
extending five grids in each direction will be laid out across the area. Each square within the grid
will be approximately 3 ft by 3 ft.
The procedures listed in Section 2.0 of the Pre-Demonstration Sampling Plan for completing the
field analysis, soil sample collection, sample processing, and for maintaining sample integrity
will be followed. The soil sample will be collected using a decontaminated shovel to fill the five-
gallon bucket. The background soil sample will be collected from an undisturbed area in the
northeast corner of the site. The background soil sample will be collected by removing the
vegetative and woody debris and then using a clean shovel to fill the five-gallon bucket.
The required sample volumes to be collected and the relative concentration ranges will be
included. Preliminary estimates of the volume of soil sample and clean soil sample required for
the demonstration are 10 pounds of site soil and 10 pounds of background or "clean" soil.
CN-2
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Kennedy Athletic, Recreational & Social Park Site
Site-specific Field Sampling Plan
1.0 Site-specific Objectives
The Kennedy Athletic, Recreational & Social (KARS) Park was selected as a sample material source
site for the X-ray fluorescence (XRF) technologies demonstration. Native and contaminated soil and
sediment from gun range operations at the site contain the elements targeted for the demonstration.
The specific elements of concern for the KARS Park site include antimony, arsenic, chromium,
copper, lead, and zinc. This site-specific addendum to the pre-demonstration sampling and analysis
plan (SAP) defines the site location, proposed sample locations, and methodology for collecting soil
samples.
2.0 Site and Sample Locations
The KARS Park site is located at the Kennedy Space Center in Merritt Island, Florida. KARS Park
was purchased in 1962 and has been used by employees of the National Aeronautics and Space
Administration (NASA), other civil servants, and guests as a recreational park since 1963 (NASA
2003). KARS Park occupies an area of Kennedy Space Center property located just outside the Cape
Canaveral base. Contaminants in the park resulted from historical facility operations and impacts
from the former gun range. The land north of KARS is owned by NASA and is managed by the U.S.
Fish and Wildlife Service (USFWS) as part of the Merritt Island National Wildlife Refuge (NASA
2003).
Soil and sediment collected from the KARS Park site will be targeted by the XRF demonstration.
Table Al presents existing analytical data for soil and sediment at KARS Park
3.0 Site-Specific Soil and Sediment Sampling Procedures
This section discusses specific sampling procedures to be used at KARS Park. The procedures listed
in Section 2.0 of the pre-demonstration SAP will be followed for completing the field analysis,
collecting soil samples, sample processing, and for maintaining sample integrity.
The in situ and bulk sample XRF analysis will be completed using the procedures described in the
SAP. The element of primary interest for sample collection at the KARS Park site is antimony. Other
elements of interest that are known to be present at the site include lead, arsenic, and chromium.
Based on this primary collection objective, the end point of the XRF screening analysis will be
optimized at a 10 percent relative standard difference for antimony.
KP-1
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TABLE KP-1.
ANALYTICAL DATA
KARS PARK SITE
Metal
Antimony
Arsenic
Chromium
Copper
Lead
Zinc
Concentration"'"
(mg/kg)
8,500
1,600
40.2
290,000
99,000
16,200
mg/kg = milligrams per kilogram
a Data for metals data generated using procedures defined by the
U.S. Environmental Protection Agency (EPA) Contract
Laboratory Program Inorganic Statement of Work.
b Data generated using XRF; concentrations in the table represent
the maximum detected in sediment samples collected by the
National Aeronautics and Space Administration.
Soil Samples
Historical data will be used to identify general areas where element-contaminated and background soil
and sediment samples will be collected. Sampling areas will be delineated and refined by establishing
a pattern of 4-foot by 4-foot grids in the vicinity of known hot spots. The XRF field screening will be
used to outline regions of hot spots as well as uncontaminated areas at the site. Concentrations of the
target elements will be determined by field measurements at a station spacing of less than 4 feet near
known hot spots.
It may be necessary at some locations to remove vegetation before the XRF screening measurement
can begin. To minimize the impact of sample collection on the park grounds, h situ XRF analysis will
help confirm that the proposed sample locations contain the desired concentrations of the target
elements. XRF analysis will be carried out in accordance with the procedures detailed in the SAP.
Samples for field screening will be collected using a decontaminated shovel or similar sampling
device. After XRF screening confirms the composition of the soil, the sample material will be
collected using a decontaminated shovel or similar sampling device, in accordance with the procedures
detailed in the SAP. The samples will be sieved using a coarse mesh size to eliminate fragments of
lead shot from the soil. After the soil has been sieved, the remaining portion of soil will be placed in a
5-gallon bucket, which will be packaged at the site and shipped to the analytical laboratory.
Sediment Samples
Sediment samples will be collected from the swampy areas of the site where historical analytical data
indicate relatively high concentrations of the target elements; however, specific sample locations may
be adjusted in the field. Sediment samples will be collected using a decontaminated shovel or similar
sampling device and immediately transferred to a 5-gallon bucket. Water will be decanted from the
collection buckets, and the sediment samples will be allowed to air dry until the moisture content is
KP-2
-------
sufficiently low to allow a screening measurement by XRF. Sediment samples will be selected for
shipment to the analytical laboratory based on the results of the XRF field screening.
Based on conversations with site managers familiar with soil and sediment sampling at the site,
sediment samples with relatively high concentrations of the target elements may be collected in a
swampy area located north of the gun range, in the vicinity of former NASA sampling locations KSC-
KPI-914b, KSC-KPI-9021, KSC-KPI-9244, KSC-KPI-9239, KSC-KPI-9240, KSC-KPI-9010, and
KSC-KPI-9137. Additional or alternative sediment sample locations may be selected in the field based
on the results of the XRF field screening of sediment.
4.0 REFERENCES
National Aeronautics and Space Administration. 2003. Confirmatory Sampling Work Plan for the
Kennedy Athletic Recreation & Social Park I (KARS I) at the John F. Kennedy Space Center,
Florida. September.
KP-3
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Leviathan Mine
Site-specific Field Sampling Plan
1.0 Site-specific Objectives
The Leviathan Mine (Leviathan) site was selected as a sample material source site for the X-ray
fluorescence (XRF) technologies demonstration. The site contains native and contaminated soil as a
result of steel manufacturing operations and has some of the key elements being targeted for the
demonstration. The specific metals of interest for the Leviathan site include arsenic, copper, and nickel
This site-specific addendum to the Pre-demonstration Sampling and Analysis Plan (SAP) describes the
site location, proposed sample locations, and soil sample collection methodology.
2.0 Site and Sample Locations
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. The mine occupies approximately 253
acres at an elevation that ranges from 7,700 to 7,900 feet on the northwestern flank of Leviathan Peak in
Alpine County, California. The site is approximately 6 miles east of Markleeville, California; the closest
metropolitan area is Carson City, Nevada.
The 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
overburden and waste rock in nearby streams led to the creation of acid rock drainage and environmental
impacts in the 1950s. Environmental impacts noted at this time included large fish kills (California
Regional Water Quality Control Board—Lahontan Region 1995).
The historical mining activity resulted in the distribution of waste rock around the mine site and the
presence of an open pit, adits, and solution cavities through mineralized rock. Oxygen contacting the
waste rock and mineralized rock in the adits oxidizes sulfur and sulfide minerals leading to the generation
of acid. Water contacting the waste rock and flowing through the mineralized rock mobilizes the acid
into the environment. The acid dissolves metals including aluminum, arsenic, copper, iron, and nickel,
which create conditions toxic to insects and fish in Leviathan, Aspen, and Bryant creeks downstream of
the Leviathan Mine.
LV-1
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TABLE LV-1.
HISTORICAL ANALYTICAL DATA
LEVIATHAN MINE SITE
Metal
Arsenic
Cadmium
Chromium
Copper
Nickel
Maximum Concentration" (rag/kg)
2,510
25.7
279
837
2670
mg/kg = milligrams per kilogram
a Metals data generated using procedures defined by the EPA Contract
Laboratory Program Inorganic Statement of Work.
3.0 Site-Specific Soil and Sediment Sampling Procedures
This section discusses specific sampling procedures to be used at Leviathan Site. The procedures listed in
Section 2.0 of the pre-demonstration SAP for completing the field analysis, collecting soil samples,
sample processing, and for maintaining sample integrity will be followed.
The in situ and composite soil samples for XRF analysis will be completed using the procedures
described in the pre-demonstration SAP. The elements of interest at the Leviathan Site for sample
collection are arsenic, cadmium, chromium, copper, and nickel
Historical data at the Leviathan site was used to generally identify areas where metals-containing soil and
background soil will be collected. Sampling areas will be delineated and refined by establishing 10-foot
by 10-foot grids in the vicinity of known hot spots. Each grid will be subdivided into 1-foot by 1-foot
grid-cells. For each grid, soil samples will be collected from five of the grid-cells and homogenized for
XRF field screening. The sample design and homogenization procedures to be followed in the field are
described in more detail in the pre-demonstration SAP.
It may be necessary at some locations to remove vegetation before performing the XRF screening
measurement. The XRF field screening of soil and sediment will be performed in accordance with the
procedures detailed in the SAP. If the sediment samples contain large amounts of water, the free liquid
will be drained from the samples prior to XRF analysis. Following field screening of soil and sediment
confirming that elements of interest are present, soil samples will be collected using a decontaminated
shovel or similar sampling device. The soil and sediment will then be placed in a 5-gallon bucket, which
will be packaged at the site, and shipped to the characterization laboratory for sample processing and
analysis.
LV-2
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Sulphur Bank Mercury Mine
Site-specific Field Sampling Plan
Tie Sulphur Bank Mercury Mine (SBMM) site was selected as a sample material source site for the X-
ray fluorescence (XRF) technologies demonstration. The site contains native and contaminated soil as a
result of steel manufacturing operations and has some of the key elements being targeted for the
demonstration. The specific metals of interest for the SBMM site include arsenic, copper, and nickel
Tliis site-specific addendum to the Pre-Demonstration Sampling and Analysis Plan (SAP) describes the
site location, proposed sample locations, and soil sample collection methodology.
1.0 Site and Sample Locations
SBMM is located approximately 80 mi north of San Francisco, California within the Coast Ranges
geomorphic province of California. SBMM is a 160-acre site located on the eastern shore of the Oaks
Arm of Clear Lake, Lake County, California. The major site feature of the site, Herman Impoundment, is
located in the North l/z, Southwest 1A, Section 5, Township 13 North, Range 7 West (Mount Diablo Base
arid Meridian). The site is reached by driving west on State Highway 20 from Interstate 5 in California's
Central Valley; or by following State Highway 29 north from Vallejo, California to State Highway 53
north, and then turning west onto State Highway 20 north of the town of Clear Lake. Access to the site
c£in be accessed by along the northwestern side of Sulphur Bank Drive, about 1.5 mi south-southwest of
its intersection with State Highway 20.
The site is approximately 0.5 mi south of Clearlake Oaks (population 2,677) and 5 mi northwest of the
town of Clear Lake (population 15,200). SBMM is bound to the west by the Oaks Arm of Clear Lake, to
the north by the Sulphur Bank Rancheria (Rancheria) and a wetland adjacent to Clear Lake, to the east by
property used for agricultural purposes, to the south by forested slopes, and to the southeast by the
residential area of Sulphur Bank Point. The Rancheria is also known as the Elem Tribal Colony of
Southeastern Porno Native Americans. The Rancheria contains residential housing for the tribal
members.
Between 1864 and 1957, SBMM was the site of underground and open pit mining operations that
spatially coincided with the hydrothermal vents and hot springs. Mining disturbed about 160 ac at
SBMM and generated overburden (soil and rock removed to allow mining activity), waste rock (rock not
containing economic concentrations of mercury that was removed from the mine to gain access to ore),
tailings (ore that was processed to remove the mercury), and ore (rock containing economic
concentrations of mercury that was mined and stockpiled for mercury extraction). The overburden, waste
rock, tailings, and ore are distributed in piles throughout the mine site. Remnants of the mill and other
mine related structures are also present at the site.
SB-1
-------
TABLE SB-1
WEST WASTE ROCK PILE XRF DATA
SULPHUR BANK MERCURY MINE SITE
Metal
Arsenic
Antimony
Mercury
Maximum Concentration " (mg/kg)
532
3,724
4,296
mg/kg = milligrams per kilogram
a Metals data generated using x-ray fluorescence.
2.0 Site-specific Soil Sampling Procedures
This section discusses specific sampling procedures to be used at the SBMM site. The procedures listed
in Section 2.0 of the pre-demonstration SAP for completing the field analysis, collecting soil samples,
sample processing, and for maintaining sample integrity will be followed.
The in situ and composite soil samples for XRF analysis will be completed using the procedures
described in the pre-demonstration SAP. The elements of interest at the SBMM site for sample collection
are arsenic, antimony, and mercury.
Soil Samples
Historical data at the SBMM site was used to generally identify areas where metals-containing soil and
background soil will be collected. Sampling areas will be delineated and refined by establishing 10-foot
by 10-foot grids in the vicinity of known hot spots. Each grid will be subdivided into 1-foot by 1-foot
grid-cells. For each grid, soil samples will be collected from five of the grid-cells and homogenized for
XRF field screening. The sample design and homogenization procedures to be followed in the field are
described in more detail in the pre-demonstration SAP.
It may be necessary at some locations to remove vegetation before performing the XRF screening
measurement. The XRF field screening will be performed in accordance with the procedures detailed in
the SAP. Following field screening of soil and confirming that elements of interest are present, soil
samples will be collected using a decontaminated shovel or similar sampling device. The sample material
will be sieved using a coarse mesh size to remove any large fragments of metal or other debris from the
soil. After the soil has been sieved, the remaining portion of soil will be placed in a 5-gallon bucket,
which will be packaged at the site, and shipped to the characterization laboratory for sample processing
and analysis.
Preliminary estimates for the sample volumes of contaminated soil and clean soil required for the
demonstration are 80 pounds of contaminated soil and 40 pounds of clean soil.
SB-2
-------
Torch Lake Superfund Site
Site-specific Field Sampling Plan
1.0 Site-specific Objectives
The Torch Lake Superfund site was selected as a sample material source site for the X-ray
fluorescence (XRF) technologies demonstration. Native and contaminated sediment from copper
mining, milling, and smelting activities contain the elements targeted for the demonstration. The
specific metals of concern for the Torch Lake Superfund site include arsenic, chromium, copper,
lead, mercury, selenium, silver, and zinc. This site-specific addendum to the pre-demonstration
sampling and analysis plan (SAP) defines the site location, proposed sampling locations, and
methodology for collecting sediment samples.
2.0 Site and Sample Locations
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 (EPA 2004). 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 approximately 20 percent of
the lake's original volume (EPA 2001). 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: poor rock piles, slag and slag-enriched sediments, stamp sands, and abandoned settling
ponds for mine slurry.
Some of the wastes deposited in Torch Lake and on the shoreline were dredged up during the
early 1900s and were processed to reclaim copper. According to the U.S. Environmental
Protection Agency (EPA), Torch Lake also has received "mine pumpage, leaching chemicals,
explosive residues, and by-products." hi 1972, approximately 27,000 gallons of cupric
ammonium carbonate were discharged into the lake from storage vats. Peninsula Copper
Company (Peninsula Copper), which reclaims copper oxide from scrap electronic circuit boards,
is currently the only active facility along the lake's shoreline. During the early 1980s, Peninsula
Copper reportedly dumped processing water, containing 2,400 times the local sewage authority's
allowable limits for copper and 100 times the limit for ammonia, into the Tamarack lagoon
system (EPA 2004).
EPA began an investigation at Torch Lake in 1988, focusing on locating drums buried in the
tailings piles on the western shore and at the bottom of Torch Lake. Twenty drums were located
on the surface and samples were collected from the drums. In 1990, 12 additional drum locations
were excavated and sampled. EPA removed the contaminated drums and soil beneath the drums
from the lake.
In 1990, EPA performed field work that involved characterizing tailings and slag piles (EPA
2004). hi 1992, EPA selected a remedy that involved (1) covering approximately 800 acres of
TL-1
-------
tailings and slag piles with soil and vegetation, and (2) long-term monitoring of Torch Lake.
Design of the remedy began in fall 1992 and was completed in September 1998. Also in 1992,
EPA sampled surface water, sediment, and groundwater contaminated by the tailings piles.
Based on the analytical results, EPA in early 1994 selected a "No Action" remedy since
contamination levels were within safety standards (EPA 2004).
Construction of the soil and vegetative cap began in September 1998, and on-site construction
started in the summer of 1999. By fall 2002, approximately 500 acres of mine tailings along the
western shore of Torch Lake and about 115 acres along the northern shores of Portage Lake had
been remediated. A partial National Priorities List delisting of the Lake Linden portion of the site
and all of Operable Unit 2 was finalized in April 2002. Long-term monitoring of Torch Lake was
initiated in 1999 with the first monitoring event (the baseline study) and was completed in August
2001. Results of the baseline study are included in the baseline study report dated August 2001.
In addition, the 5-year review was completed on March 4, 2003 (EPA 2004).
Sediment collected from Torch Lake will be processed as sample material for the XRF
demonstration. Table TL-1 presents existing analytical data for sediments in the lake. Sediment
samples will be collected from the lake using a vibracorer or ponar sampler.
TABLE TL-1
ANALYTICAL DATA
TORCH LAKE SUPERFUND SITE
Metal
Arsenic
Chromium
Copper
Lead
Mercury
Selenium
Silver
Zinc
Concentration"'"
(rag/kg)
40
90
5,850
325
1.2
0.7
6.2
630
mg/kg = milligrams per kilogram
a Data for metals were generated using procedures defined by
the EPA Contract Laboratory Program Inorganic Statement
of Work.
b Concentrations in the table represent the maximum detected
in sediment samples collected by the EPA in 1999 and 2000.
3.0 Site-specific Sediment Sampling Procedures
This section discusses specific sampling procedures to be used at the Torch Lake Superfund Site.
The procedures listed in Section 2.0 of the pre-demonstration SAP for completing the field
analysis, collecting soil samples, sample processing, and maintaining sample integrity will be
followed. Sediments samples will be collected using (1) a ponar sampler for surface sediment
samples, or (2) a vibracorer for deep sediment samples. Sample locations will be selected based
TL-2
-------
on previous sediment sampling locations and analytical data (EPA 2001). Samples of
background sediment will be collected from locations in the lake where the targeted elements
were not detected above the laboratory reporting limits
Contaminated and background sediment samples will be collected using a ponar sampler or
vibracorer, depending on the sampling depth targeted. A boat-mounted mobile vibracoring
system, provided by EPA's Great Lakes National Program Office (GLNPO), will be used to
collect the sediment samples. A ponar sampler will also be available on the boat to collect
shallow sediment samples. GLNPO personnel will operate the vibracorer system and the ponar
sampler.
Vibracorer sediment samples will be collected with 3.75-inch-diameter cellulose acetate butyrate
(CAB) tubes in 10-foot lengths. A stainless steel nose piece with core catcher is attached to the
lower end of the core tube assembly to retain the maximum amount of sediment in the core tube
(AScI Corporation 2004). In addition, the vibra head contains a ball check valve to help retain
sediments when the tube is extracted. However, the sediments in Torch Lake are unconsolidated,
so steps will be taken to ensure maximum recovery of sediments contained in the vibracorer core
tube. Immediately after the vibracorer is retrieved to the surface of the lake, a 5-gallon bucket
will be placed under the core tube to allow the sediments to drain into the bucket. Each sediment
sample will be contained in a separate 5-gallon bucket.
Surface sediment samples (from depths of up to 2 inches below the top of the sediment surface)
will be collected using a ponar sampler. The sediment collected using the ponar sampler will be
placed in a 5-gallon bucket immediately after the sampling device is retrieved.
Table TL-2 lists the EPA sample identification numbers and the XRF sampling identification
number to be used for this sediment sampling project.
Each sediment sample (collected in a separate 5-gallon bucket) will be packaged at the site and
shipped to the designated analytical laboratory for preparation. The samples will be dried at the
laboratory. The sediment samples will be screened by Tetra Tech EM Inc. personnel at the
laboratory for the target elements using an XRF once the moisture content is sufficiently low to
allow proper XRF analysis. The bulk sample XRF analysis will be completed using the
procedures described in the SAP. The metals of most interest at Torch Lake are copper, lead, and
zinc. The available site data indicates that when one of these metals are present, the other metals
are also present. The end point for field XRF analysis will be selected as 10 percent relative
standard difference for copper.
TL-3
-------
TABLE TL-2.
SAMPLE IDENTIFCATION NUMBERS AND TARGET ELEMENTS FOR EACH
SAMPLE LOCATION
U.S. EPA Location ID/
Sample ID Number2
TL0002/TLOOPON0201
TL0007/TLOOPON0601
TL9915/TL99SED1001,
TL99SED1004
TL9916/TL99SED1601
TL9903/TL99SED0303
TL9910/TL99SED0701
through 0704
TL0005/TLOOPON0501
TL9904/TL99SED0203
Sample Location
(X/Y)
25894640.28/876510.33
258992256.39/874703.29
25884416.34/861831.7983
25893267.66/875363.9579
25898638.11/875438.4122
25894743.84/869792.4411
25899424.95/874897.41
25894086.33/876157.7201
XRF
Demonstration
ID Number
TL-U-01
TL-U-02
TL-U-03
TL-U-04
TL-U-05
TL-U-06
TL-U-07
TL-U-08
Surface or
Deep Sample
Surface
Surface
Deep
Deep
Deep
Deep
Surface
Deep
Target Dements1
Arsenic,
Chromium, Copper,
Lead, Silver, Zinc
Arsenic,
Chromium,
Copper, Lead,
Silver, Zinc
Mercury
Arsenic, Chromium,
Copper, Lead,
Silver, Zinc
Arsenic, Chromium,
Copper, Silver,
Zinc
Background
Background
Arsenic, Chromium,
Copper, Lead,
Silver, Zinc
1 Bold denotes that the highest concentration was detected at that location.
2 Sample coordinates in Michigan State Plane North, NAD1983, in feet.
4.0 REFERENCES
AScI Corporation. 2004. Collecting Sediment Samples by Vibracoring
(Submersible or Pole System), Standard Operating Procedure.
U.S. Environmental Protection Agency. 2001. Torch Lake Superfund Site, Houghton County,
Michigan. August.
U.S. Environmental Protection Agency. 2004. Torch Lake Superfund Site.
http://www.epa.gov/region5/sites/torchlake/. Accessed July 12, 2004.
TL-4
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Roaster Slag Pile
Wickes Smelter Site
Site-specific Field Sampling Plan
1.0 Site-specific Objectives
The roaster slag pile at the Wickes Smelter site was selected for inclusion in the demonstration of
X-ray fluorescence (XRF) technologies for measuring elements in soil and sediments because
elevated concentrations of elements of interest have been detected in samples at this site. This
site-specific addendum to the Pre-demonstration Sampling and Analysis Plan defines the site
location, proposed sample location, and sample collection methodology.
2.0 Site and Sample Locations
The Wickes Smelter site is located in the unincorporated town of Wickes, Jefferson County,
Montana. The wastes present at the Wickes Smelter site include waste rock, slag, flue bricks, and
amalgamation waste. The wastes are found in discrete piles and mixed with soil. The waste
targeted by the XRF demonstration is the roaster slag mixed with soil. Table WS-1 presents
existing analytical data for the targeted slag pile. The roaster slag pile has easy access and is
exposed at the surface with no vegetative cover. A sample of relatively clean soil will be
collected from the hillside north of the smelter.
TABLE WS-1.
HISTORICAL ANALYTICAL DATA"
ROASTER SLAG PILE
Metal
Antimony
Arsenic
Cadmium
Chromium
Copper
Iron
Lead
Mercury
Nickel
Selenium
Silver
Zinc
Maximum Concentration (mg/kg)
79.02
3182
69.7
13.55
947.6
24,780
33,500
Not Analyzed
7.29
Not Detected
83.09
5,299
mg/kg = milligrams per kilogram
Other detected parameters not included.
WS-1
-------
3.0 Site-specific Soil Sampling Procedures
High concentrations of several elements of interest for this XKF demonstration were found in a
previously collected sample of this roaster slag during the pre-demonstration sampling. The
roaster slag pile will be targeted for sampling using a grid centered on the previous analyzed
sample location.
The procedures listed in Section 2.0 of the Pre-Demonstration Sampling Plan for completing the
field analysis, soil sample collection, sample processing, and for maintaining sample integrity
will be followed. The soil samples will be collected using a decontaminated shovel to fill the
five-gallon buckets. The background soil samples will be collected from an undisturbed area on
the hill north of the site. The background soil sample will be collected by removing the
vegetative and woody debris and then using a clean shovel to fill the five-gallon bucket.
Preliminary estimates of the volume of roaster slag pile material and background soil needed to
be collected for the demonstration are 125 pounds of roaster slag pile material and 280 pounds of
background or "clean" soil.
WS-2
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Appendix B
Health and Safety Plan
-------
I Tetra Tech EM Inc.
HEALTH AND SAFETY PLAN
Site Name: Kennedy Athletic, Recreational & Social (KARS)
Park
Location: Kennedy Space Center in Merritt Island, Florida
EPA I.D. No. NA
Project No. G9008.42.001.00
Project Manager: Julia Capri
EPA Client Contact: Or. Stephen Billets
NASA Contact: Mark Speranza/ Michael Delitz
Date of Proposed Activities: January 24 - 28, 2005
Objectives:
A demonstration of innovative XRF technologies will be conducted in a
building previously used as a convenience store at the site.
Participating developers will be presented samples that were
previously prepared and containerized for analysis by field portable
instrumentation. These samples will contain a variety of elements that
include metals that will be analyzed. The technologies will be
evaluated while performing analysis to determine performance
evaluation objectives for the program. No additional sampling will be
performed during the demonstration.
Site Type: Check as many as applicable.
I X I Active I I Confined space I I
I I Inactive I I Landfill [ I
I X I Secure I I Uncontrolled I I
I I Unsecure I I Industrial I Xl
Telephone: 513-564-8342
Telephone: 702-798-2232
Date: January 03, 2005
Well field
Unknown
Underground storage tank
Other (specify)
Park
Site Description and History:
The KARS Park site is located at the Kennedy Space Center in Merritt Island, Florida (Figure A1). 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 (NASA 2003). KARS
Park occupies an area of Kennedy Space Center property located just outside the Cape Canaveral base. Contaminants in the park resulted from historical facility
operations and impacts from the former gun range. Previous sampling events indicated the presence of inorganic contamination, including antimony, arsenic,
chromium, copper, lead, and zinc at the site. The land north of KARS is owned by NASA and is managed by the U.S. Fish and Wildlife Service (USFWS) as part
of the Merritt Island National Wildlife Refuge (NASA 2003).
During the XRF demonstration activities, no sampling will occur. Developers will analyze previously prepared and containerized samples using field portable
instrumentation. Areas on-site that have been identified as contaminated will not be used or accessed by personnel conducting the demonstration. All personnel
on site, including Tetra Tech and site visitors, must be informed of the site emergency response procedures and any potential fire, explosion, health, or safety
hazards associated with on-site activities. Developers, EPA personnel, and site visitors may choose to follow the health and safety procedures outlined in this
plan. However, each employer is directly and fully responsible for the health and safety of its own employee. Exposure to potential chemical hazards will be
limited to personnel handling the prepared samples that will be evaluated by XRF. These samples will be contained in sample vials and therefore the potential for
direct contact with these materials is low.
Note: A site map is provided on Page 9 of 12. Definitions and additional information about this form are provided on Page 12 of 12.
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I Tetra Tech EM Inc.
HEALTH AND SAFETY PLAN
Waste Management Practices:
Contaminants in the park resulted from historical facility operations and impacts from the former gun range. During performance of the demonstration waste
generated from sample analysis will be collected in specially labeled drums for proper disposal. No sampling or decontamination activities will be conducted
during the demonstration. If any potentially hazardous materials are brought to the demonstration site by developers, they are required to provide Tetra Tech
with an MSDS for these materials as required by the hazard communication standard.
Waste Types:
Liquid
Solid
Sludge
Gas
Unknown
Waste Characteristics:
Corrosive
Toxic
Inert
Ignitable
Flammable
Volatile
I I Reactive
I I Radioactive
I I Unknown
I I Other (specify)
Hazards of Concern:
I XI Heat stress
CD Cold stress
I I Explosion or fire hazard
I I Oxygen deficiency
I I Radiological hazard
I I Underground storage tanks
I I Surface tanks
I I Buried utilities
I I Overhead utilities
I I Biological hazard
I I Noise
I Xl Inorganic chemicals
I I Organic chemicals
I I Heavy equipment
I XI Other (specify) Wildlife (alligators, snakes)
Explosion or Fire Potential: I I High
Medium
Low
Unknown
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Iretra Tech EM inc. HEALTH AND SAFETY PLAN
Chemical Products Tetra Tech EM Inc. Will Use or Store On Site: (Attach a Material Safety Data Sheet [MSDS] for each item.)
I I Alconox®orLiquinox®
I I Hydrochloric acid (HCI)
I I Nitric acid (HNO3)
I I Sodium hydroxide (NaOH)
I I Sulfuric acid (H2SO4)
I I Other (specify)
I I Other (specify)
I I Other (specify)
I I Other (specify)
I I Other (specify)
I I Other (specify)
I I Other (specify)
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I Tetra Tech EM Inc.
HEALTH AND SAFETY PLAN
Chemicals Present at
Site
Antimony
Arsenic
Chromium
Copper (dusts and mists)
Lead
Zinc
Highest Observed
Concentration
(specify units and
media)
301 ppm in soil
26.8 ppm in soil
1 12 ppm in soil
1,520 ppm in soil
16, 900 ppm in soil
5,110 ppm in soil
PEL/TLV
(specify
ppm or
mg/m3)
0.5 mg/m3
0.5 mg/m3
0.5 mg/m3
(NIOSH); 1.0
mg/m3 (OSHA)
1 mg/m3
0.1 00 mg/m3
(NIOSH); 0.050
mg/m3 (OSHA)
NA
IDLH Level
(specify
ppm or
mg/m3)
50 mg/m3 (as
Sb)
N.D.
250 mg/m3 (as
Cr)
100 mg/m3
100 mg/m3 (as
Pb)
NA
Symptoms and Effects of Acute Exposure
Irrit eyes, skin, nose, throat, mouth; cough; dizz;
head; nau, vomit, diarr; stomach cramps; insom;
anor; unable to smell properly
In animals: irrit skin, possible derm; resp distress;
diarr; kidney damage; muse tremor, sez; possible Gl
tract, terato, repro effects; possible liver damage
Irrit eyes, skin; lung fib (histologic)
Irrit eyes, nose, pharynx; nasal pert; metallic taste;
derm; in animals: lung, liver, kidney damage; anemia
Weak, lass, insom; facial pallor; pal eye, anor, low-
wgt, malnut; constip, abdom pain, colic; anemia;
gingival lead line; tremor; para wrist, ankles;
encephalopathy; kidney disease; irrit eyes;
hypotension
NA
Photo-
ionization
Potential
(eV)
NA
NA
NA
NA
NA
NA
Notes: NIOSH Pocket Guide to Chemical Hazards
A = Air
CARC = Carcinogenic
eV = Electron volt
GW = Groundwater
IDLH = Immediately dangerous to life or health
mg/m3 = Milligram per cubic meter
NA = Not available
NE = None established
PEL = Permissible exposure limit
ppm = Part per million
S = Soil
SW = Surface water
TLV = Threshold limit value
U = Unknown
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I Tetra Tech EM Inc.
HEALTH AND SAFETY PLAN
Field Activities Covered Under This Plan:
Task Description
Type
Level of Protection
Primary
Contingency
Date of Activities
1 Soil and sediment analysis of prepared samples
I I Intrusive
I X I Nonintrusive
i i c m c
To be worn during
clean-up if a sample
container breaks.
January 24-28, 2004
2 NA
I I Intrusive
I I Nonintrusive
LJ D
NA
Site Personnel and Responsibilities (include subcontractors):
Employee Name and Office Code
Task
Responsibilities
Julie Capri -CN
Stephanie Wenning - CN
Stan Lynn - CN
Judith Wagner-AH
Project Manager: Directs investigation and field activities, informs site safety coordinator
(SSC) of pertinent project developments and plans, and maintains communications with
client as necessary.
Site Safety Coordinator (SSC): Ensures that appropriate personal protective equipment
(PPE) is available, enforces proper utilization of PPE by on-site personnel, suspends
investigative work if she believes that site personnel may be exposed to an immediate
health hazard, implements the health and safety plan, and reports any observed
deviations from anticipated conditions described in the health and safety plan to the
health and safety representative.
Site Superintendant: Supervises on-site project activities, complete tasks as directed by
the project manager, field team leader, and SSC and follow all procedures and guidelines
established in the Tetra Tech, Inc., Health and Safety Manual.
Reviews and approves health and safety plan; overall director of Tetra Tech's Health and
Safety program.
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I Tetra Tech EM Inc.
HEALTH AND SAFETY PLAN
Protective Equipment: (Indicate type or material as necessary for each task; attach additional sheets as necessary)
Task: I~x1 1
Level: I I C
I X I Primary
RESPIRATORY
I X I Not needed
I I APR:
I I Cartridae:
I I Escape mask:
I I Other:
HEAD AND EYE
I I Not needed
I X I Safety glasses:
I I Face shield:
I.,., , J Goaales:
I I Hard hat:
| | Other:
FIRST AID EQUIPMENT
I I Not needed
I X I Standard First Aid
I I Portable eyewash
OTHER (specify) Sandals
areas where samples are
Note: APR = Air purifying
I I Contingency
PROTECTIVE CLOTHING
I X I Not needed
I I TyvekfiQ coveralls:
I I Saranex® coveralls:
I I Coveralls:
I I Other:
GLOVES
I I Not needed
| ] Underaloves:
I X I Gloves: Nitrile or latex
examination gloves while
handlino. samples
I I Overaloves:
BOOTS
I X I Not needed
kit C^| Work boots:
I I Overboots:
i or other open-toed shoes are not permitted in
beina analyzed.
respirator
Task: [XI 1
Level: I I C
I I Primary
RESPIRATORY
I X I Not needed
I I APR:
|^ Cartridae:
I I Escape mask:
| | Other:
HEAD AND EYE
I I Not needed
I Xl Safety classes:
I I Face shield:
[ | Goaales:
I I Hard hat:
I I Other:
FIRST AID EQUIPMENT
I I Not needed
I Xl Standard First Aid kit
I I Portable eyewash
OTHER (soeciM Sandals or other o
where samples are beina analyzed.
I 2
j[] D
I X I Contingency
PROTECTIVE CLOTHING
I I Not needed
I I Tyvek® coveralls:
I I Saranex® coveralls:
| Xl Coveralls: If needed
| | Other:
GLOVES
I I Not needed
I I Underaloves:
I Xl Gloves: latex or vinyl
examination gloves while
handling samples
I I Overaloves:
BOOTS
I Xl Not needed
I I Work boots:
[— ]
pen-toed shoes are not permitted in areas
Hearina protection should be utilized if
needed.
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1 Tetra Tech EM Inc.
HEALTH AND SAFETY PLAN
Monitoring Equipment: (Specify instruments needed for each task; attach additional sheets as necessary)
Instrument
Combustible gas indicator model:
02 meter model:
Radiation survey meter model:
Photoionization detector model:
CZI n.7eV
I 1 10.2eV
dH 9.8 eV
CZ] eV
Flame ionization detector model:
Detector tube models:
Respirable dust monitor model:
Other: (specify)
XRF Instrumentation (various vendor
equipment)
Task
en 1
CZI 2
CZI 1
en 2
cm 1
C=l 2
C=] 1
a 2
en 1
en 2
en 1
en 2
C=l 1
C=] 2
en 1
C=l 2
Instrument Reading
Oto 10%LEL
10 to 25% LEL
>25% LEL
>23.5% O2
23. 5 to 19. 5% O2
<19.5%O2
<2 mrem per hour
Three times background
>2 mrem per hour
Background or no instrument response
Background to 5 ppm
5 to 500 ppm
Background or no instrument response
Background to5 ppm
5 to 500 ppm
Specify:
Specify:
Specify:
Action Guideline
No explosion hazard
Potential explosion hazard; notify SSC
Explosion hazard; interrupt task;
evacuate site; notify SSC
Potential fire hazard; evacuate site
Oxygen level normal
Oxygen deficiency; interrupt task;
evacuate site; notify SSC
Normal background
Notify SSC
Radiological hazard; interrupt task;
evacuate site; notify SSC
Level D
Level C
Evacuate site; notify SSC
Level D
Level C
Evacuate site; notify SSC
Specify:
Specify:
Specify:
Comments
I X I Not needed
I X I Not needed
Note: Annual exposure not to exceed | X I Not needed
1,250 mrem per quarter
Note: These action guidelines are used I X I Not needed
when monitoring unknown organic
vapors.
Note: These action guidelines are used | X I Not needed
when monitoring unknown organic
vapors.
Note: The action level for upgrading the | X I Not needed
level of protection is one-half of the
contaminant's PEL. If the PEL is
reached, evacuate the site and notify
the SSC.
[ x I Not needed
Note: Instruments will measure I I Not needed
concentrations of metals in soil only, and will
not be used for determining H&S hazards
Notes:
eV = Electron volt
LEL = Lower explosive limit
mrem = Millirem
O2 = Oxygen
PEL = Permissible exposure limit
ppm = Part per million
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I Tetra Tech EM Inc.
HEALTH AND SAFETY PLAN
Additional Comments:
Emergency Contacts:
Telephone
The XRF technologies that will be evaluated during the demonstration use small
radioactive isotope or x-ray tube sources. The potential for exposure to ionizing
radiation from these sources is minimal. Tetra Tech personnel will not be
operating these technologies, and the instrument vendor is responsible for
limiting any access to, or any activities conducted near the equipment by EPA,
Tetra Tech, and any site visitors.
800-424-8802
800-535-5053
911 or 321-467-7911
911 or 321-467-7911
U.S. Coast Guard National Response Center
InfoTrac
Fire Department
Police Department
Tetra Tech EM Inc. Personnel:
Human Resource Development: Norman Endlich 703-390-0626
Health & Safety Representative: Judith Wagner 847-818-7192
Office Health & Safety CoordinatonStephanie Wenning 513-241-0149
Project Manager/ Field Manager: Julia Capri 513-241-0149
Julia Capri (cell) 513-708-5982
Site Safety Coordinator: Stephanie Wenning 513-241-0149
Stephanie Wenning (cell) 513-225-6692
Personnel Decontamination and Disposal Method:
Medical Emergency:
Personnel will follow the U.S. Environmental Protection Agency's "Standard
Operating Safety Guides" for decontamination procedures for Level D personal
protection (with Level C contingency). The following decontamination stations
should be set up in each decontamination zone:
Segregated equipment drop
Boot and glove wash and rinse
• Disposable glove, bootie, and coverall removal and segregation station
Safety glasses and hard hat removal station
Hand and face wash and rinse
If site conditions require upgrade to Level C, a station must be set up for
respirator removal, respirator decontamination, and cartridge disposal.
All disposable equipment, clothing, and wash water will be double-bagged or
containerized in an acceptable manner and disposed of in accordance with local
regulations.
Hospital Name:
Hospital Address:
Hospital Telephone:
Cape Canaveral Hospital
701 West Cocoa Beach Causeway
Cocoa Beach, Florida 32931-3583
Emergency - 911
General-(321) 799-7111
Ambulance Telephone: 911
Route to Hospital: Starting at E. Hall Rd. at Audubon Road, Merritt Island,
Florida, Go west on Hall Rd. (E) for 2.9 miles. Turn left onto SR-3 South
(Courtenay Parkway N) and travel 2.1 miles. Turn left on ramp to SR-528
E (SR-A1A). Continue onto SR-A1A S (Astronaut Blvd) for 3.9 miles.
Turn right onto SR-520 W (Cocoa Beach Csway W) 0.8 miles to 701 W.
Cocoa Beach Cswy, Cocoa Beach, Florida. (Hospital is on the right.)
Note: This page must be posted on site
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HEALTH AND SAFETY PLAN
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I Tetra Tech EM Inc.
HEALTH AND SAFETY PLAN
Cape Canaveral Hospital
701 West Cocoa Beach Causeway
Cocoa Beach, Florida 32931-3585
Hospital Route Map (if available):
Phone Number: (321) 799-7111
Starting at E Hall Road at Audubon Road, Merritt Island, Florida (KARS Park)
Go West on Hall Road E for 2.9 miles.
Turn left onto SR-3 South (Courtenay Parkway North) and travel 2.1 miles.
Turn left on ramp to SR-528 E (SR-A1A S).
Continue on SR-528 E (SR-A1AS) for 4.6 miles.
Continue onto SR-A1A S (Astronaut Blvd) for 3.9 miles.
Turn right onto SR-520 W (Cocoa Beach CSWY W) 0.8 miles to 701 West Cocoa Beach
Causeway, Cocoa Beach, Florida (Hospital is on the right).
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Iretra Tech EM inc. HEALTH AND SAFETY PLAN
APPROVAL AND SIGN-OFF FORM
Project No. G9008.37.003.01
I have read, understood, and agree with the information set forth in this Health and Safety Plan and will follow the direction of the Site Safety
Coordinator as well as procedures and guidelines established in the Tetra Tech, Inc., Health and Safety Manual. I understand the training and
medical requirements for conducting field work and have met these requirements.
Name Signature Date
Name Signature Date
Name Signature Date
Name Signature Date
APPROVALS: (Two Signatures Required)
Site Safety Coordinator Date
Health and Safety Representative or Designee Date
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Iretra Tech EM inc. HEALTH AND SAFETY PLAN
DEFINITIONS
Intrusive - Work involving excavation to any depth, drilling, opening of monitoring wells, most sampling, and Geoprobe® work
Nonintmsive - Generally refers to site walk-throughs or field reconnaissance
Levels of Protection
Level D - Hard hat, safety boots, and safety glasses, Level D may include protective clothing such as gloves, boot covers, and Tyvek® or Saranex® coveralls
Level C - Hard hat, safety boots, glasses, and air purifying respirators with appropriate cartridges, Level C may include protective clothing such as gloves, boot
covers, and Tyvek® or Saranex® coveralls
Emergency Contacts
InfoTrac - For issues related to incidents involving the transportation of hazardous chemicals; this hotline provides accident assistance 24 hours per day, 7 days
per week
U.S. Coast Guard National Response Center- For issues related to spill containment, cleanup, and damage assessment; this hotline will direct spill information
to the appropriate state or region
Health and Safety Plan Short Form
• Used for field projects of limited duration and with relatively limited activities; may be filled in with handwritten text
Limitations:
— No Level B or A work
— No more than two tasks
— No confined space entry
— No unexploded ordnance work
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Appendix C
Field Forms
Daily Tailgate Safety Meeting Form
Daily Site Log
Accident and Illness Investigation Report
Field Audit Checklist
Respiratory Hazard Assessment
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TETRA TECH EM, INC.
DAILY TAILGATE SAFETY MEETING FORM
Date: Time: Project No.
Client: Site Location:
Site Activities Planned for Today:
Safety Topics Discussed
Protective clothing and equipment:
Chemical hazards:
Physical hazards:
Environmental and biohazards:
Equipment hazards:
Decontamination procedures:
Other:
Review of emergency procedures:
Employee Questions or Comments:
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TETRA TECH EM, INC.
DAILY TAILGATE SAFETY MEETING FORM (Continued)
Attendees
Printed Name
Signature
Meeting Conducted by:
Name
Title
Signature
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TETRA TECH EM, INC.
DAILY SITE LOG
Site Name:
Date:
Name (print)
Time
Company
In
Out
Comments:
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TETRATECHEM,INC.
ACCIDENT AND ILLNESS INVESTIGATION REPORT
To:
Subsidiary Health and Safety Representative
Cc:
Workers Compensation Administrator
Project name:
Project number.
Information Regarding Injured or III Employee
Name:
Home address:
Home telephone number:
Occupation (regular job title):
Department:
Date of Accident:
Time Employee Began Work:
Location of Accide nt
Street address:
City, state, and zip code:
County:
Prepared by:
Position:
Office:
Telephone number:
Fax number:
Office:
Gender: M CD F CD No. of dependents:
Marital status:
Date of birth:
Social Security Number:
Time of Accident: a.m. CD p.m. CD
CD Check if time cannot be determined
Was place of accident or exposure on employer's premises? Yes CD No CD
Information About the Case
What was the employee doing just before the incident occurred?: Describe the activity, as well as the tools,
equipment, or material the employee was using. Be specific. Examples: "climbing a ladder while carrying roofing materials"; "spraying
chlorine from hand sprayer"; "daily computer key -entry."
What Happened?: Describe how the injury occurred. Examples: "When ladder slipped on wet floor, worker fell 20 feet"; "Worker
was sprayed with chlorine when gasket broke during replacement"; "Worker developed soreness in wrist over time."
This form contains information relating to employee health and must be used in a manner that protects the confidentiality of the
employee to the extent possible while the information is being used for occupational safety and health purposes.
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TETRA TECH EM, INC.
ACCroENT AND ILLNESS INVESTIGATION REPORT (Continued)
Information About the Case (Continued)
What was the injury or illness? Describe the part oft
"hurt," "pain," or "sore." Examples "strained back"; "chemical
Describe the Object or Substance which Directly
"radial arm saw." If this question does not apply to the incidf
Did the employee die? Yes D No D
Was employee performing regular job duties? Yes [
Was safety equipment provided? Yes CD No CD
Note: Attach any police reports or related
he body that was affected and how it was affected; be more specific than
burn, right hand"; "carpal tunnel syndrome, left wrist."
Harmed the Employee: Examples: "concrete floor"; "chlorine";
:nt, enter NA.
Date of death:
H No CD
Was safety equipment used? Yes CD No CD
diagrams to this accident report.
Witness(es):
Name:
Company:
Street address:
City:
Telephone number:
State: Zip code:
Name:
Comnanv:
Street address:
City:
Telephone number:
Medical Treatment Required? CD Yes CD
Name of physician or health care professional:
If treatment was provided away from the work-site,
Facility name:
State: Zip.code:
No CD First Aid only
where was it given?
Street address:
City:
Telephone number:
Was die employee treated in an emergency room?
State: Zip code:
CD Yes CD No
This form contains information relating to employee health and must be used in a manner that protects the confidentiality of the
employee to the extent possible while the information is being used for occupational safety and health purposes.
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TETRA TECH EM, INC.
ACCmENT AND ILLNESS INVESTIGATION REPORT (Continued)
Was the employee hospitalized overnight as an in-patient? LJ Yes CH No
Corrective Action(s) Taken by Unit Reporting the Accident:
Corrective Action Still to be Taken (by whom and when):
Name of Tetra Tech employee the injury or illness was first reported to:
Date of Report: Time of Report:
I have reviewed this investigation report and agree, to the best of my recollection, with its contents.
Printed Name of Injured Employee
Telephone Number
Signature of Injured Employee
Datee
The signatures provided below indicate that appropriate personnel have been notified of the incident.
Title
Project or Office Manager
Site Safety Coordinator
Printed Name
Signature
Telephone Number
Date
This form contains information relating to employee health and must be used in a manner that protects the confidentiality of the
employee to the extent possible while the information is being used for occupational safety and health purposes.
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EH!
TETRA TECH EM, INC.
ACCIDENT AND ILLNESS INVESTIGATION REPORT (Continued)
To be completed by the Subsidiary Safety and Health Representative:
Classification of Incident:
CD Injury CD Illness
Result of Incident:
D First Aid Only
CD Days Away From Work
CD Remained at Work but Incident Resulted in Job Transfer or Work Restriction
CD Incident Involved Days Away and Job Transfer or Work Restriction
CD Medical Treatment Only
No. of Days Away From Work
Date Employee Left Work
Date Employee Returned to Work
No. of Days Placed on Restriction or Job Transfer:
OSHA Recordable Case Number
To be completed by Human Resources:
SSN:
Date of hire:
Wage information: $ per
Position at time of hire:
Current position:
State in which employee was hired:
Status: CD Full-time CD Part-time
Temporary job end date:
Hire date in current job:
D Hour D Day CD Week CD Month
Shift hours:
Hours per week: Days per week:
To be completed during report
Date reported:
Confirmation number:
to workers' compensation carrier:
Reported by:
Name of contact:
Field office of claims adjuster:
This form contains information relating to employee health and must be used in a manner that protects the confidentiality of the
employee to the extent possible while the information is being used for occupational safety and health purposes.
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TETRA TECH EM, INC.
FIELD AUDIT CHECKLIST
Project Name: _
Field Location:
Project Manager:
Project No.:
Completed by:
Site Safety Coordinator:
General Items
Health and Safety Plan Requirements
1
2
3
4
5
6
7
8
9
10
11
12
Approved health and safety plan (HASP) on site or available
Names of on-site personnel recorded in field logbook or daily log
HASP compliance agreement form signed by all on-site personnel
Material Safety Data Sheets on site or available
Designated site safety coordinator present
Daily tailgate safety meetings conducted and documented
On-site personnel meet HASP requirements for medical examinations, fit
testing, and training (including subcontractors)
Compliance with specified safe work practices
Documentation of training, medical examinations, and fit tests available from
employer
Exclusion, decontamination, and support zones delineated and enforced
Windsock or ribbons in place to indicate wind direction
Illness and injury prevention program reports completed (California only)
Emergency Planning
13
14
15
16
17
18
Emergency telephone numbers posted
Emergency route to hospital posted
Local emergency providers notified of site activities
Adequate safety equipment inventory available
First aid provider and supplies available
Eyewash stations in place
Air Monitoring
19
20
21
23
Monitoring equipment specified in HASP available and in working order
Monitoring equipment calibrated and calibration records available
Personnel know how to operate monitoring equipment and equipment manuals
available on site
Environmental and personnel monitoring performed as specified in HASP
In Compliance?
Yes
No
NA
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TETRA TECH EM, INC.
FIELD AUDIT CHECKLIST (Continued)
Safety Items
Personal Protection
1
2
3
4
5
6
7
8
9
Splash suit
Chemical protective clothing
Safety glasses or goggles
Gloves
Overboots
Hard hat
Dust mask
Hearing protection
Respirator
Instrumentation
10
11
12
Combustible gas meter
Oxygen meter
Organic vapor analyzer
Supplies
13
14
15
Decontamination equipment and supplies
Fire extinguishers
Spill cleanup supplies
In Compliance?
Yes
No
NA
Corrective Action Taken During Audit:
Corrective Action Still Needed:
Note: NA = Not applicable
Auditor's Signature
Site Safety Coordinator's Signature
Date
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TETRATECHEM,INC.
RESPIRATORY HAZARD ASSESSMENT
Project Name: Project No.:
Location: Project Manager:
Type: D Baseline C Reassessment Date: Valid for days
Job/Task Description: D Routine
D Escape
Hazard Identification and Source: Workp
Ten
Hu
Oth
Chemical:
PEL:
ACGIH TLV:
Form (part/gas/vapor):
IDLH:
Eye Irritant (Y/N):
Skin Absorption(Y/N):
Monitoring (Y/N) :*
Frequency:
Maximum Concentration
Estimated:**
* Monitoring Method:
D PID D NIOSH method:
D FID D Vapor badge:
D Detector tube: D Other:
** If concentrations exceed the immediately dangerous to life and health
(IDLH) value, use air-supplied systems.
Cartridge/Filter Selection
D N100 Cl R100 D P100
D N99 D R99 D P99
D N95 d R95 D P95
C] Organic vapor C Acid gas
D Ammonia D Mercury D Formaldehyde
D Combo:
D Other:
Completed by Date
lace Factors:
nperature:
Tiidity:
er:
User Factors:
Work rate:
Protective clothing:
Other:
Respirator Type:
O Half-face disposable Brand:
D Half-face reusable
D Full-See
D Air-supplied airli
D Air-supplied SC
D PAPR
D ESCBA
Brand:
Brand:
ne Brand:
8A Brand:
Brand:
Brand:
Vapor and Gas Cartridge Exchange:
ESLI: D Yes D No
Exchange frequency:
Basis for Exchange Free
Cl Manufacturer's d
1H Experimental me
C] Predictive mode
D OSHA Regulatic
D Other:
uency
ata U Workplace simulations
mods D AIHA "Rules of Thumb"
ing CD Analogous chemical structure
n:
Reviewed by Date
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RESPIRATORY HAZARD ASSESSMENT (Continued)
DEFINITIONS AND ACRONYMS
ACGIH American Conference of Governmental Industrial Hygienists
AHA American Industrial Hygiene Association
EI3LI End of service life indicator
Fl'D Flame ionization detector
E)LH Immediately dangerous to life and health
N1OSH National Institute for Occupational Safety and Health
N100/99/95 Non-oil-proof paniculate filter
OSHA Occupational Safety and Health Administration
P100/99/95 Oil-proof paniculate filter
PEL Permissible exposure limit
PID Photoionization detector
PPE Personal protective equipment
R100/99/95 Oil-resistant paniculate filter
SCBA Self-contained breathing apparatus
TLV Threshold limit value
Note: This form must be reviewed by a regional health and safety representative or subsidiary health and
safety representative (or designee) only and must be attached to the site-specific health and safety
plan once completed. A copy must also be placed in the project files.
Page 2 of 2
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Appendix D
XRF Demonstration Project Schedule
-------
XRF Demonstration Project Schedule
MILESTONE
Contract awarded
Prepare project schedule
Select preliminary elements of concern for evaluation
Prepare preliminary developer invitation list
Prepare test plan annotated outline
Conduct first conference call
Distribute summary notes from first conference call
Prepare draft sample homogenization procedure
Submit request for technical proposal and cost estimate to
potential reference laboratory candidates
Obtain metals -contaminated soil from a site and test
homogenization procedures
Develop sampling and homogenization procedures
Receive proposals from reference laboratories
Draft sample strategy to accommodate all target elements.
Conduct second conference call
Distribute summary notes from second conference call
Deliver PE samples to proposed reference laboratories
Complete soil and sediment sample collection
Conduct third conference call
Distribute summary notes from third conference call
Complete audits for proposed reference laboratories
Complete first draft demonstration plan and submit to EPA
and developers
Complete final selection of reference laboratory
(KEY MILESTONE)
Receive comments on first draft demonstration plan
Distribute pre-demonstration samples to developers
(KEY MILESTONE)
Submit second draft demonstration plan to EPA, developers,
peer reviewers, and technical advisors
Receive comments on second draft demonstration plan
Distribute third (final) demonstration plan to EPA, developers,
peer reviews, and SITE demonstration participants for final
review
Receive pre-demonstration sample results from developer and
reference laboratory
Receive comments on final demonstration plan
SCHEDULED COMPLETION
DATE
April 1,2004
April 12, 2004
April 19, 2004
April 26, 2004
April 26, 2004
May 10, 2004
May 17, 2004
May 24, 2004
May 31, 2004
June 14, 2004
June 28, 2004
June 30, 2004
July 5, 2004
July 19, 2004
July 26, 2004
August 10, 2004
August 14, 2004
October 13, 2004
October 20, 2004
October 22, 2004
October 25, 2004
October 27, 2004
November 5, 2004
November 12, 2004
November 16, 2004
November 30, 2004
January 4, 2005
December 20, 2004
January 14, 2004
-------
XRF Demonstration Project Schedule (Continued)
MILESTONE
Finalize demonstration plan
(KEY MILESTONE)
Conduct fourth conference call
Distribute summary notes from fourth conference call
Conduct field demonstration
(KEY MILESTONE)
Submit first draft ITVR to EPA
Submit final draft of first ITVR to EPA
Submit final draft of other ITVRs to EPA
Submit all ITVRs for developer and peer review
Submit final ITVRs
SCHEDULED COMPLETION
DATE
January 2005
January 11, 2005
January 18, 2005
January 24-28, 2005
May 30, 2005
June 30, 2005
August 3 1,2005
September 30, 2005
tbd
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